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PROBLEM DESCRIPTION

Production of Specialty Chemicals from a Coal

Gasification Acid Gas Waste Stream

Background

A feasibility study is to be performed to investigate the possibility of producing high-

value, specialty sulfur chemicals from a sulfur-rich, acid gas waste stream produced by a

coal gasification facility. In this facility, a Shell gasifier is used to process approximately

16,000 tons of coal per day into a synthesis gas used primarily to produce higher alcohol

oxygenates and fuel additives. The process produces a waste gas stream of 50,000 kg / hr

with the following composition:

Carbon Dioxide 62.07 mol %

Hydrogen Sulfide 33.18 mol %

Carbonyl Sulfide 3.34 mol %
Ammonia 0.81 mol %
Methanol 0.56 mol %

The traditional method for the treatment of a waste gas of this type is a sequential
application of the Claus and Beavon processes, resulting in elemental sulfur suitable for
landfill [1,2]. The goal is to explore the possibility of producing sulfur chemicals from
the stream. Bulk chemicals such as sulfuric acid are to be avoided.

The results of the feasibility study show that a reaction method, which is preferred

over the Claus and Beavon method, is most profitable. This requires the production of

sulfur dioxide via the combustion hydrogen sulfide. The SO 2 is then processed into

carbon disulfide, ammonium sulfate, sodium sulfite, and sodium bisulfite. Carbon

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disulfide is used in the manufacture of rayon, carbon tetrachloride, soil disinfectants, and

as a solvent for phosphorus, sulfur, selenium, bromide, iodine, fats, resins, and rubbers.

Ammonium sulfate is used in fertilizers, flame proofing, and galvanization. Sodium

sulfite is used in the chemical pulping of wood, water treatment, photography, ore

floatation, and textile processing and sodium bisulfite is used as a disinfectant, a bleach,

and as a preservative in the bleaching of food.

Process Description

A simplified BFD of the overall process is shown in Figure 1.

Unit 200-Carbon Disulfide Production

Figure 3 is the process flow diagram for carbon disulfide production (Unit 200).
This process receives hydrogen sulfide (Stream 2) from Unit 100 at a pressure of 300
kPa.

Stream 2 is compressed to a pressure of 350 kPa and is mixed with natural gas

(Stream 1). The resulting Stream 4 is then sent to heat exchanger E-201 where it is

heated to a temperature of 1060°C. Stream 5 leaving E-201 proceeds to reactive fired

heater R-201 where it is heated further to 1100°C. It is attractive to recover the this heat.

However, the design of E-201 requires non-conventional techniques, with unusual

materials of construction and the inclusion of radiant heat transfer. An alternative for

recovering this heat may be attractive. Stream 7 enters heat exchanger E-202 where it is

cooled to 50°C (Stream 8) before entering absorber T-201. Absorber T-201 uses

Telura-407 (Stream 9); a blend of naphthenic oils sold by Exxon, as the solvent to

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remove the carbon disulfide product (CS2) from Stream 8. The bottom stream exiting T-

201 (Stream 11), containing Telura-407, some hydrogen sulfide, and CS2, enters distillation

column T-202 where the hydrogen sulfide is removed. Stream 14, containing CS2 and Telura-

407, is then sent to a second distillation column, T-204, which removes the Telura-407

(Stream 17) from the CS2 product (Stream 18). Stream 17 is then recycled back to be mixed

with Stream 9 before it enters absorber T-201. The top stream exiting T-201 (Stream 12),

containing mostly hydrogen and hydrogen sulfide, is cooled and sent to absorber T-203,

which uses monoethanolamine, MEA, (Stream 20) as the solvent to remove the hydrogen in

Stream 22. The hydrogen leaves T-203 in Stream 24, leaving MEA and hydrogen sulfide in

Stream 23. Stream 23 enters distillation column T-205 where the MEA is removed and

recycled back to mix with Stream 20. The top stream exiting T-205, Stream 25, is mixed

with Stream 15 leaving the top of T-202 and then sent to Unit 500 to be burned.

Necessary Information and Simulation Hints

The conversion of carbonyl sulfide to hydrogen sulfide was accomplished through a

carbonyl sulfide hydrolysis reaction. The design for the hydrolysis reactor was based on work
done by Tong et al. [3] in the area of kinetic modeling of the hydrolysis of carbonyl sulfide.

Equipment Descriptions
C-201 Feed Compressor
E-201 Reactor Preheater
E-202 Gas Cooler
E-203 Partial Condenser
E-204 Thermosiphon Reboiler
E-205 Total Condenser
E-206 Thermosiphon Reboiler
E-207 Telura-407 Cooler
E-208 Gas Cooler
E-209 Partial Condenser
E-210 Thermosiphon Reboiler

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E-211 MEA Cooler

P-201 A/B Pump
P-202 A/B Reflux Pump
P-203 A/B Reflux Pump
P-204 A/B Recycle Pump
P-205 A/B Reflux Pump
R-201 Reactive Fired Heater
T-201 Carbon Disulfide Absorber
T-202 Hydrogen Sulfide Tower
T-203 Hydrogen Sulfide Absorber
T-204 Product Tower
T-205 MEA Tower
V-201 Knockout Drum
V-202 Reflux Drum
V-203 Knockout Drum

References

1. Kohl, A. and F. Riesenfeld, Gas Purification 4th ed., Gulf Publishing, Houston, TX, 1985.
pp. 446-451, 739-753.

2. Kohl, A. and F. Riesenfeld, Gas Purification 4th ed., Gulf Publishing, Houston, TX, 1985.
pp. 739-743.

3. Tong, S., I.G. Dalla Lana, and K.T. Chuang, “Kinetic Modelling of the Hydrolysis of
Carbonyl Sulfide Catalyzed by Either Titania or Alumina,” The Canadian Journal
of Chemical Engineering, 71 (3), 392-400 (1993).

4. U.S. Patent # 3,594,985 Acid Gas Removal From Gas Mixtures.

5. McKetta, J.J. Encyclopedia of Chemical Processing Design, Vol. 52., Marcel

Dekker Inc., New York, 1995, pp.458-472.

6. Erekson, “Gasoline from Natural Gas by Sulfur Processing,” 1995 Coal

Liquefaction and Gas Conversion Contractors Review Conference.

7. U.S. Patent # 4,250,160 Process for Manufacture of Ammonium Sulfate.

8. U.S. Patent # 5,266,296 Cocurrent Flow Process for the Manufacture of Sodium
Sulfite and Bisulfite Solutions.

Unit 200-Carbon Disulfide Production

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Stream 1 2 3 4 5 6 7 8
Temp. (°C) 81.4 45 60.7 65.1 1060 1100 220.2 50
Press. (kPa) 500 300 350 350 330 300 300 280
Vapor Fraction 1 1 1 1 1 1 1 1
Total Flow (kmol/h) 36.8 140.99 140.99 177.79 177.79 242.39 242.39 242.39
Total Flow (kg/h) 667.81 4835.94 4835.94 5503.75 5503.75 5503.75 5503.75 5503.75
Component Flows (kmol/h)
Ammonia -- 2.510 2.510 2.510 2.510 2.510 2.510 2.510
Carbon Dioxide -- 7.830 7.830 7.830 7.830 7.830 7.830 7.830
Carbon Disulfide -- -- -- -- -- 32.300 32.300 32.300
Ethane 1.840 -- -- -- -- 1.840 1.840 1.840
Hydrogen -- -- -- -- -- 129.200 129.200 129.200
Hydrogen Sulfide -- 129.200 129.200 129.200 129.200 64.600 64.600 64.600
Methane 33.120 -- -- -- -- 0.820 0.820 0.820
Methanol -- 1.340 1.340 1.340 1.340 1.340 1.340 1.340
Monoethanolamine -- -- -- -- -- -- -- --
Propane 1.840 -- -- -- -- 1.840 1.840 1.840
Telura-407 -- -- -- -- -- -- -- --
Water -- 0.113 0.113 0.113 0.113 0.113 0.113 0.113

Stream 9 10 11 12 13 14 15 16
Temp. (°C) 25 50 57.8 50.8 57.8 162.8 37.4 159.3
Press. (kPa) 260 260 280 280 350 370 350 120
Vapor Fraction -- -- -- 1 -- -- 1 0.12
Total Flow (kmol/h) 0.11 155.01 189.88 207.52 189.88 186.21 3.67 186.21
Total Flow (kg/h) 26.45 37275.3 39871.6 2997.35 39871.6 39649.6 132.04 29649.6
Component Flows (kmol/h)
Ammonia -- -- 0.010 2.500 0.010 -- 0.010 --
Carbon Dioxide -- -- 0.003 7.827 0.003 -- 0.003 --
Carbon Disulfide -- -- 31.300 1.000 31.300 31.200 0.100 31.200
Ethane -- -- -- 1.840 -- -- -- --
Hydrogen -- -- -- 129.200 -- -- -- --
Hydrogen Sulfide -- -- 31.500 61.450 3.150 -- 3.150 --
Methane -- -- -- 0.82 -- -- -- --
Methanol -- -- 0.260 1.080 0.260 0.001 0.259 0.001
Monoethanolamine -- -- -- -- -- -- -- --
Propane -- -- 0.150 1.690 0.150 -- 0.150 --
Telura-407 0.110 155.010 155.000 0.002 155.000 155.000 -- 155.000
Water -- -- 0.002 0.111 0.002 -- 0.002 --

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Stream 17 18 19 20 21 22 23 24
Temp. (°C) 319 52.7 319.2 35 35 35 71.96 35.1
Press. (kPa) 140 110 280 220 220 240 240 220
Vapor Fraction -- -- -- -- -- 1 -- 1
Total Flow (kmol/h) 154.85 31.36 154.85 0.17 149.41 207.52 223.35 133.59
Total Flow (kg/h) 37237.9 2411.72 37237.9 10.38 9117.64 2997.35 11707.5 407.54
Component Flows (kmol/h)
Ammonia -- -- -- -- -- 2.500 2.500 --
Carbon Dioxide -- -- -- -- 0.320 7.830 8.150 --
Carbon Disulfide -- 31.200 -- -- -- 1.000 1.000 --
Ethane -- -- -- -- -- 1.840 -- 1.840
Hydrogen -- -- -- -- -- 129.200 0.004 129.200
Hydrogen Sulfide -- -- -- -- 0.090 61.450 61.450 --
Methane -- -- -- -- -- 0.820 -- 0.820
Methanol -- 0.001 -- -- -- 1.080 1.080 --
Monoethanolamine -- -- -- 0.170 149.000 -- 148.960 0.040
Propane -- -- -- -- -- 1.690 -- 1.690
Telura-407 154.850 0.155 154.850 -- -- 0.002 0.002 --
Water -- -- -- -- 0.002 0.111 0.126 --

Stream 25 26 27 28 29 30
Temp. (°C) 87.5 84.4 199.5 199.5 35 50
Press. (kPa) 240 240 260 240 220 260
Vapor Fraction 1 1 -- -- -- --
Total Flow (kmol/h) 74.1 77.75 149.24 149.24 149.24 154.9
Total Flow (kg/h) 2600.33 2732.38 9107.25 9107.25 9107.25 37237.9
Component Flows (kmol/h)
Ammonia 2.500 3.510 -- -- -- --
Carbon Dioxide 7.830 7.830 0.320 0.320 0.320 --
Carbon Disulfide 1 1.100 -- -- -- --
Ethane -- -- -- -- -- --
Hydrogen 0.004 0.004 -- -- -- --
Hydrogen Sulfide 61.450 64.600 0.090 0.090 0.090 --
Methane -- -- -- -- -- --
Methanol 1.080 1.340 -- -- -- --
Monoethanolamine 0.130 0.130 148.830 148.830 148.830 --
Propane -- 0.150 -- -- -- --
Telura-407 0.002 0.003 -- -- -- 154.900
Water 0.111 0.113 0.002 0.002 0.002 --

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Figure 1: BFD of Specialty Sulfur Chemicals

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Figure 2: PFD for Unit 200--Carbon Disulfide Production