University of Cape Town

Removal of Benzene From Gasoline

CHE4049F Project 1: Flowsheet Development and Description

Table of Contents
1. 2. Process Summary ............................................................................................ 1 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. 6. 7. 8. Thinking about the Benzene Extraction Process ............................................ 13 Health, Safety and Environmental Impact Evaluation ..................................... 14 Appendix A1: Various Extractive Distillation Options ...................................... 15 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. 11. Appendix A4: Enlarged Diagram of Integration of Tasks (Unit Operations) .... 21 References ..................................................................................................... 22

1. Process Summary
The benzene extraction process begins with combining a Naphtha and C5+ 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 C5 and C6 molecules from the heavier components. The distillate from Column 1 is sent to an Extractive Distillation unit (Column 2) to separate benzene from the C5 and C6 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 C7 and C8s from the heavy (C9+) 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 Naphtha 25 000 kg/hr 40.0 C 9.88 atm Catalytic Reforming Gasoline 34 300 kg/hr 182 C 8.89 atm Raffinate Stream 8400 kg/hr 44 C

Benzene Recovery Unit

Aromatic Gasoline 32 800 kg/hr 44 C 10.5 atm Heavy Aromatics 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 Naphtha 25 000 kg/hr 40.0 C 9.88 atm
Extractive Distillation Column PreDistillation Column Solvent Recovery Column

Benzene 10 900 kg/hr 44 C

Catalytic Reforming Gasoline 34 300 kg/hr 182 C 8.89 atm

Aromatic Gasoline 32 800 kg/hr 44 C 10.5 atm

Aromatic Gasoline Distillation Column

Heavy Aromatics 7200 kg/hr 44 C 10.5 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 C5 components and the majority of the C6 compounds are recovered to the top of the column. It was noted that because some C7 isomers have boiling points close to the feed temperature (85 C) a certain fraction will leave the column in the distillate stream. The heavier C7+ molecules all exit Column 1 via the bottoms. Column 2 is the GTC Extractive Distillation column. Here, benzene is separated from the remaining C5, C6 and C7 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 C9 hydrocarbons. The distillate of Column 3 is the gasoline stream with a benzene specification that meets the new regulations (maximum of 1 volume %).
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Eliminate Differences in Temperatures, Pressures and Phases

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 1 Distillate (DC2 Feed) is heated to 100 C *Column 1 Bottoms (DC3 Feed) is heated to 145 C Column 2 Distillate is cooled to 44 C *Column 2 Bottoms (DC4 Feed) is heated to 120 C Column 3 Distillate is cooled to 44 C Column 3 Bottoms is cooled to 44 C
*Above temperatures for column feed streams are determined as approximate bubble point temperatures (See Appendix A3, Eqn 3)

Column 2 Distillate is pressurised to 3.5 atm. Column 4 Distillate is pressurised to 3 atm. Column 3 Distillate is pressurised to 10.5 atm. Column 3 Bottoms is pressurised to 10.5 atm. Condensers on all columns change vapour phase distillate to saturated liquid phase Reboilers on all columns partially vaporise liquid phase bottoms stream to vapour phase

Integration of Tasks (Unit Operations)

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 C5 and C6 compounds from the heavier C7+ 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 C8 aromatics to the distillate along with the C7 components from the heavier C9+ molecules.
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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-C7 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-P-03

101-V-02 cw 10 101-H-13 15 Raffinate

8 LPS 101-C-02 LPS 101-H-04 cw 101-P-04 11 101-H-02 LPS 6 101-H-10 cw 101-H-07

101-H-11 12 101-P-01 cw P-15 Naphtha 101-L-01 2 3 101-L-02 4 101-H-01 5 101-P-07 101-V-04 16 101-H-14 Reformate Gasoline 1 LPS 101-C-01 101-H-03 HPS 101-H-12 101-C-04 cw 101-V-01

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Benzene

101-P-02

101-P-08

cw MPS 101-H-05

101-H-08

101-L-03 101-P-05 101-V-03 13 9 101-H-15 cw 18 Aromatic Gasoline

cw HPS 101-C-03 101-H-09 101-P-06 14 101-H-16 19 Heavy Aromatics

CHE4049F Project 1 PFD for Benzene Recovery Unit [Area 101] Nicholas Munsami [MNSNIC002] 01 March 2013 8
Figure 5: PFD of Proposed Benzene Extraction Process

Equipment List
Table 2: Equipment List for Benzene Extraction Process

Equipment ID
101-C-01 101-C-02 101-C-03 101-C-04 101-H-01 101-H-02 101-H-03 101-H-04 101-H-05 101-H-06 101-H-07 101-H-08 101-H-09 101-H-10 101-H-11 101-H-12 101-H-13 101-H-14 101-H-15 101-H-16 101-L-01 101-L-02 101-L-03 101-P-01 101-P-02 101-P-03 101-P-04 101-P-05 101-P-06 101-P-07 101-P-08 101-V-01 101-V-02 101-V-03 101-V-04

Name
Pre-Distillation Column (PDC) Extractive Distillation Column (EDC) Aromatic Gasoline Distillation Column (AGDC) Solvent Recovery Column (SRC) PDC Feed cooler PDC Distillate condenser PDC Bottoms reboiler EDC Feed heater AGDC Feed heater EDC Distillate condenser EDC Bottoms reboiler AGDC Distillate condenser AGDC Bottoms reboiler SRC Feed heater SRC Distillate condenser SRC Bottoms reboiler EDC Raffinate cooler Benzene Product cooler Aromatic Gasoline cooler Heavy Aromatics cooler Naphtha Feed Pressure reduction valve PDC Feed Pressure reduction valve AGDC Distillate Pressure reduction valve PDC Reflux pump PDC Bottoms pump EDC Reflux pump EDC Bottoms pump AGDC Reflux pump AGDC Bottoms pump SRC Reflux pump SRC Bottom pump PDC Reflux drum EDC Reflux drum AGDC Reflux drum SRC Reflux drum

Description
Carbon steel shell 316 Stainless steel trays Carbon steel shell 316 Stainless steel trays Carbon steel shell 316 Stainless steel trays Carbon steel shell 316 Stainless steel trays Carbon steel (85 C) Carbon steel (68.4 C) 316 Stainless steel (111 C) 316 Stainless steel (100 C) 316 Stainless steel (145 C) Carbon steel (55.3 C) 316 Stainless steel (80.1 C) Carbon steel (116 C) 316 Stainless steel (170 C) 316 Stainless steel (120 C) Carbon steel (80 C) 316 Stainless steel (200 C) Carbon steel (44 C) Carbon steel (44 C) Carbon steel (44 C) Carbon steel (44 C) High strength steel alloy 9.88 - 8.89 atm High strength steel alloy 8.89 - 1.1 atm High strength steel alloy 10.5 - 1.1 atm Stainless steel centrifugal pump 1.2 atm. Operating P. Stainless steel centrifugal pump 1.2 atm. Operating P. Stainless steel centrifugal pump 3.5 atm. Operating P. Stainless steel centrifugal pump 1.1 atm. Operating P. Alloy 20 centrifugal pump 10.5 atm. Operating P. Alloy 20 centrifugal pump 10.5 atm. Operating P. Stainless steel centrifugal pump 3 atm. Operating P. Alloy 20 centrifugal pump 1.2 atm. Operating P. Carbon steel Carbon steel Carbon steel Carbon steel

Stream Table

Table 3: Stream Table for Benzene Extraction Process

Stream Pressure Temperature Total Mass Flow Total Molar Flow Component
1-Pentene Branched Paraffins Cyclopentane C6 Paraffins Cyclohexane Benzene C7 Paraffins C7 Dienes Toluene C8 Paraffins Ethyl Benzene Styrene Xylene C9 Paraffins Cumene C10s Cyclic Paraffins Naphthalene C11 HCs

1 8.89 182 34300 370 Wt-% 5.50 1.20 2.50 5.60 0 14.6 4.60 0.35 39.5 0.25 20.0 0.05 0 1.90 0 2.75 0 0 1.20 atm C Kg/hr Kmol/hr Mole % 7.27 1.54 3.30 4.71 0 17.3 4.26 0.338 39.7 0.204 17.4 0.044 0 1.37 0 1.79 0 0 0.711 8.89 40 25000 262 Wt-% 0 3 0 0 10.2 23.5 10.5 0 16.2 7 0 0 8.9 6.2 3.6 0 9.3 1.6 0

2 atm C Kg/hr Kmol/hr Mole % 0 3.98 0 0 11.6 28.7 10.0 0 16.8 5.86 0 0 8.01 4.62 2.86 0 6.34 1.19 0 8.89 122 59300 637 Wt-% 3.18 1.96 1.44 3.24 4.30 18.4 7.09 0.203 29.7 3.10 11.56 0.0287 3.76 3.71 1.52 1.59 3.92 0.675 0.694

3 atm C Kg/hr Kmol/hr Mole % 4.22 2.53 1.92 3.50 4.76 21.9 6.59 0.196 30.0 2.53 10.14 0.0256 3.29 2.70 1.18 1.04 2.61 0.490 0.413 1 122 59300 637 Wt-% 3.18 1.96 1.44 3.24 4.30 18.4 7.09 0.203 29.7 3.10 11.6 0.0287 3.76 3.71 1.52 1.59 3.92 0.675 0.694

4 atm C Kg/hr Kmol/hr Mole % 4.22 2.53 1.92 3.50 4.76 21.9 6.59 0.196 30.0 2.53 10.1 0.0256 3.29 2.70 1.18 1.04 2.61 0.490 0.413 1 85 59300 637 Wt-% 3.18 1.96 1.44 3.24 4.30 18.4 7.09 0.20 29.7 3.10 11.6 0.0287 3.76 3.71 1.52 1.59 3.92 0.68 0.69

5 atm C Kg/hr Kmol/hr Mole % 4.22 2.53 1.92 3.50 4.76 21.9 6.59 0.20 30.0 2.53 10.1 0.0256 3.29 2.70 1.18 1.04 2.61 0.49 0.41 1 68.4 20300 257 Wt-% 9.28 5.72 4.22 9.45 11.9 52.0 7.24 0.177 0 0 0 0 0 0 0 0 0 0 0

6 atm C Kg/hr Kmol/hr Mole % 10.5 6.28 4.76 8.69 11.2 52.7 5.73 0.146 0 0 0 0 0 0 0 0 0 0 0 1 111 39000 379 Wt-% 0 0 0 0 0.327 0.838 7.01 0.216 45.1 4.71 17.6 0.0436 5.71 5.65 2.31 2.42 5.97 1.03 1.06

7 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0.400 1.10 7.20 0.231 50.4 4.25 17.0 0.0431 5.54 4.54 1.98 1.75 4.38 0.824 0.695 1 100 20300 257 Wt-% 9.28 5.72 4.22 9.45 11.9 52.0 7.24 0.177 0 0 0 0 0 0 0 0 0 0 0

8 atm C Kg/hr Kmol/hr Mole % 10.48 6.28 4.76 8.69 11.2 52.7 5.73 0.146 0 0 0 0 0 0 0 0 0 0 0 1 145 39000 379 Wt-% 0 0 0 0 0.327 0.838 7.01 0.216 45.1 4.71 17.6 0.0436 5.71 5.65 2.31 2.42 5.97 1.03 1.06

9 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0.400 1.10 7.20 0.231 50.4 4.25 17.0 0.0431 5.54 4.54 1.98 1.75 4.38 0.824 0.695 3.5 55.3 9750 122 Wt-% 19.3 11.9 8.78 19.7 24.9 0.108 15.0 0.366 0 0 0 0 0 0 0 0 0 0 0

10 atm C Kg/hr Kmol/hr Mole % 22.1 13.3 10.1 18.4 23.7 0.111 12.0 0.306 0 0 0 0 0 0 0 0 0 0 0

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Table 4: Stream Table for Benzene Extraction Process continued

Stream Pressure Temperature Total Mass Flow Total Molar Flow Component 1-Pentene Branched Paraffins Cyclopentane C6 Paraffins Cyclohexane Benzene C7 Paraffins C7 Dienes Toluene C8 Paraffins Ethyl Benzene Styrene Xylene C9 Paraffins Cumene C10s Cyclic Paraffins Naphthalene C11 HCs 1 80.1 10550 135 Wt-% 0 0 0 0 0 99.9 0.0976 0.00341 0 0 0 0 0 0 0 0 0 0 0

11 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0 99.9 0.0761 0.00277 0 0 0 0 0 0 0 0 0 0 0 1 120 10550 135 Wt-% 0 0 0 0 0 99.9 0.0976 0.00341 0 0 0 0 0 0 0 0 0 0 0

12 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0 99.9 0.0761 0.00277 0 0 0 0 0 0 0 0 0 0 0 10.5 116 32800 335 Wt-% 0 0 0 0 0.389 0.995 8.33 0.256 53.6 5.60 20.9 0.0477 6.52 3.36 0 0 0 0 0

13 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0.454 1.25 8.16 0.262 57.1 4.81 19.3 0.0449 6.02 2.57 0 0 0 0 0 10.5 170 6200 46.0 Wt-% 0 0 0 0 0 0 0 0 0 0 0 0.0220 1.44 17.8 14.6 15.3 37.7 6.48 6.66

14 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0 0 0 0 0 0 0 0.0285 1.83 18.7 16.3 14.4 36.1 6.80 5.73 3.5 44 9750 122 Wt-% 19.3 11.9 8.78 19.7 24.9 0.108 15.0 0.366 0 0 0 0 0 0 0 0 0 0 0

15 atm C Kg/hr Kmol/hr Mole % 22.1 13.3 10.1 18.4 23.7 0.111 12.0 0.306 0 0 0 0 0 0 0 0 0 0 0 3 80 10550 135 Wt-% 0 0 0 0 0 99.9 0.0976 0.00341 0 0 0 0 0 0 0 0 0 0 0

16 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0 99.9 0.0761 0.00277 0 0 0 0 0 0 0 0 0 0 0 3 44 10550 135 Wt-% 0 0 0 0 0 99.9 0.0976 0.00341 0 0 0 0 0 0 0 0 0 0 0

17 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0 99.9 0.076 0.00277 0 0 0 0 0 0 0 0 0 0 0 10.5 44 32800 335 Wt-% 0 0 0 0 0.389 0.995 8.33 0.256 53.6 5.60 20.9 0.0477 6.52 3.36 0 0 0 0 0

18 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0.454 1.25 8.16 0.262 57.1 4.81 19.3 0.0449 6.02 2.57 0 0 0 0 0 10.5 44 6200 46.0 Wt-% 0 0 0 0 0 0 0 0 0 0 0 0.0220 1.44 17.8 14.6 15.3 37.7 6.48 6.66

19 atm C Kg/hr Kmol/hr Mole % 0 0 0 0 0 0 0 0 0 0 0 0.0285 1.83 18.7 16.3 14.4 36.1 6.80 5.73

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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 C5 and C6 compounds will be in the vapour phase inside the column since cyclohexane has the highest boiling point. Because the C7 paraffins in the feed stream boil at temperatures close to the feed temperature (90 - 98 C), it was assumed that a fraction of the C7s 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 C7 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 (nC7). 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-C7 and benzene was found over a range of temperatures. These factors were compared to the enhanced separation factor ( = 2.44) whe n using the Techtiv100 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, C8 was separated (at 145 C) from C9+ with some C9 (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.
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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.

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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.

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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 Techtiv-100 Sulfolane N-formyl Morpholine CAROM

Solvent-to-Feed ratio 3.00 3.00 3.00 3.00

Relative Volatility (nC7/Benzene) 2.44 2.00 1.89 1.35

The table above (Kolmetz et al.) shows that for a given solvent-to-feed ratio, Techtiv100 (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.

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8. Appendix A2: Criterion for Separation of Components

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

Component 1-Pentene Branched Paraffins Cyclopentane C6 Paraffins Cyclohexane Benzene C7 Paraffins C7 Dienes Toluene C8 Paraffins

Boiling Point (C) Tlow Thigh 30.0 9.50 27.7 44.3 49.7 68.8 80.7 80.1 90.1 98.5 90 108 111 99.3 126

Component Ethyl Benzene Styrene Xylene C9 Paraffins Cumene C10s Cyclic Paraffins Naphthalene C11 HCs

Boiling Point (C) Tlow Thigh 136 145 140 143 151 152 174 171 181 218 196

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 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) 65 70 75 80 85 90

Pvap (with solvent) atm 0.144 0.170 0.200 0.234 0.272 0.316

Pvap (normal) atm 0.613 0.725 0.852 0.997 1.16 1.34

Temperature (C) 91 92 93 94 95

Pvap (with solvent) atm 0.364 0.417 0.477 0.543 0.782

Pvap (normal) atm 1.38 1.42 1.46 1.51 1.55 16

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 Operating Pressure Benzene recovery Cyclohexane recovery C7 paraffins recovery C7 dienes recovery : : : : : : 85C 1 atm (for all columns) 98 wt-% to distillate 97 wt-% to distillate 35 wt-% to distillate 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 : 100 C

All non-aromatic C6 and C5 to distillate stream C7s recovery Benzene recovery : : 99 wt-% to distillate 0.1 wt-% to distillate

Aromatic Gasoline Distillation Column Operating Temperature Xylene recovery C9s recovery : : : 145 C 96 wt-% to distillate 50 wt-% to distillate

All other C7/C8 compounds to distillate and remaining heavy C9+ leaves via bottoms. Solvent Recovery Column Operating Temperature : 120 C

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

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A2.2. Final Product Stream Information

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

(Aromatic Gasoline Stream) Compound Cyclohexane Benzene C7 Paraffins C7 Dienes Toluene C8 Paraffins Ethyl Benzene Styrene Xylene C9s Total Volumetric Flow (m3/hr) 0.164 0.372 4.03 0.118 20.3 2.64 7.91 0.0172 2.48 1.54 39.5 Volume % 0.414 0.941 10.2 0.299 51.3 6.67 20.0 0.0435 6.27 3.89 Density (kg/m3) 779 877 677 710 867 696 867 909 861 716 Mass Flowrate (Kg/hr) 128 326 2730 84.0 17600 1840 6850 15.6 2140 1100 32800

Recovery of feed C8 aromatics to gasoline stream : Purity of benzene product stream Non-aromatics in benzene product stream : :

99.0 wt-% 99.9 wt-% 0.10 wt-%

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

? Phase

Raffinate Stream 9750 kg/hr 55.3 C, 3.50 atm

?P

?T Raffinate Stream 9750 kg/hr 44 C, 3.50 atm

Column 2 Feed 59 300 kg/hr 100 C, 1 atm

Extractive Distillation Column

? Phase ?T

Column 2 Distillate 9750 kg/hr 55.3 C, 1 atm

? Phase

Column 2 Bottoms 10 550 kg/hr 80.1 C, 1 atm

?T Naphtha 25 000 kg/hr 40 C, 9.88 atm Naphtha 25 000 kg/hr 40 C, 8.89 atm Column 1 Feed 59 300 kg/hr 122 C, 1 atm ? Phase P P Column 4 Feed 10 550 kg/hr 120 C, 1 atm Column 4 Distillate 10 550 kg/hr 80 C, 3 atm Purified Benzene 10 550 kg/hr 44 C, 3 atm

?P

?P

?T

PreP-15 Distillation Column

Column 1 Distillate 20 300 kg/hr 68.4 C, 1 atm

?P

?T

Column 1 Feed 59 300 kg/hr 85 C, 1 atm CR Gasoline 34 300 kg/hr 182 C, 8.89 atm

Solvent Recovery Column

? Phase

? Phase

P Column 1 Bottoms 39 000 kg/hr 111 C, 1 atm

?T

? Phase

Aromatic Gasoline 32 800 kg/hr 116 C, 1 atm

Aromatic Gasoline 32 800 kg/hr 44 C, 1 atm

Aromatic Gasoline 32 800 kg/hr 44 C, 10.5 atm

Column 3 Feed 39 000 kg/hr 145 C, 1 atm

Aromatic Gasoline Distillation Column

?T

?P

? Phase

Heavy Aromatics 6200 kg/hr 170 C, 1 atm

Heavy Aromatics 6200 kg/hr 44 C, 1 atm

Heavy Aromatics 6200 kg/hr 44 C, 10.5 atm

?T

?P

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

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.

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10.

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

Cooling Water Condenser

Extractive Distillation Column

Column 2 Feed 59 300 kg/hr 100 C, 1 atm Low Pressure Steam Heater 1 atm

Pump Reflux Drum

Cooling Water Condenser Raffinate Stream 9750 kg/hr 55.3 C, 3.50 atm Raffinate Stream 9750 kg/hr 44 C, 3.50 atm

Low Pressure Steam Reboiler

Pump Column 2 Bottoms 10 550 kg/hr 80.1 C, 1 atm

Cooling Water Condenser

Low Pressure Steam Heater

Cooling Water Condenser Purified Benzene 10 550 kg/hr 44 C, 3 atm Cooling Water Condenser High Pressure Steam Reboiler Column 4 Distillate 10 550 kg/hr 80 C, 3 atm

Naphtha 25 000 kg/hr 40 C, 8.89 atm

Column 1 Feed 59 300 kg/hr 122 C, 1 atm Cooling Water Cooler

PreDistillation Column
1 atm

Pump

Reflux Drum

Column 4 Feed 10 550 kg/hr 120 C, 1 atm

Low Pressure Steam Reboiler

Column 1 Distillate 20 300 kg/hr 68.4 C, 1 atm

Solvent Recovery Column

1 atm

Pump

Reflux Drum

CR Gasoline 34 300 kg/hr 182 C, 8.89 atm

Column 1 Feed 59 300 kg/hr 85 C, 1 atm

Pump

Pump

Column 1 Bottoms 39 000 kg/hr 111 C, 1 atm Medium Pressure Steam Heater Cooling Water Condenser Aromatic Gasoline 32 800 kg/hr 116 C, 10.5 atm Aromatic Gasoline 32 800 kg/hr 44 C, 10.5 atm

Column 3 Feed 39 000 kg/hr 145 C, 1 atm

Aromatic Gasoline Distillation Column

1 atm

Pump

Reflux Drum

Cooling Water Condenser

High Pressure Steam Reboiler

Heavy Aromatics 6200 kg/hr 170 C, 1 atm Cooling Water

Heavy Aromatics 6200 kg/hr 44 C, 1 atm

Heavy Aromatics 6200 kg/hr 44 C, 10.5 atm

Condenser

Pump

Figure 7: Enlarged Diagram for Integration of Tasks (Unit Operations)

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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 NonAromatics 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

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