Process and Plant Design 1

Group 11
Members:
Andy Tan Eng Tat
Leonard Tan Jian Zheng
Lim Su Wei
Leow Kok Chung
Ong Ching Yeh

Production Of Ethyl Acetate

Purpose of The Presentation

To investigate the current problems or issues
pertaining to the ethyl acetate production
process and formulate solutions in
overcoming the problems
Three parts - Task 1,2,3
Task 1 Market Demand, Location, Pathway
Task 2 Process Description, Preliminary
Process Synthesis, Heuristics
Task 3 Unit Operation and Simulation

Task 1 Outlines
1.
2.
3.
4.
5.
6.
7.

Properties of Ethyl Acetate

Applications of Ethyl Acetate
Problem Statement
Global Market of Ethyl Acetate
Choosing the Right Plant Location
Selecting the Most Promising Reaction Pathways
Drawbacks and Improvements of Esterification
Reaction

Properties of Ethyl Acetate

Organic Compound
Formula C4H8O2
Colorless
Volatile
Flammable
Fruit Smell
Slightly Soluble In Water/ Soluble In Organic
Solvents

Applications of Ethyl Acetate

Artificial Fruit Enhancer

Applications of Ethyl Acetate

Solvent/Thinner

Applications of Ethyl Acetate

Flexible Packaging

Problem Statement
Two Aspects
1. Business
To Find The Most Promising Pathway
Maximize Profits
Minimize Production Cost
Sustainability of Market
2. Social and Moral
Environmental Concerns

Global and Regional Markets of Ethyl

Acetate
2005-2013

Global Markets of Ethyl Acetate

Choosing The Right Plant Location

Consider following factors
1. Political Stability and Government Policies
2. Availability of Raw Materials
3. Connectivity/Transportation
4. Power and Water Supply
5. Waste Management Disposal
6. Flood and Fire Prevention
7. Human Resources (Skilled/Unskilled)
8. Proximity to The Market

Locations Considered
1. Yanbu Industrial City, Yanbu Al-Bahr, Saudi
Arabia (THE SELECETED LOCATION)
2. Mount Kuring-Gai, New South Wales,
Australia
3. YanTianGang Free Trade Zone, Yantian
District, Shenzhen City, China

Why Yanbu Industrial City in Saudi

Arabia ?
Petroleum derived raw materials are cheap in
Saudi Arabia
Shortage of ethyl acetate supply in Saudi
Arabia
Strategic Location(Located along Red Sea and
near Suez Canal) which can cater for Western
Asia and Europe markets
Chinas market is saturated
Expensive labor cost in Australia

Yanbu Industrial City, Yanbu Al-Bahr

Saudi Arabia

Yanbu Industrial City, Yanbu Al-Bahr

Saudi Arabia

Selecting the Most Promising Reaction

Pathways
1.
2.
3.
4.
5.

Esterification (The Selected Pathway)

Tischenko Reaction
Addition of Ethylene and Acetic Acid
Dehydrogenation of Ethanol
Oxidation of Ethanol

Esterification

CH CH OH

+ CH COOH

CH COOCH CH

+ H O( )

Reversible reaction
Remove water by-product to drive reaction to the right
Advantages

Disadvantages

Ease of raw material

availability
Non-toxic, less harmful raw
materials
Less cost of catalyst

Ethanol conventional air

pollutant
Water as waste product
impeding reaction
eventually

Tishchenko Reaction

Two equivalents of acetaldehydes

Advantages

Disadvantages

Raw material acetaldehyde

is not costly

Acetaldehyde is a very toxic

substance

Addition of Ethylene and Acetic Acid

Avada
H C = CH

+ CH COOH

CH COOCH CH

Advantages

Disadvantages

Energy efficient,
environmentally friendly

Ethylene requires special

safety and fire fighting
facilities

Oxidation of Ethanol
C H OH + O

CH CHO + H O

CH CHO + O
C H OH + CH COOH

CH COOH
CH COOC H + H O

Advantages

Disadvantages

Availability of raw material

ethanol

Weak metal support

interaction
High risk of explosion
requires larger reactor size
and costs

Dehydrogenation of Ethanol
Carried out in four process stages
2CH CH OH g CH COOCH CH g + 2H g
Advantages

Disadvantages

Ethanol is easily available

Complicated Unit
Operations
Acetaldehyde has high
toxicity

Why Esterification is Chosen ?

Why Esterification is Chosen?

6 Points
Raw Material
Safety, Health and Environment
Utilities
Simplicity of The Process
Operating Conditions
Conversion and Selectivity

Why Esterification is Chosen?

Raw Materials for Tishchenko Reaction cannot
be found in Saudi Arabia
Technology of dehydrogenation of ethanol is
still developing
Catalysts used in oxidation of ethanol are
expensive despite the reaction gives highest
profit

Why Esterification is Chosen?

Avada process has short reaction rate and
depends highly on the performance of
catalysts
Avoid usage of Acetaldehyde as raw material
as it is toxic and very harmful

Drawbacks and Improvements of

Esterification Reaction
Heterogeneous catalyst replaces
homogeneous catalyst
Reactive Distillation is suggested for
Esterification Reaction
Heuristic studies are conducted to avoid
repeating the same mistakes in the future

Drawbacks and Improvements of

Esterification Reaction
Reactive Distillation
Shifting chemical equilibrium and thus results in an increase of conversion
of raw material by simultaneous reaction and separation product.
Suppression of side reaction and thus higher purity of desired product can
be obtained.
Utilization of heat of reaction (esterification is an exothermic reaction) for
mass transfer operation.
These features on the process can further lead to economic benefits which
are shown below:
Lower capital investment (reactive distillation combined both the function
of reactor and distillation column)
Lower energy cost (heat generated from the process in used as the mass
transfer purpose)
Higher product yield (Suppression of water by-product )

Task 2 Outlines
1. Process Description
2. Preliminary Process Synthesis
3. Heuristics

Process Description
EtOH + HAc EtAc + H2O
Azeotropic mixture
Total of 4 azeotropes
Mixtures

Compositions
(mole fraction)

Temperature (oC)

EtOH/H2O

(0.9037, 0.0963)

78.18

EtAc/EtOH

(0.6885, 0.3115)

71.81

EtAc/H2O

(0.6885, 0.3115)

70.37

EtAc/EtOH/H2O

(0.1126, 0.5879, 0.3085)

70.09

Compositions and Temperatures for EtAC System

Ternary Azeotrope Diagram

Process Description

Single double-feed reactive distillation column incapable to produce high

purity EtAc
Two-column design with decanter
Decanter as liquid-liquid separator

Preliminary Process Synthesis

Step 1: Eliminate Differences in Molecular
Types
Step 2: Distribution of Chemicals
Step 3: Eliminate Differences in Composition
Step 4: Eliminate Differences in Temperature,
Pressure and Phase
Step 5: Task Integration

Step 1: Eliminate Differences in

Molecular Types
Reaction

Pathway 1

Pathway 2

Pathway 3

Pathway 4

Pathway 5

Availability

Easily

Not easily

Easily

Available

Available

available

available

available

0.3566

0.2951

0.3221

0.6667

0.6873

Corrosive

Highly toxic

Corrosive

Flammable

Flammable

and

and

and

raw material

raw material

flammable

flammable

flammable

raw material

raw material

raw material

Gross Profit
($/Ib EtAc)

Safety Consideration

 Reaction Pathway 1 (Esterification):

CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O
Reaction Pathway 2 (Tishchenko Reaction):
CH3CHO CH3COOCH2CH3
Reaction Pathway 3 (Avada):
C2H4 + CH3COOH CH3COOCH2CH3
Reaction Pathway 4 (Oxidation of Ethanol):
CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O
Reaction Pathway 5 (Dehydrogenation of Ethanol):
1
C H OH + O
2
1
CH CHO + O
2
C H OH + CH COOH

CH CHO + H O
CH COOH
CH COOC H + H O

Step 2: Distribution of Chemicals

Assumptions:
1) Conversion of acetic acid, HAc is 100%
2) Operation time for plant set to 8400 hours per year; 350
days per year: 6012.35 kg/hr for 10,000 tonnes of product
3) Outlet composition of the reactive distillation column is
near minimum ternary azeotrope
4) Outlet composition of the stripper is obtained from the
process design of the stripper
5) Components in the decanter is in equilibrium

 Overall balance:

A = 3471.582068 kg Ethanol/hr
B = 4198.91034 kg HAc/hr
C = 1658.142408 kg/hr
Ethyl acetate product at 6012.35 kg/hr

Step 3: Eliminate Differences in

Composition
Reactive distillation column for reversible chemical
reaction
Simultaneous separation of products and recycle of
incompletely consumed reactants

Part of Process Flow Diagram Top of RDC and

Decanter

Step 4: Eliminate Differences in

Temperature, Pressure and Phase

Process Flow Diagram

 Reboiler heated up before feed stream is fed

to reboiler
Top RDC product as vapour passes through
condenser and changed to liquid form
Liquid phase to decanter
Manipulating heat input to stripper to
maintain same temperature of bottom
temperature to stripper
Final product stream passed through cooler to
reduce temperature of final product

Step 5: Task Integration

Condenser

Decanter

Reactive
Distillation

Reboiler

Process Flow Diagram

Stripping
Tower

 Reactive Distillation (RD) Column and

Condenser
Separation being done; consist of two
sections:1) Reactive section
2) Rectifying zone

Stripper and Condenser

Decanter
Cooler
Control Valves

Heuristics
Heuristic 1: Select raw materials and chemical reactions to avoid,
or reduce, the handling and storage of hazardous and toxic
chemicals.
Heuristic 2: Use an excess of one chemical reactant in a reaction
operation to completely consume a second valuable, toxic, or
hazardous chemical reactant.
Heuristics 8: For reversible reactions, especially, consider
conducting them in a separation device capable of removing the
products, and hence, driving the reactions to the right. Such
reaction-separation operations lead to very different distributions of
chemicals.

 Heuristics 9: Separate liquid mixtures using distillation and

stripping towers, and liquid-liquid extractors, among similar
operations, and so on, with the unreacted chemicals recovered in
a liquid phase and recycled to the reaction operation.
Heuristic 22: For less exothermic heats of reaction, circulate
reactor fluid to an external cooler, or use a jacketed vessel or
heating coils. Also, consider the use of intercoolers between
adiabatic reaction stages.

Task 3 Outline
Mass and energy balance
Hysys simulation

Mass Balance

Stream number

1
Acetic acid
feed to
C001

2
Ethanol
feed to
C001

3
RDC top
product
before
condense
r E002

Liquid

Liquid

Vapor

4
5
6
7
8
9
10
11
12
RDC top Organic Organic Organic Aqueous Stripper
Stripper
Ethyl
Ethyl
product part
feed to reflux to product
top
top
acetate acetate
after
from stripper C001
from
product
product product product
condens decante C002
FL001
before
after
before
after
er E002 r FL001
condenser condenser cooler
cooler
E003
E003
E005
E005

Name of the stream

Phase

Mass flow rate

(kg/hr)

Liquid

Liquid

Liquid

Liquid

Liquid

Vapor

Liquid

Liquid

Liquid

3471.58207 4198.91034 25940.15 25940.1 33310.4 16655.21 16655.21 1658.142 9028.4097 9028.4097 6012.35 6012.35

wt%

wt%

wt%

wt%

wt%

wt%

wt%

wt%

wt%

wt%

wt%

wt%

Ethyl acetate

82.6

82.6

92.03

92.03

92.03

1.58

95.77

95.77

99.5

99.5

Water

4.5

2.12

2.12

2.12

95.88

1.93

1.93

Ethanol

95.5

8.4

8.4

4.1

4.1

4.1

2.5

2.3

2.3

0.5

0.5

Acetic acid

99

Energy Balance

Enthalpy
The enthalpy for each stream is given by

H T ,i H

f , 298.15 K

298.15 K

C p ,i dT

Stream

Acetic
Acid Ethanol RDC top before
Feed
Feed
condenser 1
Phase

Liquid

Liquid

Temperature
(K)
298.15 298.15

RDC top after

condenser 1

Organic part Organic feed

from Decanter to Stripper

Vapour

Liquid

Liquid

Liquid

342.8

313.15

313.15

313.15

-277.605

-277.755

-277.755

-277.755

-450.1

-457.7

-457.7

-457.7

-284.316

-285.332

-285.332

-285.332

Enthaply
(kJ/mol)
Ethanol

-277.63

Acetic Acid -486.18

Ethyl Acetate
Water

-285.84 -285.84

Stream

7
Organic
Reflux

Aqueous Stripper Top Product

Product
before condenser

10
Stripper Top
Product after
condenser

11

12
Ethyl Acetate
Ethyl Acetate Product after
before cooler
cooler

Phase

Liquid

Liquid

Vapour

Liquid

Liquid

Liquid

Temperature
(K)

313.5

313.15

343.75

313.15

353.15

308.15

-277.755

-277.755

-277.615

-277.755

-277.47

-277.6105

-457.7

-449.2

-457.7

443.1

-460.15

-285.332

-284.1

-285.332

-283.977

-285.5

Enthaply
(kJ/mol)
Ethanol
Acetic Acid
Ethyl Acetate -457.7
Water

-285.332

Heat Duties
Inlet
Outlet
Streams Streams

Difference in
Enthaply (kJ/mol)

Heat Duty (kW)

Reboiler of
RD

1,2,7

??

???

Condenser
of RDC

??

???

Reboiler of
Stripper

9,11

??

???

Condenser
of Stripper

10

??

???

Cooler

11

12

??

???

Aspen HYSYS Simulation

Hysys simulation (proposed flowsheet)

Hysys simulation

Conclusion

Demand
location
Pathway
Preliminary process synthesis
Mass balance
Simulation