DESIGN OF A CHEMICAL PLANT:

SYNTHESIS OF VINYL ACETATE

Bachelor of Chemical Engineering

Askhat Akhmetov

Zarina Chokparova

Svetlana Li

Rauan Seisenaly

2015
DECLARATION

We hereby declare that this report entitled “A Synthesis of Vinyl Acetate” is the result of our

own project work except for quotations and citations which have been duly acknowledged.

We also declare that it has not been previously or concurrently submitted for any other degree

at Nazarbayev University.

Names: Askhat Akhmetov

Zarina Chokparova
Svetlana Li
Rauan Seisenaly

Date: 27.11.2015

i
 Acknowledgement

Our group wishes to acknowledge our supervisor Dr. Costin-Sorin Bildea whose support and
advises helped us to complete this work.

ii
Abstract

The report is focused on a process of synthesis of vinyl acetate with a purpose of establishing

production in Kazakhstan. There are several alternatives for such process to be considered,

however, the reaction between acetic acid, acetylene and oxygen in a presence of Pd-based

catalyst is selected as the manufacture route. In addition, advantages and disadvantages of

each possible solution will be discussed and the most reliable traditional method was

selected. Other techniques are not totally studied and application of them can face safety

issues as well as high costs. The main aim of the project is to develop a chemical engineering

approach to a real industrial challenge taking into consideration economic and marketing

situation in the country and in global scale, safety issues and risks evaluation. On this stage

of Capstone project course rate of production and product purity need to be specified. The

reaction can be conducted in a plug-flow reactor with required reaction conditions followed

and necessary calculations performed. The reaction occurs in a gas phase with an emission of

carbon dioxide, removal of which will be considered by absorption techniques. In addition,

heat integration opportunities around the reactor can be estimated. In order to obtain pure

vinyl acetate, the separation section for the process will be designed by dividing it into gas

and liquid phases. After obtaining pure vinyl acetate recycle options can be provided. Finally,

the economic evaluation, risk and hazards assessment for the chemical process will be

presented. In addition, some future work considerations can be added after conclusions. As a

result, working on Capstone project by studying the experience of past research, analyzing

their weaknesses and strengths, and developing new ideas for chemical process design can

definitely be useful for better understanding of engineering and can provide a stable platform

for authors to work in a team and develop novel solutions.

iii
Table of Contents
1. Introduction ......................................................................................................................... 1
1.1. Uses of Vinyl Acetate .................................................................................................. 1
1.2. Processes for Vinyl Acetate ......................................................................................... 2
1.3. Producers/ Capacity ..................................................................................................... 5
1.4. Market Analysis ........................................................................................................... 9
1.5. Location ..................................................................................................................... 10
1.6. Conclusion: process alternative/production............................................................... 11
2. Basis of Design ................................................................................................................. 12
2.1. Raw materials ............................................................................................................ 12
2.2. Thermodynamic model .............................................................................................. 14
2.3. Reactions ................................................................................................................... 18
2.4. Catalyst selection ....................................................................................................... 19
2.5. Kinetics of the reactions ............................................................................................ 20
3. Conceptual Design ............................................................................................................ 21
3.1. Input/Output Analysis................................................................................................ 21
4. Reactor specifications ....................................................................................................... 23
4.1. Composition of reactor inlet ...................................................................................... 23
4.2. Choice of the reactor.................................................................................................. 24
4.3. Operating conditions and Feed conditions for the reactor ......................................... 27
4.4. Preliminary flowsheet ................................................................................................ 29
5. Heat Integration ................................................................................................................ 31
6. Design of separation section ............................................................................................. 32
6.1. First separation step ................................................................................................... 32
6.2. Gas separation............................................................................................................ 33
6.3. Liquid separation ....................................................................................................... 34
7. Overall preliminary flowsheet and mass balance ............................................................. 36
8. Economic analysis ............................................................................................................ 39
8.1. OPEX/CAPEX calculation ........................................................................................ 39
9. Risk Analysis .................................................................................................................... 41
9.1. Characteristics of Vinyl Acetate Monomer ............................................................... 41
9.2. Precautions in the storage of VAM ........................................................................... 42
9.3. Elimination of risks ................................................................................................... 42
9.4. Shipping Classification .............................................................................................. 43
9.5. First Aid ..................................................................................................................... 43
10. Future work ................................................................................................................... 45
11. Conclusion ..................................................................................................................... 46
12. References: .................................................................................................................... 47

iv
List of Tables

Table 1.1 Application of Vinyl Acetate.................................................................................................................... 2

Table 1.2 Physical description of components for acetic acid and acetylene method ............................................ 3

Table 1.3 Physical characteristics of the components for synthesis gas method .................................................... 3

Table 1.4 Fixed Bed reactor performance of different catalysts ............................................................................. 8

Table 2.1 Physical properties of components ....................................................................................................... 14

Table 2.2 Data for azeotropic mixture of water and vinyl acetate ........................................................................ 17

Table 2.3 Kinetic parameters for synthesis of vinyl acetate with catalyst............................................................. 20

Table 3.1 Requirements for raw materials ............................................................................................................ 21

Table 3.2 Ideal input/output mass balance ......................................................................................................... 21

Table 4.1 Typical operation conditions for VAM reactor (Dimian & Bildea, 2008) ............................................ 23

Table 4.2 Expected composition of streams inlet and outlet of the reactor .......................................................... 23

Table 4.3 Description of types of reactor (Nanda, 2008)...................................................................................... 25

Table 4.4 Table of properties of the reactor inlet stream...................................................................................... 26

Table 6.1 Composition of streams in terms of molar flow rates and molar fractions ........................................... 32

Table 6.2 Gas separation section results .............................................................................................................. 33

Table 6.3 Results of separation of liquids ............................................................................................................. 35

Table 7.1 Preliminary mass balance ..................................................................................................................... 38

Table 9.1 VAM classification in Europe ............................................................................................................... 42

Table 9.2 US DOT (Department of Transportation), Canadian TDG (Transport of Dangerous Goods) and EU

shipping requirements for VAM ............................................................................................................................ 43

Table 9.3 Exposure effects on human health ......................................................................................................... 43

v
List of Figures

Figure 1.1 Capacities of main vinyl acetate producers in 2008 ............................................................................. 5

Figure 1.2 Global Vinyl Acetate Demand by Region (2014) .................................................................................. 9

Figure 1.3 Global vinyl acetate monomer (VAM) market volume by application, 2012-2020 (kilotons) ............. 10

Figure 2.1 T-xy diagram of vinyl acetate and acetic acid ..................................................................................... 15

Figure 2.2 T-xy diagram of acetic acid and water ................................................................................................ 16

Figure 2.3 T-xy diagram of vinyl acetate and water ............................................................................................. 16

Figure 2.4 T-xy diagram of oxygen and ethylene .................................................................................................. 17

Figure 2.5 T-xy diagram of oxygen and carbon dioxide ....................................................................................... 18

Figure 2.6 T-xy diagram of ethylene and carbon dioxide ..................................................................................... 18

Figure 4.1 Temperature profile of reactor with unacceptable configurations ...................................................... 24

Figure 4.2 Multi-tubular catalytic reactor ............................................................................................................ 26

Figure 4.3 Temperature profile of the stream in reactor obtained in Aspen Plus ................................................ 29

Figure 4.4 Flowsheet of reactor with separation as black box and two recycle streams constructed in Aspen Plus

.............................................................................................................................................................................. 30

Figure 5.1 Heat integration across the reactor .................................................................................................... 31

Figure 6.1 Flash separation streams .................................................................................................................... 32

Figure 6.2 Gas separation section ........................................................................................................................ 33

Figure 6.3 Liquid separation section. ................................................................................................................... 34

Figure 6.4 Ternary diagram of the water/acetic acid/vinyl acetate mixture ......................................................... 35

Figure 7.1 Preliminary flowsheet with mass balance ........................................................................................... 37

vi
List of Abbreviations

 CAPEX – Capital expenditure

 CSTR – Continuous Stirred Tank Reactor
 E - Ethylene
 EVOH – Ethylene Vinyl Alcohol
 KOAc – Potassium Acetate
 NRTL-HOC – Non-Random Two Liquid model with Hayden O’Connell option
 OPEX – Operating expenditure
 PFR – Plug-Flow Reactor
 PVA – Polyvinyl Acetate
 PVAc – Polyvinyl Acetals
 PVB – Polyvinyl Butyral
 PVOH – Polyvinyl Alcohol
 TAC – Total Annual Cost
 VA – Vinyl Acetate
 VAE – Vinyl Acetate Ethylene
 VAM – Vinyl Acetate Monomer

vii
1. Introduction

1.1. Uses of Vinyl Acetate

Vinyl acetate monomer (VAM) is a colorless, flammable liquid with a low flash point and
characteristic odor. Even though it is not soluble in water, vinyl acetate is soluble in most
common organic solvents. Vinyl acetate is a precursor to produce polyvinyl acetate
homopolymers and copolymers for a wide variety of industrial and consumer products.

In terms of application, vinyl acetate is classified into polyvinyl acetate/polyvinyl acetals

(PVA/PVAc), polyvinyl alcohol (PVOH), ethylene-vinyl alcohol (EVOH), ethylene-vinyl
acetate (EVA)and others.

It is estimated that approximately 80% of VAM produced is used for PVA and PVOH
production. Having good adhesion properties to different substrates such as wood, paper,
metals and plastic films, PVA is widely used in adhesive industry. Similarly, it has an
application in paints and coatings. PVOH, the second largest consumer of VAM after PVA, is
used for producing paints, coatings and water soluble packaging. PVAc directly obtained
from PVA has essential role in producing safety glass interlayer, wash primers, coating and
magnetic wire insulation (www.grandviewresearch.com).

EVOH is observed as fastest growing application of vinyl acetate due to utilizing it as barrier
resin for plastic bottles, food packaging, gasoline tanks and engineering polymers. EVA,
which promise to grow steadily in market demand due to packaging industry, has also
applications in shower curtain and footwear manufacturing (ibid.).

In addition, polyvinyl butyral (PVB) and vinyl acetate ethylene (VAE) are also manufactured
from VAM. PVB helps to make safety glass production used in buildings and automobiles
sectors, while VAE is extensively used for architectural coating since it has low
environmental impact (ibid.).

Thus, Vinyl Acetate is a widely used synthetic chemical whose application varies from
food to oil industries. Due to the absence of vinyl acetate producing plant in Kazakhstan,
Kazakhem Company is forced to import this product. Therefore, this project suggests
the innovative design of Vinyl Acetate plant in Kazakhstan that will allow Kazakhem to
use national product and avoid import.

1
The summary of the application of vinyl acetate monomer can be found in Table 1.1.

Table 1.1 Application of Vinyl Acetate

VAM is raw material for various adhesive products. Emulsion that has
Adhesives polyvinyl acetate gives outstanding adhesion to a host of substrates such as
wood, paper, porcelain and metal.
Its unique chemical structure and useful chemical functionality permits to
Chemical
VAM be used as molecular building blocks or intermediates. Moreover, it is
Intermediates
used as monomer for different types of polymers.

VAM is broadly used in coating formulations as well as in water-based

Coatings
coatings.

VAM is widely used to make food contact materials used in adhesives, paper
Food and paperboard coatings, and printing inks.

VAM is used in the manufacture of plastics.VAM is used to form acrylic

Plastics fibers and is also converted to polyvinyl acetals, which are used for inter-
layers for safety glass and magnetic wire.

Fabric treatments, pigments and adhesives fields are also done by the help of
Textiles
polymers, created by VAM.

1.2. Processes for Vinyl Acetate

In this work, three main alternatives for Vinyl Acetate production were reviewed. They are
different in terms of operating conditions, reactants, used catalysts. In some methods,
number of reaction is not one only, thereby more by-products are formed. Every method has
some advantages as well as disadvantages. They are: 1) reaction of acetic acid and acetylene;
2) synthesis gas method; 3) reaction of acetic acid, ethylene and oxygen. In the following, in-
deep analysis on each method will be shown.

Acetic acid and acetylene

The first route for production, the reaction of acetic acid and acetylene, is operated in the gas
phase at temperature of 170-2500C. In this method, acetylene conversion varies from 60% to
70%, and amount of selectivity of acetylene, acetic acid is more than 93% each (Dimian and
Bildea, 2008). The reaction of this method is

HC≡CH+CH3COOH → H2C=CH-O-(CO)CH3

In the following, physical properties of each component are shown.

2
 Table 1.2 Physical description of components for acetic acid and acetylene method

Component Molecular State Boiling Point Melting Point

formula

Acetic acid CH3COOH Colorless liquid 1170C 16.60C

Acetylene HC≡CH Colorless gas - 80.80C

Zinc acetate is preferable catalyst of the reaction, however there are two supporting materials
that are widely used: charcoal and porous carbon spheres. Zinc acetate dominates because it is
less toxic, cheap and easily available (Yan et al, 2010). Charcoal is contemporary supporting
material, however, Yan et al (2010) suggested better supporting material in terms of
mechanical strength, pore size distribution, surface area. This is porous carbon sphere.

However, in the world, this process is less utilized due to an economical reason. The cost of
acetylene as a raw material is considerably high. Generally, it is economically less beneficial
than the case of ethylene instead of acetylene (Yan et al, 2010).

Synthesis gas method

Synthesis gas is the mixture consisting of carbon monoxide, carbon dioxide and hydrogen. It
is produced when carbon containing fuel is transformed to a gaseous product (biofuel.org.uk).
This product has some heating value. As an example of synthesis gas production, gasification
of coal emissions, steam reforming of coke can be said (ibid.).

In this report, esterification with ketene will be considered as an example of synthesis gas
method. The reagents are acetaldehyde and acetic anhydride. This reaction proceeds with the
formation of EDA (Ethylenediamine )intermediate, which is thermodynamically less
preferable (Dickson and Tustin, 1999). There are 2 reactions, which are reversible. The
reactions are held in the presence of a Bronsted acid catalyst at a temperature of 800C, in this
case, acetaldehyde is synthesis gas.

CH3CHO + (CH3CO)2O => CH3CH(CH3CO2)2

CH3CH(CH3CO2)2 => H2C=CH-O-(CO)CH3 + CH3COOH

Table 1.3 Physical characteristics of the components for synthesis gas method

Component Molecular formula State Boiling point Melting point

3
Acetaldehyde CH3CHO Colorless liquid 20.20C -123.370C
Acetic (CH3CO)2O Colorless liquid 139.80C -73.10C
anhydride

Ethylidene CH3CH(CH3CO2)2 Colorless liquid 1670C 18.90C

diacetate

Acetic acid CH3COOH Colorless liquid 1180C 160C

In both reactions, ethylidene diacetate is participated. Since ethylidene diacetate is less

volatile than acetaldehyde, acetic acid, acetic anhydride and vinyl acetate, heating of
ethylidene diacetate results in the separation of acetaldehyde, acetic acid, acetic anhydride and
vinyl acetate due to the volatilization. To prevent the loss of the components due to the
volatilization, the pressure is increased at high temperature. It resulted to other reactions such
as aldol condensation and oligomerization which forms undesirable tar-like materials
(Dickson and Tustin, 1999).

In addition, it was calculated that capital and utility costs are higher than the suggested third
method, despite the cost of raw material is advantageous (ibid.).

Acetic acid, ethylene and oxygen

The choice for VA production is the reaction of acetic acid, ethylene and oxygen. It is
economically most profitable method vinyl acetate production (Yan et al, 2010). Today, this
process has dominating position in the VA manufacturing. This process contains two
reactions, and these reaction occur in gas phase:

C2H4 + CH3COOH+ 0.5O2 → H2C=CH-O-(CO)CH3 +H2O

C2H4 + 3O2→2CO2 + 2H2O (secondary reaction)

Ethylene (C2H4) is the colorless flammable gas, simplest alkene group which has boiling point
of -103.70C and melting point of -169.20C . It is produced in petrochemical industry with
steam cracking (wikipedia.org). It is planned to construct ethylene producing plant in Atyrau
in 2017 (www.forbes.kz). Atyrau is located in west part of Kazakhstan.

Pd-based catalysts are used for the process (Dimian and Bildea, 2008). However, there are
other alternative catalysts for the production. First alternative, mixture of metallic palladium,
gold and cupric acetate, has been utilized by Celanese (Nicolau, Broussard and Coling,

4
2001). Second alternative, catalyst of palladium-gold is manufactured in Lyundell Basell
(Salisbury, Hallinan and Oran, 2010). Thirdly, Pd/KOCH3O2 catalyst widely used in DuPont
(www.dupont.t2h.yet2.com). For the plant, the catalyst of metallic palladium, gold and cupric
acetate is selected because it has higher activity and lower selectivity to CO2 compared with
contemporary catalysts (Nicolau, Broussard and Coling, 2001).

1.3. Producers/ Capacity

Vinyl Acetate production companies constantly modernize their technologies to improve the
quality as well as to decrease production cost . For example, Celanese developed a technology
to increase the yield by 95% and to decrease the production cost by 15%. Another eminent
company Praxair has increased the yield by 5% (www.export.by). Vinyl acetate is widely
used in different areas, and it is expected that the demand growth will continue. Thereby, VA
producer companies keep work to improve quality-to-cost ratio.

Vinyl acetate production market is shared between different well known companies. There are
leaders VAM producer companies such as Celanese (USA), Dow Chemical (USA), Lyondell
Basell (USA), DuPont (USA), INEOS (Great Britain), Wacker Chemie (Germany), Acetex
Chimie (France), Companhia Alcoolquimica Nacional (Brazil), Stavrolen (Russia), SSME
Azot Association (Ukraine), Doljchim (Romania), Achema (Lithuania) (www.export.by). The
capacities of each company are shown on Figure 1.1. However, in the near future, it is
predicted that more vinyl acetate producing factories will appear.

1300
1200
1100
1000
900
thousand tones

800
Capacities,

700
600
500
400
300
200
100
0
Celanese, Lyondell Dow DuPont, INEOS, Wacker Acetex CAN, Stavrolen, SSME Azot Doljchim, Achema,
USA Basell, Chemical, USA Great Britain Chemie, Chhimni, Brazilia Russia Association, Romania Lithuania
USA USA Germany France Ukraine

Figure 1.1 Capacities of main vinyl acetate producers in 2008

5
It can be seen that four USA companies take leading positions in Vinyl Acetate production.
On the following, the detailed information about the structures of the three leading companies
and, the methods they use will be introduced.

Celanese

It can be seen that four USA companies take leading positions in Vinyl Acetate production. A
significant amount of VA is produced by one giant company, namely Celanese, USA. This
company's vinyl acetate capacity is about 1200 thousand tons/year, and the overall number of
employees is 7500 (www.celanese.com). The company keeps strong environmental guidelines
to manufacture and sell the products. Celanese offers different certificates to verify the
meeting of the environmental requirements: ISO certification, Regulatory Data Sheets (RDS),
ECO labeling (www.celanese.com).

Celanese prepares vinyl acetate by the reaction of ethylene, oxygen and acetic acid with low
carbon selectivity. The catalyst comprises of metallic palladium, gold and cupric acetate
(Nicolau, Broussard and Coling, 2001). They believe that the copper in cupric acetate
impacts to decrease secondary reaction leading to carbon dioxide. In addition, the copper
enhances vinyl acetate productivity. There is wide range of shapes of the support material in
the in the catalyst (e.g. spheres, tablets, rings, stars, cylinders). The dimensions of them are 1
to 10 mm of in length, and 2 to 9mm in width (Nicolau, Broussard and Coling, 2001).
However, it is more preferred to utilize sphere-shaped support materials with diameter of 4 to
about 8mm (ibid.) This company uses appropriate porous substances such as silica, titania,
zirconia, silica-alumina, silicates, titanates, spinel, silicon carbide, and carbon for support
material. The support material has a surface area of aboiut 10 to 350m2/g , and the average
pore size varies from 50 to 2000 angstroms (ibid.).

The preparation of the support material of the catalyst consists of several steps. Firstly, it is
enabled to impregnate catalytic amounts of palladium and gold into the porous surface of the
support material. For this reason, aqueous solutions consisting of water-soluble components
of palladium and gold are used. For example, for water-soluble palladium compounds,
sodium palladium (II) chloride, palladium (II) chloride, potassium palladium (II) chloride,
palladium (II) nitrate or palladium (II) sulfate can be reacted with water; for water-soluble
gold compound, alkali metal, namely potassium salt of chloride acid can be utilized.
Secondly, the above mentioned metals are precipitated as a water-insoluble compound. To
precipitate, viable alkaline components such as silicate, borate in aqueous solution are used.

6
The metal can be fixed by the incipient wetness method in which permeated support is dried
at a temperature of 1500C

Lyondell Basell

Vinyl Acetate capacity of Lyondell Basell is 380 thousand tons/year, which is about three
times less than the leading company Celanese. This American company was the third largest
independent chemical manufacturer in US in 2013 (www.wikipedia.org). Their suppliers are
located in Africa-Middle East, Europe, North America, South America and Central America.
This company manages 30 different performance standards in the areas of manufacturing,
transportation as well as health, safety and environmental (HSE) performance.

Lyundell Basell produces vinyl acetate by the reaction of acetic acid, oxygen and ethylene
with the catalyst of palladium-gold (Salisbury and Osment, 2010). However, the price for
palladium and gold is high, therefore, the company has made considerable effort to increase
the catalytic activity reducing the quantity of catalyst. Thereby, they invented a method to
complete these two missions. This method contains of several steps. Firstly, ethylene, acetic
acid and oxygen are reacted in the presence of the catalyst. Secondly, gas stream involving
vinyl acetate, acetic acid, ethylene, water and carbon dioxide leaves the reactor. Thirdly, with
the aid of separator, two streams are produced: the first stream, ethylene stream, contains of
ethylene and carbon dioxide, and second stream, primary VA product stream, comprises of
vinyl acetate, acetic acid and water. Fourthly, the ethylene stream is separated in two streams:
recovered ethylene stream and a carbon dioxide stream. Fifthly, the primary VA product
stream is divided in two streams: a vinyl acetate product stream and a recovered acetic acid
stream. On the following, the recovered acetic acid stream of the fifth step and the recovered
ethylene stream of the fourth step are recycled to the reactor (Salisbury and Osment, 2010).
The concentration of each component is measured by Raman spectroscopic analysis (ibid.).

DuPont

This company produces 340ktons/year VA by the reaction of acetic acid, ethylene and oxygen
in the presence of a precious metal catalyst. The catalyst is not claimed by the company.
However, Thompson (2004) states that the company researched the selectivity of different
catalysts, and found the catalyst which has best performance in terms of selectivity. The test
was held in the conditions of 1650C and 115psig, and the selectivity was measured after
40hours for appropriate calculations (ibid.). As a result, Pd/KOAc catalyst showed high
selectivity.

7
 Table 1.4 Fixed Bed reactor performance of different catalysts

Catalysts Selectivity, %
Au/Pd/KOAc 93.6
Pd/KOAc 95.4
Au/Pd 91.6
Pd 94.7

They state that roughly 95% of the ethylene is converted to VA, the remained products are
converted to carbon dioxide and water. Vinyl acetate production process involves four main
parts: reaction section, carbon dioxide section, refining section, and tar system
(www.dupont.t2h.yet2.com). On the following, each step will be discussed.

Reaction section contains of fixed bed reactor, in which pure oxygen is mixed with acetic acid
and ethylene in the gas phase. Valuable metal catalyst (e.g Pd/KOAc) is supported with an
inert gas (www.dupont.t2h.yet2.com). On the bottom of the reactor, condensable components,
namely water, VA and unreacted acetic acid are separated from the remained non-
condensable gas of unreacted ethylene, carbon dioxide and oxygen (ibid.). Some unreacted
components are recycled to the reactor with fresh raw materials, and high purity VA goes to
refining section. CO2 component of VA is sent to the carbon dioxide system (ibid.).

Carbon dioxide system separates carbon dioxide produced in the reactor from the unreacted
ethylene. This system uses the hot potassium carbonate process for absorption of the CO2
separating it from the recycle gas stream, thus potassium bicarbonate is formed. Thereby,
90% of the CO2 in the feed gas is separated from the process. CO2 is released from potassium
bicarbonate, and then CO2 is sent to a dry ice manufacturing. The reconstituted potassium
carbonate can be recycled for further absorption of CO2 (www.dupont.t2h.yet2.com)

Refining section contains different units such as distillation columns, strippers, decanters,
tanks and heat exchangers. This section aims to separate VA from unreacted acetic acid and
other by-products. For this reason, most distillation streams are recycled to advance material
usage and to increase the yield. The heat produced from the reaction is utilized in other units
of the process. To prevent formation of polymers, an inhibitor is added
(www.dupont.t2h.yet2.com).

The purpose of tar system is to recover acetic acid from the acetic acid purge. In addition,
high boiling impurities and residues are removed in this system (ibid.).

8
1.4. Market Analysis

The vinyl acetate industry is so called oligopoly, where limited competition in market among
producers occurs. The reason behind,this is the high capital costs and limited process
technologies, which are huge obstacle to market entry. Another barrier in this market is the
demand for VAM. For instance, since the local producers have to compete with imports from
Asia Pacific region, some producer plants ceased their operations in Brazil, Mexico and
Western Europe in 2013 (www.ihs.com). Nevertheless, this tendency shows that Asia region
still needs their own producers in the market.

The demand for VAM grows year by year owing to construction, furniture and packaging
industries, which need adhesives in large amounts. Other industries that drive the demand for
VAM are end-user industries such as paints and coatings. Likewise, the demand for EVOH
films in food industry allow it grows up in the next years. Additionally, other factors of such
high demands in the market for VAM are volatile prices of raw materials, limited technology
and over production. It must be said that this tendency will continue for the coming years.

Figure 1.2 Global Vinyl Acetate Demand by Region (2014)

Figure 1.2 demonstrates the global vinyl acetate demand in a world for the past 2014 year. As
it can be noticed the main demand has been coming from Asia Pacific region, while North
America and Europe have taken slightly above 25% of the all demand (www.mcgroup.co.uk).
Moreover, it is predicted that until 2019 Chinese consumption of VAM will increase by 5%
annually, whereas the U.S. will be the witness of 3% of growth each year; regarding the other
regions as Japan and Western Europe, it is expected to have less than 1% of annual growth

9
(ibid.). Consequently, Asia Pacific region will continue to lead in the global market demand
of VAM for the coming years.

As it is previously stated, the applications of VAM are classified into several groups. The
following figure shows the VAM market volume by application for the past 4 years and
forecast for the 5upcoming years. It is expected that global VAM market demand will reach
the number of 7,934 kilotons by 2020 (www.grandviewresearch.com).

Figure 1.3 Global vinyl acetate monomer (VAM) market volume by application, 2012-2020 (kilotons)

It can be concluded that PVA and PVOH are still the main markets of VAM. However, other
sectors such as EVA are observed as fast growing sectors in the market. Overall, it is
anticipated that annual growth of vinyl acetate market will be around 4.5% (mcgroup.co.uk).
Apart from China, currently, the main producers of VAM are USA, Japan, Germany, Taiwan.

Eventually, it is evaluated that plant will be capable to produce 0.63% (50kt/year) of global
demand in 2020.

1.5. Location

It was decided to construct the plant near city Taldykorgan. It is located in South East of
Kazakstan, 200km away from one the main cities of Kazakhstan - Almaty. The main reason is
due to logistics. Firstly, Taldykorgan is near China, which continues to be a leader in the
global market demand. Secondly, it opens the routes for exporting the vinyl acetate to other
Asia Pacific countries. Thirdly, the transportation in this region is more developed. Finally,
Kazakhstan will have their own product, which will be exported to other countries.
Undoubtedly, it will push forward the development of chemical industry in Kazakhstan.

10
1.6. Conclusion: process alternative/production

In 1.2 section, four different methods were discussed and the reaction of acetic acid, ethylene
and oxygen was selected as an operating reaction. This reaction is used in all leading vinyl
acetate producing companies, however, the catalysts with supporting materials are various.
Celanese utilizes palladium, gold and cupric acetate with sphere-shaped supporting material
of silica, and our plant is considered to use the same catalyst and supporting material.
Nicolau, Broussard and Colling (2001) states that preferable operating temperature range is
150-2200C, and pressure should not exceed 20bar.

The plant is planning to produce 50ktons annually. It is expected that plant will cover 0.63%
of global demand by 2020.

11
2. Basis of Design

2.1. Raw materials

Ethylene (𝑪𝟐 𝑯𝟒 ) is an extremely flammable colorless organic gas with a slightly sweetish
odor. Ethylene tends to cause hazardous reactions such as spontaneous polymerization and
even explosion in contact with definite chemicals, namely fluorine, acetylene, hydrogen and
oxides (IFA, 2015). Moreover, it can exhibit hazardous properties by formation of explosive
mixtures in contact with air. In addition, there are several toxic effects that can be caused by
contact with ethylene, such as local frostbite and tissue damage; inhalation of gas may hurt
the central nervous system (ibid). From the chemical structure perspective, ethylene is the
simplest alkene, as it has two carbon atoms coupled by double bond and four hydrogens
attached to them. It is a rigid molecule and high energy is required to break the π-bond (ibid).
This double bond region is very electron dense and prone to attach electrophilic molecules.
Ethylene’s UV-vis spectroscopy results are simple and can be used for testing of theoretical
data and reference (NIST, 2011). Ethylene can be stored in containers at temperature
conditions lower than 50 ºC and in well ventilated space to avoid accidence due to
combustible properties of the material (Abeles et al, 2012). For the industrial purposes and in
petro chemistry ethylene can be produced by steam cracking, which implies obtaining of
smaller hydrocarbon from larger ones and separation of the component through the procedure
of repeated compression and distillation (Kniel, Winter and Stork, 1980). The global demand
for ethylene is rapidly increasing from year to year and is about 149 million tons per year
(Brelsford, 2014).

Acetic acid (𝑪𝟐 𝑯𝟒 𝑶𝟐 ), or ethanoic acid, is a colorless liquid representing a simple carboxylic
organic compound. It can be distinguished by pungent odor and sour taste (Sherertz, 2010).
By combining water with acetic acid at volume fraction of approximately 3-9% vinegar can
be produced. In addition, it has properties precursory to cellulose and polyvinyl acetates
production Acetic acid has wide application in such chemical industry processes as dimethyl
terephthalate production (Chenier, 2002). Moreover, it is broadly used in food industry as an
additive, condiment or acidity regulator (ibid). Despite the fact, that from view of chemistry
acetic acid is considered as a weak acid, at high concentration it can induce corrosive effect
and even damage to human skin. Analogically to water or ethanol, the liquid acetic acid
molecule is hydrophilic protic solvent. The miscibility properties of the component decrease
with the increase of the alkanes lengths, so it is not anymore miscible with octane and higher

12
alkanes (Wojcik and Ikeda, 2002). In addition, acetic acid readily mixes with solvents
independently from polarity, namely polar inorganic salts and non-polar oils, iodine or sulfur
(ibid). Generally, there are two ways of acetic acid production: industrial synthesis,
specifically methanol carbonylation, and bacterial fermentation (Cheung et al, 2011). The
demand for acetic acid in a global scale is approximated as 6.5 million tons per year, the
larger fraction of this amount is produced form petrochemical feedstock (ibid).

Oxygen (𝑶𝟐 ) is one of the most significant chemical compounds. Oxygen gas is odorless,
colorless, tasteless element and it represents 21% by weight of the Earth’s atmospheric layer
(Jakubowski & Henry, 2008). Also, it can be found in various mineral environments, rocks,
water and organic compounds. This is one of the essential compounds for respiration and
energy production of living organisms. Elemental oxygen can be produced by algae, plants
and microorganisms, such as cyanobacteria, through the photosynthesis process. From the
perspective of chemical properties, diatomic oxygen has two atoms bounded with double
bound. In terms of chemical reactivity, oxygen can interact with almost all types of atoms
except noble gases (Barrett, 2002). Generally, the oxidation of organic molecules occurs
slowly from kinetics view, but are preferable from thermodynamics side. Presence of pure
oxygen is harmful to organisms and biological cells. Processing of aging and diseases are the
secondary actions of oxidative effects on living organisms. Despite oxygen can support
combustion, it does not burn itself. In its liquid and solid forms oxygen remains clear sky-blue
colored substance (Air Liquide Gas Encyclopedia, 2013). Pure oxygen is widely used in
industry to manufacture ethylene oxide, vinyl acetate monomer, propylene oxide, titanium
dioxide, ethylene dichloride, ferric sulfate through the chemical oxidation reaction and to
produce synthesis gas. In addition, it can be applied for melting of glass, non-ferrous primary
manufacturing and secondary smelting of iron and steel (ibid).

Table 2.1 presents numerical data for characterization of physical properties of raw materials
and products:

13
 Table 2.1 Physical properties of components

Component/ Ethylene Acetic Oxygen Water Carbon Vinyl Acetate

Property Acid Dioxide
Molecular 𝐶2 𝐻4 𝐶2 𝐻4 𝑂2 𝑂2 𝐻2 𝑂 𝐶𝑂2 𝐶4 𝐻6 𝑂2
formula
Molecular
structure

Appearance colorless colorless colorless clear colorless colorless liquid

gas liquid gas liquid gas
Molecular 28.05 60.05 31.99 18.02 44.01 86.09
weight
(kg/kmol)
Density at 1.18 1049.0 4.47 999.97 1562.0 933.8
normal
conditions
(kg/m3)
Normal -103.7 118.5 -182.9 100 -78.5 72.9
boiling point
(ºC)
Freezing -169.2 16.5 -218.8 0 -56.6 -92.8
point (ºC)
Specific 0.975 1.055 1.105 1 1.530 0.934
gravity
Critical 9.2 320.0 -118.6 373.9 30.98 246.0
temperature
(ºC)
Critical 50.42 57.8 50.43 220.64 73.77 39.52
pressure
(bar)
Heat of 13.553 23.7 - 40.66 63.9 31.49
vaporization
(kJ/mol)

2.2. Thermodynamic model

A proper selection of the thermodynamic method is crucial for performance of process

simulation. Some of the components are highly polar species and mixture comprises both
condensable and supercritical compounds (Dimian & Bildea, 2008). To simulate the synthesis
process of vinyl acetate NRTL-HOC (Non-Random Two Liquid model with Hayden
O’Connell option) model was chosen in Aspen Plus software. Liquid-activity model, in this
case NRTL, is used in order to proceed with liquid separation of condensable species, which
will be described further, and HOC is applied to take into account the dimerization of the
acetic acid in a vapor phase. Such method includes application of Henry law to allow
14
treatment of gaseous components (ibid). NRTL model allows interaction between acetic acid,
water and vinyl acetate, whereas mixing with HOC determines parameters for gaseous
ethylene, oxygen and carbon dioxide.

T-xy diagrams

To provide some data on vapor-liquid equilibrium conditions of mixtures Figures 2.1 - 2.6
were included. The upper lines on each graph represent dew point temperatures and the region
above it is in a vapor phase, whereas the lower lines show bubble point temperatures and the
region below it is a liquid phase. The area between these lines indicate the equilibrium
between vapor and liquid.

Figure 2.1 T-xy diagram of vinyl acetate and acetic acid

According to Figure 2.1 the area of vapour liquid equilibrium is relatively wide, therefore, it
requires less steps in separation. As a result, separation of acetic acid from vinyl acetate can
be easily performed.

15
 Figure 2.2 T-xy diagram of acetic acid and water

In case of separation of water and acetic acid on Figure 2.2, pure water can be obtained in an
easier manner than pure acetic acid, as for higher concentration of acetic acid in the mixture
composition the dew point and bubble point lines are very close to each other.

Figure 2.3 T-xy diagram of vinyl acetate and water

From the Figure 2.3 above it can be observed that water and vinyl acetate form a
heterogeneous azeotropic mixture (Table 2.2). The molar weights of these components
considerably differ from each other – it is much lower for water; therefore, azeotrope is

16
observed at higher molar fraction of vinyl acetate in composition of binary mixture. The
molar and mass compositions of azeotrope are presented on Table 2.2.

Table 2.2 Data for azeotropic mixture of water and vinyl acetate

Component Mole basis fraction Mass basis fraction Temperature (ºC)

Vinyl acetate 0.74 0.93

61.84
Water 0.26 0.07

Figures 2.4 – 2.6 describe T-xy behavior of gaseos components with low boiling points. Thus,
separation by distillation is diffucult as it required very low temperature values.

Figure 2.4 T-xy diagram of oxygen and ethylene

17
 Figure 2.5 T-xy diagram of oxygen and carbon dioxide

Figure 2.6 T-xy diagram of ethylene and carbon dioxide

In addition, to separate carbon dioxide from the gaseous mixture special method, namely
absorption, described in section 1.3 should be applied.

2.3. Reactions

Basically, the process of synthesis of vinyl acetate, described in this project, is performed
according to the reaction between acetic acid, ethylene and oxygen. Firstly, ethylene
18
undergoes the oxyacetylation reaction to form vinyl acetate (2.3.1). The standard heat of this
reaction is -176.2 kJ/mol. Previous technologies of the synthesis were based on liquid phase
reaction at 110-130ºC temperature and 30-40 bar pressure ranges (Dimian and Bildea, 2008).
However, this project is going to design a process involving the reaction in gaseous phase, as
this can maintain more effective yield and lessen the corrosive effect of redox catalyst (ibid).

Primary reaction:

𝐸𝑡ℎ𝑦𝑙𝑒𝑛𝑒 + 𝐴𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑 + 0.5 𝑂𝑥𝑦𝑔𝑒𝑛 = 𝑉𝑖𝑛𝑦𝑙 𝐴𝑐𝑒𝑡𝑎𝑡𝑒 + 𝑊𝑎𝑡𝑒𝑟

𝐶2 𝐻4 + 𝐶2 𝐻4 𝑂2 + 0.5𝑂2 → 𝐶4 𝐻6 𝑂2 + 𝐻2 𝑂 (2.3.1)

Next, there is the secondary reaction (2.3.2) of ethylene combustion resulting in CO2
emissions, which is extremely undesired output of the process. Such outcome affects the yield
to be lower and causes difficulties in reaction heat removal. Standard heat of the reaction is -
1322.8 kJ/mol.

Secondary reaction:

𝐸𝑡ℎ𝑦𝑙𝑒𝑛𝑒 + 3 𝑂𝑥𝑦𝑔𝑒𝑛 = 2 𝐶𝑎𝑟𝑏𝑜𝑛 𝑑𝑖𝑜𝑥𝑖𝑑𝑒 + 2 𝑊𝑎𝑡𝑒𝑟

𝐶2 𝐻4 + 3𝑂2 → 2𝐶𝑂2 + 2𝐻2 𝑂 (2.3.2)

As a result, if both reactions are allowed to occur, the process of vinyl acetate synthesis
becomes exothermic with an approximate heat effect of - 250 kJ/mol.

2.4. Catalyst selection

Generally, catalyst is a substance which can increase the reaction rate without changing the
chemical structure of raw materials and products (Li and Liu, 2003). Additionally, when the
catalyst is used, it is not consumed during the reaction and the activation energy is decreased
(Masel, 2001). The catalyst used for the reaction in synthesis of vinyl acetate is palladium
(Pd) based with an approximate lifetime of 1-2 years (Dimian and Bildea, 2008). Noble
metals, mainly gold, and small (5 mm) silica particles soaked in acetates of alkali metals can
be used as the catalyst activators (ibid). As a result, the fast reaction occurs in a thin layer of
the particles’ surfaces. The operating temperature range for such catalyst is above 150-160ºC,
while temperature conditions exceeding 200 ºC can lead to the deactivation of the catalyst
(ibid). Pressure range should be between 8 and 10 bar, as the high pressure can maintain
higher concentration of components, thus, higher reaction rate can be achieved.

19
2.5. Kinetics of the reactions

For the primary reaction:

𝛼 𝛽
𝑟𝑉𝐴 = 𝑘1 𝑝𝐸𝑡1 𝑝𝑂𝑥1 (2.5.1)

−𝐸1
where 𝑟𝑉𝐴 is the rate of formation of vinyl acetate, 𝑘1 = 𝐴1 𝑒 𝑅𝑇 is the reaction constant, 𝑝𝐸𝑡 is
partial pressure of ethylene and 𝑝𝑂𝑥 is the partial pressure of oxygen; 𝛼1 and 𝛽1 are partial
reaction orders derived experimentally, 𝐴1 is a pre-exponential factor.

For the secondary reaction:

𝛼 𝛽
𝑟𝐶𝐷 = 𝑘2 𝑝𝐸𝑡2 𝑝𝑂𝑥2 (2.5.2)

−𝐸2
Analogically to the previous equation 𝑟𝐶𝐷 is the carbon dioxide formation rate, 𝑘2 = 𝐴2 𝑒 𝑅𝑇
is the reaction constant, 𝛼2 and 𝛽2 are partial reaction orders, 𝐴2 is a pre-exponential factor.

Table 2.3 represents numerical data required for the reactions:

Table 2.3 Kinetic parameters for synthesis of vinyl acetate with catalyst

Reaction 𝜶 𝜷 E (J/mol) A (𝒎𝒐𝒍 𝒌𝒈_𝒄𝒂𝒕−𝟏 𝒔−𝟏 𝑷𝒂−(𝜶+𝜷) )

1 0.36 0.20 15 000 0.000265

2 -0.31 0.82 21 000 0.000750

20
3. Conceptual Design

3.1. Input/Output Analysis

The main decision on the raw materials depend on the cost versus purity of the compositions
with the consideration of additives that are highly undesirable. Thus the acetic acid and
ethylene as an input raw materials are required to be of high purity. As soon as it is
complicated to obtain 100% pure raw materials, acetic acid is allowed to contain acetaldehyde
and formic acid in amount less than 0.1%. Ethylene is allowed to contain less than 1% of
ethane, however constrains on CO and sulfur are required for the protection of catalyst
(Dimian & Bildea, 2008). Table 3.1 illustrates the requirements for the raw materials
discussed before:

Table 3.1 Requirements for raw materials

Ethylene Acetic acid

Purity 99.9% 99.9%
Impurities Ethane < 1% Formic acid and
CO and sulfur – negligible Acetaldehyde – negligible
amount (in ppm) amount (in ppm)

Here, the selectivity is the main point of decision. At a preliminary stage of design, selectivity
value as σVA/E = 92% has been chosen (allowed in accordance with Table 4.1). In ideal case it
could be assumed that the process implies no losses, and the preliminary input-output mass
balance could be observed in table below:

Table 3.2 Ideal input/output mass balance

Input Output
kg/h kmol/h kg/h kmol/h
Ethylene 2286 81.5 - -
Acetic acid 4503.75 75 - -
Oxygen 1824 57 - -
Vinyl acetate - - 6456.75 75
Water - - 1584 88
CO2 - - 286 6.5
Overall 8613.75 206.5 8326.75 169.65

The production rate has been chosen as 50 kton/year previously, and thus we have that:

21
 50000000 𝑘𝑔/𝑦𝑒𝑎𝑟 𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙
= 72 ~75
86 𝑘𝑔/𝑘𝑚𝑜𝑙 ∗ 8000ℎ/𝑦𝑒𝑎𝑟 ℎ ℎ

Here, the calculations for the mass balance have been performed using the following formula:

Reactions:

𝐶2 𝐻4 + 𝐶2 𝐻4 𝑂2 + 0.5𝑂2 → 𝐶4 𝐻6 𝑂2 + 𝐻2 𝑂 - 1st reaction

𝐶2 𝐻4 + 3𝑂2 → 2𝐶𝑂2 + 2𝐻2 𝑂 - 2nd reaction

𝜎𝑉𝐴/𝐸 = 0,92 - selectivity

If 𝜁1 , 𝜁2 are assumed as the extents of 1st and 2nd reactions respectively than we have that:

𝜁1
𝜎𝑉𝐴/𝐸 = = 0,92
𝜁1 + 𝜁2

From the reactions stoichiomentry:

𝑘𝑚𝑜𝑙
𝑉𝐴 = 𝜁1 = 75 - amount of vinyl acetate produced by 1st reaction
ℎ

𝑘𝑚𝑜𝑙
𝐶𝑂2 = 𝜁2 = 6,5 - amount of carbon dioxide produced by 2nd reaction
ℎ

𝑘𝑚𝑜𝑙
𝐸 = 𝜁1 + 𝜁2 = 81,5 - amount of ethylene consumed by 1st and 2nd reaction
ℎ

𝑘𝑚𝑜𝑙
𝐴𝑐𝑂𝐻 = 𝜁1 = 75 - amount of ethylene consumed by 1st reaction
ℎ

𝑘𝑚𝑜𝑙
𝑂2 = −1/2𝜁1 − 3𝜁2 = −57 - amount of oxygen consumed in 1st and 2nd reaction
ℎ

𝑘𝑚𝑜𝑙
𝐻2 𝑂 = 𝜁2 = 88 - amount of water produced by 2nd reaction
ℎ

This calculations of extents for each component help to calculate preliminary mass balance
which will be demonstrated below. Besides, from the preliminary balance some conclusions
are possible to be made beforehand, for instance the output has certain amount of carbon
dioxide, and therefore safety restrictions might be taken into consideration.

22
4. Reactor specifications

4.1. Composition of reactor inlet

Here, the composition of input of the reactor is possible to be determined in accordance with
general operation composition for the reactor (Dimian & Bildea, 2008) demonstrated on
Table 4.1 below:

Table 4.1 Typical operation conditions for VAM reactor (Dimian & Bildea, 2008)

Component Composition mol% Conversion % Selectivity %

Ethylene 50 8 – 10 91 – 94
Acetic acid 10 - 20 15 – 30 >99
Oxygen 6–8 60 – 70 60 – 70
CO2 10 - 30 - -
inerts N2 or Ar - -

Here, from the Table 4.1 above the input of the reactor has been calculated with the account
of maximum conversion of acetic acid and the lowest amount of oxygen due to the
exothermal properties of the reaction. The conversion is low due to heat-removal constraints
for the reactor (ibid) and also high exothermal properties do not allow the conversion to be
higher, because higher conversion will imply higher concentration of the reactants, namely
ethylene, and therefore there is a risk of explosion. Moreover, simulation of reactor in Aspen
Plus software has shown that the higher conversion will require longer reactor and as a result
the reaction will be slower and this kind of reactor is not economically feasible for this middle
size plant. Therefore, the input of the reactor has been calculated and it is presented in table
below along with the expected output with the consideration of calculations above:

Table 4.2 Expected composition of streams inlet and outlet of the reactor

Component Composition of input Conversion % Composition of

[kmol/h] output [kmol/h]
Ethylene 850 9 768.5
Acetic acid 350 22 275
Oxygen 107 70 50
CO2 300 25 306.5
Vinyl acetate - - 75
Water - - 88

Thus, the conversion for acetic acid is 22% and therefore, the amount of it has to be
approximately four times greater than required amount of product, whereas amount of carbon
dioxide flowing into the reactor is required to be 1.5 times greater due to exothermal
23
properties of the reaction, i.e. in order to decrease the temperature of the reaction and its
exothermal properties the reactants should be diluted with carbon dioxide. The simulation in
Aspen Plus has shown that with lower amount of CO2 the temperature of the stream in the
reactor is greater than 200⁰C (see Figure 4.1) which is not applicable for catalyst used, as it
operates at a temperature 150⁰C - 220⁰C as it was stated before. Additionally, higher
temperature of inlet stream also implies higher temperature in the reactor. Figure 4.1 below
represents the temperature profile of the reactor with unacceptable configurations used,
namely low concentration of CO2 and high inlet temperature. Besides, this reactor operated
with suggested heat transfer coefficient set basing on educated guess without calculations and
therefore, resulted temperature profile shows high maximum temperature. Detailed
calculations of heat transfer coefficient will be demonstrated below.

Temperature
238
236
234
232
Temperature [C]

230
228
226
224
222
220
218
216 Process stream
214
0 1 2 3 4 5 6 7 8 9

Length [m]

Figure 4.1 Temperature profile of reactor with unacceptable configurations

It should be noted that the composition of oxygen is required to be less than 8% in order to
avoid ignition in accordance with safety considerations (ibid).

4.2. Choice of the reactor

Since the composition of the reaction is two phase (gas reaction mixture, solid catalyst) the
type of reactor is heterogeneous. Thus, Table 4.3 below illustrates three possible reactors:
Batch, CSTR and Plug Flow reactor:

24
 Table 4.3 Description of types of reactor (Nanda, 2008)

# Reactor type Advantages Disadvantages Area of application

1 Batch Reactor - Used for small scale
production
- Suitable for long-time
reactions
- Suitable for very high
selectivity
2 Continuous Stirred - Stepped-up
Tank Reactor concentration gradient
(CSTR) - Highly flexible
- By products can be
removed during the
process between the
reactions
3 Tubular reactor - Reactants can be
(PFR) immersed at different
locations
- Can be multi-tubular
- Has higher efficiency
value in comparison with
CSTR
- Not applicable for Chemical industry
large scale with small scale
- Closed system
- Complex and Chemical industry
expensive in with gas or liquid
comparison with reactions
tubular reactor
- Perfect mixing is
assumed
- Not economically Chemical production
suitable for small scale with high pressure,
production considerable heat
transfer
requirements,
critically low or high
temperatures

Thus, Table 4.3 shows all of the disadvantages for current process highlighted with red color
and all of the advantages with green color. As both reactions are catalytic, perfect mixing
cannot be assumed. Moreover, the production scale is not small enough for batch reactor.
Therefore multi-tubular catalytic reactor will be used for the production, which is more
economically suitable and less complex for VAM plant. Multi-tubular reactor will be
designed with a coolant in order to provide temperature control in view of the highly
exothermal reactions, as it is shown on Figure 4.2 below.

25
 Figure 4.2 Multi-tubular catalytic reactor

The heat transfer coefficient for the reactor can be calculated using the following data:

Table 4.4 Table of properties of the reactor inlet stream

# Property Value Comments

1 Gas velocity, us 0.5 m/s Considered for a predesign
calculations
2 Diameter of the particle, dp 0.005m Dimian and Bildea, 2008
3 Diameter of the tube, dtube 0.03m Considered for a predesign
calculations
4 Viscosity, ηg 2.047*10-5 Ns/m2 Corresponds to reactor-inlet
retrieved from Aspen Plus
stream report
5 Density of gas, ρg 9.564 kg/m3 Corresponds to reactor-inlet
retrieved from Aspen Plus
stream report
6 Thermal conductivity, λg 0.0362 W/m·K Corresponds to reactor-inlet
retrieved from Aspen Plus
stream report

Here, characteristics for the gas flow such as density, viscosity and conductivity of gas, are
possible to be obtained from Aspen Plus software, and velocity of the gas flow has been
chosen in range from 0.5m/s to 1.5m/s that was stated as optimal for this type of reactor by
Dimian and Bildea (2008),

Using formulas below the heat transfer coefficient for the reactor can be calculated:

𝑢𝑠 𝑑𝑝 𝜌𝑔
𝑅𝑒 = - (4.2.1)
𝜂𝑔

26
 4.6𝑑𝑝
𝑁𝑢 = 3.5𝑅𝑒𝑝0.7 exp(− ) - (4.2.2)
𝑑𝑡

Thus, the following results were obtained using the formulas above:

Re = 1168, Nu = 228.2

Heat transfer coefficient can be calculated as:

𝜆𝑔
𝛼𝑤 = 𝑁𝑢 ∗ 𝑑 - (4.2.3)
𝑡

So, for this reactor:

𝑊
𝛼𝑤 = 275.4 𝑚∗𝐾 - partial heat transfer coefficient (tube side)

Therefore, taking into consideration the thermal resistances in the shell-side of the reactor, the
value of 250 W/m*K for heat transfer coefficient at preliminary design has been used.

4.3. Operating conditions and Feed conditions for the reactor

Dimian and Bildea (2008) state that the typical operating conditions for the reactor are as
following:

Pressure – 5-12 atm

Temperature – 140-180⁰C

The ranges are as follows due to the fact that reactor is desired to operate in almost isothermal
conditions and as soon as the reactions are highly exothermal, the temperature of the reaction
will be higher than 150⁰C and therefore, the temperature of the inlet stream of the reactor is
preferable to be as close to the temperature of the outlet of the reactor as possible. However,
higher temperatures can decrease the selectivity, also higher pressure negatively influences
the selectivity, and has positive impact of productivity, thus middle values of these ranges
should be considered. Therefore, taking these ranges into consideration, reactor will operate
with inlet stream at:

Temperature = 160⁰C

Pressure = 8 atm

As the reactor is multitubular, the number of tubes is required to be calculated:

27
Velocity of the gas ug = 0.5m/s and volumetric flowrate Fvol = 0.633m3/s, (corresponding to
inlet-stream from Aspen Plus calculations) therefore cross sectional area of the tubes can be
calculated as:
2
𝐹𝑣𝑜𝑙 𝜋𝑑𝑡𝑢𝑏𝑒
𝑆= = ∗ 𝑁 = 1.266𝑚2 - where N is the number of tubes required
𝑢𝑔 4

N = 1792

Reactor operates with the catalyst bed voidage of 0.5 and particle density of 1000 kg/m 3.
Coolant is present in the reactor due to highly exothermal reaction and temperature of the
coolant is 150⁰C which is 10⁰C less than the temperature of feed stream controlled by the heat
exchanger. This temperature allows cooling of reaction stream without significant impact on
productivity, as lower temperature implies decrease of productivity. Besides, lower
temperature of a coolant prevents the occurrence of the reactions. Thus, several trials of
coolant temperatures in a range from of 140⁰C to 150⁰C, length of the tube in a range from
7.5 to 15 m, and velocity of gas in simulation of reactor in Aspen Plus has shown that the
results obtained with the following design specifications of the reactor are in a best agreement
with previous studies (Dimian, Bildea, 2008) and result is close to mathematical model
presented before (see Table 4.2):

Number of tubes = 1792

Diameter = 30mm

Length = 10 m (each tube)

The length has been determined using Aspen Plus varying in a range from 7.5m to 15m in
order to obtain appropriate result. Thus, several trials in Aspen Plus simulation of the reactor
has demonstrated that values above show good results of conversion, close to the
mathematical model in Table 4.2 and appropriate temperature profile in the reactor (Figure
4.3) which also are in a good agreement with previous studies (ibid).

28
 Temperature Profile
165,0

164,5

164,0

163,5
Temperature C

163,0

162,5

162,0

161,5

161,0

160,5

160,0
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5 9,0

Length [m]

Figure 4.3 Temperature profile of the stream in reactor obtained in Aspen Plus

Figure 4.3 shows the temperature of the stream in the reactor that changes with the length.
The increase in temperature shows, that reaction is highly exothermal, however it is still
below the limits for the catalyst mentioned before as maximum temperature is below 165⁰C.
After rapid increase temperature drops gradually due to the coolant in the reactor. This
Temperature profile has been obtained in Aspen Plus as optimal for the considerations of inlet
temperature, concentration of reagents and temperature of the coolant.

It should be noted that the second reaction is a combustion reaction and as Table 4.2 shows
only about 9% of ethylene goes to the combustion process, the rest 91% is consumed by vinyl
acetate production.

4.4. Preliminary flowsheet

Figure 4.4 below illustrates the preliminary flowsheet with reactor and two recycle streams,
namely acetic acid and gas recycle, which are sent to the mixer in order to be combined with
feed fresh streams of oxygen, acetic acid and ethylene. Black box illustrates the separation
section which will be discussed later.

29
Figure 4.4 Flowsheet of reactor with separation as black box and two recycle streams constructed in Aspen Plus

It should be noted that recycle streams are not possible to be designed in Aspen Plus due to
the fact that separation section cannot be fully designed yet (i.e. absorption column and liquid
separation), however the existence of recycle streams is possible to be predicted at
preliminary stage of design.

30
5. Heat Integration

This chapter refers to the considered possible ways to decrease the heat consumption by the
plant. At this preliminary stage of design the main decision on heat integration is only
possible across the reactor due to the fact that separation section has not been designed in
details yet.

Figure 5.1 below illustrates suggested possibility of heat integration for this plant:

Figure 5.1 Heat integration across the reactor

Here the inlet stream of the reactor is the combination of three feed streams of ethylene, acetic
acid and oxygen and two recycle streams from the separation section. Due to the fact that
design of separation section has not been completed yet, temperature of inlet stream cannot be
determined at this stage, however theoretically due to the fact that reaction is exothermal,
temperature of the outlet stream will be higher. Therefore, in order to save energy and heat
consumption, heat exchanger might be installed before the entrance of the reactor. Outlet of
reactor is used here as heating stream with higher temperature. Heater is installed here to the
need of controlling the reactor inlet temperature in case of any uncertainties from heat
exchanger.

31
6. Design of separation section

The outlet reactor stream consists of 44.5 mol% ethylene, 26.5 mol% carbon dioxide, 5.8
mol% water, 15.5 mol% acetic acid 2.6 mol% oxygen and 5.1 mol% vinyl acetate. The
concept of separation for such mixture is to perform it in two steps - for gas and for liquid
(Dimian & Bildea, 2008).

6.1. First separation step

The inlet into separation section stream has a pressure of 8 bar and temperature of 162ºC.
Using a Flash separation unit in Aspen Plus, which operates at 30ºC and 4 bar, this stream can
be divided into vapor on the top and liquid in the bottom (Figure 6.1) and the results are
presented in Table 6.1. After this, some part of vinyl acetate is still missing from the liquid
stream as there is some amount found in vapor phase. Therefore, to recover it a multistage
equilibrium separation should be implemented in the absorption column. Acetic acid can be
used instead of a solvent. In addition, cooling is required to achieve higher recovery.

Figure 6.1 Flash separation streams

Table 6.1 Composition of streams in terms of molar flow rates and molar fractions

Component Inlet stream Top stream Bottom stream

Molar Molar Molar Molar Molar Molar
flow rate fraction flow rate fraction flow rate fraction
(kmol/hr) (kmol/hr) (kmol/hr)
Vinyl 76.6825 0.0685 14.9729 0.0181 61.7097 0.2103
acetate
Acetic acid 148.318 0.1325 2.94313 0.0035 145.374 0.4955
Water 84.2789 0.0753 4.26423 0.0052 80.0147 0.2727
Oxygen 20.2642 0.0181 20.2464 0.0245 0.01781 > 0.0001
Ethylene 669.519 0.5983 664.943 0.8053 4.57607 0.0156
32
 Carbon 120.096 0.1073 118.377 0.1434 1.71985 0.0059
dioxide
Total 1119.16 1 825.746 1 293.412 1

6.2. Gas separation

Vapor stream mainly comprises ethylene, carbon dioxide, oxygen and significant amount of
vinyl acetate. Due to the fact that further separation is performed in absorption unit (refer to
Table 6.2 for results), acetic acid was chosen as absorber. After passing through the column
feed divide into liquid and vapor product streams (Figure 6.2). In addition excess carbon
dioxide should be removed to avoid its accumulation. This can be performed by washing
techniques using solutions of potassium carbonate or amines (Dimian & Bildea, 2008).

Figure 6.2 Gas separation section

Table 6.2 Gas separation section results

Component Flash top Absorbent Liquid product Vapor product

outlet (kmol/hr) stream (kmol/hr) stream (kmol/hr)
(kmol/hr)
Vinyl acetate 14.9729 0 0 14.9729
Acetic acid 2.94313 4.85148 0 2.94313
Water 4.26423 0 0 4.26423
33
 Oxygen 20.2464 0 20.2464 0
Ethylene 664.943 0 664.943 0
Carbon 118.377 0 118.377 0
dioxide

6.3. Liquid separation

On this stage of the project, the total design of separation will not be presented, as it is
expected to be delivered in Capstone II. Actually, liquid separation system is quite
complicated. Therefore, only simulation through the component separator in Aspen Plus was
implemented (Figure 6.3). Liquid separation inlet stream consists of Flash bottom outlet and
the liquid stream outgoing from the absorption column. As a result, it is expected to produce
pure vinyl acetate, pure water and pure acetic acid, as well as some vapor containing of
ethylene, carbon dioxide and oxygen gases. Separation results are presented in Table 6.3.

Figure 6.3 Liquid separation section.

34
 Table 6.3 Results of separation of liquids

Component Separation Vapor Vinyl acetate Acetic acid Water

inlet outlet (kmol/hr) (kmol/hr) (kmol/hr)
(kmol/hr) (kmol/hr)
Vinyl 76.6825 0 76.6825 0 0
acetate
Acetic acid 153.169 0 0 153.169 0
Water 84.2789 0 0 0 84.2789
Oxygen 0.01781 0.01781 0 0 0
Ethylene 4.57607 4.57607 0 0 0
Carbon 1.71985 1.71985 0 0 0
dioxide

Residue Curve Map (RCM) analysis produces ternary diagram of water/acetic acid/vinyl
acetate mixture presented on Figure 6.4 below. Point on water composition axis indicated the
azeotrope, point with composition of 35 wt% vinyl acetate, 60 wt% acetic acid and 56 wt%
water indicated the mixture entering the separation section. Point on the left side shows
bottom stream separated and point on the right side represents top streams. Extracted water
stream can be sent to the biological treatment (Dimian & Bildea, 2008).

Figure 6.4 Ternary diagram of the water/acetic acid/vinyl acetate mixture

35
7. Overall preliminary flowsheet and mass balance

Figure 7.1 below illustrates ideal preliminary flowsheet with calculated mass balance, where
the separation units are assumed to work perfectly. Inlet stream of the reactor has a
temperature which is set by the up-stream by heater, and the outlet of the reactor flows to
flash for separation of gases from liquids. However, the upper stream contains a mixture of
vapor with significant amount of vinyl acetate, therefore the adsorption column is
implemented. After the process in absorption column, the liquid stream mixes with lower
stream of Flash and goes to Liquid separation unit (distillation column is likely to be used),
where liquids are separated on product – vinyl acetate monomer, and by-product water, and
excess of acetic acid. Acetic acid is split and one part goes to absorber column as a wash, and
another part flows to the mixer as a recycle stream. The amount of Acetic acid for wash was
decided basing on previous literature reports (Lyuben and Tureus, 1997), more detailed
analysis will be described in Capstone 2. Top stream of absorption column is then sent to
another separation, where 5.2 kmol/h of CO2 is separated and the other part of vapor is a gas
recycle stream, which flows to Mixer. Fresh feed combines with gas and acetic acid recycle
streams and performs an inlet stream of the reactor.

Preliminary Mass balance is displayed in form of the table and on the flowsheet below. As it
is possible to observe, the inlet and outlet of the reactor obtained from simulation is close to
mathematical model calculated with the aid of reaction extends in section 3.1 and all the
calculations have been completed without consideration of any losses during separation
section. Percentages for water and vinyl acetate flowrates across the Flash unit were made
basing on Aspen Plus simulation. As it could be observed, the results from Aspen Plus in
Preliminary Mass balance table (Table 7.1) below are in a good agreement with calculated
ideal mass balance, demonstrated in Table 3.2.

36
Figure 7.1 Preliminary flowsheet with mass balance

37
 Table 7.1 Preliminary mass balance

Flowrate by streams in kmol/h

# Component 1 2 3 4 5 6 7 8 9 10
1 Acetic Acid 75 350 273.6 5.42 268.2 - 178.4 100 - -
2 Ethylene 81.5 850 768.5 762.32 6.174 - - - 762.32 -
3 Oxygen 57 107 53.44 53.4 0.0532 - - - 53.4 -
4 Carbon dioxide - 300 310.25 305.2 5.08 - - - 300 5.2
5 Water - - 86.6 3.97 82.66 86.6 - - - -
6 Vinyl Acetate - - 76.4 13.77 62.59 76.4 - - - -

38
8. Economic analysis

An appropriate economic analysis in terms of Total Annual Cost (TAC) will be calculated
considering installed cost of each unit, energy cost for payback period of 10 years. The Total
Annual Cost (TAC) indicates the total cost of financing without considering the terms and
different financial products (www.banxico.org).

𝑡𝑜𝑡𝑎𝑙 𝑐𝑎𝑝𝑖𝑡𝑎𝑙𝑐𝑜𝑠𝑡
TAC = + 𝑡𝑜𝑡𝑎𝑙 𝑜𝑝𝑒𝑟𝑎𝑡𝑖𝑛𝑔 (Zaharia, Bildea and Muntean, 2015)
𝑝𝑎𝑦𝑏𝑎𝑐𝑘𝑝𝑒𝑟𝑖𝑜𝑑

For calculation of total cost, the following formula will be used:

Capital cost (US$/m3) = (M & S index/280) * (957.9 * D1.066 * H0.82)*(2.18+Fc)

Fc = Fm * Fp

Fp=1+ 0.0074*(P - 3.48) + 0.00023 * (P-3.48)2

Fm = 1

Here, Fc is cost factor, Fm is material factor, Fp is pressure factor, D is diameter, H is height,

P is pressure

8.1. OPEX/CAPEX calculation

Economic evaluation of the plant will not be completed in Capstone Project 1 due to the fact
that the total design of separation section containing flash and adsorption column is not fully
presented. Economic aspect of the plant will be finished in Capstone Project 2, when the
detailed design of each operating unit is completed. However, in this section, the preliminary
plan for the economic calculation, in terms of OPEX (Operating Expenditure) and CAPEX
(Capital Expenditure), will be introduced.

Firstly, it is necessary to explain the terms of OPEX and CAPEX. OPEX is a continuing cost
for running a product, business or system, and CAPEX (Capital Expenditure) is the cost of
developing non-consumable parts of the product. OPEX includes day-to-day functioning of
the plant such as utilities, repairs, wages of the employees, and depreciation of the plant and
equipment. Repair works, depreciation issues cannot be predicted, however, the cost of
utilities and wages can be suggested. In Taldykurgan, The cost of cooling water is
31.57KZT/m3 (0.1US$/m3), steam is 0.00154KZT/kJ (5*10-6 US$/kJ ) and the electricity cost

39
is 5.22KZT/kWh (0.017US$/kWh). In chemical industry, the average salary is 103071KZT
(336US$) (www.mojazarplata.kz). These values can be used for further economic calculation
works in Capstone Project 2.

CAPEX emphasizes amount of money which is consumed to construct the plant. As it was
said before, the design of the plant is not finished, however, general formula for calculation of
CAPEX is following: CAPEX = Cost of Operating Units + Cost of Installation Works

Cost of Operating Units include the costs of reactor, mixers, separation units (adsorbent,
flash, and splitter). The costs of these units cannot be calculated due to the fact that the design
is not completed. However, Economic evaluation will be demonstrated in Capstone 2, basing
on CAPEX/OPEX methods of evaluation.

There the installation works include wages of workers/plant designers, cost of energy required
for construction, cost of the landscape for the construction. The wages of the construction
workers in other VA plants (e.g. Celanese, Lyondell Basell, DuPont) is not claimed due to
confidential policies of the companies. Due to the fact that there is no any analogous Vinyl
Acetate plant in Kazakhstan, it is impossible to calculate the salaries of construction workers.
Cost of energy for construction of the plant is not also possible for the same reason. The cost
of landscape for industrial reason is not found, however, it can be suggested that it is roughly
the same with the cost of landscape for housing estate, and this cost in Taldykurgan varies
from $1000 to $2000 for 100m2 (krisha.kz).

40
9. Risk Analysis

Each worker in a plant has to be entirely informed about VAM hazards and its safe handling
and emergency response procedures. Everyone must be trained fully trained by persons with
sufficient knowledge and experience prior to work with VAM. This section will describe
VAM characteristics, storage and first aid in emergency situations.

9.1. Characteristics of Vinyl Acetate Monomer

VAM is a highly flammable, reactive, colorless liquid that is partially soluble in water. Vinyl
acetate has a sweet smell, which could be very sharp and irritative at higher levels. Therefore,
it must be stored in marked bulk containers.

As it was stated, it is flammable liquid due to its flash point that is 37C and the mixing with
air at room temperature will form a flammable vapor.

Since VAM molecules are reactive, it can polymerize intensely if safety precautions are not
met. However, if it is properly inhibited, all recommended handling and storage conditions
are satisfied, VAM is considered to be stable. It has to be said that prolonged contact with
heat, x-rays and sunlight will lead to polymerization. Polymerization inside those containers
may result in rupturing of insufficiently vented containers, which will cause to liquid spill,
generation of vapor and eventually fire (www.msdssearch.dow.com).

Regarding the health effects of VAM, it is irritating to the upper respiratory tract, and may
cause redness and tumor on eyes. Thus, skin and eyes so contact with vinyl acetate vapor or
liquid must be avoided. The outcome of health effect depends on duration of exposure time
certainly. Unfortunately, laboratory experiments with animals revealed that inhalation of
VAM have cancer effects; and for this reason the International Agency for Research on
Cancer (IARC) has denoted VAM as a Group 2B carcinogen, which means that there is
possibility to human acquire cancer. It should be said that this classification has not been
reconsidered since 1995 (ibid.).

The release of VAM into the environment, the half-life of it can be various. If it is released to
water, it will undergo hydrolysis and it is evaluated that at pH=7 and 25C, the half-life of
VAM is full 7 days. Whereas, the in the air the half-life will be around 0.6 days. Additionally,
there is not anticipated that VAM adsorb to soils or sediments.

41
Finally, VAM is not considered as environmental hazard or eco-toxiological risk for the
environment (EU 2008a, Canada 2009).

To conclude, the EU's Technical Committee on Classification and Labelling has determined
to classify VAM as presented in Table 9.1 below (msdssearch.dow.com).

Table 9.1 VAM classification in Europe

Classification Risk Phase Definition

F R11 Highly flammable
Carcinogen category 3 R40 Limited evidence of a
Carcinogenic effect
Xn R20 Harmful by inhalation
Xi R37 Irritating to respiratory
system

9.2. Precautions in the storage of VAM

In order to prevent emergency situations such as hazardous polymerization, drums and

containers have to be stored in cool, well-ventilated area. Container must be from stainless
steel or aluminum, and only approved containers must be utilized. Besides, there are usually
coated with heat or light reflective coatings. It is recommended that at least two exits from the
storage room should be existed. Moreover, operations with significant amount of VAM must
be conducted in outdoor type structures; and in the case of explosion venting windows, roof
and wall panels, skylights, diaphragms, etc, are highly recommended to minimize the building
damage (msdssearch.dow.com).

The temperature measuring device is considered as highly important device in VAM storage,
because sharp increase in temperature will be the indication of VAM polymerization. For
large tanks these measuring devices should be installed at different altitudes since local
polymerization could occur.

Emission control devices or vapor recovery systems will give advantage in reducing the VAM
emissions from point sources (ibid.).

9.3. Elimination of risks

The safety is always the first priority in a plant; and in order to minimize the risk the
following procedures has to be handled: responsibilities among workers has to be well known,

42
emergency procedure must be conducted periodically, emergency response equipment has to
be operated by qualified individuals. Again, sufficient venting must be provided for storage,
handling and processing vessels. Inspection of equipment and storage facilities for corrosion
and leaks should be done in a regular manner. Immediate actions against emergency situation
must be done.

9.4. Shipping Classification

As it is known in internal or external businesses VAM is transported via highway, rail and
water. Certainly, strict regulations are required to prevent emergency situations. The table
below shows the shipping regulation for VAM in the US, Canada and Europe
(msdssearch.dow.com).

Table 9.2 US DOT (Department of Transportation), Canadian TDG (Transport of Dangerous Goods) and EU
shipping requirements for VAM

US DOT Canadian TDG EU

Shipping name Vinyl Acetate, Vinyl Acetate, Vinyl Acetate,
Inhibited Stabilized Stabilized
Hazard Class 3 (Flammable 3 3
Liquid)
UN/NA ID Number UN 1301 UN 1301 UN 1301
Packing Group II II II
Reportable Quantity 2270 kg 187 kg
Placard Flammable Flammable Liquid Flame
Label Flammable Liquid Flammable Liquid Highly Flammable
Liquid and Vapour

9.5. First Aid

Table 9.3 extensively shows the exposure effects on human health (msdssearch.dow.com).
This section will give the knowledge of giving the first aid in such trouble situations.

Table 9.3 Exposure effects on human health

Effect Assessment Result

Acute toxicity Considered as low acute toxicity by skin
contact and inhalation toxicity. Irritation of
the upper respiratory tract can be observed
Irritation May cause skin and eye irritation
Sensitization Not considered to be a skin sensitizer.
Carcinogenicity Laboratory experiments have shown that
VAM has produced swelling in rats and mice
at high exposure concentrations. However,
under realistic human exposure conditions

43

Toxicity after repeated exposure
Toxicity for reproduction
occurring of swelling is unlikely to be.
Irritation of the upper respiratory tract may be
observed, especially to the tissues lining the
nose
Not considered to be a reproductive.

In case of inhalation of VAM, the person has to go to the fresh air; and he or she must be
given oxygen, if breathing is still difficult.

In case of skin contact, closing and shoes should be removed. Affected zones have to be
washed with water and soap for at least 15 minutes. Likewise, in case of eye contact, eyes
must be flushed also for at least 15 minutes with plenty of water.

In case of ingestion, 125-250mL of water or milk should be drunk. Furthermore, it is

prohibited to induce vomiting; it will prevent aspiration into lungs (ibid.).

Undoubtedly, medical personnel/physician must be called on each case.

Finally, it has to be said that in case of huge release of vinyl acetate, all workers near the
exposure should be evacuated to a safe location.

44
10. Future work

Next stage of the work is Capstone 2. In Capstone 2 the work completed in Capstone 1 will be
continued in more detailed format. Each of the units will be designed separately and in more
details. Additionally, Energy integration and Economic evaluation will be discussed and
analyzed with more details. Besides, after the design of separation section is completed, the
recycle streams will be possible to construct. All of units in separation section will be
completed in Capstone 2 with all required information, such as design specification and heat
requirements. Furthermore, the dynamic simulation of the plant will be presented for the
consideration of the behavior of the plant. Also, possible controllers will be considered for the
optimization of the plant. Thus, detailed design and analysis of the Vinyl Acetate production
plant will be completed in Capstone 2.

45
11. Conclusion

In conclusion, this work describes the preliminary design of Vinyl Acetate Monomer plant
that is decided to be built in Taldykurgan city, Kazakhstan. Method of production of vinyl
acetate from acetic acid and ethylene has been chosen due to the fact that it is the most
reliable, safe and economically feasible in comparison with other methods. Additionally,
evaluation of the demand for vinyl acetate and its production in the world allowed the
calculation of designed plant’s market fraction. After the method has been chosen, the raw
materials and rates of reactions were analyzed, also azeotrope has been evaluated and
described. Pd-based catalysts with activators were stated as suitable for this type of reactions.
Moreover, mathematical model was introduces and calculated during the input/output analysis
along with the typical conversions of the raw materials obtained from literature review. Next,
the reactor has been described, and multi-tubular catalytic reactor has been stated as the most
suitable among compared types of reactors. The reactor has been characterized through the
calculation of heat transfer coefficient and number of tubes. The simulation in Aspen Plus has
shown that the reactor operates with good conversion and selectivity. Besides, several trials of
different configurations of the reactor allowed comparison of temperature profiles in order to
obtain the most desirable results. Next, separation section has been decided to consist of two
parts: liquid separation and gas separation. Due to the fact that this is preliminary design, the
design separation section has not been fully completed, however, literature review and current
results allowed to predict outcomes of separation section and possibility of two recycle
streams. Therefore, preliminary flowsheet and mass balance was possible to be obtained.
Finally, risk evaluation and requirements for the storage and transportation of products and
raw materials has been analyzed.

It can be concluded, that Capstone 1 is a good pre-stage for a design of a plant, as it provides
a platform for more detailed analysis and research. Due to the fact that design of a plant
implies accurate results and analysis, the precision can be maintained by division of process
into two steps (Capstone 1 and 2). Besides, Capstone 1 shows clearer plan for Capstone 2, and
allows prediction of results and outcomes.

46
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