PROCESS ENGINEERING

Preliminary Decision-Making

ALVARO ORJUELA

Before we start.
Minimum information
Reactions and reaction conditions
Production rate
Desired purity, price vs. purity
Raw materials, price vs. purity
Rate of reactions, rate of deactivation
Any process constrains
Plant and site data
PhysicalPhysical-chemical properties of all components
Information on safety, toxicity, environmental impact
Cost data (byproducts, equipment, utilities)
Other

Before we start.
Reaction information
Stoichiometry of all reactions
Range of temperatures and pressures
Phase of the reactive system
Product distribution vs. conversion, kinetic models,
reaction temperature, molar ratio and/or pressure
Conversion vs. residence time
Information about the catalysts (homogeneous, slurry,
packed bed, powder)
Regenerability and process to do so

Hierarchy of decisions
1. Batch vs. Continuous
2. InputInput-output structure of flowsheet
3. Recycle structure of flowsheet
4. General structure of separation systems
a. Vapor recovery system
b. Liquid separation system
5. Heat Exchanger Network

Decision-making in Process Synthesis

LEVELLEVEL-1 Batch vs. Continuous
Continuous operates 24/7 and only is shut down for
maintenance
Batch are design to start and stop operations
frequently, and several cycles are observed: loading,
processing, draining, cleaning, and rere-conditioning
There are continuous steps in batch processes and
vice versa
Distinction may be fuzzy
fuzzy deactivation of catalysts,
adsorbents saturation, cakecake-building in filters

Decision-making in Process Synthesis

Batch Characteristics
Economical for small scale
Easily adaptable from used equipment
Flexible adapting different product formulations
Flexible in changing production rate (# of batches)
Multiproduct multiprocess equipment
Best for cleaning and sterilization
Easy to scale up form lab scale
Product are identified by batch number
BatchBatch-toto-batch differences

Decision-making in Process Synthesis

LEVELLEVEL-1 Batch vs. Continuous
Production rates 10x106 lb/yr are usually continuous,
while 1x106 lb/yr are usually batch. Batch are more
flexible for multimulti-product
Market forces seasonal products (storage space and
costs), lifelife-time of products (colors, fibers, fragrances,
etc)
Operational problems slow reactions (batch),
pumping difficulties (slurry), fouling materials
Multiple operations in the same vessel multipurpose
equipment saving idle and transfer times.

Decision-making in Process Synthesis

LEVELLEVEL-2 InputInput-Output Structure
Should we purify feed streams before they enter the
process?
Should we remove or recycle a reversible byproduct?
Should we use a gas recycle and purge streams?
Should we recover and recycle reactants?
How many product streams will there be?
What are the design variables for the inputinput-output
structure, what is the economic tradetrade-off?

Decision-making in Process Synthesis

Purification
Purification of feeds No certain decisions can be made
because the separation system has not been designed. How
ever there are some guidelines:
If feed impurity is not inert and present in significant quantities
quantities
Remove it
If feed impurity is in gas phase Process it
If feed impurity is a byproduct of the process Evaluate
feeding in the separation system
If feed impurity is in large concentration Remove it
If feed impurity is an azeotrope Process it
If feed impurity is and inert and more easily removed from
products Process it
If feed impurity is catalyst poison Remove it

Decision-making in Process Synthesis

Recycle and recovery of reversible byproducts
Economic tradetrade-off Byproduct recycling will oversize
equipment (accumulation) but will decrease raw material
consumption
Gas recycle and purge
If light
light reactant contains either a light
light feed impurity or a
light
light byby-product Use gas recycle and purge
Light Boiling point lower than propylene ((-48 C)
Light will require compression and refrigerants ($$$). It is
usually cheaper to lose some reactant in the purge than purify
it and recycle it as pure component

Decision-making in Process Synthesis

Recycle and recovery of some reactants?
Design specification for valuable materials 99% recovery
Air and water are usually cheap, so we can use excess and
no recovery. Pollution and waste treatment? (trade(trade-off)
Be certain that byby-products and inerts leave the system!!!
Number of streams (vapor(vapor-liquid, single product) never
separate streams and later mix them together
List all components leaving the process
Classify components and give a destination
Order components by normal boiling points
Group neighboring components with the same destination
Outlet streams are the number of groups (not considering
recycling streams)

Destination code and component

classification
Destination Code
Vent
Recycle and Purge
Recycle
Excess-vent
Excess-waste
Primary product
Valuable by-product
Fuel
Waste

Component Classification
Gaseous by-product and feed impurity
Gaseous reactant + inert gases and/or
gaseous byproducts
Reactant, intermediates, azeotropes with
reactants?, reversible by-products?
Gaseous reactant not recovered and recycled
Liquid reactant not recovered and recycled
Primary product
Separate destination for different by-products
By-product to fuels
By-product to waste treatment

Decision-making in Process Synthesis

Design variables
Degrees of freedom to define the problem: molar ratio,
conversionconversion-selectivity, temperature, pressure, reactants not
recovered or gas recycle and purge (when excess)
Overall Material Balance
Develop expression depending on design variables
Start with the given product rate
Calculate inlet raw material
Calculate byby-products and its impurities
Limitations
Assumption of complete recovery of reactants
No heuristic for design variables

Practice
HydroHydro-dede-alkylation of Toluene HDA Process
S=

H2

CH4
x=

Moles of Benzene in reactor outlet

Moles of Toluene converted in reactor

Moles of Toluene converted in reactor outlet

Moles of Toluene fed to reactor

H2
S = 1

0.0036

(1 x )1.544

x < 0.97

Reaction inlet T > 1150 F (for reasonable x), P=500 psia

Gas phase, no catalyst
Production rate of benzene: 265 mol/h
Product purity of benzene: 0.9997
Raw materials: Pure Toluene at ambient conditions, H2 stream containing
H2 95% and CH4 5%, at 550 psia and 100 F
Constrains: H2/Aromatic 5 at reactor inlet (to prevent coking), reactor
outlet T < 1300 F. Rapid quench of reactor outlet stream

Practice
HydroHydro-dede-alkylation of Toluene HDA Process

Component Tb ( C)
H2
CH4
Benzene
Toluene
Diphenyl
FUEL

-253
-161
80
111
253

HC
(BTU/mol)
0.123x106
0.383x106
1.41x106
1.68x106
2.688x106

Cost data
1.14$/mol
9.04$/mol
6.40/mol
4$/MMBTU

Practice
H2

CH4

H2

Production of benzene PB=265 mol/h

Fresh toluene FFT is used to produce benzene and it is not the inlet flow to
the reactor: if we assume complete recovery of benzene and no losses
losses of
toluene in outlet streams
S=

Moles of Benzene in reactor outlet

,
Moles of Toluene converted

P
FFT = B
S

Produced methane PR,CH4: by stoichiometry is the same toluene

consumed
P
PR, CH 4 = FFT = B
S

Practice
Production of diphenyl PD
Moles of Benzene in reactor outlet
,
Moles of Toluene converted
Moles of Benzene as part of diphenyl
1 S =
Moles of Toluene converted
S=

PD =

FFT (1 S ) PB (1 S )
=
2
S
2

Hydrogen consumed in reaction: Used by converted Toluene minus

produced by diphenyl
P
P (1 S )
FFT PD = B B
2
S
S
PB (1 S ) PB 2 1 + S
1
=
2
S
S 2
PB
(1 + S )
2S

Practice
Hydrogen fed into the process: FH2 = Hydrogen consumed in reaction +
excess
P
FH 2 = B (1 + S ) + FH 2, Exc
2S

Hydrogen in feed stream

FH 2 = yH 2 FG

Methane in feed stream

FCH 4 = (1 yH 2 ) FG

Methane leaving the process: inlet plus produced

PCH 4 = FCH 4 + PR, CH 4
P
PCH 4 = (1 yH 2 ) FG + B
S

Total purge flow PG: methane plus hydrogen excess

PG = FH 2, Exc + PCH 4

P
PG = FH 2, Exc + (1 yH 2 ) FG + B
S

Practice
Rather than using FH2, Exc as variable (is not bounded), we can use
concentration of hydrogen in the purge stream yH2, Purge. Only Excess
hydrogen will be removed in the purge. From the hydrogen balance
P
FH 2 = yH 2 FG = B (1 + S ) + FH 2, Exc
2S
P
FH 2, Exc = y H 2 FG B (1 + S )
2S

Concentration of hydrogen in the purge

y H 2, Purge =

yH 2, Purge =

Solving for the total inlet gas flow FG

FH 2, Exc
PG

FH 2, Exc
PG

PG yH 2, Purge = FH 2, Exc
P
PG yH 2, Purge = y H 2 FG B (1 + S )
2S
PB
PG y H 2, Purge +
(1 + S )
2S
FG =
yH 2

Practice
Solving for the total purge flow PG
PG = FH 2, Exc + PCH 4
P
PG = FH 2, Exc + (1 yH 2 ) FG + B
S

Recalling hydrogen in the purge

yH 2, Purge =

FH 2, Exc
PG

PG yH 2, Purge = FH 2, Exc

We can solve to obtain total purge flow in terms of design variables

variables
P
PG = FH 2, Exc + (1 y H 2 ) FG + B
S
P
PG = PG y H 2, Purge + (1 y H 2 ) FG + B
S
PB

PG y H 2, Purge + 2S (1 + S ) PB
PG = PG y H 2, Purge + (1 y H 2 )
+
yH 2

Practice
Total purge flow in terms of design variables
PB

PG yH 2, Purge + 2 S (1 + S ) PB
PG = PG yH 2, Purge + (1 yH 2 )
+
yH 2

PG = PG yH 2, Purge +
PG PG y H 2, Purge

(1 yH 2 )
yH 2

(1 yH 2 )
yH 2

PG yH 2, Purge +
PG yH 2, Purge =

(1 yH 2 ) PB
yH 2

2S

(1 y H 2 ) PB
yH 2

2S

(1 + S ) +

PB
S

(1 + S ) +

PB
S

(1 yH 2 ) PB
(1 yH 2 )
P
PG 1 yH 2, Purge
yH 2, Purge =
(1 + S ) + B
y
y
S
S
2
H2
H2

(1 yH 2 ) PB
P
(1 + S ) + B

y
S
S
2
H2

PG =

(1 yH 2 )
yH 2, Purge
1 yH 2, Purge
y
H2

Millones

Economic Potential
8
7
6

$/y

5
4

0.1

0.3

0.5

0.7
0.9

0
0

0.2

0.4

0.6

Conversion

0.8