PRODUCTION OF 100,000 TONNE OF 2-ETHYLHEXYL ACRYLATE 145

CHAPTER 5

CHAPTER 5

MASS BALANCE

5.1 INTRODUCTION

Material balances are the basis of process design. A material balance taken over the complete
process will determine the quantities of raw materials required and products produced.
Balances over individual process units set the process stream flows and compositions. The
general equation for mass balance used in manual calculation is:

If there is no chemical reaction

Important information

1. Production flowrate: 100 000 metric tones of 2-EHA

2. The operating hours is 24 hour continuously
3. Assume the operating day is 335 per year.
4. 100% efficiency of equipment

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For ease of calculation, the basic assumptions for our material balance are:

1. No leakage in any equipment in the system

2. The total input for any substance is equal to the total output of the substance where no
reaction occurs.
3. Assume an ideal gas in all gaseous compounds
4. The system is at steady state
5. All components in the system behave as ideal condition

All calculation are done in mass flow rate (kg/h) and molar flow rate (kgmol/h)

5.2 SAMPLE CALCULATIONS

The material used throughout this mass balance and will be denoted as in Table 5.1.

Table 5.1: Component used for Production of 2-EHA

Component

Formula

Molecular weight
(kg/kmol)

Acrylic acid

C3H4O2

72.06

2-Ethylhexanol

C8H18O

130.23

2-Ethylhexylacrylate

C11H20O2

184.28

Water

H20

18.02

DAA

C6H8O4

144

Octene

C8H16

112.21

Mass fractions of composition of acrylic acid were show in Table 5.2.

Table 5.2: Composition of AA.

Composition

Mass fraction

Acrylic acid

0.997

Acetic acid

0.001

Propionic acid

0.0004

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DAA

0.0008

H2O

0.0006

MEHQ

0.0002

To simplify, we assume our raw materials are pure since the component composition is very
small thus does not give much effect on production of 2-EHA.
5.2.1

Mass Balance around Second Distillation Column, T-102

For the second distillation column, is the final stage of the process of purification of
production of 2-ethylhexylacrylate. Based on literature review, the product purity
achieved as high as 99.7% purity while high boiling residue is discharged through the
bottom stream of distillation column.

Table 5.3 shows the specifications of second distillation column based on literature
review.

Table 5.3: Specification of T-102

Reflux ratio

0.3-0.5

No of stages

20 - 25

Top product

Product

Bottom product

High boiling residue

Top P

18 mmHg

Bottom P

10 100 mmHg

For production of 2-EHA,

Operating day = 335 day
Operating hour = 24hour
Minimum production = 100 000 metric tones

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12437.8109 kg/h
S22

0.0002 kg C8H18O/kg
0.9933 kg C11H20O2/kg
0.0065 kg C6H8O4/kg
Reflux ratio : 0.5
No of stage : 20
Top pressure : 18 mmHg
Bottom pressure : 100 mmHg
Feed tray : 10th

T-102

S21

0.0001 kg C8H18O/kg
0.9709 kg C11H20O2/kg
0.0289 kg C6H8O4/kg
S23

0.0013 kg C11H20O2/kg
0.9987 kg C6H8O4/kg

Figure 5.1: Inlet and outlet stream of T-102

C11 H20O2 Balance:

(1)

C6H8O4 Balance:

(2)

Solve both equations simultaneously, (2) into (1):

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Table 5.4: Summary calculation in T-102
Component

Input (kg/h)
S21

C3H4O2

C8H16
Total

Component
C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16
Total

S23

Total Output

0.0000

0.0000

0.0000

1.8708

1.8708

0.0000

1.8708

12355.2103

12354.6804

0.3672

12355.0476

0.0000

0.0000

0.0000

0.0000

368.0616

81.2597

286.9179

0.0000
12725.1427

0.0000

0.0000
12725.0960

H20
C6H8O4

S22
0.0000

C8H18O
C11H20O2

Output (kg/h)

Input (kgmole/h)
S21

368.1776
0.0000

Output (kgmole/h)
S22

S23

Total Output

0.0000

0.0000

0.0000

0.0000

0.0144

0.0144

0.0000

0.0144

67.0459

67.0430

0.0020

67.0450

0.0000

0.0000

0.0000

0.0000

2.5560

0.5643

1.9925

2.5568

0.0000
69.6162

0.0000

0.0000
69.6161

0.0000

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5.2.2

Mass Balance around First Distillation Column, T-101

The purpose of second distillation column is to recover unreacted reactant to recycle

back for further process.

Based on literature review, Table 5.7 shows the specifications of distillation column.

Table 5.5: Specification of T-101

Reflux ratio

3-5

No of stages

10-20

Top product

Unreacted raw materials and impurities

Bottom product

Product and high boiling residue

Top P

75 mmHg

Bottom P

10 100 mmHg

(Source: Erpenbach, H., Guhrmann, K., & Joest, H. (1981). Patent No. 4280009. United States.
Riondel, A., & Bessalem, J. (2005). Patent No. US 6956130 B2. United States.)

S18

T-101

S17

0.0135 kg C8H18O/kg
0.6402 kg C8H18O/kg
0.3011 kg C11H20O2/kg
0.0042 kg H2O/kg
0.0087 kg C6H8O4/kg
0.0325 kg C8H16/kg

0.0192 kg C3H4O2/kg
0.9136 kg C8H18O/kg
0.0149 kg C11H20O2/kg
0.0059 wt%H2O
0.0463 wt% kg C8H16/kg

12725.1427 kg/h

Reflux ratio : 5
No of stage : 15
Top pressure : 70 mmHg
Bottom pressure : 100 mmHg
Feed tray : 9th

S21

0.0001 kg C8H18O/kg
0.9709 kg C11H20O2/kg
0.0289 kg C6H8O4

Figure 5.2: Inlet and outlet stream of T-101

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C8H18O Balance:

(1)

C11 H20O2 Balance:

(2)

Solve both equations simultaneously, (2) into (1)

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Table 5.6: Summary calculation in T-101
Component
C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16
Total

Component
C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16
Total

Input (kg/h)
S17

Output (kg/h)
S18

S21

Total output

571.9189

571.9343

0.0000

571.9343

27211.8077

27210.6712

1.8707

27212.5419

12797.8796

444.7387

12355.2132

12799.9519

176.6393

176.6440

0.0000

176.6440

367.9976

0.0002

368.0588

368.0590

1380.4394

1380.4766

0.0000

1380.4766

42506.6825

42509.6077

Input (kgmole/h)
S17

Output (kgmole/h)
S18

S21

Total output

7.9367

7.9369

0.0000

7.9369

208.9519

208.9432

0.0144

208.9576

69.4480

2.4134

67.0459

69.4593

9.8024

9.8027

0.0000

9.8027

2.5555

0.0000

2.5560

2.5560

12.3023

12.3026

0.0000

12.3026

310.9969

311.0150

152

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5.2.3

Mass balance around mixer

The purposed of mixer in this process is to mix all raw materials with recycle streams.
Since there is no chemical reaction occur in this stage. The input fed into the mixer is
same with the output coming out from mixer.

Input = output

29784.4650 kg/h
S20
0.0192 kg C3H4O2/kg
0.9141 kg C8H18O/kg
0.0149 kg C11H20O2/kg
0.0059 kg H2O/kg
0.0458 kg C8H16/kg
S15
0.0794 kg
0.5445 kg
0.0642 kg
0.0033 kg
0.0007 kg
0.3080 kg

C3H4O2/kg
C8H18O/kg
C11H20O2/kg
H2O/kg
C6H8O4/kg
C8H16/kg

MIX-101

S5
0.1276 kg
0.8037 kg
0.0139 kg
0.0039 kg
0.0508 kg

C3H4O2/kg
C8H18O/kg
C11H20O2/kg
H2O/kg
C8H16/kg

S3
1.0 kg C3H4O2/kg
S4
1.0 kg C8H18O/kg

Figure 5.3: Inlet and outlet stream of mixer

Assuming that:

C8H16 Balance:

(1)

153

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C11H20O2 Balance:
(2)

Solve both equations simultaneously, (2) into (1):

C3H4O2 Balance:

Overall Mass Balance:

154

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Table 5.7: Summary calculation in mixer
Input (kg/h)
Component
C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16

S3
5190.1591
0.0000

S4

S20

0.0000

571.8617

8931.8130 27211.0872

Output (kg/h)
S15
262.7061

Total input

S5

6022.2935

6024.727

1802.3803 37930.3524

37945.28

0.0000

0.0000

443.7885

212.6906

655.991

656.4791

0.0000

0.0000

175.7283

10.8452

187.3224

186.5735

0.0000

0.0000

0.0002

2.1534

2.2823

0.0000

0.0000

1379.0207
47216.7985

1019.5857

Total

2444.4174

Input (kgmole/h)

2.1536
2398.606
47216.7985

Output

Component

(kgmole/h)
S3

S4

S20

S15

Total

S5

input
C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16
Total

72.0255

0.0000

7.9359

3.6457

85.2312

83.6071

0.0000

68.5849

208.9464

13.8400

297.0687

291.3713

0.0000

0.0000

2.4082

1.1542

3.6353

3.5624

0.0000

0.0000

9.7519

0.6018

10.3952

10.3537

0.0000

0.0000

0.0000

0.0150

0.0158

0.015

0.0000

0.0000

12.2896
410.2855

9.0864

21.7843

21.376
410.1605

155

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5.2.4

Mass balance around tee splitter, TEE-100

The purpose of tee splitter is to split mixture with ratio 0.8:0.2 for recycle and purge. The
ratio of purge is based on literature review to remove octene from the process.

S13

TEE-100

S10
0.0794 kg C3H4O2/kg
0.5446 kg C8H18O/kg
0.0643 kg C11H20O2/kg
0.0029 kg H2O/kg
0.0007 kg C8H16/kg

0.0794 kg
0.5446 kg
0.0643 kg
0.0029 kg
0.0007 kg

C3H4O2/kg
C8H18O/kg
C11H20O2/kg
H2O/kg
C8H16/kg

I-21
S12

Recycle : Purge
0.8 : 0.2

0.0794 kg
0.5446 kg
0.0643 kg
0.0029 kg
0.0007 kg

C3H4O2/kg
C8H18O/kg
C11H20O2/kg
H2O/kg
C8H16/kg

Figure 5.4: Inlet and outlet stream of TEE-100

Assuming that:

According to ratio 0.8:0.2,

156

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Table 5.8: Summary calculation in TEE-100

Component

Input (kg/h)
S10

S13

S12

328.6397

262.9118

65.7279

328.6397

2253.4030

1802.7224

450.6806

2253.403

265.8866

212.7093

53.1773

265.8866

11.9162

9.5330

2.3832

11.9162

2.6920

2.1536

0.5384

2.692

1275.4142
4137.952

1020.3314

255.0829

1275.4143

C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16
Total

Component
C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16
Total

5.2.5

Output (kg/h)

4385.8979

Input (kgmole/h)
S10

Total output

Output (kgmole/h)
S13

S12

Total output

4.5606

3.6485

0.9121

4.5606

17.3033

13.8426

3.4607

17.3033

1.4428

1.1543

0.2886

1.4429

0.6613

0.5290

0.1323

0.6613

0.0187

0.0150

0.0037

0.0187

11.3663
35.3530

9.0931

2.2733
35.3530

11.3664

Mass balance around decanter

The purpose of this equipment is to separate two liquid phases in the stream which are organic
phase and aqueous phase. Aqueous phase is then discharged to the wastewater treatment if
required while organic phase is recycled back into the reactor for further reaction.

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4137.9518 kg/h
DECANTER

S9
0.0618 kg C3H4O2/kg
0.4234 kg C8H18O/kg
0.0500 kg C11H20O2/kg
0.2247 kg H2O/kg
0.0005 kg C6H8O4/kg
0.2396 kg C8H16/kg

S10
0.0794 kg C3H4O2/kg
0.5446 kg C8H18O/kg
0.0643 kg C11H20O2/kg
0.0029 kg H2O/kg
0.0007 kg C6H8O4/kg
0.3082 kg C8H16/kg
S11
0.0004 kg C3H4O2/kg
0.9996 kg H2O/kg

Figure 5.5: Inlet and outlet stream of decanter

C3H4O2 Balance:

C8H18O Balance:

Overall Mass Balance

158

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Table 5.9: Summary calculation in decanter
Component

Input (kg/h)
S9

C3H4O2
C8H18O

Total

Component
C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16
Total

S11

Total outlet

328.6397

0.4646

329.1043

2253.4364

2253.4030

0.0097

2253.4127

265.8894

265.8866

0.0000

265.8866

1195.9045

11.9162

1184.0314

1195.9476

2.6920

2.6920

0.0000

2.692

1275.4276

1275.4142

0.0000
5322.4576

1275.4142

C6H8O4
C8H16

S10
329.1078

C11H20O2
H20

Output (kg/h)

5322.4576
Input (kgmole/h)
S9

Output (kgmole/h)
S10

S11

Total outlet

4.5671

4.5606

0.0064

4.567

17.3035

17.3033

0.0001

17.3034

1.4429

1.4428

0.0000

1.4428

66.3654

0.6613

65.7065

66.3678

0.0187

0.0187

0.0000

0.0187

11.3664
101.0640

11.3663

0.0000
101.0661

11.3663

159

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5.2.6

Mass balance around reactor

The purpose of this equipment is to evaporate water formed from esterification reaction
between acrylic acid with 2-Ethyl hexanol. Vapor mixtures are fed into condenser while
liquid mixture containing product, unreacted reactant, high boiling residue and byproduct are fed into distillation column.

The esterification reaction occurs in reactor heater are:

Main reaction
Side reaction

According to Patterson et al. , Iffland et al., the reaction conversion is in range of 70-85%
conversion. In this process 85% conversion has been chosen for both reactions where
79% conversion for main reaction and 6% conversion for side reaction based on limiting
reactant.

Temp : 125 C
Pressure : 100 mmHg
S8

0.0618 kg C8H18O/kg
0.4234 kg C3H4O2/kg
0.0500 kg C11H20O2/kg
0.2247 kg H20/kg
0.0005 kg C6H8O4/kg
0.2395 kg C8H16/kg

47216.1591 kg/h
S7
0.1276 kg C3H4O2/kg
0.8037 kg C3H4O2/kg
0.0139 kg C11H20O2/kg
0.0039 kg H20/kg
0.0508 kg C8H16/kg

R-101

S16

0.0135 kg C8H18O/kg
0.6402 kg C3H4O2/kg
0.3011 kg C11H20O2/kg
0.0042 kg H20/kg
0.0087 kg C6H8O4/kg
0.0325 kg C8H16/kg

Figure 5.6: Inlet and outlet stream of reactor

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For inlet stream S7;

C3H4O2 Balance:

C8H18O Balance:

C11H20O2 Balance:

H20 Balance:

C8H16 Balance:

-------------------------

For Acrylic acid (C3H4O2),

Overall conversion 85%, so 15% unreacted raw materials

(1)

For 2-Ethylhexanol (C8H18O);

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(2)

Solve simultaneously, (2) into (1) :

kgmole/h

kgmole/h

So, for unreacted material,

C3H4O2:

C8H18O:

C11H20O2:

H2O:

162

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C6H8O4:

C8H16:

For outlet stream,

C3H4O2 Balance:

(1)

C8H18O Balance:

(2)

Solve simultaneously, (2) into (1):

kg/h

163

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Table 5.10: Summary calculation in reactor
Input
Component

S7
kgmole/h

C3H4O2
C8H18O
C11H20O2
H20
C6H8O4
C8H16

Output

83.6079

S8
kg/h
6024.7853

291.3893 37947.6285
3.5615

656.3132

10.2188

184.1428

0.0000

0.0000

21.3758

2398.5785

410.1533

47211.4483

Total

kgmole/h
4.3395

S16
kg/h
312.7069

16.4461 2141.7772
1.3715

252.7398

63.0839 1136.7712

kgmole/h
7.7770

Total stream
kg/h

kgmole/h

kg/h

560.4106

12.1165

873.1175

204.8084 26672.1957

221.2545

28813.973

68.0775 12545.3238

69.449

12798.064

9.6095

173.1640

72.6934

1309.9352

2.5589

2.5051

360.7371

2.5229

363.296

10.7974 1211.5714

12.0516

1352.3120

22.849
400.8853

2563.8834
46722.269

0.0178

164

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5.2.7

Overall Mass Balance

12437.8109 kg/h
S22
8931.813 kg/h
S4

5190.1591 kg/h
S3

287.2851 kg/h
S23

827.7904 kg/h
S12
1184.5058 kg/h
S11

Figure 5.7: Overall mass balance diagram

For overall mass balance,

165