Вы находитесь на странице: 1из 24

University of Cape Town

Removal of Benzene From Gasoline

CHE4049F Project 1: Flowsheet Development and Description

Table of Contents

1. Process Summary

1

2. Process

Synthesis

2

Eliminate Differences in Molecular Types

2

Distribute Chemicals by Matching Sources and Sinks (Mixing and Recycling) 3

Eliminate Differences in Composition (Separations)

4

Eliminate Differences in Temperatures, Pressures and Phases

5

Integration of Tasks (Unit Operations)

6

3. Process Flow Diagram for Benzene Extraction Process using GTC Extraction

Technologies

8

Equipment List

9

Stream Table

10

4. Rationale

12

Pre-Distillation Column (PDC)

12

Extractive Distillation Column (EDC)

12

Solvent Recovery (SRC) and Aromatic Gasoline Distillation (AGDC) Columns

 

12

5. Thinking about the Benzene Extraction Process

13

6. Health, Safety and Environmental Impact Evaluation

14

7. Appendix A1: Various Extractive Distillation Options

15

8. Appendix A2: Criterion for Separation of Components

16

A2.1. Specifications for Distillation columns:

17

A2.2. Final Product Stream Information

18

9. Appendix A3: Additional Information for Temperature, Pressure and Phase

Changes

19

10. Appendix A4: Enlarged Diagram of Integration of Tasks (Unit Operations)

21

11. References

22

1.

Process Summary

The benzene extraction process begins with combining a Naphtha and C 5 + Catalytic Reformate gasoline stream at a high pressure to ensure adequate mixing. The mixed stream's pressure is then reduced to 1 atm. before it enters Distillation Column 1 to separate the C 5 and C 6 molecules from the heavier components. The distillate from Column 1 is sent to an Extractive Distillation unit (Column 2) to separate benzene from the C 5 and C 6 molecules using a polar solvent.

Benzene leaves with the solvent via the bottoms of Column 2 and is separated at Distillation Column 4 to yield a high purity stream. The solvent is recycled in a closed loop back to Column 2. The bottoms product from Column 1 goes to Distillation Column 3 to separate an aromatic gasoline stream containing C 7 and C 8 ’s from the heavy (C 9 +) molecules. The heavy molecules exit the column via the bottoms with the gasoline stream leaving as the distillate of Column 3.

2.

Process Synthesis

Eliminate Differences in Molecular Types

The benzene extraction process involves no chemical reactions; it comprises only of the separation of benzene from the gasoline stream. There are, however, a variety of methods available to achieve this separation. These include:

Sulfolane Extractive Distillation Process

Morphylane Extraction Technology

Distapex Extraction Process

GTC Extractive Distillation Technology

Sulfolane Process:

The Sulfolane system is the most widely used process (in terms of market share) utilised to extract Benzene from gasoline.

Morphylane Process:

Utilises a single-tower configuration to extract the aromatic compounds from gasoline.

Distapex Process:

Solvent is non-corrosive and, along with modest operating conditions, means that the overall plant can be constructed from carbon steel.

GTC Extractive Distillation Process:

Requires fewer, and simpler, pieces of equipment (lower capital requirements) than other extractive distillation systems. The solvent (Techtiv-100) has a lower toxicity and is less corrosive than solvents utilised in other systems whilst still increasing the boiling point of benzene by the greatest factor.

There are many more advantages for each of these systems. However, the process chosen to separate benzene from the given gasoline stream is that of GTC Extractive Distillation. This is because GTC Technologies offers the most feasible choice in terms of required capital investment. It also has the smallest impact on the environment (most energy efficient) due to its solvent-to-feed ratio being the lowest (See Appendix A1).

Distribute Chemicals by Matching Sources and Sinks (Mixing and Recycling)

Benzene 10 900 kg/hr 44 ° C Raffinate Stream Naphtha 8400 kg/hr 25 000 kg/hr
Benzene
10
900 kg/hr
44
° C
Raffinate Stream
Naphtha
8400
kg/hr
25
000 kg/hr
44
°C
40.0
°C
9.88
atm
Benzene
Aromatic Gasoline
32
800 kg/hr
Catalytic Reforming
Recovery
44
°C
Gasoline
10.5
atm
34
300 kg/hr
Unit
182 °C
Heavy Aromatics
8.89
atm
7200
kg/hr
44
°C
10.5
atm

Figure 1: Overall summary of the Benzene Extraction system

The only mixing point in the system is between that of the two feed streams. The naphtha and reformate streams are mixed at high pressure to ensure that the various volatile components remain as liquids in the stream.

The solvent (Techtiv-100) is loaded into the Extractive Distillation section as a batch unit of 30 000 kg. This mass is circulated internally around the system via a recycle loop between the Solvent Recovery unit and the Extractive Distillation unit with negligible losses to the respective product streams.

Eliminate Differences in Composition (Separations)

Raffinate Stream 8400 kg/hr 44 °C Extractive Distillation Column Benzene Pre - 10 900 kg/hr
Raffinate Stream
8400 kg/hr
44 °C
Extractive
Distillation
Column
Benzene
Pre -
10
900 kg/hr
Distillation
44
° C
Column
Solvent
Recovery
Column
Aromatic Gasoline
32 800 kg/hr
44 °C
10.5 atm
Aromatic
Gasoline
Distillation
Heavy Aromatics
Column
7200 kg/hr
44 °C
10.5
atm

Naphtha

25 000 kg/hr

40.0 °C

9.88 atm

Catalytic Reforming

Gasoline

34 300 kg/hr

182 °C

8.89 atm

Figure 2: Proposed separation process to remove benzene from the gasoline stream

There are significant differences in the boiling points of the various components in the naphtha and reformate streams (See Appendix A2, Table 6). Thus, a series of distillation columns can be used to separate the lighter components from the heavier ones. These columns are to operate at 1 atm. and moderate temperatures to negate the need to use more exotic materials of construction required when operating a distillation column at high pressures.

Column 1 (Pre-Distillation unit) operates such that all the C 5 components and the majority of the C 6 compounds are recovered to the top of the column. It was noted that because some C 7 isomers have boiling points close to the feed temperature (85 °C) a certain fraction will leave the column in the distillate stream. The heavier C 7 + molecules all exit Column 1 via the bottoms.

Column 2 is the GTC Extractive Distillation column. Here, benzene is separated from the remaining C 5 , C 6 and C 7 compounds due to the presence of the polar solvent. The solvent (Techtiv-100) increases benzene's boiling point (See Appendix A2, Table 7) to allow it to be recovered as the bottoms product of Column 2. Benzene is then separated from the solvent in Column 4 (Solvent Recovery unit) to produce a bottoms stream consisting of pure solvent which is recycled back to the Extractive Distillation column.

In Column 3 (Aromatic Gasoline recovery unit), separation occurs between the C 8 and C 9 hydrocarbons. The distillate of Column 3 is the gasoline stream with a benzene specification that meets the new regulations (maximum of 1 volume %).

Eliminate Differences in Temperatures, Pressures and Phases

Eliminate Differences in Temperatures, Pressures and Phases Figure 3: Flowsheet with Temperature, Pressure and

Figure 3: Flowsheet with Temperature, Pressure and Phase-change operations in Benzene Extraction process (See Appendix A3 for enlarged diagram)

The two feed streams entering the Benzene Extraction system are at different temperatures and pressures. Due to the naphtha stream being at a greater pressure, its pressure is reduced to 8.89 atm. The resultant mixed stream's temperature of 122 °C was approximated by calculating a weighted average stream temperature (See Appendix A3, Eqn 2). The pressure of the mixed stream is then reduced to 1 atm. The following T, P or Phase changes occur throughout the rest of the process:

Table 1: Summary of Changes in Phase, Temperature and Pressure for the Major streams in Benzene Extraction Process

*Column 1 Feed is cooled to 85 °C

Column 2 Distillate is pressurised to 3.5 atm.

*Column 1 Distillate (DC2 Feed) is heated to 100 °C

Column 4 Distillate is pressurised to 3 atm.

*Column 1 Bottoms (DC3 Feed) is heated to 145 °C

Column 3 Distillate is pressurised to 10.5 atm.

Column 2 Distillate is cooled to 44 °C

Column 3 Bottoms is pressurised to 10.5 atm.

*Column 2 Bottoms (DC4 Feed) is heated to 120 °C

Condensers on all columns change vapour phase

Column 3 Distillate is cooled to 44 °C

distillate to saturated liquid phase

Column 3 Bottoms is cooled to 44 °C

Reboilers on all columns partially vaporise liquid

*Above temperatures for column feed streams are determined as approximate bubble point temperatures (See Appendix A3, Eqn 3)

phase bottoms stream to vapour phase

Integration of Tasks (Unit Operations)

Integration of Tasks (Unit Operations) Figure 4: Flowsheet showing Task Integration for Benzene Extraction process (See

Figure 4: Flowsheet showing Task Integration for Benzene Extraction process (See Appendix A4 for enlarged diagram)

1. Pre-Distillation Column (PDC). Operating at 85 °C and 1 atm, it separates the C 5

and C 6 compounds from the heavier C 7 + molecules. This column is of paramount importance as it reduces the load placed on the Extractive Distillation Column. This is due to there being other heavier aromatic compounds present in the feed stream. The PDC thus aids in producing a final benzene stream which meets the required specifications.

2. Extractive Distillation Column (EDC). It is at this point that benzene actually gets removed from the system. In the EDC a polar solvent (Techtiv-100) flows from the top of the column to absorb benzene from the non-aromatic hydrocarbons. The GTC process is able to remove 99.9 wt-% of the benzene entering the column. The aromatic-lean raffinate flows out the top of the column where it is condensed, cooled to 44 °C and then pressurised to 3.5 atm to ensure the most volatile components remain as a saturated liquid.

3. Aromatic Gasoline Distillation Column (AGDC). The AGDC is responsible for

recovering the majority (99 wt-% min.) of the C 8 aromatics to the distillate along with

the C 7 components from the heavier C 9 + molecules.

4. Solvent Recovery Column (SRC). A 99.9 wt-% pure benzene stream is recovered via the distillate of the SRC while the pure solvent stream is sent back to the EDC. The operating temperature was found to be 120 °C at a pressure of 1 atm.

This temperature was calculated using the enhanced relative volatility between n-C 7 and benzene and estimating the new boiling point of benzene after it is absorbed into the solvent stream (See Appendix A2, table 7). Because its boiling point is so much greater than the hydrocarbons, it was assumed that no solvent exits with the distillate stream. Thus the solvent loaded into the system initially is operating in a closed loop manner.

5. Condensers and Coolers. Since none of the overhead streams required cooling

to below 40 °C, it was deemed unnecessary to utilise refrigerated water to provide cooling duty to the condensers. These systems are more energy intensive than traditional cooling water streams (re-cooling utilities stream to 10 °C vs. 30 °C). The same logic was applied to the other various cooling units.

6. Reboilers and Heaters. The type of steam used in the reboiler was dependent on

the required temperature of the stream. If a stream required heating to below 135 °C,

low pressure steam was used. Between 135 and 170 °C, medium pressure is to be used and greater than 170 °C would require high pressure stream for adequate heating duty. The use of steam is more feasible and ecological than the use of fuel gas heater.

3.

Process Flow Diagram for Benzene Extraction Process using GTC Extraction Technologies

cw 101-H-06 101-V-02 101-P-03 cw 10 15 101-H-13 8 LPS 101-H-07 101-C-02 LPS 101-P-04 101-H-04
cw
101-H-06
101-V-02
101-P-03
cw
10
15
101-H-13
8
LPS
101-H-07
101-C-02
LPS
101-P-04
101-H-04
1
1
LPS
6
101-H-10
cw
101-H-11
1
2
cw
101-V-04
101-P-07
16
17
101-H-14
HPS
101-H-12
101-C-04
101-P-08
7

MPS

Raffinate
Raffinate
101-H-14 HPS 101-H-12 101-C-04 101-P-08 7 MPS Raffinate cw 101-H-02 101-V-01 101-P-01 cw P-15 Naphtha 2
cw 101-H-02 101-V-01 101-P-01 cw P-15 Naphtha 2 3 4 5 101-L-02 101-L-01 101-H-01 Reformate
cw
101-H-02
101-V-01
101-P-01
cw
P-15
Naphtha
2
3
4
5
101-L-02
101-L-01
101-H-01
Reformate
1
Gasoline
LPS
101-C-01
101-H-03
101-P-02
Reformate 1 Gasoline LPS 101-C-01 101-H-03 101-P-02 Benzene cw 101-H-08 101-L-03 cw 101-V-03 101-P-05
Benzene
Benzene
cw 101-H-08 101-L-03 cw 101-V-03 101-P-05 Aromatic 13 18 Gasoline 101-H-15 cw 14 19 Heavy
cw
101-H-08
101-L-03
cw
101-V-03
101-P-05
Aromatic
13
18
Gasoline
101-H-15
cw
14
19
Heavy Aromatics
HPS
101-H-16
101-C-03
101-H-09
101-P-06
CHE4049F Project 1
PFD for Benzene Recovery Unit [Area 101]
Nicholas Munsami [MNSNIC002]
01 March 2013

101-H-05

9
9

8

Figure 5: PFD of Proposed Benzene Extraction Process

Equipment List

Table 2: Equipment List for Benzene Extraction Process

Equipment ID

Name

 

Description

 

101-C-01

Pre-Distillation Column (PDC)

 

Carbon steel shell

316

Stainless steel trays

101-C-02

Extractive Distillation Column (EDC)

 

Carbon steel shell

316

Stainless steel trays

101-C-03

Aromatic Gasoline Distillation Column (AGDC)

 

Carbon steel shell

316

Stainless steel trays

101-C-04

Solvent Recovery Column (SRC)

 

Carbon steel shell

316

Stainless steel trays

101-H-01

PDC Feed cooler

Carbon steel

 

(85 °C)

101-H-02

PDC Distillate condenser

Carbon steel

 

(68.4 °C)

101-H-03

PDC Bottoms reboiler

316

Stainless steel

(111 °C)

101-H-04

EDC Feed heater

316

Stainless steel

(100 °C)

101-H-05

AGDC Feed heater

316

Stainless steel

(145 °C)

101-H-06

EDC Distillate condenser

Carbon steel

 

(55.3 °C)

101-H-07

EDC Bottoms reboiler

316

Stainless steel

(80.1 °C)

101-H-08

AGDC Distillate condenser

Carbon steel

 

(116 °C)

101-H-09

AGDC Bottoms reboiler

316

Stainless steel

(170 °C)

101-H-10

SRC Feed heater

316

Stainless steel

(120 °C)

101-H-11

SRC Distillate condenser

Carbon steel

 

(80 °C)

101-H-12

SRC Bottoms reboiler

316

Stainless steel

(200 °C)

101-H-13

EDC Raffinate cooler

Carbon steel

 

(44 °C)

101-H-14

Benzene Product cooler

Carbon steel

 

(44 °C)

101-H-15

Aromatic Gasoline cooler

Carbon steel

 

(44 °C)

101-H-16

Heavy Aromatics cooler

Carbon steel

 

(44 °C)

101-L-01

Naphtha Feed Pressure reduction valve

 

High strength steel alloy 9.88 - 8.89 atm

101-L-02

PDC Feed Pressure reduction valve

 

High strength steel alloy

 

8.89

- 1.1 atm

101-L-03

AGDC Distillate Pressure reduction valve

 

High strength steel alloy

 

10.5

- 1.1 atm

101-P-01

PDC Reflux pump

Stainless steel centrifugal pump

 

1.2

atm. Operating P.

101-P-02

PDC Bottoms pump

Stainless steel centrifugal pump

 

1.2

atm. Operating P.

101-P-03

EDC Reflux pump

Stainless steel centrifugal pump

 

3.5

atm. Operating P.

101-P-04

EDC Bottoms pump

Stainless steel centrifugal pump

 

1.1

atm. Operating P.

101-P-05

AGDC Reflux pump

 

Alloy 20 centrifugal pump

10.5

atm. Operating P.

101-P-06

AGDC Bottoms pump

 

Alloy 20 centrifugal pump

10.5

atm. Operating P.

101-P-07

SRC Reflux pump

Stainless steel centrifugal pump 3 atm. Operating P.

101-P-08

SRC Bottom pump

 

Alloy 20 centrifugal pump

1.2

atm. Operating P.

101-V-01

PDC Reflux drum

 

Carbon steel

 

101-V-02

EDC Reflux drum

 

Carbon steel

 

101-V-03

AGDC Reflux drum

 

Carbon steel

 

101-V-04

SRC Reflux drum

 

Carbon steel

 
Stream Table Table 3: Stream Table for Benzene Extraction Process Stream 1 2 3 4
Stream Table
Table 3: Stream Table for Benzene Extraction Process
Stream
1
2
3
4
5
6
7
8
9
10
Pressure
8.89
atm
8.89
atm
8.89
atm
1
atm
1
atm
1
atm
1
atm
1
atm
1
atm
3.5
atm
Temperature
182
°C
40
°C
122
°C
122
°C
85
°C
68.4
°C
111
°C
100
°C
145
°C
55.3
°C
Total Mass Flow
34300
Kg/hr
25000
Kg/hr
59300
Kg/hr
59300
Kg/hr
59300
Kg/hr
20300
Kg/hr
39000
Kg/hr
20300
Kg/hr
39000
Kg/hr
9750
Kg/hr
Total Molar Flow
370
Kmol/hr
262
Kmol/hr
637
Kmol/hr
637
Kmol/hr
637
Kmol/hr
257
Kmol/hr
379
Kmol/hr
257
Kmol/hr
379
Kmol/hr
122
Kmol/hr
Component
Wt-%
Mole %
Wt-%
Mole %
Wt-%
Mole %
Wt-%
Mole %
Wt-%
Mole %
Wt-%
Mole %
Wt-%
Mole %
Wt-%
Mole %
Wt-%
Mole %
Wt-%
Mole %
1-Pentene
5.50
7.27
0
0
3.18
4.22
3.18
4.22
3.18
4.22
9.28
10.5
0
0
9.28
10.48
0
0
19.3
22.1
Branched Paraffins
1.20
1.54
3
3.98
1.96
2.53
1.96
2.53
1.96
2.53
5.72
6.28
0
0
5.72
6.28
0
0
11.9
13.3
Cyclopentane
2.50
3.30
0
0
1.44
1.92
1.44
1.92
1.44
1.92
4.22
4.76
0
0
4.22
4.76
0
0
8.78
10.1
C6 Paraffins
5.60
4.71
0
0
3.24
3.50
3.24
3.50
3.24
3.50
9.45
8.69
0
0
9.45
8.69
0
0
19.7
18.4
Cyclohexane
0
0
10.2
11.6
4.30
4.76
4.30
4.76
4.30
4.76
11.9
11.2
0.327
0.400
11.9
11.2
0.327
0.400
24.9
23.7
Benzene
14.6
17.3
23.5
28.7
18.4
21.9
18.4
21.9
18.4
21.9
52.0
52.7
0.838
1.10
52.0
52.7
0.838
1.10
0.108
0.111
C7 Paraffins
4.60
4.26
10.5
10.0
7.09
6.59
7.09
6.59
7.09
6.59
7.24
5.73
7.01
7.20
7.24
5.73
7.01
7.20
15.0
12.0
C7 Dienes
0.35
0.338
0
0
0.203
0.196
0.203
0.196
0.20
0.20
0.177
0.146
0.216
0.231
0.177
0.146
0.216
0.231
0.366
0.306
Toluene
39.5
39.7
16.2
16.8
29.7
30.0
29.7
30.0
29.7
30.0
0
0
45.1
50.4
0
0
45.1
50.4
0
0
C8 Paraffins
0.25
0.204
7
5.86
3.10
2.53
3.10
2.53
3.10
2.53
0
0
4.71
4.25
0
0
4.71
4.25
0
0
Ethyl Benzene
20.0
17.4
0
0
11.56
10.14
11.6
10.1
11.6
10.1
0
0
17.6
17.0
0
0
17.6
17.0
0
0
Styrene
0.05
0.044
0
0
0.0287
0.0256
0.0287
0.0256
0.0287
0.0256
0
0
0.0436
0.0431
0
0
0.0436
0.0431
0
0
Xylene
0
0
8.9
8.01
3.76
3.29
3.76
3.29
3.76
3.29
0
0
5.71
5.54
0
0
5.71
5.54
0
0
C9 Paraffins
1.90
1.37
6.2
4.62
3.71
2.70
3.71
2.70
3.71
2.70
0
0
5.65
4.54
0
0
5.65
4.54
0
0
Cumene
0
0
3.6
2.86
1.52
1.18
1.52
1.18
1.52
1.18
0
0
2.31
1.98
0
0
2.31
1.98
0
0
C10s
2.75
1.79
0
0
1.59
1.04
1.59
1.04
1.59
1.04
0
0
2.42
1.75
0
0
2.42
1.75
0
0
Cyclic Paraffins
0
0
9.3
6.34
3.92
2.61
3.92
2.61
3.92
2.61
0
0
5.97
4.38
0
0
5.97
4.38
0
0
Naphthalene
0
0
1.6
1.19
0.675
0.490
0.675
0.490
0.68
0.49
0
0
1.03
0.824
0
0
1.03
0.824
0
0
C11 HCs
1.20
0.711
0
0
0.694
0.413
0.694
0.413
0.69
0.41
0
0
1.06
0.695
0
0
1.06
0.695
0
0

Table 4: Stream Table for Benzene Extraction Process continued

Stream

 

11

 

12

 

13

 

14

 

15

 

16

 

17

 

18

 

19

Pressure

1

atm

1

atm

10.5

atm

10.5

atm

3.5

atm

3

atm

3

atm

10.5

atm

10.5

atm

Temperature

80.1

°C

120

°C

116

°C

170

°C

44

°C

80

°C

44

°C

44

°C

44

°C

Total Mass Flow

10550

Kg/hr

10550

Kg/hr

32800

Kg/hr

6200

Kg/hr

9750

Kg/hr

10550

Kg/hr

10550

Kg/hr

32800

Kg/hr

6200

Kg/hr

Total Molar Flow 135 Kmol/hr 135 Kmol/hr 335 Kmol/hr 46.0 Kmol/hr 122 Kmol/hr 135 Kmol/hr
Total Molar Flow
135
Kmol/hr
135
Kmol/hr
335
Kmol/hr
46.0
Kmol/hr
122
Kmol/hr
135
Kmol/hr
135
Kmol/hr
335
Kmol/hr
46.0
Kmol/hr

Component

Wt-%

Mole %

Wt-%

Mole %

Wt-%

Mole %

Wt-%

Mole %

Wt-%

Mole %

Wt-%

Mole %

Wt-%

Mole %

Wt-%

Mole %

Wt-%

Mole %

1-Pentene

0

0

0

0

0

0

0

0

19.3

22.1

0

0

0

0

0

0

0

0

Branched Paraffins

0

0

0

0

0

0

0

0

11.9

13.3

0

0

0

0

0

0

0

0

Cyclopentane

0

0

0

0

0

0

0

0

8.78

10.1

0

0

0

0

0

0

0

0

C6 Paraffins

0

0

0

0

0

0

0

0

19.7

18.4

0

0

0

0

0

0

0

0

Cyclohexane

0

0

0

0

0.389

0.454

0

0

24.9

23.7

0

0

0

0

0.389

0.454

0

0

Benzene

99.9

99.9

99.9

99.9

0.995

1.25

0

0

0.108

0.111

99.9

99.9

99.9

99.9

0.995

1.25

0

0

C7 Paraffins

0.0976

0.0761

0.0976

0.0761

8.33

8.16

0

0

15.0

12.0

0.0976

0.0761

0.0976

0.076

8.33

8.16

0

0

C7 Dienes

0.00341

0.00277

0.00341

0.00277

0.256

0.262

0

0

0.366

0.306

0.00341

0.00277

0.00341

0.00277

0.256

0.262

0

0

Toluene

0

0

0

0

53.6

57.1

0

0

0

0

0

0

0

0

53.6

57.1

0

0

C8 Paraffins

0

0

0

0

5.60

4.81

0

0

0

0

0

0

0

0

5.60

4.81

0

0

Ethyl Benzene

0

0

0

0

20.9

19.3

0

0

0

0

0

0

0

0

20.9

19.3

0

0

Styrene

0

0

0

0

0.0477

0.0449

0.0220

0.0285

0

0

0

0

0

0

0.0477

0.0449

0.0220

0.0285

Xylene

0

0

0

0

6.52

6.02

1.44

1.83

0

0

0

0

0

0

6.52

6.02

1.44

1.83

C9 Paraffins

0

0

0

0

3.36

2.57

17.8

18.7

0

0

0

0

0

0

3.36

2.57

17.8

18.7

Cumene

0

0

0

0

0

0

14.6

16.3

0

0

0

0

0

0

0

0

14.6

16.3

C10s

0

0

0

0

0

0

15.3

14.4

0

0

0

0

0

0

0

0

15.3

14.4

Cyclic Paraffins

0

0

0

0

0

0

37.7

36.1

0

0

0

0

0

0

0

0

37.7

36.1

Naphthalene

0

0

0

0

0

0

6.48

6.80

0

0

0

0

0

0

0

0

6.48

6.80

C11 HCs

0

0

0

0

0

0

6.66

5.73

0

0

0

0

0

0

0

0

6.66

5.73

4. Rationale

Solving the mass balance for the Benzene Extraction unit involved making various assumptions with regards to the degree of separation occurring in the respective distillation columns.

Pre-Distillation Column (PDC)

The feed temperature of the column was taken as 85 °C because of cyclohexane. This ensured that all C 5 and C 6 compounds will be in the vapour phase inside the column since cyclohexane has the highest boiling point.

Because the C 7 paraffins in the feed stream boil at temperatures close to the feed temperature (90 - 98 °C), it was assumed that a fraction of the C 7 s exits in the distillate of the column (35 % to top). The components that did not distribute were those which had boiling points 15 + °C higher or lower than the feed temperature as they will either be all vapour or liquid in the column. The final distribution of C 7 was found such that the minimum specification for the benzene product stream was achieved.

Extractive Distillation Column (EDC)

In a traditional GTC Extraction process, benzene is separated relative to n-heptane (n- C 7 ). However, in this EDC system, benzene is separated relative to cyclohexane. Since these compounds have near-identical boiling points, the solvent would have increase the relatively volatility substantially. To approximate this difference, the relative volatility between n-C 7 and benzene was found over a range of temperatures. These factors were compared to the enhanced separation factor (α = 2.44) when using the Techtiv- 100 solvent (See Appendix A1) to determine the EDC feed temperature (T = 100 °C).

Solvent Recovery (SRC) and Aromatic Gasoline Distillation (AGDC) Columns

The SRC was the simplest column to solve since the solvent has a boiling very much higher than benzene. Thus, perfect separation was assumed to occur in the SRC. In the AGDC, C 8 was separated (at 145 °C) from C 9 + with some C 9 (50 %) being recovered to the distillate due to its boiling point range (145 to 151 °C). All chosen splits were based on the boiling points of the respective components.

5.

Thinking about the Benzene Extraction Process

The current design of the system does not show any emergency relief/dump valves. In reality these will be readily available if the benzene stream is to be purged for some safety concerns. This purge stream will not, however, simply be vented to the atmosphere since benzene is carcinogenic in nature.

A safer option would be to send the purge stream to a flare to carefully combust the vented benzene, under strictly-controlled conditions, to release carbon dioxide and water into the atmosphere rather.

The GTC Extraction process ensures that the maximum amount of benzene can be recovered from the gasoline stream. Ideally one would like to be operating the system well above the minimum required specifications in order to maximise product production. However, this may not be feasible in reality.

A better approach would be to operate the system such that the minimum specifications are met. Hence the plant would be operating at its most efficient state to produce quality product. This was the type of design philosophy considered when configuring the proposed system.

6.

Health, Safety and Environmental Impact Evaluation

With all chemical plants, there is the inherent danger associated with the production/separation of various chemical species. The Petrochemical industry specifically, utilises highly volatile organic compounds (VOCs) in the production and refinement of various fuels as is the case with the proposed design.

To make the proposed design inherently safer, streams containing highly volatile components are pressurised above the minimum pressure required for the stream to be a saturated liquid when stored. This ensures that the vapour content in the system, and hence flammability limits, are not reached in the system.

Furthermore, the distillation columns are operated at 1 atm to avoid utilising multiple high-pressure vessels on a single plant unit. Once again, this decreases the risk associated with having multiple volatile compounds in the system (reduced explosion risk due to potential vessel ruptures when operating at high pressures).

Benzene, specifically, is of grave concern as it is both flammable and carcinogenic. Thus extra care has to be taken to ensure that pipelines neither leak nor have benzene vapours forming inside them. To avoid vapours in the pipelines, the benzene product stream is pressurised to 3 atm at a temperature of 44 °C even though it would be a liquid at 1 atm and 44 °C.

7.

Appendix A1: Various Extractive Distillation Options

Sulfolane Process:

Utilises both liquid-liquid extraction and extractive distillation techniques to achieve separation.

Technology has been available since the 1960s (well-established operating procedures).

Can achieve a benzene recovery of 99.9 wt-% with levels of non-aromatics being less than 100 ppm in the benzene product stream.

Solvent has some corrosive properties in the solvent extraction unit.

Morphylane Process:

Does not require a raffinate wash stream (unlike Sulfolane process)

Single column configuration reduces capital costs for plant

Single column design is more complicated than other process designs (less inherently safe plant design).

Distapex Process:

Information on this process not readily available (proprietary information)

Requires benzene feed concentrations of above 80% to achieve 99.5% benzene recovery.

GTC Extractive Distillation Technology

Table 5: Comparison of solvent effect on the relative volatility of n-heptane to benzene

Solvent

Solvent-to-Feed ratio

Relative Volatility (nC 7 /Benzene)

Techtiv-100

3.00

2.44

Sulfolane

3.00

2.00

N-formyl Morpholine

3.00

1.89

CAROM

3.00

1.35

The table above (Kolmetz et al.) shows that for a given solvent-to-feed ratio, Techtiv-

100 (GTC solvent) would require the least amount of solvent as it has the greatest effect

on the boiling point of benzene. This, along with the simple, yet effective process

operation results in GTC extraction technologies being the process of choice.

8.

Appendix A2: Criterion for Separation of Components

Table 6: Boiling point temperatures of gasoline feed stream components at 1 atm.

Component

Boiling Point (°C)

Component

Boiling Point (°C)

T

low

T high

T

low

T

high

1-Pentene

 

30.0

Ethyl Benzene

 

136

 

Branched Paraffins

9.50

27.7

Styrene

 

145

 

Cyclopentane

 

44.3

Xylene

 

140

 

C6 Paraffins

49.7

68.8

C9 Paraffins

143

151

Cyclohexane

 

80.7

Cumene

 

152

 

Benzene

 

80.1

C10s

 

174

 

C7 Paraffins

90.1

98.5

Cyclic Paraffins

171

181

C7 Dienes

90

108

Naphthalene

 

218

 

Toluene

 

111

C11 HCs

 

196

 

C8 Paraffins

99.3

126

 

Note that for the unknown hydrocarbons, the isomers with the lowest and highest boiling points were used as a range to approximate the distribution of those various components.

The following formula was used to account for the effect that the solvent has on benzene's boiling point:

Equation 1

Where theta is an enhancement factor. Theta was calculated over a range of temperatures (65-95 °C) to yield and average value of 4.16 (since α ij is constant). This enhancement factor was then utilised to determine benzene's vapour pressure when it is dissolved in the solvent by dividing benzene's normal vapour pressure by theta.

Table 7: Comparison of vapour pressures for Benzene before and after absorption into solvent between 65 and 95 °C

Temperature (°C)

P vap (with solvent) atm

P vap (normal) atm

Temperature

(°C)

P

vap

P

vap

(with solvent)

(normal)

65

0.144

0.613

atm

atm

70

0.170

0.725

91

 

0.364

 

1.38

75

0.200

0.852

92

 

0.417

 

1.42

80

0.234

0.997

93

 

0.477

 

1.46

85

0.272

1.16

94

 

0.543

 

1.51

90

0.316

1.34

95

 

0.782

 

1.55

A2.1. Specifications for Distillation columns:

The following specifications were used to meet all the specifications of the design brief:

Pre-Distillation Column

Operating Temperature

:

85°C

Operating Pressure

:

1 atm (for all columns)

Benzene recovery

:

98 wt-% to distillate

Cyclohexane recovery

:

97 wt-% to distillate

C 7 paraffins recovery

:

35 wt-% to distillate

C 7 dienes recovery

:

30 wt-% to distillate

All other components were assumed to be non-distributing (light components all went to the distillate while the heavier compounds all went to the bottoms).

Extractive Distillation Column

Operating Temperature

All non-aromatic C6 and C5 to distillate stream

:

100 °C

C 7 s recovery

:

99 wt-% to distillate

Benzene recovery

:

0.1 wt-% to distillate

Aromatic Gasoline Distillation Column

Operating Temperature

:

145 °C

Xylene recovery

:

96 wt-% to distillate

C 9 s recovery

:

50 wt-% to distillate

All other C 7 /C 8 compounds to distillate and remaining heavy C9+ leaves via bottoms.

Solvent Recovery Column

Operating Temperature

Perfect separation occurs between benzene (distillate) and the heavy solvent (bottoms).

:

120 °C

A2.2. Final Product Stream Information

Table 8: Mass and Volumetric flowrates for the Aromatic Gasoline stream (Benzene vol-% < 1%)

 

(Aromatic Gasoline Stream)

 

Compound

Volumetric Flow (m 3 /hr)

Volume %

Density (kg/m 3 )

Mass Flowrate (Kg/hr)

Cyclohexane

0.164

0.414

779

128

Benzene

0.372

0.941

877

326

C7 Paraffins

4.03

10.2

677

2730

C7 Dienes

0.118

0.299

710

84.0

Toluene

20.3

51.3

867

17600

C8 Paraffins

2.64

6.67

696

1840

Ethyl Benzene

7.91

20.0

867

6850

Styrene

0.0172

0.0435

909

15.6

Xylene

2.48

6.27

861

2140

C9s

1.54

3.89

716

1100

Total

39.5

 

32800

Recovery of feed C8 aromatics to gasoline stream :

99.0 wt-%

Purity of benzene product stream

:

99.9 wt-%

Non-aromatics in benzene product stream

:

0.10 wt-%

9.

Appendix A3: Additional Information for Temperature, Pressure and Phase Changes

Naphtha 25 000 kg/hr 40 °C , 9 .88 atm ? P
Naphtha
25
000 kg/hr
40
°C , 9 .88 atm
? P
Naphtha 25 000 kg/hr 40 °C , 8. 89 atm
Naphtha
25
000 kg/hr
40
°C , 8. 89 atm
, 9 .88 atm ? P Naphtha 25 000 kg/hr 40 °C , 8. 89 atm
CR Gasoline 34 300 kg/hr 182 °C , 8. 89 atm
CR Gasoline
34 300 kg/hr
182 °C , 8. 89 atm
? Phase Raffinate Stream 9750 kg/hr 55.3 °C , 3 .50 atm P ?P ?T
? Phase
Raffinate Stream
9750
kg/hr
55.3 °C , 3 .50 atm
P
?P
?T
Extractive
Raffinate Stream
Distillation
Column 2 Distillate
9750 kg/hr
9750 kg/hr
Column
44 °C, 3. 50 atm
55. 3 °C , 1 atm
? Phase
P
Column 2 Bottoms
10 550 kg/hr
80.1 °C , 1 atm
?T
Column 4 Distillate
Purified Benzene
? Phase
10
550 kg /hr
10
550 kg/hr
80
°C, 3 atm
44
°C , 3 atm
Column 4 Feed
10 550 kg/hr
1 20 °C , 1 atm
P
?P
?T
Solvent
Recovery
Column
? Phase
°C , 1 atm P ?P ?T Solvent Recovery Column ? Phase P Aromatic Gasoline 32
P
P
Aromatic Gasoline 32 800 kg/hr 44 °C , 10. 5 atm
Aromatic Gasoline
32
800 kg/hr
44
°C , 10. 5 atm
P Aromatic Gasoline 32 800 kg/hr 44 °C , 10. 5 atm Column 2 Feed 59
Column 2 Feed 59 300 kg/hr 100 °C , 1 atm
Column 2 Feed
59 300 kg/hr
100 °C , 1 atm
?T
?T
? Phase Column 1 Feed 59 300 kg /hr P P 122 °C , 1
? Phase
Column 1 Feed
59
300 kg /hr
P
P
122 °C , 1 atm
Pre-
Column 1 Distillate
P- 15
Distillation
20 300 kg/hr
? P
? T
68.4 °C, 1 atm
Column
Column 1 Feed
59
300 kg/hr
85
°C , 1 atm
? Phase
Column 1 Feed 59 300 kg/hr 85 °C , 1 atm ? Phase P Column 1
Column 1 Feed 59 300 kg/hr 85 °C , 1 atm ? Phase P Column 1
P
P
Column 1 Bottoms 39 000 kg /hr 111 °C , 1 atm
Column 1 Bottoms
39 000 kg /hr
111 °C , 1 atm
? Phase P Column 1 Bottoms 39 000 kg /hr 111 °C , 1 atm ?T
?T Column 3 Feed 39 000 kg /hr 145 °C , 1 atm
?T
Column 3 Feed
39 000 kg /hr
145 °C , 1 atm
Aromatic Gasoline ? Phase 32 800 kg /hr 116 °C , 1 atm P Aromatic
Aromatic Gasoline
? Phase
32
800 kg /hr
116 °C , 1 atm
P
Aromatic
Gasoline
Distillation
Heavy Aromatics
Column
6200
kg /hr
170 °C , 1 atm
? Phase

Aromatic Gasoline

32

44

800 kg/hr

°C , 1 atm

Aromatic Gasoline 32 44 800 kg/hr °C , 1 atm Heavy Aromatics 6200 kg/hr 44 °C

Heavy Aromatics

6200 kg/hr

44 °C , 1 atm

kg/hr °C , 1 atm Heavy Aromatics 6200 kg/hr 44 °C , 1 atm ?T Heavy

?T

Heavy Aromatics 6200 kg/hr 44 °C , 10.5 atm
Heavy Aromatics 6200 kg/hr 44 °C , 10.5 atm
Heavy Aromatics 6200 kg/hr 44 °C , 10.5 atm
Heavy Aromatics
6200 kg/hr
44 °C , 10.5 atm
kg/hr °C , 1 atm Heavy Aromatics 6200 kg/hr 44 °C , 1 atm ?T Heavy
kg/hr °C , 1 atm Heavy Aromatics 6200 kg/hr 44 °C , 1 atm ?T Heavy
?T
?T

Figure 6: Enlarged Diagram for Temperature, Pressure and Phase Changes

19

The temperature of the feed stream was estimated by taking a weighted average of the temperatures of the two streams in terms of mass flow rates. It is given by the following:

Equation 2

A similar method was used to estimate the temperatures of the distillate and bottoms streams leaving the various distillation columns; except that the weighted average was now in terms of mole fractions and boiling point temperatures.

Equation 3

A more accurate method to determine these stream temperatures is to use the Antoine equation for vapour pressures to solve for the temperature at which the Bubble/Dew point pressure is equal to the system's pressure.

However, due to time constraints and insufficient information with regards the actual composition of the gasoline stream, it was not possible to calculate these temperatures more accurately at this time using the previously mentioned method.

10.

Appendix A4: Enlarged Diagram of Integration of Tasks (Unit Operations)

Cooling Water Condenser Cooling Reflux Drum Water Pump Extractive Distillation Condenser Column Raffinate
Cooling
Water
Condenser
Cooling
Reflux Drum
Water
Pump
Extractive
Distillation
Condenser
Column
Raffinate Stream
Raffinate Stream
1 atm
Low
Column 2 Feed
9750 kg/hr
9750 kg/hr
Pressure
59 300 kg/hr
55.3
°C , 3.50 atm
44 °C , 3 .50 atm
Steam
100 °C, 1 atm
Reboiler
Low
Pressure
Pump
Steam
Cooling
Heater
Water
Column 2 Bottoms
10
550 kg /hr
Condenser
80. 1 °C , 1 atm
Low
Pressure
Steam
Cooling
Water
Heater
Naphtha
Column 1 Feed
Purified Benzene
Condenser
25
000 kg/hr
59 300 kg/hr
10
550 kg/hr
40
°C , 8 .89 atm
122 °C, 1 atm
Column 4 Feed
44
°C , 3 atm
Pump
Reflux Drum
Pre-
10
550 kg /hr
Cooling
1 20 °C , 1 atm
Water
Cooling
Distillation
Water
Reflux Drum
Solvent
Pump
Column
Cooler
Column 1 Distillate
Recovery
Condenser
1 atm
20 300 kg/hr
Low
Column
Column 4 Distillate
68. 4 °C , 1 atm
High
Pressure
10
550 kg/hr
1 atm
Pressure
Steam
80
°C , 3 atm
Steam
Reboiler
CR Gasoline
Column 1 Feed
Reboiler
34 300 kg/hr
59
300 kg/hr
182 °C , 8 .89 atm
85
°C , 1 atm
Pump
Pump
Column 1 Bottoms
39
000 kg /hr
111
°C , 1 atm
Medium
Cooling
Pressure
Water
Steam
Aromatic Gasoline
Aromatic Gasoline
Condenser
Heater
32
800 kg /hr
32
800 kg /hr
116
°C , 10.5 atm
44
°C, 10.5 atm
Column 3 Feed
39 000 kg/hr
Cooling
145
°C , 1 atm
Aromatic
Water
Reflux Drum
Pump
Gasoline
Condenser
Distillation
Column
Heavy Aromatics
Heavy Aromatics
Heavy Aromatics
High
1 atm
6200
kg /hr
6200 kg/hr
6200 kg/hr
Pressure
44
°C , 10.5 atm
170
°C , 1 atm
44 °C , 1 atm
Steam
Reboiler
Cooling
Water
Condenser
Pump

11.

References

Kolmetz, K., et.al. (2008). "Guidelines for BTX Distillation Revamps." GTC Proprietary Licensed Technologies. UOP LLC, (1999). "Sulfolane Process." Aromatics and Derivatives. Colwell, R.F, (2010). "Benzene in Gasoline: Regulations and Remedies". Process Engineering Associates, LLC Petrochemical Processes 2005, Hydrocarbon Processing Netzer, D, et.al. (2002). "Improve benzene production from refinery sources". Process Technology-Petrochemical, 71 - 78. Biaohua, C., Zhigang, L., and Jianwei, L. (2003). "Separation on Aromatics and Non- Aromatics by Extractive Distillation with NMP."Journal of Chemical Engineering of Japan 36(1), 20 - 24 Yee, C.F, et.al. (2000)."Application of Extractive Distillation for the Separation of Benzene and Cyclohexane Mixture." Symposium of Malaysian Chemical Engineers (SOMChE 2000) Duvekot, C., (2008). "Fast Detailed Hydrocarbon Analysis of Naphtha". Varian, Inc. Mehrotra, A.K., Tiwary, D., (2006). "Understand Temperature Change in Process Stream Mixing". Heat Transfer, 33 - 38