PRODUCTION OF VINYL ACETATE

MONOMER )VAM)
(60,000 TON/YEAR)
Project Design Research
Submitted to Faculty of Engineering / Chemical Engineering Department in Partial
of Fulfillment of the Requirements for the Degree of Bachelor of Chemical
Engineering

Supervised by: M.Sc. Ali Abd ALhassan

Prepared by:
Karrar Hayder Majeed
Mustafa Falah Kadhim Ruqaya Abd ALhamza Ksheesh

Mehdi Redha Abd Almahdi Zainab Abd Madlool Jabbar

Um Albaneen Hardan Saadoun

2018-2019
 ‫بسم اهلل الرمحن الرحيم‬
‫ً‬
‫ينبت لكم به الزرع والزيتون ‪‬هو الذي انزل من السماء ماء لكم منه شراب ومنه شجر فيه تسيمون‬

‫‪‬والنخيل واالعناب ومن كل الثمرات ان يف ذلك الية لقوم يتفكرون‬

‫صدق اهلل العلي العظيم‬

‫االية (‪ )11-10‬النحل‬

‫‪V‬‬
 ‫االهـــــــــــداء‬

‫بسم هللا الرحمن الرحيم‬

‫وصلى هللا على محمد وعلى آله الطيبين الطاهرين وبعد‪:‬‬

‫اهدي هذا الجهد المتواضع الى الذي اخرجنا من الظلمات الى النورالذي قاتل على‬
‫التنزيل الرسول االمجد ابي القاسم محمد والى آله الطاهرين ‪.‬‬

‫إلى الينبوع الذي ال يمل العطاء إلى من حاكت سعادتي بخيوط منسوجة من قلبها إلى‬
‫والدتي العزيزة‪.‬‬

‫إلى من سعى وشقى ألنعم بالراحة والهناء الذي لم يبخل بشيء من أجل دفعي في‬
‫طريق النجاح الذي علمني أن أرتقي سلم الحياة بحكمة وصبر إلى والدي العزيز‪.‬‬

‫إلى من حبهم يجري في عروقي ويلهج بذكراهم فؤادي إلى إخواني وأخواتي‪.‬‬

‫إلى من سرنا سويا ً ونحن نشق الطريق معا َ نحو النجاح واإلبداع إلى زمالئي و‬
‫زميالتي‪.‬‬
‫إلى من علمونا حروفا من ذهب وكلمات من درر وعبارات من أسمى وأجلى عبارات‬
‫في العلم إلى من صاغوا لنا علمهم حروفا ومن فكرهم منارة تنير لنا سيرة العلم‬
‫والنجاح إلى أساتذتنا الكرام‪.‬‬

‫‪V‬‬
 ‫شكر وتقدير‬
‫اوله واخرهِ اىل هللا سبحانهُ وتعاىل الذي منحنا القوة والصرب‬
‫الشكر يف ِ‬

‫ألجناز هذا املشروع ‪.‬‬

‫كما نتقدم ابلشكر لالستاذ الفاضل االستاذ علي عبد احلسن كتعبري‬
‫بسيط ملساعدته واشرافه يف اجناز املشروع ‪.‬‬

‫وكافة االساتذة االفاضل يف جامعة املثىن –كلية اهلندسة – قسم‬

‫اهلندسة الكيمياوية‪.‬‬

‫وكذلك نتقدم ابلشكر اجلزيل اىل كل من نصحنا ولو بكلمة واحدة‬

‫واىل كل من ساندان عند حاجتنا اليه ‪.‬‬

‫داعني املوىل القدير هلم التوفيق واحلصول على الدرجات العلى ودوام‬
‫الصحة والعافية ‪.‬‬

‫‪V‬‬
 CERTIFICATE SUPERVISOR
We certify, as an examining committee, that we have read this project entitled
“PRODUCTION OF VINYL ACETATE MONOMER” has been carried out by
Karrar Hayder, Mustafa Falah, Mehdi Redha , Ruqaya Abd ALhamza and Um
Albaneen Hardan, Zaineb Abd Madlool ,in its contents and found it meets the
standards of the final year project for the degree of Bachelor of Science in Chemical
Engineering.

Signature:

Name: M.Sc. Ali Abd Alhassn

(Supervisor)

Date: / /

Signature:

Name: Dr. Adil Hattem Rasheed

(Head of Department)

Date: / /

V
 CERTIFICATE EXAMINERS
We certify, as an examining committee, that we have read this project entitled
"PRODUCTION DRYING OIL" has been carried out by Walaa Adel Thageel ,
Hadia Kadhim , Hanan Nassem , and Hawraa Alaa ,in its contents and found it
meets the standards of the final year project for the degree of Bachelor of Science in
Chemical Engineering.

Signature:

Name:

Date: / /

Signature: Signature:

Name: Name:

(Member) (Chairman)

Date: / / Date: / /

Approval of the Chemical Engineering Department

Signature:

Name: Dr. Adil Hattem Rasheed

(Head of Department)

Date: / /

V
 List of Contents
Content Page
List of Contents .......................................................................................................................... VII
Chapter one Introduction ............................................................................................................ 1
1.1 Historical Overview ............................................................................................................. 2
1.2 Product Definition ............................................................................................................... 6
1.3 Physical Properties: ............................................................................................................. 7
1.4 Chemical Properties ............................................................................................................ 8
1.5 Uses and Applications: ........................................................................................................ 9
1.6 Production Methods: ........................................................................................................ 10
1.7 Process Selection: ............................................................................................................. 11
1.8 Production Process using Ethylene, Acetic Acid and Oxygen:............................................. 11
Chapter Two Material Balance................................................................................................... 19
2.1: Introduction ..................................................................................................................... 21
2.2: Basic calculations ............................................................................................................. 22
2.3 Material Balance on Reactor ............................................................................................. 24
2.4 Material Balance on Separator (knockout): ....................................................................... 27
2.5 Material Balance on Absorber: .......................................................................................... 31
2.6 Material Balance on Mixer 1: ............................................................................................ 33
2.7 Material Balance on Distillation: ........................................................................................ 35
2.8 Material Balance on Decanter: .......................................................................................... 38
2.9 Material balance on CO2 removal ...................................................................................... 39
2.10 Material Balance on evaporator: ..................................................................................... 41
2.11 Material Balance on Mixer 2:........................................................................................... 43
Chapter Three Energy Balance ................................................................................................... 44
3.1 Introduction ...................................................................................................................... 45
3.2 Properties required to calculate energy balance ............................................................... 46
3.3 Reactor Energy balance : ................................................................................................... 48
3.4 Heat Exchanger (1) Energy balance ................................................................................... 54
3.5 Condenser Energy balance : .............................................................................................. 57
3.6 Separator Energy balance:................................................................................................. 62
3.7 Compressor Energy balance: ............................................................................................. 64
3.8 Absorber Energy balance : ................................................................................................. 69
3.9 CO2 Removal Energy balance: .......................................................................................... 72

V
 3.10 Mixer1 Energy balance: ................................................................................................... 74
3.11 Heater Energy balance: ................................................................................................... 76
3.12 Distillation Energy balance: ............................................................................................ 79
3.13 Divider Energy balance : .................................................................................................. 87
3.14 Cooler Energy balance : ................................................................................................... 88
3.15 Mixer 2 Energy balance : ................................................................................................. 90
3.16 Evaporator Energy balance : ............................................................................................ 92
Chapter Four Design Equipment ................................................................................................ 94
4-1 Plug Flow Reactor Design: ................................................................................................. 95
4.2 Design of cooler: ............................................................................................................. 108
Chapter five Plant Layout & Treatment ................................................................................... 117
5.1: Plant Layout ................................................................................................................... 118
5.1.1: Site Considerations .................................................................................................. 118
5.1.2: Site Layout ............................................................................................................... 120
5.1.3: Vinyl Acetate Monomer Plant Location: ................................................................... 121
5.2: Health & Safety Information ........................................................................................... 122
5.3: Pollutants: ...................................................................................................................... 122
Chapter Six Cost Estimation ..................................................................................................... 123
6.1: Economic Studies: .......................................................................................................... 124
6.2: Cost of designed equipment: .......................................................................................... 125
6.2.1: Reactor Cost ............................................................................................................ 125
6.2.2 Cooler cost:............................................................................................................... 126
6.3: Conclusions: ................................................................................................................... 128
APPENDIX A ............................................................................................................................. 130
APPENXDIX B ........................................................................................................................... 142
REFERENCES: ............................................................................................................................ 143

V
Chapter one
Introduction

1
1.1 Historical Overview

It is not known whether Vinyl Acetate occurs naturally. Vinyl acetate

is a man-made compound that was first produced by (Fritz Klatte) in 1912
as by product in the synthesis of ethylidene diacetate. This reaction involved
bubbling acetylene through a mixture of mercurous sulfate and anhydrous
acetic acid.

During the 1920, the Germans converted this liquid-phase process to

a vapor-phase process that allowed Germany to achieve a production volume
of 12000 ton per year by the 1940 and which accounted for most of the
world's production of vinyl acetate until about 1970.
Currently, the manufacturing process most widely used to produce
vinyl acetate is the vapor phase ethylene process (William 1992). The total
capacity for vinyl acetate production was more than 1 million tonnes per year
in 1965 (Roscher 2004).
The vapor phase ethylene process was developed in 1967, after
ethylene had become one of the cheapest raw materials in the chemical
industry, it was obvious that vinyl acetate should be produced from ethylene
instead of acetylene, and came into widespread use in the 1970. By 1981, the
vapor phase ethylene process accounted for 92% of U.S.
Various firms in the United States, Japan, West Germany, and the
United Kingdom have independently and/or jointly modified the vapor phase
ethylene process by using different types of catalysts in the reaction. The
catalyst is usually palladium or its salt, although salts of rhodium, gold,
platinum, ruthenium, vanadium, and iridium have also been used. The
advantage of these processes is that the catalyst lasts longer and undergoes
less corrosion.

2
 A less important commercial manufacturing process for vinyl acetate
involves the reaction between acetaldehyde and acetic anhydride. This
process was used in the United States until the 1960, and may still be in use
at small plants in China, India, and Mexico (William 1992).
In 1970, vinyl acetate was still being produced by three processes. Since
then, the two older processes - the addition of acetic acid to acetylene and
the two-step reaction of acetaldehyde with acetic anhydride through the
intermediate ethylidene diacetate – have been increasingly replaced by the
modern acetoxylation of ethylene process. In new plants, this process is used
almost exclusively (Weissermel et al., 2003).
New methods for vinyl manufacture were being developed in 1982
that were to utilize synthetic gas as a feedstock. The gas would undergo a
series of carbonylation reactions to yield ethylidene diacetate, which can be
pyrolytically converted to vinyl acetate and acetic acid (William 1992).

In many countries, vinyl acetate production has stabilized following a

dramatic growth period. Production VAM for several countries are
summarized in table(1.1):

Table (1.1): Vinyl Acetate production (in 1000 Ton/year)

12

Country 1990 1992 1994

USA 1157 1207 1377

W. 553 570 582

Europe
Japan 500 540 537

3
 The world capacity for vinyl acetate in 1995 was about 3.8 million tonnes
per year, with about 1.5, 0.59, and 0.70 million tonnes per year in the USA,
Japan, and Western Europe respectively. The largest producer of vinyl
acetate is Hoechst, mainly in the USA and Europe with a capacity of roughly
1.0 million tonnes per year (1995). In 1996, about 88% of the vinyl acetate
capacity worldwide was based on ethylene acetoxylation (Weissermel et al.,
2003). No information has been found that would indicate whether or not
such new methods have been perfected or adopted for industrial production
(William 1992).
The worldwide production of vinyl acetate was about 5 million
tonnes per year in 2005,6,154,000 tonnes per year in 2007, with most
capacity concentrated in the United States (1,585,000 all in Texas),
China (1,261,000), Japan (725,000) and Taiwan (650,000) ,with rapid
growth in the emerging markets.

Table (1.2) below shows VAM capacities of in differnet countries at

2008.

4
 Table (1.2): The Vinyl Acetate capacities of individual countries .
(Roscher 2004).

Country Process Capactiy

(Ton/Year)
United States Ethylene Bayer –Hoechst 1429
and National Distillers
Canada Ethylene Bayer – 54
Mexico Ethylene Bayer –Hoechst 100
South America Acetylene, Ethylene 100
Hoechst
National Distillers
Germany Ethylene Bayer –Hoechst 280
France Acetylene 150
Spain Ethylene Bayer – 100
Hoechst, Acetylene
United Kingdom Ethylene Bayer –Hoechst 100
Italy Acetylene 60
Eastern Europe Ethylene Bayer – 288
Hoechst, Acetylene
Japan Ethylene Bayer –Hoechst 612
and National Distillers,
Acetylene
Near East Ethylene Bayer –Hoechst 90
and National Distillers
India Ethylene Bayer –Hoechst 50
Korea Ethylene Bayer –Hoechst 150
Taiwan Ethylene Bayer –Hoechst 100
China Ethylene Bayer-Hoechst, 224

5
1.2 Product Definition
Vinyl acetate monomer (VAM) is an organic compound with the
general formula (CnH2nO2 ) CH3CO2CHCH2 from the esters group
with the structure (RCOOR) consists of a carbon double bonded to
oxygen single bonded to carbon and (R) (where R is refer to H or organic
groups). As shown in figure(1.1)

Figure (1.1) Structure of Vinyl Acetate Monomer

6
1.3 Physical Properties:
Table (1.3) shows the physical properties of VAM
Table (1.3): Physical Properties of Vinyl Acetate (Kirk et al., 2001)
Property Value

formula weight 86.09 g/mole

physical state Liquid

Flash point −8 °C
Boiling point at 101.3 kPa 72.7 °C
Phase change point −93.33 °C
Density 0.934 g/𝑐𝑚3
viscosity at 20°C 0.43 cps
Solubility in water Immiscible
Odor not unpleasant, sweetish smell in
small quantities
color Clear and colorless

critical temperature 246 °C

critical pressure 3950 kPa

heat of combustion at 25°C –495.0 kcal/mol

heat of vaporization (1 atm) 87.6 cal/g

heat of formation (liquid at 25°C) –349.4 kJ/mol

specific heat at 20°C (liquid) 0.46 cal/g °C

surface tension at 20°C 23.6 mN/m

7
1.4 Chemical Properties
Vinyl Acetate Monomer (VAM) is an ESTER organic compound with
the formula (CH3COOCH=CH2), is completely soluble in organic liquids but
not in water. At 20º C a saturated solution of the monomer in water can
contain between 2-2.4% of vinyl acetate, while a saturated water solution in
vinyl acetate contains 1% of water. At 50ºC the solubility of the monomer in
water increases in 0.1% in regards to 20ºC, while the solubility of water in
vinyl acetate doubles at 50º.
The most important reaction of vinyl acetate is the polymerization by
free radicals which is fast and exothermic. It can be polymerized, either by
itself to make polyvinyl acetate or with other monomers to prepare
copolymers such as ethylene-vinyl acetate (EVA), vinyl acetate-acrylic acid
(VA/AA) and polyvinyl chloride acetate (PVCA) (Contreras et al.,2000) .
Due to the fact that the vinyl acetate is an Ester, it presents the reactive
properties of said group. Keeping in mind that the corresponding chain of
alcohols is unsaturated, the compound presents some differences in regards
to the Ester group.
VAM is a reactive molecule. Unless inhibited, or if proper handling
and storage precautions are not met, VAM can polymerize uncontrollably.
Properly inhibited, VAM is stable under recommended storage conditions.
Prolonged or intense exposure to heat, sunlight, ultraviolet light or x-rays
may result in polymerization. Spontaneous polymerization may also result
from exposure to amines, strong acids, alkalis, silica, alumina, oxidizing
agents (e.g., peroxides, hydroperoxides, hydrogen peroxide) or
polymerization initiators. Heat and pressure generated during such
polymerization may rupture insufficiently vented containers, leading to
liquid spill, vapor generation and possibly fire.

8
 The speed of hydrolysis of the vinyl acetate is 1,000 times greater than
it’s saturated analogous in an alkaline medium, and it was researched that its
speed of hydrolysis is significantly lower at a p.H. of 4.4 (Vinyl 2010).

1.5 Uses and Applications:

The primary use for vinyl acetate is as a monomer in the production
of polyvinyl acetate (PVAc) and polyvinyl alcohol (PVOH or PVA). These
products, synthesized via polymerization of vinyl acetate, accounted for
75%-80% of total U.S. consumption in 1982. Vinyl acetate is also
polymerized with vinyl chloride to produce copolymers. Polyvinyl butyral,
polyvinyl acetals, ethylene-vinyl acetate copolymers, and acrylonitrile
copolymers (for acrylic fibers) are also produced. It is also used in polymeric
lubrication oil additives.
Polyvinyl acetate is used in paints, adhesives, paper coatings and
textile treatments, while polyvinyl alcohol is used in the production of
adhesives, coatings, and water soluble packaging, and textile warp sizing.
VAM is also used to make polyvinyl butyral (PVB) which is used in
laminated safety glass for cars and buildings. Ethylene-vinyl acetate (EVA)
resin is also made from VAM and is used in the manufacture of packaging
film, heavy-duty bags, extrusion coating, wire and cable jacketing, hot-melt
adhesives and cross-linked foam. Other products made from VAM are
ethylene-vinyl alcohol (EVOH) resins which are used as a gas barrier in
multi-layered food and beverage packages, and as a barrier layer in
automobile tanks (Roscher 2004).
Polyvinyl acetate emulsions (homopolymer and copolymer), the
major derivatives of vinyl acetate, are widely used in adhesives for
packaging and construction (wood gluing) and in water-based paints. Other
important uses

9
include nonwoven textile fibers, textile sizings and finishes, paper coatings,
and inks. Polyvinyl alcohol is widely used in textile finishing, adhesives, and
as a raw material for polyvinyl butyral, which is used as the adhesive
interlayer in architectural and automobile laminated safety glass.
Uses of other polymers made from vinyl acetate include barriers in
packaging, paint coatings applications, plastic floor coverings, phonograph
records, flexible film and sheeting (including plastic films used for wrapping
food), food starch modifier, and moulding and extrusion compounds
(William 1992).

1.6 Production Methods:

There are various possible routes for vinyl acetate production(Roscher
2004):
1) Addition of acetic acid to acetylene:
a) In the liquid phase in the presence of homogeneous mercury salt catalysts.
𝐇𝐠
CH3COOH + 2C2H4 → CH3COOCH=CH2 + C2H2
b) In the gas phase in the presence of heterogeneous catalysts containing zinc
salts.
𝐙𝐧
2C2H4 + CH3COOH + → CH3COOCH=CH2
2) Addition of acetic anhydride to acetaldehyde giving ethylidene diacetate,
and subsequent cleavage of the latter to form vinyl acetate and acetic acid.
CH3CHO+ (CH3CO)2O → CH3CH(OCOCH3)2
CH3CH(OCOCH3)2 → CH3CO2CH=CH2 + CH3CO2H
3) Reaction of ethylene with acetic acid and oxygen:
a) In the liquid phase in the presence of palladium/copper salts as
homogeneous catalysts.
𝐏𝐝𝐂𝐥𝟐
C2H4 + CH3CO2H → CH3CO2CH=CH2 + 2HCl + Pd
b) In the gas phase on heterogeneous catalysts containing palladium.

10
CH2=CH2 + CH3CO2H + 1/2O2 → CH3CO2CH=CH2 + H2O
4) Vinyl acetate can also be synthesized in high yields by reacting vinyl
chloride with sodium acetate in solution at 50 °C-75°C, using palladium
chloride as a catalyst.
CH2=CHCl + CH3CO2Na → CH3CO2CH=CH2 + NaCl

1.7 Process Selection:

Processes in (1), Acetylene, which is expensive, so we should relative
this route. The processes (2) no longer used (experimental), processes in (4)
are highly expensive. The process that considered in this project (3) in which
the reaction of Ethylene with Acetic acid and Oxygen, where Ethylene is a
cheap raw material and the gas phase instead of the liquid phase because the
sever corrosion that occurs in the liquid phase reaction, and form high
undesirable by products.

1.8 Production Process using Ethylene, Acetic Acid and

Oxygen:
In the Vinyl Acetate (VAM) process, there are 10 basic unit
operations, which include a vaporizer, a catalytic plug flow reactor, a feed-
effluent heat exchanger, a separator, a gas compressor, an absorber, a carbon
dioxide (CO2) removal system, and distillation column with a decanter.
There are six chemical components in the VAM process. Pure Ethylene
(C2H4), pure oxygen (O2), and acetic acid (HAC) are converted into the vinyl
acetate (VAM) product, water (H2O) and carbon dioxide (CO2) are by-
products. figure (1.3) shows the flowsheet of this process . The basic
chemical reactions that take place are given as follows (Chen et al.):
CH2=CH2 + CH3CO2H + 1/2O2 → CH3CO2CH=CH2 + H2O
C2H4 + 3O2 → 2CO2 + 2H2O
The project deals with a VAM plant capacity of 60000 ton per year
for an effective operation time of 350 day . The process will be based on

11
the acetoxylation of ethylene conducted in gas phase in the presence of a
palladium - based solid catalyst (Alexandre et al., 2008).
The exothermic reactions occur in a reactor containing tubes packed
with a precious metal catalyst on a silica support. The reacting gases flow
downward through the bed instead of upward to avoid fluidization and
minimize entrainment of catalyst in the exit gases (Harry et al., 2003). Heat
is removed from the reactor by generating steam on the shell side of the
tubes. Water flows to the reactor from a steam drum, to which makeup water
(boiler feeder water; BFW) is supplied. The steam leaves the drum as
saturated vapor. This vapor is used in other part of the process. The reactions
are irreversible and the reaction rates have an Arrhenius-type dependence on
temperature. The following rate expressions were derived from the
experimental kinetic data in Samanos et al. (1971) for a particular vinyl
acetate catalyst.

Where r1, has units of moles of vinyl acetate produced per minute per
gram of catalyst,
T is the absolute temperature in Kelvin and Pi is the partial pressure of
component i (O is oxygen, E is ethylene, A is acetic acid, and W is water) in
Psia.

The ideal-gas standard state heat of reaction is (– 42.1 kcal/mol) of

vinyl acetate for first reaction, and (– 316 kcal/mol) of ethylene for second
reaction. Thus the reactions are quite exothermic, particularly the

12
combustion reaction to carbon dioxide, which also is more sensitive to
temperature because of the higher activation energy (Luyben et al., 1999).
To prevent excessive ethylene losses in the removed gas, it is
preferable to use pure oxygen rather than air as the oxidizing agent (Alain et
al., 1986).
Reactor inlet temperature must greater than 130oC to prevent
condensation in the reactor. The reactor temperature along the length of the
tube must remain below 200oC to avoid catalyst ageing (Alexandre et al.,
2008).
The principal requirements of a packing are that it should provide a
large surface area, Have an open structure: low resistance to gas flow and
Promote uniform vapor gas flow across the reactor cross-section (Sinnott ea
al., 2005)
Packing for tubular reactors constructed from ceramics for higher
temperature applications (Sunggyu et al., 2006).
The amount of CO2 formed by reaction is quite limited, denoting good
catalyst selectivity; only about 11% from ethylene is consumed by
combustion, the rest 89% going into vinyl acetate (Alexandre et al., 2008).
Selection criteria for catalysts:
1- High durability
2- High selectivity
3- High production rates per unit volume of catalyst
4- Low cost

Table (1.4) below shows Comparison between Few Alternative catalysts.

13
 Table (1.4): Comparison between Few Alternative catalysts.

The catalyst plays a crucial role in technology. Previously, catalysts

were based on palladium of 1 to 5 wt% impregnated on silica with alkali
metal acetates as activators. Modern catalysts employ as enhancers noble
metals, mostly gold technology (C). A typical Bayer - type catalyst consists
of 0.15 – 1.5 wt% Pd, 0.2 – 1.5 wt% Au (Alexandre et al., 2008).
The reaction is very fast and takes place mainly inside a thin layer on the
particle surface. Typical catalyst lifetime is 1–2 years. Preferred operation
conditions are temperatures around 140 to 160 °C and pressures 8 to 10 bar..
The selectivity and heat - removal constraints the reactor is designed at low
per - pass conversion, generally 15 – 35% for the Acetic acid and 8 – 12%
for Ethylene, 50-65% for the Oxygen (Alexandre et al., 2008), and the
overall conversion to form vinyl acetate 20 – 25 % (Alain et al., 1986).
This project it is considered the conversion values are: 10.9% for
Ethylene, 24.9% for Acetic acid, and 57.2% for Oxygen. Higher pressure has
a positive effect on productivity, but affects the selectivity negatively since
increased adsorption of ethylene on the catalytic sites favors the combustion
reaction. A strong safety constraint is the concentration of oxygen in the
reaction mixture. In general, the oxygen concentration at the reactor inlet
should be below 8 mol% in order to avoid ignition, based on an acetic - acid
- free mixture (Alexandre et al., 2008).

14
 The reactor effluent flows through a process-to-process heat
exchanger, where the cold stream is the gas recycle. The reactor effluent is
then cooled with cooling water, and the vapor (oxygen, ethylene and carbon
dioxide) and liquid (vinyl acetate, water, and acetic acid) are separated. The
vapor stream from the separator goes to the compressor and the liquid stream
from the separator becomes a part of the feed to the distillation column. The
gas from the compressor enters the bottom of an absorber, where the
remaining vinyl acetate is recovered. A liquid stream from the base is re-
circulated through a cooler and fed to the middle of the absorber. Liquid
acetic acid that has been cooled is fed into the top of the absorber to provide
the final scrubbing. The liquid bottoms product from the absorber combines
with the liquid from the separator as the feed stream to the distillation
column. The overhead gas exiting the absorber enters the carbon dioxide
removal system. The removal of CO2 – usually by a wash with KOH solution
– negatively affects the overall economics. This could be one of several
standard industrial CO2 removal processes. The CO2 removal system is
assumed to be a component separator that removes just carbon dioxide at
certain efficiency as potassium carbonate and water according to the
following reaction

CO2 + 2KOH → K2CO3 + H2O

The rest combines with the large recycle gas stream and goes to the
feed-effluent heat exchanger. The fresh ethylene feed stream is added. The
gas recycle stream, the fresh acetic acid feed, and the recycle liquid acetic
acid stream enter the vaporizer, where heater is used to vaporize the liquid.
Fresh oxygen is added to the gas stream from the vaporizer just prior to the
reactor to keep the oxygen composition in the gas recycle loop outside the
exclusivity region (Luyben et al., 1999).

15
 The purposes of using Oxygen instead of air are the disposal of
nitrogen, pollution regulation, and investment capital and flammability
limitations (Alain et al., 1986).
The azeotropic distillation column separates the vinyl acetate and
water from the unconverted acetic acid. The overhead product is condensed
with cooling water and the liquid goes to a decanter, where the vinyl acetate
and water phases separate. The organic and aqueous products are sent for
further refining to another distillation section. Here it is ignore the additional
separation steps required to produce vinyl acetate of sufficient purity because
there is no recycle from the refining train back to the reaction loop.
Separations in which the relative volatility of the key components is close to
unity or which exhibit azeotropic behavior should be performed in the
absence of non key components (Luyben et al., 1999). In other words,
perform the most difficult separation last. Sequences that remove the lightest
components alone one by one in column overheads should be favored. It
means that favor the direct sequence. A component composing a large
fraction of the feed should be removed first.
Favor near-equimolar splits between top and bottom products in individual
column.
Possible Sequence:
A: Vinyl Acetate
B: Water
C: Acetic acid

16
 Figure (1.2): Phase separation sequences in azeotropic distillation.

The bottoms product from the distillation column contains acetic acid,
which recycles back to the vaporizer along with fresh makeup acetic acid.
Part of this bottom stream is the wash acid used in the absorber after being
cooled (Luyben et al., 1999).
The large amount of wastewater will involve non-negligible costs for
neutralization and biological treatment. Similarly, the process develops
inherently CO2. Therefore, some ecological penalties have to be taken into
account when estimating the economic potential. The selection of raw
materials takes into accountthe price variation versus purity, with constraints
on undesired species (Alexandre et al., 2008).
By adding the separstion factor of substances such as Acetic Acid to
the VAM mixture and water, the interaction between the molecules changes
in the substance and the mixture becomes non-azitropy.But that process
required another separation to remove VAM and H2O from the top and HAC
from the bottom. The material that adding to azetropic distillation is
aluminum silicate. to increasing the efficiency of separation. (Kister,1992)

17
 Mixer

18
Mixer

Divider

Figure(1.3) : the flow sheet of the process.

Chapter Two
Material Balance

19
 CO2 Removal
Mixer

Absorber

20
Decanter

Separator

Reactor
Mixer
Distillation

Evaporator
Figure(2.1) : the flow sheet of Material balance
2.1: Introduction
The general form quoted for a mass balance is The mass that enters
a system must, by conservation of mass, either leave the system or
accumulate within the system .

Mathematically the mass balance for a system without a chemical

reaction is as follows:

Input = Output + Accumulation

The accumulation is negleged for steady state process

The process of producing Vinyl Acetate Monomer (VAM)

includes chemical reactions The first reaction involves the reaction of
ethylene, oxygen and acetic acid (HAC) and The second reaction
involves the reaction of ethylene and oxygen to produce carbon
dioxide and water.

The production capacity of the project is 60,000 tons / year, and

The maintenance time is 15 days.

94% is the ethylene Yeild (Alexandre et al.,2008).

Article VAM produced by comparing the equation we extracted

reactive Materials.

21
2.2: Basic calculations

HAC : Acetic Acid (CH3COOH)

VAM : Vinyl Acetate Monomer (𝐶𝐻3𝐶𝑂𝑂𝐶𝐻𝐶𝐻2 )

Main Reaction:
𝟏
𝑪𝟐 𝑯𝟒 + 𝑯𝑨𝑪 + 𝑶𝟐 → 𝑽𝑨𝑴 + 𝑯𝟐 𝑶 … … … . (𝟐. 𝟏)
𝟐

Mwt 28 60 32 86 18

Basis= 1 hr

Production capacity of VAM = (60000 𝑡𝑜𝑛\𝑦𝑒𝑎𝑟)(8400) = 7142.85 kg\

hr
7142.85
𝑉𝐴𝑀 (𝑝𝑟𝑢𝑑𝑜𝑐𝑡 ) = = 83.056 𝑘𝑔𝑚𝑜𝑙
86
𝑉𝐴𝑀(𝑝𝑟𝑜𝑑𝑢𝑐𝑡)
𝑦𝑒𝑖𝑙𝑑 𝑜𝑓 𝐶2𝐻4 =
𝑖𝑛𝑝𝑢𝑡
83.05
0.94 =
𝑖𝑛𝑝𝑢𝑡

𝑖𝑛𝑝𝑢𝑡 𝐶2𝐻4 = 88.357 𝑘𝑔𝑚𝑜𝑙

Using Stoichiomatric From Reaction (2.1) :

𝐶2𝐻4 𝑅𝑒𝑎𝑐𝑡 = 83.056 𝑘𝑔𝑚𝑜𝑙 = 2325.568 𝑘𝑔

𝐶𝐻3 𝐶𝑂𝑂𝐻 𝑅𝑒𝑎𝑐𝑡 = 83.05 𝑘𝑔𝑚𝑜𝑙 = 4983.36 𝑘𝑔

𝐻2𝑂 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = 83.056 𝑘𝑔𝑚𝑜𝑙 = 1495.008 𝑘𝑔

82.056
𝑂2 𝑅𝑒𝑎𝑐𝑡 = = 41.528 𝑘𝑔𝑚𝑜𝑙 = 1328.896 𝑘𝑔
2
𝑖𝑛𝑝𝑢𝑡𝐶2𝐻4 = 𝑟𝑒𝑎𝑐𝑡 + 𝑢𝑛𝑟𝑒𝑎𝑐𝑡

88.357 = 83.056 + 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑢 𝐶2𝐻4

𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝐶2𝐻4 = 5.301 𝑘𝑔𝑚𝑜𝑙

22
 𝑪𝟐 𝑯𝟒 + 𝟑𝑶𝟐 → 𝟐 𝑯𝟐 𝑶 + 𝟐𝑪𝑶𝟐 … … … (𝟐. 𝟐)

Mwt 28 32 18 4

𝑟𝑒𝑎𝑐𝑡 𝐶2𝐻4 = 5.301 𝑘𝑔𝑚𝑜𝑙

Using Stoichiomatric From Reaction (2.2) :

𝑂2 ( 𝑟𝑒𝑎𝑐𝑡) = 3 ∗ 5.301 = 15.903 𝑘𝑔𝑚𝑜𝑙 = 508.896 𝐾𝑔

𝐻2𝑂 (𝑃𝑟𝑜𝑑𝑢𝑐𝑡) = 2 ∗ 5.301 = 10.602 𝑘𝑔𝑚𝑜𝑙 = 190.836 𝐾𝑔

𝐶𝑂2 (𝑃𝑟𝑜𝑑𝑢𝑐𝑡) = 2 ∗ 5.301 = 10.602 𝑘𝑔𝑚𝑜𝑙 = 466.488𝑘𝑔

𝑖𝑛𝑝𝑢𝑡 (𝑜𝑣𝑒𝑟𝑎𝑙𝑙 ) = 𝐶2𝐻4 + 𝐶𝐻3𝐶𝑂𝑂𝐻 + 𝑂2

= 2473.996 + 4983.36 + 1837.76 = 9295.116 𝑘𝑔

𝑜𝑢𝑡 𝑝𝑢𝑡 (𝑜𝑣𝑒𝑟𝑎𝑙𝑙 ) = 𝐻2 𝑂 + 𝐶𝑂2 + 𝐶𝐻3𝐶𝑂𝑂𝐶𝐻𝐶𝐻2

= ((83.056 + 10.602) ∗ 18) + (10.602 ∗ 44)
+ (83.056 ∗ 86) = 1685.844 + 466.488 + 7142.818
= 9295.148 𝑘𝑔

Table (2.2) show the basic calculations material balance.

Table (2.2) Basic Calculations M.B.

Comp. Input (kg) Input (kgmol) Output(kg) Output(kgmol)

VAM ---------- ---------- 7142.816 83.056
CO2 ---------- ---------- 466.488 10.602
O2 1837.76 57.43 ---------- ----------
C2H4 2473.996 88.357 ---------- ----------
Acid 4983.36 83.056 ---------- ----------
H2o ---------- 1685.844 93.658
Total 9295.11 228.84 9295.14 187.316

23
2.3 Material Balance on Reactor

A unit for containing and controlling a chemical reaction, The plug flow
reactor model (PFR, sometimes called continuous tubular reactor, CTR, or piston
flow reactors) is a model used to describe chemical reactions in continuous, flowing
systems of cylindrical geometry. The PFR model is used to predict the behavior of
chemical reactors of such design, so that key reactor variables, such as the
dimensions of the reactor, can be estimated.

The feed is oxygen , ethylene and acetic acid to product the vinyle acetate
,water and CO2 from the tow reaction (primary and side reaction )

The conversion values are: 10.9% for Ethylene, 24.9% for Acetic acid, and 57.2% for
Oxygen. (Alexandre et al.,2008).

And unreacted component will recycled to process .

F3 = 1137.33 kgmol

C2H4 mol% =67.3

HAC mol%=24.9

O2 mol% =7.72

F4 = 1097.713kgmol

C2H4 mol%=61.84

HAC mol%=18.256

CO2 mol%=0.965

VAM mol% =7.566

H2O mol% =8.5321

O2 mol% = 2.83

24
 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝐶2𝐻4(𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑎𝑖𝑜𝑛 ) =
𝑖𝑛𝑝𝑢𝑡
0.109=83.056/input 𝐶2𝐻4

𝑖𝑛𝑝𝑢𝑡 𝐶2𝐻4 = 761.981𝑘𝑔𝑚𝑜𝑙

𝑖𝑛𝑝𝑢𝑡𝐶2𝐻4 = 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 + 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑
761.92 = 83.05 + 𝑢𝑛𝑟𝑒𝑎𝑐𝑡

𝑢𝑛𝑟𝑒𝑎𝑐𝑡 𝐶2𝐻4 = 678.925𝑘𝑔𝑚𝑜𝑙

reacted
HAC(𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑎𝑖𝑜𝑛 ) =
input
83.056
0.249 =
input
𝑖𝑛𝑝𝑢𝑡 (𝐻𝐴𝐶 ) = 333.558 𝑘𝑔𝑚𝑜𝑙

𝑢𝑛𝑟𝑒𝑎𝑐𝑡 (𝐻𝐴𝐶 ) = 𝑖𝑛𝑝𝑢𝑡 − 𝑟𝑒𝑎𝑐𝑡ed = 333.558 − 83.056

= 250.502 kgmol

𝐻𝐴𝐶 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑟 = 0.2 ∗ 250.502 = 50.1004 𝑘𝑔𝑚𝑜𝑙

𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑣𝑎𝑝𝑟𝑖𝑧𝑜𝑟 = 250.501 − 50.1004 = 200.4 𝑘𝑔𝑚𝑜𝑙

𝐻𝐴𝐶 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 = 200.4 + 83.056 = 283.456 𝑘𝑔𝑚𝑜𝑙

𝑟𝑒𝑎𝑐𝑡
𝑂2 (𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑎𝑖𝑜𝑛 ) =
𝑖𝑛𝑝𝑢𝑡

41.528
0.572 =
input𝑂2

𝑖𝑛𝑝𝑢𝑡𝑂2 = 72.601 𝑘𝑔𝑚𝑜𝑙

𝑖𝑛𝑝𝑢𝑡𝑂2 = 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 + 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑

𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑂2 = 72.601 − 41.528 = 31.073 𝑘𝑔𝑚𝑜𝑙

𝑇𝑜𝑡𝑎𝑙 𝐻2𝑂 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = 93.658 ∗ 18
= 1685.844 𝑘𝑔 𝑓𝑟𝑜𝑚 𝑏𝑜𝑡ℎ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝐶𝑂2 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = 10.601 ∗ 44 = 466.444 𝑘𝑔

25
𝑉𝐴𝑀𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = 83.056 ∗ 86 = 7142.816 𝑘𝑔
𝑖𝑛𝑝𝑢𝑡𝐶2𝐻4 (𝑡𝑜𝑡𝑎𝑙 ) = 5.301 + 761.92 = 767.22 𝑘𝑚𝑜𝑙 = 767.22 ∗ 282
= 21483.896 𝑘𝑔

𝑖𝑛𝑝𝑢𝑡𝑂2 = 72.601 + 15.908 = 88.503 ∗ 32 = 2832.096 𝑘𝑔

𝑖𝑛𝑝𝑢𝑡 𝐻𝐴𝐶 = 283.456 ∗ 60 = 17007.36 𝑘𝑔

𝑖𝑛𝑝𝑢𝑡 (𝑟𝑒𝑎𝑐𝑡𝑜𝑟) = 𝑖𝑛𝑝𝑢𝑡 𝐶2𝐻4 + 𝑖𝑛𝑝𝑢𝑡 𝑂2 + 𝑖𝑛𝑝𝑢𝑡 𝑎𝑐𝑖𝑑

= 21483.896 + 2832.096 + 17007.36 = 41323.35 𝑘𝑔
𝑜𝑢𝑡𝑝𝑢𝑡 (𝑟𝑒𝑎𝑐𝑡𝑜𝑟)
= 𝑜𝑢𝑡𝑝𝑢𝑡 𝐶2𝐻4(𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 ) + 𝑜𝑢𝑡𝑝𝑢𝑡 𝑂2
+ 𝑜𝑢𝑡𝑝𝑢𝑡 𝐻𝐴𝐶 (𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 ) + 𝑜𝑢𝑡𝑝𝑢𝑡𝑉𝐴𝑀 + 𝑜𝑢𝑡𝑝𝑢𝑡 𝐻2 𝑂
+ 𝑜𝑢𝑡𝑝𝑢𝑡𝐶𝑂2
= (678.925 ∗ 28) + (31.073 ∗ 32) + (200.4 ∗ 60)
+ (83.056 ∗ 86) + (93.658 ∗ 18) + (10.601 ∗ 44)
= 41323.34 𝑘𝑔

Table (2.2) shows the material balance on reactor .

Table (2.2) M.B on Reactor .

Comp. F3 (Kg) F3 (Kgmol) F4 (kg) F4 (kgmol)

VAM ----------- ----------- 7142.81 (83.05
CO2 ----------- ----------- 466.444 10.601
O2 2832.09 88.503 994.336 31.07
C2 H 4 21483.89 767.22 19009.9 678.92
HAC 17007.36 283.45 12024 200.4
H 2O ------------ ----------- 1685.844 93.65
Total 41323.35 1097.31 41323.34 1097.31

26
 2.4 Material Balance on Separator (knockout):

This unit used in several industrial applications to separate a vapor–liquid

mixture.

A vapor–liquid separator, knock-out drum compressor inlet drum. When used to

remove suspended water droplets from streams of air, it is often called a demister.

The vapor stream outlet from top , and liquid stream outlet from bottom so the
bottom out contain VAM , HAC and water while the top stream contain CO 2 ,C2H4 and
O2 with litille amount of (VAM ,HAC ,H2O)

F5 = 732.972 kgmol

C2H4 mol%=92.62

HAC mol%=1.446

CO2 mol%=0.286
F4 = 097.713kgmol
VAM mol% =0.389
C2H4 mol%=61.84
H2O mol% =1.013
HAC mol%=18.256
O2 mol% = 4.23
CO2 mol%=0.965

VAM mol% =7.566 F6 =364.741kgmol

H2O mol% =8.5321 VAM mol%=20.73
O2 mol% = 2.83 H2O mol% =25.103

HAC mol%= 54.16

27
F4 =1097.713 Kgmol

K-Values : estimate by using Antoni equations at 35C and 70 Psia :

B
ln p*=A+
T+C

B
𝑝∗ = EXP(A + )
𝑇+𝐶
A,B and C Antoni equation s constant .
P∗
K=
PT

Then calculate the K-value for each component .

Table (2. 3) shows that Antoni equation results.

Table (2. 3) Antoni equation results.

Comp. A B C P* K Xi
O2 9.2 0 273 9897.13 141.388 0.0283
CO2 7.937 0 273 2798.95 39.985 0.00965
C2H4 9.497 -313 273 4821.14 68.873 0.61849
VAM 12.6564 -2984.45 226.66 3.49 0.0499 0.07566
H2O 14.6394 -3984.92 233.426 0.8137 0.0116 0.0953
HAC 14.5236 -4457.83 258.45 0.5129 0.0073 0.18256

X i(1−Ki)
∑ =0
α + Ki

by try and error

α=0.5079
𝐿
α : it is a separation ratio of liquid to vapor =
𝑉

F6
α=
F5

F4 =F5 + F6 →F6 =F4 − F5

F4 −F5
α=
F5

28
 F4
F5 =
α+1

F5 =727.928 Kgmol , F6 =369.784 Kgmo

Y=K X ………. (2.1)

Where :

Y: Vapor mole fraction.

X: liquid mole fraction.

F4 Xi =F5 Y +F6 X ……… (2.2)

Sub. Equation (2.1) in equation (2.2) to get equation (2.3)

F4 Xi=F5 (K X) +F6 X ……….. (2.3)

Find mole fraction for each component in vapors out with stram F5 by
using equation (2.3)

Then find mole fraction for each component liquids out with stram F6 by
using equation (2.1)

Table (2.4 ) shows the results of mole fractions for liquids and vapors.

Table (2.4 ) mole fraction o liquids and vapors .

Comp. X Y
Mol% Mol%
C2H4 ---------- 0.926264
O2 ---------- 0.042393
HAC 0.541617 0.014463
VAM 0.207348 0.003888
H2O 0.251035 0.010133
CO2 ---------- 0.002859
Total 1 1

In=93.658 Kgmol ,

F5 =2.0953 Kgmol = 21169.55 kg

F6 =91.5626 Kgmol =20153.78 kg

29
Checking:

In=F4 =1097.317 Kgmol=41323.34 Kg

Table (2.5) shows the material balance on separator .

Table (2.5) M.B on Separator .

Comp. F4 (Kg) F4(kgmol) 𝐅𝟓 (kg) 𝐅𝟓 (kgmol) 𝐅𝟔 (Kg) F6(kgmol)
𝐂𝟐 𝐇𝟒 19009.9 678.92 18870.7 678.92 ------- -------
𝐂𝐎𝟐 466.44 10.601 460.59 2.09 ------- -------
𝐎𝟐 994.33 31.07 990.77 31.07 ------- -------
𝐇𝟐 𝐎 1685.84 93.65 37.71 7.42 1648.12 91.56
VAM 7142.81 83.05 638.76 2.84 6504.01 197.55
HAC 12024 200.4) 170.9 10.601 11853.06 75.62
Total 41323.34 1097.31 21169.55 732.97 20153.78 364.74

30
 2.5 Material Balance on Absorber:

In this unit that use to absorb the gases by using special solvent capble to absorb

the gases needed to remove ,packed columns are used for absorption to increase the

surface contact between the solvent and the inlet gas by sending both streams through

a packed region.

The solute in the rich gas, or solute-containing gas, is absorbed by the fresh liquid.

The cause of using absorber is to separate the amount of VAM outler with vapor in

separator by sunig acetic acid as a solvent

G =720.6 kgmol
C2H4 mol% =94.21
R2=50.1 kgmol
CO2 mol% =1.47
HAC
O2 mol% =4.31
F5 = 732.972 kgmol

C2H4 mol%=92.62
M =62.47 kgmol
HAC mol%=1.446
HAC mol% = 84.75
CO2 mol%=0.286 VAM mol% =11.89
VAM mol% =0.389 H2O mol% = 3.4
H2O mol% =1.013

O2 mol% = 4.23

31
 𝐶𝑂2 𝐼𝑁 = 10.601 𝑘𝑔𝑚𝑜𝑙 = 𝑜𝑢𝑡

𝐶2𝐻4𝐼𝑛 = 678.925 𝑘𝑔𝑚𝑜𝑙 = 𝑜𝑢𝑡

𝑂2 𝐼𝑁 = 31.073 𝑘𝑔𝑚𝑜𝑙 = 𝑜𝑢𝑡

𝐴𝑐𝑖𝑑 𝐼𝑛 = 2.849 + 50.1 = 52.949 𝑘𝑔𝑚𝑜𝑙 = 𝑜𝑢𝑡

𝑉𝐴𝑀 𝐼𝑛 = 7.427 𝑘𝑔𝑚𝑜𝑙 = 𝑜𝑢𝑡

𝐻2 0 𝐼𝑁 = 2.095 𝑘𝑔𝑚𝑜𝑙 = 𝑜𝑢𝑡

𝐺 = 10.601 ∗ 44 + 31.073 ∗ 18 + 678.925 ∗ 2 = 20470.68𝑘𝑔

𝑀 = 7.427 ∗ 86 + 52.949 ∗ 60 + 2.095 ∗ 18 = 3853.471 𝑘𝑔

Checking

𝐼𝑛 = 𝐹5 + 𝑅2 = 21318.07 + 3006 = 24324.151 𝑘𝑔

𝑂𝑢𝑡 = 𝐺 + 𝑀 = 20470.68 + 3853.471 = 24324.151 𝑘𝑔

Table (2.6) shows the material balance on absorber .

Table (2.6) M.B on Absorber.

Como. In In G G M M
(Kg) (kmol) (Kg) (kgmol) (Kg) (kgmol)
VAM 638.763 7.42 ----------- ---------- 638.763 7.42
HAC 3176.99 52.4 ----------- ---------- 3176.99 2.84
H2O 37.715 2.09 ----------- ---------- 37.715 2.09
C2H4 19009.9 678.92 19009.9 678.92 ----------- -----------
O2 994.336 31.07 994.336 31.07 ----------- -----------
CO2 466.444 10.601) 466.444 10.601 ----------- -----------
Total 24324.15 732.97 20470.68 720 3853.4 12.37

32
 2.6 Material Balance on Mixer 1:

It is used to mix the liquid outside from the separation tower and the liquid
outside from the absorption tower to send to the distillation tower

M = 12.37 kgmol

HAC mol% = 23.03

VAM mol% =60.03

H2O mol% = 16.93

F6 =364.741 kgmol F7 = 427.21 kgmol

HAC mol%=20.73 VAM mol% = 19.44

HAC mol% = 58.63
H2O mol% =25.103 H2O mol% = 21.92

VAM mol%= 54.16

HAC = 82.831 wt%

33
𝑴. 𝑩 (𝑽𝑨𝑴)

𝐼𝑛 = 𝑜𝑢𝑡

6504.052527 + 638.7634731 = 7142.816 𝑘𝑔

𝑴. 𝑩 (𝑨𝑪𝑰𝑫)

𝐼𝑛 = 𝑜𝑢𝑡

11853.00801 + 3176.991986 = 15030 kg

𝑴. 𝑩 (𝑯𝟐 𝑶)

𝐼𝑛 = 𝑜𝑢𝑡

1648.128 + 37.715 = 1685.844 𝑘𝑔

𝐹6 = 20005.1889𝑘𝑔

𝑀 = 3853.471095kg

𝑪𝒉𝒆𝒄𝒌𝒊𝒏𝒈

𝑰𝒏(𝒕𝒐𝒕𝒂𝒍) = 𝑭𝟔 + 𝑴

20005.1889 + 3853.471095 = 23858.66 𝑘𝑔

𝑶𝑼𝑻(𝑭𝟕 ) = 𝑽𝑨𝑴 + 𝑨𝑪𝑰𝑫 + 𝑯𝟐𝑶

= 7142.816 + 15030 + 1685.844 = 23858.66 𝑘𝑔

Table (2.7) shows the material balance on Mixer 1 .

Table (2.7) M.B on Mixer 1 .

Comp. F6 F6 M M F7 F7
(Kg) (kgmol) (Kg) (kgmol) (Kg) (kgmol)
VAM 6504.05 197.55 638.76 7.42 7142.81 83.05
HAC 11853.008 75.62 3176.99 2.84 15030 250.5
H2O 1648.12 91.56 37.71 2.09 1685.84 93.65
Total 20005.18 364.741 3853.47 12.37 23858.6 427.21

34
 2.7 Material Balance on Distillation:
Distillation is a process used to separate a mixture of two (or more)
components into its virgin state by heating the mixture to a temperature between
their respective boiling points.

The distillation column is made up of a series of stacked plates. A liquid feed

containing the mixture of two or more liquids enters the column at one or more
points. The liquid flows over the plates, and vapor bubbles up through the liquid via
holes in the plates. As liquid travels down the column, the vapor comes in contact
with it several times due to the multiple plates – a critical process in distillation
columns.

The liquid and vapor phases are brought into contact because as one
molecule of higher boiling material converts from vapor to liquid phase by energy
release, another molecule of the low boiling material utilizes the free energy to
convert from liquid to vapor phase.The base of the distillation column contains a large
volume of liquid consisting mostly of the liquid with higher boiling poin. Out of the
base flows some of this liquid, some of which is heated in the re boiler and returned
to the column. This is called the boil up.
D=176.71 kgmol

VAM mol%=80.905

H2O mol%=19.0951

F7 =427.21 kgmol

VAM mol% = 19.44

HAC mol% = 58.63

H2O mol% = 21.92

R=250.5 kgmol

HAC mol%= 1

35
VAM in =VAMout =83.056kgmol

VAM product= 83.056* 86=7142 kg

H2O in=H2O out=93.658kgmol

H2O product= 93.658*18 =1685.844 kg

HAC in=HAC out =250.5kgmol

HAC product=250.5*60=15030 kg

For strem D =VAM+H2O

VAM=7142 kg

H2O=1685.844 kg

D=8828.66

Let to consider the bottom product is pure HAC (assume 100% HAC)

HAC=250.5 kgmol =15030 kg

R=HAC=15030 kg

Checking:

F7=D+R

=8828.66+15030=23858.66 kg

Table (2.8) shows the material balance on Distillation column .

36
 Table (2.8) M.B on Distillation .

C0MP. F7 F7 D D R R
(kg) (Kgmol) (kg) (kgmol) (Kg) (kgmol)
VAM 7142.816 83.05 7142.816 83.05 ----- -------

H2O 1685.844 93.65 1685.844 93.65 ---------- -------

HAC 15030 250.5 --------- 15030 250.5
TOTAL 23858.66 427.21 8828.66 176.71 15030 250.5

The Acetic acid at stream R will devided into two streams .

First stream R3will recycle to the evaporator , and second stream R2

will use as a solvent in absorber.

Divided ratio = 0.2 for R2

R2 = 0.2* R= O.2*250 =50.1 Kgmol =3006 kg

R3 =250.5-50.1= 200.4 kgmol = 12024 kg

37
2.8 Material Balance on Decanter:

A device used to separate liquids based on densities .Due to the difference

between the density of water and the vam, the material with the lowest density
(VAM) and the material with the highest (water).

Assume that the seperation process is 100%

D=176.71 kgmol Decanter P=83.056 kmol

VAM mol%=47 VAM=1 mol%

H2Omol%=53
W=93.654 kmol

H2O=1 mol%

VAM in= VAM Out = 83.056 kgmol

VAMproduct=83.056*86=7142.816 kg

H2O in= Out =93.658 kgmol

H2Oproduct=83.056*18= 1685.844 kg

Checking:

In=F=8828.66kg

Out=D+w=7142.816+1685.844=8828.66kg

38
2.9 Material balance on CO2 removal

The carbon dioxide removal device is used to remove and treat carbon dioxide
because it affects the environment was treated with potassium hydroxide to
produce potassium sulfate to be sold on the market and used as a profit

And the other gases C2H4 and O2 Will recycled to feed process

𝐶2𝐻4 𝐼𝑁 = 687.925 𝑘𝑚𝑜𝑙/ℎ = 19009.9 𝑘𝑔

𝑂2 𝐼𝑁 = 31.073 𝑘𝑚𝑜𝑙 = 994.336 𝑘𝑔
𝑇ℎ𝑒 𝐶2𝐻4 𝑎𝑛𝑑 𝑂2 𝑜𝑢𝑡 𝑡𝑜 𝑟𝑒𝑐𝑦𝑐𝑙𝑒 (𝑅)
𝑅 = 𝐶2𝐻4 + 𝑂2 = 19009.9 + 944.336 = 20004.236 𝐾𝑔

39
 KOH will add to removal to react with CO 2 and produce K2CO3 and water
at stream (S).
The reaction :
2𝐾𝑂𝐻 + 𝐶𝑂2 → 𝐾2 𝐶03 + 𝐻2 𝑂 … … … . (2.3)

Mwt 56 44 138 18

𝐶𝑂2 𝐼𝑁 = 𝐶𝑂2 𝑟𝑒𝑎𝑐𝑡 = 10.601 𝐾𝑔𝑚𝑜𝑙 = 466.444 𝐾𝑔

Using Stoichiomatric From Reaction (2.3) :
2
𝐾𝑂𝐻 𝐼𝑁 = 𝐾𝑂𝐻 𝑟𝑒𝑎𝑐𝑡 = (10.601) = 21.202 𝑘𝑔𝑚𝑜𝑙 = 1187.312 𝑘𝑔
1
1
𝐾2 𝐶03 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = (10.601) = 10.601 𝐾𝑔𝑚𝑜𝑙 = 1462.938 𝐾𝑔
1

1
𝐻2 𝑂 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = (10.601) = 10.601 𝑘𝑔𝑚𝑜𝑙 = 190.818 𝑘𝑔
1
𝑆 = 𝐾2𝐶03 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 + 𝐻2 𝑂 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 = 1462.938 + 190.818
= 1653.756 𝐾𝑔
Checking :
𝐼𝑛 = 𝐶2𝐻4 𝐼𝑁 + 𝑂2 𝐼𝑁 + 𝐶𝑂2 𝐼𝑁 + 𝐾𝑂𝐻 𝐼𝑁
= 19009.9 + 994.336 + 466.444 + 1187.312
= 21657.992 𝐾𝑔
Table (2.2) shows the material balance on CO2 Removal .

Table (2.9) M.B on Removal .

Comp. F8 F8 G G S S R1 R1
(Kg) (Kgmol) (kg) (Kgmol) (kg) (Kgmol) (kg) (kgmol)
CO2 ------------ ----------- 466.444 10.601 ------------ ------------ ------------ ----------
C2H4 ------------ ----------- 19009.9 678.92 ------------ ------------ 19009.9 678.92
O2 ------------ ----------- 994.336 31.07 ------------ ------------ 994.336 31.07
KOH 1187.312 21.202 ------------ ------------ ------------ ------------ ------------ ----------
K2CO3 ------------ ----------- ------------ ------------ 1462.938 10.601 ------------ ----------
H2O ------------ ----------- ------------ ------------ 190.818 10.601 ------------ ----------
Total 1187.312 21.202 20470.68 720 1653.756 21.202 20004.236 708.99

40
2.10 Material Balance on evaporator:

In evaporator there are just adding the amount of C2H4 and HAC (As
main feed) with all recycled stream from distillation and removal to offset
the reactivity quantities and convert the all liquids to gases because the react
in gas phase .

F2 = 1081.8 kgmol
C2H4 mol% = 70.9
HAC mol% = 26.2
O2 mol% = 2.87

R1 =709.99 kg mol
C2H4 mol %=95.6
O2 mol% = 4.37

C2H4 =88.35 kgmol

C2H4 mol% = 1

R3 = 200.4 kgmol
HAC = 83.056 kgmol HAC%=1

41
Acid M.B

𝑎𝑐𝑖𝑑 𝐼𝑛𝑝𝑢𝑡 + 𝑅3 = 𝑎𝑐𝑖𝑑 𝑂𝑢𝑡𝑝𝑢𝑡

83.056 + 200.4 = 283.456 𝑘𝑔𝑚𝑜𝑙

C2H4 M.B:

𝐶2𝐻4 𝐼𝑛𝑝𝑢𝑡 + 𝐶2𝐻4 𝑟𝑒𝑐𝑦𝑐𝑙𝑒𝑑 (𝑅1) = 𝐶2𝐻4 𝑂𝑢𝑡𝑝𝑢𝑡

(88.35 + 678.925) = 767.27 𝑘𝑔𝑚𝑜𝑙

O2 M.B:

𝑂2 𝑂𝑢𝑡𝑝𝑢𝑡 = 𝑂2 𝑅𝑒𝑐𝑦𝑐𝑙𝑒𝑑 𝑖𝑛 (𝑅1) = 31.072𝑘𝑔𝑚𝑜𝑙

𝐹1 = 𝑅1 + 𝐶2𝐻4

𝐹1 = 20004.236 + 88.35 ∗ 28 = 22478.036 𝑘𝑔

𝑪𝒉𝒆𝒄𝒌𝒊𝒏𝒈:

𝑰𝒏𝒑𝒖𝒕 = 𝑅3 + 𝐹1 + 𝑎𝑐𝑖𝑑

= 12024 + 22478.036 + 83.056 ∗ 60 = 39485.396 𝑘𝑔

𝑶𝒖𝒕𝒑𝒖𝒕 = 𝐹2 = (31.072 ∗ 32) + (767.27 ∗ 28) + (283.456 ∗ 60)

= 39485.396 𝑘𝑔

42
2.11 Material Balance on Mixer 2:

This mixer using to adding the oxygen for the out from
evaporator , to prepare the reactor feed

A = 57.43 kgmol F3 = 1137.33 kgmol

Only O2 C2H4 mol% =67.3

HAC mol%=24.9

O2 mol% =7.72
F2 = 1081.8 kgmol
C2H4 mol% = 70.9
HAC mol% = 26.2
O2 mol% = 2.87

𝒂𝒄𝒊𝒅 𝑴. 𝑩:
𝐼𝑛 = 𝑂𝑢𝑡
𝐼𝑛 = 283.456 𝑘𝑚𝑜𝑙 = 𝑂𝑢𝑡

𝑪𝟐𝑯𝟒 𝑴. 𝑩:
𝐼𝑛 = 𝑂𝑢𝑡
𝐼𝑛 = 767.27 𝑘𝑚𝑜𝑙 = 𝑂𝑢𝑡

𝑶𝟐 𝑴. 𝑩:
𝐼𝑛 = 𝑂𝑢𝑡
𝐼𝑛 = 31.072 + 57.43 = 88.503𝑘𝑔𝑚𝑜𝑙 = 𝑂𝑢𝑡

Checking:
𝑰𝒏𝒑𝒖𝒕 = 𝐹2 + 𝐴
= 39485.396 + 1837.79 = 41323.186 𝑘𝑔

𝑶𝒖𝒕𝒑𝒖𝒕 = 𝐹3 = 41323.186 𝑘𝑔

43
Chapter Three
Energy Balance

44
3.1 Introduction

Energy balance, in terms of energy economics, is concerned with all

processes within an organization that have a reference to energy. It derives
from the ecobalance and has the ambition to analyze and verify the
emergence, transformation and use of energy resources in
an organization in detail. Energy balances serve as a major statistical data
base for energy policy and energy management decisions. They contain
important information such as the amount and composition of energy
consumption, its changes or the transformation of energy.

Energy accounting is a system used in energy management

systems to measure and analyze energy consumption to improve energy
efficiency within an organization. Organisations such as Intel corporation
use these systems to track energy usage.

Various energy transformations are possible. An energy balance can

be used to track energy through a system. This becomes a useful tool for
determining resource use and environmental impacts. How much energy is
needed at each point in a system is measured, as well as the form of that
energy. An accounting system keeps track of energy in, energy out, and
non-useful energy versus work done, and transformations within a system.
Sometimes, non-useful work is what is often responsible for environmental
problems.

The overall energy balance :

Heat input + heat generation = heat output + heat accumulation

45
 3.2 Properties required to calculate energy balance
Specific Heat as a function of temperature (gas phase)

The heat capacity of gases is given by equation

Cpgas=A +B T+ C T2 + D T3 + E T4….. (1) From [perry 1997]

Where : A,B,C,D,E are constants

Cpgas = heat capacity in of gas ( KJ/Kmol.K) , T =temperature in K

From thermodynamic the change in enthalpy '∆H' at constant pressure is

T2 T2
Q=∆H= n ∫T1 Cp ∗ dT = n ∫T1 (A + B T + C T 2 + D T 3 + E T 4 )dT

B C D
Q=∆H= A(T2 − T1) + 2 (T22 − T12 ) + (T23 − T13 ) + (T24 − T14 ) +
3 4
E
(T25 − T15 )
5

Table (3.1) Specific Heat (gas phase) …… From → [ perry 1997]

Comp. A B C D E T min T max

VAM 27.664 2.3366E-01 6.2106E-05 -1.6972E-07 5.7917E-11 100 1500

H2O 33.933 -8.4186E-03 2.9906E-05 -1.7825E-08 3.6934E-12 100 1500

HAC 34.850 3.7626E-02 2.8311E-04 -3.0767E-07 9.2646E-11 50 150

O2 29.526 -8.8999E-03 3.8083E-05 -3.2629E-08 8.8607E-12 50 1500

CO2 27.437 4.2315E-02 -1.9555E-05 3.9968E-09 -2.9872E-13 50 5000
C2H4 32.083 -1.4831E-02 2.4774E-04 -2.3766E-07 6.8274E-11 60 1500

46
Specific Heat as a function of temperature (liquid phase)

The heat capacity of liquid is given by equation

Cpliquid=A +B T+ C T2 + D T3 …… (2) from [ perry 1997]

Where : A,B,C,D are constants

Cpliquid = heat capacity in of gas ( KJ/Kmol.K) , T =temperature in K

From thermodynamic the change in enthalpy '∆H' at constant pressure is

T2 T2
Q=∆H= n ∫T1 Cp ∗ dT = n ∫T1 (A + B T + C T2 + D T3 )dT

B C D
Q=∆H= A(T2 − T1) + (T22 − T12 ) + (T23 − T13 ) + (T24 − T14 )
2 3 4

Table(3.2) Specific Heat (liquid phase)……. From → [ perry 1997]

Comp. A B C D T min T max

VAM 63.910 7.0656E–01 –2.2832E–03 3.1788E–06 181 181

H2O 92.053 –3.9953E–02 –2.1103E–04 5.3469E–07 273 615

HAC 18.944 1.0971E+00 2.8921E–03 2.9275E–06 291 533

47
3.3 Reactor Energy balance :

Q1
Q Steam
C2H4
T=145 ℃ HAC

O2
In
T=150 ℃

Water T=25 ℃

Q2

C2H4

HAC

O2

CO2

VAM

H2O
T=150 ℃

reactor we find heat of input to reactor at 150o C and heat generation for
both reactions and heat of out at 150oC then we calculate the heat of steam
and mass of steam required for cooling. The PFR reactor was used to suit
the materials involved in exothermic reaction .

150oC 150oC

Path 2 Path 3

Q1 Q2

25oC 25oC
Path 2

ΔHr1 + ΔHr2

48
Tref = 298 K
Isothermal Reactor = 150 oC (423 K) Pressure = 120 Psia
Tin =Tout=150oC
The overall balance around the PFR reactor:
Heat input + heat generation = heat output + heat accumulation
Heat accumulation = 0 (steady state)
Isothermal operation (Tin =Tout)
Q1 + Qgen = Q2 + Qsteam
ΔHr1 = -176.2 kJ/mol *1000 mol/kmol = -176200 kJ/kmol
From(Alexandre 2008) .
ΔHr2 = -1322.8 kJ/mol*1000 mol/kmol = - 1322800 kJ/kmol From
(Alexandre 2008).
T
Q1 = ninput ∫T in CpV dT … … (3) Q1 heat of input → from [Vol. 6]
ref

Where :- n moles of input , 𝐶𝑝𝑉 Specific Heat of vapor

dT = Temperature Difference
Tin = (150+273)℃ = 423K
Tref = (25+273) ℃ = 298 K
Tout = (150+273) ℃ = 423K
Cp 𝑉 =A +B T+ C T2 + D T3 + E T4……(1) → From[ Perry 1997]
A ,B,C,D,E are constants
𝐶𝑝𝑉 Specific Heat of vapor → Taken from (A.2)
Q1 = QO2 + QC 2H 4 + QHAC
Q1= Σn*Cpv*ΔT → 𝑓𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]
Q1= Σn*Cpv*(Tin-Tref)
Path 1=Q1 = QO2 + QC 2H 4 + QHAC
8.899∗10−3
QO2 = 88.503*[29.526(423 – 298) – ( )*( 4232 – 2982)
2
3.808∗10−5 3.2629∗10−9
+( )*( 4233– 2983) – ( )*( 4234 – 2984)
3 4

49
 8.86∗10−12
+( )*( 4235 – 2985)]
5

Heat of O2 329029.9 kJ
−1.483∗10−2
QC 2H 4 = 761.981*[32.083(423 – 298) + ( )*( 4232 – 2982)
2
2.477∗10−4 −2.3766∗10−7
+( )*( 423 – 298 )+ (
3 3
)*( 4234 – 2984)
3 4
6.827∗10−11
+( )*( 4235 – 2985)]
5
= 4551517 kJ Heat of C 2H 4
−3.7626∗10−2
QHAC =283.456*[34.85(423– 298) + ( )*( 4232 – 2982)
2
2.8311∗10−4 −3.076∗10−7
+( )*( 423 – 298 ) + (
3 3
)*( 4234 – 2984)
3 4
9.2646∗10−11
+( )*( 4235 – 2985)]
5
= 2506036 kJ Heat of HAC
Q1 =7386583 kJ Total heat of input
423
Q 2 = 𝑛𝑜𝑢𝑡𝑝𝑢𝑡 ∫298 𝐶𝑝𝑉 𝑑𝑇…………… (4) Q 2 : heat of output → 𝑓𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]

Where :- n moles of output (Product + Unreacted) , 𝐶𝑝𝑉 Specific Heat of

vapor , dT = Temperature Difference
From (A.2) Taken 𝐶𝑝𝑉
Q2=Σ n* Cpv *ΔT
Q2=Σ n* Cpv *(Tout-Tref)
Path 3=Q2 = QO2 + QCO2 + QC2H4 + QVAM + QH2O + QHAC
8.899∗10−3
QO2 =31.073*[29.526(423 – 298) – ( )*( 4232 – 2982)
2
3.808∗10−5 3.2629∗10−9
+( )*( 423 – 298 ) – (
3 3
)*( 4234 – 2984)
3 4

50
 8.86∗10−12
+( )*( 4235 – 2985)]
5

=115520.9 kJ Heat of O2
−4.2315∗10−2
QCO2 =10.601* [27.437(423 – 298) + ( )*( 4232 – 2982)
2
−1.955∗10−5 4.9968∗10−9
+( )*( 423 – 298 ) + (
3 3
)*( 4234 – 2984)
3 4
−2.9872∗10−13
+( )*( 4235 – 2985)]
5
= 53425.86 kJ Heat of CO2
−1.483∗10−2
Q C 2H 4 = 678.925*[32.083(423 – 298) + ( )*( 4232 – 2982)
2
2.477∗10−4 −2.3766∗10−7
+( )*( 423 – 298 )+ (
3 3
)*( 4234 – 2984)
3 4
6.827∗10−11
+( )*( 4235 – 2985)]
5
=4055402 kJ Heat of C 2H 4
2.3366∗10−1
QVAM =83.056*[27.664(423 – 298) + ( )*( 4232 – 2982)
2
6.2106∗10−5 −1.6972∗10−7
+( )*( 423 – 298 ) + (
3 3
)*( 4234 – 2984)
3 4
5.7917∗10−11
+( )*( 4235 – 2985)]
5
= 1161332 kJ Heat of VAM

−8.418∗10−3
QH 2O =93.658* [33.933(423 – 298)+ ( )*( 4232 – 2982)
2
2.9906∗10−5 −1.7825∗10−8
+( )*( 423 – 298 )+ (
3 3
)*( 4234 – 2984)
3 4
3.6934∗10−12
+( )*( 4235 – 2985)]
5
51
 = 397618.2kJ Heat of H2O
−3.7626∗10−2
QHAC =200.4 *[34.85(423– 298) + ( )*( 4232 – 2982)
2
2.8311∗10−4 −3.076∗10−7
+( )*( 423 – 298 ) + (
3 3
)*( 4234 – 2984)
3 4
9.2646∗10−11
+( )*( 4235 – 2985)]
5
= 1771738 kJ Heat of HAC
Path 3=Q2 =7555036 kJ Total heat of output from Reactor
QR1 = -14634467.2 kJ heat generated from 1st reaction
QR2 =-14024325.6 kJ heat generated from 2nd reaction
Path 2=Qgen = QR1 + QR2
= - 28658792.8 kJ total heat of generation of Reaction
Q steam= 28490340.5 kJ = n*Cpv*ΔT
From (A.2) take Cpv
Tin = 298 K , T = 418 K ,

52
n steam =572.77 kmol
m steam = n steam* MWt
= 572.77* 18
=10310 kg mass of steam

53
3.4 Heat Exchanger (1) Energy balance

Q Recycle

C2H4

O2

Q2 T=40 oC
Q3
C2H4
C2H4
HAC
HAC
O2
O2
CO2
CO2
VAM
VAM
H2O QHX
H2O
o
T=150 oC T=145 C
T= 101.5 o C

The heat of output from reactor at temp. 150 oC is use to heat the gas recycle
from CO2 Removal by heat exchanger from 40 oC to 145 oC so we
calculate the heat at of H.X and then calculate the temperature of out.
Q2 + QRecycle in = QHX + Q3
Q2 = 7555036 kJ heat from outlet reactor
𝐓𝐢𝐧
𝐐 = 𝐧𝐢𝐧𝐩𝐮𝐭 ∫ 𝐂𝐩𝐕 𝐝𝐓 𝐚𝐜𝐜𝐨𝐫𝐝𝐢𝐧𝐠 𝐭𝐨 𝐞𝐪𝐮𝐚𝐭𝐢𝐨𝐧 (𝟑)
𝐓𝐫𝐞𝐟

Tref=298 K
Tin=313 K
313
Qrecycle = ninput ∫ CpV dT … … heat of recycle in → from [Vol. 6]
298

QRecycle = Σn*Cpv*ΔT
QRecycle = Σn*Cpv*(Tin-Tref) , Tin= 313 K , Tref=298 K
54
QRecycle = Q𝑂2 + Q C 2H 4
From (A.2) take Cpv
8.899∗10−3
QO2 = 31.073*[29.526(313– 298) – ( )*( 3132 – 2982)
2
3.808∗10−5 3.2629∗10−9
+( )*( 3133– 2983) – ( )*( 3134 – 2984)
3 4

8.86∗10−12
+( )*( 3135 – 2985)] =13717.73 kJ heat of O2
5

−1.483∗10−2
QC 2H 4 =687.925*[32.083(313– 298) + ( )*( 3132 – 2982)
2
2.477∗10−4 −2.3766∗10−7
+( )*(313 3– 2983)+ ( )*( 3134 – 2984)
3 4
6.827∗10−11
+( )*( 3135 – 2985)] = 447052.5kJ heat of C2H4
5
QRecycle =460770.2kJ Total heat of Recycle
QHX =QO2+QC2H4
THX=418 K , Tref=298 K
418
𝑄 = 𝑛𝑜𝑢𝑡𝑝𝑢𝑡 ∫ 𝐶𝑝𝑉 𝑑𝑇 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑡𝑜 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (4) ℎ𝑒𝑎𝑡 𝑜𝑓 𝐻. 𝑋 → 𝑓𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]
298

From (A.2) take Cpv

8.899∗10−3
QO2 =31.073*[29.526(418– 298) – ( )*( 4182 – 2982)
2
3.808∗10−5 3.2629∗10−9
+( )*( 418 – 298 ) – (
3 3
)*( 4184 – 2984)
3 4

8.86∗10−12
+( )*( 4185 – 2985)]=97182.03 kJ heat of O2
5
−1.483∗10−2
Q C2H4=678.925*[32.083(418– 298) + ( )*( 4182 – 2982)
2
2.477∗10−4 −2.3766∗10−7
+( )*( 418 – 298 )+ (
3 3
)*( 4184 – 2984)
3 4
55
 6.827∗10−11
+( )*( 4185 – 2985)] = 3431892 kJ heat of C2H4
5
QHX=3529020kJ total heat of H.X
Q2+QResycle-QHX=Q3
Q3=4455463kJ heat of outlet From H.X
Q3=QO2+QC2H4+QCO2+QVAM+QHAC +QH2O
By trial and error Tout=101.5 o C

56
3.5 Condenser Energy balance :

Q4

C2H4

HAC

O2
CO2
VAM
H2O
T=35 oC

Qc

H2O
Tin=25oC

Q3 Tout=40oC

C2H4

HAC
O2

CO2
VAM
H2O

T=101.5 oC
In condenser the gases outlet from heat exchanger are cooled from
101.5 oC to 35 oC using cooling water so we calculate the heat outlet from
condenser and heat of cooling then we calculate mass of cooling water
Tref=298 K
Qp = Σ n*Cpv*(T-Tref) + n* ΔHcond ……….. (5) → 𝑓𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]
Where Qp : is Heat of input to condenser
ΔHcond : is heat of condensation (change phase )
n : is moles( un reacted and produce ) of comp.
57
 374.5
Qp = n ∫298 CPv dt according eq.(3) → 𝑓𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]

Cpgas = A + BT + CT2 + DT3 +ET4 ………according eq.(1)

From (A.2) take Cpgas

8.899∗10−3
QO2 = 31.073* [29.526(374.5 – 298) – ( )*( 374.52 – 2982)
2

3.808∗10−5 3.2629∗10−9
+( )*( 374.5 – 298 ) – (
3 3
)*( 374.54 – 2984)
3 4

8.86∗10−12
+( )*( 374.55 – 2985)] = 70364.71 kJ Heat of O2
5

−4.2315∗10−2
QCO2 = 10.601 ∗* [27.437(374.5 – 298) + ( )*( 374.52 –
2
−1.955∗10−5 4.9968∗10−9
2
298 ) +( )*( 374.5 – 298 ) + (
3 3
)*( 374.54 – 2984)
3 4
−2.9872∗10−13
+( )*( 374.55 – 2985)]= 32113.72 kJ heat of CO2
5

−1.483∗10−2
QC2H4 = 678.925* [32.083(374.5 – 298) + ( )*( 374.52 –
2
2982)
2.477∗10−4 −2.3766∗10−7
+( )*( 374.5 – 298 )+ (
3 3
)*( 374.54 – 2984)
3 4
6.827∗10−11
+( )*( 374.55 – 2985)]= 2393041 kJ heat of C2H4
5

2.3366∗10−1
QVAM = 83.056* [27.664(374.5 – 298) + ( )*( 374.52 – 2982)
2

58
 6.2106∗10−5 −1.6972∗10−7
+( )*( 374.5 – 298 ) + (
3 3
)*( 374.54 – 2984)
3 4

5.7917∗10−11
+( )*( 374.55 – 2985)] + 83.056*(-36006)
5
= - 2312261 kJ heat of VAM

−8.418∗10−3
QH2O = 93.658* [33.933(374.5 – 298)+ ( )*( 374.52 – 2982)
2

2.9906∗10−5 −1.7825∗10−8
+( )*( 374.5 – 298 )+ (
3 3
)*( 374.54 – 2984)
3 4

3.6934∗10−12
+( )*( 374.55 – 2985)] + 93.658*(-44731)
5
= - 3947161 kJ heat of H2O

−3.7626∗10−2
QHAC =200.4 * [34.85(374.5 – 298) + ( )*( 374.52 – 2982)
2

2.8311∗10−4 −3.076∗10−7
+( )*( 374.5 – 298 ) + (
3 3
)*( 374.54 – 2984)
3 4

9.2646∗10−11
+( )*( 374.55 – 2985)]+ 200.4*(-22500)
5
= -3469569 kJ heat of HAC

Qp = - 7233471 kJ total heat of input to condenser

Qp = Q4 + QC

Q4 = Σ n*Cpv+L*(Tout-Tref) → 𝑓𝑟𝑜𝑚 [𝑉𝑜𝑙. 6] , Tout = 308 K , Tref= 298 K

59
 308
Q4 = n ∫298 CP v+L dt according eq.(4) → 𝑓𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]

Q4 = QO2 + QCO2 + QC2H4 +QVAM + QH2O + QHAC

From (A.2) Take CpL For liquids and Take Cpv For gases
−8.899∗10−3
QO2 = 31.073 ∗* [29.526(308 – 298) + ( )*( 3082 – 2982)
2
3.808∗10−5 −3.2629∗10−9
+( )*( 363 – 298 )+ (
3 3
)*( 3084 – 2984)
3 4

8.86∗10−12
+( )*( 3085 – 2985)]= 9141.082 kJ heat of O2
5
−4.2315∗10−2
QCO2 = 10.601 ∗* [27.437(308 – 298) + ( )*( 3082 – 2982)
2
−1.955∗10−5 4.9968∗10−9
+( )*( 3083– 2983) + ( )*( 3084 – 2984)
3 4
−2.9872∗10−13
+( )*( 3085 – 2985)]= 4089.248 kJ heat of CO2
5
−1.483∗10−2
QC2H4 =678.925* [32.083(308 – 298) + ( )*( 3082 – 2982)
2
2.477∗10−4 −2.3766∗10−7
+( )*( 3083– 2983)+ ( )*( 3084 – 2984)
3 4

6.827∗10−11
+( )*( 3085 – 2985)] = 296846.2 kJ heat of C2H4
5

Cpliquid = A + BT + CT2 + DT3 according eq (2)

Take Cpliquid from (A.2)
7.0656∗10−1
QVAM = 83.056* [63.910(308 – 298) + ( )*( 3082 – 2982)
2

60
 −2.2832∗10−3 3.1788∗10−6
+( )*( 308 – 298 ) +(
3 3
)*( 3084 – 2984)]
3 4
= 130242.3 kJ heat of VAM
−3.9953∗10−2
QH2O =93.658* [92.053(308 – 298) + ( )*( 3082 – 2982)
2
−2.1103∗10−4 5.3469∗10−7
+( )*( 308 – 298 ) + (
3 3
)*( 3084 – 2984)]
3 4
=70664 kJ Heat of H2O
1.0971
QHAC = 200.4* [-18.944(308 – 298) + ( )*( 3082 – 2982)
2
−2.8921∗10−3 2.9275∗10−6
+( )*( 308 – 298 ) + (
3 3
)*( 3084 – 2984)]
3 4
= 259320.2 kJ heat of HAC
Q4 = 9141.082 + 4089.248 + 296846.2 + 130242.3 + 70664
+ 259320 = 640061 kJ total heat of outlet from condenser
QC = Qp - Q4 = - 7233471 – 640061= -7873532 kJ heat of cooling water
QC = n*CpL*(Tout-Tin) → 𝑓𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]
Tin =298 K, Tout= 313 K
From (A.2) Take CpL
−3.9953∗10−2
7873532 = n* [92.053(313 – 298) + ( )*( 3132 – 2982)
2
−2.1103∗10−4 5.3469∗10−7
+( )*( 313 – 298 ) + (
3 3
)*( 3134 – 2984)]
3 4
n = 6960 kmol
m = 6960 * 18 = 125000 kg mass of cooling water

61
3.6 Separator Energy balance:

Q5

C2H4

HAC
Q4
O2
C2H4
CO2
HAC
VAM
O2
H2O
CO2
T=35 oC
VAM
H2O
Q6
T=35 oC
C2H4
HAC

O2
CO2
VAM
H2 O

T=35 oC

In separator we calculate the heat to top gases at 35 oC and the heat of

liquids at the bottom
Tout=35 oC

Q4 = 640061 kJ Heat from out of condenser

Q6 = Σ n*CpL*(Tout-Tref) , Tout = 308 K ,Tref=298 K
From (A.2) Take CpL according eq (2)
Q6 = QVAM +QH2O + QHAC

62
 7.0656∗10−1
QVAM = 75.6284 * [63.910(308 – 298) + ( )*( 3082 – 2982)
2
−2.2832∗10−3 −6
+( )*( 3083– 2983) +(3.1788∗10 )*( 3084 – 2984)]
3 4

= 118842.4 kJ Heat of VAM

−3.9953∗10−2
QH2O = 91.5626* [92.053(308 – 298) + ( )*( 3082 – 2982)
2
−2.1103∗10−4 5.3469∗10−7
+( )*( 308 – 298 ) + (
3 3
)*( 3084 – 2984)]
3 4
= 69080.59 kJ Heat of H2O
1.0971
QHAC =197.55 *[-18.944(308 – 298) + ( )*( 3082 – 2982)
2
−2.8921∗10−3 2.9275∗10−6
+( )*( 308 – 298 ) + (
3 3
)*( 3084 – 2984)]
3 4
= 256132.5 kJ Heat of HAC
Q6 = 108582.2 + 63339.2+ 228123
= 444055.5 kJ Total heat of Liquids products at bottoms
Q4 = Q5 + Q6
640061 = Q5 + 444055.5
→ Q5 = 196005.5 kJ Total heat of Vapours products at top

63
3.7 Compressor Energy balance:
Q5 Q7

C2H4 C2H4
HAC HAC
O2 O2
CO2 CO2
VAM VAM
H2 O H2O
T=35 oC T=83.75 oC

In the compressor will be compressed the gases mixture at 35°C from 70

psia to 126 psia. And we calculate the outlet temperature of compressor
𝑃2
T1 =308 K, Compression ratio = = 1.8 from [Alexandre 2008]
𝑃1

Where P1 Inlet pressure , P2 outlet pressure , Tref=298 K

F5 = 727.928 kmol From top of Separator From M.B

T = 273 K (Standard Condition),
υ = specific volume at (Standard Condition) = 22.4 m3/kmol
From (A.1) Take the value of TC and Pc of Comp.
Pc(mix) = 730*0.9258 + 838.69*0.0039 + 617*0.0102 + 3200*0.0028
+ 1071*0.014 + 732.06*0.0425 = 752.62 Psia
Tc(mix) = 282.5*0.9258 + 593*0.0039 + 525*0.0102 + 647*0.0028
+ 304.25*0.014 + 154.6*0.0425 = 281.96 K
𝑃1
𝑃𝑟 = → 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6]
𝑃𝑐
70
= = 0.09 Reduced Pressure
752.62

64
 𝑇
𝑇𝑟 = → 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6]
𝑇𝑐
308
= = 1.09 Reduced Temp.
281.96

Z = Compressibility factor = 0.97 (from figure (10) from (A.5 )

𝑇1 ∗𝑃
Volumetric flow rate =𝐹5 ∗ 𝑣 ∗ Equation above from [𝑣𝑜𝑙. 6]
𝑇∗𝑃1

where : 𝐹5 is total mole of feed , υ: specific volume, T1 inlet temp. ,

T :standard temp. , P : Standard pressure , P1 :inlet pressure
𝑘𝑚𝑜𝑙 𝑚3 308 1 ℎ𝑟
= 727.928 ∗ 22.4 ∗ ∗ ∗
ℎ𝑟 𝑘𝑚𝑜𝑙 273 4.761 3600 𝑠𝑒𝑐

𝑚3
= 1.07 Volumetric flow rate
𝑠
Ep : centrifugal compressor
For this flow rate a centrifugal compressor would be used, Ep = 74 percent
(Sinnott et al., 2005)

𝐶𝑝
𝑘= from [𝑣𝑜𝑙. 6]
𝐶𝑣
Where k are constant , Cp specific capacity at constant pressure ,
Cv specific capacity at constant volume
kVAM =1.09, kC2H4 = 1.23, kO2 = 1.39, kH2O = 1.32, kHAC = 1.14, kCO2 = 1.27
YVAM = 0.0102, YHAC = 0.0039, YH2O = 0.0028, YO2 = 0.0425
YCO2 = 0.014, YC2H4 = 0.9258
k = Σ k*Y
k = (1.09*0.0102) + (1.23*0.9258) + (1.39* 0.0425) + (1.32*0.0028) +
(1.14*0.0039) +(1.27*0.014) = 1.23 of mixture

𝑘−1 1.23−1
𝑚= = = 0.25 from [𝑣𝑜𝑙. 6]
𝑘∗𝐸𝑝 1.23∗0.74

Where m are exponent

1 1
𝑛= = = 1.33 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6]
1 − 𝑚 1 − 0.25
65
Where n are exponent of poly tropic
𝑃2
𝑇2 = 𝑇1 ∗ ( )𝑚 … … … 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6]
𝑃1
= 308 ∗ (1.8)0.25 = 356.75 𝐾 𝑜𝑢𝑡𝑙𝑒𝑡 𝑡𝑒𝑚𝑝. 𝑜𝑓 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑜𝑟

𝑛 𝑃2 (𝑛−1)
Work (per kmol)= 𝑍1 ∗ 𝑇1 ∗ 𝑅 ∗ ( ) ∗ [( ) 𝑛 − 1] . . 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6]
𝑛−1 𝑃1

Z = 0.97, R = 8.314 kJ/kmol.K constant of gases

1.33 (
1.33−1
)
W = 0.97 ∗ 308 ∗ 3.814 ∗ ( ) ∗ [(1.8) 1.33 − 1]
1.33 − 1
=1571 kJ/kmol work of compressor
𝐹5 ∗ W
Compressor Power = … … … . 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6]
𝐸𝑃
727.928 ∗ 1571
=
3600 ∗ 0.74
= 430 𝑘𝑤 𝑝𝑜𝑤𝑒𝑟 𝑜𝑓 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑜𝑟

Q7 = Q out from compressor

From (A.2) take Cpv
Q7 = Σ n*Cpv*(Tout-Tref) , Tout = 356.75 K
Q7 = QO2 + QCO2 + QC2H4 +QVAM + QH2O + QHAC
−8.899∗10−3
QO2 = 31.073* [29.526(356.75 – 298) + ( )*( 356.752 – 2982)
2
3.808∗10−5 −3.2629∗10−9
+( )*( 356.75 – 298 )+ (
3 3
)*( 356.754 – 2984)
3 4
8.86∗10−12
+( )*( 356.755 – 2985)]= 53946.18 kJ heat of O2
5

66
 −4.2315∗10−2
QCO2 = 10.601* [27.437(356.75 – 298) + ( )*( 356.752 –
2
−1.955∗10−5 4.9968∗10−9
2
298 ) +( )*( 356.75 – 298 ) + (
3 3
)*( 356.754 –
3 4
−2.9872∗10−13
4
298 ) + ( )*( 356.755 – 2985)]
5
= 24494.95 kJ heat of CO2
−1.483∗10−2
QC2H4 = 678.925*[32.083(356.75 – 298) + ( )*( 356.752 –
2
2.477∗10−4 −2.3766∗10−7
2
298 ) + ( )*( 356.75 – 298 )+ (
3 3
)*( 356.754 –
3 4
6.827∗10−11
4
298 ) + ( )*( 356.755 – 2985)]= 1812642 kJ heat of C2H4
5
2.3366∗10−1
QVAM = 7.327*[27.664(356.75 – 298) + ( )*( 356.752 – 2982)
2
6.2106∗10−5 −1.6972∗10−7
+( )*( 356.75 – 298 ) + (
3 3
)*( 356.754 – 2984)
3 4
5.7917∗10−11
+( )*( 356.755 – 2985)]= 45124.89 kJ heat of VAM
5
−8.418∗10−3
QH2O = 2.0953*[33.933(356.75 – 298)+ ( )*( 356.752 – 2982)
2
2.9906∗10−5 −1.7825∗10−8
+( )*( 356.75 – 298 )+ (
3 3
)*( 356.754 – 2984)
3 4
3.6934∗10−12
+( )*( 356.755 – 2985)]
5
=4155.852 kJ heat of H2O

67
 −3.7626∗10−2
QHAC = 2.849[34.85(356.75 – 298) + ( )*( 356.752 – 2982)
2
2.8311∗10−4 −3.076∗10−7
+( )*( 356.753– 2983) + ( )*( 356.754 – 2984)
3 4
9.2646∗10−11
+( )*( 356.755 – 2985)] = 11165.75 kJ heat of HAC
5

Q7 = 53946.18 + 24494.95 + 1812642 + 45124.89 + 4155.852

+ 11165.75= 1951530 kJ total heat of outlet from compressor

68
3.8 Absorber Energy balance :
Q9

C2H4
O2

Q8 CO2

HAC T=40 oC

T=40 oC

Qc

Q7 T=40 oC

C2H4
HAC
O2
CO2 Q10

VAM VAM

H2O HAC

T=83.75 oC H2O

T=50 oC

In absorber we calculate the heat of HAC input at 40 oC and heat of

liquids (VAM , HAC ,H2O) and heat of top gas (C2H4 ,O2) and then
calculate heat of cooling and mass of cooling water

T=40 oC Operation Temp.

Q7 + Q8 + QC = Q9 + Q10
Q7 = 2596867.38 kJ Heat From compressor
Q8 = n* CpL *(Tin-Tref) → from [vol. 6]
Tin = 313 K , Tref=298 K
From (A.2) take CpL
1.0971
Q8 = QHAC = 50.1*[-18.944(313 – 298) + ( )*( 3132 – 2982)
2

69
 −2.8921∗10−3 2.9275∗10−6
+( )*( 313 – 298 ) + (
3 3
)*( 3134 – 2984)]
3 4
= 79525kJ Heat of HAC
Q9 = Σn*CpV*(Tout-Tref) → from [vol. 6] ,Tref=298 K , Tout= 313 K
Q9 = QO2 + QCO2 + QC2H4
From (A.2) take Cpv
8.899∗10−3
QO2 = 31.073**[29.526(313– 298) – ( )*( 3132 – 2982)
2

3.808∗10−5 3.2629∗10−9
+( )*( 313 – 298 ) – (
3 3
)*( 3134 – 2984)
3 4

8.86∗10−12
+( )*( 3135 – 2985)] = 13717.73kJ Heat of O2
5

−4.2315∗10−2
QCO2 = 10.601*[27.437(313– 298) + ( )*( 3132 – 2982)
2
−1.955∗10−5 4.9968∗10−9
+( )*( 313 – 298 ) + (
3 3
)*( 3134 – 2984)
3 4
−2.9872∗10−13
+( )*( 3135 – 2985)] = 6146.378 kJ Heat of CO2
5
−1.483∗10−2
QC2H4 = 678.925**[32.083(313– 298) + ( )*( 3132 – 2982)
2

2.477∗10−4 −2.3766∗10−7
+( )*( 3133– 2983)+ ( )*( 3134 – 2984)
3 4

6.827∗10−11
+( )*( 3135 – 2985)] = 447052.5kJ Heat of C2H4
5

Q9 = 466916.6 kJ Total heat of gas at top

Q10 = Σn*CpL*(Tout-Tref) → from [vol. 6] Tref=298 K , Tout = 328 K
Q10 = QVAM + QH2O + QHAC
From (A.2) take CpL

70
 2.3366∗10−1
QVAM = 7.427 *[27.664(323– 298) + ( )*( 3232 – 2982)
2

6.2106∗10−5 −1.6972∗10−7
+( )*(323 – 298 ) + (
3 3
)*(3234 – 2984)
3 4

5.7917∗10−11
+( )*(3235 – 2985)] = 29404.7 kJ Heat of VAM
5

−8.418∗10−3
QH2O = 2.095*[33.933*(323– 298)+ ( )*( 3232 – 2982)
2

2.9906∗10−5 −1.7825∗10−8
+( )*( 3233– 2983)+ ( ) ∗ ( 3234 – 2984)
3 4

3.6934∗10−12
+( )*(3235 – 2985) = 3909.633 kJ Heat of H2O
5

1.0971
QHAC = 52.9498*[-18.944(323 – 298) + ( )*( 3232 – 2982)
2
−2.8921∗10−3 2.9275∗10−6
+( )*( 3233– 2983) + ( )*( 3234 – 2984)]
3 4

= 180782.6 kJ Heat of VAM

Q10 = 214097 kJ Total Heat of liquids products at bottom

QC = Q9 + Q10 – Q7 – Q8

= -1368042 kJ Heat of cooling

QC = n*CpL*(Tout-Tin) → from [vol. 6] , Tout = 313 K , Tin = 298 K ,

Value of CpL = 75.55 kJ/kmol.K

1368042= n * 75.55 *(313-298) = 1209.548 kmol

m = 1209.548 *18 = 21771.86 kg mass of cooling

71
3.9 CO2 Removal Energy balance:

Q Recycle=460770kJ

C2H4
O2
T=40 oC

QKOH=0

T = 25 oC
Qout=6146.4 kJ
Q9=466916.6 kJ K2CO3
C2H4 T=40oC
O2
CO2
T=40 oC

Q9=466916.6kJ heat from top of Absorber

QRecycle = Σn*Cpv*(Tin-Tref) → from [vol. 6] , Tin= 313 K , Tref=298 K

QRecycle = Q𝑂2 + Q C 2H 4
From (A.2) take Cpv
8.899∗10−3
QO2 = 31.073* [29.526(313 – 298) – ( )*( 374.42 – 2982)
2

3.808∗10−5 3.2629∗10−9
+( )*( 313 – 298 ) – (
3 3
)*( 3134 – 2984)
3 4

8.86∗10−12
+( )*( 3135 – 2985)]
5
= 13717.7 kJ Heat of O2

72
 −1.483∗10−2
QC2H4 =678.925* [32.083(313 – 298) + ( )*( 3132 – 2982)
2

2.477∗10−4 −2.3766∗10−7
+( )*( 313 – 298 )+ (
3 3
)*( 3134 – 2984)
3 4
6.827∗10−11
+( )*( 3135 – 2985)]= 447052.5 kJ Heat of C2H4
5

Q Recycle= QC 2H 4+ QO 2 =460770kJ total heat of Recycle

Q 9 + Q KOH = Q Recycle + Q out

Q KOH = n * C p * (T – T ref) → 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6] (T=T ref =298)

= 0 kJ
Q out = Q 9 + Q KOH – Q R = 466916.6+ 0 –460770
Q out =6146.4 kJ total heat of Removal outlet

73
3.10 Mixer1 Energy balance:
Q10=214097kJ

VAM

HAC

H2O

T=50 oC

Q6=44055.5kJ Q11=658152.5kJ

VAM VAM

HAC HAC

H2O H2O

T=35 oC T=37.52oC

Energy stream from bottom of both absorber and separator enter to mixer
to calculate the heat of mixer outlet and the temperature of outlet

Q 10 =214097 kJ Heat from bottom Absorber

Q 6 = 44055.5 kJ Heat from bottom separator
Q 11 = Q 6 + Q 10
Q 11 =44055.5 +214097 = 658152.5 kJ Heat of outlet mixer
Q 11 = ∑ n * C pL * (Tout – T ref) → 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6] ,
From (A.2) Take C pL
T ref =298 K, Tout =?
Q 11 = Q VAM + Q HAC + Q H2O
7.0656∗10−1
Q VAM = 83.056 * [63.910(T – 298) + ( )*( T2 – 2982)
2
−2.2832∗10−3 3.1788∗10−6
+( )*( T3– 2983) +( )*( T4 – 2984)]
3 4

74
 1.0971
QHAC =250.5 *[-18.944(T – 298) + ( )*( T2 – 2982)
2
−2.8921∗10−3 2.9275∗10−6
+( )*( T3– 2983) + ( )*( T4 – 2984)]
3 4

−3.9953∗10−2
QH2O =93.658* [92.053(T – 298) + ( )*( T2 – 2982)
2
−2.1103∗10−4 5.3469∗10−7
+( )*( T3– 2983) + ( )*( T4 – 2984)]
3 4

By try and error → T = Tout = 310.52 K outlet temperature of mixer

75
3.11 Heater Energy balance:
Qin=9817492 kJ

Steam

T=145oC

Q11 = 658152.5 kJ Qfeed=4368171 kJ

VAM VAM
HAC HAC
H2O H2O
Qout =6110660 kJ
T=37.52oC T=105 oC
Steam

T=100 oC

In heater we use steam from the outlet of reactor coil to heat the energy
stream outlet from the mixer to bubble point before enter to distillation
column
Q 11 =658152.5kJ heat from mixer outlet
Q feed = ∑ n * C pL * (Tout – T ref) → 𝑓𝑟𝑜𝑚 [𝑣𝑜𝑙. 6] ,
Q feed : Total heat of outlet (Feed)
From (A.2) Take C pL
T ref = 298 K, Tout =378 K
Q 11 = Q VAM + Q HAC + Q H2O
7.0656∗10−1
Q VAM = 83.056 * [63.910(378 – 298) + ( )*( 3782 – 2982) +
2
−2.2832∗10−3 3.1788∗10−6
( )*( 3783– 2983) +( )*( 3784 – 2984)]
3 4

= 1099985.19 kJ Heat of VAM

1.0971
QHAC =250.5 *[-18.944(378 – 298) + ( )*( 3782 – 2982)+
2

76
 −2.8921∗10−3 2.9275∗10−6
( )*( 3783– 2983) + ( )*( 3784 – 2984)]
3 4

= 2703280 kJ Heat of HAC

−3.9953∗10−2
QH2O =93.658* [92.053(378 – 298) + ( )*( 3782 – 2982)
2
−2.1103∗10−4 5.3469∗10−7
+( )*( 3783– 2983) + ( )*( 3784 – 2984)]
3 4

=564905.5kJ Heat of H2O

Q feed = QVAM+QH2O+QHAC=4368171.6089 kJ Total heat of outlet (Feed)
Qh=Qin-Qout
Qh= 3.71 *106 kJ Heat of heating

Heating medium
In : T=418 K,T ref = 298 K
−8.418∗10−3
QH 2O =n* [33.933(418 – 298)+ ( )*( 4182 – 2982)
2
2.9906∗10−5 −1.7825∗10−8
+( )*( 4183– 2983)+ ( )*( 4184 – 2984)
3 4
3.6934∗10−12
+( )*( 4185 – 2985)] ………(a)
5

Out : T=373 K , T ref = 298 K

−8.418∗10−3
QH 2O =n* [33.933(373 – 298)+ ( )*( 3732 – 2982)
2
2.9906∗10−5 −1.7825∗10−8
+( )*( 3733– 2983)+ ( )*( 3734 – 2984)
3 4
3.6934∗10−12
+( )*( 3735 – 2985)]……………(b)
5

QOut-Qin= 3.71 *106 kJ

77
From eq (a) and eq(b) → n = 2410 kmol mole of steam
m = 18*2410=43400 kg mass of steam

78
 3.12 Distillation Energy balance:

C.W

QD=195994.8743kJ

VAM
Qfeed=4368171.608kJ T=40oC
VAM

HAC
QW=105930.5667kJ
H2O
H2O
o
T=105 C
QReboiler=5858731.997kJ T=40 oC

QHAC=3158348.188kJ

HAC

T=118oC

The outlet from heater enter to distillation column as saturated vapor to

separation VAM ,H2O at top and HAC at the bottom depend on boiling
point ,then VAM ,H2O are condensed and enter to Decanter to separate
them as liquid depend on Density, we calculate the value of Ract(Reflux)
,Latent Heat of mixture ,top temp, Heat input and output from condenser
,Bottom temp , Heat of HAC , and finally heat of reboiler

Q feed + Q reboiler = Q D + Q W + Q HAC + Q C

∝i ∗ xi.f
∑ = 1 − q … … … … . From (Vol. 6)
∝i − θ
Where
q=1 (feed at bubble point)
xi.f = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑓𝑒𝑒𝑑 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡𝑠
∝i = 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡
Θ=constant
xVAM = 0.19441 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑉𝐴𝑀 𝐹𝑟𝑜𝑚 𝑀. 𝐵

79
xH2O = 0.21923 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓H2O 𝐹𝑟𝑜𝑚 𝑀. 𝐵
xHAC = 0.58636 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐻𝐴𝐶 𝐹𝑟𝑜𝑚 𝑀. 𝐵
𝐵
Ln P = A − 𝐴𝑛𝑡𝑜𝑛𝑖 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝐹𝑟𝑜𝑚 (𝑃𝑒𝑟𝑟𝑒𝑦 1997)
𝑇+𝐶

Where T : is the temperature in O C

P : Component vapor pressure in Psia are calculated using Antoine

equation, using Antoine coefficients In A,B,C (A.3) Take coefficients

2984.45
ln PVAM = 12.6564 −
226.66 + 105
PVAM = 38.7789 psi 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑉𝐴𝑀
3984.92
ln PH2O = 14.6394 −
233.426 + 105
PH2O = 17.5409 psi Pressure of H2O
4457.83
ln PHAC = 14.5236 −
258.45 + 105
PHAC = 9.56664 psi Pressure of HAC
Pi
K= … … … . . 𝑓𝑟𝑜𝑚 (𝑣𝑜𝑙. 6)
PT

Where K is hennery costant , Pi vapor pressure of component

PT Total pressure = 14.7 psia
38.7789
K VAM = = 2.63802= K1 hennery costant of VAM
14.7
17.5409
K H2O = =1.19326= K 2 hennery costant of H2O
14.7
9.56664
K HAC = = 0.65079 = K 3hennery costant of HAC (ℎ𝑒𝑎𝑣𝑦 𝑘𝑒𝑦 )
14.7
K1 2.63802
∝13= = = 4.05356156 Volatility of VAM
K 3 0.65079
K2 1.19326
∝23 = = = 1.83355158 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝐻2𝑂
K3 0.65079

K 3 0.65079
∝33 = = = 1 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝐻𝐴𝐶
K 3 0.65079

80
∝13∗ xVAM ∝23∗ xH2O ∝33 ∗ xHAC
+ + = 1−1
∝13− θ ∝23− θ ∝33 − θ
4.05356156 ∗ 0.19441 1.83355158 ∗ 0.21923 1 ∗ 0.58636
+ + =0
4.05356156 − θ 1.83355158 − θ 1−θ

θ = 1.44
For TOP:
∝i ∗ xi.d
∑ = 𝑅𝑚𝑖𝑛 + 1 … … … 𝑓𝑟𝑜𝑚 (𝑉𝑜𝑙. 6)
∝i − θ
Where
xi.d = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐷𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑒 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡
∝i = 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝑐𝑜𝑚𝑝𝑛𝑒𝑛𝑡
Θ=constant
𝑅𝑚𝑖𝑛 = 𝑚𝑖𝑛𝑚𝑢𝑚 𝑟𝑒𝑓𝑙𝑢𝑥 𝑟𝑎𝑡𝑖𝑜
xVAM = 0.47 mole fraction of VAM at Top
xH2O = 0.53 𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐻2𝑂 𝑎𝑡 𝑇𝑜𝑝
B
ln Pi = A + … … … … . . 𝐴𝑛𝑡𝑜𝑛𝑖 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝐹𝑟𝑜𝑚 (𝑃𝑒𝑟𝑟𝑒𝑦 1997)
C+T
Where T is the temperature in O C

Pi Component vapor pressure in Psia are calculated using Antoine

equation, using Antoine coefficients In A,B,C

From (A.3) Take coefficients

2984.45
ln PVAM = 12.6564 −
226.66 + 87.216
PVAM = 23.1381 psi 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑉𝐴𝑀
3984.92
ln PH2O = 14.6394 −
233.426 + 87.216
PH2O = 9.05286 psi Pressure of H2O
4457.83
ln PHAC = 14.5236 −
258.45 + 87.216
81
PHAC = 5.04898 psi Pressure of HAC
Pi
K= … … … . . 𝑓𝑟𝑜𝑚 (𝑣𝑜𝑙. 6)
PT

Where K is hennery costant , Pi vapor pressure of component

PT Total pressure = 14.7 psia
23.1381
K VAM = = 1.57402=K1 hennery costant of VAM
14.7
9.05286
K H2O = = 0.61584=K 2 hennery costant of H2O
14.7
5.04898
K HAC = = 0.34347 = K 3 hennery costant of HAC(Heavy key)
14.7
K1 1.57402
∝13= = = 4.58272554 Volatility of VAM
K 3 0.34347
K 2 0.61584
∝23 = = = 1.7930093 Volatility of H2O
K 3 0.34347
K 2 0.34347
∝33 = = = 1Volatility of HAC
K 3 0.34347
∝13∗ xVAM ∝23∗ xH2O
+ = 𝑅𝑚𝑖𝑛 + 1
∝13− θ ∝23− θ
4.58272554 ∗ 0.47 1.7930093 ∗ 0.53
+ = 𝑅𝑚𝑖𝑛 + 1
4.58272554 − 1.44 1.7930093 − 1.44
𝑅𝑚𝑖𝑛 =1.4
Ract= 1.4 *1.5 = 2.1 Actual Reflux Ratio
D = 83.056 kmol From M. B
W=93.658 kmol From M.B
R=2.1
V = R + D + W = 2.1+83.056+93.658 =178.814 kmol of vapor at top
LV mix = X VAM * LV VAM + X H2O * LV H2O ……..from (perry 1997)
Where X VAM mole fraction of VAM at Top
X H2O mole fraction of H2O at Top
LV VAM Latent heat of VAM of Vaporization=30382.7 kJ/kmol
LV H2O Latent heat of Vaporization =40091.8 kJ/kmol

82
ΔH vap mix = 0.47 * 30382.7 + 0.53 * 40091.8
= 35528.5 kJ/kmol Latent heat for mixture

Condenser Energy Balance:

Q C = Q out – Q in
From (A.3) Take the boiling Point of VAM and H2O
T in = 0.53 * 100 + 0.47 * 72.8 = 87.216o C Top Temperature
Q in = Q VAM + Q H2O + ΔH vap. * V
T
QVAM = n ∫T CpV dT … … . . according eq (4)
ref

360.216
QVAM = n ∫ CpV dT
298

Cpgas = A + BT + CT2 + DT3 +ET4 ……. according eq (1) (kJ/kmol.k)

From (A.2) Take CpV

2.3366∗10−1
Q VAM =83.056*[27.664(360.216 – 298) + ( )*( 360.2162 – 2982)
2
6.2∗10−5 −1.7∗10−7
+( )*( 360.2163– 2983) + ( )*( 360.2164 – 2984)]
3 4

=543644.225kJ Heat of VAM

T
QH2 O = n ∫ CpV dT … … . 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
Tref
360.216
QH2 O = n ∫ CpV dT
298

From (A.2) Take CpV

−8.418∗10−3
Q H2O = 93.658*[33.933(360.216 – 298)+ ( )*( 360.2162 – 2982)
2
2.9906∗10−5 −1.7825∗10−8
+( )*( 360.2163– 2983)+ ( )*( 360.2164 –
3 4

2984)]=196779.404kJ Heat of H2O

83
Q in = 543644.225+196779.404 +35528.5 *178.814
=7093416 kJ Total heat input to condenser
Q out = Q VAM + Q H2O
T
QVAM = n ∫ CpL dT … … … . 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
Tref

T=313 K , Tref=298 K
Cpliquid = A + BT + CT2 + DT3…….according eq(2)
From (A.2) take CpL
7.0656∗10−1
Q VAM =83.056 * [63.910(313– 298) + ( )*( 3132 – 2982)
2
−2.2832∗10−3 3.1788∗10−6
+( )*( 3133– 2983) +( )*( 3134 –
3 4

2984)]=195994.874kJ Heat of VAM

T
QH2 O = n ∫ CpL dT … … … . 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
Tref

From (A.2) take CpL

T=313 K , Tref=298 K
−3.9953∗10−2
Q H2O =93.658* [92.053(313 – 298) + ( )*( 3132 – 2982)
2
−2.1103∗10−4 5.3469∗10−7
+( )*( 3133– 2983) + ( )*( 3134 –
3 4

2984)]=105930.567kJ Heat of H2O

Q out =195994.874 + 105930.567 = 301925.441 kJ heat outlet of condenser

Q C = 301925.441 –7093416= 6761490 .559kJ Total heat of condenser

84
QD=QVAM heat of VAM Input to Decanter
T
QVAM= n ∫T CpL dT … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
ref

T=313 K , Tref=298 K
Cpliquid = A + BT + CT2 + DT3…….according eq(2)
From (A.2) take CpL
7.0656∗10−1
QVAM =83.056 * [63.910(313– 298) + ( )*( 3132 – 2982)
2
−2.2832∗10−3 3.1788∗10−6
+( )*( 3133– 2983) +( )*( 3134 –
3 4

2984)]=195994.874kJ Heat of VAM

QW=QH2O In decanter
T
QH2 O = n ∫ CpL dT … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
Tref

T=313 K , Tref=298 K
From (A.2) take CpL
−3.9953∗10−2
QH2O=93.658* [92.053(313 – 298) + ( )*( 3132 – 2982)
2
−2.1103∗10−4 5.3469∗10−7
+( )*( 3133– 2983) + ( )*( 3134 –
3 4

2984)]=105930.567kJ Heat of H2O

From (A.1) Take Tbp of HAC
THAC = 1 * 118 = 118 Co
𝑇
𝑄𝐻𝐴𝐶 = 𝑛 ∫ 𝐶𝑝𝐿 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
𝑇𝑟𝑒𝑓

T=391 K , Tref=298 K
From (A.2) take CpL
1.0971
Q HAC =250.5 *[-18.944(391 – 298) + ( )*( 3912 – 2982)
2
−2.8921∗10−3 2.9275∗10−6
+( )*( 3913– 2983) + ( )*( 3914 –
3 4

2984)]=3158348.19kJ Heat of HAC

85
Q reboiler = Q D + Q W + Q HAC + Q C – Q Feed
Q reboiler = 195994.874+ 105930.567 +3158348.19 + 6761490 .559 -
4368171.608
Q reboiler = 5853592.622 kJ

86
3.13 Divider Energy balance :
Q12=631669 kJ
HAC

T=118 oC

QHAC=3158348 kJ Q13=2526678 kJ
HAC HAC
T=118 oC T=118 oC

The bottom from distillation of HAC enter to Divider 20% of HAC goes to
cooler and the other amount back to evaporator ,so we find heat feed tp
cooler and heat back to evaporator

QHAC = 3158348 kJ Heat From distillation

𝑇
𝑄𝐻𝐴𝐶 = 𝑄12 = 𝑄13 = 𝑛 ∫ 𝐶𝑝𝐿 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
𝑇𝑟𝑒𝑓

T=391 K , Tref=298 K
From (A.2) take CpL
1.0971
Q12 = 50.1* [-18.944(391 – 298) + ( )*( 3912 – 2982)
2
−2.8921∗10−3 2.9275∗10−6
+( )*( 391 – 298 ) + (
3 3
)*( 3914 – 2984)]
3 4
= 631669 kJ Heat of HAC
1.0971
Q13 = 200.4 *[-18.944(391 – 298) + ( )*( 3912 – 2982)
2
−2.8921∗10−3 2.9275∗10−6
+( )*( 391 – 298 ) + (
3 3
)*( 3914 – 2984)]
3 4
= 2526678 kJ Heat of HAC

87
3.14 Cooler Energy balance :

T𝐻2𝑂 =25oC

Q13=631669.638 kJ Q8=97525.9689 kJ

T acetic acid=118oC T acetic acid =40oC

T𝐻2 𝑂 =40 oC

Q13=631669.638 kJ Heat From Divider

𝑇
𝑄8 = 𝑛 ∫ 𝐶𝑝𝐿 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞 (4)
𝑇𝑟𝑒𝑓

T=313 K , Tref=298 K
From (A.2) take CpL

1.0971
Q8 = 50.1* [-18.944(313 – 298) + ( )*( 3132 – 2982)
2
−2.8921∗10−3 2.9275∗10−6
+( )*( 313 – 298 ) + (
3 3
)*( 3134 – 2984)]
3 4
= 97525.9689 kJ Heat of HAC Out from Cooler

Qc =Q13-Q8= 534143kJ Heat of cooling of HAC

88
Cooling Medium

𝑇
𝑄gain = 𝑛 ∫𝑇 𝐶𝑝𝐿 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
𝑟𝑒𝑓

25
𝑄H₂O(𝑖𝑛) =n∫25 𝐶𝑝𝐿 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)

T=298 K , Tref=298 K
From (A.2) take CpL

−3.9953∗10−2
QH2O =n* [92.053(298 – 298) + ( )*( 2982 – 2982)
2

−2.1103∗10−4 5.3469∗10−7
+( )*( 2983– 2983) + ( )*( 2984 – 2984)]
3 4

=0 kJ heat of H2O at input

40
𝑄H₂O(𝑜𝑢𝑡)=n∫25 𝐶𝑝𝐿 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(4)
T=313 K , Tref=298 K
From (A.2) take CpL
−3.9953∗10−2
QH2O =n* [92.053(313 – 298) + ( )*( 3132 – 2982)
2
−2.1103∗10−4 5.3469∗10−7
+( )*( 3133– 2983) + ( )*( 3134 – 2984)]
3 4

QOut-Qin=534143 kJ
n˚= 472.22 kmol mole of water

m˚=n˚ . 𝑀𝑤𝑡water

= 472.22 × 18

=8500 kg Mass of water

89
3.15 Mixer 2 Energy balance :

Q15= 0 kJ Q1=7386583 kJ

O2 HAC

T=25 oC C2H4

O2

Q14=7386583 kJ T=150 oC

HAC

O2

C2H4

T=153.39 oC

The output energy stream from evaporator and feed energy stream input to
mixer then we find the temperature input to mixer

Q1= 7386583 kJ heat in to reactor

Q1 = Q14 + Q15
Q1= Q14 =7386583 kJ Heat of input of mixer
𝑇
𝑄15 = 𝑛 ∫ 𝐶𝑝𝑣 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞 (3) 𝐹𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]
𝑇𝑟𝑒𝑓

T=298 K , Tref=298 K
From (A.2) take Cpv
8.899∗10−3
QO2 = 57.43*[29.526(298 – 298) – ( )*( 2982 – 2982)
2
3.808∗10−5 3.2629∗10−9
+( )*( 298 – 298 ) – (
3 3
)*( 2984 – 2984)
3 4

8.86∗10−12
+( )*( 2985 – 2985)] = 0 kJ Heat of O2
5

90
 𝑇
𝑄14 = 𝑛 ∫𝑇 𝐶𝑝𝑣 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞 (3) 𝐹𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]
𝑟𝑒𝑓

Q14 = QO2 + QC2H 4+ QHAC

T=? K , Tref=298 K
From (A.2) take Cpv
−1.483∗10−2
QC 2H 4 = 761.981*[32.083(T – 298) + ( )*( T2 – 2982)
2
2.477∗10−4 −2.3766∗10−7
+( )*( T – 298 )+ (
3 3
)*( T4 – 2984)
3 4
6.827∗10−11
Heat of C2H4 +( )*( T5 – 2985)]
5

8.899∗10−3
QO2 =31.073*[29.526(T – 298) – ( )*( T2 – 2982)
2
3.808∗10−5 3.2629∗10−9
+( )*( T – 298 ) – (
3 3
)*( T4 – 2984)
3 4

8.86∗10−12
+( )*( T5 – 2985)]……... Heat of O2
5

−3.7626∗10−2
QHAC =283.456 *[34.85(T– 298) + ( )*( T2 – 2982)
2
2.8311∗10−4 −3.076∗10−7
+( )*( T – 298 ) + (
3 3
)*( T4 – 2984)
3 4
9.2646∗10−11
+( )*( T5 – 2985)]…… Heat of HAC
5
Q14 = QO2 + QC2H 4+ QHAC = 7386583 kJ

By try and error 𝑇 = 426.39𝑘 = 153.39 ℃ 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑖𝑛𝑙𝑒𝑡 𝑡𝑜 𝑚𝑖𝑥𝑒𝑟

91
3.16 Evaporator Energy balance :

Q14=7386583 kJ
QHX=3529020 kJ
C2H4 +HAC
C2H4 +O2
T=153.39 oC
T= 145 oC

Q16=0

C2H4 Q13 =1282377 kJ

T=25 oC HAC

T=118 oC

Q17=0
Steam
HAC

T=25 oC

QHX=3529020 kJ Heat From Heat Exchanger

Q13 =1282377 kJ Heat From Divider
QChange phase 1 = n ∗ λ → 𝐹𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]

Where λ is latent heat of HAC , n is mole of HAC Input to vaporizer

𝑄Change phase 1 = 200.4 ∗ 23506
= 4710602.4 kJ Heat of HAC input to vaporizer
𝑇
𝑄16 = 𝑄17 = 𝑛 ∫𝑇 𝐶𝑝𝑣 𝑑𝑇 … … … 𝑎𝑐𝑐𝑜𝑟𝑑𝑖𝑛𝑔 𝑒𝑞(3) → 𝐹𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]
𝑟𝑒𝑓

T=298 K , Tref=298 K
From (A.2) take Cpv
−1.483∗10−2
Q16= QC2H4 = 83.056*[32.083(298 – 298) + ( )*( 2982 – 2982)
2

92
 2.477∗10−4 −2.3766∗10−7
+( )*( 298 – 298 )+ (
3 3
)*( 2984 – 2984)
3 4
6.827∗10−11
+( )*( 2985 – 2985)]=0 Heat of C2H4
5
1.0971
Q17 = QHAC= 83.056 [-18.944(298 – 298) + ( )*( 2982 – 2982)
2

−2.8921∗10−3 2.9275∗10−6
+( )*( 298 – 298 ) + (
3 3
)*( 2984 – 2984)]
3 4
= 0 Heat of HAC

QChange phase 2 = n ∗ λ → 𝐹𝑟𝑜𝑚 [𝑉𝑜𝑙. 6]

Where λ is latent heat of HAC , n is mole of HAC Input to reactor
𝑄Change phase 2 = 83.065 ∗ 23506 =1952314.34 kJ Heat of HAC
Qin = Q16+QHX +Q17+ QChange phase 2 +Q13+ QChange phase 1
QIn= 14327100.92 kJ Total heat input to vaporizer
Qout = Q14=7386583kJ Total heat output from vaporizer
Qsteam =Qin-Qout= 6940517.497 kJ Heat of Steam

93
 Chapter Four
Design Equipment

94
 Chapter four

The process contain 10 basic unit operations which involves : a vaporizer ,

a catalytic plug flow reactor , a heat exchanger , separator , a gas
compressor , an absorber , a carbon dioxide removal system , azeotropic
distillation

The equipments have been designed including :4-1 plug flow reactor , 4-2
design of cooler

4-1 Plug Flow Reactor Design:

Reactor conversion = 25 % (Vinyl Acetate Monomer)

Isothermal Reactor = 150 oC (423 K) Pressure = 120 Psia

Step 1: Volume of the Catalyst

Basic performance equation for Plug Flow Rector is:

𝑋
𝑑𝑥
𝑉 = 𝐹𝐴𝑂 ∫
0 −𝑟𝑒

V = volume of catalyst

𝐹𝐴𝑂 = molar flow rate feed to reactor

−𝑟𝑒= rate of kinetic reaction

𝑑𝑥 = period of change in conversion

𝑑𝑥 gram moles
𝑉= = −𝑟𝑒
𝑑𝑤 gram catalyst . min

95
The rate expression for Vinyl Acetate system is: (process control)

(Samanos et al. (1971)

−3674 PO PE PA (1 + 1.7 PW )
re = 0.1036 exp ( )[ ]
T [1 + 0.53 PO (1 + 1.7 PW )](1 + 6.8 PA )

Where re , has units of moles of vinyl acetate produced per minute per

gram of catalyst . Pi is the partial pressure of component i (O is oxygen, E

is ethylene, A is acetic acid, and W is water) in Psia. The reactions are

irreversible and the reaction rates have an Arrhenius-type dependence on

temperature.

−3674
𝐾 = 0.1036 ∗ exp ( ) ((Samanos et al. (1971))
𝑇

gram moles
𝐾= rate constant of reaction
gram catalyst .min.Psia

𝑇 = reactor temperature in (kelvin)

−3674 gram moles

𝐾 = 0.1036 ∗ exp ( ) = 1.75 ∗ 10−5
423 gram catalyst .min.Psia

FT = 761.981 + 333.558 + 88.503= 1184.04 kmol/hr

YE = 0.64

YA = 0.29

YO = 0.07

PTV=z n RT → PT= zCERT

96
PT= total pressure

V= volume

Z = compressibility factor

n= number of moles of gas

R= gas constant

T= temperature of gas

𝐶𝐸𝑂 (1 − 𝑥)
𝐶𝐸 =
(1 + Ɛ𝑥 )

𝐶𝐸 = conctration of ethylene

𝐶𝐸𝑂 = initial concentration of ethylene

𝑥 = conversion

stoichiometry of product−stoichiomertry of reactant

Ɛ=
stoichiometry of reactant

𝑃𝐸 (1 − 𝑥) (1 − 𝑥)
= 𝑃𝐸𝑂 → 𝑃𝐸 = 𝑃𝐸𝑂
𝑧𝑅𝑇 𝑧𝑅𝑇(1 + Ɛ𝑥 ) (1 + Ɛ𝑥 )

Similarly:

(Ɵ𝑊 + 𝑥)
𝑃𝑊 = 𝑃𝐸𝑂 ,
(1 + Ɛ𝑥 )

(Ɵ𝑂 − 0.5𝑥)
𝑃𝑂 = 𝑃𝐸𝑂 (smith(J, m). ,1981)
(1 + Ɛ𝑥 )
97
 (Ɵ𝐴 − 𝑥)
𝑃𝐴 = 𝑃𝐸𝑂
(1 + Ɛ𝑥 )

𝑃𝑊 = partial pressure of water

Ɵ𝑊 = stoichiometry water/stoichmetry ethylene

𝑃𝑂 = partial pressure of oxygen

Ɵ𝑂 = stoichiometry oxygen/stoichiometry ethylene

𝑃𝐴 = partial pressure of acetic acid

Ɵ𝐴 = stoichiometry acetic acid /stoichiometry ethylene

𝑃𝐸𝑂 = partial pressure ethylene

1
C2H4 + CH3COOH + O2 → CH3COOCHCH2 + H2O
2

28 60 32 86 18 MWT

2 − 2.5
Ɛ= = −0.2
2.5

𝐶𝐸𝑂 𝐶𝐴𝑂
Ɵ𝐸 = =1 , Ɵ𝐴 = =1
𝐶𝐸𝑂 𝐶𝐸𝑂

𝐶𝑂 𝐶𝑊
Ɵ𝑂 = = 0.5 , Ɵ𝑊 = =0
𝐶𝐸𝑂 𝐶𝐸𝑂

PEO = YE*PT = 0.65*120 = 78 Psia

(1 − 𝑥 )
𝑃𝐸 = 78
(1 + Ɛ𝑥 )

98
 (𝑥)
𝑃𝑊 = 78
(1 − 0.2 𝑥 )

(Ɵ𝑂 − 0.5𝑥) (0.5 − 0.5𝑥) (1 − 𝑥)

𝑃𝑂 = 𝑃𝐸𝑂 = 78 = 39
(1 + Ɛ𝑥 ) (1 − 0.2 𝑥 ) (1 − 0.2 𝑥 )

(1 − 𝑥)
𝑃𝐴 = 78
(1 − 0.2𝑥 )

FEO = 12629.76 mol/min = 12.62976 kmol/min

PV = Z*n*R*T

Tc mix = 0.64*9.2+0.29*320+0.07*-118.6=90.386 oC

P c mix =0.64*50.42+0.29*57.8+0.07*50.43=52.56 bar

Tr =1.659 , Pr=0.152

Z =0.97 (from figure 10 Appendix A.5 )

𝑍 ∗ 𝑛 ∗ 𝑅 ∗ 𝑇 0.97 ∗ 12.62976 ∗ 8.314 ∗ 423

𝑣= = = 52.35 𝑚3/𝑚𝑜𝑙
𝑃 827.14

𝐹𝐸𝑂 12.62976
𝐶𝐸𝑂 = = = 0.241 𝑘𝑚𝑜𝑙/𝑚3
𝑣 52.35

𝑑𝑥
𝐹𝐸𝑂 = = −𝑟𝐸
𝑑𝑤

𝑑𝑥
𝑑𝑤 = 𝐹𝐸𝑂
−𝑟𝐸

99
𝑤 0.25
𝑑𝑥
∫ 𝑑𝑤 = 𝑊 = 𝐹𝐸𝑂 ∫
−𝑟𝐸
0 0

0.25
𝑑𝑥
∫ = 0.0146 Numerically using Matlab (Appendix B)
−𝑟𝐸
0

12.62976 ∗ 0.0146 ∗ 105

W=
1.75

W= 10536.82 kg=10.53682 tone

Step 2: Space time.

𝐶𝐸𝑂 ∗ 𝑊
τ=
𝐹𝐸𝑂

𝐶𝐸𝑂 = initial concentration of ethylene

𝑊 = weight of catalyst

𝐹𝐸𝑂 = rate of ethylene feed to reactor

τ = space time

0.241 ∗ 10536.82
= = 201 𝑚𝑖𝑛 = 3.35 ℎ𝑟
12.62976

Step 3: space velocity.

1 1
Space velocity = = = 0.298 hr −1
τ 3.35

100
Step 4: Volume of Catalyst.

weight of catalyst 10536.82

Vol. of catalyst = = = 10.53682 m3
density of catalyst 1000

Step 5: Catalyst Dimensions

Diameter of catalyst = 5mm

Voidage = 45%

Density = 1000 kg/m3

Volume of vessel = VB =?

𝑉𝐵 − 𝑉𝑃 𝑉𝐵 − 10.53682
𝑒 = 0.45 = = = 19.15 𝑚3
𝑉𝐵 𝑉𝐵

Step 6: No. of Tubes.

Standard diameter of tube of reactor is 25 – 40 mm

Inside diameter of tube = di = 37 mm

Length of tube = L = 7.5 m

𝜋
Volume of tube = 𝑉𝑡 = ∗ (𝑑𝑖 )2 ∗ 7.5 = 0.0081 𝑚3
4

𝑉𝐵 19.15
No. of tubes = = = 2364 𝑤𝑖𝑡ℎ𝑖𝑛 𝑟𝑎𝑛𝑔𝑒 ( 2000 − 4000)
𝑉𝑡 0.0081

Step 7: Shell Diameter.

Outside diameter of tube = do = 42 mm

Square pitch = 1.25*do = 1.25*42 = 52.5 mm

101
One pass & one shell

K1=0.215, n1=2.207

𝑁𝑇 1
𝐷𝑏 = 𝑑𝑜 ( ) 𝑛1
𝐾1

𝐷𝑏 = bundle diameter

𝑑𝑜 = outside tube diameter

𝑁𝑇 =number of tubes

2364 1
= 42 ∗ ( )2.207 = 2846𝑚𝑚 = 2.846 𝑚
0.215

For the graph along the fixed tube

Clearance = 37 mm (From figure (5) A.5)

Ds = Db + Clearance = 2.846 + 0.037 = 2.883 m

Step 8: Pressure Drop

𝑃 ∗ 𝑀𝑤𝑡
𝝆𝒎𝒊𝒙 =
𝑅𝑇

𝑀𝑤𝑡 = 0.64*28 + 0.07*32 + 0.29*60 = 37.56 kg/kmol

827.14 ∗ 37.56
𝝆𝒎𝒊𝒙 = = 8.83 𝑘𝑔 /𝑚3
8.314 ∗ 423

μ = 1.5*10-5 Pa.s

102
 𝜋 𝜋
Area of one tube = ∗ (𝑑𝑖 )2 = ∗ (37 ∗ 10−3)2 = 0.00108 𝑚2
4 4

Area of tubes = 0.00108* 2364 = 2.553 m2

1184.04 ∗ 37.56
𝑮= = 12.35 kg/sec
3600

12.35
𝒖= = 0.547 𝑚/𝑠
8.83 ∗ 2.553

Using Ergun’s equation:

−Δp (1 − e)2 (1 − e) ∗ ρ ∗ u2
= 150 3 ∗ μ ∗ u + 1.75
L e ∗ dp 2 e3 ∗ dp

−Δp= difference in pressure

L = length of tube

e = voidage

dp = diameter of catalyst

ρ = density of the mixture feed

u = velocity

μ = viscosity

−Δ𝑃 (1 − 0.45)2 1.5 ∗ 10−5 ∗ 0.547

= 150
7.5 (0.45)3 ∗ (0.005)2

(1 − 0.45) ∗ 8.83 ∗ (0.547)2

+ 1.75
(0.45)3 ∗ 0.005

103
−Δ𝑃 = 43066.85 𝑃𝑎 = 0.425 𝑎𝑡𝑚 = 6.249 𝑃𝑠𝑖𝑎

−Δ𝑃 = 𝑃1 − 𝑃2 = ⟶ 𝑃2 = 120 − 6.249 = 113. 751 𝑃𝑠𝑖𝑎

Step 9: Reactor Vessel Design

Diameter of Reactor = 2.883 m

Height of Reactor = Length of tubes + 0.3 Length of tubes

= 7.5 + 0.3 x 7.5 = 9.8 m = 10 m

Design pressure = 8.3 bar

Taking 10% above operating pressure = (8.3) * 1.1 = 9 bar = 0.9 N/ mm2

For Stainless – Steel at T = 150 oC

f = 140 N/ mm2 ( From Table (1) Appendix A.4)

Step 10: Cylindrical Section

𝑃𝑖 ∗ 𝐷𝑖
𝑡=
2 ∗ 𝑓 ∗ 𝑗 − 𝑃𝑖

t= wall thickness

𝑃𝑖 = internal pressure

𝐷𝑖 = inside diameter

𝑓 = design stress

𝑗 = the joint factor

0.9 ∗ 2.883 ∗ 1000

= = 9 𝑚𝑚
2 ∗ 140 ∗ 1 − 0.9

104
Corrosion allowance = 2 mm

t = 9 + 2 =11 mm

Design of domed ends

For pressure bellow 10 bar, using ellipsoidal heads

𝑃𝑖 ∗ 𝐷𝑖 0.9 ∗ 2.883 ∗ 1000

𝑡= = = 9 𝑚𝑚
2 ∗ 𝑓 ∗ 𝑗 − 0.2 ∗ 𝑃𝑖 2 ∗ 140 ∗ 1 − 0.2 ∗ 0.9

Step 11: Inlet and Outlet nozzles

Physical properties:

Vapor :

𝑀𝑤𝑡 ∗ 𝑇1 ∗ 𝑃
𝜌𝑣 =
22.7 ∗ 𝑇 ∗ 𝑃1

Where:

P1 = 1 bar, T1 = 298 K, P = 8.27 bar, T = 423 K

Input Nozzle:

Dm = 293 m0.53 ρ-0.37

m= flow rate (kg/sec)

ρ= density of mixture

O2 = 8.32 kg/m3, HAC = 15.61 kg/m3,C2H4 = 7.28 kg/m3

= 8.32*0.07+15.61*0.29+7.28*0.64 = 9.768 kg/m3

m = 761.981*28 +333.558*60+88.503*32 = 44181.04kg/hr = 12.27 kg/sec

105
Dm = 293 (12.27)0.53 (9.768)-0.37 = 476 mm

Output nozzle

Dm = 293 m.0.53 ρ-0.37

CO2 = 11.45 kg/m3, VAM = 22.37 kg/m3,

H2O= 4.68 kg/m3,O2 = 8.32 kg/m3,

C2H4 = 7.28 kg/m3,HAC = 15.61 kg/m3

Vapor = Σ *Y = 11.45*0.009 + 22.37*0.075 + 7.28*0.618 + 4.68*0.085 +

8.32*0.028 + 15.61*0.182 = 9.751 kg/m3

m = 41323.34 kg/hr = 11.47 kg/sec

Dm = 293 (11.47 )0.53 (9.751)-0.37 = 460 mm

Water input nozzle:

Dm = 293 m.0.53 ρ-0.37

Dm = 293 (2.863)0.53 (1000)-0.37 = 40 mm

Water out nozzle:

Dm = 293 (2.863)0.53 (925)-0.37 = 41 mm

Step 12: Weight of reactor:

Weight of tube = Vt * t 

𝜋
𝐴i = ∗ (0.037)2 = 0.00108 𝑚2
4

𝜋
𝐴o = ∗ (0.042)2 = 0.00139 𝑚2
4

106
Area of tube metal = 0.00139 – 0.00108 = 0.00031 m2

Volume of tube metal = 0.00031*7.5 = 0.00229 m3

st.st = 8000 kg/m3

W = 8000*0.00229 = 18.33 kg say 19 kg (weight of ne tube)

Weight of tubes = 19*2364 = 44916kg = 44.916 tone

Weight of shell = V s *s 

𝜋
𝐴s = ∗ (2.883)2 = 6.524𝑚2
4

𝜋
𝐴o = ∗ (2.883 + 0.011)2 = 6.574 m2
4

Area of shell metal = 6.574 – 6.524 = 0.05 m2

Vs = A*h=0.05*10 = 0.5 m3

Ws = 0.5*8000 =4000 kg

Weight of reactor = weight of catalyst + weight of tubes + weight of shell +

weight of other metals in reactor
= 10.53682+ 44.916 + 4 + 1 = 60 tone
The vessel support used for the reactor is conical skirt.

107
4.2 Design of cooler:
Heat exchangers are devices that facilitate the exchange of heat
between two fluids that are at different temperatures while keeping
them from mixing with each other .The type that we used in our
project is the shell and tube .The prime objective in the design of an
exchanger is to determine the surface area required for the specified
duty (rate of heat transfer) using the temperature differences
available.

118 ºc

40 ºc
40 ºc

25 ºc

Figure (4.1) temperature profile

Diameter:
for acetic acid (hot) ∶ T1 = 118℃ , T2 = 40℃

for water (cold) ∶ t1 = 40℃ , t 2 = 25℃

∆T1 = 78℃ , ∆T2 = 15℃

kg
Q(water) = 8500 = 2.361kg/s (from energy balance)
hr

∆T1 − ∆T2 78 − 15
∆Tlm = =
ln(∆T1 /∆T2 ) ln(78/15)

∆Tlm = 38.21 ℃

108
assume 1 shell and 2 tube (Figure (4) 𝐴𝑝𝑝𝑒𝑛𝑑𝑖𝑥 𝐴. 5 )

t 2 − t1 40 − 25
S= = = 0.161
T1− t1 118 − 25

T1 − T2 118 − 40
R= = = 5.2
t 2 − t1 40 − 25

(Figure (4) 𝐴𝑝𝑝𝑒𝑛𝑑𝑖𝑥 𝐴. 5)

Ft = 0.87

∆Tm = Ft ∗ ∆Tlm = 0.87 ∗ 38.21

= 33.24℃

to find U from Figure (4) 𝐴𝑝𝑝𝑒𝑛𝑑𝑖𝑥 (𝐴. 5)

w
U = 300 (The overall heat transfer coefficient)
m2 .℃

Q = U ∗ A ∗ ∆Tm

Q 148.318∗103
A= = = 14.87 m2 (Provisional area)
U∗∆Tm 300∗33.24

choose (20 mm 𝑑𝑜 ) , (16 mm 𝑑𝑖 ) , L = 2.44m

area of one tube = π d l = π ∗ 20 ∗ 10−3 ∗ 2.44 = 0.153m2

14.87
number of tube = = 97.2 = 98
0.153

The organic acetic acid causes corrosion , fouling and high temp.

So, We put it in the tube and the water put in the shell.

water is reletively clean to use squre pitch

109
Bandle diameter:

1
(𝑁𝑡 ) 𝑛1
𝐷𝑏 = 𝑑0 ( )
𝑘1

(𝑆𝑖𝑛𝑛𝑜𝑡𝑡 𝑅. 𝐾. 2005)(12) , Where:

k1 , n1 constant take from tabel (5) (A. 4)

𝑁𝑡 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑡𝑢𝑏𝑒𝑠

𝐷𝑏 = 𝑏𝑢𝑛𝑑𝑙𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝑚𝑚

𝑑𝑜 = 𝑡𝑢𝑏𝑒 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝑚𝑚

k1 = 0.156 , n1 = 2.291

1
(98) 2.291
Db = 20 ( ) = 332.94 mm
0.156

Bandle diameter clerance = 55 mm Figure (5) 𝐴. 5

Ds = 55 + 332.94 = 387.94 mm

𝐓𝐮𝐛𝐞 𝐬𝐢𝐝𝐞 𝐜𝐨𝐨𝐟𝐢𝐜𝐢𝐞𝐧𝐭 ∶

mean acetic acid temp = 79 ℃

π π
the cross sectional area = ∗ d2 = (16)2 = 201mm2
4 4

98
tube per pass = = 49
2

total flow area = 49 ∗ 201 ∗ 10−6 = 9.8 ∗ 10−4 m2

3006 kg
acetic acid mass velocity = = 852.04
3600 ∗ 9.8 ∗ 10−3 m2 . s
kg
ρ(acetic acid) = 975
m3
110
 852.04 m
acetic acid liear velocity = = 0.873
975 s

μ (acetic acid): 0.6 ∗ 10−3 𝑝𝑎 ∗ 𝑠

𝑘𝐽
CP (acetic acid) = 2.13*
𝑘𝑔.℃

w
K(acetic acid) = 0.15
m. c

ρ ∗ u ∗ di 975 ∗ 0.873 ∗ 16 ∗ 10−3

Re = = = 22698
μ 0.6 ∗ 10−3

cp ∗ μ 2.13 ∗ 103 ∗ 0.6 ∗ 10−3

pr = = = 8.52
k 0.15

𝐿
At Re = 22698 and = 122 →
𝐷
𝑤
jh From Figure (6) A. 5 𝑗ℎ = 3.7 ∗ 10−3
𝑚2 .℃

(hi ∗ di )/k f = jh ∗ Re ∗ pr^0.33

hi = (kf ∗ jh ∗ Re ∗ pr 0.33)/di

(𝑆𝑖𝑛𝑛𝑜𝑡𝑡 𝑅. 𝐾. 2005)(12) , Where:

𝑊
hi = 𝑖𝑛𝑠𝑖𝑑𝑒 ℎ𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡,
𝑚2 . 𝐶 𝑜

di = 𝑡𝑢𝑏𝑒 𝑖𝑛𝑛𝑒𝑟 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟

𝑊
k f = 𝑓𝑙𝑢𝑖𝑑 𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦,
𝑚2 . 𝐶𝑜

jh = ℎ𝑒𝑎𝑡 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑓𝑎𝑐𝑡𝑜𝑟

Re = 𝑅𝑒𝑦𝑛𝑜𝑙𝑑𝑠 𝑛𝑢𝑚𝑏𝑒𝑟

111
pr = 𝑃𝑟𝑎𝑛𝑑𝑡𝑙 𝑛𝑢𝑚𝑏𝑒𝑟

0.15 ∗ 3.7 ∗ 10−3 ∗ 22698 ∗ 8.520.33

=
16 ∗ 10−3
w
hi = 1596.63
m. ℃

𝐬𝐡𝐞𝐥𝐥 𝐬𝐢𝐝𝐞 𝐜𝐨𝐨𝐟𝐢𝐜𝐢𝐞𝐧𝐭 ∶

Ds 387.94
choose baffle spacing = = = 77.588 mm
5 5

tube pitch = 1.25 ∗ 20 = 25 mm

(pt − do ) ∗ Ds ∗ lB
cross flow area (As ) =
pt

(𝑆𝑖𝑛𝑛𝑜𝑡𝑡 𝑅. 𝐾. 2005)(12) , Where:

pt = 𝑡𝑢𝑏𝑒 𝑝𝑖𝑡𝑐ℎ

do = 𝑡𝑢𝑏𝑒 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟

Ds = 𝑠ℎ𝑒𝑙𝑙 𝑖𝑛𝑠𝑖𝑑𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝑚

lB = 𝑏𝑎𝑓𝑓𝑙𝑒 𝑠𝑝𝑎𝑐𝑖𝑛𝑔, 𝑚

(25 − 20) ∗ 387.94 ∗ 77.588 ∗ 10−6

As = = 6.0198 ∗ 10−3 m2
25
w
K = 0.59
m. k

µ =0.8*10−3 𝑝𝑎 ∗ 𝑠

𝑘𝐽
Cp=4.2
𝑘𝑔.℃

2.361 𝑘𝑔
Gs =6.0198∗10−3 = 392.205 (The shell-side mass velocity)
𝑚2. 𝑠

112
Re = (Gs ∗ de )/μ

392.205 ∗ 19.74 ∗ 10−3

= = 9677.6
0.8 ∗ 10−3

CP ∗ μ 4.188 ∗ 103 ∗ 0.8 ∗ 10−3

Pr = =
Kf 0.59

Pr = 5.678

from fig( 8 ) A. 5 , at Re = 9677.6

Jh = 5.8 ∗ 10−3
1
hs ∗de
Nu = = Jh ∗ R e ∗ (pr)3 )
Kf

(𝑆𝑖𝑛𝑛𝑜𝑡𝑡 𝑅. 𝐾. 2005)(12) , Where:

Nu = 𝑁𝑢𝑠𝑠𝑒𝑙𝑡 𝑛𝑢𝑚𝑏𝑒𝑟

1
K f ∗ Jh ∗ Re ∗ (pr)3
hs =
de

1
0.59 ∗ 5.8 ∗ 10−3 ∗ 9677.6 ∗ (5.678)3
hs =
19.74 ∗ 10−3
w
hs = 2991.55
m. ℃

estimate wall temp. equation can be written for the shell side ∶

ho (t w − t) = U ∗ (T − t)

118 + 40
mean temp. in the shell = = 79℃
2

40 + 25
mean temp. in the tube = = 33 ℃
2

113
mean temp. differences across all resistance = 79 − 33 = 46 ℃

U 300
across water film = (t w − t) = ∗ ∆t = ∗ 46 = 4.61 ℃
hs 2991.55

do
1 1 1 do ∗ ln ( ) do 1 do 1
di
= + + + ∗ + ∗
Uo ho hod 2 kw di hid di hi

(𝑆𝑖𝑛𝑛𝑜𝑡𝑡 𝑅. 𝐾. 2005)(12) , Where:

Uo = 𝑡ℎ𝑒 𝑜𝑣𝑒𝑟𝑎𝑙𝑙 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑏𝑎𝑠𝑒𝑑 𝑜𝑛 𝑡ℎ𝑒 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 𝑎𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑡𝑢𝑏𝑒

w
ho = 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 𝑓𝑙𝑢𝑖𝑑 𝑓𝑖𝑙𝑚 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡,
m. ℃
w
hi = 𝑖𝑛𝑠𝑖𝑑𝑒 𝑓𝑙𝑢𝑖𝑑 𝑓𝑖𝑙𝑚 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡,
m. ℃
w
hod = 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 𝑑𝑖𝑟𝑡 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 (𝑓𝑜𝑢𝑙𝑖𝑛𝑔 𝑓𝑎𝑐𝑡𝑜𝑟),
m. ℃
w
hid = 𝑖𝑛𝑠𝑖𝑑𝑒 𝑑𝑖𝑟𝑡 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡,
m. ℃
w
kw = 𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑡𝑢𝑏𝑒 𝑤𝑎𝑙𝑙 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙,
m. ℃

di = 𝑡𝑢𝑏𝑒 𝑖𝑛𝑠𝑖𝑑𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝑚

do = 𝑡𝑢𝑏𝑒 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 𝑑𝑖𝑎𝑚𝑒𝑡𝑒𝑟, 𝑚

20
1 1 1 20∗10−3 ∗ln( ) 20 1 20 1
16
= + + + ∗ + ∗
Uo 2991.55 3000 2∗16 16 5000 16 1596.63

w
U = 543.48
m. ℃

114
𝐩𝐫𝐞𝐬𝐬𝐮𝐫𝐞 𝐝𝐫𝐨𝐩 𝐟𝐨𝐫 𝐭𝐮𝐛𝐞:

from fig (7 ) A − 5 at Re = 22698

JF = 3.4 ∗ 10−3

L ρu2
∆Pt = NP [8 ∗ Jf ( ) + 2.5] ∗
di 2

(𝑆𝑖𝑛𝑛𝑜𝑡𝑡 𝑅. 𝐾. 2005)(12) , Where:

𝑁
∆Pt = 𝑡𝑢𝑏𝑒 − 𝑠𝑖𝑑𝑒 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑑𝑟𝑜𝑝,
𝑚2

NP = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑡𝑢𝑏𝑒 − 𝑠𝑖𝑑𝑒 𝑝𝑎𝑠𝑠𝑒𝑠

𝑚
𝑢 = 𝑡𝑢𝑏𝑒 − 𝑠𝑖𝑑𝑒 𝑣𝑒𝑙𝑜𝑐𝑖𝑡𝑦,
𝑠

L = 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑜𝑛𝑒 𝑡𝑢𝑏𝑒, 𝑚

−3
(2.44) 975 ∗ (0.873)2
∆Pt = 2 [8 ∗ 3.4 ∗ 10 ∗( ) + 2.5] ∗
16 ∗ 10−3 2
N
∆Pt = 4939.96 = 4.93996kpa
m2

𝐟𝐨𝐫 𝐬𝐡𝐞𝐥𝐥 ∶
from fig ( 9 ) A. 5 at Re = 9677.6

Jf = 5 ∗ 10−2

Ds L ρu2
∆P = 8 ∗ Jf ( ) ∗ ( ) ∗
de lB 2

(𝑆𝑖𝑛𝑛𝑜𝑡𝑡 𝑅. 𝐾. 2005)(12) , Where:

115
L = 𝑡𝑢𝑏𝑒 𝑙𝑒𝑛𝑔𝑡ℎ

lB = 𝑏𝑎𝑓𝑓𝑙𝑒 𝑠𝑝𝑎𝑐𝑖𝑛𝑔

−2
387.94 2.44 ∗ 103 995 ∗ 0.3941 2
∆P = [8 ∗ 5 ∗ 10 ∗( )∗ ]∗
19.74 77.588 2

∆P = 19101.99 pa = 19.101kpa

116
 Chapter five
Plant Layout &
Treatment

117
5.1: Plant Layout
The laying out of a plant is still an art rather than a science. It involves the
placing of equipment so that the following are minimized:
1- Damage to persons and property in case of a tire or explosion.

2- Maintenance costs.

3- The number of people required to operate the plant.

4- Other operating costs.

5- Construction costs.

6- The cost of the planned future revision or expansion.

All of these goals cannot be met. For example, to reduce potential losses in
case of fire, the plant should be spread out, but this would also result in
higher pumping costs, and might increase manpower needs. The engineer
must decide within the guidelines set by his company which of the
aforementioned items are most important (William)

5.1.1: Site Considerations

The location of the plant can have a crucial effect on the profitability of a
project, and the scope for future expansion. Many factors must be
considered when selecting a suitable site, the principle factors to consider
are:
1-Marketing area :
For materials that are produced in bulk quantities; such as cement, mineral
acids, and fertilizers, where the cost of the product per tone is relatively
low and the cost of transport a significant fraction of the sales price, the
plant should be located close to the primary market. This consideration will
be less important for low volume production, high-priced products; such as
pharmaceuticals.

118
2- Raw materials
The availability and price of suitable raw materials will often determine the
site location. Plants producing bulk chemicals are best located close to the
source of the major raw material; where this is also close to the marketing
area.

3- Transport
The transport of materials and products to and from the plant will be an
overriding consideration in site selection.

4- Availability of labor
Labor will be needed for construction of the plant and its operation. Skilled
tradesmen will be needed for plant maintenance.

5- Utilities (services)
Chemical processes invariably require large quantities of water for cooling
and general process use, and the plant must be located near a source of
water of suitable quality. Process water may be drawn from a river, from
wells, or purchased from a local authority.

6- Environmental impact and effluent disposal.

All industrial processes produce waste products, and full consideration
must be given to the difficulties and cost of their disposal. An
environmental impact assessment should be made for each new project, or
major medication or addition to an existing process.
7- Land (site considerations)

119
Sufficient suitable land must be available for the proposed plant and for
future expansion. The land should ideally be flat, well drained and have
suitable load-bearing characteristics.

8- Climate
Adverse climatic conditions at a site will increase costs. Abnormally low
temperatures will require the provision of additional insulation and special
heating for equipment and pipe runs. Stronger structures will be needed at
locations subject to high winds (cyclone/hurricane areas) or earthquakes.

5.1.2: Site Layout

The process units and ancillary buildings should be laid out to give the
most economical flow of materials and personnel around the site.
Hazardous processes must be located at a safe distance from other
buildings. The ancillary buildings and services required on a site, in
addition to the main processing units (Buildings) will include:
1- Storages for raw materials and products: tank farms and warehouses.

2- Maintenance workshops.

3- Stores, for maintenance and operating supplies.

4- Laboratories for process control.

5- Fire stations and other emergency services.

6- Utilities: steam boilers, compressed air, power generation, refrigeration,

transformer stations.

7- Effluent disposal plant.

8- Offices for general administration

120
9- Canteens and other amenity buildings, such as medical centers (Sinnott
et al ., 2005)

Figure (5-1): A typical site plant

5.1.3: Vinyl Acetate Monomer Plant Location:

Based on these previous factors which are required in Vinyl acetate
monomer manufacturing plant, we select Al-Samawa city as plant location
in a place at which the wind pass through the plant must not hit the cities.
This location will provide to the plant utilities which need since it near Al-
Samawa Refinery which provide low cost of transport requirement of
ethylene, also labors and local community which satisfied the labor
requirement.

121
5.2: Health & Safety Information
Vinyl acetate is slightly or moderately toxic to humans and animals. The
vapor irritates the eyes starting with 20 ppm. Released into the environment
the vinylacetate evaporates easily, being degraded rapidly by
photochemical reactions, as well as biodegraded by either anaerobic or
aerobic mechanisms. Therefore, the bioaccumulation of vinyl acetate in the
ecosphere is unlikely . Vinyl acetate is dangerous when exposed to heat,
flame or oxidizers, and as a consequence, it requires adhering to the safety
measures when stored or manipulated by operators. The same precaution is
valid for the raw materials. Ethylene is highly explosive in mixture with
oxygen, the explosion limit being at 10% vol. The acetic acid is a highly
toxic and corrosive substance. Stainless steel of Cr/Ni/Co type is employed
for operations involving acetic – acid solutions in boiling conditions, but
normal stainless steel may be used for vapor - phase operations (Alexandre
et 2008).

5.3: Pollutants:

1-Carbon dioxide
Since carbon dioxide is produced as a byproduct from the side reaction in
large quantity and it's highly undesirable product, we can remove carbon
dioxide by potassium hydroxide solution to produce potassium carbonate
and water in the removal unit.
2-Saturated steam
Saturated steam out from the reactor can be re-circulated for another uses
such as the vaporizer and reboiler.
3-Waste water

The large amount of wastewater will involve non - negligible costs for
neutralization and biological treatment.

122
 Chapter Six
Cost Estimation

123
6.1: Economic Studies:
To determine whether a project is feasible and attractive enough for
investment, Acceptable plant design must present a process that is capable
of operating under conditions which will yield a profit.
Economic Potential
EP = Revenue – Raw Material

Raw materials cost

Component Mass Price($/kg) Total Value of
(kg/hr) hours product
in year $/year
Acetic acid 4983.36 1.1 8400 46046246
Oxygen 1837.79 0.044 8400 679247.184
Ethylene 2473.8 0.442 8400 9184724.64

Total raw materials=55910218 $

Component Mass Price($/kg) Total Value of
(kg/hr) hours product
in year $/year
Vinyl 7142.816 1.123 8400 67379611.89
acetate

VAM products= 67379611.89 $

E.C=VAM product – raw materials

=67379611.89-55910218

=11469394 $

124
6.2: Cost of designed equipment:
The choice of appropriate equipment often is influenced by considerations
of price. A lower efficiency or a shorter life may be compensated for by a
lower price. Funds may be low at the time of purchase and expected to be
more abundant later, or the economic life of the process is expected to be
limited.

6.2.1: Reactor Cost

Height =10 m
D = 2.883 m
Using figure 6, 5b, VOL. (6)
Vessel cost = Bare cost from fig. * Type factor * Pressure factor
Vessel cost = 40,000 * 2 * 1.1 = 88,000 $ @ 2004

Cost index in year 2019

Cost in year 2019 = Cost in year 2004 ∗
Cost index in year 2004

From figure 6.1a, finding the cost index by extrapolation

152
Cost in year 2019 = 88,000 ∗ = 120504 $
111

Cost of packing = 10.53682* 600 = 6322 $

No. of tubes = 2364
Height = 7.5 m
D = 42 mm
Cost of 1 tube = 147 $
Cost of tubes = 2364 * 147 = 347508 $
Cost of Reactor = 347508 + 6322+ 120504 = 474334$

125
6.2.2 Cooler cost:
Heat transfer area = 14.87 m2

Pressure =1 bar

Material of constriction :

Shell ( stainless steel )

Tube ( stainless steel )

Pressure factor = 1

Type factor = 0.85 ( U tube )

From figure

Cost = 30000 $

Purchased cost = ( bare cost from figure ) * pressure factor * type factor

= 30000 * 1* 0.85 =25500 $

Raw Material cost

Acetic acid =1.1 $/kg (from fig.)

𝑚0 Acetic acid =3006 kg/hr

Acetic acid =3306.6 $

126
Utilities cost

Cooling water =1 c/t (from fig.)

Where:

1$=100c

1 t=1000kg

𝑚0 Water=8500 kg/hr

Cooling water=0.085 $

Total cost of cooler = cost of equipment +cost of Material+ cost of

utilities

=25500 +3306.6 + 0.085

= 28806.685 $

127
6.3: Conclusions:
The case study of the synthesis of vinyl acetate emphasizes the benefits of a
systematic design based on the analysis of the reactor/separation/recycles
structure. The core of the process is the chemical reactor, whose behavior in
recycle depends on the kinetics and selectivity performance of the catalyst,
as well as the safety and technological constraints. Moreover, the recycle
policy depends on the reaction mechanism of the catalytic reaction. Thus, for
palladium/Au catalysts the adsorption of the acetic acid on the active sites is
fast and not rate limiting.

In consequence, the designer should respect the composition of the reaction

mixture at the reactor inlet that is compatible with the experimental
conditions in which the kinetics of the catalytic process has been studied.
From the reactor - design viewpoint this implies keeping the recycles of
reactants, ethylene and acetic constant on a ratio of 3 – 4: 1, while oxygen is
made up to the maximum limit allowed by safety reasons. Because of
selectivity reasons, low per - pass conversion has to be kept for both ethylene
and acetic acid.

The secondary combustion reaction can be limited by keeping both the

pressure and temperature on the lower side. Two designs are compared, for
slow and fast catalysts.

Based on the separation system, it was evident the need to separate the liquid
phase from the gaseous phase with the objective of purifying the final
product and to recycle some raw material that did not react and are very
expensive.
The separation section takes advantage of the heterogeneous a zoetrope
formed by vinyl acetate and water, acetic acid with very low reciprocal
solubility.

128
However, because of lower water content the recovery of VAM requires a
high reflux rate and a large amount of energy. Significant energy saving, up
to 70%, can be obtained by making use of a dehydration gas pretreatment. In
this way, the exothermic reaction can cover up to 90% from the energy
requirements of the distillations.

129
 APPENDIX A
A-1: Basic physical properties of the main components.

Name Ethylene Acetic Acid VAM Water

Molecular formula C2H4 C2H4O2 C4H6O2 H2O
Molecular weight 28 60 86 18
Normal boiling point, K 162 391 345.95 373.15
Melting point, K 104 289.93 180.35 273.15
Critical temperature, K 282.34 594.45 519.15 674.14
Critical pressure, bar 50.41 57.90 40.3 220.64

Liquid density, kg/m3 (°C) 477 (-110) 1049.2 (20) 934 (20) 1000 (15)

Vaporization heat at nbp,

13.553 22.5 31.49 40.66
kJ/mol

A-2: Heat capacities:

The heat capacity expressions uses have the following temperature
dependence:
Cp=a+bT
Where C p is in kJ/kg.K and T is the temperature in K

C p Liquid (a - b) C p vapor (a - b)
Component
KJ/kmol.K KJ/kmol.K
O2 40.15 ; 0 29.173 ; 0.01338
CO2 110.4 ; 0 42.322 ; 0
C2H4 70.26 ; 0 43.325 ; 0.082
VAM 158.247 ; 0.3954 104.372 ; 0.216
H2O 74.523 ; 0.015 42.184 ; 0.1205
HAC 115.423 ; 0.3011 130.57 ; 0.1757

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C p liquid = A + B T + C T2 + D T3 kJ/kmol.k

Comp. A B C D T min T max

VAM 63.910 7.0656E–01 –2.2832E–03 3.1788E–06 181 472

H2O 92.053 –3.9953E–02 –2.1103E–04 5.3469E–07 273 615

HAC 18.944 1.0971E+00 2.8921E–03 2.9275E–06 291 533

C p gas = A + B T + C T2 + D T3 + E T4 kJ/kmol.k

Comp. A B C D E T min T max

5.7917E-11
VAM 27.664 2.3366E-01 6.2106E-05 -1.6972E-07 100 1500

H2O 33.933 -8.4186E-03 2.9906E-05 -1.7825E-08 3.6934E-12 100 1500

HAC 34.850 3.7626E-02 2.8311E-04 -3.0767E-07 9.2646E-11 50 150

O2 29.526 -8.8999E-03 3.8083E-05 -3.2629E-08 8.8607E-12 50 1500

4.2315E-02 -2.9872E-
CO2 27.437 -1.9555E-05 3.9968E-09 50 5000
13
32.083
C2H4 -1.4831E-02 2.4774E-04 -2.3766E-07 6.8274E-11 60 1500

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A-3: Antoine equation

Component vapor pressure P* in Psia are calculated using Antoine

equation, using Antoine coefficients listed below:

𝐵
ln p∗ = A −
𝑇+𝐶

Where T is the temperature in CO

Component A B C

O2 9.2 0 273

CO2 7.937 0 273

C2H4 9.497 313 273

VAM 12.6564 2984.45 226.66

H2O 14.6394 3984.92 233.426

HAC 14.5236 4457.83 258.45

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A-4: Process Unit Operational Parameters.

Unit Operation Parameter Value

Inlet Temperature 150 °C

Outlet Temperature 150 °C

Packed Bed Reactor
Inlet Pressure 120 Psia

Outlet Pressure 113.7 Psia

Cold Side Inlet Temperature 40 °C

Cold Side Outlet Temperature 101.5 °C

Heat Exchanger
Hot Side Inlet Temperature 150 °C

Hot Side Outlet Temperature 145°C

Exit Temperature 35 °C
Vapor/Liquid Separator
Outlet Pressure 70 Psia

Compression Ratio 1.8

Compressor
Outlet Temperature 83.75 °C
Top Temperature 40 °C
Absorber
Bottoms Temperature 50 °C
Top Temperature 86.84 °C
Azeotropic Distillation Column
Bottoms Temperature 118 °C
Inlet Temperature 25 °C
Vaporizer Exit Temperature 151 °C
Inlet Pressure 14.7 Psia

133
 Table (1):Typical Design stress [6]

Table (2) typical values of fouling factors (coefficients) [6]

134
 Table(3) Raw Material and product cost

Table(4) Utility cost (12)

Table(5) Constants for estimating bundle diameter (12)

135
A-5: The Diagrams

(12)
Figure (1): Process Engineering index

Figure (2): Cost of Shell and tube heat exchanger,

Time base mid-2004 (12)

136
 (12)
Figure (3): Overall coefficients

Figure (4): Temperature correction factor: 1 shell pass;

2 or more even tube passes (12)

137
Figure (5): Shell-bundle clearance (12)

138
Figure (6) Tube-side heat-transfer factor [6]

Figure (7) Tube-side friction factors (12)

139
Figure (8) Shell-side heat-transfer factors, segmental baffles (12)

Figure (9) Shell-side friction factors, segmental baffles (12)

140
Figure (10) Compressibility Factor Z (12)

141
 APPENXDIX B
Calculations using MATLAB

B-1: Reactor design

142
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