Anda di halaman 1dari 216

CPD NR 3281

Conceptual Process Design


Process Systems Engineering
DelftChemTech - Faculty of Applied Sciences
Delft University of Technology

Subject:
Industrial green catalytic oxidation of 1-butanol
in an aqueous solvent.

Authors
C.I.S. Lesueur
S. Sijbesma
J.F. Cornax
S. Balkenende

(Study nr.)
(1160052)
(1057669)
(9162255)
(9032401)

Telephone
0613912140
0641190577
0647576626
0614481783

Keywords:
green catalytic oxidation 1-butanol butanal aqueous palladium bathophencuproine homogeneous

Assigment Issued:
Report Issued:
Appraisal:

September 30, 2002


December 31 , 2002
January 14, 2002

Summary
A conceptual process design is presented for oxidation of 1-butanol to butanal (butyraldehyde)
with a novel green catalytic method. The catalytic method used is under development at Delft
University of Technology. This new catalytic process is based on a water soluble bathophencuproine palladium complex. No other (design) application is known until now. A single aqueous
phase reactor at 21 bar and 403 K is designed. Butanal is mainly separated by ashing and
stripping and butanoic acid, a by-product, is separated by distillation and sold. Some process
options are developed and a process with preseparation of 1-butanol and 2-butanol is used for
design. Total capacity of the plant is 121 kton/y of butanal.
Butane is increasingly produced in nafta crackers due to change in polyethylene market. Ethylene production is decreased and larger olens are produced. Butane fraction in the product
stream of the nafta crackers increases with the increasing production of larger olens. Butane
is used as fuel, but by converting it to butanal via 1-butanol a valuable intermediate for polymer industry can be synthesized. Prices for butane, 1-butanol, butanal and butyric acid are
$188/ton, $772/ton, $1234/ton and $1000/ton respectively.
Global butanal market demand exceeds 1000 kton/y. Competitive market players (BASF,
Ruhrchemie, etc.) produce 300 kton/y, mainly by hydroformylation of propene (LP OxoT M
Low Pressure Oxo Process). Minor processes in use are hydrogenation of crotonaldehyde and
dehydrogenation of butanol. Impact of the designed plant on global market is expected to be
minimal because growing butanal demand and own use for polymer division.
Total investment for the plant will be 12.07 M$, and economical life time is expected to be
20 years. Additional time for designing and construction will be 4 years. An on-stream factor of
0.91 is expected. The process is liquid based, no solids are present and low fouling is expected.
The NPW is M$ 211 (based on discount rate of 10%), DCFROR is 55% and ROR will be 88%.
10% higher variable cost and 10% lower income results in a DCFROR of 29% and a ROR of
19%.
From the design it can be concluded that the plant is feasible (high cash ow and ROR),
the plant is safe according to DOW F&EI and HAZOP studies, little waste is produced and
no (environmental) toxic chemicals are used. Recommendations for further studies and detailed design are necessary to obtain more information on catalyst deactivation and catalyst
performance at higher temperatures. Also verication of reaction constants from experimental
data and possible use of in-situ membrane reactor for decreasing amount of catalyst in process
equipment is recommended.

Contents
Summary
1 Introduction
1.1 Project objective . .
1.2 Novel catalytic cycle
1.3 Product . . . . . . .
1.4 Market situation . .
1.5 Design strategy . . .

xvi
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

2 Process options and selection


2.1 Product selection . . . . . . .
2.1.1 Existing processes . .
2.2 Butanol production . . . . . .
2.3 Mode of operation . . . . . .
2.4 Block scheme selection . . . .
2.4.1 Block scheme options

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

3 Basis of design
3.1 Description of design . . . . . . . . .
3.1.1 Included in design . . . . . .
3.1.2 Excluded from design . . . .
3.2 Process denition . . . . . . . . . . .
3.2.1 Process concept . . . . . . . .
3.2.2 Stoichiometry and catalyst .
3.2.3 Kinetics . . . . . . . . . . . .
3.2.4 Experimental data . . . . . .
3.2.5 Process conditions . . . . . .
3.2.6 Blockscheme . . . . . . . . .
3.2.7 Thermodynamic properties .
3.2.8 Pure component properties .
3.3 Basic assumptions . . . . . . . . . .
3.3.1 Plant capacity . . . . . . . .
3.3.2 Location . . . . . . . . . . . .
3.3.3 Battery limit . . . . . . . . .
3.3.4 Streams across battery Limit
3.4 Economic margin . . . . . . . . . . .

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
iii

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.

1
1
1
2
2
3

.
.
.
.
.
.

5
5
5
6
7
7
7

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

11
11
11
11
11
11
11
12
12
13
14
15
15
15
15
16
16
17
18

CPD 3281 - Basis of Design


4 Thermodynamic properties and reaction kinetics
4.1 Thermodynamic properties . . . . . . . . . . . . . . . . . . . .
4.1.1 Thermodynamic and physical properties of components
4.2 Thermodynamic model . . . . . . . . . . . . . . . . . . . . . . .
4.3 Solubility data . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.1 1-butanol in water . . . . . . . . . . . . . . . . . . . . .
4.3.2 Catalyst complex in water . . . . . . . . . . . . . . . . .
4.4 Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4.1 Catalytic cycle . . . . . . . . . . . . . . . . . . . . . . .
4.4.2 Reaction order in alcohol concentration . . . . . . . . .
4.4.3 Reaction order in oxygen . . . . . . . . . . . . . . . . .
4.4.4 Reaction order in palladium concentration . . . . . . . .
4.4.5 Rate expression . . . . . . . . . . . . . . . . . . . . . . .
4.4.6 1-butanol vs. 2-butanol competition . . . . . . . . . . .
4.4.7 Selectivity . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4.8 Catalyst deactivation . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

19
19
19
20
21
21
21
23
23
23
24
24
24
26
26
26

5 Process structure and description


5.1 Pre-reaction section . . . . . . . . . . . .
5.2 Conversion section . . . . . . . . . . . . .
5.2.1 Conceptual reactor design . . . . .
5.2.2 Assumptions for the reactor design
5.2.3 Reactor design decisions . . . . . .
5.2.4 Oxygen recycle . . . . . . . . . . .
5.3 Product purication and catalyst recycle .
5.3.1 General considerations . . . . . . .
5.3.2 Catalyst separation and recycle . .
5.3.3 Butanal recovery . . . . . . . . . .
5.3.4 Alcohol recycle . . . . . . . . . . .
5.4 Process Flow Scheme (PFS) . . . . . . . .
5.4.1 Section 100 . . . . . . . . . . . . .
5.4.2 Section 200 . . . . . . . . . . . . .
5.4.3 Section 300 . . . . . . . . . . . . .
5.5 Utilities . . . . . . . . . . . . . . . . . . .
5.6 Process Yields . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

29
29
29
29
31
31
35
35
36
37
37
38
38
39
39
39
39
40

6 Process Control
6.1 Pre-reaction section . . . . . . .
6.2 Conversion section . . . . . . . .
6.2.1 Reactor . . . . . . . . . .
6.3 Product purication and catalyst
6.3.1 Vapor/liquid separator . .
6.3.2 Collection vessels . . . . .
6.3.3 Flash drum . . . . . . . .
6.3.4 Stripping column . . . . .
6.3.5 Decanter . . . . . . . . .
6.3.6 Splitter . . . . . . . . . .
6.3.7 Distillation column . . . .

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

41
41
41
41
42
42
42
42
43
43
43
44

. . . .
. . . .
. . . .
recycle
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
iv

.
.
.
.
.
.
.
.
.
.
.

CONTENTS
7 Mass and heat balances
7.1 Reactor balance set-up . . .
7.1.1 Mass balance . . . .
7.1.2 Heat balance . . . .
7.2 Balance for total streams .
7.2.1 Individual units . . .
7.2.2 Total plant . . . . .
7.3 Stream component balance
7.4 Total plant imbalance . . .
7.5 Heat pinch . . . . . . . . .

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

8 Process and equipment design


8.1 Process simulation in ASPEN . . . . . . . . . .
8.2 Pre-reaction separation . . . . . . . . . . . . . .
8.2.1 Unit C101, alcohol distillation . . . . . .
8.2.2 Reux drums and collection vessels . . .
8.2.3 Pumps and compressors . . . . . . . . .
8.3 Conversion section . . . . . . . . . . . . . . . .
8.3.1 Reactor optimization and design . . . .
8.3.2 Hydrodynamic ow regime . . . . . . .
8.3.3 Temperature . . . . . . . . . . . . . . .
8.3.4 Reactor composition . . . . . . . . . . .
8.3.5 Pressure . . . . . . . . . . . . . . . . . .
8.3.6 Reactor dimensions . . . . . . . . . . . .
8.3.7 Heat removal . . . . . . . . . . . . . . .
8.3.8 Unit V201, vapor / liquid separation . .
8.4 Product purication and catalyst recovery . . .
8.4.1 Unit V304, decanter . . . . . . . . . . .
8.4.2 Unit C301, butanal stripper . . . . . . .
8.4.3 Unit C302, butanal distillation . . . . .
8.4.4 Unit C303, butanol recycle purication

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

9 Wastes
9.1 Direct waste summary . . . . . . . . . . . . . . . . . . . . . .
9.2 Direct waste . . . . . . . . . . . . . . . . . . . . . . . . . . . .
9.2.1 Excess water, <319> . . . . . . . . . . . . . . . . . . .
9.2.2 Bleed streams, <313> & <320> . . . . . . . . . . . .
9.3 Prevention of waste by design . . . . . . . . . . . . . . . . . .
9.3.1 Alcohol vapor recycle . . . . . . . . . . . . . . . . . .
9.3.2 Pure oxygen as O2 source . . . . . . . . . . . . . . . .
9.3.3 Pre-separation of 2-butanol . . . . . . . . . . . . . . .
9.4 Further waste reduction possibilities . . . . . . . . . . . . . .
9.4.1 Excess water use . . . . . . . . . . . . . . . . . . . . .
9.4.2 Optimization of column C302 and C303 . . . . . . . .
9.4.3 Decrease of hydrocarbon concentration in excess water
v

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

45
45
45
47
47
47
47
47
47
48

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

49
49
49
49
51
51
52
52
53
53
54
56
57
60
62
63
63
64
65
65

.
.
.
.
.
.
.
.
.
.
.
.

67
67
67
67
68
68
68
69
69
69
69
69
69

CPD 3281 - Basis of Design


10 Process safety
10.1 HAZOP . . . . . . . . . . . . . . . .
10.1.1 Reactor HAZOP study . . . .
10.2 Dow Fire & Explosion Index . . . .
10.3 Explosion limits . . . . . . . . . . . .
10.3.1 Pure components . . . . . . .
10.3.2 Explosion limits in a mixture

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

71
71
71
72
73
73
73

11 Economy
11.1 Investment . . . . . . . . . . . . . . . . . . . . . . . .
11.1.1 Section 100: 1-butanol/2-butanol separation . .
11.1.2 Section 200: Reaction section . . . . . . . . . .
11.1.3 Section 300: Separation section . . . . . . . . .
11.1.4 Total Investment . . . . . . . . . . . . . . . . .
11.1.5 Catalyst investment . . . . . . . . . . . . . . .
11.2 Operating costs . . . . . . . . . . . . . . . . . . . . . .
11.2.1 Utilities . . . . . . . . . . . . . . . . . . . . . .
11.2.2 Raw material . . . . . . . . . . . . . . . . . . .
11.2.3 Waste . . . . . . . . . . . . . . . . . . . . . . .
11.2.4 Labour costs . . . . . . . . . . . . . . . . . . .
11.2.5 Total . . . . . . . . . . . . . . . . . . . . . . . .
11.3 Income . . . . . . . . . . . . . . . . . . . . . . . . . . .
11.4 Cash ow . . . . . . . . . . . . . . . . . . . . . . . . .
11.5 Economic criteria . . . . . . . . . . . . . . . . . . . . .
11.5.1 Discounted cash ow . . . . . . . . . . . . . . .
11.5.2 Discounted cash-ow rate of return (DCFROR)
11.5.3 Rate of Return (ROR) . . . . . . . . . . . . . .
11.5.4 Project cash ow diagram . . . . . . . . . . . .
11.6 Sensitivities . . . . . . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

75
75
75
75
76
76
77
77
77
78
78
78
78
79
79
79
79
79
79
80
80

12 Creativity and group process achievements


12.1 Creativity . . . . . . . . . . . . . . . . . . . . . . . .
12.1.1 Goals . . . . . . . . . . . . . . . . . . . . . .
12.1.2 Creativity: First approach . . . . . . . . . . .
12.1.3 BOD review: Change in approach . . . . . .
12.1.4 Creative session with Mr. Grunwald and Mrs.
12.1.5 Creativity: nal approach . . . . . . . . . . .
12.1.6 Review creativity tools and results . . . . . .
12.2 Group interaction . . . . . . . . . . . . . . . . . . . .
12.2.1 Participation prole (4/10/02) . . . . . . . .
12.2.2 BOD review meeting (4/11/02) . . . . . . .
12.2.3 First team performance review (5/11/02) . .
12.2.4 DOW trip (11-12/11/02) . . . . . . . . . . .
12.2.5 Second team performance review (19/11/02)

. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
Arends (7/11/02)
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .
. . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

81
81
81
81
84
84
85
86
87
87
87
88
88
89

13 Conclusions and Recommendations


13.1 Conclusions . . . . . . . . . . . . . . .
13.1.1 Strengths & weaknesses . . . .
13.1.2 Technical and economical risks
13.1.3 Creative designing . . . . . . .

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

91
91
91
91
92

.
.
.
.
.
.

vi

.
.
.
.
.
.

.
.
.
.

.
.
.
.
.
.

.
.
.
.

.
.
.
.
.
.

.
.
.
.

.
.
.
.
.
.

.
.
.
.

.
.
.
.
.
.

.
.
.
.

.
.
.
.
.
.

.
.
.
.

.
.
.
.
.
.

.
.
.
.

.
.
.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

CONTENTS
13.2 Recommendations . . . .
13.2.1 Design reliability .
13.2.2 Cost reduction . .
13.2.3 HES performance .
13.2.4 Creative designing

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

92
92
93
93
93

List of symbols

94

Bibilography

97

A LP OxoT M Low Pressure Oxo Process

101

B Literature research
103
B.1 Initial research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
C Process options and selection
C.1 Block scheme selection . . . . . . . .
C.1.1 Option 1, no alcohol separation
C.1.2 Option 2, alcohol separation . .
C.1.3 Comparison option 1 and 2 . .

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

D Denition of all streams crossing battery limits


D.1 1-Butanol/2-butanol feedstock . . . . . . . . . .
D.2 Catalyst . . . . . . . . . . . . . . . . . . . . . . .
D.2.1 Paladiumacetate . . . . . . . . . . . . . .
D.2.2 Ligand . . . . . . . . . . . . . . . . . . . .
D.3 Oxygen . . . . . . . . . . . . . . . . . . . . . . .
D.4 1-Butanol/2-butanol sidestream . . . . . . . . . .
D.5 Water . . . . . . . . . . . . . . . . . . . . . . . .
D.6 Butanal . . . . . . . . . . . . . . . . . . . . . . .
D.7 Butanoic acid . . . . . . . . . . . . . . . . . . . .
D.8 Exhaust Gasses . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

105
105
105
105
105

.
.
.
.

.
.
.
.

.
.
.
.
.
.
.
.
.
.

107
. 107
. 107
. 107
. 107
. 107
. 108
. 108
. 108
. 108
. 108

E Thermodynamic model

111

F Thermophysical properties
F.1 Heat capacities of gaseous pure components
F.2 Heat capacities of liquid pure components .
F.3 Vapour pressure of pure components . . . .
F.4 Density of the pure liquid components . . .
F.5 Viscosity of the pure components . . . . . .

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

113
113
114
115
116
117

G PhenS*Pd(OAc)2 solubility
G.1 Introduction . . . . . . . .
G.2 Experimental . . . . . . .
G.3 Results . . . . . . . . . . .
G.4 Conclusion & discussion .

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

119
119
119
119
120

experiments
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .

.
.
.
.

H PFS and tables

121

I Process control method

127
vii

CPD 3281 - Basis of Design


J Balance for stream components

129

K Ternary diagrams reactor system

133

L Cooling equipment design


L.1 Symbols used . . . . . .
L.1.1 regular . . . . . .
L.1.2 Greek . . . . . .
L.1.3 Subscripts . . . .

.
.
.
.

.
.
.
.

M Mass transfer of oxygen


M.1 Introduction . . . . . . . . .
M.2 Transfer coecient value kL
M.3 Interfacial area . . . . . . .
M.3.1 Bubble column . . .
M.3.2 Stirred unit . . . . .
M.3.3 kLa value inuencing

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

. . . . .
. . . . .
. . . . .
. . . . .
. . . . .
factors

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.

135
137
137
138
138

.
.
.
.

.
.
.
.

.
.
.
.
.
.

139
. 139
. 139
. 140
. 140
. 141
. 141

N Solubility of gasses in liquids


143
N.1 Oxygen solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
N.2 Henry constant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
O Henry constant in pure liquids
O.1 Henry constant of oxygen in water . . . . . . . . . . . . . . . . . . . . . . . . .
O.2 Henry constant of oxygen in butanol . . . . . . . . . . . . . . . . . . . . . . . .
O.3 Henry constant of oxygen in butanal . . . . . . . . . . . . . . . . . . . . . . . .

145
. 145
. 145
. 146

P Pre-reactor separation
P.1 Trayed column . . . . . . . . . . . . . . . . . . . .
P.1.1 Minimum reux ratio and number of stages
P.1.2 RadFrac model . . . . . . . . . . . . . . . .
P.1.3 Column eciency . . . . . . . . . . . . . . .
P.2 Packed column . . . . . . . . . . . . . . . . . . . .
P.2.1 Packing design . . . . . . . . . . . . . . . .

.
.
.
.
.
.

147
. 147
. 147
. 147
. 148
. 148
. 148

.
.
.
.
.
.
.

151
. 151
. 152
. 152
. 153
. 153
. 153
. 154

Q Stirrer design
Q.1 Geometric parameters . . . . . .
Q.2 Power consumption . . . . . . . .
Q.2.1 Single liquid phase system
Q.2.2 Two-phase stirred system
Q.3 Mass transfer parameters . . . .
Q.3.1 Gas holdup . . . . . . . .
Q.3.2 Interfacial area . . . . . .

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

R Equipment summary & specication sheets

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.

155

S HAZOP study on reactor


167
S.1 Start-up and shut-down procedures . . . . . . . . . . . . . . . . . . . . . . . . . . 167
S.1.1 Start-up procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
S.1.2 Shut-down procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
viii

CONTENTS
T Dow Fire & Explosion Index sheets

171

U Purchased equipment costs


U.1 Section 100: 1-butanol/2-butanol separation
U.1.1 Column shell and internals . . . . .
U.1.2 Reboiler . . . . . . . . . . . . . . . .
U.1.3 Condenser . . . . . . . . . . . . . . .
U.1.4 V101 . . . . . . . . . . . . . . . . . .
U.2 Section 200: reaction section . . . . . . . .
U.2.1 Oxygen compressor . . . . . . . . . .
U.2.2 Reactor with agitator . . . . . . . .
U.2.3 Oxygen recycle compressor . . . . .
U.2.4 Feed pump . . . . . . . . . . . . . .
U.2.5 Liquid recycle pump . . . . . . . . .
U.2.6 V202 . . . . . . . . . . . . . . . . . .
U.3 Section 300: separation section . . . . . . .
U.3.1 C301 . . . . . . . . . . . . . . . . . .
U.3.2 C302 . . . . . . . . . . . . . . . . . .
U.3.3 C303 . . . . . . . . . . . . . . . . . .
U.3.4 V302 . . . . . . . . . . . . . . . . . .
U.3.5 V303 . . . . . . . . . . . . . . . . . .
U.3.6 V305 . . . . . . . . . . . . . . . . . .
U.3.7 V306 . . . . . . . . . . . . . . . . . .
V Creativity tools and results
V.1 Creative technique inventory . . . . . .
V.2 Literature research (8/10/02) . . . . .
V.3 Matec (25/10/02) . . . . . . . . . . . .
V.4 Grunwald Session (7/11/02) . . . . . .
V.4.1 Innite amount of small reactors
V.4.2 Doughnut shaped reactor . . . .
V.4.3 Flexible reactor . . . . . . . . . .
V.5 Butanoic acid removal . . . . . . . . . .

ix

.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

189
189
189
189
189
189
189
189
190
190
190
190
190
190
190
190
190
191
191
191
191

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

193
. 193
. 193
. 193
. 195
. 195
. 195
. 196
. 197

List of Figures
2.1 Brief description on process sequence . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Block scheme for 1-butanol oxidation without preseparation . . . . . . . . . . . .
2.3 Block scheme for 1-butanol oxidation with preseparation of reactants . . . . . . .
3.1
3.2
3.4
3.3

7
8
8

Structure of the active palladium-bathocuproine complex . . . . . . . . . . . . .


Main reactions occuring in the oxidation process . . . . . . . . . . . . . . . . . .
Block scheme for 1-butanol oxidation with preseparation of reactants . . . . . . .
The bubble and dewpoint curves for a 1-butanol, 2-butanol, butanal, butanone
and water mixture (mass fraction: 1:1:1:1:3). The model used is UNIQUAC . . .
3.5 Streams crossing the battery limits . . . . . . . . . . . . . . . . . . . . . . . . . .

12
12
14

4.1
4.2
4.3
4.4
4.5

xy diagram for a 2-butanol/1-butanol mixture at P = 1.013 bar [17, p. 150]. .


Ternary diagram for water/1-butanol/butanal at 30 bar and 393 K . . . . . .
Proposed catalytic cycle for alcohol oxidation by PhenS*Pd(II)[3] . . . . . . .
PhenS*Pd(OAc)2 dimer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Rate constant as a function of the number of carbon atoms of the molecule .

.
.
.
.
.

.
.
.
.
.

21
22
23
24
25

5.1
5.2
5.3
5.4
5.5

The conversion versus space time for a PFR and a CSTR


Reactor with feeds and products. . . . . . . . . . . . . . .
The recycle structure for oxygen . . . . . . . . . . . . . .
Residue curve map for butanal/water/1-butanol at 1 bar.
Process blockscheme with yields . . . . . . . . . . . . . .

.
.
.
.
.

.
.
.
.
.

32
34
36
38
40

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

14
17

7.1 Streams entering and leaving the reactor . . . . . . . . . . . . . . . . . . . . . . . 45


8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8

Txy diagram of 2-butanol/1-butanol at 1.013 bar . . . . . . .


Two dierent types of column packing . . . . . . . . . . . . .
Liquid volume versus conversion at given temperatures. . . .
The ternary diagram of the reactor composition at 30 bar and
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Artist impression of reactor design . . . . . . . . . . . . . . .
Gas-liquid separator V201 sketch . . . . . . . . . . . . . . . .
Decanter V304 sketch . . . . . . . . . . . . . . . . . . . . . .

. . . . .
. . . . .
. . . . .
130C :
. . . . .
. . . . .
. . . . .
. . . . .

.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

49
50
54
55
59
60
63
64

10.1 Simple reactor scheme with in and out ows . . . . . . . . . . . . . . . . . . . . . 72


11.1 The project cash ow for the rst 10 years of the project . . . . . . . . . . . . . . 80
12.1 Preliminairy reactor idea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
12.2 Possible set-up for a tubular membrane reactor . . . . . . . . . . . . . . . . . . . 85
12.3 Detailed group prole (4/10/02) . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
xi

CPD 3281 - Basis of Design


A.1 Schematic overview of a LPO process [31]. . . . . . . . . . . . . . . . . . . . . . . 101
E.1 xy diagram for a water/1-butanol mixture at P = 1.013 bar [16, p. 245-253]. . . 111
E.2 xy diagram for a butanal/water mixture at P = 1.013 bar [16, p. 212 - 218] . . . 112
E.3 xy diagram for a 2-butanol/1-butanol mixture at P = 1.013 bar [17, p. 150 - 154].112
F.1
F.2
F.3
F.4
F.5

Heat capacity of the gaseous pure components as a function of temperature


Heat capacity of the liquid pure components as a function of temperature .
Vapour pressure of the pure liquids as a function of temperature . . . . . .
Density of the pure liquids as a function of temperature . . . . . . . . . . .
Viscosity of the pure liquids as a function of temperature . . . . . . . . . .

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

114
115
116
117
118

H.1
H.2
H.3
H.4
H.5

Process stream summary . . . . . . .


Process stream summary (continued)
Process stream summary (continued)
Process yield values . . . . . . . . .
Summary of utilities . . . . . . . . .

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

123
124
125
125
126

J.1
J.2
J.3

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

K.1 Ternary diagram for water/1-butanol/butanal, at various temperatures . . . . . . 133


P.1 N*(R+1) versus N, optimum number of stages according to shortcut . . . . . . . 147
P.2 SULPAK input parameters and results for calculation on packing for the 1butanol/1-butanol separation tower . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Q.1 Drawing of a multiple turbine stirrer tank . . . . . . . . . . . . . . . . . . . . . . 151
T.1
T.2
T.3
T.4
T.5
T.6
T.7
T.8
T.9
T.10
T.11
T.12
T.13
T.14
T.15
T.16
T.17

Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire
Dow Fire

and
and
and
and
and
and
and
and
and
and
and
and
and
and
and
and
and

Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion
Explosion

Index sheet for


Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for
Index sheet for

equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment
equipment

C101 .
E101 .
P101 .
E201 .
E202 .
K201 .
K202 .
P201 .
R201 .
C301 .
C302 .
C303 .
E303 .
E304 .
P305 .
V301 .
V304 .

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.

172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188

V.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
V.2 Dialysis for acid / catalyst separation. . . . . . . . . . . . . . . . . . . . . . . . . 198

xii

List of Tables
1.1 Main butanal proccesses world wide . . . . . . . . . . . . . . . . . . . . . . . . .

2.1
2.2
2.3
2.4
2.5

.
.
.
.
.

6
6
7
9
9

3.1 Pros and Cons of use of high pressure in the Green Catalytic Oxidation method
3.2 Pros and Cons of use of high temperature in the Green Catalytic Oxidation
method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Pure component properties, part 1 . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4 Pure component properties, part 2 . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5 Mass ows of In- and Out-going streams . . . . . . . . . . . . . . . . . . . . . .
3.6 Important equipment inside battery limits . . . . . . . . . . . . . . . . . . . . . .
3.7 Stream numbers crossing the battery limits . . . . . . . . . . . . . . . . . . . . .
3.8 Margin calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

13

Overview of choice of product to be produced . . . .


Prices of butane, 1-butanol and butanal . . . . . . .
Preferred process conditions butane fermentation[41]
Separation opportunities . . . . . . . . . . . . . . . .
Separation diculties . . . . . . . . . . . . . . . . .

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

4.1 Thermodynamic properties of pure components at standard state . . . . . . . .


4.2 Heat of reaction, Gibbs free energy of reaction and entropy generated at standard
state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3 Used databases for binairy interaction parameters . . . . . . . . . . . . . . . . .
4.4 binary data for 1-butanol/water . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5 binary data for butanal/water . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6 Calculated henry coecients for oxygen in dierent solvents . . . . . . . . . . .
4.7 Rate constant values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.8 Rate constant values versus temperature for 1-butanol . . . . . . . . . . . . . .
4.9 Catalyst deactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

13
16
16
17
17
18
18

. 19
.
.
.
.
.
.
.
.

20
20
21
22
22
25
26
27

5.1 Estimation of the oxygen price versus its purity . . . . . . . . . . . . . . . . . . . 34


6.1
6.2
6.3
6.4
6.5
6.6

Controlled
Controlled
Controlled
Controlled
Controlled
Controlled

and
and
and
and
and
and

manipulated
manipulated
manipulated
manipulated
manipulated
manipulated

variables
variables
variables
variables
variables
variables

for the rst distillation column


for the reactor . . . . . . . . .
for the mixers . . . . . . . . .
for the ash drum . . . . . . .
for the stripping column . . .
for the rst distillation column

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

41
42
42
43
43
44

7.1 Cooling requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48


7.2 Heating requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
xiii

CPD 3281 - Basis of Design


8.1
8.2
8.3
8.4
8.5
8.6
8.7
8.8
8.9
8.10
8.11
8.12
8.13
8.14

Cost estimation for a trayed 1-butanol/2-butanol distillation column . . . . . .


Cost estimation for a packed 1-butanol/2-butanol distillation column . . . . . .
Vessel geometric data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pump characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Compressor characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Inuence of temperature in the reactor . . . . . . . . . . . . . . . . . . . . . . .
Reactor composition and temperature . . . . . . . . . . . . . . . . . . . . . . .
Parameters determining reactor pressure . . . . . . . . . . . . . . . . . . . . . .
Reactor composition, temperature and necessary pressure for a bubble column
Number and size of the reactor for dierent temperatures . . . . . . . . . . . .
Reactor dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Feed stream temperature after heat exchange . . . . . . . . . . . . . . . . . . .
Heat transfer properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cooling water properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.

51
51
52
52
52
53
56
56
57
58
60
61
61
62

9.1 Waste stream summary, 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67


9.2 Waste stream summary, 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
10.1
10.2
10.3
10.4
10.5

Deviations generated by each guide word . . . . . . . . . . . . . . . . . . . . . . .


Heat of combustion for dierent components . . . . . . . . . . . . . . . . . . . . .
Explosion limits for substances in pure oxygen . . . . . . . . . . . . . . . . . . .
Composition of the mixture in the overhead of the reactor, without oxygen dilution
Composition of the mixture in the overhead of the reactor, with oxygen dilution

71
73
73
74
74

11.1
11.2
11.3
11.4
11.5
11.6

Equipment in the pre separation section . . . .


Equipment in the reaction section . . . . . . . .
Equipment in the separation section . . . . . .
Raw material costs . . . . . . . . . . . . . . . .
Income from product sales . . . . . . . . . . . .
Sensitivities to worse economical circumstances,

.
.
.
.
.
.

.
.
.
.
.
.

75
76
76
78
79
80

12.1
12.2
12.3
12.4
12.5

Delft Design Matrix and implemented creativity methods . . . . . . . . . . . .


Results from the MATEC method . . . . . . . . . . . . . . . . . . . . . . . . .
Brief representation creative session guided by Mr. Grunwald and Mrs. Arends
not pursued creative ideas during design period . . . . . . . . . . . . . . . . . .
Identied team strengths and weaknesses . . . . . . . . . . . . . . . . . . . . .

.
.
.
.
.

82
83
85
86
88

. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
. . . . . . . . . . . . . . .
costs +10%, income -10%

.
.
.
.
.
.

.
.
.
.
.
.

13.1 Strengths of the design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91


13.2 Weaknesses of the design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
A.1 Process properties LPO process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
D.1
D.2
D.3
D.4
D.5
D.6
D.7
D.8
D.9

Stream
Stream
Stream
Stream
Stream
Stream
Stream
Stream
Stream

properties of the alcohol stream . . . . . .


properties of the Palladium catalyst stream
properties of the ligand stream . . . . . . .
properties of the oxygen/air stream . . . .
properties of the alcohol stream . . . . . .
properties of the water stream . . . . . . .
properties of the butanal stream . . . . . .
properties of the butanoic acid stream . . .
properties of the exhaust gas stream . . . .
xiv

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.

107
108
108
109
109
109
109
110
110

LIST OF TABLES
E.1 Used databanks for binairy parameters . . . . . . . . . . . . . . . . . . . . . . . . 111
F.1
F.2
F.3
F.4
F.5

Heat capacities for gaseous components . .


Heat capacities for liquid components . . .
Vapour pressure data for pure components .
Density data for pure components . . . . .
Liquid viscosity data for pure components .

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

.
.
.
.
.

113
114
115
116
117

G.1 The catalyst complex solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119


I.1

Control objectives and explanation of their inuence . . . . . . . . . . . . . . . . 128

L.1 Physical properties of reactor mixture (303 K) and cooling water (averaged) . . . 136
L.2 Input and results of heat exchange calculations . . . . . . . . . . . . . . . . . . . 137
L.3 Calculated values for heat transfer calculations . . . . . . . . . . . . . . . . . . . 138
M.1 orders of magnitude of mass transfer parameters for a bubble column . . . . . . . 139
M.2 liquid lm transfer coecient versus temperature . . . . . . . . . . . . . . . . . . 140
O.1
O.2
O.3
O.4
O.5

Henry constant of
Henry constant of
Henry constant of
Henry constant of
Henry constant of

oxygen
oxygen
oxygen
oxygen
oxygen

in
in
in
in
in

pure
pure
pure
pure
pure

water . . . . . . . . . . . . . . . . .
butanol . . . . . . . . . . . . . . . .
butanol comparison . . . . . . . . .
butanol used to calculate the reactor
butanal . . . . . . . . . . . . . . . .

. . . . .
. . . . .
. . . . .
pressure
. . . . .

.
.
.
.
.

145
145
146
146
146

Q.1 geometrical parameters for a turbine stirrer tank . . . . . . . . . . . . . . . . . . 152


S.1
S.2
S.3
S.4
S.5
S.6

HAZOP
HAZOP
HAZOP
HAZOP
HAZOP
HAZOP

study, guide word


study, guide word
study, guide word
study, guide word
study, guide word
study, guide word

NONE . . . .
MORE OF . .
LESS OF . . .
PART OF . .
MORE THAN
MORE THAN

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

.
.
.
.
.
.

168
169
169
170
170
170

T.1 Degree of hazard according to the Dow Fire & Explosion Index for every equipment171
V.1
V.2
V.3
V.4

Creativity methods . . . . . . . . . . . . . . .
coming out of the brainstorm session . . . . .
Matrix with chain associations from oxygen
Matrix with chain associations from water .

xv

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

.
.
.
.

193
194
194
194

1 | Introduction
In this report a design is presented which is designed within the framework of the course
Conceptual Process Design at the DelftChemTech (DCT) Department of the Faculty of Applied
Sciences (TNW) at Delft University of Technology (DUT). In this course students are supposed
to produce an innovative, integrated, consistent and sound process design [28, p. i]. In this
chapter the project objective, benets of the design, available processes, current market, impact
of plant design on market and design strategy will be presented.

1.1

Project objective

The projects objective is:


A novel catalytic method for the oxidation of alcohols has been developed.
An industrial application for this new, green technology is to be found.
Improvements in environmental burden and economical performance must
be realized
The Biocatalysis and Organic Chemistry research group at the DCT Department of TNW
at DUT has issued the stated objective and the research group presented by principal Dr. I.
Arends. Dr. Arends is employed with the Biocatalysis and Organic Chemistry department and
participated in the development of the novel catalytic method. Her interest in the project is
the industrial application of this experimental catalytic oxidation method.

1.2

Novel catalytic cycle

The catalytic oxidation method has big advantages. The special features of this method are:
use of water as a solvent
no stoichiometric amounts of heavy metal oxidants as waste
selective towards reactant and desired product
use of oxygen as oxidant
A whole range of possible reactants are described[3]. The environmental advantages are
obvious: no organic solvent is used and less waste is generated. Smaller waste streams reduces
costs for waste removal. The specic economic advantages will depend on the type of process
which will be designed. The oxidations described [3] have a high yield and are very selective.
The only main by-product is caused by the over-oxidation of aldehydes to the corresponding
acids. Also oxidation of impurities can occur. Some expected design diculties were the limited
1

CPD 3281 - Basis of Design


solubility of the oxidant (molecular oxygen) and the limited solubility of the alcohol. In the
design these diculties were overcome by working at little elevated temperature to obtain a
total miscible phase.
Due to the state of the art catalytic method the amount of accessible and present information
is small. During the design some assumptions had to be made to overcome this problem. A
test on catalyst solubility was performed to obtain information for reactor design optimization.
More details on the catalytic method and the catalytic cycle are presented in chapter 4.

1.3

Product

After elaborate literature research and exploration of industrial oxidizing reactions (see chapter
2), we decided to design a plant for butanal production from 1-butanol. This process is currently
under investigation by the Japanese company Asahi-Kasei. Experiments on oxidation of butanol
are at the moment investigated at DUT by Mr. T. Kodama, a guest researcher of Asahi-Kasei
at the biocatalysis and organic chemistry research group. The conceptual design is based on
the main product butanal.
Butanal is a colorless, ammable liquid with a pungent penetrating odor. The vapor has
a narcotic eect and irritates mucous membranes. Butanal is miscible with organic solvents,
such as alcohols, ethers, and benzene [31]. More details on product properties can be found in
paragraph 3.2.8.
Butanal has moderate toxicity to aquatic life. By itself it is not likely to cause environmental
harm at levels normally found in the environment. Butanal can contribute to the formation of
photochemical smog when it reacts with other volatile substances in air [5].
Butanal is of special interest to Asahi-Kasei for the production of 2-ethyl-2-(hydroxymethyl)1,3-Propanediol (Etriol), a cross-linking agent for the polymer industry. Butanal is used as a
chemical intermediate in the production of plasticizers, rubber accelerators, synthetic resins,
solvents and high molecular weight polymers [4].
The main butanal producing processes used are [31] given in table 1.3 in order of industrial
use.
Table 1.1: Main butanal proccesses world wide
Reactants
Main products
Temperature
range
[K]
Hydroformylation Propylene, syn- n-Butanal,
363 - 453
of propene
thesis gas
i-butanal
Hydrogenation
Acetaldehyde,
n-Butanal, wa- of crotonalde- hydrogen
ter
hyde
Dehydrogenation Butanol
Butanal, hydro- of butanol
gen
Process

1.4

Pressure range
[Bar]
25 - 350
-

Market situation

The polyethylene production of Asahi-Kasei in Japan is currently under pressure. Cheap polyethylene from Saudi Arabia is putting prices down. Therefore, Asahi-Kasei is changing its
output of its nafta crackers in Japan from ethylene to heavier components. Most of these
2

1.5. DESIGN STRATEGY


components oer a good alternative to ethylene. Butane however, which is now also produced
increasingly, has almost no value. It is currently used or sold as fuel. The biological process
which will be used for producing butanol from cheap butane is currently under investigation.
The butanal produced via the butanol oxidation provides a valuable feedstock for Asahi-Kaseis
polymer divisions. Details on the economical feasibility are presented in chapter 11.
Throughout the world more than 3.2106 tons of butanal is manufactured each year by the
hydroformylation of propylene (e.g. LP Oxo T M Low Pressure Oxo Process patented by DOW).
A block scheme of this process is shown in appendix A. Large-scale plants such as those in
operation at BASF, CWH, Ruhrchemie, or UCC each have an annual output of 200 3.0105tons.
The hydroformylation process is by far the largest process used in butanal production [31].
Butanal is produced in very large amounts (almost 0.910 6tons in 1992) by ve companies in
the United States. U.S. demand for butyraldehyde is likely to remain steady for the next several
years [5]. The production volume indicates that the world wide market situation is large.
It is not expected that operating this plant will have signicant impact on the world market.
Demand for intermediates in polymer industry is growing as an eect on growing demand for
plastics.

1.5

Design strategy

For the design planning and splitting up design in distinct levels the Delft design matrix (DDM)
was used. DDM provides design teams with a structured approach on the design. Also a method
for reactor design and evaluation developed by R. Krishna and S.T. Sie [21] was utilized to
facilitate reactor design. Creativity methods and methods to enhance group dynamics improved
team performance and cooperation during the design trajectory. Applied methods and results
are presented in chapter 12.

2 | Process options and selection


2.1

Product selection

The project objective requires the novel catalytic method to be used in a process which results
in lower environmental burden and an increase in economic performance. Dierent components
and processes for synthesis of these components were investigated for potential design or redesign.

2.1.1

Existing processes

An important environmental benet of the new alcohol oxidation method is the use of molecular oxygen as oxidant. This is a great advantage over the use of stoichiometric amounts of
metal oxidants. The generation of waste is avoided and the atom eciency of the process is
dramatically increased. The use of metal oxidants for alcohol oxidation in industry is nowadays
limited to the ne chemicals production. Our rst focus was on this branch of industry.
Fine chemical industry
A large amount of aldehydes produced are used in avors and fragrances and in medicine
industry. Several sources (IFF, Givaudan, Diosynth, NEA, VNCI) were consulted. Dierent
other sources were investigated which are pointed out in chapter 12 Industry was not willing
to provide detailed information on processes, production quantities, products and raw material
prices. Substances found in literature are given in appendix B.
Information of companies (IFF, Givaudan and Diosynth) pointed out that the chromium
salt oxidation is hardly performed. Chromium salts are used because of high selectivity, high
yield and easy usage. Especially selectivity is important. Alcohols can have other active groups
(steroidalcohols, Amine groups, Sulphur groups, double bonds etc.). The new catalyst can not
handle components with other active groups due to coordination to the active site, and this will
prevent the hydroxyl group from reacting.
Bulk processes
A large amount of bulk aldehydes are produced in gas phase processes with heterogenous catalysis. These processes are widely used and have large production capacities (benzaldehyde,
formaldehyde etc.). Benzene derivatives are mostly produced, and are not or little soluble in
water. This is one of the main issues why the process based on water as a solvent cannot compete with gas phase synthesis. Margins on the products are relatively low compared to avors
and fragrances.
5

CPD 3281 - Basis of Design


Possible substrates and products
After an extensive search on suitable substrate we found several products which might be
produced using the novel catalytic method. Some are presented in table 2.1.
Table 2.1: Overview of choice of product to be produced
Product
Advantage and/or disadvantage
Pentanoic acid
Small amount of available data.
3,3-dimethylbutanal
Used for neotame production. Mainly
produced in gasfase reactions[44]. No
big benets expected.
Menthone
Produced by other processes than alcohol oxidation.
4-tert-Butyl--methylhydrocinnamic
Synthesis from corresponding alcohol
aldehyde
is not ecient.
2-Methyl-3-(4-tert-butylphenyl)Oxidation of the corresponding alcopropanal (Lilial)
hol is not ecient.
Butanal
Soluble alcohol, no other active
groups,

The design team decided to use green oxidation method for a butanal process
This process is currently under investigation by the Japanese company Asahi-Kasei. Experiments are currently conducted by a guest research worker of Asahi-Kasei at the research group
Organic Chemistry at DUT.
Butane is produced in large amounts (100,000 tons/year) by Asahi-Kasei. The price of
butane, calculated from fuel price [6, page 135]. Prices are shown in table 2.1.1. Butanal will
be worth at least 6.5 times the value of butane.
Table 2.2: Prices of butane, 1-butanol and butanal
Component Price
$/ton
Butane
188
1-Butanol
772
Butanal
1234

2.2

Butanol production

To make a sound decision on to use unit operations, combinations of operations and eventually
integration of unit operations dierent options have to be investigated. The designed oxidation
process is a part of a sequence of distinct processes which is briey described in gure 2.1.
6

2.3. MODE OF OPERATION

Figure 2.1: Brief description on process sequence


Butane is produced in the nafta crackers. Butane will be fermented to 1-butanol. The
process which will be used is also selected by the design team, but is not designed. 1-Butanol
will be converted to butanal by the designed plant. Etriol is produced by aldol condensation
at elevated temperature in an aqueous basic mixture with methanal. The process for etriol will
not be discussed in this report.
The 1-butanol production by fermenting butane is described in [41]. Mentioned process
in this patent is capable of oxidizing butane. Processes described in other patents [41, page
13] are mainly limited to oxidizing hexane or higher alkanes. The process described in [41] is
chosen as the process which will supply the feed for the reactor based on high selectivity towards
1-butanol. The process conditions are shown in table 2.2[41].
Table 2.3: Preferred process conditions butane fermentation[41]
Temperature [oC]
20 - 40
Pressure [bar]
1 - 10
pH [-]
5.5 - 8
modes of operation
batchwise, fed-batch and continuous
oxidizing agent
O2
product composition 5% 2-butanol, 95% 1-butanol
We assume that the products of the fermentation will be separated from the broth by the
fermentation plant. The product of the alcohol fermentation plant and thus the feed of the
designed plant will consist solely of alcohols. Details on feed stream are given in appendix D.

2.3

Mode of operation

The decision between batch or continuous is made using guidelines from [6, page 108]. From a
production rate point of view, the process will be a continuous. The capacity of the plant to be
designed will exceed 100,000 ton/y of 1-butanol. This is way beyond the upper limit for batch
processes (capacity batch processes 500 - 5,000 t/y).
The reaction rate is not high, but it is expected that it is suciently fast for realizing
a continuous process without excessive large equipment. Butanal isnt a season depending
product and no operational problems within a continuous process for butanal are expected
(high throughput, no solids).
A continuous process will be designed

2.4
2.4.1

Block scheme selection


Block scheme options

As described in the preliminary basis of design report [42], a choice between two dierent block
schemes is made. Both block schemes are presented in gure 2.2 and 2.3.
7

CPD 3281 - Basis of Design

Figure 2.2: Block scheme for 1-butanol oxidation without preseparation

Figure 2.3: Block scheme for 1-butanol oxidation with preseparation of reactants
The main dierence between the two owsheets is separation of 2-butanol from 1-butanol
before the reaction section. The choice for whether or not to use pre-separation is based on
margin dierence, number of needed theoretical separation steps and expected equipment size.
A short overview on separation sections of both owsheets is presented in appendix C.1.
Results from the comparison between the mentioned block scheme are shown in table 2.4 and
2.5.
8

2.4. BLOCK SCHEME SELECTION

Table 2.4: Separation opportunities


Both
Without preseparation
With preseparation
Flashing product mixture Butanone will be present in Distillation possible for 2will remove excess water low quantities (5%)
butanol separation from 1and aldehyde from recylce
butanol
stream
Separation by extraction of
No 2-butanol will be
aldehyde and ketone is pospresent in reactor
sible
Table 2.5: Separation diculties
Both
Without preseparation
With preseparation
Distillation for water re- Butanal/butanone separa- An extra separation step
moval is not favored
tion (by distillation) is very is necessary to remove 2dicult ( 1:01)
butanol from reactant mixture
Removal of butanoic acid Waste water will contain 1-butanol should be pure,
from aqueous catalyst recy- larger amount of 2-butanol this results in high purity
cle stream is necessary
and its products
separation
An extra separation step is
necessary for butanone removal.
As has been pointed out in the preliminary BOD report, the margin dierence (rst stage
economical potential analysis) is small. Margin of the rst block scheme is 39 M$=y and
38 M$=y for the second block scheme. The dierence between margins is too small to make
a sound decision for one of both options. Equipment size will reduce with option 2, because
2-butanol does not have to be processed. This will reduce volume and power/heat duty of
process equipment. Because of the expected advantages in separation, low margin dierence
between block schemes, the block scheme with pre separation will be used for the design.
Block scheme with pre separation of 2-butanol will be used for the design

3 | Basis of design
3.1

Description of design

A process will be designed for the conversion of 1-butanol into butanal on a large scale in an
aqueous environment with homogeneous catalyst. The method described in [3] is used for this.
The target production is 112 ton/year. The catalyst is the water soluble palladium acetate
PhenS* complex. The feed is a mixture of 95% 1-butanol and 5% 2-butanol. A separation
section is designed to separate 1- from 2-butanol. 1-butanol is converted into butanal in the
reactor. A downstream separation section separates the product and produced water from
catalyst and by-products.

3.1.1

Included in design

A butanal production unit, product and catalyst separation will be designed. An economic
evaluation of the whole production and separation will be performed.

3.1.2

Excluded from design

The design of the plant will not be t in an existing complex although it is assumed that the
new plant will be placed on an existing site. Reason is that nothing is known about on-site
utilities and other plants. The utilities, oxygen supply and waste water treatment will not be
designed. Those are assumed to be available.

3.2
3.2.1

Process denition
Process concept

The incoming 1-butanol/2-butanol mixture will be separated rst. The 1-butanol will be fed
to a reactor. After the reactor, catalyst will be separated from the product and product from
unreacted reactants. The catalyst and reactants will be recycled to the reactor. The product
stream will contain butanal and may contain water as this is not harmful for the downstream
application.
A continuous reactor will be designed which produces about 100 kiloton per year. It will
operate at elevated pressure to facilitate oxygen transfer to the liquid phase. Elevated temperature is necessary for a reasonable rate of reaction. The exothermic reaction requires the reactor
to be cooled. Oxygen is a reactant and thus or air or oxygen is introduced in the reactor.

3.2.2

Stoichiometry and catalyst

The catalyst is a water soluble complex of palladium with bathocuproine, stable and recyclable,
whose formula in neutral aqueous solution is PhenS*Pd2+ and shown in gure 3.1.
11

CPD 3281 - Basis of Design


SO3Na

NaO 3S

N
H3C

N
2+

Pd

CH3

Figure 3.1: Structure of the active palladium-bathocuproine complex


The 1-butanol feed contains 2-butanol, which leads to two products: butanal and butanone.
The reactions leading to those products are shown in gure 3.2.

Figure 3.2: Main reactions occuring in the oxidation process


The selectivity of the catalyst is high. The catalyst selectively reacts with alcohols to produce
their corresponding aldehyde or ketone. Experiments showed selectivities of 90% and higher[3].

3.2.3

Kinetics

The rate of reaction is rst order in alcohol and half order in catalyst. The rate constant k has
a value between 2.3E-3 `1=2 :mol1=2 :s1 (at 100 C) and 3.31E-2 `1=2 :mol1=2 :s1 (at 150 C).
The rate expression used is
1
rA = k [alcohol] [catalyst] 2
(3.1)

Diculty in this expression is the concentration. In systems where the solute does not contribute
to the total volume, concentration expressed in mol per unit volume can be used. In our case,
the concentration of 1-butanol is too high to neglect the volume eect. Calculations will be
done on a mol per mol basis.

3.2.4

Experimental data

The most important document as a source for experimental data is the Ph.D. thesis Green
Catalytic Oxidations, by G.J. ten Brink[3]. This is as far as we know the only document
containing information on the palladium bathocuproine complex catalyzed oxidation of alcohols
in water. In the thesis, various alcohol oxidations are described, but regretfully no C4-alcohol
oxidations. Nevertheless, the data presented in the thesis is very useful, because very similar
12

3.2. PROCESS DEFINITION


alcohols are used in the experiments. With these data, predictions will be made for the 1-butanol
and 2-butanol oxidations.

3.2.5

Process conditions

Temperature and Pressure in the reaction section


The temperature and pressure used in the available experimental data on the reaction is 100 C
and 30 bar. Instead of copying these values for the large scale process, rst the pros and cons
of high temperature and pressure in the reaction section are considered. Then, an estimation
is made for the ideal temperature and pressure for the large scale process. The pros and cons
are presented in table 3.1 and 3.2.
Table 3.1: Pros and Cons of use
pros
rate
higher O2 solu- ++
bility

of high pressure in the Green Catalytic Oxidation method


cons
rate other
rate
higher
cap- - product will be ital
costs
a liquid at high
(equipment,
P
compressors)
higher
oper- - ating
costs
(power)

Table 3.2: Pros and Cons of use of high temperature in the Green Catalytic Oxidation method
pros
rate
cons
rate
higher reaction rate
++
lower O2 solubility
-higher alcohol solubility ++
higher aldehyde solubility heating necessary
+/Next to these considerations in tables 3.1 and 3.2 for choosing the pressure and temperature,
certain constraints can be identied:
Water should be a liquid
No critical pressure and/or temperatures are allowed
No explosive mixtures should be possible
Temperature should be below autoignition temperature
The high pressure used in the laboratory experiments is only necessary to maintain a certain
level of oxygen dissolved in the reaction mixture. Also, temperature and pressure conditions
of the upstream and downstream blocks are important. For example, when high pressure is
needed anyway in an upstream or downstream process, the cons of using high pressure in the
reaction section become less important. The operation point in the reactor will be far from the
bubble point, as can be seen in gure 3.3.
13

CPD 3281 - Basis of Design

Figure 3.4: Block scheme for 1-butanol oxidation with preseparation of reactants

Figure 3.3: The bubble and dewpoint curves for a 1-butanol, 2-butanol, butanal, butanone and
water mixture (mass fraction: 1:1:1:1:3). The model used is UNIQUAC

3.2.6

Blockscheme

The chosen blockscheme diers from the rejected scheme only slightly. The dierence is an
extra separation section before the reactor. Explanation on the choice can be found in chapter
2. Main reason is easier separation of 1- and 2-butanol than butanal and butanone. This will
reect on process economy. Figure 3.4 shows the chosen blockscheme.
The incoming stream enters the rst separation section where 1-butanol is separated of 214

3.3. BASIC ASSUMPTIONS


butanol. 1-butanol is then fed to the reaction section where the oxidation reaction with the same
components (except 2-butanol) as in the rst process takes place. In this separation section, the
catalyst is continuously recycled and the butanoic acid removed. The mixture that comes out
of the reaction section is fed to the separation section where 1-butanol, butanal and butanoic
acid are separated. The unconverted 1-butanol is then recycled to the reactor.

3.2.7

Thermodynamic properties

This paragraph contains key thermodynamic information. A more elaborate thermodynamic


study is presented in chapter 4. Where applicable and possible, modelled data is veried with
data from the Dechema data series[11].
Thermodynamic model
The thermodynamic model used is UNIQUAC. This model is capable of predicting thermodynamics of polar systems at elevated pressures. NRTL is also suitable for these type of systems
but UNIQUAC is more capable of handling components with very dierent properties (for
instance water and butanal).
Catalytic cycle
In the catalytic cycle, the palladium dimer reacts selectively with the alcohol, with the corresponding aldehyde and water as a product. Oxygen regenerates the catalyst to its original state
after which it reacts again with alcohol. If no oxygen is available after the aldehyde split-o,
the catalyst will degenerate to palladium black, which makes the catalyst useless.
Solubility of 1-butanol and butanal in water
A study is done to the solubility of 1-butanol and butanal in water. The immiscibility area in
the ternary system gets smaller at higher temperature. There is a small area where the organics
are dissolved in water and a much larger area where water is dissolved in the organics.

3.2.8

Pure component properties

Tables 3.3 and 3.4 present the pure component properties[10][43].

3.3
3.3.1

Basic assumptions
Plant capacity

The available amount of butane as a raw material for the butanol process is about 100,000
ton/y. Assumed is that the butanol plant will produce about 124,000 ton per year. The
incoming butanol stream is 60.30 mol/s on a 8000 production hours per year basis and has a
composition of 95% 1-butanol and 5% 2-butanol. With 8000 production hours per year the
planned and unplanned downtime and possible production losses due to capacity limitations or
lack of feed are included. The chemicals used in catalytic amount are considered to stay in the
system, no degradation of catalyst and other substances is reviewed. The economical plant life
is 20 years. See chapter 11. Table 3.5 shows the incoming and outgoing streams.
Utilities at the existing site probably will not have the capacity to supply extra steam to
the plant. A rough estimation will be made on necessary steam and power generating utilities.
15

CPD 3281 - Basis of Design

Table 3.3: Pure component properties, part 1


property
MW
BP (1) MP(1) 25
MAC
o
o
3
unit
[kg/kmol] C
C
kg=m mg/m3
oxygen
32.00
-183
-218
1.31
n.e.
butanal
72.11
75
-100
797
n.e.
butanone
72.11
80
-86
799
590
2-butanol
74.12
99
-89
805
300
water
18.02
100
0
998
n/a
1-butanol
74.12
118
-89
806
300
butanoic acid
88.11
164
-4.5
953
n.e.
PhenS*
564.6
n/a
~300
n.e.
n.e.
Palladium acetate
224.5
n/a
~195
n.e.
n.e.
Sodium actate
82.04
n/a
324
1528
n.e.
(n.e.: not established; n/a: not applicable)
(1) at atmosperic pressure

property
unit
oxygen
butanal
butanone
2-butanol
water
1-butanol
butanoic acid
PhenS*
Palladium acetate
Sodium acetate

3.3.2

LD50 OR
mg/kg
n.e.
2490
3400
6480
n/a
790
2940
n.e.
2100
6891

Table 3.4: Pure component properties, part 2


CAS #
formula
LD50 SR solubility
in
water(20 oC;1 bar)
[-]
[-]
mg/kg
g/l
7782-44-7 O2
n.e. 100
123-72-8 C4H8O
3560 85
78-93-3 C4H8O
13,000 275
78-92-2 C4H10O
- 125
7732-18-5 H2 O
n/a n/a
71-36-3 C4H10O
3400 77
10792-6 C4H8O2
530 1
52698-84-7 C24 H14 N2 Na2O6S2
n.e.
3375-31-3 P d(OAc)2
n.e.
127-09-3 N aOAc
10

Location

The Asahi-Kasei company is located in near Osaka in Japan, not far from the sea. The butanal
plant will be built on the site of Asahi-Kasei. Infrastructure, some utilities, sewers, etc. are
present. The new plant will possibly use more steam and energy than can be generated by
existing equipment. There probably are possibilities for integration of some parts of the old and
new plant.

3.3.3

Battery limit

The main equipment is shown in table 3.6. The block scheme of the process can be seen in
gure 3.4. Cooling water, LP and MP steam and electricity are assumed available from outside
battery limits. A wastewater cleaning facility is assumed to be present outside battery limits.
16

3.3. BASIC ASSUMPTIONS

Table 3.5: Mass ows of In- and Out-going streams


stream
substance
In [ton/h] Out [ton/h]
1-butanol
14.64
1.46
2-butanol
0.77
0.08
butanal
12.17
butanone
0.67
butanoic acid
0.78
O2
3.14
H2O
3.21
Table 3.6: Important equipment inside battery limits
Equipment
Purpose
Distillation column 1 purication of feed
Reactor
conversion of feed
Compressor 1
oxygen supply
Flash vessel
rst catalyst separation step
Stripping column
second catalyst separation step
Distillation column 2 product separation
Distillation column 3 butanoic acid removal

3.3.4

Streams across battery Limit

1- and 2-butanol will be supplied by pipeline. The butanal is transported by pipeline from
outside battery limits. A are is assumed to be present on the site. The emergency release
system for a part of the process will be connected to it. Water will be made in stoichiometric
quantities of 1 mole of water per mole of butanal during the oxidation reaction. Water with
organic impurities will be transported outside battery limits by pipeline. A summarizing gure
on streams entering and leaving the battery limits is gure 3.5. References to descriptions of
the in- and outgoing streams are given in table 3.7.

Figure 3.5: Streams crossing the battery limits

17

CPD 3281 - Basis of Design

Table 3.7: Stream numbers crossing the battery limits


Stream
Stream number Table in appendix D
1&2 butanol
<101>
D.1
catalyst
D.2 and D.3
1&2 butanol
<105>
D.5
Oxygen
<201>
D.4
butanal
<314>
D.7
exhaust gasses
<213>
D.9
waste water
<319>
D.6
butanoic acid
<318>
D.8
butanone
<314>
D.7

3.4

Economic margin

The margin of the process is the dierence between the value of the product stream and the
feedstock stream. Table 3.8 shows the mass ow and costs per year of the product streams and
the feedstock streams. Values are recalculated from paragraph 11.3 and paragraph 11.2.2.
Table 3.8: Margin calculation
Products
Feedstocks
kton/y M$/y kton/y M$/y
1-butanol
122.4
94.4
2-butanol
6.3
4.9
oxygen
26.2
1.2
butanal
114.3 141.2
butanoic acid
19.3
19.3
1-, 2-butanol
7.8
1.1
Total
141.4 161.5
155.0 100.5
The calculated margin is M$ 61.0 per year. This is higher than calculated in the preliminary
BOD report [42]. This is due to higher production volume in terms of butanal and butanoic
acid production. The added value in terms of margin is 61%. According to the margin, the
process is likely to be economical protable. More details on economy are given in chapter 11.

18

4 | Thermodynamic properties and


reaction kinetics
4.1
4.1.1

Thermodynamic properties
Thermodynamic and physical properties of components

For all the components the heat of formation, Gibbs energy of formation and entropy at standard
state are tabulated in table 4.1[47].
Table 4.1: Thermodynamic properties of pure components at standard state
o
o
o
o
Components Hf;liquid
Hf;gas
Sliquid
Sgas
Unit
1-butanol
2-butanol
butanal
butanone
butanoic acid
oxygen
water

[kJ/kmol]
-327.3
-342.6
-239.2
-247.3
-533.8
0
-285.8

[kJ/kmol]
-274.9
-292.8
-204.8
-215.7
-475.9
0
-241.8

[J/kmol K]
225.8
214.9
246.6
239.0[?]
222.2
70.0

[J/kmol K]
361.98 [?]
359.5
343.7
353.26 [?]
205.2
188.8

Enthalpy, entropy and Gibbs free energy of reaction are calculated by equations 4.1, 4.2,
4.3.
o
o
Hro = Hreactants
H products
o
o
Sro = Sreactants
Sproducts
Gor = Hro T Sro

(4.1)
(4.2)
(4.3)

Oxidation reactions are exothermic. The amount of heat produced during the reactions
at standard state are shown in table 4.2. The reaction of 1-butanol to butanal is moderate
exothermic.
In appendices F.1, F.2, F.3, F.4 and F.5 tables are presented with coecients for correlations
on specic thermodynamic and physical properties. No data on solubility of pure components
in water is shown, because of the multicomponent process and components inuence on activity
coecients. Data shown was obtained from [10].
The heat capacity of the gaseous pure components as a function of temperature is given in
gure F.1. Heat capacity of the liquid pure components as a function of temperature is given
in gure F.2. The vapor pressure of the liquid pure components as a function of temperature
is given in gure F.2.. Density of the pure liquid components as a function of temperature is
19

CPD 3281 - Basis of Design

Table 4.2: Heat of reaction, Gibbs free energy of reaction and entropy generated at standard
state
o
o
Reaction
HR
SR
GoR
Unit
kJ/mol [kJ/molK] kJ/mol.K]
1-butanol to butanal
-197.7
-0.0118
-194.18
2-butanol to butanone
-190.5
-0.0085
-187.97
butanal to butanoic acid
-294.6
-0.1270
-256.75

given in gure F.4. The viscosity of the pure liquid components as a function of temperature is
given in gure F.5. Data is obtained from [10] and the coecients are shown in appendix F.5.

4.2

Thermodynamic model

To make a sound decision on thermodynamic models for modelling LL and VLL equilibria, polar
properties, dipole-dipole interactions, hydrogen bonding, etc. should be taken into account. The
process which has to be modelled consists mainly of alcohols, water, aldehyde and ketone. The
elevated pressure, elevated temperature and the number of components have to be taken into
account as well when a decision on a thermodynamic model has to be made. The number
of components is high, which results in a large amount of interaction parameters. Due to the
hydrogen bonding, dipole-dipole interactions, number of components, two generally used models
can be applied: NRTL and UNIQUAC. The Wilson model can only be applied when no phase
separation will occur.
NRTL and UNIQUAC models can handle strong polar, multicomponent systems. The
UNIQUAC model is favored, because this model is capable of handling dierent components
with very dierent properties [46]. The Wilson model is discarded because phase separation is
expected.
The thermodynamic model is veried by comparing Dechema experimental data with ASPEN generated data. UNIQUAC was chosen as a model, and binary interaction parameters
are retrieved from dierent databases within ASPEN. Table 4.3 presents some examples of the
dierent binary interaction parameters which are used for modelling. It is very important to
choose correct binary interaction parameters for modelling.

Table 4.3: Used databases for binairy interaction parameters


mixture
Used database
1-butanol/water
LLE-LIT
butanal/water
VLE-RK
1-butanol/2-butanol VLE-LIT
1-butanol/butanal
VLE-RK
The model ts very well to the experimental data as can be seen in gure E.3.
20

4.3. SOLUBILITY DATA

xy diagram 2-butanol/1-butanol`

vapour mole fraction 2-butanol

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

liquid mole fraction 2-butanol


Dechema

ASPEN+ VLE-LIT

Figure 4.1: xy diagram for a 2-butanol/1-butanol mixture at P = 1.013 bar [17, p. 150].
Figures with data from the model and data from literature are presented in appendix E.

4.3
4.3.1

Solubility data
1-butanol in water

A ternary diagram of the reactor composition (water, 1- butanol and butanal) is used to nd the
suitable operation region. 2-butanol, butanone and butanoic acid are not taken into account,
this because of their small molar fraction. The temperature is taken 393 K: The objective was
to nd out at what range of compositions no organic phase exists. ASPEN is used to calculated
the compositions of the two dierent phases at certain feed compositions. In order to validate
the model with the used parameters the calculation was compared with literature. Data for two
binary systems was used, taken from [12] and [11]. In table 4.4 and 4.5 the values are shown.
Table 4.4: binary data for 1-butanol/water
T = 393 K
Solubility of 1-butanol in water (mole %)
Dechema
ASPEN
4.3
4.5
solubility of water in 1-butanol (mole %)
Dechema
ASPEN
78.7
80
A decanter block in ASPEN is used to calculate at what compositions liquid phase splitting
occurs, and the corresponding compositions of the two dierent liquid phases are calculated.
The resulting ternary diagram is given is gure 4.2.

4.3.2

Catalyst complex in water

The rate expression is half order in catalyst concentration. A higher catalyst concentration
can therefore result in smaller reactor size and lower residence time. Catalyst concentration described in [3] resulted in a large reactor volume. To obtain a reasonable rate per unit volume and
as a result an acceptable reactor volume, solubility tests with PhenS*Pd(OAc)2 were performed
21

CPD 3281 - Basis of Design

Table 4.5: binary data for butanal/water


T = 311 K
Solubility of butanal in water (mole %)
Dechema
ASPEN
2.0
1.9
solubility of water in butanal (mole %)
Dechema
ASPEN
13
14

Figure 4.2: Ternary diagram for water/1-butanol/butanal at 30 bar and 393 K


to investigate solubility of this component. Results from this test are described in appendix G.
A concentration of 1.438 mmol/l was taken for reactor design. At higher cocentrations oxygen
transfer can be limiting and heat removal becomes a problem (pragraph 8.3.7).
Oxygen
Solubility data for oxygen in organic and inorganic components at dierent temperatures is
dicult to obtain. Most data presented in literature is at standard state conditions. An exception is the binairy system of water and oxygen. This system is studied thoroughly. Solubility
data for oxygen is obtained from [26]. To obtain Henry coecients at dierent temperatures a
method described in [25, page 607] was used. This method is described in appendix N. Henry
coecients at reaction temperature (403 K) for oxygen in dierent components are presented
in table 4.6.
Table 4.6: Calculated henry coecients for oxygen in dierent solvents
Solvent
HO2
[bar]
water
6.5910 4
1-butanol 3.8010 2
butanal
3.4310 2
22

4.4. KINETICS
With these coecients a henry coecient for the mixture was calculated of 3.99104 bar.
See appendix N for details.

4.4

Kinetics

4.4.1

Catalytic cycle

A catalytic cycle was proposed for alcohol oxidation [3]. The catalyst is a bathophencuproinedisulphonate palladium complex (PhenS*Pd(OAc)2 ). The cycle is shown in gure 4.3. The
separate reactions are shown below.

Figure 4.3: Proposed catalytic cycle for alcohol oxidation by PhenS*Pd(II)[3]


1.
2.
3.
4.
5.

(Pd2 (OH)2)2+ + ROH ! PdOH ROH +


PdOH ROH + ! H2O + P dRO +
PdRO+ ! RO + Pd+
Pd+ + O2 ! PdO+
2
1 (Pd (OH) )2+ + H O
PdO+
+
H
O
!
2
2
2 2
2
2
2
1
2

"P d"

(Pd2 (OH )2 )2+ = palladium dimer


PdOH ROH + = palladium with alcohol
PdRO + = complex with aldehyde
Pd+ = palladium hydride complex
PdO+
2 = reoxidated palladium complex

6. H2O2 ! H2O + 12 O2
It must be noted that this catalytic cycle is a proposed cycle, it has not been proven yet. A
detailed description of this cycle and experimental data can be found in [3].

4.4.2

Reaction order in alcohol concentration

The reaction order in alcohol is pseudo zero order for little soluble alcohols. The limited solubility makes the concentration of the alcohol constant, and with making sure that no diusion
limitation existed, a pseudo zero-order in alcohol concentration could be established. The real
order of alcohol concentration is determined using a completely soluble alcohol , then an order
of one is observed.
23

CPD 3281 - Basis of Design

Figure 4.4: PhenS*Pd(OAc)2 dimer

4.4.3

Reaction order in oxygen

The re-oxidation of the palladium complex (step 5) is done with oxygen. In the experiments
oxygen pressure had little inuence on the reaction rate. The rate of reoxidation of the complex
per unit volume reaction mixture was not the rate determining step during the experiments.
Oxygen transfer might become limited in a large scale process. Then, the oxygen pressure
probably will have inuence on the reaction rate.

4.4.4

Reaction order in palladium concentration

The order in palladium concentration was shown to be half order. The reason for this is that
probably the catalytically active palladium monomer is in equilibrium with the dihydroxybridged palladium dimer. The palladium dimer is shown in gure 4.4.
The optimum ratio of ligand (PhenS*) to palladium (Pd(OAc)2 ) has been investigated. The
variation of the ligand to palladium showed that the ratio ligand:palladium of 1:1 was optimal.
Many alcohol oxidations are carried out in presence of a base. Without going into the
mechanistic details, it is stated here that during experiments there was no inuence of base on
the reaction rate.

4.4.5

Rate expression

The rate expression will be used as a basis for reactor calculations. The rate constant k will be
discussed below.
1
rA = k [alcohol] [catalyst] 2
(4.4)
In systems where the solute does not contribute to the total volume, concentration expressed
in mol per unit volume can be used. In our case, the concentration of 1-butanol is too high to
neglect the volume eect. Calculations will be done on a mol per mol basis.
Rate constant
Reliable data on reaction kinetics are needed as a basis to judge the inuence of temperature
on the reactors eciency and scale.
It turns out that no experiments with butanol were carried out in [3]. This has been done
in comparison with the experiments with 1-pentanol, 1-hexanol and 1-heptanol [3, page 62],
whose reaction rates are calculated in table 4.7 by means of equations from 4.5 to 4.7, in a
batch reactor at 100C without any oxygen transfer limitation, which is assumed to be the case
in our reactor.
Z X
dX
t = FA0
(4.5)
r
v VR
o
24

4.4. KINETICS
where t is the reaction time, FA0 the ux of reactant A in the inlet and dX the conversion
derivative.
rv = k [Pd]1=2 [OH ]
k=

(4.6)

ln (1 X)

(4.7)

[Pd]1=2 t

Yields table 4.7 and gure 4.5 at 100 C, leading to equation 4.8.
Table 4.7: Rate constant values
reactant
k [`1=2 :mol1=2:s1]
1-pentanol 2.29103
1-hexanol 2.19103
1-heptanol 1.79103

Rate constant versus number of carbon atoms

k [l1/2.mol-1/2.s-1]

2.5E-03
2.0E-03
1.5E-03
1.0E-03
5.0E-04
0.0E+00
4

5
6
number of carbon atoms

Figure 4.5: Rate constant as a function of the number of carbon atoms of the molecule
k = 2:3 10 3 ` 1=2:mol 1=2:s1 at 100 C

(4.8)

Temperature dependence rate constant


A problem in investigation of the kinetics is a lack of experimental data versus the temperature
in [3]. Experiments were performed at 100C, so that the temperature dependency has not been
investigated. From [3] a value for the activation energy of Ea = 70 kJ/mol was obtained.
To calculate the rate constant at dierent temperatures, the Arrhenius Law is used (equation
4.9). Table 4.8 presents the rate constant values for a temperature range from 100 to 150 C.
Ea
)
(4.9)
RT
where kT is the rate constant at the desired temperature T (K) and A is the frequency factor.

Ea
1
1
k2 = k1 exp
( )
(4.10)
R
T2 T1
kT = A exp(

25

CPD 3281 - Basis of Design

Table 4.8: Rate constant values versus temperature for 1-butanol


T [C] k [` 1=2:mol1=2:s1]
100
2.3103
110
4.14103
120
7.25103
130
1.23102
140
2.04102
150
3.31102
Calculations are performed on 1-butanol. The assumption is made that the rate constant of
2-butanol is the same as the one of 1-butanol.

4.4.6

1-butanol vs. 2-butanol competition

In the oxidation of the primary and the secondary alcohols together (gure 2.2) , the alcohols
have to compete (intermolecular competition). Dierent factors inuence this competition:
dierent solubility
dierent molecular structure (dierent steric properties)
increased electron density of the secondary alcohol
No literature data is available on the competition between palladium catalyzed oxidation of
1-butanol and 2-butanol. However, on comparable alcohols competition experiments were done.
In the case of alcohols with one carbon atom less, the isomeric propanols, competition did not
show any clear preference (kprim /ksec v1). But on the intermolecular competition between the
two alcohol functionalities on 1,5-hexanediol, the oxidation of the primary alcohol functionality
showed a clear preference (kprim /ksec v 0:2).
For the design, it has been assumed that 1-butanol and 2-butanol have the same rate constant. Calculations were proceeded with the rate constant of 1-butanol.

4.4.7

Selectivity

The selectivity of the reaction to aldehyde is assumed to be 100%. The only possible side
reaction is the over-oxidation of aldehyde to butanoic acid. This over-oxidation will occur in
the organic phase only because water acts as a anti-oxidant. Competition between 1-butanol
and 2-butanol is expected. Nevertheless, the amount of 2-butanol is very small in comparison
to the amount of 1-butanol, so oxidation of 2-butanol and possible side reactions are not taken
into account for the design. This results in three main reactions:
1.
2.
3.

4.4.8

1-butanol + 0.5 O2 ! butanal + H2O


butanal + 0.5 O2 ! butyric acid + H2 O
2-butanol + 0.5 O2 ! butanone + H2O

Catalyst deactivation

The catalyst deactivation has been studied as showed in the table 4.9. The experiment has been
carried out with 10 mmol 1-hexene, leading to 2-hexanone, 0.1 mmol PhenS*Pd(OAc)2, 42.5 g
water, 30 bar air, 100 C, 10h.
26

4.4. KINETICS

cycle

1st
2nd
3rd

Table 4.9: Catalyst


with 10 mmol NaOAC
1-hexene con- selectivity to 2version
hexanone
48
99
44
96
40
95

deactivation
without NaOAc
1-hexene conversion
47
28
15

selectivity to 2hexanone
99
97
96

These values are obtained in a laboratory were all the reconversion steps have to be made
by hand. In a plant, this reconversion can be much more ecient.

27

5 | Process structure and


description
The translation from the selected blockscheme in chapter 2 to unit operations will be done in
this chapter.
As explained in chapter 2, the plant is divided into three parts. Three sections are dened:
section 100 pre-reaction separation, section 200 conversion section and section 300 product
purication and catalyst recycle. All process parts such as vessels or streams are numbered
accordingly.

5.1

Pre-reaction section

The incoming 1-butanol needs to be puried from 2-butanol. This is done in section 100.
A high purity of 1-butanol is required because all 2-butanol left in the 1-butanol will also be
converted. This will result in impurities in the butanal product. 1-butanol and 2-butanol
have little dierent properties. Their molecular weight is the same, they both have a hydroxyl
group, have similar solubility properties in several solvents. Their main physical dierence is
the boiling point of the pure substances; 1-butanol boils at 118 C and 2-butanol at 99 C (at
1 bar). The separation based on dierence in boiling point is therefore a good choice. Besides
that, distillation is generally the least expensive mean of separating mixtures of liquids when
the relative volatility is higher than 1.1[6, page 175].
Distillation will be used for the separation of 1-butanol and 2-butanol
The feed stream is pre-heated before it is fed to the distillation unit. 2-butanol is the lowest
boiler and is removed over the top. 2-butanol will be sold. 1-butanol is pumped to section 200.

5.2

Conversion section

This paragraph will deal with the development of the reactor concept and the oxygen recycle
loop. The conceptual reactor design (paragraph 5.2.1) will explain the ideas which are at the
basis of the design of the reactor. Assumptions made in paragraph 5.2.2 are necessary to
continue with practical reactor design in paragraph 5.2.3. The realization of the oxygen recycle
over the reactor is done in paragraph 5.2.4.

5.2.1

Conceptual reactor design

Krishna and Sie [21] developed a strategy for reactor design at three dierent levels. With this
structured approach on reactor design it is possible to arrive at an optimal reactor conguration.
The three design levels are reviewed for the conversion of 1-butanol to butanal using the required
29

CPD 3281 - Basis of Design


catalyst complex. After the review, a wish list for the reactor is put together. With this wish
list, design decisions are made in the practical reactor design (paragraph 5.2.3).
Level I: Catalyst
The catalyst properties are xed. The complex is dissolved in the water. Disadvantage of the
catalyst in homogenous form is the limited solubility. Because of this low solubility, the water
phase has to be large to convert the stated ow of butanol.
The oxidation reaction is relatively slow (see paragraph 4.4). For slow reactions a high ratio
of liquid phase volume relative to diusion layer volume should be chosen.
Level II: Injection and dispersion
Over oxidation of butanal to butanoic acid occurs in the organic phase. The ultimate way to
prevent over oxidation is making sure that no organic phase is present. For a high reaction
rate a high alcohol concentration should be present, preferably the maximum amount of 1butanol soluble. Pure 1-butanol should be added preferably in small sized bubbles. No more
alcohol than the amount which will dissolve has to be added. Because of the possibility of auto
oxidation, the concentration of butanal in the water and/or organic phase should be kept at a
minimal amount.
A high solubility of O2 in the liquid phase is wanted. A high solubility increases the driving
force for diusion of O2 into the liquid and will therefore decrease the chance on oxygen mass
transfer limitation. This high solubility is achieved by high (partial) O2 pressure at the reaction
temperature.
The reactant may be supplied in situ by mass transfer from a dispersed organic phase.
Extraction in situ is also considered. When it is possible to extract the butanal from the
process, less oxidation of butanal to butanoic acid can occur. A benet of the current process is
that no organic solvents are used. So by introducing a (organic) solvent this benet is reduced.
Preferably no vapor mixture of hydrocarbons and O2 should be present. This increases
process safety.
Level III: Hydrodynamic ow regime
A high ratio of liquid phase with catalyst and gas phase with oxygen should be used. A
homogenous gas liquid ow regime is therefore necessary.
Wish list
A wish list is composed after evaluating the three levels of reactor design. The reactor should:
have a high selectivity towards butanal
have high conversion
have a high reactor volume eciency
be capable of handling 13 tons 1-butanol/h
prevent over oxidation of butanal
use the catalyst in an eective way
contain a low organic fraction for safety reasons
30

5.2. CONVERSION SECTION


operate at lowest possible pressure
have a high reaction rate per m3
encourage high O2 transfer
be at its maximum solubility of 1-butanol in order to have a maximum rate of reaction

5.2.2

Assumptions for the reactor design

Catalyst deactivation
The catalyst deactivation is an important parameter because it will have an impact on the
margin of our process. Some data on catalyst deactivation is presented in paragraph 4.4.8.
Although this data shows that catalyst deactivation did occur during laboratory experiments,
the assumption is made that plant conditions will be created in such a way that no catalyst
deactivation occurs.
No catalyst deactivation will be taken into account
Catalyst solubility
The catalyst complex solubility has been under investigation. The data which is used for
the design is presented in paragraph 4.3.2. This data is obtained at 50C for pure water
at atmospheric pressure. The data is used for the design, not taking the process condition
dierences into account.
Eects on volume of mixing
No volume eects are considered. This means that mixing for example half a liter of water with
half a liter of 1-butanol will result in 1 liter of mixture.

5.2.3

Reactor design decisions

Using the wishlist given in paragraph 5.2.1, a series of design decisions are made in this paragraph. Decisions on reactor phase, reactor type, oxygen supply and process conditions will be
made.
Phases in the reactor
A choice must be made whether to operate with two liquid phases present, or one. The rst
liquid phase is the aqueous one, with the catalyst complex. The second might be an organic
phase. Presence of an organic phase in the reactor together with oxygen creates the possibility
of over oxidation of butanal. The use of TEMPO seems to be the only way to stop over oxidation
in the organic phase. TEMPO has two major inconveniences:
It has to be split from the liquid in order to be reused. Using TEMPO implies then
introducing an extra separation step
Some TEMPO is consumed in the process and new TEMPO has to be added continuously.
The price of TEMPO is quite high, a rst inquiry resulted in $100 per 10g[43]. In the
laboratory only small quantities are needed, but on plant scale this would have a signicant
impact on operating costs
31

CPD 3281 - Basis of Design

Figure 5.1: The conversion versus space time for a PFR and a CSTR
Taking the two big disadvantages of TEMPO use into account:
The reactor will be operated in one phase only
Reactor type selection
The second consideration was whether to use a plug ow type of reactor (plug ow reactor,
PFR) or a innitely mixed type of reactor (continuously stirred tank reactor, CSTR). Design
equations for a CSTR, 5.1 and a PFR, 5.2 combined with the reaction rate equation, 5.3, lead
to equations 5.4 and 5.5. With these equations, a comparison between standard operation for
a CSTR and a PFR can be made in terms of conversion and space time necessary for the
conversion. In gure 5.1 this comparison is made1 .
FAO (Xout Xin)
(rv )out
Z Xout
dX
= FA0
Xin rv

VR =

(5.1)

VR

(5.2)

r = k [Pd]1=2 [OH]
1=2

X =

k [Pd]

1=2

1 + k [Pd]

X = 1 exp(k [Pd]1=2 )

(5.3)
(5.4)
(5.5)

From the gure it can be concluded that working with a PFR is advantageous in terms of
space time and therefore the necessary reactor volume. On top of that using a PFR permits
to avoid or at least decrease the backmixing in the reactor and thus preventing a reaction rate
drop since the reaction rate is a rst order function of the alcohol concentration.
1

Assumed is that the alcohol concentration is maximum in the inlet.

32

5.2. CONVERSION SECTION


The above given comparison works with a stated reactor feed of water with maximum
dissolved alcohol, without creating an organic phase. Then, for a 95% conversion, the outgoing
butanal ow FP is given in equations 5.6 and 5.7. Residence time is given in equations 5.8
and 5.9. This leads to a liquid volume VR calculated by equation 5.10 and given in equation
5.11, where FP is the outow of the desired product butanal (mol/s), FA0 the inow of butanol
and X the conversion.
= FA0 X
= 54 mol=s = 14 mol=h
1
=
ln(1 X)
k [P d]1=2
= 11:5 h
Z X out

dX
FA0
VR =
= FA0
=
ln(1 X)
1=2
0
Xin rv
k [Pd] [OH ]t=0
VR = 1750 m3

FP
FP

(5.6)
(5.7)
(5.8)
(5.9)
(5.10)
(5.11)

This yields a far too high space time and residence time to have a 95% alcohol conversion
in a PFR, which is not geometrically practicable.
Since the reaction rate is very low, the idea came up to continuously feed the PFR with 1butanol at multiple places along the reactor to continuously work at its maximum concentration
in water avoiding the formation of an organic layer and maximizing reaction rate. Continuously
feeding a PFR is equivalent to building a CSTR in which the alcohol concentration is maximum.
The investigation of the design of a CSTR with a maximum solubility of alcohol in the outlet
has been proposed.
A CSTR type of reactor, working at maximum
concentration of 1-butanol will be designed
Characteristic of a continuous stirred tank reactor (CSTR) is an output concentration which
is equal to the concentration of the bulk. The aqueous inlet is saturated with 1-butanol and
the outlet should also be saturated with 1-butanol. 1-butanol is converted in the reactor and
therefore additional pure 1-butanol needs to be added. This probably needs to be done at
several places in the reactor in order to prevent an organic phase from occurring.
A rst sketch of the reactor with its feeds and products is given in gure 5.2.
A stream of water saturated with 1-butanol and catalyst is fed to the reactor. 1-butanol is
fed to the reactor in order to keep the concentration at its maximum. Air, oxygen or another
oxygen mixture is sparged into the reactor to supply oxygen for the catalyst cycle. Possible
vapor is withdrawn from the top. An aqueous stream containing alcohol, aldehyde and catalyst
complex is taken out of the reactor as product stream. The product stream is fed to a separation
unit where the aldehyde, a stoichiometric amount of water and possibly 1-butanol are separated
from the bulk of the stream. The aqueous stream containing the catalyst complex and possibly
1-butanol is recycled to the reactor inlet.
Oxygen supply
The cheapest oxygen supply is air, in terms of feed costs. However, using pure oxygen has
distinct advantages over using air or a O2/N2 mixture. One is the dierence in pressure required
in the reactor. In order to facilitate oxygen transfer from the gas phase to the liquid phase
33

CPD 3281 - Basis of Design

Figure 5.2: Reactor with feeds and products.


elevated pressure is needed. The driving force is higher with pure O2 than for example with air.
Less high pressure is needed for pure oxygen.
Another advantage of pure O2 over air is the ease of not consumed O2 recycle. Air contains
80 % of gases not necessary in the reactor, but which have to be compressed anyway. Using
air would means that recycling the unconsumed O2 would not be possible without dicult
separation of O2 and N2/CO2. With pure O2 less compression power is needed to get the same
amount of O2 in the reactor. This result is lower investment cost and lower operating costs.
Pure oxygen will be used as O2 source
In considering using pure O2 it is necessary to check the feasibility in terms of pure O2
costs. Companies selling pure oxygen were contacted. The prices indicated in the following
table are from Air Liquide. The price calculations are based on the amount of oxygen needed,
the pressure at which it has to be delivered and the purity required.
For a consumption of almost 1 kg/s, the most economical solution would be either on-site
dedicated O2 production or delivery through an O2 network, if possible. Liquid bulk delivery
with on-site liquid storage and vaporization would not be appropriate. If on-site production is
required, a 99% purity imposes the use of a cryogenic production method. The O2 production
price depends mainly on the electricity price, which will set the oxygen price at $35 to $50 per
ton, the lower price being for O2 supply from network, the higher one for dedicated on-site
production.
When a 93% O2 purity is envisaged, on-site production sets the price at $40-45 per ton,
which is cheaper than the on site dedicated cryogenic production for a 99% pure oxygen but
still more expensive than O2 delivery by network. The price of oxygen when delivered by a
network is $30-35 per ton. Impurities are nitrogen (6%) and argon (1%).
Table 5.1: Estimation of the oxygen price versus its purity
purity production on site delivered by network
%
$/t
$/t
99
50
35
93-95
40-45

34

5.3. PRODUCT PURIFICATION AND CATALYST RECYCLE


Process conditions
Important process conditions are: hydrodynamic ow regime, vapor feed rate, reactor composition, temperature and pressure. All these conditions are connected and must be considered
together in order to fully optimize the reactor. To optimize the reactor means to minimize reactor volume, pressure, energy consumption/yield, etc. Because of the inuence of the process
conditions on the nal reactor dimensions, the optimization of the process conditions is not
given here, but in paragraph 8.3.1.
Global process conditions can already be given, they will resemble experimental conditions:
about 100C, elevated pressure (10 - 50 bar).
Catalyst complex concentration
The concentration used in the experiments[3] was 1 mmol/l. For the design, the increase of
reaction rate per unit volume has been realized by using an increased catalyst concentration.
The concentration used in the reactor depends in this design on the concentration of the complex
in the recycle. This is further explained in step 6 in paragraph 7.1.1. For the design, a catalyst
complex concentration in the reactor of 1.438 mmol/l is used.

5.2.4

Oxygen recycle

Because pure oxygen is used as O2 supply, it is possible to recycle unconsumed O2. The vapor
ow coming from the top of the reactor will probably also contain water, 1-butanol and butanal
vapor. This can easily be separated in a conderser at high pressure. The condensed water
and hydrocarbons are mixed with the reactor liquid exit and the O2 is repressurized only to
compensate for the pressure drop in the condenser and fed back into the reactor.
A condensor operating at reactor pressure is
used to separate unconsumed O2 and water
and hydrocarbon vapor
With an O2 stream continuously being recycled over the reactor, somewhere in the recycle
the make up O2 for the oxidation needs to be added. After simulating the reactor at given
process conditions (O2 ow, pressure, temperature) in ASPEN, the top vapor ow was compared
with the explosion limits for the resulting hydrocarbons, water and oxygen vapor mixture. This
comparison is given in paragraph 10.3 (safety chapter). From this comparison it is clear that
the overhead needs to be diluted in order to make sure that the overhead is not within explosion
limits.
Make up O2 for the reaction is used to dilute
the overhead of the reactor
A blockscheme of the reactor with the condenser and oxygen recycle is given in gure 5.3.

5.3

Product purication and catalyst recycle

The process objective of section 300 is the delivery of puried butanal product and recycle of
the dissolved catalyst complex and unconverted 1-butanol. In order to realize such a process
rst some general considerations on separation possibilities and impossibilities are made on the
topic (paragraph 5.3.1). After that paragraphs 5.3.2, 5.3.3 and 5.3.4 deal with the dierent
separation steps and explain which units which will be used.
35

CPD 3281 - Basis of Design

Figure 5.3: The recycle structure for oxygen

5.3.1

General considerations

The liquid mixture from the reactor contains around 50 mol% water, around 20 mol% 1-butanol
and 20 mol% aldehyde. Next to this, some by-product will be present in the form of butanoic
acid. In this mixture the catalyst complex is dissolved, together with sodium acetate. Section
300 will deal with this stream so that:
A butanal stream is produced with or without water but without hydrocarbons
Excess water which is produced in the reaction is removed
A liquid recycle contains all the catalyst, the water needed in the reactor and the unconverted 1-butanol.
As an initial exploration, the lists of heuristic rules for column sequencing in distillation
from [6, page 177] are reviewed to get an idea of the applicability of these rules on the product
purication and catalyst recycle. The results from this review for the process:
1. The most plentiful component should be removed rst. This is in our case the dissolved
catalyst in water.
2. High recovery separations last. This would imply the purication of butanal.
3. Lightest, or easiest rst. This will mean that the stream from the reaction section should
be cleaned of organics rst.
Separation impossibilities
The catalyst complex is expensive and a 100 % recovery for recycle is pursued. An important
impossibility in separation of the complex is the thermal instability at high temperatures. The
catalyst mixture should therefore not be contacted with surfaces with a temperature higher
than about 150C. A reboiler in a distillation column would need heating with steam with
a temperature around 150 C. Therefore, before the complex is removed, distillation is not
considered as a separation option.
Next to the limit of temperature on the catalyst complex, a high water content in a liquid
stream does also not favor distillation.
36

5.3. PRODUCT PURIFICATION AND CATALYST RECYCLE


Azeotropes
When the water with catalyst is removed, the butanal must be taken out of a mixture of water
and 1-butanol. In this system azeotropes exist in the investigated range of 1 to 35 bar. At
dierent pressures, the azeotropes have dierent molar fractions. The identied azeotropes are
(see also gure 5.4):
1. 1-Butanol/Water (in the range 1 to 35 bar at dierent mol fractions)
2. Water/Aldehyde (in the range of 1 to 35 bar at dierent mol fractions)

5.3.2

Catalyst separation and recycle

The catalyst can be separated from the reaction mixture by performing a ash operation on the
reactor outlet, i.e. a sudden lowering of the pressure, resulting in a decrease of the boiling point
of all components and thus evaporation. The catalyst complex and all other ionic components
present will not evaporate and they will stay in the liquid phase.
Three phase ash is used as a rst separation
between liquid recycle containing catalyst and
butanal
The ash accomplishes a rst separation between the catalytic complex in water and the
hydrocarbons, without the use of a reboiler.
The liquid resulting from the ash operation might or might not consists of phases. This
will depend on the actual reactor composition and the evaporation in the ash. If liquid/liquid
separation occurs, the organic aqueous phase will contain almost all the hydrocarbons left in
the liquid, together with water and catalyst. The organic aqueous phase still contains catalyst
and cannot be distilled yet. Instead of distillation a stripper is chosen for removing butanal.
The stripper is operated a moderate temperature and does not have a reboiler.
A stripper is used for removing the remaining
butanal in the organic aqueous liquid from the
three phase ash
The bottom stream is added to the aqueous phase from the three phase ash unit and
recycled to the reactor. The vapor products from both the stripper and from the three phase
ash are mixed. This stream does not contain catalyst and butanal can now be recovered using
distillation.

5.3.3

Butanal recovery

Before distilling the vapor mixture from the ash and stripper, water is removed by condensing
the vapor and decanting the resulting two phase liquid. The removal of water is necessary
to minimize energy consumption of the distillation upstream and for recovering some water
without butanal for addition in the liquid recycle.
A decanter will be used to remove water from butanal
Distillation will be used for recovering the butanal product
37

CPD 3281 - Basis of Design

Figure 5.4: Residue curve map for butanal/water/1-butanol at 1 bar.


The pressure of the organic aqueous stream from the decanter will be between approximately
1 and 2.7 bar. Distillation boundaries are present due to the azeotropes occurring at these
pressures in the water/butanal/1-butanol mixture. In gure 5.4 can be seen that the system
has 2 distinct regions which dene the separation possibilities. Two limited regions in the
residue curves can be identied. Depending on the composition separation is limited to the
boundaries of these regions.
Separation possibilities are limited in composition within the regions BDE or ACDE. When
a mixture within region ACDE is heated, the composition will approach pure 1-butanol. When
a mixture within region BDE is heated, the remaining liquid will nally consist of pure water.
The mixture after the decanter is within ACDE and it is therefore possible to separate the
mixture into the butanal/water azeotrope and 1-butanol. The column will be designed in such
a way that the organic impurities will leave through the bottom with the 1-butanol.

5.3.4

Alcohol recycle

The bottom product of the butanal recovery distillation contains mainly 1-butanol with some
water and butanoic acid as impurity. The butanoic acid must be removed, preferably in a pure
form so it can be sold as a product.
Distillation will be used for 1-butanol recycle purication
1-butanol is removed over the top. It is partly condensed for reux and the vapor is fed to
the stripper as vapor ow. Butanoic acid is the bottom product.

5.4

Process Flow Scheme (PFS)

The PFS is given in appendix H. In the paragraphs 5.4.1, 5.4.2 and 5.4.3 the PFS will be
explained. The stream summary which belongs to the PFS is given appendix H.
38

5.5. UTILITIES

5.4.1

Section 100

The 1-butanol entering battery limits, <101> is pre heated in E101 and fed to C101 for purication from 2-butanol. The pure 1-butanol leaves section 100 as <104>. The 2-butanol with a
minimal amount of 1-butanol is removed over the top of C101 and leaves the site as <105>.

5.4.2

Section 200

Reactor
Alcohol feed <104> is cooled down in E201. This is done because of heat duty limits for the
reactor. It is fed together with the catalyst/water/1-butanol recycle <214> to R201. <214>
has also been cooled down for the same reasons. Liquid leaving the reactor is mixed with <210>
in V202 and then led to section 300.
Oxygen recycle
The reactor has two vapor feeds, <212> to supply the oxygen which is dispersed in the liquid
and <203> containing make up oxygen.<203> has been pressurized in a multistage compressor
K201 to reactor pressure. <203> is used to dilute the overhead of R201 in order to make sure
that this vapor mixture is outside explosion limits. The vapor leaving the reactor <208> is
partly condensed at high pressure in V201 to recovery hydrocarbons and water. The almost
pure oxygen <211> is repressurized with K202 and fed back in R201.

5.4.3

Section 300

Catalyst recycle
The liquid stream <301> at 21 bar containing all the reaction products is ashed in a three
phase ash vessel (V301) at 1 bar. <303> is pre heated in E301 and then stripped from its
butanal in stripper C301. C301 uses the 1-butanol recycle, <317> as vapor feed. The liquid
product <309> from C310 contains mainly water and 1-butanol and the catalyst complex and
is ready for recycle. It is send to the liquid recycle collection vessel V303. The top product is
removed as a vapor and condensed together with the vapor from V301 in E303. The resulting
two phase liquid mixture, <310> is decanted in V304. Almost pure water <312> is partly
added to the liquid recycle in V303. About one third of <312> is removed from the site via
<319> as excess water. From V303 the catalyst recycle mixture is fed back to R201 after being
pumped up to 21 bar again with P305.
Butanal recovery and 1-butanol recycle
The aqueous organic phase from V304 is distilled in C302. The butanal product containing
about 10 weight percent water, <314>, is removed over the top. The bottom product <315> is
puried from butanoic acid in C303. The almost pure butanoic acid leaves the site with <318>.
The top product <317> is fed as a vapor to C301 to serve a vapor ow for stripping.

5.5

Utilities

The utility summary is presented in gure H.5 in appendix H. It is clear that overall more
cooling that heating is required. Large heat producers are the reactor (R201) and the decanter
feed cooler (E303). Large heat consumers are the stripper feed heater (E301), the reboilers of
the alcohol distillation (E103) and the reboiler of the butanal recovery (E306).
39

CPD 3281 - Basis of Design


Large heat producers and consumers might be heat integrated to yield a higher process
eciency. More on this in paragraph 7.5. The integration of condensers and reboilers with heat
pumps improves the process in terms of steam consumption.

5.6

Process Yields

The tables presenting the process yields for raw materials, products, wastes and utilities are
given in appendix H, gure H.4. The yields are shown in gure 5.5.
Steam
26.6 t/h
(1.87 t/t)
[ $0.0247/$]

1-Butanol
Feed

Cooling
Water
954 t/h
(67.2 t/t)
[ $0.002/$]

Electricity
544 kWh/h
(38.3 kWh/t)
[ $0.0026/$]

1-Butanol Oxidation to Butanal

15.3 t/h
(1.08 t/t)
[$0.669/$]

$ / $ butanal product

butanal
product

14.2 t/h
(1.00 t/t)
[ $ 1/$]

2-butanol
product

0.785 t/h
(54.9 kg/t)
[ $0.0075/$]

butanoic acid
product

0.212 t/h
(14.8 kg/t)
[ $0.137/$]

Project ID Number :
Completion Date
:

Figure 5.5: Process blockscheme with yields

40

CPD3281
December 20th 2002

6 | Process Control
This chapter is based on theory presented in appendix I. The abbreviations used are: TC:
temperature controller, PC: pressure controller, LC: level controller, FC: ow controller and
CA: composition analyzer.

6.1

Pre-reaction section

The distillation column C101 is designed to work at a certain pressure and with a given temperature of the stream <103>. A PC on the top of the column is thus required. The manipulated
variable is the required duty ow in the cooling system E102 which precedes the reux drum
V101. The temperature of the feed stream <103> wants being xed. A TC is required to
control the temperature of duty ow used in the heat exchanger E101 on the stream <103>. A
vapor safety valve is needed to prevent any unsafe pressure reach.
A degree of freedom analysis leads to a degree of freedom for the distillation column of 6.
Advice for a distillation column process control can be found in [37, page 87 and 90]. Among
those 6 variables, 2 disturbances can be dened (feed ow rate and feed ow composition of the
stream <103>) and 4 are control objectives. Table 6.1 presents the controlled and manipulated
variables to reach the objectives.
Table 6.1: Controlled and manipulated variables for the rst distillation column
Controlled variables
Controllers Manipulated variables
composition of the stream <105>
CA
reux ow
composition of the stream <104>
CA
duty ow at the reboiler E103
liquid hold-up in the reux drum V101
LC
stream <105> ow
liquid hold-up at the base of the column LC
stream <202> ow
Compositions need to be checked because it is very important for the following to keep low
the amount of 2-butanol and the liquid hold-ups are to be controlled to avoid damaging the
equipment (pumps). Controlling the liquid level in the column also prevents the pump P201
that transports 1-butanol to the reaction section from damages.

6.2
6.2.1

Conversion section
Reactor

The reaction occurring in the reactor R201 is exothermic. Providing the reactants at low
temperature is not enough to remove the heat formed by reaction and mixing. A coolant jacket
and two coils need thus to be installed in the reactor. The degree of freedom of this reactor is
6, to which 2 disturbances have to be subtracted (ow and composition of the stream <204>).
41

CPD 3281 - Basis of Design


Yields a degree of freedom of 4. Table 6.2 presents the controlled and manipulated variables for
the reactor.
Table 6.2: Controlled and manipulated variables for the reactor
Controlled variables
Controllers Manipulated variables
temperature
TA
duty ow in the coils
pressure
PA
stream <212> ow
liquid hold-up in the reactor
LC
stream <207> ow
composition of the stream <207> LC
stream <214> ow
It is favoured to control the ow in the coils in comparison to the coolant jacket since the
coils take more energy. To control the ow of the stream <204>, a vessel needs to be placed
on the stream <204>.
A safety valve needs to be installed at the top of the column to prevent any increase in
pressure. Care has to be paid to avoid explosive mixture composition. A composition analyzer
is set up at the top of the reactor. The manipulated variable is the stream <201> ow.

6.3
6.3.1

Product purication and catalyst recycle


Vapor/liquid separator

The vapor stream <208> from the reactor R201 does not only contain oxygen but also organics,
which are recovered by condensation of the vapor and then separation in the vapor/liquid
separator V201. The vapor stream <215> containing mainly oxygen is then compressed to
be recycled in the reactor. This stream should not contain any liquid. Thus the level in
the vessel is a controlled variable and the cooling uid ow in the heat exchanger E202 is a
manipulated variable. The composition of the vapor outlet is a function of the equilibrium.
When the composition has to be controlled, the controlled variable is the vapor pressure and
the manipulated one the ow of the stream <211>.

6.3.2

Collection vessels

A couple of vessels are foreseen in the design to collect 2 or more streams and harmonize their
composition. Only one variable is controlled for these vessels. It is the level hold-up in the
vessel and the manipulated variable in that case is the mixer outgoing ow. Table 6.3 shows a
checklist of the vessels and a summary of the manipulated variables.
Table 6.3: Controlled and manipulated variables for the mixers
vessel Manipulated variables
V 202 ow of the stream (301)
V 303 ow of the stream (321)

6.3.3

Flash drum

As the liquid is ashed from a high pressure of the inlet stream <301> to the lower one of
the drum V301, vapor (stream <302>) is produced and reaches equilibrium with the remaining
liquid (streams <304> and <304>). Steam owing through a coil supplies the necessary heat
42

6.3. PRODUCT PURIFICATION AND CATALYST RECYCLE


for maintaining the desired temperature in the drum, despite any variations in the operating
conditions.
For the ash drum V301, the number of controlled variables is equal to 3 [37, page 465].
Table 6.4 presents the controlled variables and the manipulated variables.
Table 6.4: Controlled and manipulated variables for the ash drum
Controlled variables Controllers Manipulated variables
temperature
TC
heating uid ow
pressure
PC
vapor stream <302> ow
level in the drum
LC
liquid stream <304> ow

6.3.4

Stripping column

The vapor pressure in the stripper C301 is controlled by the required duty ow in the cooling
system E302 which precedes the reux drum. The temperature of the incoming stream <305>
is xed by manipulating the heat duty of E301.
The principle is the same as for a distillation column. However, there is no reboiler but one
additional inlet (butanol vapor stream <317>). The global consequence is that the number
of degrees of freedom is brought down to 5. The inlet ows and compositions are once again
disturbances. Yields 3 controlled variables. Table 6.5 presents the controlled and manipulated
variables. Remark has to be made that when one wants to control the stream <319> ow, one
has to do it with regard of the process control of the distillation column C303.
Table 6.5: Controlled and manipulated
Controlled variables
composition of the stream <308>
liquid hold-up in the stripping column
liquid hold-up in the reux drum V302

6.3.5

variables for
Controllers
CA
LC
LC

the stripping column


Manipulated variables
reux ow
stream <309> ow
stream <308> ow

Decanter

Decanter V304 is placed to split water from butanal (stream <310>) and to come out with
the stream <312> of pure water and the stream <311> containing butanal and water but
with a ratio more favorable to butanal. Decanters are essentially tanks which give sucient
residence time for the separation of the liquid into 2 phases. In a decanter, 3 bands can be
distinguished: clear heavy liquid, separating dispersed liquid and clear light liquid. The position
of the dispersion zone is the only variable that can be controlled [27, page 438]. Thus a LC is
needed and the manipulated variable is the heavy liquid ow (stream <312>).

6.3.6

Splitter

The role of the decanter V304 is to remove as much water as possible from the liquid stream
<311> to make easier the distillations afterwards. It entails thereby a need to recycle part of
the clear water stream <312> that has been removed in V304. This is done in the splitter S301.
The degree of freedom is 1. The controlled parameter is the composition of the stream <321>
and the manipulated is the ow of the stream <324>.
43

CPD 3281 - Basis of Design

6.3.7

Distillation column

Two distillation columns are recommended for the post-reaction section. One is to recover
butanal (column C302) and the other to recycle butanol by discharging it from butanoic acid
(column C303). The process control for these two distillation columns is similar to the one for
the pre-reaction section.
In these two distillation columns however, the need is to control the ow of the top streams
<314> and <317>. Thus table 6.6 presents the controlled and the manipulated variables for
the both distillation columns. The pressure in the columns is controlled in accordance with
the same rules and considerations as in the pre-reaction section. In other words, the pressure
in the columns is measured at their top by a PC and controlled by the duty ow in the heat
exchangers E305 and E307.
Table 6.6: Controlled and manipulated variables for the rst distillation column
Controlled variables
Controllers Manipulated variables
composition of the stream <314>/<317> CA
reux ow
stream <314>/<317> ow
FA
ow from the reboiler
liquid hold-up in the reux drum
LC
stream <314>/<317> ow
liquid hold-up at the base of the column
LC
stream <315>/<318> ow

44

7 | Mass and heat balances


The results of the check on mass and heat balances for the units and for the total process is
presented in this chapter. Next to this check the construction of the mass balance for the reactor
is claried. The reactor mass balance is used in paragraph 8.3.1 for the design of the reactor
itself.

7.1
7.1.1

Reactor balance set-up


Mass balance

Liquid phase
A block scheme of the reactor with a 100% ecient separation step for the product and byproducts is pictured in gure 7.1.
The mass balance for the reactor is set-up via the following steps:
1. A conversion for the feed (fresh 1-butanol with recycled 1-butanol) is stated.
2. With the stated conversion and the stated necessary feed (56.66 mole/s, plant capacity),
the resulting 1-butanol recycle ow with 100% separation eciency is calculated:
Fol;in =

Fol;0
X

(7.1)

3. With the amount of alcohol leaving the reactor in mole/s, a necessary amount of water is
calculated for dissolving the alcohol:
Fwat;out = Fol;out

1 Sol
Sol

Figure 7.1: Streams entering and leaving the reactor


45

(7.2)

CPD 3281 - Basis of Design


This amount of water includes both the recycle (with catalyst) and the excess water which
is produced with the reaction.
4. The molar ow rate of the produced butanal (Fal;out ) from the reactor is with an downstream separation eciency of 100% also 56.66 mole/s (1:1 reaction). This also accounts
for the excess water which is produced in the reaction (Fwat;excess).
5. The ow rate of the water recycle is calculated from:
Fwat;recycle = Fwat;out Fwat;excess

(7.3)

6. The concentration of catalyst in the recycle is taken maximal, in this way, it will also be
maximal in the reactor. From this concentration and the amount of water is the recycle,
the amount of catalyst (Fcat;recycle , mole/s) may be calculated which is fed to the reactor.
Now, together with the amount of water leaving the reactor, the catalyst concentration
in the water leaving the reactor, and thus in the reactor (Scat;reac) can be calculated:
Fcat;recycle = water;recycle Scat;max
[Pd]reac =

Fcat;recycle
wat;out

(7.4)
(7.5)

7. With the now known catalyst and alcohol concentration ([OH]reac, equal to the stated
Sol ) , a rate of reaction per unit volume (rV ) can be calculated, according to paragraph
4.4. From this, the necessary reaction volume is calculated:
Vreaction =

Fol;in Fol;out
rV

(7.6)

Gas phase
The calculation steps give above are focused on the aqeuous liquid phase. The critical point in
the mass balance for the gas phase is the supply of oxygen to the water, taking into account
the mass transfer from the gaseous phase to the liquid. Pure oxygen is supplied to the reactor.
The required oxygen for the reaction is half of the molar amount of produced butanal, or 28.33
mole/s (FO2;0). The amount of oxygen in the recycle should be minimized, because the larger
the recycle the larger the costs for the recycle equipment.
The mass transfer of oxygen into the liquid phase and the necessary oxygen pressure is
estimated using:
O2 = kLa (CL CL )
(7.7)

For a certain consumption rate of alcohol per unit volume, a transfer of oxygen from the gas
phase into the liquid phase per unit volume of catalyst solution is necessary. For starters, the
overall reaction is assumed to be mass transfer limited in oxygen, thus CL is zero. It is stated
as a design decision:
The reactor is operated at the limit of mass transfer limitation of oxygen: CL = 0
The kLa value depends on a, the interphase surface per unit volume (m2=m3), and kL the
rate. The higher the kL a the higher the transfer, the lower the pressure needed. However, to
induce a high kLa will cost energy. A detailed calculation of the kLa in the reactor is given
in appendix M. The actual ow of oxygen depends on the reactor operation. The oxygen feed
ow which is used is equal to 56 mol/s. The calculation of this number is claried in paragraph
8.3.6.
46

7.2. BALANCE FOR TOTAL STREAMS

7.1.2

Heat balance

Heat is produced in the reaction. Also, heat eects occurs due to mixing in the reactor. The
heat duty of the reactor is taken from ASPEN. With this given heat duty, a cooling system is
designed and presented in paragraph 8.3.1 and appendix L.

7.2
7.2.1

Balance for total streams


Individual units

The mass and heat balance check is performed on the units given in appendix H. The mass
balance check on the units is done by comparing the in and out going streams for the units on
a total mass and heat basis. The data is taken from the stream summary, already presented
in appendix H. The results of the check are presented in appendix (Heat & Mass Balance for
Streams Total). All the units are consistent in terms of their mass balance.

7.2.2

Total plant

The total plant is checked by comparing the streams in terms of total mass and heat crossing
the battery limits. This then, also includes the utility streams. The results of the check are
given in appendix J. From the data it is clear that the plant is in mass balance, and that moles
are produced. In total, heat is produced in the plant.

7.3

Stream component balance

The check on mass balance consistency for the components is only done over the total plant and
not per unit. The result is given in appendix J, gure J.3. From the data it can be concluded
that:
Butanal is not produced on a 1:1 basis to the fed 1-butanol (57.29 mol/s IN against 55.47
mol OUT).
The whole process is not in mass balance in terms of water (56.03 mol/s is produced
against 55.47 mol/s butanal, which should be 1:1).
Not all of the O2 is consumed, some leaves the process dissolved in the liquid products.
Some 2-butanol is consumed in the process (in R201).
The reason why the process is not entirely in balance in terms of water is explained in
paragraph 7.4.

7.4

Total plant imbalance

The mass imbalance as observed in paragraph 7.3 is due to the use of an almost, but not
entirely converging ASPEN owsheet. The total process is modelled is ASPEN and two of
three recycle loops have successfully been connected. The loops which have been connected
are the (1) oxygen recycle, stream <212>, as feed for R201, and (2) the pure alcohol recycle,
stream <317> as vapor feed for C301. Recycle loop number (3), connecting stream <322> and
<R322>, could not be successfully be connected. The dierence in ASPEN between <322>
and <R322> however is very small. This dierence probably causes the dierence observed in
47

CPD 3281 - Basis of Design


paragraph 7.3. More on the use of ASPEN for the process model can be found in paragraph
8.1.

7.5

Heat pinch

A heat pinch study is not completely performed due to time pressure. The heat requirements
and heat releases of all heat exchangers, reboilers and condensers are calculated. Table 7.1
shows the cooling requirements of the equipment. Cooling of pumps is not taken into account.
Table 7.2 shows the heating requirements of the process. Not all released heat can be used

Equipment
K201
E102
E201
E202
E302
E303
E304
E305
E307
R201
Total

Table 7.1: Cooling requirements


Capacity [MW] Tin [C] Tout [C]
0.33
215.3
4.25
105.1
102.5
1.25
131.3
40.0
0.39
130.0
40.0
2.21
98.5
88.2
7.35
86.5
52.5
1.30
81.0
40.0
4.39
76.0
53.5
0.35
124.6
124.5
6.37
120.0
28.17

Equipment
E101
E103
E301
E306
E308
Total

Type
Compressor
Condenser
Cooler
Partial Condenser
Condenser
Condenser
Cooler
Condenser
Condenser
Reactor

Table 7.2: Heating requirements


Capacity [MW] Tin [C] Tout [C]
0.69
40.0
90.0
4.84
129.4
129.9
5.75
83.5
99.0
4.67
124.0
125.2
5.75
83.5
99.0
16.94

Type
Heater
Reboiler
Heater
Reboiler
Reboiler

for heating purposes because the quality of some streams is too low. The heat from E102 can
be used for E101. Heat from E201, E202 and R201 can be used to heat E301 and E308. The
temperature requirements of E103 and E306 are too high to be heated by other process streams
thus about 10MW is necessary for heating. Compressor K201 releases heat at high temperature,
this can be used for many heating purposes. Cooling water can be used to get rid of low value
heat. Excess low pressure steam can be used to generate electricity or to perform work. A pinch
analysis is necessary to give better insight in heat integration.

48

8 | Process and equipment design


8.1

Process simulation in ASPEN

As mentioned in chapter 7, ASPEN has been used to simulate the process. The process blocks
have been put together in a chronological order. At rst, the three recycle loops in the sheet
(oxygen <212>, liquid recycle <322> and the alcohol recycle <317>) were not connected. After
putting in all the blocks and having the reactor work at the right composition the recycle loops
were closed one by one. First the oxygen and then the alcohol. Only while closing the liquid
recycle the sheet didnt converge completely. This has been tried several times, but regrettably
without complete success. Nevertheless the design project had to be continued with the almost
converging sheet because of time pressure. A lot of project subjects depended on the completion
of the sheet, and therefore it had been decided to continue with the not completely converging
ASPEN sheet.

8.2
8.2.1

Pre-reaction separation
Unit C101, alcohol distillation

Before fed to the reactor, 1-butanol should be puried by removing 2-butanol which is a competitive reactant. Distillation will be used as separation technique. At atmospheric pressure,
1-butanol and 2-butanol forms a system with a relative volatility varying from 1.83 to 1.98.
Figure 8.1 shows the Txy diagram at 1.013 bar.
120

T-xy for N-BUT-01/2-BUT-01


T-x 1.0133 bar

100

Temperature C
105
110
115

T-y 1.0133 bar

0.2

0.4
0.6
Liquid/Vapor Molefrac 2-BUT-01

0.8

Figure 8.1: Txy diagram of 2-butanol/1-butanol at 1.013 bar


49

CPD 3281 - Basis of Design

Figure 8.2: Two dierent types of column packing


Target purities
The target composition of the 1-butanol stream is set at 99.9% pure. The target composition
of the top stream is set to 80% 2-butanol. The loss of 1-butanol via this stream is not that big
because the incoming stream contains only 5% 2-butanol. Via the top stream, there is a loss of
0.76 mol/s of 1-butanol.
Trayed columns
Trayed columns contain trays where liquid is contacted with vapor. More volatile components
will be transferred from the liquid to the vapor and heavier components to the liquid. A cascade
of plates enables continuous separation of a mixture.
Packed columns
Instead of using plates for contacting liquid and vapor, packing can be used in order to facilitate
this. There are generally 2 types of packings, random and structured. Random or dumped
packing consist of pieces of metal, ceramic or platic of certain shape. Figure 8.2 (a) shows a
typical random packing. The liquid ows over the surface and is constantly contacted with the
vapor. Structured packings consist of layers of wire mesh packed in the column. See gure 8.2
(b) for an example of a structured packing. The advantage of structured over random packing
is the higher eciency per unit volume of packing. Besides that, the pressure drop is much
lower. The structured packing is chosen to make a design with. The program SULPAK 2.1 is
used for the calculations. This program is issued by Sulzer Chemtech Ltd.
Cost estimation
Now all major dimensions of the trayed and the packed column are known, a shortcut cost
estimation can be done. The price of equipment is found in the DACE book[22]. The height
and the width of the columns is known, the number of trays is known. The price of the packing
is not listed in DACE, but after inquiries at the API laboratory at the TUD, Dr. Oluijc came
up with a price indication. The results of this cost estimation is shown in tables 8.1 and 8.2.
The auxillaries are not taken into account because these are almost the same for both cases.
This shortcut calculation shows that the packed column needs less investment than the
trayed column. Even at the high end of the price range of the packing, the investment is lower.
Packed columns are often heavier, resulting in heavier foundation of the column but in this case,
50

8.2. PRE-REACTION SEPARATION

Table 8.1: Cost estimation for a trayed 1-butanol/2-butanol distillation column


Diameter
2.2 m
Height
23.5 m
N
47 Wall thickness
9 mm
Area
3.8 m2
Volume
89.3 m3
Mass
32300 kg
price shell
181,281 $
1 tray
922 $
all trays
43,346 $
total cost
224,627 $
Table 8.2: Cost estimation for a packed 1-butanol/2-butanol distillation column
Diameter
1.9 m
Height
10 m
Wall thickness
7 mm
Area
2.84 m2
Volume
28.4 m3
Mass
9600 kg
Price shell
65,424 $
per m3 packing (min)
3,000 $
per m3 packing (max)
5,000 $
total packing (min)
85,058 $
total packing (max)
141,764 $
total cost (min)
150,483 $
total cost (max)
207,189 $
the weight will probable equal out because the trayed column is 2 times taller and somewhat
wider.

8.2.2

Reux drums and collection vessels

[27, chapter 13] provides a vessel calculation guideline. 4 reux vessels (V101, V302, V305 and
V306) and 2 collection vessels (V202 and V303) need to be designed. All the vessels except V202
are subject to a pressure ranging between 1 and 1.3 bar whereas the vessel V202 is working at
around 20 bar. A residence time of 5 minutes is used as a basis of calculation. It provides the
volume of liquid (Vliquid [m3]), which is increased to allow the level process control and leads
to the vessel volume (Vvessel [m3]). From this volume, diameter (D (m)) and length (L [m]) of
the vessel are calculated. The vessels are assumed to be cylindrical, horizontal, and made of
stainless steel. Table 8.3 presents the results.

8.2.3

Pumps and compressors

The design puts at stake 13 pumps and 2 compressors, among which one is a multi-stage
compressor. Only 2 pumps (P-101 and P-305) and the 6-stage centrifugal compressor K-201
were designed according to [27].
51

CPD 3281 - Basis of Design

Vessel
V101
V302
V305
V306
V202
V303

P [bar]
1.013
1.013
1.3
1.3
20
1

Table 8.3: Vessel geometric data


Vliquid [m3 ] Vvessel [m 3] L [m]
2.8
3.2
4
0.23
0.6
1.5
2.4
3.4
3.
0.65
1
2
0.075
0.13
1
2.9
3.1
4

D [m]
1
0.7
1.2
0.8
0.4
1

e [mm]
5
3.5
8
5
45
5

The estimated total head and given ow rate lead to choose single-stage, horizontal, overhung, centrifugal 3500 rpm pumps. Calculations of specic speeds (Ns [rpm]) gives the required
pump impeller type. Calculations of the power done by the pump (W[kW]), neglecting the
pressure drop due to friction (miscellaneous losses and equipment losses) for a rst design yields
the power at shaft (Ws [kW]). The eciency of the pump () is determined from [27, page
206]. The Net Positive Suction Head (NPSH) should also be calculated to be sure of avoiding
cavitation in the pumps but the lack of data makes it impossible. Table 8.4 summarizes the
results.
Table 8.4: Pump characteristics
P-101 P-305
Ns[rpm]
520
635
pump impellers radial radial
W[kW]
11.2
18.7

0.7
0.7
Ws[kW]
16.6
25.4
The interstage pressures of the compressor are selected to give equal work in each stage.
The total work done (Wd ) is thus the sum of the work for each stage. The eciency of the
compressor of 0.65 for the given ow leads to the required power (Wr ). Table 8.5 presents a
summary of the results.
Table 8.5: Compressor characteristics
K-201
1
Wd /stage [kJ : kg ] 41.6
Wd [kJ : kg 1 ]
249.8
Wd [kW]
227.1
Wr [kW]
349.5

8.3
8.3.1

Conversion section
Reactor optimization and design

The reactor design depends on numerous parameters. Reactor type (hydrodynamic ow regime),
temperature, composition and pressure are the most important here. These parameters all
inuence each other and an optimal combination needs to be found. The parameters and their
52

8.3. CONVERSION SECTION


inuence on the equipment design will be discussed in the following paragraphs (8.3.2 until
8.3.5). Paragraph 8.3.6 concludes with the design in real, equipment space.

8.3.2

Hydrodynamic ow regime

A rst direction for reactor type and ow regime was given in paragraph 5.2.3. A short summary:
The idea is to work within a CSTR type of operation in order to assure a complete mixing
and have a constant alcohol concentration in the reactor, not too low to avoid a reaction
rate drop and not too high to avoid the formation of a second phase.
From the Krishna and Sie method analysis (paragraph 5.2.1), it was pointed out that a
homogeneous bubbly ow regime is necessary since the reaction takes place slowly and in
the water phase. A homogeneous ow regime results in a high liquid fraction, with a high
a as possible.
From this the decision is made:
A bubble column or a stirred reactor working with homogeneous bubble ow will be designed
Whether a stirrer is necessary depends on a and the pressure needed. This is further
explained in paragraph 8.3.5.

8.3.3

Temperature

The inuence of reactor temperature is given in table 8.6.


Table 8.6: Inuence of temperature in the reactor
parameters
T increase
remarks
alcohol solubility
inmiscibility gets less
the presence of the aldehyde decreases the alcohol
solubility
reaction rate, k value
k value increases, overall re- see paragraph 4.4.5 for the
action rate increases
calculation of k
oxygen solubility
the solubility decreases
the presence of the alcohol and aldehyde also inuence the solubility, the
larger the T increase the
higher P needed for mass
transfer
oxygen transfer rate, kL the mass transfer in in- inuence in minimal, calcuvalue
creased slightly
lation is in appendix M
The increase of temperature (higher than experimental conditions[3]) has the obvious advantage of decreasing the reactor volume. The eect of a higher alcohol solubility will increase
the overall reaction rate (paragraph 4.4). A higher k value results in a higher rV . A higher rV
means a smaller reaction mixture volume, and a smaller reactor. The trade o which is made
here is against pressure. For a higher mass transfer rate of oxygen per unit volume will be
needed with an equal conversion of alcohol per a smaller reaction volume.
53

CPD 3281 - Basis of Design

Figure 8.3: Liquid volume versus conversion at given temperatures.


The mass balance is solved for the dierent temperatures with dierent conversions. The
resulting reactor volume for each temperature at the dierent conversions are plotted in gure
8.3.
Figure 8.3 shows clearly that when temperature is increased the resulting reaction volume
is less. However, the necessary pressure for oxygen transfer is not yet taken into account.
Obviously, a small volume for the same butanal production rate requires higher mass transfer
rates, and thus higher oxygen pressures.

8.3.4

Reactor composition

The reactor composition can be chosen in terms of water, 1-butanol and butanal mole fraction.
The inuence of choosing a composition is pointed out in the following step.
1. First, the dierent ternary diagrams for the components in the reactor at various temperatures are plotted. The diagrams for 40 C, 100 C, 120C, 130 C and 150 C are given in
appendix K. From these diagram, possible operating areas could be identied. The objective is complete miscibility (no organic phase) with the phase present to be an aqueous
one. The mixture should be in the top half of the triangle (close to total water), but not
in the phase separation area (the tie lines).
2. For each temperature, dierent conversions are stated (from 0 to 1 ), and the mass balance
for the reactor is solved(paragraph 7.1.1). The mass balance can be solved in such a way
that for each conversion the alcohol mole fraction is stated, for example 0.2. In this way, a
line can be drawn of operating regions at the dierent temperatures for a certain alcohol
mole fraction on the reactor. An example of this can be seen in gure 8.4.1
3. Some constraints are opposed on the reactor composition:
(a) First the denition of a lower limit for the mole fraction of water in the reactor.
The lower limit depends on the solubility of the catalyst (the catalyst is a water soluble
catalyst). It is assumed at:
1

Pressure does not have a signicant inuence on LL equilibria.

54

8.3. CONVERSION SECTION

Figure 8.4: The ternary diagram of the reactor composition at 30 bar and 130C :
Minimum mole fraction water: xwater;min 0.5
(b) The second step now is to dene a maximum mole fraction for the aldehyde. This
fraction must not be too high, otherwise over oxidation will occur. The maximum molar
fraction of aldehyde is assumed at:
Maximum mole fraction aldehyde: xaldehyde;max 0.2
(c) Now, the immiscibility area together with the constraints mentioned in a and b constricts the operating region to the part of the diagram which is given in gray in gure
8.4. The extent of this area depends on the temperature. The higher the temperature
the smaller the immiscibility area is. Also, at higher temperatures, the catalyst is more
soluble in any phase.
The choice of where to operate within the constraints (the grey area in gure 8.4) depends
on the conversion necessary and on the resulting recycle of water with catalyst, on the resulting
reactor volume necessary and on the pressure needed to dissolve enough oxygen. In terms of
composition:
There is an optimum in alcohol concentration. Increasing the alcohol fraction will speed
up the reaction (paragraph 4.4). A too high alcohol fraction however, will decrease the
catalyst concentration in the reactor. This is a result of the catalyst recycle, it is explained
in paragraph 7.1.1. For all dierent temperatures, this optimum lies at the minimum
alcohol fraction in the diagram.
One wants to be as close to the aldehyde as possible because it is the product.
One want as little water as possible because a high water content has negative consequences
in the separation section after the reactor.
55

CPD 3281 - Basis of Design


Concluding on the reactor composition:
The alcohol mole fraction is xed, depending on the dierent temperatures.
The aldehyde mole fraction is always approximately 0.20.
The water fraction is now also xed, as a result of the xed alcohol and aldehyde concentration.
Table 8.7 gives the compositions for the temperature range studied.
Table 8.7: Reactor composition and temperature
T [C] x1bu tan ol xbu tan al xwater
100
0.35
0.152
0.50
110
0.30
0.20
0.50
120
0.25
0.20
0.55
130
0.20
0.20
0.60
140
0.18
0.20
0.62
150
0.15
0.20
0.65

8.3.5

Pressure

The reactor pressure is calculated. It is not chosen, but it results from dierent parameters.
These are given in table 8.8.
Table 8.8: Parameters determining reactor pressure
parameters
increase of parameter
remarks
reaction rate per unit volume, pressure will be higher
the more oxygen is needed per
rV
unit volume, the more has te
be transferred per unit volume
oxygen transfer rate, kL
pressure will be lower
if the rate of oxygen transfer is
higher, the necessary solubility
( pressure) can be lower
interfacial area, a
pressure will be lower
a high interfacial area will decrease the need for a high oxygen solubility
The inuences given in table 8.8 can directly be derived from equation which assumes
operation on the limit of oxygen mass transfer limitation(see also paragraph 7.1.1):
Q = kLaCL

(8.1)

The maximum oxygen solubility (CL ) depends on the oxygen pressure. For the dierent
temperatures and mixture compositions, dierent maximum solubilities are required in order to
fulll the condition of operation on the limit if oxygen mass transfer limitation.
The kL and a value for the reactor are calculated in appendix M. It must be noted that
initially, the a value is used for a normal, unstirred bubble column. For the dierent mixtures at
the dierent temperatures the necessary oxygen pressure can now be calculated. The rst step
herein is determining the necessary oxygen solubility at the rV with the calculated kLa. Then
56

8.3. CONVERSION SECTION

Table 8.9: Reactor composition, temperature and necessary pressure for a bubble column
T
x1butanol xbutanal xwater CL
Hmixture
PO2
Vreactor

[ C] [-]
[-]
[-]
[mol/l]
[bar]
[bar] [m3]
100
0.35
0.15
0.50 2.85E-02 3.63E+04
33
141
110
0.30
0.20
0.50 3.62E-02 3.57E+04
42
101
120
0.25
0.20
0.55 5.62E-02 3.79E+04
65
59
130
0.20
0.20
0.60 8.34E-02 3.99E+04
96
37
140
0.18
0.20
0.62 1.20E-01 3.91E+04
134
24
150
0.15
0.20
0.65 1.64E-01 3.86E+04
178
16
using the theory given in appendix M a corresponding necessary pressure can be calculated.
The results are given in table 8.9.
From the table it can be seen that at low temperatures a combination of relative low
pressure with a high reactor volume is needed. At higher temperatures, it is the other way
around.
The pressure needed is rather high. A way to improve this is stirring the reactor, thus
creating a higher a and decreasing the necessary CL and therefore the necessary P. The reactor
type now changes from a unstirred bubble column to a mechanically stirred unit:
A stirred reactor with homogeneous bubble regime will be designed

8.3.6

Reactor dimensions

From the previous paragraph it is clear that a stirred unit will be designed. A turbine as stirrer
is recommended by [14, page 306][19, page 556] for our gas/liquid system.
A 6 at blade turbine stirrer is used for the design
The volume, pressure and power requirements of this unit will be determined for the 6
mixture possibilities (dened in table 8.7) given above. Then, from these six options, the best
one is chosen in terms of volume, pressure and power necessary for stirring minimization. A
step wise method is given below:
1. First, a maximum volume for the vessel is dened. From this, the number of reactors can
be calculated from the total liquid volume necessary and a estimated gas fraction (gas
fraction will be checked in step (6)).
2. Second, the tank height (Hv ) over tank diameter (Tv ) ratio is dened. This is ideally 2[14,
page 305]. With the volume from (1) and the ratio the Hv and Tv can be calculated.
3. The impeller is dimensioned (diameter (Di ), number of impellers, height of impeller
blade(w)) using the method given in appendix Q.
4. The minimum number of revolutions is determined with the correlation given in [19, page
266].
5. The actual number of revolution depends on the tip speed which is used and is still
adjustable. The minimum value for the tip speed is taken from [19, page 566], the upper
value is only limited by the power consumption of the stirrer.
57

CPD 3281 - Basis of Design


6. The gas fraction present is calculated from the correlation given in [19, page 266]. This
fraction is checked with the one used in step (1) and adjusted accordingly (iteration loop).
7. From the impeller dimensions and a stated tip speed the Reynolds number for an unaerated
reactor can be determined:
NR Di2
Re =
(8.2)
mixture
8. With the Reynolds number, the Power number is determined using the correlation given
in [14, page 305].
9. The Power number is used to determine the power input (per impeller present) by stirring:
Po =

PL
NR3 D5i

(8.3)

10. The actual power input for an aerated reactor is less than for a non aerated reactor. A
fraction of 0.4[19, page 266] is taken.
11. The power input of all impellers present per reactor is summarized.
12. The power input by bubbling[19, page 258] is calculated with:
PG
= VSG g
VL

(8.4)

13. With the total power input and the liquid volume known (stirring and bubbling) the a is
determined using the correlation given in [19, page 266].
Table 8.10 shows the results for the key values which are stirring independent calculated in
steps 1 till 13.
Table 8.10: Number and size of the reactor for dierent temperatures
mixture T
Vnecessary nreactors Vper reactor

[ C] [m3]
[-]
[m 3]
1 100
151
4
38
2 110
108
3
36
3 120
63
2
32
4 130
40
1
40
5 140
25
1
25
6 150
17
1
17
From the table it can be seen that only for the higher temperatures a single reactor can be
used. Because higher temperatures will result in higher pressures, the minimal temperature is
chosen for which a single reactor operation is possible:
The reactor with temperature of 130 C will be designed
An operating virtual velocity needs to be chosen. In the design, 0.04 m/s will given a very
high excess of oxygen, 174 mol/s (against 29 mol/s needed). With a virtual gas velocity of 0.01,
the feed ow is 56 mol/s (at the given pressure and temperature).
58

8.3. CONVERSION SECTION

Figure 8.5:

56 mol/s is chosen as oxygen feed ow

In step 5 a stirrer speed needs to be determined. Figure 8.5 shows the variation of power
input and pressure for the mixture at 130 C for variation of the tip speed. As can be seen in
gure 8.5, using a higher tip speed will decrease the necessary power in the unit (calculated
with the new a), but will also increase the power consumption of the unit. The trade o here
is between power consumption of the stirrer and the pressure needed in the reactor.
The pressure in the reactor will cost energy: (1) for pressurizing the uids and (2) for
pressurizing the oxygen supply. The best way to solve the trade o is to calculate variable
and xed cost for all possibilities. Here it is sucient to only select a reasonable pressure by
intuition.

The stirred unit will be designed at 20 bar

The nal result for the stirred unit at 130 C and 20 bar are presented in table 8.11.
Note that for the head space 1 m is taken.
An artist impression of the reactor is presented in gure 8.6.
59

CPD 3281 - Basis of Design

property
liquid volume

symbol
VL

gas volume

VG

gas fraction

"G

total reactor volume


reactor height

reactor diameter
temperature

Tv
T

pressure

Th

Table 8.11: Reactor dimensions


unit quantity property
[m3]
33 impeller diameter
3
[m ]
7 impeller blade
width
[-]
0.174 space between
impellers
[m3]
40 height of impeller
[m]
6.87 number of impellers
[m]
2.94 rotation speed
[C]
130 power input by
stirring
[bar]
20 power input by
bubbling

symbol
D

unit
[m]

quantity
0.882

Di

[m]

0.220

NR

[m]

2.05

[m]

0.176

nimpeller

[-]

NR
Pstirring

[1/s]
[W]

2.04
5.25E+04

Pbubble

[W]

9.39E+03

Figure 8.6: Artist impression of reactor design

8.3.7

Heat removal

In the reactor heat is produced by dierent sub processes. Heat is produced as mixing eect
and heat of reaction. Due to the diculties with manual calculation of these properties in
multicomponent systems ASPEN was used to calculate the total heat eect. In the reactor at
60

8.3. CONVERSION SECTION


130 C and 21 bar 10.6 MJ/s is generated. Several options exist to remove energy in the form
of heat in our process by:
Feeding cold feed streams
Installing a cooling jacket
Installing a coil
Combination of options above
In preliminary design the temperature of streams entering the reactor was not adjusted. As
a rst option cooling of the feed streams was introduced. Two heat exchangers were installed
to cool feed streams. Feed stream temperatures were lowered to create extra cooling capacity.
Temperatures are presented in table 8.12.
Table 8.12: Feed stream temperature after heat exchange
Stream
Temperature
[K]
reactant, <204>
313
recycle, <214>
313
oxygen, <212>
319
Due to this cooling eect the excess energy was lowered to 6.37 MW. To remove all the heat
a jacket and two coils were designed. Details on design calculations are presented in appendix
L. For reactor lay-out see gure 8.6. Details on cooling equipment are shown in table 8.3.7.
The jacket is ba-ed to increase ow and heat transfer.
The overall heat transport by coils and jacket is calculated by equation 8.5.
Q = (Ujacket Ajacket + Ucoilpack1 Acoilpack1 + Ucoilpack2Acoilpack2) log T
Table 8.13: Heat transfer properties
Value
Jacket
U
361 W/m2K
A
56.5 m 2
Coil 1
U
1.36E3 W/m2K
D tube
5E-2 m
A
51.3 m 2
Coil 2
U
1.36E3 W/m2K
D tube
5E-2 m
A
54.2 m 2
logT
42 K
Overall
Q
6.64 MW

61

(8.5)

CPD 3281 - Basis of Design


To be able to use released energy low pressure steam at a pressure of 2 bar will be generated.
The condensation energy can be used by heat integration with other process streams. This low
pressure steam can be integrated with the Etriol reaction in a latter stage, or can be integrated
with butanol production to sterilize broth.
The steam fraction which will be produced will be 0:8 mcooling water . When water will be
present, dissolved salts can not precipitate on heat exchange area. This system is not modelled
because of lengthily calculations and the limited time. No detailed design of the heat exchange
system is presented due to before mentioned reason. Equation 8.6 was derived to obtain the
mass ow of cooling water.

m =

Q
(Cpaverage (Tcooling water;out Tcooling water;in ) + xHvap)

(8.6)

Table 8.14: Cooling water properties


Property
Value
Cpwater (average)
4200 J/kgK
Tcooling water;in
293 K
Tcooling water;out
393 K
Hvap(@2bar; 303K) 2202.2 kJ/kg
m
3.04 kg/s
Sea water can be used as a cooling medium. If necessary this water can be desalinated.

8.3.8

Unit V201, vapor / liquid separation

The design reactor has a overhead stream from which the oxygen recycle is prepared. The
overhead apor is rst partially condensed in E202. Then, the partial condensed vapor from
R201 is separated in a liquid and a vapor stream in V201. The design of this unit is done
according to [27, page 458-63]. The stream to split is a vapor containing few liquid. Thus,
a long liquid hold-up time is not required and a vertical separator is designed. The settling
velocity of the liquid droplets is calculated and multiply with a factor 0.15 due to the fact that
no demister pad will be specied since the separation of the condensate is not attended to be
critical. This leads to the diameter of the separator. The space between the gas inlet and the
liquid level has to be half of the diameter. The height of the vessel outlet above the gas inlet
should be ecient to allow for disengagement of the liquid drops. A height equal to the diameter
of the vessel should be used. A minimum required liquid hold-up of 10 minutes brings to the
required liquid depth. It is made a bit bigger to allow the positioning of the level controller in
the vessel. The calculated dimensions are D V = 1.25 m, HV = 2.2 m, VV = 2.7 m3 . Figure 8.7
summarizes the results.
62

8.4. PRODUCT PURIFICATION AND CATALYST RECOVERY

Vapor outlet

1.25 m

1.25 m

Feed
0.625 m
0.3 m

Liquid outlet

Figure 8.7: Gas-liquid separator V201 sketch

8.4
8.4.1

Product purication and catalyst recovery


Unit V304, decanter

The decanter design is based on [27, pages 438-43]. The organic phase on the one hand is
supposed to be the light liquid and the continuous phase whereas on the other hand the water
phase is the heavy liquid and the dispersed phase. The composition, ow and properties as
density and viscosity are taken from the ASPEN sheet.
Assumed settling droplet size (dd ) of 150 m leads to a settling velocity of the dispersed
phase droplets Ud = 3.63E-3 m =s and an interface area Ai = 1:9m2 . Noticed has to be that
the size of the continuous phase droplets which could be entrained with the dispersed phase has
to be checked and not exceed 150 m.
A choice has to be made between designing a vertical or a horizontal decanter. This has
to be done with regards of the continuous ow rate, which is small enough to match a vertical
decanter. The dimensions are calculated: decanter diameter Dd = 1:6 m, decanter height Hd
= 4:7 m and dispersion band depth dB = 0:47 m : The residence time of the droplets in the
dispersion band is 2 min where 2 to 5 min are recommended.
The velocity of the dispersed phase as well as the droplet size are recalculated. Droplet
diameter dd = 71 m : This is satisfactory since the assumed droplet size dd = 150 m. The
pipping arrangement calculation leads to a pipe diameter Pd of 13 cm and to gure 8.8.
63

CPD 3281 - Basis of Design

1.6 m

Light liquid
Heavy liquid
Feed
4m
2.3 m

1.2 m

Figure 8.8: Decanter V304 sketch

8.4.2

Unit C301, butanal stripper

The butanal is separated from the catalyst / alcohol recycle in C301, the butanal stripper.
ASPEN is used to model and optimize the stripper. The results are presented below.
DSTWU
The pre-heated feed from V301, <305>, enters the column on stage 2 (top of the column).
The hot 1-butanol vapor, <317>, is fed at the bottom. There is no reboiler, there is a partial
condenser. The light key is butanal, the heavy key the water (with catalyst complex). An
estimated number of trays of 30 and a reux ratio of 0.5 is taken from DSTWU and used in the
RadFrac model.
RadFrac model
With the RadFrac model and the tray sizing utility in ASPEN the necessary data is acquired
(K values, viscosities).
Column eciency
The columns eciency is calculated with the OConnell correlation [27, page 549]:
Eo = 51 32:5 log(a a )

(8.7)

The relative volatility is dened as


=

KLK
KHK

(8.8)

and the average is taken over the whole column. This yields an overall eciency of 53 %. The
actual number of trays is thus (30 - 1)/0.53 = 55.
64

8.4. PRODUCT PURIFICATION AND CATALYST RECOVERY


Column geometry
The tray sizing utility in ASPEN is used to calculate the column diameter. The diameter is
0.83 m. The column height is 55 * 0.5 m = 27 m. The pressure drop is 0.00612 bar per stage,
the column pressure drop is 0.18 bar.

8.4.3

Unit C302, butanal distillation

DSTWU model
ASPEN is used to model the column. First, a DSTWU model is used for shortcut design. Light
key is butanal and the recovery is set at 0.999, heavy key is 1-butanol and the recovery for this
component in the distillate stream is 1e-05. Pressure is set at 1.3 bar so the temperature of
the top stream is above 50C but the bottom temperature as low as possible. The calculation
is ASPEN yields a minimum reux ratio of 0.189 and a minimum number of stages of 13.55.
ASPEN also provides a list of theoretical stages with corresponding reux ratios. The optimum
number of stages is chosen where N*(R+1) has a minimum. N = 26 and R = 0.379. NF = 11.
Distillate to feed ratio is 0.839.
RadFrac model
The numbers found with the DSTWU model were used as a starting point for the RadFrac
model. Trial and error optimization yields N=30 and R=0.45. A design specication was set
on the recovery of butanal in the distillate stream, with the distillate rate as variable. Recovery
is 0.9999 and the molar distillate rate is 83.58 mol/s. The DSTWU model is did the prediction
not correct. This can be caused by the binary azeotropes formed with water and every organic
component.
Column eciency
The columns eciency is calculated with equation 8.7. The relative volatility is dened in 8.8.
Values are taken from ASPEN. Viscosity of the liquid at every stage is also taken from ASPEN.
This yields an overall eciency of 44.68%. The actual number of trays is thus (30 - 1)/0.4468
= 65.
Column geometry
ASPEN calculated the column diameter. The biggest diameter is 2.0 m at theoretical stage 19
(from top). The column height is 65 * 0.5 m = 32.5 m. The pressure drop is 0.0047 bar per
stage, the column pressure drop is 0.31 bar.

8.4.4

Unit C303, butanol recycle purication

DSTWU model
Aspen is used to model the column. First, a DSTWU model is used for shortcut design. Light
key is 1-butanol and the recovery is set at 0.9999999, heavy key is butanoic acid and the recovery
for this component in the distillate stream is 1e-08. Pressure is set at 1.3 bar so the temperature
of the top stream is above 50 C but the bottom temperature as low as possible. The calculation
is Aspen yields a minimum reux ratio of 0.307 and a minimum number of stages of 23.14.
Aspen also provides a list of theoretical stages with corresponding reux ratios. The optimum
65

CPD 3281 - Basis of Design


number of stages is chosen where N*(R+1) has a minimum. N = 43 and R = 0.542. NF = 23.
Distillate to feed ratio is 0.958.
RadFrac model
The numbers found with the DSTWU model were used as a starting point for the RadFrac
model. The number of trays is still 43 but the reux ratio is increased slightly to 0.5445. The
distillate to feed ratio 0.95439. The prediction of the DSTWU model was very good. This can
be explained by the zeotropic nature of the system.
Column eciency
The columns eciency is calculated with equation 8.7. The relative volatility is dened in 8.8.
Values are taken from Aspen. Viscosity of the liquid at every stage is also taken from Aspen.
This yields an overall eciency of 44.22%. The actual number of trays is thus (43 - 1)/0.4422
= 95.
Column geometry
Aspen calculated the column diameter. The biggest diameter is 0.81 m at theoretical stage 22
(from top). The column height is 95 * 0.5 m = 47.5 m. The pressure drop is 0.0062 bar per
stage, the column pressure drop is 0.59 bar.

66

9 | Wastes
This chapter deals only with direct wastes and does not regard indirect wastes. As the process
used is a green catalytic oxidation using water as solvent and oxygen as oxidant, only few waste
is generated.

9.1

Direct waste summary

The direct waste streams are summarized in table 9.1. These streams are given in the owsheet.
Direct waste streams which are not given in the owsheet but which are probably occurring are
given in table 9.2. The streams will be discussed in the accompanying paragraph.

stream nr.
name
component
1-butanol
2-butanol
water
butanal
butanone
oxygen
butanoic acid
eect

Table 9.1: Waste stream summary, 1


<319>
<313>
excess water
O2 recycle bleed
m%
kg/day m%
1.43
664
0.02
0.06
28
0.00
93.15
43351
0.20
5.08
2362
2.33
0.01
3
0.00
0.09
41
97.45
0.19
90
0.00
Liquid stream to be
discharged in closed
sewer system and
treated o site.

Vapor stream containing some hydrocarbons


which need to be incinerated.

<320>
Liquid recycle bleed
m%
46.34
0.92
25.92
4.83
0.01
0.01
21.97
Liquid stream containing catalyst. Needs
catalyst
recovery.
Could be used for
continuous
catalyst
regeneration.

For the bleed stream only the mass percentages are given, and not the ows. This is because
the ow of these bleed streams will depend on the amount of non considered impurities in the
feeds of the plants.

9.2
9.2.1

Direct waste
Excess water, <319>

The excess water has no use in the plant and has to be disposed of. It is a stream of about 48
m3 = day, which is a rather small volume. Two possibilities are considerable for this water:
67

CPD 3281 - Basis of Design

name
cooling water bleed
vapors from excess water
sewer discharge

Table 9.2: Waste stream summary, 2


source
cooling water system
waste water treatment system
oces, plant area

components
water, salts, water conditioners
hydrocarbons
water, organics, pump uids

Clean it in situ on outside battery limits


Sell it to a wastewater treatment plant
When the company owns a wastewater plant on the site, the rst option is favoured. As no
information is known about this plant capacity, it can be considered that the water, containing
only hydrocarbons as wastes, can be sent to a wastewater treatment plant. An important
problem with this waste stream will be the smell. Butanoic acid has a very strong and dirty
smell. A closed sewer system for this aqueous waste stream will be required.

9.2.2

Bleed streams, <313> & <320>

The bleed streams are not incooperated in the design and have a ow of zero in the mass
balance. They are discussed however, because in practice, they might be needed.
<313>
The necessity of a vapor bleed depends on the type and amount of vapor impurities in the
oxygen. The vapor impurities will leave the process through the liquid product and waste
streams, just like some oxygen does. Only if the impurities are very bad soluble in the reaction
mixture, then a build up will occur and a vapor bleed will be necessary.
<320>
Whether a liquid bleed will be necessary will depend on the same reason as the vapor bleed.
Only impurities which will not vaporize in V301 and C301 need to be removed via <320>. In
either case, <320> can be used to take o catalyst for regeneration.

9.3

Prevention of waste by design

The major prevention of waste through a design choice has been done at forehand by the project
principle. The technology applied in this process has already been described as green (paragraph
1.2). There are also choices made by the design team which will prevent waste generation.

9.3.1

Alcohol vapor recycle

The stripping column was designed to operate with steam as vapor ow. This has the eect
that more waste water was produced. The steam has been replaced with the alcohol recycle.
This has reduced the waste water ow considerably. It also had the eect of a kind of heat
integration between the 1-butanol recycle purication and the stripper: the C303 condenser has
a lower heat duty, this heat is inserted and used in C301.
68

9.4. FURTHER WASTE REDUCTION POSSIBILITIES

9.3.2

Pure oxygen as O2 source

By using pure oxygen for the reactor a vapor waste stream of oxygen depleted air is prevented.
Only the discharge of air would not be a problem, but the vapor from the reactor would even
after the partial condensing still contain some hydrocarbons. These hydrocarbons would have
to be incinerated, causing the need of a incinerator.

9.3.3

Pre-separation of 2-butanol

The choice of pre-separating 2-butanol instead of separating butanone in the product purication
has advantages in terms of waste and environmental burden. The separation of the alcohols is
easier, and therefore less energy consuming. Butanone which would form without pre-separation
has a higher NFPA rating than 2-butanol, making its environmental release less acceptable.

9.4

Further waste reduction possibilities

Further waste reduction is always possible, in every process. The question however is, whether
further reduction pays o. Not only in economical sense, but also in a sense of environmental
burden.

9.4.1

Excess water use

The excess water which is now discharged after cleaning might be used for the cooling water
system. The advantages of stream <319> is that is doesnt contain any salts, which makes it
excellent applicable for the cooling water system. The hydrocarbons present in <319> however,
should be rst removed, without adding new substances (e.g. bacteria and/or a nitrogen source
for bacterial cleaning). This would imply a separate purication systems, which is probably not
justied by the advantage of using the excess water instead of other water.

9.4.2

Optimization of column C302 and C303

These columns havent been fully optimized yet. As with C101 (paragraph 8.2.1), packing
instead of trays might be applicable for C302 and C303. This would render decreased xed
costs and energy savings. Less energy consumption of course, would imply less CO2 discharge.

9.4.3

Decrease of hydrocarbon concentration in excess water

By decreasing the temperature of V304 (the decanter), a more favorable equilibrium can be
reached. In the design it is about 55C, it could be lowered to 40 C : At lower temperatures,
the hydrocarbons will be less soluble in water and so <319> will contain less hydrocarbons.

69

10 | Process safety
10.1

HAZOP

A Hazard and Operability (HAZOP) study is performed to get to a qualitative hazard analysis
of the process in a systematical manner. A limited HAZOP study will be performed on the
reactor only.
The study is done by asking questions with the six guide words. For every word, What if
questions are asked. A meaning is given to the guide words in table 10.1, which is taken from
[34, page 8].

Guide Word
NONE
MORE OF
LESS OF
PART OF
MORE THAN
OTHER THAN

10.1.1

Table 10.1: Deviations generated by each guide word


Deviations
No forward/reverse ow when there should be ow
More of any relevant physical property than there should be (temperature,
pressure, feed)
Less of any relevant physical property than there should be (temperature,
pressure, feed)
Composition of system dierent from what it should be
More components present in the system than there should be (extra phase,
impurities, etc.)
What else can happen apart from normal operation: start-up, shut-down,
uprating, maintenance, etc.

Reactor HAZOP study

For this study only the two feeds and the two outlets are considered. The recycles are not
considered. Figure 10.1 shows a scheme of the reactor with numbered streams.
71

CPD 3281 - Basis of Design

3
2

Figure 10.1: Simple reactor scheme with in and out ows


Now What if questions are asked according to the guide words given above. The results
and intermediate remarks are given in tables S.1 to S.6 in appendix S. For the Other than
guide word, a start-up and shut-down procedure is proposed and these procedures are given in
paragraph S.1 of appendix S.
The recommendations for improved process safety are given below:
Low level alarm on reactor with valve control on stream 1 and 3
Stirrer speed and temperature control
Low level alarm on reactor with O2 supply control
Low ow alarm on stream 2. May not happen!

Composition control on vapor. Flush with N2 or O2 to stay away from the explosion limits
Emergency pressure take-o on reactor
Low stirrer speed alarm with ow control on streams 1, 2, 3 and 4. Prevent oxygen going
into stream 3
Adjust feed temperature to control reactor temperature
Analyze stream 2. Adjust the purge to prevent accumulation of gaseous impurities
Flush with N2 before and use ex-proof equipment during maintenance

10.2

Dow Fire & Explosion Index

The Dow Fire & Explosion Index is a measure of the realistic re, explosion and reactivity
potential of process equipment and its contents. Appendix T shows the sheets as provided
by [40] lled in. Some parameters were calculated, for instance the Quantity of ammable
or unstable material. This is the amount of combustion energy released via a leakage for 10
minutes. The energy content is calculated from the stream to or from the piece of equipment
having a leakage for 10 minutes. The heat of combustion of the components are listed in table
10.2. Values are taken from [39]. Not every piece of equipment is reviewed, only the major
equipment. Auxiliaries of distillation columns are lumped with the column.
As can be seen in appendix T, the reactor is the most hazardous piece of equipment, according to the Dow F&EI. The reactor is intermediate hazardous and all other the others are
light hazardous. Most eort should be put in safety measures for the reactor.
72

10.3. EXPLOSION LIMITS

Table 10.2: Heat of combustion for dierent components


component
Hc [kJ/mol]
butanal
-2477.1
1-butanol
-2670.0
2-butanol
-2660.6
oxygen
n.a.
butanone
-2444.2
water
n.a.
butanoic acid
-2183.5

10.3

Explosion limits

10.3.1

Pure components

The explosion limits found in literature are the volumetric fractions of substance in air. There
are two limits given: the lower explosion limit (LEL) and upper explosion limit (UEL). In the
designed oxidation process, pure oxygen is used instead of air. Therefore, the LEL and UEL
need to be recalculated. The composition of air is assumed to be 79/21 N2 /O2 and gasses
behave ideal. The LELO2 and the UELO2 are calculated with the following formulas:
LELO2 =
U ELO2 =

LEL
LEL + 21
UEL
UEL + 21

(10.1)
(10.2)

where the LEL and UEL values are in percentages of hydrocarbons. The results for the gasses
in the process are given in table 10.3. Values are taken from [30].
Table 10.3: Explosion limits for substances in pure oxygen
% in air
fraction
% in oxygen
LEL UEL LELO2 UELO2 LELO2 UELO2
1-butanol
1.4
11.2 0.063
0.348
6.3
34.8
butanal
2.0
10.0 0.087
0.323
8.7
32.3
butanoic acid 2.5
12.5 0.106
0.373
10.6
37.3
2-butanol
1.7
9.8
0.075
0.318
7.5
31.8
butanone
1.8
10
0.079
0.323
7.9
32.3

10.3.2

Explosion limits in a mixture

For a mixture of hydrocarbons the principle of Le Chatelier[10, page 557] is used to calculate
the LEL and UEL:
LELmix =
U ELmix =

1
yi
LEL
i
1
yi
U EL
i

(10.3)
(10.4)

The yi is on a combustible basis, this means the fraction relevant to the combustible
compounds, and not to the total mixture.
73

CPD 3281 - Basis of Design


Reactor overhead
To make sure that the reactor overhead is not within explosive limits, the reactor is simulated in
ASPEN with given process conditions (paragraph 5.2.3 and 8.3.1). The reactor is rst simulated
with only oxygen feed in the bottom. The results for the vapor mixture are given in table 10.4.
Table 10.4: Composition of the mixture in the overhead of the reactor, without oxygen dilution
components
mole fraction yi
1-butanol
0.01
0.11
2-butanol
0.00
0.00
water
0.12
butanal
0.08
0.87
butanone
0.00
0.00
O2
0.79
butanoic acid 0.00
0.01
Total
1.00
1.00
The LEL for the mixture is according to equation 10.3 9.84 % and the UEL according to
equation 10.4 37.01 %. The volume fraction of combustibles in the overhead is 0.0921 of 9.21
%. This is very close to the LEL for this mixture.
A way to avoid operating so close to the LEL, dilution of the overhead in the reactor with
the make up oxygen is considered. The new composition and LEL and UEL for this mixture is
given in table 10.5.
Table 10.5: Composition of the mixture in
components
1-butanol
2-butanol
water
butanal
butanone
O2
butanoic acid
Total

the overhead of the reactor, with oxygen dilution


mole fraction yi
0.00
0.11
0.00
0.00
0.05
0.04
0.87
0.00
0.00
0.90
0.00
0.01
1.00
1.00

The LEL for the mixture is according to equation 10.3 9.84 % and the UEL according to
equation 10.4 37.01 %. The volume fraction of combustibles in the overhead is now 0.0427 of
4.27 %. This is far enough from the LEL for this mixture.

74

11 | Economy
11.1

Investment

The stepwise method which is used to arrive at the total investment required is given in [27,
page 259]. In paragraphs 11.1.1 till U.3 the purchase costs for the major the equipment will be
estimated using the Lang method[27, page 293]. In paragraph 11.1.4 the total physical plant
costs (PCC), indirect costs, total xed capital (TFC), working capital and total investment
required will be calculated. Equipment without an estimated purchased equipment cost were
not designed in such a way that an estimation on the cost was possible. Some pumps cannot be
estimated because its duty is dependent on pressure drop in pipes which is dependent on the
length of this pipe.

11.1.1

Section 100: 1-butanol/2-butanol separation

The rst distillation column separates 1-butanol from 2-butanol. The packed column needs a
reboiler, a condenser and a reux vessel to operate. The heat exchanger is necessary to heat up
the incoming stream. The condenser is installed to condense the top vapor stream in order to
have a liquid product and a liquid downstream. The reboiler is necessary to generate a vapor
upow. The hardware needed together with their purchase costs is given in table 11.1. The
calculation is given in appendix U.
Table 11.1: Equipment in the pre separation section
equipment function
purchased equipment costs
C101
1-butanol/2-butanol separation
$150,000
E103
C101 reboiler
$17,600
V101
C101 Reux Vessel
$ 6,500
P101
Feed pump
n.e.
E101
Feed heater
n.e.
E102
C101 reux HEX
n.e.
P102
C101 reux pump
n.e.
total
$174,100
n.e.: not estimated

11.1.2

Section 200: Reaction section

The reaction section consists of the following hardware given in table 11.2. The purchased
equipment costs for all the dierent hardware will be explained in appendix U.
75

CPD 3281 - Basis of Design

Table 11.2: Equipment in the reaction section


equipment function
purchased equipment costs
R201
1-butanol conversion
$100,000
K201
pressurize for fresh oxygen
$240,000
K202
re-pressurize oxygen recycle
$14,000
P201
pressurize alcohol feed
n.e.
V201
Splitting vessel
n.e.
V202
Collection vessel
$9,600
E201
heat / cool feed
n.e.
E202
reactor top cooler
n.e.
total
$363,600
n.e.: not estimated

11.1.3

Section 300: Separation section

The product separation consists of the hardware given in table 11.3. The purchased equipment
costs for all the dierent hardware are explained in appendix U.
Table 11.3: Equipment in the separation section
equipment function
purchased equipment costs
C301
Stripper
$77,500
C302
butanal separator
$278,000
C303
butanoic acid separator
$207,500
V302
C301 reux vessel
$6,000
V303
Collection vessel
$18,000
V305
C302 reux vessel
$10,000
V306
C303 reux vessel
$6,000
P301
V301 top stream
n.e.
P302
V301 bottom stream
n.e.
P303
C301 top stream
n.e.
P304
C301 bottom stream
n.e.
P305
liquid recycle pump
n.e.
P306
C302 feed pump
n.e.
P307
V304 bottom pump
n.e.
P308
C302 top pump
n.e.
P309
C302-C303 transfer
n.e.
P310
C303 top pump
n.e.
Total
$603,000
n.e.: not estimated

11.1.4

Total Investment

The PCE is $1,140,700. 10% is added to this number to correct for not estimated equipment.
This yields a PCE of $1,254,770. The total investment required is based on the price level of
1998. To correct it, ination over 5 years is calculated. Yearly ination is set at 4%. After 5
years, money is worth 1000.96^5% = 81.54% of its original value. The PCE is now $ 1,538,891.
76

11.2. OPERATING COSTS


1. The total physical plant cost (PPC) is now calculated with:
PP C = PCE (1 + fi)

(11.1)

The PCE is the total costs for purchased equipment. The f values is the summation
of individual factors compounding the Lang factor. In this case the f includes all the
individual factors given in [27, page 251, table 6.1], f = 3.40. The PCE is equal to
$1,538,891. The PPC is then $ 5,232,230.
2. The xed capital includes the indirect costs:
f ixed capital = PCC (1 + f10 + f11 + f12)

(11.2)

3. The factors for design and engineering(f10), contractors fee(f11) and contingency(f12 )
are included. The xed capital estimation is then 1.45*PCC = $7,586,734.
4. The working capital is estimated as 15 % of the xed capital: 0.15$7,586,734 = $1,138,010
5. Finally the total investment required is the summation of the xed and the working
capital: $7,586,734 + $1,138,010 = $ 8,724,744. Catalyst investment is $ 585,000, the
ligand investment is $ 2,761,541, the total investment is $ 12,071,285.

11.1.5

Catalyst investment

The liquid volume of the reactor is 33 m3. The volume of the other equipment and pipelines
is assumed to be also this volume. The total volume containing catalyst is thus 66 m3. The
concentration outside the reactor is assumed to be the same as in the reactor for this calculation:
1.438 mmol/l. MW of Pd(AcO)2 is 224.5 g/mol. The price according to the Sigma-Aldrich
catalogue is $685/25 g or 6151.3 $/mol. The total load of catalyst is 94.9 mol. The investment
for catalyst is thus $ 585,000. The catalyst : ligand ratio is 1 : 1. The price of ligand is 29,000
$/mol. This yields a ligand investment of $ 2,761,541.
This investment is not taken into the Lang factor calculation and only added afterwards
to the total investment account. This is because the type of catalyst will not inuence the
designing and building of the plant. The catalyst investment is based on laboratory prices and
these prices are generally much higher than bulk prices. The real investment will be lower.

11.2

Operating costs

11.2.1

Utilities

The cost of utilities used is described below. Under utilities is put: steam, cooling water and
electricity.
Steam
According to [28], the cost of steam is 30 to 35 NFL/ton for steam of 3, 10 and 40 bar. Calculated
is with NFL 32.50 per ton. The total steam requirement is 29 ton per hour (see appendix H.5).
This yields a steam cost of NFL 942.50 per hour or $ 435.15 per hour (exchange rate December
2002).
77

CPD 3281 - Basis of Design


Cooling water
According to [28], the cost of cooling water is 0.05 to 0.10 NFL/m3 . Calculated is with NFL
0.08 per m 3. The total cooling water requirement is 954 m3 per hour (see appendix H.5). This
yields a cooling water cost of NFL 76.21 per hour or $ 35.23 per hour (exchange rate December
2002).
Electricity
According to [28], the cost of electricity is 0.13 to 0.22 NFL/kWh . Calculated is with NFL
0.18 per kWh. The total electricity requirement is 544 kWh per hour (see appendix H.5). This
yields an electricity cost of NFL 97.92 per hour or $ 45.21 per hour (exchange rate December
2002).
Total
The total utility cost per hour is $ 516. This can be lowered by producing steam on the plant.
This reduces both the cooling water requirement and the steam cost.

11.2.2

Raw material

Prices for butanol are found in [45]. Price for oxygen was provided by Air liquide (see 5.2.3).
Table 11.4 shows the costs for raw materials.
Table 11.4: Raw material costs
Price [$/ton] Flow [ton/hr] Costs [$/hr]
1-butanol
771.62
15.3
11,806
2-butanol
771.62
0.792
611
oxygen
45
3.28
147
Total [$/hr]
12,564

11.2.3

Waste

The cost for waste removal is not considered. Since the nature of the waste (water with organic
material) is not very toxic, the costs will not be of inuence on the total operating costs.

11.2.4

Labour costs

Labour costs do normally not exceed 15% of the total operating costs[27, page 264]. The total
without labour costs is $ 13,080 per hour. Dividing by 0.85 yields the total operating costs
including labour costs.

11.2.5

Total

The total operating costs are 13,080/0.85 = $ 15,388 per hour. On a yearly basis with 8000
operating hours, this is M$ 123.10.
78

11.3. INCOME

11.3

Income

The income is generated mainly by butanal but also by selling butanoic acid and a 1-butanol/2butanol mixture as fuel. The price of fuel is calculated with the heat of combustion obtained
from [39] and a price per BTU obtained from [6, page 135]. Table 11.5 shows the income from
the dierent product streams. Prices are taken from [45]. The price of butanoic acid is guessed
and probably higher. The amount of operating hours is 8000. The yearly income is M$ 161.51.
Table 11.5: Income from product sales
Price [$/ton] Flow [ton/hr] Income [$/hr]
butanal
1234.59
14.29
17,645
butanoic acid
1000
2.41
2412
fuel
136.57
0.97
133
Total
20,189

11.4

Cash ow

Cash ow is dened as the dierence between income and operating costs. Total operating costs
are $ 15,388 per hour. Total income is $ 20,189 per hour. The cash ow is thus $ 4800 per
hour. On a yearly basis, the cash ow is M$ 38.41

11.5

Economic criteria

11.5.1

Discounted cash ow

The net present worth (NPW) for each years earnings during the total life time of the project
is calculated using equation 11.3. For the interest rate r a value of 10 % is taken.
N PW =

estimated net cash ow in year n


(1 + r)n

(11.3)

The total NPW of the project is then each years NPW summarized: M$ 211.

11.5.2

Discounted cash-ow rate of return (DCFROR)

The DCFROR is the interest rate at which the plant would break even at the end of its lifetime.
It is the same equation as equation 11.3, but now r needs to be estimated for NPW of zero.
The interest rate at which the NPW is zero after 20 years of operating the plant is 55 %.

11.5.3

Rate of Return (ROR)

The ROR is calculated as an average over the whole project life:


ROR =

cumulative net cash ow at end of project


project life original investment

(11.4)

With the estimated project life of 20 years (excluding 4 years of design and building), an
original investment of M$12.1 (paragraph 11.1), and a net cash ow rate of M$38.4 / yr, a ROR
of 88% is calculated.
79

CPD 3281 - Basis of Design

Figure 11.1: The project cash ow for the rst 10 years of the project
Table 11.6: Sensitivities to worse economical circumstances, costs +10%, income -10%
category
costs
costs
costs
income income costs
income both
component 1oxygen utilities butanal butanoic all
all
all
butanol
acid
feed
cashow
26.7
38.3
37.9
24.3
36.5
26.1
22.3
10.0
[M$/yr]
DCFROR
47%
55%
55%
45%
54%
47%
43%
29%
ROR
59%
87%
86%
54%
83%
58%
49%
19%

11.5.4

Project cash ow diagram

The project cash ow diagram for the rst ve years is given in gure 11.1. The costs for the
rst two years are for design and engineering. From year 2 to 4 capital is needed for building
the plant and start-up. Finally work capital is needed. From year 4, the plant is running and
income is generated.

11.6

Sensitivities

The sensitivity towards higher costs and lower product prices of the cash ow rate, the DCFROR
and the ROR is investigated. The costs for utilities, 1-butanol feed and oxygen is put 10 %
higher. The income on butanal and acid is set 10 % lower. The results are shown in table 11.6.
Even in the worst case scenario of costs getting 10% higher and income getting 10% lower,
the cash ow is still 10.0 M$/yr.

80

12 | Creativity and group process


achievements
Industry is becoming more aware of the importance of creativity in process design and operation.
The importance of creativity in engineering is pointed out more and more. By innovative design
for cheaper processes it is possible for western companies to compete with cheap labour in the
far east, and to create more environment friendly processes. Also capital costs can be reduced
signicantly by innovative design and probably even more benets will occur. The awareness of
creativity and the importance of innovation is recognized by the research group Process Systems
Engineering (PSE) and implementation of creativity tools by design teams in the Conceptual
Process Design is strongly encouraged. Also tools for improving group dynamics are provided
to the teams. Group dynamics has an enormous impact on the implementation of creativity
in a teams design approach. For creativity an open and positive stimulating atmosphere is an
important basis. Our approach as a team on group dynamics will be discussed in paragraph
12.2.
We as a design team were aware of this to some extent, but became more aware of the
importance of innovation in design and system engineering. In 12.1 we will point out our goals,
tools, opportunities and results of our creative approach.

12.1

Creativity

12.1.1

Goals

The goals of the team on implementing creative tools where to:


study useful tools for creativity
implement a creativity session/tool at every design level of the DDM
use creative tools during coach meetings
use results of creative sessions if possible in the design
First an inventory of dierent methods for creativity was made. The team started by reading
articles about creativity for the creative task. One of these articles was taken from [33]. This
reader appeared to be a source of creativity tools. After studying creative methods an inventory
of creative techniques was made which is presented in appendix V.1.

12.1.2

Creativity: First approach

For the kick-o meeting the team members read dierent articles on creativity and creativity
methods. Every team member wrote summaries of the articles and wrote down personal comments on applying these methods in the design team. After reading some articles and writing
81

CPD 3281 - Basis of Design


down personal goals for the creativity task we set goals to implement these creativity methods
in our design.
From the creative technique inventory some methods where chosen to apply during the
design. The methods were chosen according to their contribution to the design levels of the
DDM. The creativity planning until the preliminary BOD can be seen in table 12.1.
Table 12.1: Delft Design Matrix and implemented creativity methods
Level
Subjects
Creativity methods
literature research
topic
brain-storm
sources
brain-storm
1. plant type & con- batch vs continuous
brain-writing
&
mindnections
mapping
multi-product vs single prod- break through presuppositions
uct
integration into upstream mind-mapping
and downstream activities
2. input/output struc- chemical feed and products
brain-storm
ture
reactions
mind-mapping
energy & auxiliaries
brainwriting
3. functional blocks
conversion & recycle struc- mind-mapping & brain-storm
ture
phase separations and puri- MATEC
cation of product
product synthesis and work- mind-mapping & brain-storm
up
We successfully applied some of the methods described in table 12.1 for the design.
Literature research (8/10/02)
According to table 12.1 we had a brainstorm session in order to answer the two questions What
to look for? and Where to search?. This resulted in a lot of obvious sources to consult, but
also some interesting sources were thought of. The results of this brainstorm are presented in
appendix V.2.
With these results we successfully contacted Givaudan (Mrs. D. Meijerink), IFF (Mrs. J.
Voost), Quest International (Mr. C. Winkel), Diosynth (Mr. P. Vrijhof) and Intervet (Mr. J.
van Beek). These companies supplied us with some information concerning industrial alcohol
oxidations. It became clear that alcohol oxidation catalyzed by Chromium salts is hardly used
nowadays. This was an unexpected nding and in contrast to provided information in the project
hand-out. After contacting Mr. T. Kodama the team was convinced of the opportunities of
using the novel catalytic method for the conversion cycle of butane towards butanal.
Results from applied methods in Delft design matrix
Mr. T. Kodama provided the team with information about the location of the plant. For
connections between plants some of the team members used their knowledge and intuition to
make decisions on some streams crossing battery limits (water, power and steam). The decision
on continuous or batch operation was made with the method described in [6]. Because of the
82

12.1. CREATIVITY
needed throughput (>100.000 tons/a) batch operation is not feasible, and no creative tool was
necessary to come to dierent conclusions.
For the input/output structure a brain-storm session was done. This was more or less
partial overlap with the literature research, and resulted from ndings from this search. No
extra inventory technique like brainstorming was used.
In order to draw the blocks schemes, we decided to use provocative techniques (break through
presuppositions and provocative questions on 23/10/02). Several block schemes were made
starting each time with what do we have as an inlet? and trying to change dierent steps
by asking what? why? where?. Answers like it is obvious, it is always done like this were
avoided or rejected.
We discovered that a lot of information was missing to be able to make sound decisions.
Remaining questions were:
What is the most dicult separation: alcohol/alcohol or aldehyde/ketone?
How high have to be the temperature and the pressure of those separation sections?
What have to be the pressure and the temperature conditions in the reactor section to
avoid an oxygen transfer limitation?
Two possible block schemes, gure 2.2 and 2.3, were constructed for the process.
We applied a creative tool to discuss a strong limiting factor: the mass transfer of oxygen.
In order to cope with the solubility/mass transfer of oxygen in water, we used the MATEC
(MATrice dEloignement Creatif) method[33, p. 82 - 84]. From this method some new ideas
were generated to tackle the problem of the oxygen mass transfer. Results of this method are
shown in table 12.2. The procedure for this method is described in V.3.
Table 12.2: Results from the MATEC method
Bisociation pasta and cow traditional, big volume, food, shape, soft/hard, water absorption, grains, lazy, warm
1. use more water
Opportunities for
2. increase the pressure and study the inuance of the temperature
3. investigate the food industry and especially the butter
industry to discover how they increase the solubility of oxygen
in water
the stated problem
4. check the reactor and the equipment as well as the shape
of the sparger
5. facilitate the absorption of oxygen by using a solid for
instance
The butter industry maybe could supply us with new insights in our problem. In butter
industry the interfacial area between the air bubble and milk is used to separate milk fat from
the milk. Solubility of air or oxygen is of no interest in this area. Other results are applied to
the design as can be seen in paragraph 8.3.1. An opportunity we did not pursue was to study
the possibility to enhance mass transfer by letting oxygen adsorb on a carrier material. This
can be pointed out as a recommendation for later research.
For the reactor design, part of the unit operation design, we followed the Krishna and Sie
method [21]. After studying this method, all team members independently designed a schematic
reactor. Results were compared, and a very promising reactor was chosen from the designs. Also
83

CPD 3281 - Basis of Design

Figure 12.1: Preliminairy reactor idea


some combinations of designs were tried. A schematic drawing is presented in gure 12.1. More
detailed information about this design is shown in chapter 2.

12.1.3

BOD review: Change in approach

After postponing the BOD review because of group dynamic reasons, which are pointed out
in paragraph 12.2, it was suggested to change our approach on implementing creativity tools.
Our approach was too technical. The team used creativity tools, but without using its intrinsic creativity. No methods described by Mr. Grunwald in [35] were used. The following
opportunities for improvement were pointed out during the pre-BOD meeting.
There is not enough attention for the (creativity) methods presented in [35]. Some were
used, but only safe ones.
Unknown and maybe more dicult techniques should also be tried.
Study methods described in [35, p. 18].
Use idea diary more frequent.
We as a team did not read [35] and applied the described methods because of several reasons.
The team was not aware of the importance of this syllabus for the CPD design course. After
scanning the document, the general idea was that most of the described methods were used
already by the team members.

12.1.4

Creative session with Mr. Grunwald and Mrs. Arends (7/11/02)

Also a creative session with Mr. Grunwald and Mrs. Arends was scheduled to get the creativity
aspect of the design on track. During this session, together with Mrs. Arends, the method
described in V.4 was used. The problems which had to be solved were:
How to remove water in the separation section with low use of energy
How to decrease reactor volume
84

12.1. CREATIVITY

Table 12.3: Brief representation creative session guided by Mr. Grunwald and Mrs. Arends
Problem
Opposite solutions
Removal of large quantities of water Freeze drying
Big reactor volume
1. Innitely amount small reactors
3. Doughnut shape reactor
4. Small reactor volume
2. Flexible wall reactor
A lot of ideas emerged from this session. A brief representation of the results is shown in
table 12.3, detailed results with results of investigation are presented in V.4.
During this meeting an interesting option for reactor lay-out was developed. One of the
team members had the idea of a exible reactor, from that to a hourglass shaped reactor,
then Mr. Grunwald made the association of turning the hourglass. Then the association of
a reversed ow reactor with membranes keeping the catalysts inside and using pervaporation
principle to remove product appeared. Pervaporation is done by using a gas partial pressure,
but maybe could also be done by using dierence in solubility. Alcohol should be used on the
other side of the membrane. This then would have two functions: Getting the aldehyde out
and continuous diusion of new alcohol into the reaction mixture. A schematic drawing of this
setup is presented in gure 12.2.

Figure 12.2: Possible set-up for a tubular membrane reactor


This idea was studied by one of the team members, but was found not to be applicable
due to many unknown properties of membranes etc. A more detailed work-out of this idea is
presented in V.4.

12.1.5

Creativity: nal approach

During the coach meetings which were held after the BOD meeting we used methods described
in [35]. The main method we used during the coach meetings was:
Closing eyes for two minutes and think of obstacles or strong points in our design
Write down opposite solutions
Write down advantages of these solutions
85

CPD 3281 - Basis of Design


Look wether you can implement these advantages in the design

First team members had to close their eyes to activate the right brain. With closed eyes
we had to think of possible solutions for the mentioned problems. The ideas where drawn
(symbolizing) or written on a piece of paper and we discussed and combined results. By writing
or drawing ideas on a piece of paper the process is stimulated by kinestatics. During these
coach meetings we discussed some problems and talked about some solutions which are shown
in table 12.1.5.
Table 12.4: not pursued creative ideas during design period
Ideas
Hour glass shaped stirred reactor to decrease bubble size
Waterjet venturi vacuum system to create low pressure in preseparation
Flushing reactor headspace with oxygen or nitrogen to satisfy explosion limits (see
10.3)
Immobilizing catalyst

12.1.6

Review creativity tools and results

Tools
The tools we used at the start of the process are suitable to solve a broad spectrum of problems.
The problem we experienced as a team with some methods (matec, mindmapping, braindrawing
etc.) was that these methods were not the methods to use as a starting design team with low
experience on expressing creativity. To be creative in a productive way it is recommendable
to become mentally more aware of it. The change in approach from using techniques which
are helpful in the creative process to techniques to become more aware of personal creative
capacities was an eye-opener for the team. We as a team appreciated the method described in
V.4. The moment of closing eyes to activate the right brain and writing down ideas makes you
calm down and the absolute silence is very helpful during the reection upon new ideas. This
method provided the opportunity to go deep into the problem.
The methods described in appendix V.1 can probably be used after some more experience in
using methods which activates personal creativity. It is also recommended to take enough time
for the activation of the right brain and writing down/symbolizing ideas. The team experienced
during the sessions that this is necessary to relax and to go mentally deep into the problem. The
team recommends to describe this method in the CPD manual, and to point out more syllabus
[35] to design teams. An opportunity for the team members is to implement the mentioned
creativity techniques in [33], [35] daily practice and not only under guidance of a coach or
creativity consultant.
Results
Results which sprung from the creative sessions are very diverse. Some very creative and some
were more applicable on short term. This is of course the teams opinion and is based on the
team members intuition. Some of the ideas are implemented in our design as is pointed out
before. These ideas were not always as innovative, but helped to become aware of the problems
and of solving them.
Another result of applying the creative methods is the awareness of use of creativity by the
team members. This provided the team members a starting point to use and to master creative
techniques.
86

12.2. GROUP INTERACTION

12.2

Group interaction

From the beginning, we were all convinced that good group interaction was the only way to
a good design. The team was aware that in a period of twelve weeks, with strong personal
interaction, deadlines, dicult topics etc. the interaction between team members should be
open, motivating, trustful and honest. Jeroen, Sander and Sijbe already knew each other as exHTS students enrolled at DUT together, Cline as an exchange student joined the team. Already
during the PSD course it became clear that Cline tted perfect in the team on personal and
technical level. To become more familiar with each other we decided to have a weekly dinner.
We introduced Cline to the Dutch Cuisine and Sijbe, Jeroen and Sander to the French Cuisine.
We also had drinks together, and Elodie Dejean joined us sometimes.

12.2.1

Participation prole (4/10/02)

To get more information on our professional contribution to the team we lled out the participation prole. Results are shown in gure 12.3.

Figure 12.3: Detailed group prole (4/10/02)


As can be seen in gure 12.3 the team has some distinct strengths and weaknesses which
are presented in table 12.2.1. After lling out the prole, we decided that we would have
a rotating secretary and chairman role. This decision was based on the fact that leadership
and coordination were opportunities for the team to work on. By changing the secretary and
chairman role every team member would have the possibility to develop skills in leadership and
administrative work.

12.2.2

BOD review meeting (4/11/02)

The BOD review meeting was postponed because several appointments which were made at the
kick-o meeting were neglected. The team did not send the articles about creativity, Jeroens
second summary, group prole and minutes from the kick-o meeting. The BOD review meeting
was postponed until these action points were completed. This was done to point out that you
have to carry out ones promise. This action had a lot of impact on the team, and the responsible
87

CPD 3281 - Basis of Design

Table 12.5: Identied team strengths and weaknesses


Strengths
Weaknesses
Technical insight
Mathematics
Systematic thinking Cost control
Leadership
Creativity
Playing safe
team members took their responsibility. After the BOD review meeting on the same day some
other appointments were not completed. The morning after we decided to discuss problems,
expectations and each others contribution to the team.

12.2.3

First team performance review (5/11/02)

During the review session, all team members wrote down strong and weak points to group
contribution of him/herself and of the team members. We discussed per team member her/his
analysis and the remarks by team members. This discussion took whole morning, and was
very relieving, because some of the issues we did not discuss before. The following topics were
discussed:
Irritating behavior: too frequently checking of E-mail, news or other internet applications
Not taking part in discussions, or no interference in endless discussions between team
members
Importance of the creativity part of the CPD design
Dedication towards group interaction/creativity
Writing down motivations for decisions during design
Negative attitude during the design period
Too focussed on planning
Ignorance on facts about group results and the eect on long term
At the end of the discussion the team members wrote down personal goals to improve their
contribution to the group . The team decided to be more active in communication among each
others on strong and weak points during work. This session led to a better understanding of
each other and to recognition of each others opportunities for better group interaction. We
also concluded that having dinner and drinks together is only a shallow, but also pleasant and
relativistic way of group interaction.

12.2.4

DOW trip (11-12/11/02)

This trip gave us the possibility to take some distance from the design and to have informal
interaction. By taking some distance problems can settle as described in [35, p. 18, method
8]. This can have positive eects on idea generating and problem solving. Also the relaxing
eect of going on a small trip was appreciated by the team members. During the excursion on
the site we became aware that large equipment is not a problem by denition.
88

12.2. GROUP INTERACTION

12.2.5

Second team performance review (19/11/02)

This session was initiated because the team was 1-2 weeks late compared to the planning.
The planning had a distinct place in our team room, and team members could check and add
remarks. In spite of this useful open planning, no action was taken, no remarks were made
although everybody was aware of being o schedule. We started the session by inventorying
the topics which had to be done already. After inventorying we made a planning for this week
to nish these topics. Then we discussed why we were late, and why nobody initiated this
discussion before. We noticed that not everybody felt fully responsible for less popular tasks
like distributing minutes, looking up information not directly related to the design etc.. The
following topics were discussed:
Some team members were not comfortable with the leader role
Some team members still do not tend to speak out their feeling and opinion towards group
results
Admittance and acceptance of mistakes by team members
Keeping main goal in mind
Lacking of responsibility of chairman in group
Some of the discussed topics were discussed before, but not everybody took advantage of it.
After the rst review it started of in a good way, but after some time the focus on these points
was less.
After the discussion we concluded that Sijbe was more keeping an eye on the whole project
than the others. It also turned out that Cline was better in the administrative part of the
project. The team was aware that by changing from a dynamic chairman/secretary rotation
towards a dedicated chairman/secretary would take away opportunities for improvement from
other team members. This change was nevertheless received in a positive way by all the team
members, and the atmosphere after was less tense. This change increased productivity. The
team also decided to use the logbook in a more structured way. We started to write down:
Short description of the day
Minutes of a daily wrap-up meeting
Technical points
Finished or to nish work
Creative ideas
Ideas concerning the process in general
Group interaction
Some of these points were highlighted with markers to increase awareness of these specic
topics.
Our coach stimulated us to use the method described in [35, p. 16] (27/11/02) method to
clarify in witch circumstance we like to work in a group. We used this method and discussed
about the ndings. Some were new, but a lot were indicated before. No details about this
session are reported because of the personal content.
89

13 | Conclusions and
Recommendations
13.1

Conclusions

13.1.1

Strengths & weaknesses

A review of the strengths and weaknesses of the design according to the team is given in table
13.1 and 13.2.
Table 13.1: Strengths of the design

strengths
ternary system occuring in reactor studied in detail
minimze the compression costs by using pure oxygen
easy pre-separation
no organic phase that is to say no use of TEMPO is required
and the reaction
optimized pressure in reactor (lower than experimental)
everything except for reactor is lowest category in DOW
F&EI
very little waste
no use of toxic chemicals
high cash ow rate and ROR

category
thermodynamic properties
process structure
process structure
process structure
unit design
safety
environment
environment
economics

Table 13.2: Weaknesses of the design


weaknesses
category
only info on catalyst solubility in pure water
thermodynamic
reaction rate not derived from 1-butanol experiments
thermodynamic
catalyst deactivation not taken into account
thermodynamic
catalyst performance at higher temperatures (as used in the thermodynamic
design) than experimental not investigated
heat exchangers not designed in detail
unit design
higher concentration of butanoic acid than expected
unit design

13.1.2

properties
properties
properties
properties

Technical and economical risks

An important technical and economical risk is the rate of catalyst deactivation (palladium black
formation, ligand stability). It has not been taken into account in the design. When catalyst
91

CPD 3281 - Basis of Design


deactivation occurs, the economical feasibility of the process might be endangered. With a cash
ow of M$38.4, and catalyst complex price of 35,150 $/mol and 95 mole present in the process,
the catalyst complex can be replaced 3 times.
The high acid concentration in the liquid recycle loop might form a danger to process
equipment and (expensive) catalyst complex. The pH eects have not been under investigation
with the assumption that a buer could be added in case of problems. The actual pH eects
need to be investigated and the possibility of addition of a buer in the process still needs to
be proved.

13.1.3

Creative designing

The design team started with applied creativity methods which proved to be limited successful.
Startup problems were overwon by looking into the theory of designing creatively. An increased
awareness of the importance and fun of generating new ideas resulted in interesting ideas,
presented in chapter 12 and appendix V. The ideas however, found limited application in the
design. Next to generating new ideas, the time which was taken for stepping away from the
problem proved useful in redening design problems. Taking distance and letting problems
settle is something that the individual team members will certainly use in future (design)
projects.

13.2

Recommendations

13.2.1

Design reliability

Experimental work on catalyst complex


More experimental work on the catalyst complex is necessary. Important points for research
are:
Solubility of complex in an organic aqueous mixture as proposed in the design
Kinetic investigation of 1-butanol oxidation in proposed mixture at given temperatures
(higher than experimental) and pressure (lower than experimental)
Catalyst deactivation investigation (optimal conditions to prevent palladium black formation)
Complex stability at higher temperatures
Rate of over oxidation of butanal in proposed mixture
ASPEN model
Model in ASPEN should have the third loop closed. The stream compositions in the ASPEN
model might change a little after the connection of the third recycle loop. This will have
implications for the reactor operation and the design of all other process equipment.
More detailed design
Some parts of the process need to be designed in higher detail to increase the technical reliability
of this report and of the economical analysis:
The heat exchangers should be designed in detail.
92

13.2. RECOMMENDATIONS
C301, C302 and C303 are not fully optimized yet, application of packings should be
investigated. This might further improve economical performance of the process.
The reactor is not ideally mixed in practice. Implications for conversion and by-product
formation should be investigated

13.2.2

Cost reduction

Heat pinch
The process conditions might be tuned in such a way that eective heat pinch is made possible. A more eective heat integration will improve process performance in terms of costs and
environmental burden.
Compressor K202 removal
The elimination of K202 might be possible by increasing pressure delivered by K201. This
increase should compensate for pressure drop over E202, V201 and V202.
Integration of unit operations
C302 and C303 might be integrated in one single distillation column, with a top, side and
bottom stream.
Integration with upstream and downstream processes
The downstream process (in the total process from butane to etriol) might be integrated in this
process, both processes are water based. The upstream process is also water based. It is not
necessary that there is no water in the alcohol feed for this design. The reduction or elimination
of water removal in the upstream process can reduce costs of the etriol nal product.

13.2.3

HES performance

Improved safety analysis on the basis of the reactor F&EI results. From this analysis additional
measures should be proposed to decrease the reactors F&EI.

13.2.4

Creative designing

Stressing the importance of using Mr. Grunwalds theory and syllabus explicitly from the
start of CPD would have prevented start up problems. The team would have then used those
techniques, instead of applying less suitable techniques.
Taking distance from design problems is done to create new ways to look at problems. This
is also done with creative session with the coach and Mr. Grunwald. Another possibility would
be to introduce other people to the teams own design obstacles, for example other CPD teams.
The interaction with other CPD teams and their design problems in daily life on the pastizaal
proved to be interesting. This interest into other projects might be used for new idea generation
for those projects.

93

List of Symbols
residence time [s]
rV reaction rate [mol:l 1:s1]
X conversion of reactant A [-]
v velocity [m:s1]
Ea activation energy [J:mol1]
R universal gas constant [8.314 J:mol 1 :K1]
k rate constant [l1=2 :mol 1=2:s1]
kL mass transfer rate [m:s1]
a interfacial area [m2 :m3]
kLa interfacial mass transfer coecient [s]
[Pd] concentration of catalyst in the reactor [mol=l]
[OH ] concentration of alcohol in the reactor [mol=l]
volumic ow [l=s]
F ow [mol=s]
H Henry coecient [bar]
S solubility [mol=mol]
CL Concentration of oxygen in the liquid phase [mol=m3]
CL Saturated concentration of oxygen in the liquid phase [mol=m3 ]
Q mass transfer rate [mol:s1]
V volume [m3]
d diameter [m]
D diameter [m]
density [g:l1] or [kg:m3]
dynamic viscosity [kg:m1 :s1 ]
95

CPD 3281 - Basis of Design


cinematic viscosity [m2:s]
M molecular weight [g:mol 1]
molar volume [mol:cm3]
surface tension [N:m1]
g gravitational acceleration [9.81 m:s2]
P power consumption [W ]
Np power number [-]
N stirrer speed [s1 ]
viscosity [mNsm2 ]
relative volatility [-]
Subscripts
ol alcohol
A reactant A
al aldehyde
V volumetric
G gas
L liquid
R reactor
S supercial
B bubble
0 inlet
m minimum
in inlet
out outlet
a average
Superscripts

96

Bibliography
[1] P.L.J. Swinkels, PROJECT DESCRIPTION CPD (ST4931) for group CPD-3281, Delft
(2002)
[2] H. Scott Fogler, Elements of Chemical Reaction Engineering, 3 rd edition, Prentice Hall,
Englewood Clis (1999)
[3] G.J. ten Brink, Green Catalytic Oxidations, Thesis TU Delft (2001)
[4] http://wey238ab.ch.iup.edu/olccii/student/butanal.htm, Christina Beach, James King,
and Eric Hopkins, Butyraldehyde, An Executive Summary, found November 2002
[5] http://www.epa.gov/opptintr/chemfact/butyr-fs.txt,U.S.
Environmental
protection
agency, Butyraldehyde Fact Sheet (CAS No. 123-72-8), found December 2002
[6] J.M. Douglas, Conceptual Design of Chemical Processes, McGraww-Hill, New York (1988)
[7] R.H. Perry, D.W. Green, Perrys Chemical Engineers Handbook, McGraww-Hill, New
York (1999)
[8] A. Kubaczka, A. Burghardt , Membrane based solvent extraction in multicomponent systems, Chemical Engineering Science, 53(5), pages 899-917, 1997
[9] http://www.frinton.com/compounds.htm, Frinton Laboratories, Rare organic compounds,
updated recently, found november 2002
[10] C.L. Yaws, Chemical Properties Handbook, McGrawhill, New York (1999)
[11] J.M. Sorensen, W. Arlt, Liquid-liquid equilibrium data collection; binary systems,
Dechema, Frankfurt am Main (1979), page 217
[12] J.M. Sorensen, W. Arlt, Liquid-liquid equilibrium data collection; binary systems,
Dechema, Frankfurt am Main (1979), page 237
[13] J.D. Seader, E.J. Henley, Separation process principles, Wiley, New York (1998)
[14] K. van t Riet, J. Tramper, Basic Bioreactor Design, Marcel Dekker Inc., New York (1991)
[15] Course book Advanced Biotechnological Engineering, Kluyver Lab, TU Delft, 1999
[16] Onken, U., Gmehling, J., Vapor-Liquid Equilibrium Data Collection; aqueous systems
(supplement 2), tables and diagrams of data for binary and multicomponent mixtures up
to moderatepressures, constants of correlation equations, vol. 1, pt. 1b, Dechema, Frankfurt
am main, (1988)
97

CPD 3281 - Basis of Design


[17] Gmehling, J., Onken, U., Arlt, W., Vapor-liquid equilibrium data collection; organic hydroxy compounds: alcohols and phenols, vol. 1, pt. 2 b, DECHEMA, Frankfurt am Main
(1978)
[18] Gmehling, J., Onken, U., Rarey, J.R., Vapor-liquid equilibrium data collection; aldehydes.
Suppl. 1, vol. 1, pt. 3a, DECHEMA, Frankfurt am main (1993)
[19] P. Trambouze,
H.Van Landeghem,
J.P.Wauquier,
Chemical
sign/engineering/operation, Gulf Publishing Company, Houston (1988)

reactors

de-

[20] D. Geldart, Gas Fluidization Technology, Wiley, Chichester (1986), p 13


[21] R. Krishna, S.T. Sie, Strategies for multiphase reactor selection, Chem. Eng. Sc, vol 49,
24A, 4029-4065
[22] Dutch Association of Cost Engineers, DACE-prijzenboekje; kostengegevens t.b.v. ramingen, 17th ed., DACE, Leidschendam (1994)
[23] P.G.T. Fogg, W. Gerrard, Solubility of gases in liquids; a critical evaluation of gas/liquid
systems in theory and practice, Wiley, Chichester, (1991)
[24] L.P.B.M Janssen, M.M.C.G Warmoeskerken, Transport phenomena data companion, 3rd
ed., Delftse Universitaire Pers, Delft (1997)
[25] J.M. Prausnitz, R.N. Lichtenthaler, E.G. de Azevedo, Molecular thermodynamics of uid
phase equilibria, 3rd ed., Prentice Hall, Englewood Clis (1999)
[26] R. Battino, A.L. Cramer, International Union of Pure and Applied Chemistry, solubility
data series, volume 7 oxygen and ozone, Pergamon, Oxford (1981)
[27] R.K. Sinnot, Coulson & Richardsons Chemical Engineering Volume 6, 3 rd ed., Butterworth
Heinemann, Oxford (1999)
[28] J. Grievink, C.P. Luteijn, P.L.J Swinkels, Instruction Manual Conceptual Design, Rev. C.,
TU Delft, (2002)
[29] G.A. Hughmark, power requirements and interfacial area in gas-liquid turbine agitated
systems, Ind.Eng.Chem.Proc.Des.Dev., volume 19, pages 638-641 (1980)
[30] R.J. Lewis, Saxs dangerous properties of industrial materials. Vol. 2, 8th ed., Van Nostrand
Reinhold, New York (1992)
[31] Ullmanns Encyclopedia 2000 Electronic Release, 6 th ed., Wiley (2000)
[32] http://www.dow.com/licensing/what/lowoxo_p.htm, Dow, LP Oxo Low Pressure Oxo
Process Technology, found november 2002
[33] Tassoul, M., Creativiteit, een Delftse benadering?, innovision, TU-Delft, Delft (2001)
[34] T. Kletz, HAZOP and HAZAN, Identifying and Assessing Process Industry Hazards, 3rd
ed., Institution of Chemical Engineers, Rugby, UK (1992)
[35] D.H. Grunwald, Process-conditions for using creativity in design work by fysical-chemical
engineering students, Grunwald Consultants, Amsterdam (1997)
98

BIBLIOGRAPHY
[36] Thomas E. Marlin, Process Control - Designing Processes and Control Systems for Dynamic
Performance, McGraw-Hill, New York (1995)
[37] George Stephanopoulos, Chemical Process Control - An Introduction to Theory and Practice, Prentice Hall, Englewood Clis (1984)
[38] K. Scott, Handbook of Industrial Membranes, 1st edition, Elsevier Advanced Technolgy,
Oxford (1995)
[39] http://webbook.nist.gov, National Institute of Standards and Technology, A gateway to
the data collections of the NIST, July 2001 release 69, found October 2002
[40] AIChE, Dows Fire & Explosion Index Hazard Classication Guide, 7 th ed., AIChE, New
York (1994)
[41] A. Khnle et al (Fraunhofer-gesellschaft zur forderung der angewandten forschung E.V.),
Verfahren zur oxidation von Kohlenwasserstoen unter verwendung von Mikroorganismen,
EP 1149918 A1, 31/10/01, Apll. 01109559.3, 18/04/01
[42] C.I.S. Lesueur et al, Conceptual process design preliminary basis of design Industrial green
catalytic oxidation of 1-butanol in an aqueous solvent, Delft (2002)
[43] http://www.sigmaaldrich.com/, 10-10-2002, searched on tempo
[44] J.R. Ebner, Z. Guo, M.D. Paster, I. Prakash, A. Hershman, L.M. Klein, W.D. McGhee
(Nutrasweet Co.), Process for the preparation of 3,3-dimethylbutanal, WO0102332, 200101-11
[45] www.chemicalmarketreporter.com
[46] Hand-out Course Thermodynamica voor ontwerpers, Production rules expert-system
Conphyde
[47] D. R. Lide, CRC Handbook of chemistry and physics : a ready-reference book of chemical
and physical data, 82nd ed, Boca Raton, CRC Press (2001)

99

A | LP OxoT M Low Pressure Oxo


Process
Butanal is nowadays mainly produced by the oxo-process. The oxo-process is based on catalyzed
hydroformylation of olens with synthesis gas to form aldehydes containing an additional carbon
atom. The most important oxo-process on industrial scale is the Low Pressure Oxo-process
(LPO-process) introduced by Union Carbide. More information can be found on [32]. This
process uses a Rhodium triphenylphosphine homogenous catalyst in a stirred tank reactor. A
schematic overview can be seen in picture A.1.

Figure A.1: Schematic overview of a LPO process [31].


The products of this process with propene as a feedstock will be a mixture of n-butanal
and butanone. Typical process conditions of this process are given in table A.1[31]. Propene
is a product of steam cracking installations which convert nafta or similar feedstocks to lower
alkenes and hydrogen gas.
Table A.1: Process properties LPO process
LPO process
Pressure
15-20 bar
Temperature 85-115 oC
S
high
n/i ratio
92:8
hydrogenation
low

101

B | Literature research
B.1

Initial research

Week one was all about initial research, understanding the project. The substances given in the
problem handout are researched in several sources like Ullmanns encyclopedia, Kurt Othmer
but also in the TU Delft library search engine and the internet. The results for these substances
are showed below:
Vanillin
Preparation by oxidation of isoeugenol not used anymore
Commercially synthesized from Guaiacol
Cinnamaldehyde
Prepared by base-catalyzed condensation of benzaldehyde with acetaldehyde
Leaf aldehyde
Mostly obtained from natural sources
No specic information on production found
Citral/Citronellal
Citronellal is mainly obtained by isolation from essential oil
During the research, some more substances were found or suggested by Dr. Arends or Prof.
Sheldon.
menthol -> menthone
No specic information on production found
4-tert-Butyl--methylhydrocinnamic aldehyde
Trade names: Lilestralis, Lysmeral, Novaeur, Lilial
Application: raw material in fragrance industry
Worldwide production of > 2500 t/y
Price EUR 440/250ml
BASF produces it by hydrogenation instead of oxidation
103

CPD 3281 - Basis of Design


Many patents were found, one describing a complete process
Pentauoropentanoic acid from pentauoropentanol
An improved method for oxidation to the corresponding carboxilic acid is found 1 .
No information on existing processes or applications available
Butanal from butanol
The guest researcher Tamotsu Kodama of the Japanese company Asahi-Kasei is
working on the green catalytic oxidation of alcohols
Asahi-Kasei produces about a million ton butane per year which can be converted
into the higher valued butanal
Butanol can be produced in a biological route, the patent on this will be free within
a few years.[41]
Yearly production of butanal is about 4 million tons per year.

http://pubs.acs.org/journals/oprdfk/article.cgi/oprdfk/1999/3/i05/pdf/op990021h.pdf

104

C | Process options and selection


C.1
C.1.1

Block scheme selection


Option 1, no alcohol separation

For option 1, no separation of the alcohols is needed. The reactant mixture will be fed to the
reaction section. The product stream from the reaction section will be an aqueous mixture of
the 2 dierent alcohols, butanal, butanone, catalyst and some butanoic acid. The nal goal of
the separation section is an aqueous butanal stream low on impurities. Because of the multiple
components present multiple separation steps are needed. Some remarks:
A molar equivalent of water to butanol and butanone must be discharged. This is wastewater, it should be free of catalyst, and minimal amounts of organic components should
be present to prevent production losses.
Water which is not discharged, is recycled. This water must contain all of the catalyst
and may contain alcohol.
The stream exiting the reaction section will contain primarily water.
Water is produced in the reaction, a separation of catalyst from excess water is needed.
The purity of produced butanal must be very high (polymer industry standard).

C.1.2

Option 2, alcohol separation

The raw material mixture of 95% 1- and 5% 2-butanol may be readily separated using distillation. The most obvious advantage is a pure 1-butanol feed is the fact that less components
will be present in the stream exiting the conversion section. This will make purication of the
butanal easier. The stream exiting the reaction section will consist of an aquatic solution of the
1-butanol, butanal, catalyst and maybe some butyric aldehyde. The remarks made for option
1 in paragraph C.1.1 are also valid for option 2.

C.1.3

Comparison option 1 and 2

In making the comparison, it would be best to optimally completely design both processes and
then decide on economical criteria which one is best. Obviously, this is not possible, so a choice
has to be made using some initial feelings, guesses and estimations on how dicult or how easy
some separations will be.
A rst distinction might be made on the minimal amount of separation processes needed.
The determination of the minimum amount of steps needed is based on the amount of components which have to be separated o. In order to get pure butanal this is for option 1: the
water with catalyst (1), the excess water produced in the reaction (2) and the butanone. For
105

CPD 3281 - Basis of Design


option 2: the 2-butanol before the conversion (1), the water is catalyst (2) and the excess water
(3). So for both process a minimum of three theoretical separation steps are needed.
In reality, the options for separation are multitude, so a precise distinction is dicult.
Therefore, a comparison is tried to be made between options 1 and 2 by identifying separation
opportunities, and diculties. These are given in table 2.4 and 2.5.

106

D | Denition of all streams


crossing battery limits
D.1

1-Butanol/2-butanol feedstock

Table D.1 shows the stream properties of the 1-Butanol/2-butanol stream. Transport will be
done with pipelines from other plants on the same site.
Table D.1: Stream properties of the alcohol stream
Stream: 1-Butanol/2-butanol (stream 101) [41]
Notes
1-butanol %mol
95.0 (1) (1) Values taken from Fraunhofer
2-butanol %mol
5.0 (1) institute. See: 2.2
Total
Process conditions & price
C
Temp
Press
bar
Phase
Price
$/ton

D.2

100
40
1.013
L
771.60

(2) price taken from the


Chemical Market Reporter

(2)

Catalyst

The catalyst will be delivered in the components of which it is built up. The palladium acetate
and the ligand will be transported by road to the plant. The catalyst complex will be made at
the plant.

D.2.1

Paladiumacetate

Table D.2 shows the stream properties of the Palladium(II) acetate stream.

D.2.2

Ligand

Table D.3 shows the properties of the ligand. This ligand is very specic, and is not common
sold. the price is very high, but other suppliers can be contacted later.

D.3

Oxygen

Table D.4 shows the stream properties of the oxygen stream. Oxygen will be produced or
delivered from outside battery limits, where it will be produced on-site or supplied.
107

CPD 3281 - Basis of Design

Table D.2: Stream properties of the Palladium catalyst stream


Stream: Palladium(II) acetate catalyst
Notes
Pd(OAc)2 %wt
99.9 (1) (1) Values taken from the Sigma-Aldrich catalogue
impurities %wt
2 (1) (2) Price for low quantity (laboratory amount)
Total
100
Process conditions & price
C
Temp
20
Press
bar
Phase
S
Price
$/25 g
684.65 (2)
Table D.3: Stream properties of the ligand stream
Stream: ligand
Notes
Ligand
%wt
?? (1) (1) Bathocuproinedisulfonic acid,
impurities %wt
?? (1) disodium salt hydrate
Total
100
(2) Price for low quantity (laboratory amount)
Process conditions & price

Temp
C
20
Press
bar
Phase
S
Price
$/g
51.54 (2)

D.4

1-Butanol/2-butanol sidestream

Table D.5 shows the stream properties of the 1-Butanol/2-butanol side stream. Transport will
be done with pipelines from other plants on the same site.

D.5

Water

Table D.6 shows the stream properties of the water stream. Water will come from outside the
battery limits. Water will be in excess on the site, and will be transported by pipe.

D.6

Butanal

Table D.7 shows the stream properties of the butanal product stream. Butanal will be transported via a pipeline through the battery limits.

D.7

Butanoic acid

Table D.8 shows the stream properties of the butanoic acid stream. Butanoic acid will be
transported via a pipeline through the battery limits.

D.8

Exhaust Gasses

Table D.9 shows the stream properties of the exhaust gas stream. Butanoic acid will be transported via a pipeline through the battery limits.
108

D.8. EXHAUST GASSES

Table D.4: Stream properties of the oxygen/air stream


Stream: Oxygen (stream 201)
Notes
Oxygen
%mol
93-99
impurities %mol
1-7
Total
100
Process conditions & price
C
Temp
20
Press
bar
1
Phase
V
Price
$/ton
45
Table D.5: Stream properties of the alcohol stream
Stream: 1-Butanol/2-butanol (stream 105)
Notes
1-butanol %mol
20.0
2-butanol %mol
80.0
Total
Process conditions & price
C
Temp
Press
bar
Phase
Price
$/ton

100
102.5
1.0
L
771.60

Table D.6: Stream properties of the water stream


Stream: Water (stream 319)
Notes
H2 O
%mol
99 (1) (1) Process water
impurities %mol
1
Total
100
Process conditions & price

Temp
C
20
Press
bar
1
Phase
L
Table D.7: Stream properties of the butanal stream
Stream: butanal (stream 314)
Notes
H2O
%mol
0.34
(1) less than 0.01 mol/s 2-butanol
butanal
%mol
0.66
and less than 0.03 mol/s butanone
impurities
traces (1)
Total
100
(2) price taken from the
Process conditions & price
Chemical Market Reporter
C
Temp
53.3
Press
bar
1.3
Phase
L
Price
$/ton
1234.6 (2)
109

CPD 3281 - Basis of Design

Table D.8: Stream properties of the butanoic acid stream


Stream: butanoic acid (stream 318)
Notes
butanoic acid %mol
91.5
(1) This is a guessed value
1-butanol
%mol
8.5
Total
Process conditions & price
C
Temp
Press
bar
Phase
Price
$/ton

100
164.3
1.3
L
1000

(1)

Table D.9: Stream properties of the exhaust gas stream


Stream: Exhaust Gasses (stream 213)
Notes
oxygen %mol
98.6
butanal %mol
1.1
water
%mol
0.4
Total
100
Process conditions & price

Temp
C
40.0
Press
bar
21
Phase
V

110

E | Thermodynamic model
Experimental data for model validation is taken from the Dechema chemistry data series [16],
[17], [18] for binary systems. The chosen thermodynamic model is UNIQUAC. The systems
presented in table E.1 where studied with binary interaction parameters from the mentioned
databases.
Table E.1: Used databanks
mixture
1-butanol/water
butanal/water
1-butanol/2-butanol
1-butanol/butanal

for binairy parameters


Used database
LLE-LIT
VLE-RK
LLE-LIT
VLE-RK

Data from the model together with experimental data is plotted in gures E.1, E.2 and.E.3.

xy diagram water/1-butanol
1
0.9

vapour mole fraction water

0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

liquid mole fraction water

ASPEN+ VLE-LIT

DECHEMA

ASPEN+ VLE-IG

Figure E.1: xy diagram for a water/1-butanol mixture at P = 1.013 bar [16, p. 245-253].
111

CPD 3281 - Basis of Design

xy diagram butanal/water

vapour mole fraction butanal

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

liquid mole fraction butanal


DECHEMA

ASPEN+ VLE-LIT

ASPEN+ USER (Aij and Aji from dechema)

Figure E.2: xy diagram for a butanal/water mixture at P = 1.013 bar [16, p. 212 - 218]

xy diagram 2-butanol/1-butanol`

vapour mole fraction 2-butanol

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

liquid mole fraction 2-butanol


Dechema

ASPEN+ VLE-LIT

Figure E.3: xy diagram for a 2-butanol/1-butanol mixture at P = 1.013 bar [17, p. 150 - 154].

112

F | Thermophysical properties
The following tables present some coecients for correlations on specic thermodynamic and
physical properties. No data on solubility of pure components in water is shown, because of
the multicomponent process we have to model. The dierent components will inuence the
solubility of each other, so solubilities have to be calculated with the use of activity coecients
etc. Data shown was obtained from [10].

F.1

Heat capacities of gaseous pure components

The heat capacity of the pure substances in the gas phase (J/mol K) is calculated with the
following equation. Coecients are found in table F.1.

Cp;gas(J=molK) = A + BT + CT 2 + DT 3 + ET 4

Component
Unit
1-butanol
2-butanol
butanal
butanone
butanoic acid
oxygen
water

Table F.1: Heat capacities for gaseous components


A
B
103C
108D
1011E
8.157
0.41032
-0.22645
6.0372 -0.62802
22.465
0.35134
-0.12858
-1.1931
1.294
64.374
0.064776
0.35143
-35.371
10.082
37.369
0.23045 0.0057387
-8.8168
2.9637
14.368
0.39591
-0.18906 -0.76472
2.0812
29.526 -0.0088999
0.038083
-3.2629 0.88607
33.933 -0.0084186
0.029906
-1.7825 0.36934
113

(F.1)

Tmin
K
200
200
200
200
298
50
100

Tmax
K
2980
1500
1500
1500
1200
1500
1500

CPD 3281 - Basis of Design

Cp (J/mol K)

5.00E+16
0.00E+00
250
-5.00E+16

300

350

400

450

1-butanol
2-butanol
butanal

-1.00E+17

butanone
-1.50E+17

butanoic acid

-2.00E+17

oxygen
water

-2.50E+17
-3.00E+17
T (K)

Figure F.1: Heat capacity of the gaseous pure components as a function of temperature

F.2

Heat capacities of liquid pure components

Cp Values (J/mol K) for liquid components at dierent temperatures can be calculated by


equation F.2. Coecients are found in table F.2.

Cp;liquid = A + BT + CT 2 + DT 3

Component
Unit
1-butanol
2-butanol
butanal
butanone
butanoic acid
water

Table F.2: Heat capacities for


A
B
103C
83.877
0.56628
-1.7208
95.037
0.56593
-1.8256
64.363
0.72566
-2.3548
61.406
0.75324
-2.3814
28.210
0.11040
-2.8523
92.053 -0.039953 -0.21103
114

liquid components
liquid
106 D
Cp;298
J/mol.K
2.2780
160
2.6675
172
3.3065
159.03
3.2240
159.75
2.9528
182.09
0.53469
75.55

(F.2)

Tmin
K
185
159
178
187
269
273

Tmax
K
507
482
473
482
565
615

F.3. VAPOUR PRESSURE OF PURE COMPONENTS

250
200

Cp (J/mol k)

150
1-butanol

100

2-butanol

50

butanal

0
-50270

320

370

420

-100

butanone
butanoic acid
water

-150
-200
-250
T (K)

Figure F.2: Heat capacity of the liquid pure components as a function of temperature

F.3

Vapour pressure of pure components

The coecients mentioned in table F.3 have to be used with equation F.3. The pressure is
expressed in mm Hg.

log10 P = A +

Component
Unit
1-butanol
2-butanol
butanal
butanone
butanoic acid
water

B
+ C log10 T + DT + ET 2
T

Table F.3: Vapour pressure data


A
B
C
39.6673 -4.0017E03
-1.095E01
49.4476 -4.2487E03 -1.3793E01
66.8411 -3.6784E03 -2.2609E01
47.7060 -3.0965E03 -1.5184E01
8.0847 -3.3219E03
2.4312
29.8605 -3.1522E03
-7.3037
115

for pure components


D
E
-3.2572E-10 8.6672E-07
6.2736E-11 2.1988E-06
1.1697E-02 2.9647E-13
7.4846E-03 -1.7084E-13
-1.1734E-02 5.7992E-06
2.4247E-09 1.8090E-06

(F.3)

Tmin
K
183.85
158.45
176.75
186.48
267.95
273.16

Tmax
K
562.93
536.01
525
535.5
628
647.13

CPD 3281 - Basis of Design

1.00E+01

P (bar)

1.00E+00
270
1.00E-01

320

370

420

1-butanol
2-butanol
butanal

1.00E-02

butanone
butanoic acid

1.00E-03

water
1.00E-04
1.00E-05
T (K)

Figure F.3: Vapour pressure of the pure liquids as a function of temperature

F.4

Density of the pure liquid components

The following equation has to be used with the coecients mentioned in table F.4. The density
is expressed in g/ml.

= AB (1 T c )^n

Table F.4: Density data for pure components


Component
A
B
n
Tc
Tmin
unit
K
K
1-butanol
0.26891 0.26674 0.24570 562.93 183.85
2-butanol
0.27343 0.26350 0.26040 536.01 158.45
butanal
0.26623 0.24820 0.28570
525 176.75
butanone
0.26760 0.25140 0.28570
535.5 186.48
butanoic acid 0.31132 0.26192 0.27997
628 267.95
water
0.34710 0.27400 0.28571 647.13 273.16
116

(F.4)

Tmax
K
562.93
536.01
525
535.5
628
647.13

Rho (kg/m3)

F.5. VISCOSITY OF THE PURE COMPONENTS

1100
1050
1000
950
900
850
800
750
700
650
600
270

1-butanol
2-butanol
butanal
butanone
water

320

370

420

T (K)

Figure F.4: Density of the pure liquids as a function of temperature

F.5

Viscosity of the pure components

The results calculated with coecients from table F.5 and equation F.5 are expressed in cP (1
cP = 1 mPa.s).

log10 liq = A +

Component
unit
1-butanol
2-butanol
butanal
butanone
butanoic acid
water

Table
A
-5.3970
-20.6736
-4.6882
-0.8761
-7.9846
-10.2158

B
+ CT + DT 2
T

F.5: Liquid viscosity data for pure components


B
C
D
liquid;298
cP
1.3256E03 6.2223E-03 -5.5062E-06
2.599
3.5493E03 4.0352E-02 -3.0937E-05
3.248
6.8181E02 1.0648E-02 -1.2871E-05
0.426
2.9257E02 -1.9833E-03 9.4354E-07
0.396
1.3636E03 1.6315E-02 -1.4511E-05
1.457
1.7925E03 1.7730E-02 -1.2631E-05
0.911
117

(F.5)

Tmin
K
250
288
275
189
268
273

Tmax
K
563
536
525
536
628
643

CPD 3281 - Basis of Design

eta (cp)

1-butanol
2-butanol

butanal

butanone

butanoic acid
water

1
0
270

320

370

420

T (K)

Figure F.5: Viscosity of the pure liquids as a function of temperature

118

G | PhenS*Pd(OAc)2 solubility
experiments
G.1

Introduction

In the experiments done by Gerd-Jan ten Brink the maximum solubility used is 0.05 mmol per
50 gram of water, or 1 mmol/l. For the conceptual design it is interesting to know if higher
solubilities of catalyst are possible. Next to the complex solubility, the pure ligand solubility
was investigated. This was simply done by trying to dissolve as much as PhenS* as possible.

G.2

Experimental

Three solutions of 10 ml were prepared at 50C: 2x, 6x and 10x the experimental catalyst
concentration. A concentrated solution (10 mmol/l) of ligand solution was prepared with a
concentration of 200 mmol/l of NaOAc (PhenS*:NaOAc = 1:20). The three solutions are given
in table G.1.
The maximum solubility of the ligand was investigated by adding more and more PhenS*
to 5 ml water at 50C. The quantities (g) added are: 0.2835, 0.2789, 0.2796, 0.2744, 0.2854 and
0.2016 (total of 1.6034 g). This is about 0.60 mol/l.

G.3

Results

Dissolving the ligand was very easy. The palladiumacetate dissolved after overnight stirring.
A peak in the UV-VIS spectrum was found for the a solution of PhenS*. The spectrum
is given in appendix 1. A spectrum for only Pd(OAc)2 could not be determined, because it
didnt dissolve. A spectrum for the catalyst complex is given as appendix 2 and for a dierent
concentration as appendix 3. The corresponding concentrations at which these peaks were
determined are given in the appendices.
The maximum solubility test for the ligand did not reached its maximum solubility, but
everything dissolved.

number
1
2
3

Table G.1:
experimental
2
4
10

The catalyst complex solutions


(PdOAc)2 (mg) solution (ml)
5
2
8.8
4
22.7
10
119

H2O (ml)
8
6
0

CPD 3281 - Basis of Design

G.4

Conclusion & discussion

The maximum solubility of catalyst complex which has been veried experimentally is 10 times
the experimental concentration, or 10 mmol/l. For now, this is enough, because higher concentrations might lead to problems in oxygen transfer in reaction conditions and/or heat removal
from the reactor problems.
The maximum ligand concentration which has been veried experimentally is 0.6 mol/l.

120

H | PFS and tables


This appendix contains:
Process Flow Diagram (fold-out)
Process Stream Summary
Process Yields Table
Summary of Utilities

121

CPD 3281 - Basis of Design


A3 size PFS from powerpoint

122

PROCESS STREAM SUMMARY


SECTION 100
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

:
:
MW
74.12
74.12
18.02
72.11
72.11
32.00
88.11

101
IN
Alcohol Feed Mixture
kg/s
mol/s
4.25
57.29
0.22
3.02

Total

4.47

Enthalpy

kW

Phase

L/V/S

Temp

oC

Press.

Bara

SECTION 200
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

60.30

0.95
0.05

Mol Frac
0.95
0.05

1.00

1.00

-19631

Total

102
P101 Discharge
kg/s
4.25
0.22

4.47

mol/s
57.29
3.02

103
C101 Feed
kg/s
4.25
0.22

mol/s
57.29
3.02

4.47

60.30

60.30

-19631

-18938

104
C101 Bottom
kg/s
4.19
0.01

mol/s
56.53
0.07

4.20

56.60

-17159

40.0

40.0

90.0

129.9

1.0

1.3

1.3

1.5

105
C101 Distillate
MW
kg/s
74.12
0.06
74.12
0.22
18.02
72.11
72.11
32.00
88.11

Wt Frac

0.27

OUT
mol/s
0.76
2.94

201
Wt Frac
0.20
0.80

3.70

1.00

Mol Frac
0.20
0.80

Oxygen
kg/s

1.00

IN
mol/s

0.91

28.42

0.91

28.42

202
Hot Feed R201
kg/s
4.19
0.01

4.20

mol/s
56.53
0.07

203
R201 Vapour Dilution
kg/s
mol/s

56.60

0.91

28.42

0.91

28.42

Enthalpy
Phase

kW
L/V/S

-1188
L

-4
V

-17137
V

89
L

Temp

oC

102.5

20.0

131.3

130.0

Press.

Bara

1.0

1.0

21.0

21.0

SECTION 200
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

204
207
208
209
210
Cold Feed R201
Liquid Discharge R201
Top Discharge R201
Condensed Top R201
Liquid Discharge V201
MW
kg/s
mol/s
kg/s
mol/s
kg/s
mol/s
kg/s
mol/s
kg/s
mol/s
74.12
4.19
56.53
3.66
49.34
0.02
0.29
0.02
0.29
0.02
0.29
74.12
0.01
0.07
0.08
1.01
0.00
0.01
0.00
0.01
0.00
0.01
18.02
2.99
165.88
0.06
3.35
0.06
3.35
0.06
3.15
72.11
4.25
59.01
0.16
2.28
0.16
2.28
0.12
1.69
72.11
0.00
0.03
0.00
0.00
0.00
0.00
0.00
0.00
32.00
1.76
55.15
1.76
55.15
0.00
0.15
88.11
1.77
20.12
0.00
0.03
0.00
0.03
0.00
0.03

Total

4.20

Enthalpy
Phase

kW
L/V/S

Temp
Press.
SECTION 200
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

56.60

12.75

-18384
L

-83332.32
L

oC

40.0

Bara

21.0

:
:
MW
74.12
74.12
18.02
72.11
72.11
32.00
88.11

295.39

2.01

61.11

2.01

1.81
-134.85

55.79

0.21

-1555.39
V/L

-1409.80
L

130.0

130.0

40.0

40.0

21.0

21.0

21.0

19.9

212
214
215
301
Oxygen Feed R201
Cooled Liquid Recycle
Vapour Discharge V201
Feed V301
kg/s
mol/s
kg/s
mol/s
kg/s
mol/s
kg/s
0.00
0.01
3.64
49.10
0.00
0.01
3.68
0.00
0.00
0.07
0.97
0.00
0.00
0.08
0.00
0.20
2.04
113.00
0.00
0.20
3.05
0.04
0.58
0.38
5.27
0.04
0.58
4.38
0.00
0.00
0.00
0.01
0.00
0.00
0.00
1.76
55.00
0.00
0.03
1.76
55.00
0.00
0.00
0.00
1.73
19.58
0.00
0.00
1.78

Total

61.11

-1162.65
V

7.85

187.95

-59712.25

1.81
-145.60

55.79

12.96
-84742.11

mol/s
49.63
1.02
169.03
60.70
0.03
0.15
20.15

302
Vapor Discharge V301
kg/s
mol/s
0.31
4.12
0.01
0.12
0.67
37.10
2.05
28.39
0.00
0.01
0.00
0.15
0.03
0.31

300.71

3.06

Enthalpy

kW

Phase

L/V/S

Temp

oC

46.4

40.0

40.0

128.7

83.5

Press.

Bara

21.0

21.0

19.9

19.9

1.0

Figure H.1: Process stream summary


123

5.32

-15877.72

70.20

CPD 3281 - Basis of Design


SECTION 300
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

:
:
MW
74.12
74.12
18.02
72.11
72.11
32.00
88.11

303
304
305
306
Liquid1 Discharge V301
Liquid2 Discharge V301
Heated Feed C301
P301 Discharge
kg/s
mol/s
kg/s
mol/s
kg/s
mol/s
kg/s
3.35
45.25
0.02
0.26
3.35
45.25
0.31
0.07
0.89
0.00
0.01
0.07
0.89
0.01
1.91
106.04
0.47
25.89
1.91
106.04
0.67
2.32
32.13
0.01
0.18
2.32
32.13
2.05
0.00
0.02
0.00
0.00
0.00
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.73
19.59
0.02
0.25
1.73
19.59
0.03

Total

9.37

Enthalpy

kW

Phase

L/V/S

Temp
Press.

oC
Bara

SECTION 300
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

203.92

-61330.95

:
:
MW
74.12
74.12
18.02
72.11
72.11
32.00
88.11

0.52

26.59

9.37

203.92

3.06

308
mol/s
4.12
0.12
37.10
28.39
0.01
0.15
0.31

C301 Top
kg/s

70.20

-7534.41

-55550.38

L/V

83.5
1.0

83.5
1.0

99.0
1.0

254.263891 ???
1.0

88.3
1.0

309
C301 Bottom
kg/s
3.63
0.07
0.70
0.32
0.00
0.00
1.69

mol/s
49.01
1.00
38.85
4.39
0.00
0.00
19.19

6.41

112.44

Total

mol/s
15.20
0.45
104.29
56.13
0.03
0.15
0.70

7.16

176.96

5.68

99.44

77.52

L/V/S

oC

99.1

52.6

53.8

53.8

53.9

Press.

Bara

1.0

1.0

1.0

1.0

1.3

315
Bottom C302
kg/s
1.10
0.03
0.00
0.00
0.00
0.00
0.06

mol/s
14.90
0.44
0.00
0.01
0.00
0.00
0.67

316
Feed C303
kg/s
1.10
0.03
0.00
0.00
0.00
0.00
0.06

mol/s
14.90
0.44
0.00
0.01
0.00
0.00
0.67

1.20

16.02

1.20

16.02

MW
74.12
74.12
18.02
72.11
72.11
32.00
88.11

Total

4.49

Enthalpy

kW

Phase

L/V/S

Temp

oC

Press.

Bara

SECTION 300
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

Wt Frac

83.42

0.00
0.00
0.11
0.89
0.00
0.00
0.00

Mol Frac
0.00
0.00
0.34
0.66
0.00
0.00
0.00

1.00

1.00

-20907.23

:
:
MW
74.12
74.12
18.02
72.11
72.11
32.00
88.11

125.2

125.2

124.5

1.3

1.6

1.6

1.3

mol/s
0.06
0.00
0.00
0.00
0.00
0.00
0.67

kW

Phase

L/V/S

Temp

oC

Press.

Bara

OUT

0.06

0.73

Wt Frac
0.07
0.00
0.00
0.00
0.00
0.00
0.93

Mol Frac
0.08
0.00
0.00
0.00
0.00
0.00
0.92

1.00

1.00

-347.55

319
OUT
Excess Water Discharge
kg/s
mol/s
0.01
0.10
0.00
0.00
0.50
27.85
0.03
0.38
0.00
0.00
0.00
0.01
0.00
0.01

0.54

28.37

Mol Frac
0.00
0.00
0.98
0.01
0.00
0.00
0.00

1.00

1.00

1.13

15.28

7.87
-58340.37

53.8

84.8

1.9

1.0

1.0

124

mol/s
14.84
0.44
0.00
0.01
0.00
0.00
0.00

321
Total Liquid Recycle
kg/s
mol/s
3.67
49.45
0.07
1.01
2.04
113.00
0.38
5.23
0.00
0.01
0.00
0.03
1.72
19.47

164.3

Figure H.2: Process stream summary (continued)

1.10
0.03
0.00
0.00
0.00
0.00
0.00

-4016.75

Wt Frac
0.01
0.00
0.93
0.05
0.00
0.00
0.00

-8031.30

99.44

317
Top C303
kg/s

53.5

mol/s
14.91
0.44
28.18
55.10
0.03
0.11
0.67

-26209.62

-5011.58

Total
Enthalpy

-21948.61

-5011.58

318
Bottom C303
kg/s
0.00
0.00
0.00
0.00
0.00
0.00
0.06

106.76

5.68

Temp

314
OUT
Top C302, Product
kg/s
mol/s
0.00
0.01
0.00
0.00
0.51
28.18
3.97
55.09
0.00
0.03
0.00
0.11
0.00
0.00

-26210.89

1.47

Phase

4.09

311
312
313
Liquid1 Discharge V302
Liquid2 Discharge V302
Feed C302
kg/s
mol/s
kg/s
mol/s
kg/s
1.11
14.91
0.02
0.28
1.11
0.03
0.44
0.00
0.01
0.03
0.51
28.18
1.37
76.11
0.51
3.97
55.10
0.07
1.04
3.97
0.00
0.03
0.00
0.00
0.00
0.00
0.11
0.00
0.04
0.00
0.06
0.67
0.00
0.03
0.06

kW

-48155.76

mol/s
11.08
0.33
67.19
27.75
0.02
0.00
0.39

-24896.82

Enthalpy

SECTION 300
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

-36888.65

310
Liquid Feed V302
kg/s
1.13
0.03
1.88
4.05
0.00
0.00
0.06

-15877.72

0.82
0.02
1.21
2.00
0.00
0.00
0.03

188.19

SECTION 300
STREAM Nr.
Name
COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc

:
:
MW
74.12
74.12
18.02
72.11
72.11
32.00
88.11

322
Hot Liquid Recycle
kg/s
mol/s
3.64
49.10
0.07
0.97
2.04
113.00
0.38
5.27
0.00
0.01
0.00
0.03
1.73
19.58

Total

7.85

324
kg/s

187.95

Enthalpy

kW

-58270.93

Phase

L/V/S

Temp

oC

85.2

53.8

Press.

Bara

1.0

1.0

0.01
0.00
0.87
0.05
0.00
0.00
0.00

mol/s
0.18
0.01
48.26
0.66
0.00
0.03
0.02

0.93

49.15

-13917.31

Figure H.3: Process stream summary (continued)

PROCESS YIELDS

Name
1-Butanol Feed
Butanal Product
2-Butanol Product
Butanoic Acid Product
Waste water
Total

Name
LP Steam
MP Steam
CW
Electricity

Ref.
Stream
<101>
<314>
<105>
<318>
<319>

Ref.
Stream
-

Process Streams
kg/s
t/h
IN
OUT
IN
OUT
4.25
15.3
3.97
14.2
0.218
0.785
0.0589
0.212
0.539
4.25
4.25
15.3
15.8

kg/s

Utilities
kW

0.0266
0.00178
0.954

t/h
26.6
1.78
954

544

Figure H.4: Process yield values


125

kWh/h

t/t butanal
OUT
1.08
1.00
0.0549
0.0148
0.0379
1.08
1.11

IN

t/t butanal kWh /


t
butanal
1.87
0.126
67.2
544
38.3

CPD 3281 - Basis of Design

Figure H.5: Summary of utilities

126

I | Process control method


To achieve a good process control, two steps have to be realized: on the rst hand, a degree of
freedom analysis has to be made and, on the other hand, the control objectives or controlled
variables have to be listed.
A process is dened by a number of variables. These variables are divided into two groups:
input variables, which denotes the eect of the surroundings on the process,
output variables, which denotes the eect of the process on the surroundings.
The input variables are further divided into two groups:
disturbances, if their values are not the result of adjustment by an operator or a control
system,
manipulated variables, if their values can be adjusted freely by the human operator or a
control mechanism.
The output variables are also classied onto the following categories:
measured output variables, if their values are known by directly measuring them,
unmeasured output variables, if they are not or cannot be measured directly.
To choose which variables are worth controlling, the process control guideline is run under
some major categories of control objectives. They are discussed in table I.1 which also provides
explanation on how each inuences the control design.
From the degree of freedom analysis, the number of disturbances and unmeasured variables
has to be counted. This leads to new number of degree of freedom which is also the maximum
allowed number of controlled variables. Care has to be exercised not to specify more control
objectives than the available number of degree of freedom.

127

CPD 3281 - Basis of Design

Table I.1: Control objectives and explanation of their inuence


Control objective
Goal
Action
safety
operate safely at expected tempera- pressure control
tures and pressures
react to major incidents such as equip- emergency system: shut
ment failures or excursions of variables down button
outside of acceptable limits
control the process and the safety in safety valve
case the sensors do not react
environmental protection convert toxic components to benign
material
equipment protection
avoid dicult and expensive replace- same as for safety
ment of the equipment, keep operating
conditions within bounds
smooth operation
prevent disturbances to downstream
units
product quality
match quality expectations such as maintain operating condicomposition, physical properties, per- tions
formance properties
prot
return a prot or provide a product at
low cost

128

J | Balance for stream components

HEAT & MASS BALANCE FOR STREAMS TOTAL


IN
Plant
Mass
kg/s

Heat
kW

3.77E-05 5.91E+02

1.71E-09

6.47E+02
6.93E+02

5.78E+03

1.10E-08

EQUIPMENT
Mass
Heat
Stream
kg/s
kW
Nr.
4.47
-18938 <103>

4.47
9.37
1.13

-18938
-55550
-4017

<305>
<317>

10.51
5.68

-59567
-26210

<313>

5.68
1.20

-5012

<316>

1.20
4.47
4.47
4.20
4.20
2.01
2.01
9.37
9.37
3.06
4.09
7.16
7.85
7.85

-5012
-19631
-19631
-17137
-17137
-1163
-1163
-61331
-61331
-15878
-24897
-40775
-58271
-58271

<101>
<202>
<208>
<303>
<306>
<308>
<322>

EQUIPM.
IDENTIF.
C101
E102
E103
V101
total
C301
E302
V302
total
C302
E305
E306
total
C303
E307
E308
total
E101
total
E201
total
E202
total
E301
total
E303
total
E304
total

Figure J.1:

129

OUT
EQUIPMENT
Stream Mass
Heat
Nr.
kg/s
kW
<104>
4.20
-17159
<105>
0.27
-1188

<308>
<309>

4.47
4.09
6.41

-18347
-24897
-36889

<314>
<315>

10.51
4.49
1.20

-61785
-20907
-5012

<317>
<318>

5.68
1.13
0.06

-5012
-4017
-348

1.20
4.47
4.47
4.20
4.20
2.01
2.01
9.37
9.37
7.16

-4364
-18938
-18938
-18384
-18384
-1555
-1555
-55550
-55550
-48156

7.16
7.85
7.85

-48156
-59712
-59712

<102>
<204>
<209>
<305>
<310>

<214>

Plant
Mass
kg/s

1.00E-05

Heat
kW

2.22E+03

5.01E+03

1.75E-04
4.84E-06
4.84E-06
1.25E+03
3.93E+02

7.38E+03
1.44E+03

CPD 3281 - Basis of Design

9.28E+01
1.08E+01

5.17E-06 2.20E+01

1.27E+00

2.40E-08

3.13E-08

3.00E-04

1.30E-03

3.62E-07

0.00
OUT - IN :

7839

0.91
-4
0.91
-4
1.81
-146
1.81
-146
4.47 n/a
4.47 n/a
4.20
-17159
4.20
-17159
3.06 n/a
3.06 n/a
0.52 n/a
0.52 n/a
7.85
-58271
7.85
-58271
5.68
-26211
5.68
-26211
1.20 n/a
1.20 n/a
4.20
-18384
7.85
-59712
1.81
-135
0.91
89
14.76 -78142.26
1.47 n/a
n/a
1.47 n/a
2.01
-1555
2.01
12.75
0.21
12.96
12.96

-1555
-83332
-1410
-84742
-84742

12.96
0.52
6.41
0.93
7.87
7.16

-84742
-7534
-36889
-13917
-58340
-48156

7.16

-48156

<201>
<215>
<101>
<104>
<302>
<304>
<322>
<311>
<315>
<204>
<214>
<212>
<203>

K201
total
K202
total
P101
total
P201
total
P301
total
P302
total
P305
total
P306
total
P309
total
R201

<312>

total
S301

<209>

total
V201

<207>
<210>
<301>

<307>
<309>
<324>
<310>

total
V202
total
V301

total
V303

total
V304

<203>
<212>
<102>
<202>
<306>
<307>
<323>
<313>
<316>
<207>
<208>

<324>
<319>
<211>
<210>
<301>

<302>
<303>
<304>
<321>

<311>
<312>

total

0.91
0.91
1.81
1.81
4.47
4.47
4.20
4.20
3.06
3.06
0.52
0.52
7.85
7.85
5.68
5.68
1.20
1.20
12.75
2.01

89
89
-135
-135
n/a
n/a

4.84E-06
-17137
-17137

n/a
n/a
n/a
n/a
-58340
-58340
-26210
-26210

Figure J.2:

130

6.94E+01

n/a
n/a
-83332
-1163

14.76
0.93
0.54
1.47
1.81
0.21
2.01
12.96

-84494.96
n/a
n/a
n/a
-146
-1410
-1555
-84742

12.96
3.06
9.37
0.52
12.96
7.87

-84742
-15878
-61331
-7534
-84743
-58340

7.87
5.68
1.47
7.16

-58340
-26211
-21949
-48159

Total

Project ID Number :
Completion Date
:

3.28E-07

8.70E-09

6.35E+03

3.10E-08

9.72E-08

6.50E-03

6.19E-06

9.70E-01

3.73E+00

0.00
0.00
CPD3281
December 20th 2002

24119
16280

Stream Nr.

COMP
1BUTANOL
2BUTANOL
WATER
BUTANAL
BUTANONE
O2
ACID
NaOAc
Total
Enthalpy

kW

Overall Component Mass Balance & Stream Heat balance


<101>
IN
<105>
OUT
<201>
<314>
<318>
<319>
Total Plant
Total Plant
Total Plant
MW
kg/s
mol/s
kg/s
mol/s
kg/s
74.12
4.25
57.29
0.07
0.93
-4.18
74.12
0.22
3.02
0.22
2.95
0.00
18.02
1.01
56.03
1.01
72.11
4.00
55.47
4.00
72.11
0.00
0.03
0.00
32.00
0.91
28.42
0.00
0.12
-0.91
88.11
0.06
0.68
0.06

5.38
-19635

88.72

Figure J.3:

131

5.36
-30474

116.21

-0.02
-10839

OUT-IN

-56.35
-0.07
56.03
55.47
0.03
-28.30
0.68

0.0000

K | Ternary diagrams reactor


system
This appendix presents the ternary diagrams at various temperatures for the reactor composition. These diagrams (the dierent lines in gure K.1) are used in the optimization of reactor
conditions.

Figure K.1: Ternary diagram for water/1-butanol/butanal, at various temperatures

133

L | Cooling equipment design


The reactor has to be cooled, because of the exothermic reaction taking place. The reaction
produces 8.9 MW of heat. After heating up feed streams (oxygen, butanol, water) the remaining
energy to remove is 6.3 MW. This heat has to be transported by a jacket and/or a coil immersed
in the reactor. First the capacity of a cooling Jacket was designed.
The general equation used for heat transport is
(L.1)

Q = UA(Tr Tcw )

A is dened by reactor geometry and is 53 m2 : The temperature dierence over the jacket
is chosen maximal. T r = 303 K and T cw = 293 K. For calculation of the overall heat transfer
coecient the values for uid lm and dirt coecients should be known. The general equations
for the heat transfer coecient is given in equation [27, p. 635]L.2.

do
d
ln
o
1
1
1
di do 1
do 1
=
+
+
+
(L.2)
U
ho hod
2
di hi di hid
To calculate the liquid lm heat transfer coecient correlations Nusselt equations have to
be used. from the Nusselt number heat transfer coecients can be calculated with equation
L.3. These equations are chosen according to the ow, which depends on reactor geometry
and operation. Calculations for coils is dierent from calculations for jacketed vessels. Nusselt
numbers can be calculated in the jacket by taking equations for forced convection in conduits.
Nu =

h
d

(L.3)

The used Nusselt equations for reactor design are:


For at blade disc turbine, ba-ed vessel, transfer to wall Re >400
Nu = 0:74Re0:67 Pr 0:33

wall

0:14

(L.4)

0:14

(L.5)

0:14

(L.6)

For at blade disc turbine, at blades, transfer to coil in a ba-ed vessel, 2000<Re<700,000
0:62

Nu = 1:10 Re

Pr

0:33

wall

Forced ow in conduits for non viscous liquids


Nu = 0:023Re

0:8

Pr

0:33

For turbulent ow in pipes, Re>10,000, Pr>0.7


135

wall

CPD 3281 - Basis of Design

Nu = 0:027Re

0:8

Pr

0:33

wall

0:14

(L.7)

The logarithmic temperature for the reactor cooling system was calculated by equation L.8.
dT m =

Tcw;in Tcw;out

cw;out
ln TTRRT
Tcw;in

(L.8)

The Prandtl number of the liquid was obtained by equation L.9.


Cp

The reynolds number for a stirred tank is calculate by equation L.10.


Pr =

Re =

2
Dstirrer
N

(L.9)

(L.10)

Data on viscosity for the mixture was taken from the ASPEN+ simulation. Data for cooling
water was obtained from [24]. The data is presented in table L.1.
Table L.1: Physical properties of reactor mixture (303 K) and cooling water (averaged)
Property
Mixture Cooling water
[W=mK]
0.146
0.69
Cp [kJ=kgK]
4940
4200
[Pa s]
2.2E-4
3.6E-4
[kg=m3]
749
971
To be able to calculate surface area of the coils and jacket the geometry of the heat exchange
equipment should be known. We stated some relations for the reactor geometry. Relation L.11
for coil tube diameter, L.12 for diameter of coil pack 1, L.13 for the diameter of coil pack 2. The
relation for the coil pitch was obtained from [27] and is given in L.14. We used a dierent pitch,
relation L.15 for the second coil to be sure that ow in the reactor would not be inuenced
too much. The coil is placed 0.45 m above the bottom of the reactor. The coil should not be
attached to the bottom because of negative eects on the ow which will decrease heat transfer
and mixing.
Dcoil tube =

Dreactor
60

(L.11)

Dcoilpack1 = 0:9Dreactor

(L.12)

Dcoilpack2 = 0:75Dreactor

(L.13)

Lpitch;coilpack1 = 2D coiltube

(L.14)

Lpitch;coilpack2 = 1:5Dcoiltube

(L.15)

Hcoilbottom = 0:45m
136

L.1. SYMBOLS USED


Assumed is that the reader is familiar with equations to calculate length, surface area and
the cross sectional area of tubes and other elementary equations.
Input for the calculations and results are presented in table
Table L.2: Input and results of heat exchange calculations
Value
Unit
Input
Dreactor
3
[m]
Treactor
403
K
Tcw;in
293
K
Tcw;out
393
K
Dreactor with jacket
3.6
m
Hreactor
6
m
Wjacketbaf fle
0.2
m
Hjacketbaf fle
0.3
m
Thickness coil
1E-3
m
Results
vcw;jacket
0.5
m/s
vcw;coils
5.1
m/s
Nujacket;eactorside
4.84E4 Nujacket;jacketside
6.50E2 Nucoilpack1;reactorside 3.26E4 Nucoilpack1;cw side
1.39E3 Nucoilpack2;reactorside 3.26E4 Nucoilpack2;cw side
1.39E3 With these results the factors which are expressed in equations L.1 and L.2 can be calculated.
Results are presented in table
The total capacity for heat transfer will be
Q = (Ujacket Ajacket + Ucoil Acoil1 + Ucoil Acoil2) dTm
Q = (361 56:5 + 1310 51:3 + 1310 54:2)42 = 6:66MW
The coils provide the largest heat transfer capacity (90%).
A schematic drawing of the reactor is shown in gure 8.6.

L.1
L.1.1

Symbols used
regular

A Area, m2
Cp Specic heat capacity, J=kgK
D Diameter, m
dT m Logarithmic temperature dierence, K
h heat transfer coecient, W=m2 K
137

CPD 3281 - Basis of Design

Table L.3: Calculated values for heat transfer calculations


Property
Value Unit
Jacket
hjacket;cw side
1.50E3 W/m2K
hjacket;reactorside
2.35E3 W/m2K
f ouling coef ficient 1.00E5 W/m2K
Ujacket
3.61E2 W/m2K
Ajacket
56.5
m2
dTm
42
K
Coilpacks
hcoilpacks;reactorside
1.58E3 W/m2K
hcoilpacks;cwside
1.92E4 W/m2K
f ouling coef ficient 1.00E5 W/m2K
Ucoils
1.31E3 W/m2K
Acoil1
51.3
m2
Acoil2
54.2
m2
dTm
42
K
Nu Nusselt number, dimensionless
P r Prandtl number, dimensionless
Re Reynolds number, dimensionless
T Temperature, K
U Overall heat transfer coecient, W=m2K

L.1.2

Greek

Heat conductivity coecient, W=m2K


Dynamic viscosity, Pa:s
Density, kg=m3

L.1.3

Subscripts

cw Cooling water
i Inside
id Inside dirt
in Ingoing
o Outside
od Outgoing dirt
out Outgoing
r reactor
138

M | Mass transfer of oxygen


references:[14, chapter 11][15][19]

M.1

Introduction

In pure systems bubbles are mobile which means that water is owing downwards along the
bubble interface, only restricted by its own surface tension, the need to accelerate sideways and
viscous forces within the liquid itself. The gas phase inside is in complete circular motion.
When the system is not completely pure, the bubble surface will be more sensitive towards
impurities. These impurities will make the interface rigid, and the bubble behaves as a solid
particle. The water ow will be inuenced by a boundary layer on the bubble. For mobile
bubbles penetration theory can be used. For rigid bubbles mass transfer behavior as for solid
particles is applied. The resistance to mass transfer due to boundary layer, low diusivity etc.
is expressed in the kL-value.
Equation M.1 is the general used equation for mass transfer calculations.
Q = kL a(CL CL)

(M.1)

Table M.1 presents some data concerning mass transfer [19, page 251].
Table M.1: orders of magnitude of mass transfer parameters for a bubble column
liquid holdup [%] gas holdup [%] kL [m=s]
interfacial area a [m1 ]
bubble column > 70
2 30
104 5 104 100 500
stirred vessel
> 70
2 30
104 6 104 200 2000
Typical bubble diameter in bubble columns is around 6 mm whereas it is around 3-4 mm in
stirred vessels. Improvement of the kL can be achieved by turbulence, ow (mobile interface)
or fresh surface area. By redispersing (perforated plates) coalesced bubbles fresh surface area
can be generated which has a good transfer rate for a short time because of non equilibrium.

M.2

Transfer coecient value kL

A large amount of correlations is available to calculate kL values in pure systems. In our case,
the liquid consists of a mixture with mainly water, 1-butanol and aldehyde which makes the
calculations much more complicated because no data is available for this specic mixture, and
only few data (solubility of oxygen, oxygen diusion coecients) for the pure components.
When data is available for the pure components, the temperature range is too small.
To estimate the mass transfer for the boundary layer around spheres, Sherwood [24, page
76] developed a correlation:
139

CPD 3281 - Basis of Design

with

Sh = 2:0 + 0:66 Re 2 Sc 3 valid for 1 < Re < 10 4, Sc > 0:7


Sh =

kL dB
d

, Re = SG B L , Sc = L
D
L
LD

(M.2)
(M.3)

The diusion constant is needed for each temperature study and calculated from the Wilke
and Chang correlation (1955) [?]:
D02 ;

H2O

= 7:4 108

T (xH2O MH2 O)0:5


O2; H2O VO0:6
2

(M.4)

Only diusivity of oxygen in water is used for kL value calculations because no data for
1-butanol and butanal is known. Equation M.4 can be used to calculate diusion coecients
where D02 ;H2 O is the diusion constant of oxygen in water, T is the temperature , xH2O is
the association factor of water (xH2O = 2:6), O2 ; H2 O is the dynamic viscosity of the mixture,
assumed to be the same as for pure water since the oxygen is diluted in water, VO2 is the
molecular volume of oxygen (cm3:mol 1).
Table M.2 presents the results for the temperature range from 100C to 150 C.
Table M.2:
T
C
100
110
120
130
140
150

M.3

liquid lm transfer coecient versus temperature


D02; H2O
Re
Sc Sh kL
105 cm2 :s1 m:s1
6.01
722
49 67 6.68 10 5
6.82
787
39 65 7.37 10 5
7.67
851
32 63 8.08 10 5
8.55
912
27 62 8.79 10 5
9.47
971
23 60 9.50 10 5
10.41
1026 19 59 1.02 10 4

Interfacial area

The interfacial area can be calculated when the gas volume fraction is known since it is also
dened as:
VG
(M.5)
VG + VL
From the latter equation, the following equation for the interfacial area can be derived:
"G =

a=

6"G
dvs (1 "G)

(M.6)

where dvs is the volume surface mean bubble diameter or Sauter mean diameter.

M.3.1

Bubble column

Values of gas holdup are preferably determined for a given gas-liquid system in a laboratory
reactor of sucient diameter DR > 0:15 m. For bubble columns, some correlations were developed. For a relatively slow liquid-phase reaction, a homogenous gas liquid ow regime should
be used, which implies thereby that the gas velocity is limited at 0.04 m=s according to the
140

M.3. INTERFACIAL AREA


Krishna and Sie method [21, page 4060]. For aqueous systems with gas velocities lower than
5 cm=s, Hughmark developed a simple correlation to calculate the gas hold up [19, page 254]:
"G =
Where UG is the gas velocity in cm=s.
This leads to:

G
30 + 2 G

"G = 0:105

(M.7)

(M.8)

in accordance with the order of magnitude of mass transfer parameters given in a table
above.
Bubbles are subject to a complex process on creation, expansion, dispersing and coalescence.
Equilibrium size depends on power input, and is about 6 mm in bubble columns and 3-4 mm in
stirred vessels. Coalescence towards equilibrium diameter is completed already at 1 or 2 meters
above the sparger. In non coalescing media this is dierent. Power input will not increase
surface area in non coalescing media. Equilibrium bubble diameter will be dB 6 mm. In
non-coalescing media the diameter will be smaller ( 3-4 mm.). A relation known as the Sauter
ratio exists between dB and dvs . For spherical or almost spherical bubbles, this ration is almost
equal to 1 [?] so that:

which leads to an interfacial area of:

dB dvs

(M.9)

a = 117 m1

M.3.2

Stirred unit

A stirred unit has some benets compared to the bubble column. A stirred unit will have
a smaller equilibrium bubble diameter, a smaller boundary layer around the bubble, better
mixing etc. Some disadvantages of the stirred unit are the power consumption of the stirrer,
the combination of a stirrer with a pressurized vessel will result in more expensive reactor
lay-out.
A 6 at blade turbine stirrer is used for the design. This is recommended by [14, page
306][19, page 556].

M.3.3

kLa value inuencing factors

The kL a value is given as the product of the liquid lm transfer coecient value and the
interfacial area. It is equal to:
kLa = 0:0353 s1

(M.10)

The factors which inuence the kLa value for oxygen transfer are: pressure, temperature
and and lumpfactors[15, table 2].
=

(kLa)actual
(kLa)standard

(M.11)

(c L)actual
(c L)standard

(M.12)

(note: a factor of = 1:8 is taken.)


=

141

CPD 3281 - Basis of Design

tc 20
ktLc a = k20
L a

(M.13)

The following types of additives inuence the before mentioned factors:


salts (increase surface tension, positive at fairly large concentration)
alcohols (lowering surface tension, positive at (very) small concentrations)
detergents (lowering surface tension, eective at very small concentrations)
oily substances (forming an extra layer at surface at very small concentrations)
Alcohols behave as surfactants and absorb to the interfacial area and may increase resistance
to mass transfer and small bubbles will become rigid. More important is the reduction of the
mobility of the surface. This will reduce rippling, and will inuence the mass transfer coecient.
When surfactants are added, the water becomes full non coalescent. At an ion strength of about
0.4 mol/L for octanol or sodium lauryl sulphate only a few mg/L will suce. Because of the
high butanol concentration (~1 mol/L) rigid bubbles will probably be present in our reactor
system. The alcohols have low inuence on viscosity, so probably no coalescence due to higher
viscosity will occur (coalescence from captured bubbles in big bubble wakes). Surfactants will
prevent coalescence of small bubbles. High viscosity (>20 mPa.s) will enhance coalescence of
bubbles.
Temperature inuence on kL is due to the inuence of temperature on diusion coecient
and both will increase. The increase of the mass transfer will be about 2.4% per oC:The negative
eect of lower oxygen solubility will decrease the mass transfer by 2.5 %. So temperature has
no eect on mass transfer because both eects cancel each other out.
Pressure has dual inuence. It increases solubility, but several mass transfer equations are
pressure dependent (interfacial area, gas ow rate, gas hold-up, bubble size,coalescence rate)
leading to gradients in well mixed reactors. This necessitates the use of characteristic values for
gas ow rates and solubility in case of reactors of more than 1 metre height. The use of half
liquid height value is of sucient accuracy.
Gas volume and reactor volume
The denition of the gas holdup and the knowledge of the liquid volume yield to the gas volume
and thus to the reactor volume.
VG =

VL "G
1 "G

Vreactor = Vliquid + Vgaz


Oxygen solubility
Oxygen solubility is inuenced by increasing oxygen pressure.

142

(M.14)
(M.15)

N | Solubility of gasses in liquids


The pressure in the reactor is directly connected to the amount of oxygen which has to be
dissolved in the reactor (half of the produced aldehyde quantity) for the reaction via the Henry
constant.

N.1

Oxygen solubility

From the oxygen transfer rate (equation N.1) for oxygen from gas to liquid, one can estimate
the maximum solubility of oxygen in the liquid in the reactor and then determine the needed
pressure.
OT R = kL a (CL CL ) =

FO2
VR

(N.1)

In this equation, it can be noticed that the smaller the volume, the bigger OTR is. Thus the
trade o between decreasing volume and increasing pressure when the temperature increases.
It has been assumed that the oxygen transfer is not reaction limiting but with a view to
simplifying the calculations, it can be considered that a kind of equilibrium is reached. In other
words, CL can be approximated by 0.
The maximum solubility of oxygen in the solution can be estimated in equation N.2 and
lead to the calculation of the needed pressure.
OT R
kL a

(N.2)

CL
total molar f low out

(N.3)

CL =

From this value of CL , one can calculate the maximum solubility in terms of molar composition, which nally provides the pressure according to the equation N.4.
x =

PO2 = Hmixture xL

(N.4)

where PO2 is the pressure, Hmixture the Henry constant of oxygen in the mixture and xL
the maximum wanted solubility of oxygen in the mixture. PO2 is the minimum pressure that
needs to be applied to dissolve the necessary amount of oxygen required for the reaction.

N.2

Henry constant

No real equation are available to calculate the Henry constant in a mixture. Nevertheless, a
rule of thumb given in equation N.5 exists and is reliable enough to provide workable Henry
values.
143

CPD 3281 - Basis of Design

Hmixture =

X
xi Hpure

(N.5)

where Hmixture is the Henry value of oxygen in the mixture, xi is the molar composition
and Hpure i is the Henry constant of oxygen in pure liquids. Remark has to be done that for
this calculation, the considered pure components are water, butanol and butanal since they are
the major ones and the concentration of the other ones is hardly signicant.
[25] is a good basis to rely on when it comes to correlations for the dissolution of oxygen in
pure liquids. The equations from N.6 to N.8 are listed to be the ones utilized for the pressure
in the reactor estimation.
L
fpure
1
=
x2
f 2G

exp(

2 2
L
Hpure
2 ( 1 2 ) 1
)=
RT
f2G

(N.6)

where 1 refers to the pure solvent and 2 to the solute, f is the fugacity, L
2 is the liquid
volume of oxygen [cm3:mol1 ], is the solubility parameter ([J:cm3 ]1=2) and 1 is the volume
fraction of solvent. L
2 and 2 are only functions of the solute and can be found in the literature[?,
page 607]. For oxygen, these values are respectively 33.0 cm3:mol 1 and 8.18 [J:cm3] 1=2
at 25 C. 1 can be assumed to be equal to 1 due to the fact that there is few oxygen in
L
water and fpure
2 is obtained from a graph available in [25, page 608], dependant only on the
critical temperature and pressure of the solute and on the temperature. Therefore, the quantity
2 2

L
2 ( 1 2 ) 1 is not temperature dependant which implies that 1 can be calculated at 25 C.
Remains 1 which is characteristic of the solvent and calculated with equation N.7.
1 =

vapU

1=2
1

vapH RT

1=2

(N.7)

where vap U is the molar internal energy of vaporization of the solvent, vapH its enthalpy
of vaporization and its molar volume.
The Henry constant value can now be obtained by means of equation N.6 as provided in
equation N.8.
2 2
L
2 ( 1 2 ) 1
)
(N.8)
RT
Equation N.8 can only be used for non polar systems. No other equation for estimating henry
coecients is available. Therefore results from calculations were compared with experimental
data. We found a constant factor between calculated and experimental data over a temperature
range for water and 1-butanol. We assumed that butanal was low polar and no corrections
had to be carried out. The factors between calculated values and experimental data [26] are
presented in O.
L
Hpure 2 = f pure
2 exp(

144

O | Henry constant in pure liquids


This chapter presents the calculations of the Henry constant of oxygen in pure liquids.

O.1

Henry constant of oxygen in water

There is no need to use the Appendix N to estimate the Henry constant of oxygen in water since
a lot of data are available for this solvent. [26, page 3] provides the Henry constant for oxygen
in pure water for a large temperature range. Table O.1 gives these data for the considered
temperatures.
Table O.1: Henry constant of oxygen in pure water
T ( C) Hwater 2 (bar)
100
7.14104
110
7.05104
120
6.86104
130
6.59104
140
6.28104
150
5.93104

O.2

Henry constant of oxygen in butanol

For butanal, the Henry constants are calculated with the method described in Appendix N and
compared to the values in the literature [26, page 264]. Table O.2 supplies the calculated data
for the considered temperatures.
Table O.2: Henry constant of oxygen in pure butanol
T (C) Hbu tan ol 2 (bar)
100
3.8810 2
110
3.8510 2
120
3.8210 2
130
3.8010 2
140
3.7810 2
150
3.7610 2
The comparison with the literature is made at 50 C and is presented in table O.3.
A facotr of 3.27 exists between the calculated and the experimental data at 50 C. This
ratio is assumed to be constant and used to recalculate the Henry constant at the dierent
temperatures. The gap between calculations and experiments is due to the fact that the polarity
145

CPD 3281 - Basis of Design

Table O.3: Henry constant of oxygen


T ( C) Hbu tan ol 2 (bar)
calculation
50
4.04102

in pure butanol comparison


H bu tan ol 2 (bar)
literature
1.32103

of the butanol is not taken into account in the calculation method. Table O.4 presents the Henry
constants used for the calculation of the pressure.
Table O.4: Henry constant of oxygen in pure butanol used to calculate the reactor pressure
T (C) Hbu tan ol 2 (bar)
100
1.27103
110
1.26103
120
1.25103
130
1.24103
140
1.24103
150
1.23103

O.3

Henry constant of oxygen in butanal

For butanal, no experimental data are available. Nevertheless, as butanal is less polar than
butanol and the correction ratio for butanol rather small, assumption is that the calculated
data have a good order of magnitude accuracy. Table O.5 presents the Henry constants of
oxygen in butanal.
Table O.5: Henry constant of oxygen in pure butanal
T (C) Hbu tan ol 2 (bar)
100
3.47102
110
3.46102
120
3.45102
130
3.43102
140
3.42102
150
3.41102

146

P | Pre-reactor separation
Before being fed to the reactor, the 2-butanol should be removed from the 1-butanol. This is
done by distillation. The calculation for a trayed and a packed column is shown below.

P.1

Trayed column

P.1.1

Minimum reux ratio and number of stages

Using the DSTWU shortcut distillation model in Aspen, the minimum number of theoretical
stages is calculated together with the minimum reux ratio. Nmin is 13.36 and Rmin is 15.14.
A Reux Ratio prole is generated also. In this prole, the reux ratio is calculated for a range
of theoretical stages. A shortcut for an optimum N/R combination is that N*(R+1) should be
minimized. Figure P.1 shows this relationship. The optimum amount of stages is found to be
25 with a reux ratio of 18.18.

1050

N*(R+1)

950
850
750
650
550
450
10

15

20

25

30

35

40

45

Figure P.1: N*(R+1) versus N, optimum number of stages according to shortcut

P.1.2

RadFrac model

The RadFrac model in Aspen is a more elaborate model for a distillation column. The values
found with the DSTWU model lled in the RadFrac model did not produce the required purity
147

CPD 3281 - Basis of Design


of the bottom stream. The numbers were adjusted, obeying the N*(R+1) rule and now, N =
27 and the reux ratio R = 26.34.

P.1.3

Column eciency

The column eciency is calculated with the OConnell correlation [27, page 549].

EO = 51 32:5log(a a )

(P.1)

where the average molar liquid viscosity a = 0:383 cP and the average relative volatility a =
1:91 [-]. The overall eciency is 55.3%. The real number of stages is calculated by substracting
the theoretical number of trays with 1 and dividing it by the eciency ratio (=%/100). The
plate spacing is stated 0.5 m as a rst estimate according to [27, page 556].

P.2
P.2.1

Packed column
Packing design

The shortcut column design tool is used to calculate the number of trays, the reux ratio,
vapour and liquid loads in the sections. The optimum reux ratio-number of trays is based
on minimization of N*(R+1). The entered relative volatility is the average over the column as
calculated with aspen and is 1.86. This is valid because the relative volatility in the system
diers only slightly. SULPAK uses the common Underwood, Fenske, Gilliland and Smoker
equations for calculation of the number of stages and the reux ratio. Chosen is to use the
Mellapak 250Y type because this is the most common type and very versatile. The physical
parameters like density, viscosity and surface tension are taken from aspen also. The width of
the column is varied in order to come close to a capacity of 80% of both sections. The width
of the columns inuences the ow factor because a wider column results is a smaller vapour
load and therefore in a lower capacity. A smaller column will drop the eciency of the packing.
Finally, the sheet shown in gure P.2 was lled in. The result is a top bed of 1.8 meter diameter
and 3.36 meter high and a bottom bed of 1.9 meter diameter and 5.67 meter high. The height
from bottom of the bottom bed to the top of the top bed including some extra space for the
feed is about 10 meter. On top of both beds is a distributor placed to distribute the liquid
equally over the bed.
148

P.2. PACKED COLUMN

Figure P.2: SULPAK input parameters and results for calculation on packing for the 1butanol/1-butanol separation tower

149

Q | Stirrer design
The most widely applied method to introduce power into a vessel is the application of a stirrer.
The types range from standard propellers and turbines to exotic types like rods and sieves. It
has been decided to use a 6 at blade turbine stirrer in the design since this stirrer has the
higher power number, whose property is to directly inuence the mixing eciency.

Q.1

Geometric parameters

A drawing of the reactor with the stirrers conguration is given in gure Q.1. For a turbine
stirrer, the geometrical conditions are given in the table Q.1. Ba-es will be used because their
presence helps to increase the specic energy input and avoids the formation of a vortex.

Tv

Di

Hv
w

Hsb

Figure Q.1: Drawing of a multiple turbine stirrer tank


The reactor volume is limited on the ground of physical considerations. In accordance with
dierent authors, the maximum size for a mechanically stirred reactor varies from 10 to 20 m3
151

CPD 3281 - Basis of Design

Table Q.1: geometrical parameters for a turbine stirrer tank


geometric parameter
symbol calculation
tank diameter
Tv
VL = 14 Tv2Hv = 12 T3v
Hv
tank height
Hv
Tv = 2
Tv
stirrer diameter
D
D = 3:33
Hsb
space between 2 stirrers Hsb
D =1
D
stirrer blade width
Di
w =4
D
stirrer blade height
w
w =5
[19, page 270] to up to 50 m3 [29, page 638], which leads to the equation Q.1. This number is
rounded to the closest integer, which provides a new reactor volume quoted VL in the following.
Nreactor =

VL
Vmax

(Q.1)

The number of stirrers, which can create complicates in the power consumption calculation
when there are 2 or more of them, has also to be calculated. As a rule of thumb [14, pages
306 and 308], the interaction with other stirrers or with the vessel bottom can be neglected as
long as the distance between 2 stirrers or between the stirrer and the vessel bottom exceeds the
stirrer diameter, which results in the equation Q.2. The result is rounded to the closest smaller
integer and the distance between 2 stirrers or between one stirrer and the vessel bottom can be
recalculated.
Nstirrer =

Q.2
Q.2.1

Hv
1
D

(Q.2)

Power consumption
Single liquid phase system

The determination of the stirrer power consumption is an important part of the design since the
mixing and thus the mass transfer are dependant on this number. The stirrer power consumption
is dened as:
1
PS = pLv 2
2

(Q.3)

where p is the pumping capacity of the stirrer [m3:s1] and v the velocity of the outowing
liquid [m:s1].
For an axially pumping stirrer and a radially pumping stirrer, the equations Q.4 and Q.5
are valid, which in all but any case lead to the equation Q.6 taking for granted the equation
Q.7 .
1
p = D2 v
4
p = DHS v

(Q.4)
(Q.5)

where D is the stirrer diameter [m] and H S is the height of the stirrer blade [m].
PS = Np LN 3D 5

(Q.6)

HS = cD

(Q.7)

152

Q.3. MASS TRANSFER PARAMETERS


where c is a constant depending on the stirrer used.
The power number is a function of the Reynolds number (dened in equation Q.8) and
usually predicted from graphs [24, page 87].
ND2 L
L

Re =

(Q.8)

It has to be noted that at low Reynolds, that is to say under laminar conditions, Np is a
function of Re only. For fully turbulent conditions the measured N p value for any stirrer type
in a ba-ed vessel is a constant.

Q.2.2

Two-phase stirred system

For the prediction of the power consumption, the presence of air is a major complication. It has
been found that the introduction of an average density of the two-phase system in equation Q.6
does not predict PS in these systems at all. The reason is that the hydrodynamic phenomena
around the stirrer blades change with the presence of air. Hughmark [29] has correlated a
large number of data for turbine stirrers including a relation between the power consumption in
unaerated and aerated mixture. However, his analysis is limited to systems in which the power
input is provided by mechanical agitation with a minimum contribution from gas sparging,
which is not the case in the developed design. For the systems where air sparging also plays a
major role, Bruyn et al (1974) show that large, gas-lled cavities originate behind the stirrer
blades. These decrease the hydrodynamic resistance of the blades and therewith the Np value
down to 0.3 to 0.5 times the unearated value. The average value of 0.4 is considered. Therefore,
the gassed power consumption can be dened:
PSG = 0:4 PS

Q.3
Q.3.1

(Q.9)

Mass transfer parameters


Gas holdup

[19, page 267] gives a correlation for the gas holdup in stirred reactors for pure liquids (equation
).
2=3 3 1=6
[N Nm ] D 2
SG
L
" = 0:31 L
+
0:45

g4L
Tv (gTv )1=2

(Q.10)

Stirrer speed
The stirrer speed is calculated from the tip speed via equation Q.11.
N=

v
D

(Q.11)

where N is the stirrer speed [s1 ] and v the tip speed [m:s1]. [19, page 556] recommends
a minimum tip speed of 4 m:s1.
153

CPD 3281 - Basis of Design


Minimum stirrer speed
The minimum stirrer speed or minimum number of revolutions is calculated from the equation
Q.12 developed by Westerterp [19, page 266].

NmD 2 L
Tv

L 3
g 4L

where for a turbine A = 1.22 and B = 1.25.

Q.3.2

1=4

=A

D
+B
Tv

(Q.12)

Interfacial area

The interfacial area is calculated from the Raith equation, Q.13 [19, page 267].
n
Pt
a= K
with 0.65 < n < 0.7
VL

(Q.13)

where for an aqueous system K = 4 and Pt is dened as the total power dissipated in the
reactor. It is expressed as the sum of the power dissipated by stirring, calculated in equation
Q.9, and of the power dissipated by air sparging given in equation Q.14 [19, page 258] .
PA
= SG L g
VL

154

(Q.14)

R | Equipment summary &


specication sheets
The following pages contain the equipment summary sheets and the equipment specication
sheets.

155

CPD 3281 - Basis of Design


RCV1

156

RCV2

157

CPD 3281 - Basis of Design


RCV3

158

PBC

159

CPD 3281 - Basis of Design


C101

160

R201

161

CPD 3281 - Basis of Design


V201

162

C301

163

CPD 3281 - Basis of Design


C302

164

C303

165

CPD 3281 - Basis of Design


V304

166

S | HAZOP study on reactor


Tables S.1 to S.6 contain the recognized hazards of operating the reactor. The following paragraph show proposed start-up and shut-down procedures for use with HAZOP study.

S.1
S.1.1

Start-up and shut-down procedures


Start-up procedure

The start-up procedure is proposed to be as follows:


The reactor is pressurized and lled with N2.
The reactor is lled with water of 130C and 20 bar.
The oxygen supply is started and released via 4.
When all N2 is gone, the 1-butanol supply is started and stream 3 is also started.

S.1.2

Shut-down procedure

The shut-down procedure is proposed to be as follows:


The alcohol supply is stopped, water keeps owing
The oxygen supply is stopped when all alcohol is reacted away
The reactor is emptied when the aldehyde concentration is negligible
The stirrer is stopped and N2 is introduced before the reactor is opened

167

CPD 3281 - Basis of Design

Property
NONE
ow 1

Hazard

Table S.1: HAZOP study, guide word NONE


Possible measure

ow 2

Iliquid level lowers ! more headspace !


more possible exposive mixture
Iliquid level below output level ! oxygen in
downstream processes
Iless resistance for stirrer ! strirrer running
too fast ! overheated stirrer
Ireactor composition changes
Ilower hydrostatic head ! pressure in 4 increases
IPalladium black will be formed

ow 3

Ilower conversion ! more alcohol in outlet


Ipressure in reactor drops ! more HCs in
vapour ! poss. entering explosion range
Ioverow of reactor

ow 4

Iliquid in vapour system ! defect compressors


Ipressure increases
Iorganic composition changes
Ihigher pressure

no stirring
no reaction

Imore headspace
Ivapour composition changes ! poss. entering explosion range
Istirring of air ! overheated stirrer motor
Ilower residence time ! lower conversion
Imore ow through 3
Ilower A value (of kL A) ! less reaction !
see above
Ioxygen soluted in 3 ! downstream problems
Imore alcohol in 3
Iow of 3 decreases (less water produced)
Iamount of HCs increases ! more HCs in
vapour ! poss. entering explosion range

168

low level alarm with valve control on 1 and 3


low level alarm with valve control on 1 and 3
stirrer
speed/temperature
alarm/control
low level alarm with O2 supply
control
low ow alarm. may not happen!
composition control.
ush
with O2 or N2
low level alarm with valve control on 1 and 3

low ow alarm.
pressure take o

emergency

low speed alarm ow control of


1,2,3 & 4
close 3, keep aerating (palladium black)
composition control.
with O2 or N2

ush

S.1. START-UP AND SHUT-DOWN PROCEDURES

Property
MORE
OF
pressure

Table S.2: HAZOP study, guide word MORE OF


Hazard
Possible measure

Imore oxygen ! more conversion


Imore oxygen in vapour ! opp. of entering
explosion range
Imore water produced ! lower HC fraction
Ihigher ow through 3 and 4
Iliquid level rises
temperature Ihigher rate of reaction/less oxygen transfer
! palladium black formation
Ihigher vapour pressure of HC ! composition of vapour changes ! poss. entering explosion range
Ipossibly coming near boiling pressure of
HCs
stirring
Ilower A ! better oxygen transfer
Ipossibility of cavitation
Ivortex ! overow of reactor ! liquid in
vapour system

Property
LESS OF
pressure

composition control.
with O2 or N2

ush

cooling by lower feed temperature


composition control.
ush
with O2 or N2

stirrer
speed/temperature
alarm/control

Table S.3: HAZOP study, guide word LESS OF


Hazard
Possible measure

Ilower oxygen transfer ! same reacation rate


! palladium black formation
IHC composition of vapour increases ! explosion limits?
Ievaporation of HCs and lower conversion !
lower temperature
temperature IO2 in outlet ! overoxidation in downstream
processing
Ilower vapour pressure ! less HCs in vapour
! explosion limits?
Ilower rate of reaction ! more alcohol in outlet
stirring
Ilower A ! lower conversion

169

cooling by lower feed temperature


composition control.
ush
with O2 or N2
decrease 2
composition control.
with O2 or N2

ush

CPD 3281 - Basis of Design

Property
PART OF
alcohol
drops

catalyst
drops
water drops

2-butanol
increase

Table S.4: HAZOP study, guide word PART OF


Hazard
Possible measure
Ilower rate of reaction ! lower oxygen consumption ! oxygen in 3 !
Ihigher ow through 4 or higher pressure
organic fraction decreases ! lower vapour
pressure ! poss. entering explosion range
Isee alcohol drops

composition control

Iphase split ! overoxidation


Isettling of catalyst ! lower rate of reaction
Iless oxygen dilluted ! lower rate of reaction
Iless cooling capacity ! temperature increase ! palladium black formation
Ilower volume ! more vapour (explosion
danger)/strirring air (over heating of motor)
Imore butanone

composition control

composition control.
with O2 or N2

ush

Iless conversion towards butanal

Table S.5: HAZOP study, guide word MORE THAN


Property
Hazard
Possible measure
MORE THAN
impurities in O2 INeed a bigger bleed samples of oxygen !
Ihigher pressure
appr. measures

Property
OTHER
THAN
Start-up
Shut-down

Table S.6: HAZOP study, guide word MORE THAN


Hazard
Possible measure

IValve fails, over pressure in reactor


IMechanical danger when stirrer is not
stopped before opening
IOxygen poisoning when reactor volume is
not ushed with N2 before opening
Plant ser- IFor steam, electricity and O2 supply failure,
vices failure see points in other tables
Maintenance IExplosion hazard
IMechanical danger when stirrer is not
stopped before opening

170

Pressure relieve
Install alarm if stirrer is on
Install gas analyzer

Flush with N2, use ex-proof


tools
Install alarm if stirrer is on

T | Dow Fire & Explosion Index


sheets
This appendix contains the Dow Fire & Explosion Index Sheets for all equipment. Table T.1
shows the Degree of hazard according to the Dow Fire & Explosion Index for every equipment.

Table T.1: Degree of hazard according to the Dow Fire & Explosion Index for every equipment
Equipment No. Figure F&EI index Degree of Hazard
C101
T.1
35 Light
E101
T.2
35 Light
P101
T.3
29 Light
E201
T.4
45 Light
E202
T.5
54 Light
K201
T.6
2 Light
K202
T.7
2 Light
P201
T.8
42 Light
R201
T.9
129 Intermediate
C301
T.10
46 Light
C302
T.11
53 Light
C303
T.12
27 Light
E303
T.13
42 Light
E304
T.14
54 Light
P305
T.15
30 Light
V301
T.16
46 Light
V304
T.17
46 Light

171

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

C101
1-butanol, 2-butanol
14-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

1-butanol
16.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.25
1.25
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.00
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.1: Dow Fire and Explosion Index sheet for equipment C101

172

0.55
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.75
2.19
35.00

Process Unit
Materials
Date
Reviewed by

E101
1-butanol, 2-butanol
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

1-butanol
16.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.20
1.20
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.30
0.00
0.00
0.18
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.2: Dow Fire and Explosion Index sheet for equipment E101

173

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.83
2.20
35.14

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

P101
1-butanol, 2-butanol
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

1-butanol
16.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.30
0.00
0.00
0.18
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.3: Dow Fire and Explosion Index sheet for equipment P101

174

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.83
1.83
29.28

Process Unit
Materials
Date
Reviewed by

E201
1-butanol, 2-butanol
19-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

1-butanol
24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.52
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.4: Dow Fire and Explosion Index sheet for equipment E201

175

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.87
1.87
44.88

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

E202
O2, water, butanal, 1-butanol, Butanoic acid, 2-butanol, butanone
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

butanal
24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.60
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.52
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.5: Dow Fire and Explosion Index sheet for equipment E202

176

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2.27
2.27
54.48

Process Unit
Materials
Date
Reviewed by

K201
O2
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

O2
1.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.52
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.6: Dow Fire and Explosion Index sheet for equipment K201

177

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.50
2.22
2.22
2.22

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

K202
O2
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

O2
1.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.52
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.7: Dow Fire and Explosion Index sheet for equipment K202

178

0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.72
1.72
1.72

Process Unit
Materials
Date
Reviewed by

P201
1-butanol, 2-butanol
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

1-butanol
16.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.20
1.20
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.30
0.00
0.00
0.54

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.8: Dow Fire and Explosion Index sheet for equipment P201

179

0.00
0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2.19
2.63
42.05

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

R201
Butanal, 1-butanol, 2-butanol, water, catalyst
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

butanal

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.50
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.25
1.75
1.00
0.20 to 0.80
0.50

1.00
0.60
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.30
0.00
0.00
0.52
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.9: Dow Fire and Explosion Index sheet for equipment R201

180

0.65
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3.07
5.37
128.94

Process Unit
Materials
Date
Reviewed by

C301
water, 1-butanol, butanal, butanoic acid, butanone, 2-butanol
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

butanal
24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.60
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.15
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.10: Dow Fire and Explosion Index sheet for equipment C301

181

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.90
1.90
45.60

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

C302
butanal, 1-butanol, 2-butanol, butanoic acid, butanone, water
19-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

butanal
24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.25
1.25
1.00
0.20 to 0.80
0.50

1.00
0.60
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.00
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.11: Dow Fire and Explosion Index sheet for equipment C302

182

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.75
2.19
52.50

Process Unit
Materials
Date
Reviewed by

C303
1-butanol, 2-butanol, butanoic acid, butanone
19-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

1-butanol
16.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.25
1.25
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.00
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.12: Dow Fire and Explosion Index sheet for equipment C303

183

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.35
1.69
27.00

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

E303
water, butanal, 1-butanol, Butanoic acid, 2-butanol, butanone
19-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

butanal
24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.60
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.00
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.13: Dow Fire and Explosion Index sheet for equipment E303

184

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.75
1.75
42.00

Process Unit
Materials
Date
Reviewed by

E304
O2, water, butanal, 1-butanol, Butanoic acid, 2-butanol, butanone, catalyst
19-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

butanal
24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.60
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.52
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.14: Dow Fire and Explosion Index sheet for equipment E304

185

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2.27
2.27
54.48

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

P305
Water, 1-butanol, catalyst
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

1-butanol
16.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.20
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.52
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.15: Dow Fire and Explosion Index sheet for equipment P305

186

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.87
1.87
29.92

Process Unit
Materials
Date
Reviewed by

V301
1-butanol, butanal, water, 2-butanol, butanone, butanoic acid, catalyst
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

butanal
24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.60
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.15
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.16: Dow Fire and Explosion Index sheet for equipment V301

187

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.90
1.90
45.60

CPD 3281 - Basis of Design

Process Unit
Materials
Date
Reviewed by

V304
1-butanol, butanal, water, 2-butanol, butanone, butanoic acid
16-12-2002
Sander Balkenende

Basic Material
Material Factor (MF)
1. General Process Hazards

Base Factor
A. Exothermic chemical reaction
B. Endothermic process
C. Material handling and transfer
D. Enclosed or Indoor Proces Unit
E. Access
F. Drainage and Spill control
General Process Hazards Factor (F1)
2. Special Process Hazards
Base Factor
A. Toxic Material(s)
B. Sub-Atmospheric Pressure (< 500mm Hg)
C. Operation in or near flammable Range
1. Tank Farms Storage Flammable Liquids
2. Process Upset or Purge Failure
3. Always in Flammable range
D. Dust Explosion
E. Pressure
F. Low Temperature
G. Quantity of Flammable/Unstable material
1. Liquids or Gases in Process
2. Liquids or Gases in Storage
3. Combustible Solids in Storage, Dust in Process
H. Corrosion and Erosion
I. Leakage - Joints and Packing
J. Use of Fired Equipment
K. Hot Oil Heat Exchange System
L. Rotating Equipment
Special Process Hazards Factor (F2)
Process Unit Hazards Factor (F1 x F2) = F3
Fire and Explosion Index (F3 x MF) = F&EI

butanal
24.00
Penalty
Penalty
Factor Range Factor
Used
1.00
1.00
0.30 to 1.25
0.00
0.20 to 0.40
0.00
0.25 to 1.05
0.00
0.25 to 0.90
0.00
0.20 to 0.35
0.00
0.25 to 0.50
0.00
1.00
1.00
0.20 to 0.80
0.50

1.00
0.60
0.00

0.50
0.30
0.80
0.25 to 2.00

0.00
0.00
0.00
0.00
0.15
0.00

0.20 to 0.30

0.10 to 0.75
0.10 to 1.50
0.15 to 1.15
0.50

Figure T.17: Dow Fire and Explosion Index sheet for equipment V304

188

0.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.90
1.90
45.60

U | Purchased equipment costs


U.1
U.1.1

Section 100: 1-butanol/2-butanol separation


Column shell and internals

The column diameter is about 2 meter and the height of the packing plus inlet is 10 meter. Extra
space at top and bottom is guessed 3 meter. From [27, page 255, g. 6.5b], a raw equipment
cost of $40.000 is found. The material and pressure factors are both 1 so the investment for the
shell is $40.000. The packing of the column needs an investment of about $110.000 (see 8.2.1).

U.1.2

Reboiler

The reboiler adds heat to the liquid to evaporate it. The temperature of the liquid is 117.7 C
and the heat duty is 4.57MW. Medium pressure superheated steam (10 bar) is used because
the condensation temperature of LP steam (3 bar) diers only 16C from the stream to be
heated. Besides that, the equipment will be larger with a lower temperature dierence. The
reduced temperature of the liquid is calculated with the critical temperature of 1-butanol since
the liquid contains only 0.1% of 2-butanol. Tr = 0.70. The mean temperature dierence is the
dierence between the condensation temperature of the steam and the boiling temperature of
the liquid. This is 180 - 117.7 = 62.3C. Reading from [27, page 740, g 12.59] yields a heat
ux of about 60 kW/m2. Dividing the heat duty by the ux yields the area: A = 74 m 2.
From [27, page 253, g 6.3b], the equipment cost is read: $22.000 for a carbon steel/carbonsteel
heat exchanger. The pressure factor is 1 and the type factor is 0.8 for a xed tube sheet. This
yields an investment of $17.600.

U.1.3

Condenser

The condenser will be aligned horizontal with condensation in the shell because dierent streams
can then be used as a cooling medium. The incoming stream of the distillation column can be
partly heated through this condenser.

U.1.4

V101

V101: L = 4 m, D = 1 m, P = 1.013 bar, MF = 1.0. Cost = $6500 (1998)

U.2
U.2.1

Section 200: reaction section


Oxygen compressor

The feed of oxygen is 0.93 kg/s or about 2587 m3=h at inlet conditions. The pressure needed
is relatively high, therefore a centrifugal compressor is selected[27, page 475]. In ASPEN a
multistage compressor, six stages, is modeled. The nett work required in the model is 419 kW.
189

CPD 3281 - Basis of Design


From [27, page 258, table 6.2] with the characteristic size parameter (S, the required work of
419 kW in this case) the cost constant (C = $960) and the index for the type of equipment (n
= 0.8) is read. The purchased equipment costs (Ce) are calculated using[27, page 252]:
Ce = C S n

(U.1)

The purchased equipment costs for the fresh oxygen compressor are $120,000. This doubles
because of a spare compressor.

U.2.2

Reactor with agitator

The bare costs for the vessel only are $12,000[27, page 255, g. 6.5b], material factor of 2.0
(stainless steel) and a pressure factor of 1.4 (20 - 30 bar). This results in a purchased costs of
$56,000. The costs for the agitator is calculated with equation U.1. The work required (the
characteristic size parameter) is about 50 kW. The cost constant is 6100 (turbine stirrer[27,
page 258, table 6.2]), the index is 0.5. Purchase cost for the agitator will be $44,000.

U.2.3

Oxygen recycle compressor

A centrifugal compressor is selected[27, page 475]. In ASPEN a compressor is modeled. The


nett work required in the model is 11 kW. From [27, page 258, table 6.2] with the characteristic
size parameter (S, the required work of 11 kW in this case) the cost constant (C = $960) and
the index for the type of equipment (n = 0.8) is read. The purchased equipment costs (Ce) are
calculated using[27, page 252]:
Ce = C S n
(U.2)
The purchased equipment costs for the fresh oxygen compressor are $7000. This doubles
because of a spare compressor.

U.2.4

Feed pump

U.2.5

Liquid recycle pump

U.2.6

V202

V202: L = 1 m, D = 0.45, P = 20 bar, MF = 2.0. Cost = $ 9,600

U.3
U.3.1

Section 300: separation section


C301

C301: L = 27 m, D = 0.83 m, P = 1 bar, MF = 2.0. Cost shell = $50,000


N = 55, Sieve, MF = 1.7. Cost per plate: $ 500

U.3.2

C302

C302: L = 32.5 m, D = 2.0 m, P = 1.3, MF = 2.0. Cost shell = $ 200,000


N = 65, Sieve, MF = 1.7. Cost per plate: $ 1200

U.3.3

C303

C301: L = 47.5 m, D = 0.81 m, P = 1, MF = 2.0. Cost shell= $ 160,000


N = 95, Sieve, MF = 1.7. Cost per plate: $ 500
190

U.3. SECTION 300: SEPARATION SECTION

U.3.4

V302

V302: L = 1.5 m, D = 0.7 m, P = 1.013 bar, MF = 2.0. Cost = $ 6,000

U.3.5

V303

V303: L = 4 m, D = 1 m, P = 1 bar, MF = 2.0. Cost = $ 18,000

U.3.6

V305

V305: L = 3 m, D = 1.2 m, P = 1.3 bar, MF = 2.0. Cost = $ 10,000

U.3.7

V306

V306: L = 2 m, D = 0.8 m, P = 1.3 bar, MF = 2.0. Cost = $ 6,000

191

V | Creativity tools and results


V.1

Creative technique inventory

An inventory of creative techniques was made to have a clear overview on possible methods.
With this inventory the most suitable technique for the problem which had to be tackled could
be chosen. The inventory is shown in V.1.

Table V.1: Creativity methods


Type of technique
Method
Inventorying techniques
mind-mapping
Associative techniques
brainstorming
brain-writing
brain-drawing
Provocative techniques
break through presuppositions
provocative questions
absurdistic problem statement
provocative splitting
Confrontative techniques
lateral thinking + random stimulus
synectics
Intuitive techniques
5 senses focus
guided fantasy
Combined techniques & procedures MATEC

V.2

Literature research (8/10/02)

Results from the brainstorm session are presented in table V.2.

V.3

Matec (25/10/02)

In order to cope with the solubility of oxygen in water, we used The MATEC (MATrice
dEloignement Creatif)[33]. The MATEC procedure can be described as:
state the problem.
underline some characteristic words.
make a chain of associations of ve words for every word.
193

CPD 3281 - Basis of Design

Table V.2: coming out of the brainstorm session


green oxidation, water soluble catalysts, air sparging, dirty processes, chromium
salts, aldehyde economics & production, existing reactor type, DMSO, what is done
with the waste, alcohol economics & production, carboxilic acids, separation, pretreatment, Wacker oxidation, aldehydes in medicine industry, fragrances & avours,
known alcohols by oxidation methods (Dess Martin, Swern, PCC, etc)
where? Internet: google search, companies, internet databases, links via organizations, ejournals, environmental organizations, e-encyclopedias, European and American
patents
Library: encyclopedia, books, Wageningen library, Leiden library, journals & magazines, biotechnology library, chemical abstracts
Personal acquaintance: Sijbes old friends, Dr.Arendscontacts (Diosynth, IFF,
Avantium), Mr.Van Beek at Intervet, Celines professors, Mr.Kodama at the Organics Department
what?

For every one of these words, make ve associations, but you should be able to draw these
associations. Put results in a matrix.
The facilitator chooses two words from the matrices which are completely dierent from
each other (nothing in common at rst sight)
Write these two words on a piece of paper
Find similarities between these two words, common aspects, connections
Come back the problem and try to reect the similarities on it
We stated the problem as there is not enough oxygen in the water phase. The two words
on which we focused were water and oxygen. Two matrices emanated from oxygen and water.
Table V.3 and the table V.4.
Table V.3: Matrix with chain associations from oxygen
air
bird
airplane
cloud
rain
lung
sky
kerosene
milk
ground
smoking atmosphere distillation column cow
greenhouse
stack
moon
reactor
grass
tomato
plume
ag
balance
Friesland
pasta
pollution mountain
bridge
ice skating boiling water

Table V.4: Matrix with


ship
steam
harbour
table
Sinterklaas chair
present
TV
paper
dust
wood
vacuum cleaner

chain associations from water


Newton apple
computer
beard
tree
CD
soup
leaf
money
balls
branch
limousine
cow
catapult
driver
spot
broken window hat
194

V.4. GRUNWALD SESSION (7/11/02)


The facilitator, Mrs. Arends, decided to choose pasta and cow to use for the forced-t
for our problem. Table 12.2 shows the bisociations of oxygen and water and the results of
forced-t to solve the problem of enhancing the oxygen content in water.

V.4

Grunwald Session (7/11/02)

During the creative session of the team with Mr. D. Grunwald and Mrs. I. Arends the following
procedure was used.
- Close your eyes, think of the main technical obstacle we have at the moment.
- Propose a solution for one problem which is completely opposite to the existing solution.
Work out this solution.
- Discuss the results in a positive way, dont let diculties stand in the way.
- Discuss what you felt during the session.
- Feed back on how this method has worked, if the result was satisfying
During this session the following ideas emerged for opposite design of a large reactor.

V.4.1

Innite amount of small reactors

The residence time is smaller and the conversion as well but since there is an innite number of
reactors, the conversion in the outlet of the last reactor can approach 100% that is to say that
we dont have to care anymore of the alcohol recycling and the modeling of the equation is far
more easy.

V.4.2

Doughnut shaped reactor

To arrive at the idea of a doughnut shaped reactor, some other ideas were generated rst:
Small reactor !small apparatus !low residence time !no reaction
Pancake reactor ! short residence time/high volume ! no reaction
Multiple reactors controlled residence time/volume. What is advantage?
Doughnut reactor
Innite recycle
multiple in- and outlets
no dead catalyst volume
evaporate aldehyde and water in-situ
Why moving? Concentration control/less inputs needed
Why circular and not a vessel? ..
CSTR like behavior in plug ow
Low catalyst hold-up (highest catalyst eciency/no dead volume)
195

CPD 3281 - Basis of Design

1-butanol
butanal

butanal

1-butanol

butanal

1-butanol

Figure V.1:
Opposites:
- small reactor
- 2 big reactors
-inverted phases
-gaseous instead of liquid
smaller reactor:
increase catalyst concentration ! not possible max. solubility reached ! change ligands
! not possible ligands are dened.
increase activity ! not possible? ! catalyst dened ! circumstances ! P and T !
increase T ! two limitations: O2 solubility and ligand stability ! action: investigate !
more water per reactor volume ! this is already done, no organic layer exists volume
of gas in reactor should be minimized keeping the oxygen transfer in mind
solubility alcohol should be maximal at all times ! what is the maximum solubility and
how can it be inuenced? ! not so P and T depended ! hydrophobic tail, decrease eect of
hydrophilicity by shielding this tail using surface, surfactant, micelles, wat/org interphase at
micro scale ! or, on the other hand, make water itself more hydrophobic...

V.4.3

Flexible reactor

Dynamic space time


Advantages of a exible reactor are that by for instance increasing the owrate from the
recycle the volume of the reactor can be modied to keep the needed residence time.
Pump
This exible reactor can also be used as a pump to empty the reactor. By forcing the exible
reactor wall back, pressure is increased and the reactor content can be pushed out of the reactor.
196

V.5. BUTANOIC ACID REMOVAL


Material
Material to construct a reactor with is maybe some sort of rubber. Rubber bilge like socks
are used between pipes to compensate the expansion and shrinkage of pipes due to heat eects.
Maybe an elastic material like this can be strong enough to handle 30 bar. A material which
is capable of resisting high pressures and continuous expansion and contraction is very hard to
nd probably. Maybe the expanding properties can be facilitated in a dierent way.
Hourglass
By building a hourglass type of reactor, pressure dierences in the reactor will occur due
to dierent liquid velocities. A lower pressure will be present in the middle of the hour glass,
which maybe can be used for separating aldehyde, or can be used to create smaller bubbles.
Tangential input
Maybe tangential input of feedstream into the reactor can have a positive eect on separation
of oxygen solubility. The hydrodynamic ow is something like ow in a cyclone.

V.5

Butanoic acid removal

The butanoic acid removal proved to be a problem in the product separation. Because the acid
is at least partly in ionic form, as the catalyst complex is, it is dicult to separate it from the
catalyst. After sitting down with the group to discuss the problem, the important dierence
between the acid and catalyst complex came to light: their charge. The complex is 2+, the
acid in its ionic form is 1-. With this fact in mind the thought of using this charge dierence
in electrodialysis with ionic selective membranes came up. The principle is illustrated in gure
V.2. The conguration shown is a creative variation on the principle found in [38, page 10,
gure 4e].
The feed enters in the middle. The eld created by the positively and negatively charged
plated attracts the dierent ions present in the feed. The complex (1) is taken through a anionic
selective membrane (B) and enters the complex solution. The charge of the complex is made
up for by acetate ions (3) diuse through the cationic selective membrane (A). The negatively
charged acid and acetate ions diuse through the cationic selective membrane (A), entering the
acid solution. Their charged is made up with the H+ atoms from the ion make up solution
diusing through the anionic selective membrane (B). Because the ion make up solutions on
both sides are connected this solution is neutral in total as well.
The only problem with this principle is the separation between the acetate and acid which
is necessary to be able to re-supply the acetate for the ion make up again.

197

CPD 3281 - Basis of Design

Figure V.2: Dialysis for acid / catalyst separation.

198