CL452 – Design Project

Spring 2019

Group 24
Production of Vinyl Acetate
Report - Final Evaluation

Members:
Triesha Singh: 150020026
Shubham Sumit: 150020092
Sudhanshu Singh: 150020124
Anshik Gupta: 150020082
Abhishek Kumar: 150020123
Vivek Bansod: 150020013

Department of Chemical Engineering

Indian Institute of Technology Bombay

Page 1
Table of Contents

List of Tables 4

List of Figures 3

1. INTRODUCTION 5
1.1 Physical Properties 5
1.2 Applications 6

2. MARKET OVERVIEW 7
2.1 Global Market 7
2.1.1 Global Consumption Pattern 7
2.1.2 Major producers globally 7
2.1.3 Global trade 8
2.1.4 Global Market Growth 9
2.2 Indian Market Overview 10

3. ROUTES OF PRODUCTION 11
3.1 Acetic Acid and Acetylene 12
3.2 Using Acetaldehyde and Acetic Acid*Synthesis Gas Method) 12
3.3 Acetic Acid, Ethylene and Oxygen 12

4. PROPOSED MEANS OF PRODUCTION 13

4.1 Comparison of methods 14
4.2 Proposed plant location 17
4.3 Plant capacity and product requirements 17

5. PROCESS 18
5.1 Reaction: 19
5.1.1 Preconditioning of the reactants 19
5.2 Separation 21
5.2.1 Phase separator (FLASH) 21
5.2.4 Dehydration of Vinyl Acetate 23

6. EMPIRICAL MASS BALANCE 25

6.2 Reactor 25
6.3 Phase Separator 25
6.4 Absorber 26
6.5 CO2 Splitter 27
6.6 Dehydrator 297
6.7 Overall Mass Balance 28

7. ASPEN PLUS Flowsheet Simulation 30

7.1 Flowsheet Development 30
7.2 ASPEN PLUS Flowsheet 32
7.3 STREAM Summary 34

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8. SENSITIVITY ANALYSIS 37
8.1 FLASH DRUM 37
8.2 ABSORPTION COLUMN 38
8.3 DISTILLATION COLUMN 40
8.4 REACTOR 41

9. EQUIPMENT SIZING AND COSTING 43

9.1 COMPRESSORS 43
9.2 COLUMNS 45
9.3 HEAT EXCHANGERS 47
9.4 FLASH DRUM 48
9.5 Pump 49
9.6 STORAGE TANK 49
9.7 REACTOR 50
9.8 Raw Material Cost and Revenue 51
9.9 Payback Period 52

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List of Tables
Table 1.1 Physical Properties of Vinyl Acetate 4
Table 1.2 Summary of uses of Vinyl acetate 6
Table 2.1 Major producers of vinyl acetate 8
Table 4.1 Comparison on the Basis of Raw Material Availability 13

Table 4.2 Comparison on the basis of Catalyst used 14

Table 4.3 Comparison on the Basis of Waste Generated/ByProducts 14
Table 4.4 Performing a safety analysis for the 3 processes 15
Table 4.5 Sustainability Analysis of the 3 methods 16
Table 4.6 Product specification 17
Table 5.1 Reactant physical properties 18
Table 6.1 Total mass input/output in the process 24
Table 6.2 Total Mass Input/Output for Reactor 25
Table 6.4 Mass input/output of the Phase Separator 26
Table 6.5 Total mass input/output to Absorber 26
Table 6.6 Mass Balance on CO2 Splitter 27
Table 6.7 Total mass input/output to Dehydrator 27
Table 6.8 Overall Mass Balance (amounts in kg/hr) 28

List of Figures
Figure 1.1 2D Structure of Vinyl Acetate 4
Figure 2.1 World Consumption of Vinyl Acetate 7
Figure 2.2 Capacities of Main Vinyl Acetate Producers in 2008 8
Figure 2.3 Global export statistics (2016) 9
Figure 2.4 Global import statistics (2016) 9
Figure 2.5 U.S. VAM Market Size, By Application, 2013-2024 10
Figure 2.6 Total value (in USD) and total volume imported 11
Figure 2.7 Import Quantity by Country 11
Figure 2.8 Import Quantity by Destination Port 11
Figure 5.1 Brief block diagram of the process 17
Figure 5.2 Tubular Bed Fixed Reactor is chosen 19
Figure 5.3 Phase Separators 20
Figure 5.4 Absorber 21
Figure 5.5 Liquid Separation Section 21
Figure 5.6 Ternary Diagram of Water-Acetic Acid and VAM system 22
Figure 5.7 Dehydration in Block Diagram 22

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Figure 5.8 Dehydration of Vinyl Acetate Monomer 23
Figure 6.1 Overall Mass Balance 28
Figure 7.1 ASPEN PLUS FLowsheet Simulation 33
Figure 8.1 Effect of temperature at certain pressure on the amount of VAM 37
(kg/hr) in Flash condensate
Figure 8.2 AA flow rate in FlashVap stream vs Temperature 38
Figure 8.4 Amount of Acetic acid vs Mass flow of VAM from absorber column 39
Effect of number of stages on VAM absorption
Figure 8.5 Effect of number of trays on reboiler and condenser heat in 40
Figure 8.6 distillation column 40
Variation in different parameters with change in number of stages
Figure 8.7 Change in Temperature of reactor with Length 41

Figure 8.8 42

CHAPTER 1
INTRODUCTION
Vinyl acetate is an organic compound with chemical formula CH3CO2CH=CH2.
Vinyl acetate is a colourless, flammable liquid with a pungent odor. It’s solubility in water is
Page 5
very low although it is soluble in a lot of organic solvents.

It is also called as ethenyl ethanoate(IUPAC), acetic acid vinyl ester and vinyl ethanoate.
It is most commonly abbreviated as VAM, Vinyl Acetate Monomer.

Figure 1.1 : 2D Structure of Vinyl Acetate

1.1 Physical Properties

Vinyl Acetate is a clear colorless liquid and is slightly soluble in water. Its vapors are heavier
than air. Its vapors, though initially pleasant, are irritating to respiratory tract. It gets
polymerized on heating or being in touch with contaminations. It is used to make adhesives,
paints, and plastics.

Table 1.1 : Physical Properties of Vinyl Acetate [1]

Property Value

Density 934 kg/m3

Boiling point 72.8°C

Melting point -93.2°C

Liquid density (at 20°C) 0.9003 g/mL

Water solubility (at 20°C) 2.0-2.4 wt % Vinyl Acetate

Relative vapor density 3.0

Vapor pressure (at 20°C) 90.2 mm Hg

Heat of vaporization (at 25°C) 379 kJ/mol

Viscosity (at 20°C) 0.43 cPs

Auto-ignition temperature 402°C

1.2 Applications
Practically all use of VAM is as a vinyl monomer to produce polyvinyl acetate homopolymers
and copolymers. The homo and copolymers are often further reacted to produce derivatives
such as polyvinyl alcohol and ethylene–vinyl alcohol (EVOH).
Two of the biggest uses of the VAM are production of polyvinyl acetate (PVA) and polyvinyl
alcohol (PVOH). It is estimated that 80% of the consumption of total VAM production in the
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world is used in the production of these 2 compounds. PVA is widely used in the adhesive
industry. PVOH is used for production of paints, coatings and water-soluble packaging. PVA
also finds its roles in safety glass inner layers, coating and magnetic wire productions.

EVOH is the fastest growing use of VAM. EVOH is used as barrier resin for plastic bottles, food
packaging, gasoline tanks and engineering polymers.

Polyvinyl Butyral (PVB) and Vinyl Acetate Ethylene (VAE) are also produced from VAM.
PVB is extensively used in glass safety wear industry. VAE is used as coating in architectural
works due to its very low environmental impacts. It is also used in packaging industry, shower
curtain manufacturing and footwear industry.

Table 1.2: Summary of Uses of Vinyl Acetate[2]

Sector Uses

VAM is a raw material for many adhesive products(mainly

PVA). Emulsion containing VAM generates really good adhesion
Adhesive for various host surfaces such as wood, paper, porcelain and
metal

VAM is used as an intermediate in manufacturing of other

useful compounds (paints and coatings, adhesives, textile
Chemical Intermediates
finishes, water-soluble films and fibers, and laminated safety
glass). It is widely used a monomer for different types of
polymers (e.g. PVAs)

Coatings Used in coatings formulations as well as wate- based coatings

It is used in making food contact material used in adhesive,

Food
paper, paperboard coatings and printing inks

VAM is widely used in plastic industry. It is used to make acrylic

Plastics fiber, polyvinyl acetals and inner lining of magnetic wire and
safety glass

Fabric Treatment, pigments are done with the help of VAM

Textiles
produced polymers

CHAPTER 2
MARKET OVERVIEW
2.1 Global Market
The global market of Vinyl Acetate in 2017 was valued at around $9.5 billion [3] with global
demand of 6.58 MMT per annum and is projected to reach $12 billion by 2026 [4]. It is expected
to grow at a CAGR of 5% in the coming years[3].

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2.1.1 Global Consumption Pattern

Sales in the primary end-use markets for vinyl acetate—paints, adhesives, textiles, and safety
glass sheet for automotive and architectural applications—depend on the performance of the
overall economy.

● The countries with highest VAM consumption percentage are China (30%), followed by
Western Europe (18%) and USA(15%). The following pie chart shows world
consumption of vinyl acetate [5]:

Figure 2.1: World Consumption of Vinyl Acetate [4]

2.1.2 Major Producers (Global)

Celanese is the largest producer (25% of worldwide production), while other significant
producers include China Petrochemical Corporation (7%), Chang Chun Group (6%) and
Lyondell Basell (5%)[6].

Table 2.1: Major producers of vinyl acetate [6]

Company Country Annual Production

(% market share)

Celanese Texas, USA 25%

China Petrochemical China 7%

Corporation

Chang Chun Group China 6%

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 Lyondell Basell Texas, USA 5%

Figure 2.2: Capacities(per annum) of major vinyl acetate producers, 2008[3]

It can be seen that four USA companies take leading positions in Vinyl Acetate production.
Celanese, which is the largest producer of VAM, had a capacity of 1200 tons per annum in
2008. The trend has been similar since a decade.

2.1.3 Global trade

As of 2016, the trade market of Vinyl acetate was $9.5 Billion [3]
The top exporters of Vinyl acetate are the United States ($446M), Singapore ($386M), Saudi
Arabia($272M), Other Asia ($253M) and Belgium-Luxembourg ($206M). The top importers are
Belgium-Luxembourg ($433M), China($187M), Germany ($180M), India ($146M) and Turkey
($87.5M).

The following figures shows the countries that export and import the VAM and their share of
trade.

Figure 2.3: Global export statistics (2017)[7]

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 Figure 2.4: Global import statistics (2017)[7]

2.1.4 Global Market Growth

The global market is expected to grow at a CAGR of 4.4% until 2020. By 2020, the market is
expected to be around US$ 10 billion.[8]
In ASEAN countries, the consumption rate is expected to witness a significant growth, with a
growth in demand from large bases, like Singapore and Thailand. Europe is a mature market
for vinyl acetate, which is expected to witness a sluggish growth rate (1-1.5%) during the
forecast period.

Fig 2.5 U.S. VAM Market Size, by Application, 2013 – 2024 (USD Billion) [8]

The major factors affecting the growth of VAM, as identified by us, are:

1. The increase in the production volume of automobiles across Asia-Pacific is likely to

drive the demand for vinyl acetate.
2. Ability to provide oxygen barrier food packaging that increases the shelf life of packed
food is leading to high growth of VAM market in developing nations

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 3. The polyvinyl acetate application (PVA) is expected to witness a growth in the coming
years, due to the rise of its demand in the plastic bottling and packaging industry.
4. The ethylene vinyl acetate (EVA) application is expected to grow rapidly, owing to the
use of EVA in the 3D printed medical drug delivery devices.
5. Increasing shale gas exploration in the U.S. is expected to benefit the market in terms
of ethylene supply, which is a key VAM feedstock and is expected to benefit the market
supply
6. Furthermore, the demand for more photovoltaic cells is expected to boost the growth
of the market over the forecast period.
7. We expect the growth to be slightly slower in the developed nations due to the
comparatively lower demand of automobiles.

2.2 Indian Market Overview

India is an importer of Vinyl Acetate and the whole demand is met through imports i.e., the
production capacity of VAM in India is nil.

Market study firmly establishes a growing demand in India for VAM, which has been increasing
at an annual rate of 9.8% from fiscal year 2008-09 to 2016-17. [4]

Fig 2.6: Total value (in USD) and total volume imported (in kgs)

Fig 2.7: Import Quantity by country Fig 2.8: Import quantity by destination port

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 The figures above show that India is a huge importer of VAM, importing VAM worth around
US $300 million annually. This coupled with the fact that CAGR of VAM in India is around
10% compared to the world CAGR of 4.4%, shows that India is a very lucrative market for
vinyl acetate monomer.

Considering our raw materials requirement and possible markets for VAM export, we set up
out plant in Rajkot, Gujarat.

CHAPTER 3
ROUTES OF PRODUCTION
Vinyl Acetate consists of the acetyl group and the vinyl group. We thus need raw materials
consisting of a saturated hydrocarbon and the acetyl group. The following three methods have
been used for large scale production of VAM[9]:

3.1 Acetic Acid and Acetylene

Acetic acid reacts with Acetylene in gas phase at operating temperature of about 170-250°C to
give vinyl acetate. Conversion in this method is about 60%-70% with selectivity of acetic acid
and acetylene being about 93%.

Zinc catalyst is used along with some support material like charcoal and porous carbon sphere.

Reaction:
HC≡CH + CH3COOH → CH3COOCH=CH2.

3.2 Using Acetaldehyde and Acetic Acid(Synthesis Gas Method)

This method was one of the first methods used for production of VAM on large scale. This
reaction has an intermediate EDA (Ethylenediamine) which is thermodynamically very less
stable and goes on to produce to give VAM.

Reaction temperature is set around 120°C-140°C.Catalyst of this reaction is FeCl3 + Hydrogen

(ions) i.e. acid

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Main Reaction:
Step 1:
CH3CHO + (CH3CO)2O → CH3CH(OCOCH3)2
Step 2:
CH3CH(OCOCH3)2 → CH2CHOCOCH3 + CH3COOH

3.3 Acetic Acid, Ethylene and Oxygen

It is the economically most profitable method of production at present. Reactants of this
reaction are ethylene and acetic acid in presence of oxygen. Catalyst used for this reaction is
Pd-based.

Many variants of Pd based catalyst are used. Pd with gold and cupric acetate is one alternate
variant of the catalyst. This has higher activity and lower selectivity for CO 2. Pd with gold is also
used by some of the major producer in the world (e.g. DuPont, Dow Chemicals). Most
economical catalyst formulation can be obtained by using Pd/KOCH3O4 .

Main Reaction:
H2C=CH2 + CH3COOH + 0.5O2 → H3C-COO-CH=CH2

Side Reaction (Combustion):

H2C=CH2 + 3O2 → 2CO2 + 2H2O

Reaction is operated at around 150°C to 170°C at a pressure of 8 to 10 bar

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 CHAPTER 4
PROPOSED MEANS OF PRODUCTION
4.1 Comparison of the 3 proposed methods
The three methods of production of VAM mentioned above have been compared on the basis
of the following factors:

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 ● Raw Material Availability
● Gross Profit
● Waste Generated/ By Products
● Sustainability Analysis of the process
● Safety Factors

4.1.1 Raw Material Availability

Table 4.1: Comparison on the Basis of Raw Material Availability

Method 2 Method 3
Method 1
(From Acetic Acid and (From Acetic acid,
(From Syngas)
Acetylene) ethylene and O2)

Acetic Anhydride: Ethylene:

This product is not available large Ethylene is widely
scale. Since acetic acid is one of Acetylene: available in the market.
the products in this process, This is produced in large Setting up the plant
Raw
acetic anhydride can also be scale. Many acetylene near Gujarat will be
Material 1
prepared in the plant. But, it is plants are present in especially beneficial
cheaper to purchase acetic Gujarat and Maharashtra. since ethylene is an
anhydride if our plant is set up in important byproduct in
Gujarat. the refineries.

Acetic Acid:
Acetaldehyde:
This is widely available Acetic Acid:
Raw Plants producing acetaldehyde
and is produced in large Widely available, plants
Material 2 are present in Gujarat. The cost
quantities and can be present in Gujarat too.
for the same is also low.
obtained at low costs.

Considering the raw materials, ethylene is the most abundantly available, hence Method 3 is
the best production method in terms of raw material availability, considering our plant to be
set up in Gujarat.

4.1.2 Catalyst

Table 4.2: Comparison on the basis of Catalyst used

Method 2 Method 3
Method 1
(From Acetic Acid and (From Acetic acid,
(From Synthesis gas)
Acetylene) ethylene and O2)

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 Pd or Pd-derivatives are
used to catalyze this
(CH3COO)2Zn + charcoal +
reaction.
porous carbon spheres
FeCl3 + Hydrogen (ions) i.e. acid Catalyst is easily
Catalyst is easily available.
The catalyst is easily available available, but is costly.
Catalyst Catalyst life is short and
and is also cheap. Catalyst is highly
needs to be changed
Conversion ~91% effective.
frequently.
Catalyst life is large
Conversion ~93%
(~2.5 years).
Conversion ~94%

Method 3 has the most effective catalyst with the best conversion. However, the catalyst is
very costly. Method 1 seems to have the best catalyst but separation of catalyst from the liquid
mixture is difficult. Catalyst used in method 2 gets deactivated very easily. In method 3,
reaction occurs in the gaseous phase and the catalyst is in solid phase, thus there is no
problem in separation. Thus, Method 3 seems like a good option.

4.1.3 Waste generated/ Byproducts

Table 4.3: Comparison on the Basis of Waste Generated/ByProducts

Method 2 Method 3
Method 1
(From Acetic Acid and (From Acetic acid,
(From Syngas)
Acetylene) ethylene and O2)

Many byproducts( by
Acetic Acid: Water and CO2 are the
reaction of reactants and
This is a very useful major byproducts of this
products, reactant and
byproduct. It has a huge process. The CO2 is
reactants, etc.) are
market in itself. It can also vented into the
ByProducts formed which have no
be used as a raw material atmosphere and is a
big market and
to make acetic anhydride, main source of pollution.
separation will require a
the raw material in this Water is used in heat
lot of capital and
process. integration.
operating cost.

Method 1 looks to be the most beneficial because the byproduct has a big market and can be
easily separated from the other products.
Method 2 is least beneficial and Method 3 has no byproducts but separation of our main
product is easy. CO2 may be sent to a dry-ice manufacturing industry.
4.1.4 Safety Aspect

Table 4.4: Performing a safety analysis for the 3 processes

Method 1 Method 2 Method 3

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 Acetylene is highly flammable (LFL: Ethylene is also flammable
2.5%, UFL 81%). although it has a much
Acetic anhydride is
Since it is required in excess, it is lower flammable range than
flammable although its
present in both the feed stream and acetylene. It is also less
reactivity is low. It reacts
in the product stream. Thus, is is reactive than acetylene.
violently with water and
present in significant quantities in Unreacted ethylene is
must be kept out of
major part of the plant. A spark can combusted to form CO2.
contact of moisture.
be very hazardous to the plant and This process is thus
extra precaution would have to be comparatively safer than
taken for safe operation of the plant. Method 2.

All methods can be hazardous, although Method 2 has a higher probability for accident.
Method 1 is the safest among the three.

4.1.5 Sustainability Analysis

It is to be noted sincerely that accurate sustainability analysis cannot be done at this stage and
would require an in-depth analysis of all the processes involved. However before opting for a
process to continue with we had a look upon a very broad overview of the 3 processes. We
will be performing a proper sustainability analysis like LCA of the process we choose.

Table 4.5: Sustainability Analysis of the 3 methods

Method 2 Method 3
Method 1
(From Acetic Acid and (From Acetic acid,
(From Synthesis gas)
Acetylene) ethylene and O2)

There is no direct
emission in this process
but the intermediate
CO2 is a major byproduct
steps (hydrogenation,
There is no direct harmful of the process and has
main reactor etc.)
byproduct, the indirect direct impact on the
ByProducts contribute to high
emissions are similar to environment. The CO2 is
indirect emissions.
method 3. directly sent into the
Catalyst is difficult to
atmosphere as emissions.
separate and can
contribute as
pollutants.

Note: Method 2 and 3 have similar intermediate steps and can be considered to have similar
impacts. No firm conclusion can be made at this stage. We will be looking at the
environmental impact at later stages.

4.2 Proposed plant location

India has a growing demand of Vinyl Acetate. Plants using older methods to produce VAM can
no longer sustain in a competitive market so they had to shut down. Now Indian demand of
VAM is being fulfilled by import. We decided to provide a portion of Indian demand by settling
a VAM plant in India.

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 Now, based on the raw material availability, transport, and availability of an industrial
ecosystem we decided to setup our plant in Gujarat. Ethylene is an important byproduct of
refineries and a huge Acetic Acid plant is being set up in Gujarat. We thus decide to our plant
in Gujarat, which would also help us in fetching the raw materials easily and cheaply.

4.3 Plant capacity and product requirements

India’s demand in 2017 was around 0.3 MMT. Keeping this in mind, we decided to initially
cover 15%-20% market demand which can be increased later. It was difficult to decide the
exact capacity as it will depend on various factors like funds available, price of product, ease of
market penetration, etc. Hence for the sake of this project we decided to go ahead with
50,000 tons per annum of VAM.

Table 4.6: Product Specification [10]

Characteristics Limit Unit

Vinyl Acetate Min. 99.9 %(w/w)

Acetaldehyde Max. 0.010 %(w/w)

Water Max. 0.04 %(w/w)

Acetic Acid Max. 0.005 %(w/w)

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 CHAPTER 5
PROCESS

Figure 5.1: Brief block diagram of the process

5.1 Brief Summary of the Process

The process of production of VAM involves reaction between acetic acid, ethylene and oxygen
to produce vinyl acetate. However, there is also a side reaction going on which is favored at
high temperatures due to its higher activation energy. This side reaction is the oxidation of
ethylene in the presence of oxygen to produce CO2 and water (combustion reaction). After the
stream leaves the reactor, the effluents are cooled in order to obtain a partial condensation of
the stream.
In phase separator, gas is separated from liquid stream. The gas, then, is washed with
acetic acid in order to recover the vinyl acetate in the absorber. Afterwards, the gas stream is
treated with K2CO3 to eliminate some part of the CO2 from the gas phase and hence recycle
ethylene and the rest of CO2 back into the reactor. (CO2 acts as an inert in the reaction. It is
sent to the reactor in excess for absorption of some amount of heat that is released in the
reaction.)
The liquid effluents from the phase separator and absorber now enter an azeotropic
distillation tower. The objective is to separate the acetic acid (bottoms) form the water and
vinyl acetate mixture (distillate). The distillate enters to a dehydration process in which
glycerol is added to it. The (VAM-Water) azeotropic mixture then is separated and VAM as
pure as 99.9% is obtained.

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As we can see in the block diagram, the process can be broadly be divided into three stages:
a. Reaction
b. Separation
c. Distillation/Dehydration

The following abbreviations have been used for the compound in the rest of the report:

Table 5.1: Abbreviations for Molecules

Molecule Abbreviation/Representation

Ethylene EL

Oxygen O2

Acetic Acid AA

Vinyl Acetate VAM

Water H2O

Carbon Dioxide CO2

5.1 Reaction

5.1.1 Preconditioning of the reactants

Table 5.2: Reactant physical properties [11]

Reactant Boiling Point (in degree C, at 10 atm)

Ethylene -55

Acetic Acid 139.5

All of the reactions occur in the gaseous phase. Ethylene remains gas at required
temperatures. A preheated stream of acetic acid and air is mixed with ethylene.

Reactor Conditions:
Temperature of the reactor: 150-160 C
Pressure in the reactor: 8-10 bar

5.1.2 Reactor Selection

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The capacity of the reactor is large as the plant has to be built keeping in mind the grooming
demand of acetic acid in India. To cater with large quantities of the product there is a need of
continuous reactor system.
 The process uses Pd-based catalyst to provide as high as ~94% selectivity. The reaction
is heterogeneous.
 Also, as mentioned, the reaction is exothermic with net heat of reaction = 42.1
kcal/mol = 204 kJ/kg VAM. We produce ~6000kg/hr of VAM. Thus, a very large amount
of heat is liberated.
 The catalyst is highly sensitive to heat and is well activated within the temperature
range of 150-200C above this temperature it suffers an irreversible mechanical
damage.
 An unfavorable secondary reaction also takes place at high temperatures leading to
oxidation of ethylene to produce CO2.

Having above mentioned points in mind we need a very efficient heat removal system.

Main Reaction:
H2C=CH2 + CH3COOH + 0.5O2 → H3C-COO-CH=CH2

Side Reaction:
H2C=CH2 + 3O2 → 2CO2 + 2H2O

Figure 5.2: Tubular fixed bed reactor is chosen

The heat removal is done by vapor generation in the shell section of the reactor. The reaction
mixture contains an excess of CO2 (2.5:1 CO2:EL) for efficient heat absorption, 3:1 ethylene,
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acetic acid ratio in the mixture. Also, to prevent any kind of explosion the concentration of
oxygen in the reactor must be kept below 8%.

5.2 Separation
The outlet reactor stream consists of ethylene, carbon dioxide, water, acetic acid, oxygen, and
vinyl acetate. The mixture is first separated into a gaseous phase and a liquid phase. Both are
further treated in separate streams to isolate the components.

5.2.1 Phase separator (FLASH)

Figure 5.3: Phase Separator

Operating conditions of the separation unit: T = 30 C, P = 4 atm

Major components:

● Phase 1: Vapor phase

○ Oxygen
○ Ethylene
○ CO2

● Phase 2: Liquid phase

○ Vinyl acetate
○ Water
○ Acetic acid

After the 1st stage of flash separation, there is still a significant amount of VAM in the vapor
phase and EL in the liquid phase. For better separation, we use a 2-stage flash.

Operating conditions of 2nd Flash Unit: T = 25 degree C, P = 2 bar

There is still a significant amount of VAM in the vapor phase. So, to recover Vinyl Acetate a
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multistage equilibrium separation should be implemented in the absorption column. Acetic
acid can be used as a solvent.

5.2.2 Absorber

Figure 5.4: Absorber

After passing through separator column, the feed is divided into liquid and gaseous streams.
As mentioned above, the gaseous stream still has some amount of VAM in vapor form so
acetic acid is used as scrubber in order to extract remaining VAM (VA is soluble in acetic acid).
The gaseous stream exiting from the top of the absorber passes through a CO2 splitter. CO2 is
absorbed such that the EL can be sent back to the reactor. The stream that has the CO2
extracted is divided in to a purge and a recycle stream that mixes with the other portion of the
stream that had no CO2 extracted. This stream can also be used to exchange heat with the
outlet stream of the reactor.

5.2.3 Liquid Separation

Figure 5.5: Liquid separation section

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The inlet of the liquid separation section comprises of flash bottom outlet and the liquid
coming from absorption column. The inlet components are water, vinyl acetate, and acetic
acid which enter into an azeotropic distillation column.
Residue curve analysis produces ternary diagram of the water-acetic acid-vinyl acetate
system. The inlet composition of the mixture corresponds to a point on ternary diagram which
is shown in fig 5.6. This point lies in the single-phase region and thus requires distillation.
Thus, the stream gets divided into 2 streams – acetic acid stream is obtained at the bottom
and is sent for recycle. The VAM+H2O mixture forms an azeotrope and is obtained at the top
of the column.

Fig: 5.6 Ternary diagram of Water-Acetic Acid-Vinyl Acetate system

A major part of acetic acid stream is sent back to the feed and a portion is used for
washing/scrubbing in the absorption column.

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5.2.4 Dehydration of Vinyl Acetate

Fig: 5.7 Dehydration in block diagram

Note that the vinyl acetate and water mixture is almost impossible to separate by normal
distillation methods. That’s why it is necessary to alter the relative volatility of the individual
components allowing the separation of vinyl acetate and water. The extractive distillation is
achieved by adding a solvent ‘glycerol’ into water-vinyl acetate solution. Glycerol and water
have a strong interaction due to extensive H-bonding. Thus, the mixture is now easily
separated. VAM is obtained from the top of the column and the water-glycerol mixture is
obtained from the bottom. Glycerol is then recovered (in an evaporator) and recycled back to
the column.

Fig: 5.8 Dehydration of Vinyl Acetate Monomer

Page 25
 CHAPTER 6
EMPERICAL MASS BALANCE
In this section we will be analyzing mass balance across each of the major equipment to be
used in our plant. Our plant has an annual vinyl acetate production capacity of around 50,000
ton per annum. Assuming that the plant has 8000 working hours, we get daily production of
around 6000 kg/hr.
We have performed a simplified linear mass balance for all the equipment. More precise mass
balance has been done in the Aspen Simulation. The same has been shown in the later
chapters.
Across all equipment, we have only considered compounds that have a significant amount in
the stream. We have not considered losses in our calculations. We have assumed almost ideal
mixtures and complete separations in absorption columns.

6.1 Overall Mass Balance[9][12]

Table 6.1 : Total mass input/output in the process

Compound Input Flow Rate (kg/hr) Output Flow Rate (kg/hr)

Ethylene 2,000 0

Acetic Acid 4,000 0

Oxygen 1,500 0

VAM 0 6,000

Water 0 1,400

Carbon Dioxide 0 400

We have assumed an overall selectivity of 94% and complete conversion of all reactants.
(Single pass conversion = 8%)

6.2 Reactor

There are several constraints in the operation of the reactor [9][12]:

 The concentration of O2 should be less than 8%.
 The ratio of Ethylene to Acetic Acid in the reactor must be between 2:1 and 3:1.
 There must be an inert present for absorption of the heat released during the reaction.
 Here, CO2 is itself used as an inert
Keeping the above constraints in mind, the single pass conversion is limited to 8%(Ethylene).

Table 6.2 : Total Mass Input/Output for Reactor

Page 26
 Compound Input Flow Rate (kg/hr) Output Flow Rate (kg/hr)

Ethylene 26,000 24,000

Acetic Acid 22,300 18,300

Oxygen 4,800 3,200

VAM 0 6,000

Water 0 1,600

Carbon Dioxide 18,000 18,300

The ethylene and acetic acid are separated from the products and recycled back to the reactor
with the feed.

6.3 Phase Separator

The phase separator operates at 4 bar and 30 degree C. We obtain the vapor and liquid
fractions and the component fraction in each of the two streams, as follows:

Table 6.3: Fraction of components in the Liquid and Vapor Phase

Component Mol Fraction, Vapour Mol Fraction, Liquid

EL 0.611202 0.01502

CO2 0.300256 0.002456

O2 0.072261 0.000169

VAM 0.009075 0.128825

AA 0.004308 0.665302

H2O 0.002898 0.188228

Page 27
 Table 6.4: Mass input/output of the Phase Separator

Mass Output, Vapour Mass Output, Liquid

Component Mass Input Stream
Stream (kg/hr)
(kg/hr)

EL 24,000 23,000 100

AA 18,300 350 17,500

O2 3,200 3200 2

VAM 6,000 1,100 4,900

H2O 1,600 100 1500

CO2 18,300 18,250 50

*The second phase separator, operating at 2bar and 25 C was added by us in the Aspen
Simulation stage since the values obtained in the Aspen simulation greatly differed from the
theoretically obtained values. This is because the model in Aspen considered the non-ideality
of the mixture as well.

6.4 Absorber
Table 6.5: Total mass input/output to Absorber
Component Mass Input(kg/hr) Mass Output(kg/hr)

EL 23,000 23,000

AA 350 + 60 410

O2 3200 2

VAM 1,100 4,900

H2O 100 1500

CO2 18,250 50

Acetic Acid is used for absorption of VAM, Water and AA from the vapor stream. Multi-
component McCabe-Thiele Method can be used to design the absorber, i.e. calculate the
number of stages and the amount of AA required for absorption.

6.5 CO2 Splitter

Table 6.6: Mass Balance on CO2 Splitter

Page 28
 Component Mass Input(kg/hr) Mass Output(kg/hr)
(As Purge)

CO2 18,000 1,000

Almost all the CO2 that is present in the reactor (formed or present prior to the reaction)
passes on to the CO2 splitter. Applying a simple mass balance on the splitter, we can calculate
the amount of CO2 released from the splitter as purge stream. K2CO3 is used to absorb the CO2
in the gaseous mixture. McCabe Thiele Diagram can be used to calculate the number of stages
and amount of K2CO3 solution required to absorb the calculated amount of CO2.

6.6 Dehydrator

Table 6.7 : Total mass input/output to Dehydrator

Component Mass Input(kg/hr) Mass Output(kg/hr)

VAM 6000 6000

H2O 1500 1400

VAM and H2O have relative volatility close to unity and thus cannot be separated by normal
distillation. So, glycerol is added, which forms a mixture with water. The mixture can now be
easily separated by distillation. We wish to obtain 99.9% pure VAM.

The accurate mass balance can be performed once simulation has been done on Aspen Plus.

6.7 Overall Mass Balance

Page 29
 Fig. 6.1: Overall Mass Balance

Table 6.1: Overall Mass Balance

(kg/hr) S1 S2 S3 S4 S5 S6 S7 S8 S9 S10
EL 2000 26000 26000 26000 24000 23000 1000 0 0 1000
AA 4000 22300 22300 22300 18300 350 17500 100 450 17950
O2 1500 4800 4800 4800 3200 3200 2 0 0 2
CO2 0 18000 18000 18000 18300 18250 50 0 0 50
VAM 0 0 0 0 6000 1100 4900 0 1100 6000
H2O 0 0 0 0 1600 100 1500 0 100 1600
GLY 0 0 0 0 0 0 0 0 0 0

(kg/hr) S11 S12 S13 S14 S15 S16 S17 S18 S19 S20
EL 100 0 0 1000 0 0 23000 1000 24000 0
AA 0 0 0 0 0 0 0 0 0 17950
O2 2 0 0 2 0 0 3200 100 3300 0
CO2 50 0 0 50 0 0 18250 250 18000 0
VAM 6000 0 6000 0 0 0 0 0 0 0
H2O 1600 0 0 1600 1600 0 0 0 0 0
GLY 0 1200 0 1200 0 1200 0 0 0 0

CHAPTER 7
ASPEN PLUS FLOWSHEET SIMULATION
7.1 Flowsheet Development

Page 30
The various streams and blocks as on the simulation have been explained below. The property
methods used have also been mentioned for all the blocks. Each block has been modelled
using either an individual ASPEN PLUS feature or a combination of 2 or more features.

1. EL, O2, AA Feed to the plant as input

2. RECYCLE, RECYCLE-AA Unreacted raw materials are sent back to the reactor via the
recycle streams

3. AA-MIXER AA (raw material) is mixed with the recycle AA stream

4. HEX-3 Heat exchanger to heat the acetic acid, mixed stream

5. MIXER-R AA is sprayed into the hot and compresses raw material stream

6. SHELLIN and SHELLOUT Streams in the shell-side of the reactor

7. COMPRESS Incoming stream is compressed to 8 bar which is the reactor pressure

8. HEX-1 The reactants are taken to 150 degree celsius before entering the reactor

9. REACTOR A multi-tubular PFR has been modelled. This has been done using the RPlug
model on ASPEN PLUS.
RINLET is the input stream to the reactor and ROUTLET is the output stream.

10. FLASH1 It acts as a primary separator for separation of the condensables(VA, AA, H2O)
from the non-condensables(EL,O2,CO2).

11. FLASH1VAP Vapour stream from FLASH1. It consists of a significant amount of VA which
needs to be extracted. So, this stream goes on for further processing

12. FLASH1LQ Liquid stream from FLASH1

13. FLASH2 A small amount of non-condensables also enter FLASH1LQ. For better
separation, a 2-stage flash is carried out.

14. FLASH2VAP Vapour stream from FLASH2

15. FLASH2LQ Liquid stream from FLASH2

16. CMPRS2 Compress the FLASH2VAP to 4 bar so it can go to absorption column

17. MIXER2 Vapor streams from both FLASH1 and FLASH2 are combined

18. FLASHMIX Combined stream from MIXER2

19. ABS1 Absorber column for absorption of VA, EL and H2O from the vapour stream

20. AA-ABSC Acetic acid is sent into the absorber as an absorbent

Page 31
21. ABSTOP Vapour stream exiting from the ABS1

22. ABS2 absorption column for absorption of CO2 from ABSTOP stream

23. K2CO3 Potassium carbonate stream as an absorbent for absorption of CO2 from the
ABSTOP stream

24. KHCO3 Potassium bicarbonate formed as a result of absorption of CO2. The stream
exits ABS2 and enters REG for CO2 regeneration

25. REG CO2 is regenerated by heating KHCO3 solution. It acts as the purge stream

26. SEP A part of regenerated CO2 is regenerated and the rest is purged via the PURGE
stream

27. SPLITTER It splits the acetic acid stream obtained from DIST1BOT to stream to be
recycled and stream for absorption

28. ABSBOT Liquid stream exiting ABS1. It consists of the acetic acid used as absorbent
along with VA, H2O and absorbed AA from FLASHMIX. It consists of a significant
amount of VA

29. MIXER3 Combines the two liquid streams, ABSBOT and FLASH2LQ.

30. LIQMIX Combined liquid stream from MIXER3

31. DIST1 First distillation column that separates AA from the azeotropic mixture of VA and
H2O

32. D1BOTTOM Bottom stream from DIST1, which mainly consists of AA, which is recycled
to the feed and to ABS1

33. D1TOP The distillate obtained from DIST1, consisting mainly of VA+H2O

34. GLYCEROL Glycerol stream, mixed with D1TOP, is used for separation of VA from H2O

35. DIST2 Distillation column used to separate VA from the mixture of H2O and Glycerol

36. D2TOP Distillate obtained from DIST2, consists of VA, ~ 92% pure

37. D2TOP Bottom stream obtained from DIST2, consisting of mixture of H2O and Glycerol

38. EVAP H2O and glycerol have a large difference in their boiling points and thus are easily
separated using an evaporator. This has been modelled using a flash drum with heat
input, QEVAP

39. QEVAP Heat input to the flash drum, used to model it as an evaporator

40. EVAPTOP Water, having a lower boiling point is obtained from the top of the
evaporator
Page 32
 41. EVAPBOT Glycerol, having a higher boiling point, stays back in the evaporator. It is
recycled back to stream GLYCEROL

42. FLASH3 To further purify the VA stream(D2BOTTOM), the stream is sent to a flash drum
for removal of EL and CO2

43. VAMFINAL VAM stream produced with required purity

7.2 ASPEN PLUS Flowsheet

Page 33
 Fig 7.1: ASPEN PLUS

Flowsheet Simulation
7.3 STREAM Summary

Page 34
 The following table shows the stream summaries - pressure, temperature and composition of
various streams.

Table 7.3.1: Stream summary from input to the Reactor Inlet

Stream Name Units EL O2 AA RECYCLE RECYC-AA CINLET COUTLET RINLET
Phase Vapor Vapor Liquid Vapor Vapor Vapor Vapor Vapor
Temperature C 30 30 30 28.4756 30 120 287.765 150
Pressure bar 1 1 1 1 2 1 8 8
Mass Flows kg/hr 2447.9 1908.65 4455.458 45499.45 17694.25735 70964.1 70964.1 70964.1
ETHENE kg/hr 2447.9 0 0 23548.5 1.28483E-10 25996.4 25996.4 25996.4
WATER kg/hr 0 0 0 9.63E-06 655.9005449 0 0 0
OXYGEN kg/hr 0 1908.65 0 2836.5 3.11272E-17 4745.15 4745.15 4745.15
GLYCEROL kg/hr 0 0 0 0 0 0 0 0
AA kg/hr 0 0 4455.458 790.252 17034.2 22280 22280 22280
CO2 kg/hr 0 0 0 18089.4 3.17628E-11 17942.6 17942.6 17942.6
VAM kg/hr 0 0 0 235.836 4.151677834 0 0 0
K2CO3 kg/hr 0 0 0 0 0 0 0 0
KHCO3 kg/hr 0 0 0 0 0 0 0 0

Table 7.3.2: Stream summary from Reactor outlet to Flash streams

Stream Name Units ROUTLET FLASH1LQ FLASH1VP FLASH2LQ FLASH2VP FLASHMIX ABSBOT
Phase Vapor Liquid Vapor Liquid Vapor Vapor Liquid
Temperature C 162 30 30 30 30 30 33.3238
Pressure bar 8 4 4 1 1 1 4
Mass Flows kg/hr 70964.1 24420.2 46544 23662.6 757.509 47301.5 8248.78
ETHENE kg/hr 23869.4 453.707 23415.7 107.44 346.267 23761.9 122.921
WATER kg/hr 1451.19 1391.32 59.8759 1387.54 3.78178 63.6576 63.6575
OXYGEN kg/hr 3153.38 5.64581 3147.74 0.157632 5.48818 3153.22 1.55682
GLYCEROL kg/hr 0 0 0 0 0 0 0
AA kg/hr 18011.1 17657.2 353.887 17635.1 22.1219 376.009 6544.16
CO2 kg/hr 18359.3 370.503 17988.8 91.8919 278.611 18267.4 99.2368
VAM kg/hr 6119.8 4541.75 1578.05 4440.51 101.239 1679.28 1417.24
K2CO3 kg/hr 0 0 0 0 0 0 0
KHCO3 kg/hr 0 0 0 0 0 0 0
Stream Name Units LIQMIX D1BOTTOM D1TOP GLYCEROL DIST2IN D2BOTTOM
Phase Mixed Liquid Liquid Liquid Mixed Liquid
Temperature C 30.5089 139.328 10.846 30 14.536 157.883
Pressure bar 1 2.06843 2.06843 2 2 4
Mass Flows kg/hr 31911.4 24965.5 6945.94 1000 7945.94 1644.88
ETHENE kg/hr 230.361 1.81E-10 230.361 0 230.361 9.14E-07
WATER kg/hr 1451.19 925.435 525.759 0 525.759 494.214
OXYGEN kg/hr 1.71445 4.39E-17 1.71445 0 1.71445 2.16E-12
GLYCEROL kg/hr 0 0 0 1000 1000 1000
AA kg/hr 24179.3 24034.2 145.076 0 145.076 144.814
CO2 kg/hr 191.129 4.48E-11 191.129 0 191.129 3.59E-07
VAM kg/hr 5857.76 5.85776 5851.9 0 5851.9 5.8519
K2CO3 kg/hr 0 0 0 0 0 0
KHCO3 kg/hr 0 0 0 0 0 0
Table 7.3.3: Stream summary of liquid streams after flash

Page 35
 Table 7.3.4: Stream summary of vapour stream from flash
Stream AA-
Name Units ABSOR ABSBOT ABSTOP K2CO3 ABS2TOP KHCO3 PURGE
Phase Liquid Liquid Vapor Liquid Vapour Liquid Vapour
Temperature C 30 33.3238 38.4756 10 22.3256
Pressure bar 1 4 4 4 4 1 1
9236.21
Mass Flows kg/hr 7000 8248.78 46052.7 8248.78 3 237
ETHENE kg/hr 0 122.921 23639 0 23639 0 0
9.63E-
WATER kg/hr 0 63.6575 05 0 9.63E-05 0 0
OXYGEN kg/hr 0 1.55682 3151.67 0 3151.67 0 0
GLYCEROL kg/hr 0 0 0 0 0 0 0
AA kg/hr 7000 6544.16 831.844 0 831.844 0 0
CO2 kg/hr 0 99.2368 18168.1 0 8456.32 0 237
VAM kg/hr 0 1417.24 262.04 0 262.04 0 0
K2CO3 kg/hr 0 0 0 9000 0 0 0
9236.21
KHCO3 kg/hr 0 0 0 0 0 3 0

Table 7.3.5: Stream Summary of stream of evaporator and flash3

Stream Name Units WASTE VAMFINAL EVAPBOT EVAPTOP
Phase Vapor Liquid Liquid Vapor
Temperature C 40 40 172.256 347.642
Pressure bar 2 2 2 2
Mass Flows kg/hr 544.462 5756.6 #REF! 1644.88
ETHENE kg/hr 205.477 24.8835 4.16E-08 9.14E-07
WATER kg/hr 3.86629 27.6793 32.2 432.014
OXYGEN kg/hr 1.69369 0.0207577 #REF! 3.24E-13
GLYCEROL kg/hr 0 0 999.623 0.377
AA kg/hr 0.00215499 0.2591 4.489 140.325
CO2 kg/hr 170.012 21.1171 #REF! 1.24E-08
VAM kg/hr 163.411 5682.64 1.5959 4.256
K2CO3 kg/hr 0 0 0 0
KHCO3 kg/hr 0 0 0 0

CHAPTER 8
SENSITIVITY ANALYSIS
ASPEN PLUS allows us to control process variables and hence improve as well as optimize the
performance of proposed plant. Having done the basic flowsheet simulation and material
Page 36
balance, here we performed a sensitivity analysis of the major equipment in the proposed
plant so as to optimize the Vinyl Acetate production. The Flash drum(two flash drums were
used), Absorber column, Distillation column and the Reactor have been analysed in this
section.

8.1 FLASH DRUM

It acts as a primary separator for separation of the condensables (VA, AA, H2O) from the non-
condensables (EL,O2,CO2). The variables chosen for sensitivity analysis for Flash Drum are
temperature and pressure. We have analyzed the effect of temperature and pressure variation
on the amount of VAM(kg/hr) in condensate.
Temperature for the purpose of analysis was varied over a range of 10°C to 150°C5 at
pressures from 1 to 10 bar.

Fig: 8.1 Plot of effect of temperature at certain pressure on the amount of VAM (kg/hr)
in Flash condensate

The graph above shows the sensitivity result of effect on VAM in condensate by varying
temperature over pressure from 1 to 10 bar. It can be observed that as we increase the
pressure in chosen temperature range, the amount of Vinyl Acetate (kg/hr) in condensate
increases. As the temperature decreases, the amount of VAM in the condensate again
increases. Thus, high pressure and low temperature are ideal for our separation.

Page 37
 Graph 8.2: AA flow rate in FlashVap stream vs Temperature

Graph 8.3: EL flow rate in FlashVap stream vs Temperature

As can be seen, as we lower the temperature, the amount of Ethylene in the Liquid stream
also increases. We wish to minimize this as well, hence cannot take the temperature too low.
We thus chose to operate the flash at 4 bar and 30 degree Celsius.

8.2 ABSORPTION COLUMN

Having passed through both of the flash drums, the feed is divided into liquid and gaseous
streams. Acetic acid is used as scrubber in order to extract remaining VAM from the gaseous
extract of the flash drum. VA is soluble in acetic acid.

The sensitivity analysis was performed to optimize the amount of Acetic Acid needed to scrub
the maximum amount Vinyl Acetate from the gaseous extract.
Page 38
 Fig: 8.4 Amount of Acetic acid vs Mass flow of VAM from absorber column

The sensitivity analysis result showed that the amount of acetic acid for optimum extraction of
vinyl acetate is approximately 6000 kg/hr. A saturation is obtained at this flow rate.

Similarly, the analysis was also performed on effect of number of stages in the absorption
column. Amount of VAM entering the column into gaseous phase is ~1200 kg/hr. From the
plots obtained, it can be concluded that as we increase the number of stages the absorption of
VA (kg/hr) into acetic acid also increases. However, after ~9 stages the absorption rate ceases
to increase. In the proposed plant, our absorption unit has 9 number of stages.

Fig: 8.5 Effect of number of stages on VAM absorption

Amount of VAM absorbed into acetic acid after optimal condition of 6000 kg/hr acetic acid
inflow and 9 stages was found to be 1180.26 kg/hr out of 1203 kg/hr.

8.3 DISTILLATION COLUMN

Page 39
Sensitivity analysis has been performed on DIST1. The inlet of the distillation column
comprises of flash bottom outlet and the liquid coming from absorption column. The inlet
components are water, vinyl acetate, and acetic acid which enter into azeotropic distillation
column.
On distillation, we obtain vinyl acetate and water(azeotrope) at the top and acetic acid at the
bottom. Since we fix the purity of the VA and AA we require (as required by ASPEN, shortcut
distillation model), another important parameter that can be studied is the reboiler and
condenser heat.

Fig: 8.6 Effect of number of trays on reboiler and condenser heat in distillation column

Vinyl Acetate is the light feed recovery whereas Acetic Acid is the heavy feed recovery.

Light feed recovery(LFR) = 0.999

Heavy feed recovery(HFR) = 0.0006

The number of stages in the distillation column has a direct effect on the amount of heating
required by reboiler or the cooling required by condenser.

The following tables were obtained from ASPEN, which include information about distillation
column variables at
a. Number of stages = 9
b. Number of stages = 15

Page 40
 Fig: 8.7 Variation in different parameters with change in number of stages

Fig:8.6 and 8.7 suggests that as number of trays in distillation column is increased reboiler
heat duty and cooling required in condenser also decrease. From the sensitivity analysis, we
fixed 23 number of trays for our distillation column. We cannot choose a large number of
trays, even if the heat duty is lesser, due to mechanical reasons.

8.4 REACTOR
A fixed bed multi-tubular reactor was selected for proposed plant of Vinyl Acetate. The reactor
condition were taken to be almost isothermal i.e. 160 degrees Celsius and 8 bar pressure. The
Page 41
inner diameter of tube was fixed to be 30mm and gas velocity was kept at 0.5 m/s. Palladium
based catalysts were chosen with a void fraction of 0.8.

Number of tubes were calculated from the given expression:

Which gives N=923 tubes.

Now we vary the length of the tube fixing the temperature at 160 degree celsius.

Fig: 8.8 Change in Temperature of reactor with Length

For reactor to operate at temperatures closer to 160 degrees, the length of the reactor was
kept at L~ 9 to 10m.

Page 42
 CHAPTER 9
EQUIPMENT SIZING AND COSTING
In this section, we size the major equipment used in the plant and also estimate the cost of
each of the equipment [13][14]. The location index for India with respect to US has been taken to
be 0.7. The Dollar to INR conversion factor has been rounded off to 70. We have used
Chemical Engineering Plant Cost Index for inflation and changes in time value of our
equipments. All equipment cost have then been converted to f-o-b basis. Direct and Indirect
costs in FCI are calculated using percentage normalization from Peters et. al. Major equipment
cost is either done from empirical formulae in Walas et. al.or by power factor scaling method
with appropriate cost indices. All equipments are mapped to 2018 cost index.

Table 9.1: Cost Indexes for years 2002 and 2018

2002 2018

9.1 COMPRESSORS
We are using two compressors in our plant. The first compressor is used to compress the inlet
feed to 8 bar before it enters the reactor. Another compressor is used to compress the vapor
stream from FLASH2 to 4 bar from 2 bar.

Calculations for first compressor are shown as under.

Model: 2-stage compressor with Inter-Stage cooling

Inlet Pressure : 1 bar.
Discharge Pressure: 8 bar
Flow Rate: 48684.2 kg/hr ( EL+O2+CO2)
Compressor ratio = (P2/P1)^(0.5) = 2.82

Page 43
 Fig 9.1: Power Required vs Purchase Cost

Calculating the work done by the compressor:

Where,
P1: Inlet pressure
P2: Outlet pressure
V1: Inlet specific volume (Which we get from Aspen)
N: Heat capacity ratio ( Cp/Cv ) ~ 1.4

Power = Work per unit mass * mass flow rate / isentropic efficiency

The power required for stage one and stage two is 1677 and 1666 kW respectively. Hence the
total power comes out to be 3343 kW. Isentropic efficiency = 0.75
We have used a centrifugal pump.
Hence,
Purchased cost for compressor with stainless steel as MoC from the adjacent graph comes out
to be ~ INR 8.7 cr. This when converted to Indian price in 2018 comes out to be INR 12.23 cr.

Page 44
 Table 9.2 Compressor Costs
Equipment Cost, INR

Compressor 1 12.23 Crores

Compressor 2 5.23 crores

9.2 COLUMNS
We have 4 columns in our plant, including two distillation columns and two absorption
columns. The sheet thicknesses were calculated using internal pressure, wind load and other
considerations. The regulation thicknesses were then calculated by giving some extra
corrosion allowance and milling tolerance. This thickness, is then used to calculate the weight
of the different columns depending upon their shape and then fabrication cost has been
calculated using standard graphs that relate weight of the erected column to the cost. In case
of distillation columns, cost of trays has been calculated again from a similar graph.
The following formula has been taken from Walas[13]:

For absorption column:

Taking lt = 0.61 , we get, from formula, D = 1.6 m
Number of trays = 9
Height of Tower = 6.1 m

For distillation column

Diameter:1.46 m
Tray Spacing: 0.6096 m (from ASPEN)
Number of trays = 23
Height of tower = 16.12m

Calculation of cost and thickness for one absorption column are shown below:

Diameter = 1.60 m
Tray Spacing = 0.61m
Number of trays = 9

Page 45
Height of Column = 5.5m
About 10% of height includes the space at the top, space for manual operations.
Thus, height = 6.1m
Operating Pressure = 4 bar
Calculating vessel thickness required:
Pw = 0.8 x 0.0025 Vw2 = 0.002 Vw2
0.8 is used as the shape factor for cylinder
Pw is the wind pressure in pound per square foot
Vw is the wind velocity in Miles per hour

Since we are setting up the plant in Gujarat, we have taken the wind velocity as 50m/s [15] or
111.8 miles/hr which is the highest in the region. Therefore,
F = G x Pw x A
Where G is Gust response factor and its value is 1.4
M = F (H/2)
tw ≥ M / [(πR^2)ESa]
Where Sa is the allowable stress
E is the corrosion allowance
M is the bending moment

Sa is calculated by dividing yield strength by a safety factor of 4

Sa = 137 MPa for stainless steel
E = 0.8
By putting the values, adding 12.5% milling tolerance and 2 mm corrosion allowance,
Tw = 10.5mm
Thus we use 10.5 mm thickness.
Volume of SS = 0.29 + 0.08 = 0.376 m3
Weight = 2320.33~2300 kg

Page 46
 Fig 9.2: Weight in Kg vs Purchase Cost for various material

Fig 9.3: Column diameter vs Installed cost/tray

Cost of Column (2018, INR): Rs 97.64 lakhs

Cost of Trays = 4.89 lakhs
Total Cost = Rs. 81.53 lakhs

Page 47
 Table 9.3: Columns and estimated costs
Equipment Component Cost (INR)
Distillation Column-1 Column 84.43 lakhs

Trays 1.25 lakhs

Reboiler 45.2 lakhs

Condenser 25.3 lakhs

Total 156.18 lakhs

Distillation Column-1 Column 90.045 lakhs

Trays 1.42 lakhs

Reboiler 48.5 lakhs

Condenser 32.52 lakhs

Total 172.485 lakhs

Absorption Column-1 Column 97.64 lakhs

Trays 4.89 lakhs

Total 101.53 lakhs

Absorption Column-2 Column 57.674 lakhs

Trays 3.89 lakhs

Total 61.564 lakhs

9.3 HEAT EXCHANGERS

There are many heat exchangers in the plant. Their cost primarily depends on the surface
area.
The following graph has been used to calculate the purchased cost of the heat exchangers.

Page 48
 Fig 9.4: Surface area required vs purchase cost for Heat Exchanger

All heat exchangers used are shell and tube heat exchangers and their MoC is Stainless Steel
316. We have taken heat integration (Chapter 12) into account to calculate the costs.

HEX Tin Tout Area (m2) Cost (INR)

HEX1 130 150 324 50.4 Lakhs
HEX2 50 30 56 7.2 Lakhs
HEX3 70 120 89.63 15.96 Lakhs
HEX4 117.6 30 102 16.1 Lakhs
HEX5 99.46 30 122 18.2 Lakhs

Area is calculated using A=Q/(U*∆LMTD ).

U is determined using Nusselt and Reynolds numbers(method shown in detail in reactor
design).
Sample Calculation for HEX3:
Cooling Agent: Cooling water at 30 C
Stream is heated from 70 to 120 C
Cooling water heated upto 40◦C
∆LMTD = 24.85◦C
Overall heat transfer coefficient (U) = 1083.66 kJ/hr/m2/K
Here, m = 22280 kg/hr
Cp = 2166.7J/kgK
Q = m·Cp·∆T = 2413703.8 kJ

A=Q/(U*∆LMTD ) = 89.63 m2

Hence,
Total cost of Heat exchangers = INR 107.86 Lakhs
Page 49
9.4 FLASH DRUM
The following formulae have been obtained from Walas [13] for calculation of uperm and hence
size the flash drum:

From ASPEN, we get:

Liquid density: 994.96 kg/m3
Vapor Density: 5.4 kg/m3

Kdrum comes out to be 0.1334 m/sec

Uperm = 1.82 m/sec
M=V×ϱ
M = A × uperm × ϱ
A = πD2/4
D = 1.294 m

For Vertical Flash Drums:

C = FMCb + Ca; where Cb represents the cost implied by the volume of MoC required and Ca
represents the cost borne out by the supplements like ladders and platforms. Here MOC is
Stainless Steel, 304 and hence FM = 1.7. From Walas[13]:

Cb = e[9.100 - 0.2889(lnW) + 0.04576(ln W)^2]

Ca ~ 246×D0.7369 × L0.7068
Ca = INR 3.1 Lakhs & Cb = INR 4.16 Lakhs.
Therefore, C= INR ~19 Lakhs
Similarly, cost of second flash drum = INR 12.5 Lakhs

Page 50
9.5 Pump

For One Stage Centrifugal Pumps[15]:-

C = FmFtCb, Cb = 1.55e8.833 - 0.6019(ln(Q×H^0.5)) + 0.0519[(ln (Q*H^0.5))2]
Where, Q is in gpm, H is in ft head and here MOC (stainless steel) has F m=2.0
Ft = e[5.1029 - 1.2217[ln(Q*H^0.5)] + 0.0771[ln(Q*H^0.5)]2

Table 9.4: Pumps and Costs

Equipment Cost, INR

Pump 1 8.64 lakhs

Pump 2 5.82 lakhs

Pump 3 6.84 lakhs

Pump 4 6.47 lakhs

9.6 STORAGE TANK

There are two types of storage tanks: Floating Head and Fixed Head. Since VAM does not react
with air, we have decided to go ahead with cone-roof fixed head tank of carbon-steel. We shall
be using two storage tanks, each with the capacity to store 1 month of VAM produced. To
store VAM produced in 1 month, the capacity of storage tank should be:

6000 kgs x 8000/12 x density = 37,36,000 liter = 3,736m 3 or 9,83,333 gallons ~ 106

From Fig 9.7, which is shown below, Cost of 10^6 gallons capacity tank in 1990 = 1.8×100000$
= 180,000 USD

Therefore Purchasing Cost in 2018 = 180,000 × (575)/357.6 = 290,000 $

Final Purchasing Cost = 290,000 USD ~ INR 2 crore

Fig 9.7: Capacity vs Purchase cost for storage tanks

Page 51
9.7 REACTOR

Reactor type is multi-tubular fixed bed reactor. Our reaction conditions guides us to operate
the reactor at 8 bar and 150 degree celsius.
Catalyst void fraction is obtained from literature to be 0.8 for our palladium based catalyst

N = 923 tubes

Table 9.5: Reactor Sizing

Number of Tubes 923

Length of each tube 9000 mm

Internal Diameter tube 30 mm

Diameter of Reactor 4500 mm

Thickness of tube(SS) 1 mm

Thickness of outer cylinder(CS) 2 mm

Table 9.6: Costs of Reactor

Mass of catalyst (Rs 875000/ kg) 800 kg

Cost of Catalyst* Rs 70 Crore

Cost of Reactor Rs 14 lakhs

*renewed every 2.5-3 years

9.8 Raw Material Cost and Revenue

Raw Material Cost:
Acetic Acid : Rs. 30000/ton * 2 ton/hr = Rs. 60,000 /hr
Ethylene : Rs. 52,500/ton * 2 ton/hr = Rs. 1,05,000 $/hr
Oxygen : Rs. 4480 /ton * 1.5 ton/hr = Rs. 6720 /hr
Raw material cost = Rs. 171720/hr = 171720*8000 working hours = Rs. 137.37 Crore

Product Cost : 1400 $/ton * 6 ton/hr = 8400 $/hr*8000 working hours = Rs. 470.4 cr/annum
Catalyst Cost = Rs. 23 crore per annum

9.9 Payback Period

To estimate the overall cost using raw material costs as basis we have made few assumptions.
During the operating period of our plant the price of our final products is assumed to be
constant. The cost of Raw material do not fluctuate during the life time of the plant.
Approximately 90% of the FCI excluding the land cost is assumed to be depreciable over a

Page 52
period of 10 years and depreciation occurs at linear rate. Bank interest applicable is 6% per
annum over TCI.Finally taxation rate is assumed to be 3%.

Table 9.7: Cost Bifurcation

Charges Percentage of Total Cost Cost in Crore INR
Raw material Cost 40 137.37

Operating labour 0.5 1.706

Supervising labour 0.3 1.025

Utilities 8 27.32

Maintenance 5 17.07

Supplies 1 3.42

Patents 1.5 5.12

Fixed charges 10 34.15

Plant overheads 8 27.32

Distribution and Marketing 10 24.15

RnD 3 10.24

Total 288.891

Total Cost of our project is Rs 288.891 Crores. Depreciable Fixed cost investment is Rs 158.45
Crores it gives us a depreciation of Rs 15.85 Crores/year.
Our Revenue per year assuming 8000 working hour per annum is Rs 470.4 crores
Gross Profit = Revenue - Total Product Cost - Depreciation per year
= Rs. (470.4-288.91-158.45-15.85)
= Rs. 7.19 Cr
Net profit = Gross Profit*(1 - taxation rate)
= Rs. (7.19)(1-0.33) = Rs. 4.8173 Cr
Interest = Bank Rate * TCI = Rs. 0.06*(Rs 288.91+158.45 Cr)
= Rs. 26.84 Cr

Thus, Payback period for our plant

Page 53
= (158.45+26.84)/(4.8173+15.85)
= 8.96 years

Payback Period = 8.96 years

Page 54
 CHAPTER 10
DETAILED EQUIPMENT DESIGN:
REACTOR
Vinyl acetate production is an exothermic process that is implemented in multi tubular,
isothermal reactor. Acetoxilation in a gaseous phase of ethylene over palladium and gold
catalyst supported on silica gel is done in the temperature range of 150 C to 160 C at 8-10 bar
pressures. There is a second unwanted reaction in the process based on the ethylene
oxidization to produce water and carbon dioxide. Typical catalyst lifetime is 2.5 years. Hot
spots above 200 ° C lead to permanent catalyst deactivation. The reactant ratio should ensure
an excess of ethylene to acetic acid of about 2 : 1 to 3 : 1. Due to an explosion danger the
oxygen concentration in the reaction mixture should be kept below 8%, based on an acetic -
acid - free mixture.

10.1 Reactor Design

To design the reactor, it was established that it had to be done isothermally trying to prevent
the sections that exceed 165°C which in turns lowers the catalyst activity. To control the
temperature effect, the use of an inert gas was applied, in this case nitrogen. Besides this, the
reactors are designed to achieve a low conversion of ethylene by each pass. It has to be taken
in to account that activation energy of the unwanted reaction is greater than the activation
energy of the wanted reaction, so at higher temperature the selectivity will be affected.

Primary reaction -
�2�4 + �2�4�2 + 0.5�2 → �4�6�2 + �2�
Secondary Reaction -
�2�4 + 3�2 → 2��2 + 2�2�
Following are the specifications:
● Conversion of Ethylene per pass = 8%
● Catalyst used is palladium and gold catalyst supported on silica gel
● Type of reactor - Multi tubular reactor
● Pressure drop (Calculated by Ergun equation) = 0.3 bar
Because of the highly exothermic effect, measures to moderate the temperature increase are
necessary, such as the dilution of the reaction mixture with some inert gas. Carbon diOxide
produced in the process is used as an inert.

Stream Composition:

Table: 10.1 Stream Composition (Input/Output) for Reactor

Compound Input Flow Rate (kg/hr) Output Flow Rate (kg/hr)

Ethylene 26,000 24,000

Acetic Acid 22,300 18,300

Page 55
 Oxygen 4,800 3,200

VAM 0 6,000

Water 0 1,600

Carbon Dioxide 18,000 18,300

Table 10.2 Catalyst Specification

Catalyst Size 4-6 mm Pd spheres

Voidage 0.8

Deactivation time 2.5 years

Density 1.202 g/cm3

Table 10.3 Reactor Dimensions

Number of Tubes 923

Length of each tube 9000 mm

Internal Diameter tube 30 mm

Diameter of Reactor 4000 mm

Thickness of tube(SS) 3 mm

Thickness of outer cylinder(CS) 8 mm

10.2 Energy Balance in Reactor

Heat of reaction = 176.2 KJ/mol VAM

Moles of VAM formed = 20 mol/sec
Heat produced = 3500 KJ/sec
Thermal Conductivity (From Aspen) = 0.037 W/mK
T_feed_inlet = 150 C
T_feed_outlet = 160 C
Heat absorbed = mCpΔT = 540 KJ/sec
(Cp = 2711.4 J/kgK, m = 19.7 kg/sec)

Calculating heat transfer coefficient using reynold and nusselt numbers, we get:

Page 56
Re = 1200, Nu = 230, hence U ~ 250 W/mK
Shell side U = 28 W/mK

Thus, we model our reactor as follows:

We calculate Pressure drop using the Ergun Equation:

Viscosity = 2.05*10^-5 Ns/m2

Density = 9.6 kg/m3
U = 0.5 m/s
e = 0.8

We get P drop ~ 0.35 bar

Baffles are needed to be installed in the reactor.

Do = 4000 mm

According to TEMA standards,

Boptimal = 0.4*Do = 1600 mm (Bmin = 800mm)
Lbmax = 52do + 532 = 2092mm

Thus, number of baffles required = 3 | single-segmented baffles

Baffle Cut = 25% of effective area.
10.3 Reaction Kinetics
A probable reaction mechanism could be formulated as follows:

Page 57
As a result, from a reactor - design viewpoint the reaction kinetics is not sensitive to the
concentration of the acetic acid.
Rate of formation of VA is given by:

�1 0.36

�1 0.20

E1(J/mol) 15,000

A1 (𝒎𝒐� 𝒌� of 𝒄𝒂�^(−�) 0.000265

* �^ (−�) * 𝑷𝒂^−(�+�)

The exponent α1 is 0.35 – 0.38 and β1 0.18 – 0.21 indicating strong adsorption limitations. The
reaction constant is given by k1 = A1 exp( −E1 / RT ) in which the energy of activation (A1)
depends on the Pd content.
Similar kinetics has been found to describe the secondary combustion reaction.

�2 -0.31

�2 0.82

E2(J/mol) 21,000

A2 (𝒎𝒐� 𝒌� of 𝒄𝒂�^(−�) 0.000750

* �^ (−�) * 𝑷𝒂^−(�+�)

TOF gives the number of molecular reactions or catalytic cycles occurring at a center per unit
of time. For a heterogeneous catalyst the number of active centers can be found by means of
sorption methods.

The catalyst is characterized by the metal weight fraction w(Me) with MW(Me) the atomic
weight, the metal dispersion coefficients D giving the fraction of active centers, and ρ(cat) the
grain catalyst density. By replacing into the relation (10.5) the following formula can be
obtained for the calculation of TOF from kinetic experiments:

Page 58
Rate of the exothermic reaction is hugely dependent on temperature. The reactor runs in the
range of 150 to 160 degrees Celsius. Dependence of reactor length on temperature can be
given as(plotted in aspen) for 8% conversion of ethylene-

10.4 Hazop Analysis

A hazard and operability study (HAZOP) is a structured and systematic examination of a
complex planned or existing process or operation in order to identify and evaluate problems
that may represent risks to personnel or equipment. It systematically questions the design to
discover how it can deviate from the design intention and can lead to undesirable
consequences.
The questions are formulated using a number of guide words to ensure a consistent and
structured approach. The guide words are normally applied in conjunction with a series of
process parameters to arrive at a meaningful deviation.
A preliminary Hazop analysis here is done on the VAM reactor taking into consideration 3
primary parameters, namely flow, temperature and pressure. The following table shows the
analysis consisting of causes, consequences and actions required for each situation.

Table 10.4 : HAZOP study of the VAM reactor

10.5 Control Strategy

Following the process parameters as mentioned in HAZOP studies, appropriate
instrumentation is to be installed to keep the operation of reactor safe.
● TC1 to control inlet temperature, should be 150 C
Page 59
 ● PC to vent off the gases in case of high pressures in the reactor
● TC2 to control hotspots

Fig 10.1: Control strategy for reactor

CHAPTER 11
ENVIRONMENTAL IMPACT ASSESSMENT
With the increasing pollution levels causing extreme climate changes in many parts of the
world, it is important that we treat all our effluents and keep a check on our emissions. This
chapters deals with all the effluent streams and how they can be treated.
Page 60
11.1 Legally Allowed Concentrations[16]

Table 11.1: Legally allowed concentrations in emission/effluents

Name Concentration Discharge point

EL 0.19- 0.68 m3/ton water

Pd 7 mg/l Water

EL LFL= 2.7, UFL = 36[17] Air

VAM 2 g/m3 Air

11.2 Emissions

11.2.1 Purge
The purge stream has the following compositions:

Table 11.2: Mass Flow rate of streams, from ASPEN Simulation

Mass Flow Rate ABSTOP/ PURGE
(kg/hr) RECYCLE
EL 23548.5 78.74
H2O 9.65e-05 10.26
O2 3151.7 2.3654
AA 831.9 13.4552
CO2 18089.4 78.7418
VAM 62.222 3.2556
Total 46053 186.819

The purge stream can be flared off since it consists of a relatively small amount of EL, which is lower
than the flammability limits.

11.2.2 WASTE Stream

The VAM obtained from the distillation column is sent to a flash column to increase the purity
of the VAM. EL and CO2 are removed from the VAM stream and we get a stream with 99.8%
purity.

As obtained from ASPEN Simulation, following is the composition of the WASTE stream:

Page 61
 Table 11.3: Composition of WASTE Stream
Component Mass Flow Rate
(kg/hr)
EL 206.477
H2O 3.86
O2 1.69
AA 0.002
CO2 170.012
VAM 163.411
Total 544.462

This stream escapes from the plant in gaseous form. We have to decide if the harmful
components (here, EL and VAM) are within allowable limits.

To find the concentration of the same, we assume that the discharge is at a height of 10m. We
calculate the concentration at 1.5m, 1m away from the flash drum. (D of the drum is 0.9m).
We use the following formula[18]:

Where x, y, z are distances from source in m. (x=downwind, y=crosswind, z=vertical);

C = Concentration in kg/m3 at (x, y, z); Gv = Vapour emission rate in kg/s; H = Height of the
source above ground level plus plume rise (m); u = wind velocity in m/s;
σx and σy are dispersion constants. We have chosen stability class F, which is the worst case
scenario.

Using above formula, we get the following concentrations:

EL = 0.016 kg/m3 = 14000 ppm < LFL
VAM = 0.013 kg/m3 > maximum limit

Thus, this stream cannot be directly vented out into the atmosphere and needs to be treated.
Since the amounts are not very high, we choose to flare the stream.

11.2.3 Stream EVAPTOP

2 streams are obtained from the evaporator. The top stream consists mainly of water and the
bottom stream consists of glycerol. The bottom stream is recycled back to the reactor with a
small amount of the stream being purged. The top stream is water, and is sent to an effluent
treatment plant.

EVAPTOP consists of 414 kg/hr of water and 10 kg/hr of glycerol.

Page 62
11.3 CO2 for plant operation using OpenLCA

OpenLCA is a software that helps us calculate the life cycle assessment of a plant. This includes
everything from setting up of a plant to its operation.
There are direct CO2 emissions from our plant, in the purge stream and the waste stream that
we flare. Apart from this, there are also indirect CO2 emission from our plant. All the process
involve some emissions which can be converted to CO2 equivalent. The electricity used, raw
materials/products transport, all the activities contribute to this. We set up our plant in Rajkot,
Gujarat. The electricity used was calculated by summing the power requirement of pumps and
compressors. All these values were put as an input in the software and the impact assessment
was done. We obtained the following result:

Table 11.4: LCA (in terms of GWP) of VAM production process, CO 2e/ ton VAM produced

GWP refers to Global Warming Potential. Thus, the emissions from the plant will be
responsible for trapping as much heat as the amounts of CO2 mentioned above would. The
environmental impact can also be measured in terms of other forms of pollution, as depicted
in the following table:

Table 11.5: LCA of VAM Production process

CHAPTER 12
HEAT INTEGRATION
A major part of the heat integration was done in chapter 10, in our reactor. The reaction is
highly exothermic and a large amount of heat is released in the reactor. This heat is in-turn
used to heat up the reactants closer to the reaction temperature. Thus, the large amount of
heat has been used efficiently.

Page 63
 Our plant also has 2 cold streams and 3 hot streams. Heat integration has been done among
these streams.

12.1 Hot and Cold streams

The following are the hot and cold streams with their required change in temperature and
gain/loss of enthalpy:

Table 12.1: Stream Table

Stream Name T in T out Delta H(J/sec)

SHELLOUT 130 150 733236.6394

AAHEAT 30 120 1206462

AAABS 120 30 -379050

K2CO3 50 30 -45833.33333

EVAPTOP 170 30 -68600

12.2 Pinch Analysis

We use the Stream table method to carry out the pinch analysis [13].

Table 12.2: Pinch Analysis Calculations(a)

Stream T Tact
T in Delta H(J/sec) Cp mass flow rate Tact out delh kw
Name out in
13.5233611 733.2366
SHELLOUOT 130 150 733236.6394 2711 48684.1 125 145
1
6.18888888 1206.462
AAHEAT 30 120 1206462 2166 22280 25 115
9
1.94444444 -379.05
AAABS 120 30 -379050 2166 7000 -125 35
4
1.52777777 -45.833
K2CO3 50 30 -45833.33333 1500 5500 55 -35
8
0.11666666 -68.6
EVAPTOP 170 30 -68600 4200 420 175 -35
7

Table 12.3: Pinch Analysis Calculations(b)

175 0 615770
145 30 1489 44670 44670 -44670 571100
125 20 3655 73100 73100 -117770 498000
115 10 4200 42000 42000 -159770 456000
Page 64
 55 60 5700 342000 342000 -501770 114000
35 20 5700 114000 114000 -615770 0
25 10 -2166 -21660 -21660 -594110 21660

From the calculations, we get

Minimum hot utility required = 615 kW
Minimum cold utility required = 21.66 kW

Pinch Temperature ~45 C

The following conclusions and changes were made:

 Stream SHELLOUT is a cold stream that needs to be heated. But, its temperature is
above the temperatures of all the cold streams and thus heating it using any of the
cold streams will not be very effective. We thus continue to use the same heat
exchanger as before.
 Stream AAHEAT is heated using the other 2 cold streams as follows:

Fig 12.1: Heat Integration between streams AAHEAT, AAABS and EVAPTOP

Table 12.4: Temperature of Streams after heat integration

Streams AAABS AAABSOUT AAHEAT AAHEATOU EVAPTOP EVAPTOPO FINAL
Temperature(C) 120 117.6 30 45 170 99.6 70

As it can be seen, there is a significant drop in T of both the hot streams and the hot stream
rises by 40 degrees. The above conclusions have been taken into account for sizing and
costing of heat exchangers.

REFERENCES
[1] PubChem; US National Library of Medicine
https://pubchem.ncbi.nlm.nih.gov/compound/vinyl_acetate (12/01/2019)

Page 65
[2] Vinyl Acetate Monomer(VAM) Uses and Market Data, ICIS
https://www.icis.com/explore/resources/news/2007/11/07/9076564/vinyl-acetate-monomer-
vam-uses-and-market-data/ (15/01/2019)
Uses and Advantages of VAM, Dow Chemicals
https://www.dow.com/en-us/product-search/vinylacetatemonomervam (15/01/2019)
Vinyl Acetate, Polyvinyl Acetate, Polyvinyl Alcohol, Ethylene Vinyl Acetate; Wikipedia
(15/01/2019)

[3] Vinyl Acetate Market – Segmented by Application, End-User Industry and Geography –
Growths, Trends and Forecast; Industry Report by Mordor Intelligence
https://www.mordorintelligence.com/industry-reports/vinyl-acetate-market (14/01/2019)

[4] Price Database, by IndianPertochem

https://indianpetrochem.com/report/vamreport?fbclid=IwAR3_kdKxDc35RBrplF8dG0-
cPt1i4Q8MALahmn aDvbMk96PwCx4lxREF77w (14/01/2019)

[6] Global Vinyl Acetate Monomer Market, Press Release, 30/01/2013

http://www.mynewsdesk.com/uk/pressreleases/global-vinyl-acetate-monomer-market-
dominated-by-the-chinese-region-832406 (14/01/2019)

[7] Vinyl Acetate, the Observatory of Economic Complexity (OEC), Macro Connections Group,
MIT Media Lab
https://atlas.media.mit.edu/en/profile/hs92/291532/ (7/04/2019)

[8] Vinyl Acetate Monomer (VAM) Market Size By Application, Global Market Insights, Mar
2018

[9] Separation Process Engineering, Phillip C Wankat, 2nd Edition, Pearson Education Inc,
2007. pp 128-195

[10] Vinyl Acetate Product Report, Celenase (Jan. 2017)

https://www.celenase.com (15/01/2019)

[11] NIST WebBook, Properties of Acetic Acid, Ethylene and Vinyl Acetate
https://www.nist.gov/

[12] A.C. Dimian, C.S. Bildea, 2008. Chemical Process Design, WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim, pp. 280- 295

[13] Towler, G. and Sinnot, R. (2008). “Chemical Engineering Design Principles, Practice and
Economics of Plant and Process Design”. Elsevier. USA

[14] Peters, M. S., Timmerhaus, A. (1991): Plant Design and Economics for Chemical Engineers
(4th ed.)

[15] Indian Meteolorogical Department, Ministry of Earth Sciences

[16] Central Pollution Control Board, http://cpcb.nic.in/effluent-emission/

Page 66
[17] Gas Data Book, 7th ed,2001, Matheson Gas Products

[18] Gaussian Plume Dispersion Model, nptel

https://nptel.ac.in/courses/105102089/air%20pollution%20(Civil)/Module-5/1.htm

[19] Dario Stacchiola, Florencia Calaza, Luke Burkholder, and Wilfred T. Tysoe, “Vinyl Acetate
Formation by the Reaction of Ethylene with Acetate Species on Oxygen-Covered Pd”,
Wisconsin, 2004

[20] D. Padwal, 2013 , “Adapting Vinyl Acetate Monomer Plant for Manufacturing Allyl Acetate
and Allyl Alcohol”, AIChE, pp. 5-7

*ASPEN version 9.0 has been used for all simulations.

*OpenLCA version 7.0 has been used to carry out the impact assessment
*MATLAB version R2016B has been used for plots and convergence calculations

Page 67