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Production of Specialty Chemicals from a Coal Gasification Acid Gas Waste Stream

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Production of Specialty Chemicals from a Coal Gasification Acid Gas Waste Stream 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 SO2 is then processed into carbon disulfide, ammonium sulfate, sodium sulfite, and sodium bisulfite. Carbon 2 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 100-Hydrogen Sulfide Separation The purpose of Unit 100 is to separate hydrogen sulfide from the carbon dioxide in the acid gas waste stream. The PFD for Unit 100 is shown in Figure 2. The acid waste gas enters Unit 100 and is heated. Stream 3 now combines with superheated steam and is sent into a fired heater, H-101. The stream is heated to the reaction temperature, and it then enters an isothermal packed bed reactor, R-101. Here carbonyl sulfide reacts with steam over a titanium oxide catalyst to form hydrogen sulfide and carbon dioxide. Cooled and partially condensed, the reactor effluent is sent to the flash unit, V-101, where the excess steam is removed as condensed water. Stream 16 enters the bottom of absorber T-101 flowing upward countercurrently against the Selexol solvent. The Selexol preferentially absorbs the hydrogen sulfide as opposed to carbon dioxide. The cleaned carbon dioxide leaves the top of the absorber and is sent to Unit 600. The hydrogen sulfide-rich Selexol solvent is preheated in heat exchanger E-106 and sent to distillation column, T-102. In T-102, the Selexol solvent is regenerated, and the absorbed waste gases are sent to absorber T-103. Heat exchanger E-105, using refrigerated water, 3 reduces the temperature of the recycled Selexol to 25°C. Fresh Selexol is added to the recovered Selexol and enters the top of T-101. The top of T-102 is sent the bottom of a second absorber, T-103, where the stream again flows counter-currently against additional Selexol solvent. Absorber T-103 removes most of the carbon dioxide from the recovered hydrogen sulfide stream. The waste gas (Stream 38) exiting the absorber is sent to Unit 600. The bottom is preheated in two heat exchangers, E-110 and E-111, and is sent to a second distillation column, T-104, where the Selexol solvent is regenerated. The purified hydrogen sulfide leaves Unit 100 and is shared by Units 200 and 500. The bottom stream preheats the tower feed in E-110 and is then pumped up, cooled and combined with fresh Selexol to re-enter T-103. 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 4 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. Unit 300 A BFD of Unit 300 is shown in Figure 4. In Unit 300, streams of ammonia gas, sulfur dioxide gas, air, and superheated steam are reacted countercurrently in a tray tower with water. The column is comprised of an upper ammonia scrubbing section, a central reaction section and a lower ammonia stripping section. The sulfur dioxide and ammonia streams are introduced into the reacting section of the tower. The air and superheated steam are introduced at the bottom of the reactor. The water is dispersed through the top of the unit. Gas released from the top of the tower is comprised of mostly unreacted sulfur dioxide. The ammonium sulfate slurry descends through the column. At each of the stages in the bottom of the column, a portion of the slurry is extracted and centrifuge 5 separators separate solid. The liquid from the top of this separation is recycled back into the column for further crystallization. The bottoms product is comprised mostly of an ammonium sulfate aqueous solution. The centrifuge product is crystalline ammonium sulfate. Two forms of the ammonium sulfate product can be produced: an aqueous solution and a crystalline form. Unit 400-Sodium Sulfite/Bisulfite Production Sodium sulfite and sodium bisulfite are produced together in Unit 400. A PFD of Unit 400 is shown in Figure 5. The process is carried out in a single absorption tower with a scrubbing section added to the top for better efficiency. Water and sodium carbonate are fed in through the top of the absorption column. Also fed to the top of the column is a sulfur dioxide containing gas being recycled from the bottom that is to be scrubbed. At the bottom of the scrubbing section the waste gases are removed, and the liquids pass into the absorbing section. A liquid seal separates these two sections. Sulfur dioxide gas enters the absorbing section, meets with the downward flowing liquid, and flows into the packing. At the bottom, the gas liquid mixture is conveyed to a receiving tank where the gaseous products are separated and sent to the scrubber section. The liquid removed is a mixture of the two sulfites. Unit 500-Steam Generation Figure 6 is the process flow diagram for steam generation. This process receives hydrogen sulfide (H2S) (Streams 1, 3, and 5) from Units 100 and 200. Stream 3 is the product stream from Unit 100 and contains mainly H2S. Stream 5 is a waste stream that contains H2S and water vapor that will be combusted in the fired heater. Stream 1 is a recycle of excess H2S from Unit 200. These streams are throttled to 130 kPa, mixed to 6 form Stream 9, and are sent into the fired reactor (R-501) to be combusted. Reactor R- 501 operates at a temperature of 600°C and combusts the H2S to form mainly SO2, SO3, and H2O. Saturated boiler feed water (Stream 14) is pumped up to a pressure of 14,000 kPa in P-501 and vaporized in R-501 to form saturated super-pressure steam at a temperature of approximately 336°C (Stream 16). This super-pressure steam is used in Units 100 and 200. There may be alternatives, such as heat transfer fluids, to using super-pressure steam, which requires very thick walled pipes. The combusted gases from the reactor (Stream 10) are sent through a heat exchanger, E-501. Low-pressure steam (Stream 19) is generated from pumping boiler feed water (Stream 17) to a pressure of 1135 kPa and vaporized at a temperature of 185°C in the shell side of E-501 for use in Unit 200.
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