King Fahd University of Petroleum &

Minerals

Chemical Engineering Department

Second Progress Report

Vinyl Acetate Production, Mass and Energy Balance

CHE 495
(181)

Name ID Section Contribution

Abdulhadi Ibrahim Al-Thawwab 201334370 1 23.75%
ALAWI HUSSAIN ALAWI ALJAROUDI 201319370 1 23.75%
AYMAN ABDULHAK AHMED IBRAHI AL AZAB 201472380 2 5%
HASSAN ALI HASSAN ALDHAIF 201315750 2 23.75%
SALEH FOUAD SALEH ALMASAOUD 201436780 2 23.75%

Prepared for Dr. ISAM AL-JUNDI

ABSTRACT
This report shows mass and energy balances calculation to produce 46.4 kmol/h of vinyl
acetate (C4H6O2). Vinyl acetate production is achieved by reaction of ethylene, acetic acid and
oxygen which is catalyzed by a catalyst composed of Pd / Au . Equipment involved in vinyl
acetate production are: reactor, flash drum, absorber, distillation columns, multiple heat
exchangers and pressure changing equipment. Reactants feed ratio is set to be 2.375: 1
ethylene to acetic acid at which desired ethylene conversion and minimization of undesired
side reaction can be achieved. Heat duties of pump, compressor and all heat exchangers
including condenser and reboiler of distillation column are determined with a maximum heat
duty of 5581.9 kW corresponding to that of the distillation column reboiler.

2
 Table of Contents
ABSTRACT 2

Table of Contents 3
List of Tables 5
INTRODUCTION 7

1. MASS BALANCE 8

1.1. Reactor 8

1.2. Mixing Points 11

1.2.1. First Mixing Point 11

1.2.2. Second Mixing Point 11

1.3. Flash Drum 12

1.4. Absorber 14

1.5. Distillation Column 15

2. ENERGY BALANCE 17

2.1. Reactor 17

2.2. Heat Exchangers 18

2.2.1. Reactor cooler 18

2.2.2. Vaporizer 19

2.2.3. Heater 19

2.2.4. First Cooler 20

2.2.5. Second Cooler 20

2.2.6. Third Cooler 21

2.2.7. Fourth Cooler 21

3
 2.3. Pumps 22

2.3. Compressor 22

2.4. Distillation Column 23

CONCLUSION 25

References 26

4
 List of Table
Table 1: Mass balance around the reactor 10

Table 2: Mass balance around first mixing point 11

Table 3: Mass balance around second mixing point 12

Table 4: K-values 12

Table 5: Inlet to the flash drum 13

Table 6: Liquid outlet from flash drum 14

Table 7: Vapor outlet from flash drum 14

Table 8: Mass balance around the absorber 15

Table 9: Mass balance around the distillation column 16

Table 10: Energy balance around the reactor 17

Table 11: Heat capacity for liquid phase components 17

Table 12: Heat capacity for gas phase components 18

Table 13: Heat of vaporization at normal boiling point 18

Table 14: Energy balance around the vaporizer 19

Table 15: Energy balance around the heater 19

Table 16: Energy balance around the first cooler 20

Table 17: Energy balance around the second cooler 20

Table 18: Energy balance around the third cooler 21

Table 19: Energy balance around the fourth cooler 21

Table 20: Inlet and outlet pump information 22

Table 21: Energy balance around the pump 22

Table 22: Inlet and outlet compressor information 23

Table 23: Energy balance around the compressor 23

5
Table 24: Energy balance around the distillation column 24

6
Introduction:
For applying mass and energy balances the law of conservation of mass and first law of
thermodynamics are used which state that “mass can neither be created nor destroyed” for
mass conservation and “energy cannot be created or destroyed but it can be transformed from
one form to another” for first law of thermodynamics. These two laws are the basis for
analyzing and solving any engineering problems and especially at chemical engineering.

For mass balance:

Input +Generation – output – consumption= Accumulation

Here is a representation the mass balance on a finite quantity in an instant in time where the
first term, and the third one represents what enters and leaves the boundary of a system.
Generation and consumption terms refer to what is generated or consumed within the process
boundary and accumulation is what builds up within the system.

For energy balance:

Accumulationrate=Input rate – output rate

Q+W =Change∈internal energy +Change∈potential Energy+Change∈kinetic Energy

Where Q represents the heat generated or consumed within the system and W defines the
work done either by the system on the surrounding or by the surrounding on the system.

1. Mass Balance

7
1.1. Reactor:
Reactions:

1
Main reaction: C 2 H 4 +C H 3 COOH + O 2 → C2 H 3 OOCC H 3 + H 2 O
2

Undesired side reaction: C 2 H 4 +3 O 2 →2 C O 2 +2 H 2 O

Single pass conversion of ethylene is 9%.

Vinyl acetate selectivity is 90 %.

Assumptions:

 Steady state operation.

 Ethylene to acetic acid ratio is 2.375:1 as 50% and 20% in the feed mixture
respectively.
 Ethylene contains 5% ethane impurity.
 Oxygen concentration in the feed mixture is 8%.
 Carbon dioxide will be used as inert as 22% in the feed mixture.
 The feed basis is 1115.9 (kmol/h).

Steady state represents a continuous process which has no accumulation. In this process an
excess of ethylene to acetic acid has to satisfy in the reactant ratio where it has to be from
2: 1 to 3: 1. This excess ratio can insure that process is under explosion limit where oxygen
concentration has to be kept 8 % and below based on free acetic acid mixture [1].

Extent of reaction:

ni =ni ,o + v i ξ

Where ni is the amount remained, or produced of component i , and ni,o is the amount of
component i fed, and vi is the stoichiometric number which is positive for products and
negative for reactants.

8
 For Ethylene (C2H4): ṅC 2 H4 =530.0525−ξ 1−ξ 2 (1)

For Acetic Acid (C2H4O2): ṅC 2 H 4 O2 =223.18−ξ 1 (2)

For Oxygen (O2): ṅO =89.272−0.5∗ξ 1−3∗ξ 2 (3)

2

For Vinyl Acetate (C4H6O2): ṅC 4 H 6 O2 =ξ1 (4)

For Carbon Dioxide (CO2): ṅC O =245.498+2∗ξ2

2
(5)

For Water (H2O): ṅ H O=ξ 1 +2∗ξ2

2
(6)

ṅC H ,o− ṅC H

Single pass conversion of ethylene (C2H4): x=
2 4 2 4
=0.09 (7)
ṅC 2 H 4 ,o

ξ1
Selectivity of Vinyl Acetate (C4H6O2): =0.9 (8)
( 2∗ξ2 ) + ( ξ1 +2∗ξ 2)

Degree of freedom:

Degree of freedom:
DF =+ number of unknowns+number of indepensant reactios−number if species−number of other information

DF =8+2−6−2=0

530.0525−ṅC H4 kmol
From equation (7): 2
=0.09 → ṅ C H =482.348
530.0525 2 4
h

Solving equations (1) and (8) simultaneously:

482.348=530.0525−ξ1−ξ2 → 47.705=ξ1 +ξ 2

9
 ξ1
=0.9→ 0.1 ¿ ξ 1=3.6∗ξ2 → ξ2 =0.0278∗ξ1
( 2∗ξ2 ) + ( ξ1 +2∗ξ 2)

kmol kmol
47.705=ξ 1+ 0.0278∗ξ1 → ξ1=46.416 ∧ξ 2=1.290
h h

Now substituting ξ 1∧ξ 2 in equations (2), (3), (4), (5) and (6):

kmol
ṅC H 4 O2 =223.18−46.416=175.480
2
h

kmol
ṅO =89.272−0.5∗46.416−3∗1.290=62.217
2
h

kmol
ṅC H 6 O2 =46.416
4
h

kmol
ṅC O =245.498+2∗1.290=248.078
2
h

kmol
ṅ H O=46.416+2∗1.290=48.996
2
h

kmol
ṅC H6 =27.898
2
h

Table 1: Mass balance around the reactor

component Formula Inlet (kmol/h) Outlet (kmol/h)

Ethylene C2H4 530.053 482.348
Acetic Acid C2H4O2 223.180 175.481
Oxygen O2 89.272 62.217
Carbon Dioxide CO2 245.498 248.076
Water H2O 0.000 48.988
Ethane C2H6 27.898 27.898
Vinyl Acetate C4H6O2 0.000 46.410
Total Flow 1115.900 1091.417

10
1.2. Mixing Points:

1.2.1. First mixing point:

The first mixing point occurs at vaporizer composed of a recycled gas
stream from absorber, portion of recycled acetic acid stream from
distillation column and fresh ethylene and acetic acid feeds.

Table 2: Mass balance around first mixing point

Recycled gases from absorber

component Formula flowrate (kmol/h)
Ethylene C2H4 482.348
Oxygen O2 62.217
Carbon Dioxide CO2 245.498
Ethane C2H6 25.387
Recycled from distillation column
component Formula flowrate (kmol/h)
Acetic Acid C2H4O2 174.228
Fresh acetic acid feed
component Formula flowrate (kmol/h)
Acetic Acid C2H4O2 48.952
Fresh ethylene feed
component Formula flowrate (kmol/h)
Ethylene C2H4 47.705
Ethane C2H6 2.500
Mixture stream
component Formula flowrate (kmol/h)
Ethylene C2H4 530.053
Oxygen O2 62.217
Carbon Dioxide CO2 245.489
Ethane C2H6 27.887
Acetic Acid C2H4O2 223.180

1.2.2. Second mixing point

The mixture stream from the first mixing point is to be mixed with fresh oxygen
feed.

11
Table 3: Mass balance around second mixing point

Mixture stream
component Formula flowrate (kmol/h)
Ethylene C2H4 530.053
Oxygen O2 62.217
Carbon Dioxide CO2 245.489
Ethane C2H6 27.887
Acetic Acid C2H4O2 223.180
Fresh oxygen feed
component Formula flowrate (kmol/h)
Oxygen O2 27.055

1.3. Flash Drum:

For gas-liquid separation, reactor effluent is exposed to a flush drum after cooling it. K-
values were approximated at 33 ⁰C and 4 bar using Wilson fluid package in Aspen Plus
software and they are provided in below table.

Table 4: K-values

component Formula K- value

Ethylene C2H4 19.1602
Acetic Acid C2H4O2 0.00686331
Oxygen O2 206.986
Carbon Dioxide CO2 18.0251
Water H2O 0.0106198
Ethane C2H6 11.608
Vinyl Acetate C4H6O2 0.0476904

Assumptions:

 No heat loss to surroundings

 Constant molar overflow
 Isothermal

12
Table 5: Inlet to the flash drum

component Formula Inlet (kmol/h) mole fraction (z) K- value

Ethylene C2H4 482.348 0.442 19.1602
Acetic Acid C2H4O2 175.481 0.161 0.00686331
Oxygen O2 62.217 0.057 206.986
Carbon Dioxide CO2 248.076 0.227 18.0251
Water H2O 48.988 0.045 0.0106198
Ethane C2H6 27.898 0.026 11.608
Vinyl Acetate C4H6O2 46.410 0.043 0.0476904
Total 1091.417

V
c
( K i−1 )∗z i
Vapor fraction in the feed
f ( )
=∑
F i=1
1+
( K i−1 )∗V (1)
F

Solving for (V/F) which makes equation (1) close to zero:

For ( VF )=0.748,
c
( K i−1 )∗z i (19.1602−1 )∗0.442 ( 0.00686331−1 )∗0.161 ( 206.986+1 )∗0.057 (18.0251−1
∑ = + + +
i=1 ( K i−1 )∗V 1+ ( 19.1602−1 )∗0.748 1+ ( 0.00686331−1 )∗0.748 1+ ( 206.986+1 )∗0.748 1+ ( 18.0251−
1+
F

So, ( VF )=0.748 and solving for vapor and liquid flowrates:

kmol kmol
V =0.748∗1091.471=816.420 ∧L=1091.471−861.420=275.051
h h

z1
x 1=
Liquid compositions: ( K 1 −1 )∗V (2)
1+
F

0.442
For ethylene: x C H = =0.0303
2 4
1+ ( 19.1602−1 )∗0.748

13
Table 6: Liquid outlet from flash drum

component Formula x (bottom) bottom (kmol/h)

Ethylene C2H4 0.030 8.274
Acetic Acid C2H4O2 0.625 170.724
Oxygen O2 0.000 0.100
Carbon Dioxide CO2 0.017 4.518
Water H2O 0.173 47.145
Ethane C2H6 0.003 0.781
Vinyl Acetate C4H6O2 0.148 40.359
Total 0.996 271.902
Vapor compositions: y 1=K 1∗x1 (3)

For ethylene: y C H =K x ∗x C H =19.1602∗0.0303=0.581

2 4 C2 H 4 2 4

Table 7: Vapor outlet from flash drum

component Formula y (top) Top (kmol/h)

Ethylene C2H4 0.581 474.108
Acetic Acid C2H4O2 0.004 3.504
Oxygen O2 0.076 62.128
Carbon Dioxide CO2 0.298 243.573
Water H2O 0.002 1.497
Ethane C2H6 0.033 27.116
Vinyl Acetate C4H6O2 0.007 5.756
Total 1.001 817.683

1.4. Absorber:
The absorber is used to remove vinyl acetate as well as acetic acid from the gas stream that
leaves the flash drum. The solvent that is used for washing is pure acetic acid and it will be
recycled to the distillation column. The operation conditions are 31 ⁰C and 8 bar.

Assumptions:

 Adiabatic operation
 Negligible heat of absorption
 Steady state

14
  100% recovery of vinyl acetate and acetic acid at the bottom

Amount of vinyl acetate at inlet gas stream is 5.756 kmol/h and for acetic acid is 3.504 kmol/ h
will be transfer to the solvent and the below table shows the detailed streams for absorber.

Table 8: Mass balance around the absorber

component Formula solvent inlet (kmol/h) solvent outlet (kmol/h) Gas inlet Gas outlet
Ethylene C2H4 0.000 0.000 474.108 474.108
Acetic Acid C2H4O2 111.590 115.094 3.504 0.000
Oxygen O2 0.000 0.000 62.128 62.128
Carbon Dioxide CO2 0.000 0.000 243.573 243.573
Water H2O 0.000 0.000 1.497 1.497
Ethane C2H6 0.000 0.000 27.116 27.116
Vinyl Acetate C4H6O2 0.000 5.756 5.756 0.000
Total 111.590 120.850 817.683 808.422

1.5. Distillation column:

In the distillation is used to separate the acetic acid from vinyl acetate and water. The feed
mixture consists of the liquid stream leaving the flash drum as well as the solvent stream
leaving the absorber.

Assumptions:

 Steady state operation

 Reflux ratio is 0.85
 All acetic acid at bottom
 All others at the distillate

Component mass balance: z i F=( x D )i D+ ( x B )i B

kmol
For acetic acid at bottom: B= ż C H O ∗F=0.728∗392.752=285.923
2 4 2
h

15
For others at distillate: D=z i F

kmol
For ethylene: D=z C ∗F=0.021∗392.752=8.274
H4 and others listed in below table.
2
h

Table 9: Mass balance around the distillation column

component Formula Feed z Distillate Bottom

Ethylene C2H4 8.274 0.021 8.274 0.000
Acetic Acid C2H4O2 285.818 0.728 0.000 285.818
Oxygen O2 0.100 0.000 0.100 0.000
Carbon Dioxide CO2 4.518 0.012 4.518 0.000
Water H2O 47.145 0.120 47.145 0.000
Ethane C2H6 0.781 0.002 0.781 0.000
Vinyl Acetate C4H6O2 46.115 0.117 46.115 0.000
Total 392.752 1.000 106.934 285.818

16
2. Energy Balance:

2.1. Reactor:
Heat of formation is the method used to calculate the energy associated with the reactor.

Assumptions:

 Steady state operation

 Heat capacity has no effect since isothermal reactor
 Kinetics, potential and shaft works are negligible

Heat of reaction: Q̇=∆ Ḣ=∑ ṅ out Ḣ out −∑ ṅ¿ Ḣ ¿ , where Ḣ=∆ Ḣ ° f at (25 ℃)
Table 10: Energy balance around the reactor

component Formula ṅ¿ (kmol/h) Ḣ ¿ (kJ/kmol) ṅ out (kmol/h) Ḣ out (kJ/kmol)

Ethylene C2H4 530.053 52510.00 482.348 52510.00
Acetic Acid C2H4O2 223.180 -461100.00 175.481 -461100.00
Oxygen O2 89.272 0.00 62.217 0.00
Carbon Dioxide CO2 245.498 -393510.00 248.076 -393510.00
Water H2O 0.000 -241514.00 48.988 -241514.00
Ethane C2H6 27.898 -83820.00 27.898 -83820.00
Vinyl Acetate C4H6O2 0.000 -314900.00 46.410 -314900.00

kJ
Q̇=−181990676.6−(−174019527.7 ) =−7971148.993 =−2214.21 kW
h
Negative (Q̇) indicates an exothermic process where 2214.21 kW of heat is produced at the
reactor.

Heat capacity for liquid phase [2]:

Table 11: Heat capacity for liquid phase components

component Formula C1 C2 C3 C4 C5
Ethylene C2H4 247,390 -4,428 40.936 -0.1697 0.00026816

17
 Acetic Acid C2H4O2 139,640 -320.8 0.8985 0 0
Carbon Dioxide CO2 8,304,300 104,370 -433.33 0.60054 0
Water H2O 276,370 -2,090.10 8.125 -0.014116 9.37E-06
Ethane C2H6 44.009 89,718 918.77 -1,886 0
Vinyl Acetate C4H6O2 136,300 -106.17 0.75175 0 0
C p ,l=C 1 +C2∗T +C 3∗T 2+ C4∗T 3+ C5∗T 4

C 12 2 C32∗t 3 C3∗C 4∗t 4 C 42∗t 5

For ethane only: C p ,l= +C2 −2∗C 1∗C 3∗t−C 1∗C 4∗t − − −
t 3 2 5

Heat capacity for gas phase [2]:

Table 12: Heat capacity for gas phase components

component Formula C1 * 1E-05 C2* 1E-05 C3* 1E-03 C4* 1E-05 C5

Ethylene C2H4 0.3338 0.9479 1.596 0.551 740.8
Acetic Acid C2H4O2 0.402 1.3675 1.262 0.7003 569.7
Oxygen O2 0.29103 0.1004 2.5265 0.09356 1153.9
Carbon Dioxide CO2 0.2937 0.3454 1.428 0.264 588
Water H2O 0.33363 0.2679 2.6105 0.08896 1169
Ethane C2H6 0.40326 1.3422 1.6555 0.73223 752.87
Vinyl Acetate C4H6O2 0.536 2.119 1.198 1.147 510

2 2
C3 C5
C p ,v =C 1 +C2∗
( ( )) ( ( ))
T

sinh 3
C
T
+C 4∗
T
C
cosh 5
T

Heat of vaporization [2]:

Table 13: Heat of vaporization at normal boiling point

component Formula Normal boiling point, K ∆Hvp (kJ/kmol)

Ethylene C2H4 162.42 13553
Acetic Acid C2H4O2 391.04 23700
Water H2O 373.15 40660
Vinyl Acetate C4H6O2 345.95 31490

2.2. Heat Exchanger:

2.2.1. Reactor cooler:

18
 For steady state operation, shell-tube heat exchanger is installed to overcome the heat of
reaction and to maintain constant temperature inside the reactor. Therefore, the duty of
shell-tube heat exchanger equals heat of reaction.

Q̇ R=Q̇=−2214.21 kJ / s, hence, 2214.21 kW heat is to be removed from the reactor.

2.2.2. Vaporizer:
Only acetic acid will vaporize, and heat of vaporization will be added, and others are at gas
phase. Inlet and outlet temperatures are 30 ⁰C and 120 ⁰C respectively.

Q̇=∑ ṅi (C p ,l +∆ H vp +C p , v )

Table 14: Energy balance around the vaporizer

component Formula inlet, T= 30 ⁰C (kmol/h) outlet, T= 120 ⁰C (kmol/h) Q̇ i (kJ/h)

Ethylene C2H4 530.053 530.053 2288404.89
Acetic Acid C2H4O2 223.180 223.180 8050530.26
Oxygen O2 62.217 62.217 166089.16
Carbon Dioxide CO2 245.498 245.498 874110.11
Water H2O 0.000 0.000 0
Ethane C2H6 27.898 27.898 147842.05
Vinyl Acetate C4H6O2 0.000 0.000 0

kJ
Q̇ v =11526976.31 =3201.94 kW
h
2.2.3. Heater:
The heater which is after the vaporizer is used to give further heat where inlet temperature
is 120 ⁰C and outlet temperature is 155 ⁰C. All species are in the gas phase.

Q̇=∑ ṅi (C p ,v )
Table 15: Energy balance around the heater

component Formula inlet, T= 120 ⁰C (kmol/h) Outlet, T= 155 ⁰C (kmol/h) Q̇ i (kJ/h)

Ethylene C2H4 530.053 530.053 1005844.59
Acetic Acid C2H4O2 223.180 223.180 633467.51
Oxygen O2 62.217 62.217 65708.11
Carbon Dioxide CO2 245.498 245.498 361051.01
Water H2O 0.000 0.000 0

19
 Ethane C2H6 27.898 27.898 65415.06
Vinyl Acetate C4H6O2 0.000 0.000 0

kJ
Q̇=2131486.279 =592.08 kW
h

2.2.4. First Cooler:

First cooler after the reactor is used to cool down reactor effluent from 155 ⁰C to 70 ⁰C
where phase change occurs to acetic acid, water and vinyl acetate. Heat of condensation
has the same value of heat of vaporization with opposite sign.

Q̇=∑ ṅi ( C p , v + (−∆ H vp ) +C p ,l )

Table 16: Energy balance around the first cooler

component Formula Inlet, T= 155 ⁰C (kmol/h) Outlet, T= 70 ⁰C (kmol/h) Q̇ i (kJ/h)

Ethylene C2H4 482.3478 482.3478 -2330789.1
Acetic Acid C2H4O2 175.481 175.481 -5916071.48
Oxygen O2 62.217 62.217 -158421.34
Carbon Dioxide CO2 248.076 248.076 -866340.38
Water H2O 48.988 48.988 -2195378.99
Ethane C2H6 27.896 27.896 -151203.78
Vinyl Acetate C4H6O2 46.410 46.410 -1933417.66

kJ
Q̇=−13551622.73 =−3764.34 kW
h

2.2.5. Second Cooler:

Second cooler after the reactor is used for further cooling from 70 ⁰C to 30 ⁰C without
phase change, where acetic acid, water and vinyl acetate are at liquid phase and others at
gas phase.

Q̇=∑ ṅi C p

20
Table 17: Energy balance around the second cooler

component Formula Inlet, T= 70⁰C (kmol/h) Outlet, T= 30 ⁰C (kmol/h) Q̇ i (kJ/h)

Ethylene C2H4 482.3478 482.3478 -876749.03
Acetic Acid C2H4O2 175.481 175.481 -911934.27
Oxygen O2 62.217 62.217 -73375.93
Carbon Dioxide CO2 248.076 248.076 -381759.48
Water H2O 48.988 48.988 -147523.44
Ethane C2H6 27.896 27.896 -62053.33
Vinyl Acetate C4H6O2 46.410 46.410 -335253.73

kJ
Q̇=−2788649.21 =−774.62kW
h

2.2.6. Third Cooler:

After the compressor the temperature is increased to 96.39 ⁰C and it is required to be
cooled down to 30 ⁰C.

Table 18:Energy balance around the third cooler

component Formula Inlet, T=96.39 ⁰C (kmol/h) Outlet, T= 30 ⁰C (kmol/h) Q̇ i (kJ/h)

Ethylene C2H4 474.108 474.108 -1472379.96
Acetic Acid C2H4O2 3.504 3.504 -31106.43
Oxygen O2 62.128 62.128 -121978.84
Carbon Dioxide CO2 243.573 243.573 -631698.23
Water H2O 1.497 1.497 -7496.91
Ethane C2H6 27.116 27.116 -103220.69
Vinyl Acetate C4H6O2 5.756 5.756 -234074
817.683 817.683 -2601955.06

kJ
Q̇=−2601955.06 =−722.77 kW
h
2.2.7. Fourth Cooler:
A portion of recycled acetic acid has to be cooled down from 130 ⁰C to 30 ⁰C before
introducing it to the absorber.

Table 19: Energy balance around the fourth cooler

component Formula Inlet, T=96.39 ⁰C (kmol/h) Outlet, T= 30 ⁰C (kmol/h) Q̇ i (kJ/h)

21
 Acetic Acid C2H4O2 285.818 285.818 -10536580.4

kJ
Q̇=−10536580.4 =−2926.83 kW
h

2.3. Pump:
After the flash drum a pump is installed to pressurize the fluid from 1 to 1.3 bar which is
going to distillation column.

Table 20: Inlet and outlet pump information

component Formula inlet outlet Molecular weight xi Density

(kmol/h) (kmol/h) (kg/kmol) (kg/m3)
Ethylene C2H4 8.274 8.274 28.059 0.015443263 1.18
Acetic Acid C2H4O2 170.724 170.724 60.052 0.681987309 1050
Oxygen O2 0.100 0.100 31.999 0.000213643 1.429
Carbon Dioxide CO2 4.518 4.518 44.010 0.013224936 1.98
Water H2O 47.145 47.145 18.015 0.056449659 998
Ethane C2H6 0.781 0.781 30.069 0.001558765 1.36
Vinyl Acetate C4H6O2 40.359 40.359 86.089 0.231122276 934
Total flow 271.902 271.902 0.999999851

kg
Average molecular weight: Ḿ w =Σ xi M w =55.056 i
kmol

kg
Mass flow rate: ṁ= ṅtot∗ Ḿ w =55.056∗271.902=14972.403 =249.540 kg /min
h

1 kg
ρmix = =45.421
x m3
∑ ρi
i

V = ṁ∗ρmix =45.421∗249.54=5.494 m 3 /min

22
 1.67∗V∗∆ P
P=
ϵ

Table 21: Energy balance around the pump

V (m3/min) 5.494
∆P 0.3
ε 0.7
P (kW) 3.932

2.4. Compressor:
After the flash drum a compressor is installed to compress the gases from 4 to 8 bar which is
going to absorber column, assuming Cp/Cv =1.4.

Table 22: Inlet and outlet compressor information

component Formula Inlet (kmol/h) outlet (kmol/h)

Ethylene C2H4 474.108 474.108
Acetic Acid C2H4O2 3.504 3.504
Oxygen O2 62.128 62.128
Carbon Dioxide CO2 243.573 243.573
Water H2O 1.497 1.497
Ethane C2H6 27.116 27.116
Vinyl Acetate C4H6O2 5.756 5.756
817.683 817.683

P2 a
( n∗R∗z 1∗T 1∗
(( ) ))
P1
−1
k −1 C P a

P ( W )=
a∗ε
, a=
k
, k = p , T 2=T 1∗ 2
Cv P1 ( )
Table 23: Energy balance around the compressor

n (kmol/h) 817.6825522
n (mol/s) 227.1340423
z1 1
k 1.4
a = (k-1)/k 0.285714286
P1 (bar) 4
P2 (bar) 8
R (J/mol.K) 8.314
T1 (K) 303.15

23
 T2 (K) 369.5439893
ε 0.75
P (kW) 585.10

2.5. Distillation column:

Assumptions:

 Steady state operation

 Reflux ratio is 0.85
 Feed temperature is 35 ⁰C
 Distillate temperature is 75 ⁰C
 Bottom temperature is 130 ⁰C
 Tref was taken as 25 ⁰C

F h F +Q c +Q R=D h D + B hB , Q c =( 1+ R ) D(h D −H v )

h F , h D , hB ∧H V can be found from heat capacity and heat of vaporization depending on the
temperatures.

( h D −H v ) can be found from the difference between gas and liquid heat capacities of vinyl
acetate from reference temperature to vaporization temperature to distillation temperature.

Table 24:Energy balance around the distillation column

component Formula Feed, T= 35⁰C Distillate, T= Bottom, T= 130

(kmol/h) 75⁰C (kmol/h) ⁰C (kmol/h) FhF (kJ/h) DhD BhR

Ethylene C2H4 8.274 8.274 0 3594.13 18800.25 0

Acetic Acid C2H4O2 285.818 0 285.818 357184.41 0 10669993

Oxygen O2 0.1004 0.1004 0 29.48 147.97 0

Carbon Dioxide CO2 4.518 4.518 0 1694.36 8690.21 0

Water H2O 47.145 47.145 0 35508.12 177522.40 0

Ethane C2H6 0.781 0.781 0 262.44 2171.94 0

Vinyl Acetate C4H6O2 46.115 46.115 0 79874.46 1857789.4 0

Total flow 392.752 106.934 285.818 478147.40 2065122.2 10669993

24
 ( 1+ 0.85 )∗106.934∗(−39620 )
Q c =( 1+ R ) D ( h D−H v ) = =−2177.20 kW
3600

Q R=D h D + B hB −F h F −Q c = ( 2065122.2
3600 ) +(
10669993
3600 ) −(
478147.4
3600 )
− (−2177.20 )

Q R=5581.91 kW

Conclusion:

In summary, mass and energy balances are conducted based on the conservation law of mass
and first law of thermodynamics. Material and energy balances were used to identify the
unknown parameters at streams. Several assumptions were stated in each equipment to
achieve the degree of freedom or to simplify process calculation. However, some of the
assumptions may not be applicable and may lead to huge difference from the real case. The
temperatures and pressures were token from scientific source [3]. However, aspen plus was
used to obtain some parameters such as K-values. The major energy consumption was
determined to be 5581.9 kW from distillation’s reboiler. All stream and energy flows were
calculated for a production of 46.4 kmol/h vinyl acetate.

25
 References

[1] Roscher , G. , Vinyl esters in Ullmans ’ s Encyclopedia of Industrial Chemistry , Wiley -

VCH, Weinheim, Germany , 2002
[2] Perry, R.  Perry’s Chemical Engineers Handbook. (8 ed.). United States of America: The
McGraw- Hill., 2008

[ 3] Dimian, Alexandre C., and Costin Sorin. Bildea. Chemical Process Design: Computer-
Aided Case Studies. Wiley-VCH, 2008

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