Enhanced tail gas treatment of sulfur recovery unit with steam swept membranes
11638898 · 2023-05-02
Assignee
Inventors
- Feras Hamad (Dhahran, SA)
- Sebastien A. Duval (Dhahran, SA)
- Milind M. Vaidya (Dhahran, SA)
- Ahmad A. Bahamdan (Dammam, SA)
- Faisal D. Al-Otaibi (Dammam, SA)
Cpc classification
B01D2311/04
PERFORMING OPERATIONS; TRANSPORTING
B01D53/229
PERFORMING OPERATIONS; TRANSPORTING
C01B17/0456
CHEMISTRY; METALLURGY
Y02P20/129
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
B01D53/34
PERFORMING OPERATIONS; TRANSPORTING
Abstract
This invention relates to a system and method for improving sulfur recovery from a Claus unit. More specifically, this invention provides a steam swept membrane tail gas treatment system and method for treating acid gas streams and minimizing sulfur dioxide emissions therefrom.
Claims
1. A method for removing sulfur-containing compounds from a sulfur recovery unit (SRU) tail gas stream, the method comprising the steps of: a) introducing the SRU tail gas stream produced by the SRU to a sulfur-converting unit to produce a membrane feed; b) introducing the membrane feed to a sulfur membrane unit, the sulfur membrane unit comprising an acid gas-selective membrane, wherein the membrane feed comprises sulfur-containing compounds; c) allowing the membrane feed to contact a feed side of the acid gas-selective membrane such that sulfur-containing compounds permeate through the membrane to a permeate side; d) supplying a steam feed to the permeate side of the acid gas-selective membrane to produce a sulfur concentrated stream, wherein the sulfur concentrated stream comprises sulfur-containing compounds, and wherein the heat used to produce the steam feed is sourced from the SRU boiler; and e) collecting the retentate gases that fail to permeate through the membrane to produce a sulfur lean stream retentate, wherein the sulfur lean stream retentate comprises retentate gases.
2. The method of claim 1 further comprising: a) collecting the sulfur concentrated stream; and b) introducing the sulfur concentrated stream to the sulfur recovery unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
3. The method of claim 1, wherein the temperature of the membrane feed is about 212° F. to about 350° F.
4. The method of claim 1, wherein the pressure of the steam feed is about 0 psig to about 1 psig.
5. The method of claim 1, wherein the temperature of the steam feed is about 212° F. to about 350° F.
6. The method of claim 1, wherein the SRU boiler is a waste heat boiler or a waste heat condenser.
7. The method of claim 1, wherein the acid gas-selective membrane separation is sweep driven.
8. The method of claim 1, wherein the sulfur-converting unit is a catalytic hydrogenation reactor, a catalytic oxidizer, or a thermal oxidizer.
9. The method of claim 1, wherein the sulfur-containing compounds comprise H.sub.2S or SO.sub.2.
10. The method of claim 1, wherein the acid gas-selective membrane allows for faster permeance of H.sub.2S or SO.sub.2 over other compounds in the membrane feed.
11. The method of claim 1, wherein the sulfur concentrated stream comprises H.sub.2S or SO.sub.2.
12. The method of claim 10, wherein the acid gas-selective membrane has a H.sub.2S to N.sub.2 permeance ratio of at least 1 and a H.sub.2S to CO.sub.2 permeance ratio of at least 1.
13. The method of claim 10, wherein the acid gas-selective membrane has a SO.sub.2 to N.sub.2 permeance ratio of at least 1 and a SO.sub.2 to CO.sub.2 permeance ratio of at least 1.
14. The method of claim 1, wherein the method comprising the steps of: a) introducing the SRU tail gas stream produced by the SRU to a catalytic hydrogenation reactor unit to produce a H.sub.2S membrane feed; b) introducing the H.sub.2S membrane feed to a sulfur membrane unit, the sulfur membrane unit comprising an H.sub.2S selective membrane, wherein the membrane feed comprises H.sub.2S; c) allowing the membrane feed to contact a feed side of the H.sub.2S selective membrane such that H.sub.2S permeates through the membrane to a permeate side; d) supplying a steam feed to the permeate side of the H.sub.2S selective membrane to produce a H.sub.2S concentrated stream, wherein the H.sub.2S concentrated stream comprises H.sub.2S, and wherein the heat used to produce the steam feed is sourced from the SRU boiler; and e) collecting the retentate gases that fail to permeate through the H.sub.2S selective membrane to produce a H.sub.2S lean stream, wherein the H.sub.2S lean stream retentate comprises retentate gases.
15. The method of claim 1, wherein the method comprises the steps of: a) introducing the SRU tail gas stream to a catalytic oxidizer or a thermal oxidizer unit to produce a SO.sub.2 membrane feed; b) introducing the SO.sub.2 membrane feed to a sulfur membrane unit, the sulfur membrane unit comprising an SO.sub.2 selective membrane, wherein the membrane feed comprises SO.sub.2; c) allowing the membrane feed to contact a feed side of the SO.sub.2 selective membrane such that SO.sub.2 permeates through the membrane to a permeate side; d) supplying a steam feed to the permeate side of the SO.sub.2 selective membrane to produce a SO.sub.2 concentrated stream, wherein the SO.sub.2 concentrated stream comprises SO.sub.2, and wherein the heat used to produce the steam feed is sourced from the SRU boiler; and e) collecting the retentate gases that fail to permeate through the SO.sub.2 selective membrane to produce a SO.sub.2 lean stream retentate, wherein the SO.sub.2 lean stream comprises retentate gases.
16. An apparatus to remove sulfur-containing compounds from a sulfur recovery unit (SRU) tail gas stream, the apparatus comprising: a) a sulfur-converting unit configured to produce a membrane feed; and b) a membrane unit fluidly connected to the converting unit, the membrane unit comprising an acid gas-selective membrane, wherein the membrane feed contacts a feed side of the acid gas-selective membrane such that the sulfur-containing compounds present in the membrane feed permeate through the acid gas-selective membrane to a permeate side, wherein the permeate side is swept with steam forming a sulfur rich stream, and wherein the heat used to produce the steam is sourced from the SRU boiler.
17. The apparatus of claim 16, further comprising a sulfur recovery unit, the sulfur recovery unit fluidly connected to the sulfur-converting unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
18. The apparatus of claim 16, wherein the sulfur-converting unit is a reducing unit, comprising: a) a reducing unit configured to produce a membrane feed, wherein the membrane feed comprises H.sub.2S; and b) a membrane unit fluidly connected to the reducing unit, the membrane unit comprising a H.sub.2S selective membrane, wherein the membrane feed contacts a feed side of the membrane such that the H.sub.2S present in the membrane feed permeates through the H.sub.2S selective membrane to a permeate side, wherein the permeate side is swept with steam forming a sulfur rich stream, and wherein the heat used to produce the steam is sourced from an SRU boiler.
19. The apparatus of claim 16, wherein the sulfur-converting unit is an oxidizing unit, comprising: a) an oxidizing unit configured to produce a membrane feed, wherein the membrane feed comprises SO.sub.2; and b) a membrane unit fluidly connected to the oxidizing unit, the membrane unit comprising a SO.sub.2 selective membrane, wherein the membrane feed contacts a feed side of the SO.sub.2 selective membrane such that the SO.sub.2 present in the membrane feed permeates through the membrane to a permeate side, wherein the permeate side is swept with steam forming a sulfur rich stream, and wherein the heat used to produce the steam is sourced from an SRU boiler.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DETAILED DESCRIPTION
(13) While the invention will be described with several embodiments, it is understood that one of ordinary skill in the relevant art will appreciate that many examples, variations and alterations to the apparatus and methods described herein are within the scope and spirit of the invention. Accordingly, the exemplary embodiments of the invention described herein are set forth without any loss of generality, and without imposing limitations, on the claimed invention.
(14) The apparatus and methods described herein describe the conversion of sulfur-containing compounds in a tail gas stream from a sulfur recovery unit to hydrogen sulfide or sulfur dioxide, the separation of the hydrogen sulfide or sulfur dioxide in a hydrogen sulfide-selective membrane or sulfur dioxide-selective membrane, and the recycle of the hydrogen sulfide or sulfur dioxide to the inlet of the sulfur recovery unit (SRU). The conversion of sulfur-containing compounds can be achieved by reducing or oxidizing the sulfur-containing compounds. A steam sweep feed can be supplied to sweep the permeate side of the hydrogen sulfide-selective membrane or sulfur dioxide-selective membrane prior to being supplied to the reaction furnace of the sulfur recovery unit, and in doing so the steam sweep feed becomes a hydrogen sulfide or sulfur dioxide enriched feed to the reaction furnace. The steam sweep lowers the hydrogen sulfide or sulfur dioxide concentration on the permeate side of the membrane, thereby causing more hydrogen sulfide or sulfur dioxide to be drawn into the membrane from the membrane feed and sent, along with the steam sweep feed, to the sulfur recovery unit. With the steam sweep feed, the hydrogen sulfide or sulfur dioxide concentration on the permeate side is lower than the hydrogen sulfide or sulfur dioxide on the feed side of the membrane.
(15) The process provides controlled slippage of sulfur-containing compounds to the atmosphere from an incinerator in order to meet environmental regulations or other process targets. In at least one embodiment, the use of a reducing unit in series with the hydrogen sulfide-selective membrane minimizes sulfur-containing compounds from the sulfur recovery system. In at least one embodiment, the use of an oxidizing unit in series with the sulfur dioxide-selective membrane minimizes sulfur-containing compounds from the sulfur recovery system. In one embodiment, the membrane recovers hydrogen sulfide or sulfur dioxide from the tail gas of the reducing or oxidizing unit before the tail gas is fed to an incinerator. The recovered hydrogen sulfide or sulfur dioxide is collected by sweeping the permeate side with a steam stream, which creates a hydrogen sulfide or sulfur dioxide rich stream. In at least one embodiment, the hydrogen sulfide or sulfur dioxide rich stream can be fed to the reaction furnace of the Claus process. In at least one embodiment, the use of the hydrogen sulfide-selective membrane or sulfur dioxide-selective membrane improves the Claus unit operability and efficiency to maximize elemental sulfur recovery and minimizes emissions of sulfur-containing compounds from an incinerator. In at least one embodiment, the hydrogen sulfide-selective membrane or sulfur dioxide-selective membrane and reducing or oxidizing unit can be retrofitted to an existing Claus unit or modified Claus process, regardless of the Claus unit and tail gas treatment unit.
(16) Advantageously, the sulfur recovery system can improve the capability of a sulfur recovery unit and can reduce the costs to build and operate, thereby improving the overall economics of a sulfur recovery system.
(17) The use of the hydrogen sulfide-selective membrane is based upon gas component separation with membranes that exhibit durable high H.sub.2S/CO.sub.2 and H.sub.2S/N.sub.2 selectivity. These selective membranes minimize recirculation of inert gases potentially present in the flue gas, such as CO.sub.2 and N.sub.2. The hydrogen sulfide-selective membrane produces a hydrogen sulfide-concentrated permeate fraction, which can be fed to the reaction furnace of the Claus unit along with the acid gas produced from acid gas removal units in NG treatment plants or refineries. The hydrogen sulfide-selective membrane also produces a hydrogen sulfide-depleted residue (retentate) fraction, which can be fed to the incinerator.
(18) The use of the sulfur dioxide-selective membrane is based upon gas component separation with membranes that exhibit durable high SO.sub.2/CO.sub.2 and SO.sub.2/N.sub.2 selectivity. These selective membranes minimize recirculation of inert gases potentially present in the flue gas, such as CO.sub.2 and N.sub.2. The sulfur dioxide-selective membrane produces a sulfur dioxide-concentrated permeate fraction, which can be fed to the reaction furnace of the Claus unit along with the acid gas produced from acid gas removal units in NG treatment plants or refineries. The sulfur dioxide-selective membrane also produces a sulfur dioxide-depleted residue (retentate) fraction, which can be fed to the stacks.
(19) Disclosed herein is a method for removing sulfur-containing compounds from a sulfur recovery unit (SRU) tail gas stream, the method comprising the steps of:
(20) a) introducing the SRU tail gas stream produced by the SRU to a sulfur-converting unit to produce a membrane feed;
(21) b) introducing the membrane feed to a sulfur membrane unit, the sulfur membrane unit comprising an acid gas-selective membrane, wherein the membrane feed comprises sulfur-containing compounds;
(22) c) allowing the membrane feed to contact a feed side of the acid gas-selective membrane such that sulfur-containing compounds permeate through the membrane to a permeate side;
(23) d) supplying a steam feed to the permeate side of the acid gas-selective membrane to produce a sulfur concentrated stream, wherein the sulfur concentrated stream comprises sulfur-containing compounds, and wherein the heat used to produce the steam feed is sourced from the SRU boiler; and
(24) e) collecting the retentate gases that fail to permeate through the membrane to produce a sulfur lean stream retentate, wherein the sulfur lean stream retentate comprises retentate gases.
(25) In some embodiments, the method further comprises:
(26) a) collecting the sulfur concentrated stream; and
(27) b) introducing the sulfur concentrated stream to the sulfur recovery unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
(28) In some embodiments, the method further comprises introducing the sulfur lean stream retentate to the final thermal oxidizer or to the stacks. In some embodiments, the method further comprises introducing the sulfur lean stream retentate to the final thermal oxidizer. In some embodiments, the method further comprises introducing the sulfur lean stream retentate to the stacks. In some embodiments, the method further comprises introducing the sulfur lean stream retentate to the SRU tail gas stream.
(29) In some embodiments, the acid gas-selective membrane is a polymeric, ceramic, or metallic membrane. In some embodiments, the acid gas-selective membrane is made from a mix of polymeric and inorganic materials.
(30) In some embodiments, the temperature of the membrane feed is about 212° F. to about 350° F. In some embodiments, the temperature of the membrane feed is about 225° F. to about 300° F. In some embodiments, the temperature of the membrane feed is about 230° F. to about 260° F. In some embodiments, the temperature of the membrane feed is about 245° F.
(31) Using steam to sweep the permeate side of the membrane unit significantly enhances the concentration (chemical potential) differential driving force for permeation of acid gas components. Therefore, the process can work with low pressure ratio (feed pressure/permeate pressure). However, small boost of the tail gas stream pressure may still be needed, but substantial compression is avoided, which can significantly improve economics of the process. The use of condensable steam to sweep the permeate side of the membrane unit is also advantageous as water vapor can be knocked down as liquid water in a later stage. This results in a smaller gas stream that is concentrated with the non-condensable gases. The resulting gas stream is small and is less expensive to further process to recover the acid gases.
(32) In some embodiments, the pressure of the steam feed is about 0 psig to about 1 psig. In some embodiments, the pressure of the steam feed is about 0 psig to about 0.5 psig. In some embodiments, the pressure of the steam feed is about 0 psig. In some embodiments, the temperature of the steam feed is about 212° F. to about 350° F. In some embodiments, the temperature of the steam feed is about 225° F. to about 300° F. In some embodiments, the temperature of the steam feed is about 230° F. to about 260° F. In some embodiments, the temperature of the steam feed is about 245° F.
(33) In some embodiments, the SRU boiler is a waste heat boiler or a waste heat condenser. In some embodiments, the SRU boiler is a waste heat boiler. In some embodiments, the SRU boiler is a waste heat condenser. In some embodiments, the entirety of the heat required to produce the steam feed is generated from the SRU. In some embodiments, a portion of the heat required to produce the steam feed is generated from the SRU. In some embodiments, a portion of the heat required to produce the steam feed is generated from a utility boiler.
(34) In some embodiments, the water liquid precipitated from the steam feed can be recycled with minimum treatment. In some embodiments, the water liquid precipitated from the steam feed can be recycled after further treatment.
(35) In some embodiments, the acid gas-selective membrane separation is sweep driven.
(36) In some embodiments, the sulfur-converting unit is a catalytic hydrogenation reactor, a catalytic oxidizer, or a thermal oxidizer. In some embodiments, the sulfur-containing compounds comprise H.sub.2S or SO.sub.2. In some embodiments, the acid gas-selective membrane allows for the faster permeance of H.sub.2S or SO.sub.2 over other compounds in the membrane feed. In some embodiments, the sulfur concentrated stream comprises H.sub.2S or SO.sub.2.
(37) In some embodiments, the sulfur-converting unit is a catalytic hydrogenation reactor. In some embodiments, the sulfur-containing compounds comprise H.sub.2S. In some embodiments, the acid gas-selective membrane allows for faster permeance of H.sub.2S over other compounds in the membrane feed. In some embodiments, the acid gas-selective membrane has a H.sub.2S to N.sub.2 permeance ratio of at least 1 and a H.sub.2S to CO.sub.2 permeance ratio of at least 1. In some embodiments, the acid gas-selective membrane has a H.sub.2S to N.sub.2 permeance ratio of at least 1. In some embodiments, the acid gas-selective membrane has a H.sub.2S to CO.sub.2 permeance ratio of at least 1. In some embodiments, the sulfur concentrated stream comprises H.sub.2S.
(38) In some embodiments, the sulfur-converting unit is a catalytic oxidizer or thermal oxidizer. In some embodiments, the sulfur-converting unit is a catalytic oxidizer. In some embodiments, the sulfur-converting unit is a thermal oxidizer. In some embodiments, the sulfur-containing compounds comprise SO.sub.2. In some embodiments, the acid gas-selective membrane allows for faster permeance of SO.sub.2 over other compounds in the membrane feed. In some embodiments, the acid gas-selective membrane has a SO.sub.2 to N.sub.2 permeance ratio of at least 1 and a SO.sub.2 to CO.sub.2 permeance ratio of at least 1. In some embodiments, the acid gas-selective membrane has a SO.sub.2 to N.sub.2 permeance ratio of at least 1. In some embodiments, the acid gas-selective membrane has a SO.sub.2 to CO.sub.2 permeance ratio of at least 1. In some embodiments, the sulfur concentrated stream comprises SO.sub.2.
(39) In some embodiments, the method comprises the steps of:
(40) a) introducing the SRU tail gas stream produced by a SRU to a catalytic hydrogenation reactor unit to produce a H.sub.2S membrane feed;
(41) b) introducing the H.sub.2S membrane feed to a sulfur membrane unit, the sulfur membrane unit comprising an H.sub.2S selective membrane, wherein the membrane feed comprises H.sub.2S;
(42) c) allowing the membrane feed to contact a feed side of the H.sub.2S selective membrane such that H.sub.2S permeates through the membrane to a permeate side;
(43) d) supplying a steam feed to the permeate side of the H.sub.2S selective membrane to produce a H.sub.2S concentrated stream, wherein the H.sub.2S concentrated stream comprises H.sub.2S, and wherein the heat used to produce the steam feed is sourced from the SRU boiler; and
(44) e) collecting the retentate gases that fail to permeate through the H.sub.2S selective membrane to produce a H.sub.2S lean stream, wherein the H.sub.2S lean stream retentate comprises retentate gases.
(45) In some embodiments, the method further comprises:
(46) a) collecting the H.sub.2S concentrated stream; and
(47) b) introducing the H.sub.2S concentrated stream to the sulfur recovery unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
(48) In some embodiments, the method further comprises:
(49) a) collecting the H.sub.2S concentrated stream;
(50) b) allowing the H.sub.2S concentrated stream to contact the feed side of a CO.sub.2 selective membrane such that CO.sub.2 permeates through the CO.sub.2 selective membrane to a permeate side;
(51) c) supplying a feed to the permeate side of the CO.sub.2 selective membrane to produce a CO.sub.2 concentrated stream;
(52) d) collecting the retentate gases that fail to permeate through the CO.sub.2 selective membrane to produce a CO.sub.2 lean stream retentate, wherein the CO.sub.2 lean stream retentate comprises H.sub.2S; and
(53) e) introducing the CO.sub.2 lean stream retentate to the sulfur recovery unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
(54) In some embodiments, the feed is a steam feed, a nitrogen feed, an argon feed, or an air feed. In some embodiments, the CO.sub.2 selective membrane separation is sweep driven or pressure driven. In some embodiments, the CO.sub.2 selective membrane is a rubbery membrane. In some embodiments, the rubbery membrane comprises PEBAX® or polydimethylsiloxane. In some embodiments, the flow configuration of the CO.sub.2 selective membrane unit is co-current, counter-current, or crossflow with the sulfur membrane unit.
(55) In some embodiments, the method further comprises collecting the CO.sub.2 concentrated stream and introducing the CO.sub.2 concentrated stream to the final thermal oxidizer.
(56) In some embodiments, the method further comprises:
(57) a) collecting the H.sub.2S concentrated stream;
(58) b) allowing the H.sub.2S concentrated stream to contact the feed side of a second H.sub.2S selective membrane such that H.sub.2S permeates through the second H.sub.2S selective membrane to a permeate side;
(59) c) supplying a feed to the permeate side of the second H.sub.2S selective membrane to produce a second H.sub.2S concentrated stream; and
(60) d) collecting the retentate gases that fail to permeate through the second H.sub.2S selective membrane to produce a second H.sub.2S lean stream retentate, wherein the second H.sub.2S lean stream retentate comprises retentate gases.
(61) In some embodiments, the method further comprises:
(62) a) collecting the second H.sub.2S concentrated stream; and
(63) b) introducing the second H.sub.2S concentrated stream to the sulfur recovery unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
(64) In some embodiments, the feed is a steam feed, a nitrogen feed, an argon feed, or an air feed. In some embodiments, the second H.sub.2S selective membrane separation is sweep driven or pressure driven. In some embodiments, the second H.sub.2S selective membrane is a rubbery membrane. In some embodiments, the rubbery membrane comprises PEBAX® or polydimethylsiloxane. In some embodiments, the flow configuration of the second H.sub.2S selective membrane unit is co-current, counter-current, or crossflow with the sulfur membrane unit.
(65) In some embodiments, the method further comprises introducing the second H.sub.2S lean stream retentate to the final thermal oxidizer. In some embodiments, the method further comprises introducing the second H.sub.2S lean stream retentate to the SRU tail gas stream.
(66) In some embodiments, the method comprises the steps of:
(67) a) introducing the SRU tail gas stream to a catalytic oxidizer or a thermal oxidizer unit to produce a SO.sub.2 membrane feed;
(68) b) introducing the SO.sub.2 membrane feed to a sulfur membrane unit, the sulfur membrane unit comprising an SO.sub.2 selective membrane, wherein the membrane feed comprises SO.sub.2;
(69) c) allowing the membrane feed to contact a feed side of the SO.sub.2 selective membrane such that SO.sub.2 permeates through the membrane to a permeate side;
(70) d) supplying a steam feed to the permeate side of the SO.sub.2 selective membrane to produce a SO.sub.2 concentrated stream, wherein the SO.sub.2 concentrated stream comprises SO.sub.2, and wherein the heat used to produce the steam feed is sourced from the SRU boiler; and
(71) e) collecting the retentate gases that fail to permeate through the SO.sub.2 selective membrane to produce a SO.sub.2 lean stream retentate, wherein the SO.sub.2 lean stream comprises retentate gases.
(72) In some embodiments, the method further comprises:
(73) a) collecting the SO.sub.2 concentrated stream; and
(74) b) introducing the SO.sub.2 concentrated stream to the sulfur recovery unit, the sulfur recovery unit configured to produce the SRU tail stream.
(75) In some embodiments, the method further comprises:
(76) a) collecting the SO.sub.2 concentrated stream;
(77) b) allowing the SO.sub.2 concentrated stream to contact the feed side of a second SO.sub.2 selective membrane such that SO.sub.2 permeates through the second SO.sub.2 selective membrane to a permeate side;
(78) c) supplying a feed to the permeate side of the second SO.sub.2 selective membrane to produce a second SO.sub.2 concentrated stream; and
(79) d) collecting the retentate gases that fail to permeate through the second SO.sub.2 selective membrane to produce a second SO.sub.2 lean stream retentate, wherein the second SO.sub.2 lean stream retentate comprises retentate gases.
(80) In some embodiments, the method further comprises:
(81) a) collecting the second SO.sub.2 concentrated stream; and
(82) b) introducing the second SO.sub.2 concentrated stream to the sulfur recovery unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
(83) In some embodiments, the feed is a steam feed, a nitrogen feed, an argon feed, or an air feed. In some embodiments, the second SO.sub.2 selective membrane separation is sweep driven or pressure driven. In some embodiments, the second SO.sub.2 selective membrane is a rubbery membrane. In some embodiments, the rubbery membrane comprises PEBAX® or polydimethylsiloxane. In some embodiments, the flow configuration of the second SO.sub.2 selective membrane unit is co-current, counter-current, or crossflow with the sulfur membrane unit.
(84) In some embodiments, the method further comprises introducing the second SO.sub.2 lean stream retentate to the stacks. In some embodiments, the method further comprises introducing the second SO.sub.2 lean stream retentate to the SRU tail gas stream.
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(86) The permeate side of the first stage is swept with low pressure steam, e.g. 0 psig and 245° F. The sweep steam is sourced from a utility boiler or from integration with SRU waste heat boilers or condensers. The permeate stream (P1), which is at high temperature, is utilized to preheat (economize) the water stream (W) sent to steam regeneration. The permeate stream (P1) is further cooled down to precipitate the majority of the water, forming the gas stream P1, in the Water Knock Drum (WKD). The precipitated water can be recycled. In
(87) The gas stream from the Water Knock Drum, which is concentrated in H.sub.2S, is sent to the second stage membrane after compressing. As shown in
(88) In
(89) More pressure driven membrane stages can be added or a different configuration can be integrated with the first stage steam swept to further concentrate the H.sub.2S content in the stream recycled to the furnace reactor (FR).
(90) As mentioned above, the steam needed to sweep the first stage can be produced by a utility boiler, or it can be produced partially or completely in the SRU by the waste heat boilers and/or condensers. The water stream (W), after the Economizer, can be recycled back partially or fully to the utility boiler, or it can be recycled partially or completely to the SRU to produce steam.
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(92) The permeate side of the first stage is swept with low pressure steam, e.g. 0 psig and 245° F. The sweep steam is sourced from a utility boiler or from integration with SRU waste heat boilers or condensers. The permeate stream (P1), which is at high temperature, is utilized to preheat (economize) the water stream (W) sent to steam regeneration. The permeate stream (P1) is further cooled down to precipitate the majority of the water, forming the gas stream P1, in the Water Knock Drum (WKD). The precipitated water can be recycled.
(93) The gas stream from the Water Knock Drum, which is concentrated in SO.sub.2, is sent to the second stage membrane after compressing. As shown in
(94) Apparatus
(95) Described herein is an apparatus for removing sulfur-containing compounds from a sulfur recovery unit (SRU) tail gas stream, the apparatus comprising:
(96) a) a sulfur-converting unit configured to produce a membrane feed; and
(97) b) a membrane unit fluidly connected to the converting unit, the membrane unit comprising an acid gas-selective membrane, wherein the membrane feed contacts a feed side of the acid gas-selective membrane such that the sulfur-containing compounds present in the membrane feed permeate through the acid gas-selective membrane to a permeate side, wherein the permeate side is swept with steam forming a sulfur rich stream, and wherein the heat used to produce the steam is sourced from the SRU boiler.
(98) In some embodiments, the apparatus further comprises the sulfur recovery unit, the sulfur recovery unit fluidly connected to the sulfur-converting unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
(99) In some embodiments, the sulfur-converting unit is a reducing unit. In some embodiments, the reducing unit is a catalytic hydrogenation reactor.
(100) In some embodiments, the apparatus comprises:
(101) a) a reducing unit configured to produce a membrane feed, wherein the membrane feed comprises H.sub.2S; and
(102) b) a membrane unit fluidly connected to the reducing unit, the membrane unit comprising a H.sub.2S selective membrane, wherein the membrane feed contacts a feed side of the membrane such that the H.sub.2S present in the membrane feed permeates through the H.sub.2S selective membrane to a permeate side, wherein the permeate side is swept with steam forming a sulfur rich stream, and wherein the heat used to produce the steam is sourced from an SRU boiler.
(103) In some embodiments, the apparatus further comprises a sulfur recovery unit, the sulfur recovery unit fluidly connected to the reducing unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
(104) In some embodiments, the apparatus further comprises a second membrane unit fluidly connected to the membrane unit.
(105) In some embodiments, the second membrane unit comprises a CO.sub.2 selective membrane, wherein the sulfur rich stream contacts a feed side of the membrane such that the CO.sub.2 present in the sulfur rich stream permeates through the CO.sub.2 selective membrane to a permeate side.
(106) In some embodiments, the second membrane unit comprises a H.sub.2S selective membrane, wherein the sulfur rich stream contacts a feed side of the membrane such that the H.sub.2S present in the sulfur rich stream permeates through the H.sub.2S selective membrane to a permeate side.
(107) In some embodiments, the sulfur rich stream is re-introduced into the sulfur recovery unit.
(108) In some embodiments, the sulfur-converting unit is an oxidizing unit. In some embodiments, the oxidizing unit is a catalytic oxidizer. In some embodiments, the oxidizing unit is a thermal oxidizer.
(109) In some embodiments, the apparatus comprises:
(110) a) an oxidizing unit configured to produce a membrane feed, wherein the membrane feed comprises SO.sub.2, and
(111) b) a membrane unit fluidly connected to the oxidizing unit, the membrane unit comprising a SO.sub.2 selective membrane, wherein the membrane feed contacts a feed side of the SO.sub.2 selective membrane such that the SO.sub.2 present in the membrane feed permeates through the membrane to a permeate side, wherein the permeate side is swept with steam forming a sulfur rich stream, and wherein the heat used to produce the steam is sourced from an SRU boiler.
(112) In some embodiments, the apparatus further comprises the sulfur recovery unit, the sulfur recovery unit fluidly connected to the oxidizing unit, the sulfur recovery unit configured to produce the SRU tail gas stream.
(113) In some embodiments, the apparatus further comprises a second membrane unit fluidly connected to the membrane unit.
(114) In some embodiments, the second membrane unit comprises a SO.sub.2 selective membrane, wherein the sulfur rich stream contacts a feed side of the membrane such that the SO.sub.2 present in the sulfur rich stream permeates through the SO.sub.2 selective membrane to a permeate side.
(115) In some embodiments, the sulfur rich stream is re-introduced into the sulfur recovery unit.
Definitions
(116) As used herein, “sulfur-containing compounds” refers to compounds that contain sulfur that can be products or reactants in the reactions of the sulfur recovery unit. The term sulfur-containing compounds is meant to be a catchall for sulfur-containing compounds. Examples of sulfur-containing compounds include, but are not limited to, hydrogen sulfide, sulfur dioxide, carbonyl sulfur, carbon disulfide, and combinations of the same.
(117) As used here, “allowable sulfur dioxide emission limit” refers to a rate of release of sulfur dioxide into the atmosphere. The rate of release can be mandated by federal, state, or local agencies.
(118) As used here, “air” refers to the collective gases that constitute earth's atmosphere. Air contains nitrogen, oxygen, argon, carbon dioxide, and water vapor. Unless otherwise indicated, oxygen-enriched air is considered air with an oxygen content of greater than 21% by volume on a dry basis. Unless otherwise indicated, the use of the term air includes all of the gases listed.
(119) As used here, “overall recovery of sulfur” or “sulfur recovery” refers to the percentage of sulfur removed based on the amount of sulfur present in the acid gas feed stream. A recovery of 99.0% means that 99.0% of the sulfur in the acid gas feed stream is recovered as part of the recovered sulfur stream.
(120) As used here, “permeate,” as a verb means to spread through or flow through or pass through a membrane of a membrane unit. As an example, liquids and gases can permeate a membrane. As a noun, permeate can refer to the liquids and gases that have permeated the membrane of a membrane unit.
(121) As used here, “sweep” refers to a gas stream that passes continuously by a membrane, such that the permeate does not sit statically against the permeate side of the membrane but is collected by the gas stream. The sweep can provide the driving force for the separation.
(122) As used here, “reducing,” “reduction,” or “reduction reactions” refers to a chemical reaction where a reactant gains electrons through the gain of a hydrogen atom.
(123) As used here, “oxidizing,” “oxidation,” or “oxidation reactions” refers to a chemical reaction where a reactant loses electrons.
(124) As used here, “stacks” refer to a gas combustion device that gases produced from an SRU pass through before entering the atmosphere.
(125) As used here, a “selective membrane” refers to semi-permeable barriers that allow faster permeance of some compounds over other compounds.
(126) As used here, a “final thermal oxidizer” or “TOX” is a thermal oxidizer that a stream passes through before the stream is passed through a waste heat boiler that is connected to the stacks.
(127) The term “about” as used in connection with a numerical value throughout the specification and the claims denotes an interval of accuracy, familiar and acceptable to a person skilled in the art. Such interval of accuracy is, for example, ±10%.
EXAMPLES
Example 1. Reference SRU Process
(128) The following example illustrates the reference SRU process as depicted in
(129) To assess the sulfur recovery rate of the SRU, the following equation is used: % Sulfur recovery=(mole rate liquid sulfur produced/mole rate of sulfur in Acid Gas feed). The acid gas fed to the SRU is 10.0 MMSCFD (˜1098 lbmol/hr) containing 76.23% (mol) H.sub.2S. Table 1-3 provides the molar rate and elemental sulfur content of the condensed liquid sulfur streams.
% Sulfur recovery=(570.9*0.9995+129*0.9998+95.2*1.0+25.3*1.0)/(1098.0*0.7623)=97.98%
(130) TABLE-US-00001 TABLE 1-1 Acid Gas to to CD-1 to To to Stream Name Feed FR HE-1 CD-1 out CV-1 CD-2 DH-1 Vapour/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temperature [F.] 131 2312 800 620 355 605 470 324 Pressure [psig] 9.0 6.6 5.6 5.6 5.1 4.7 2.4 1.9 Molar Flow 10.0 28.5 26.7 26.6 25.8 25.8 25.8 25.7 [MMSCFD] Mol Fraction Nitrogen 0.0000 0.4728 0.5042 0.5069 0.5214 0.5213 0.5354 0.5379 CO.sub.2 0.1304 0.0377 0.0403 0.0405 0.0416 0.0416 0.0471 0.0473 H.sub.2S 0.7623 0.0493 0.0526 0.0529 0.0543 0.0543 0.0076 0.0076 COS 0.0000 0.0030 0.0032 0.0032 0.0033 0.0033 0.0000 0.0000 SO.sub.2 0.0000 0.0265 0.0282 0.0284 0.0292 0.0292 0.0039 0.0039 CS.sub.2 0.0000 0.0003 0.0003 0.0003 0.0003 0.0003 0.0000 0.0000 H.sub.2O 0.0980 0.2792 0.2978 0.2993 0.3079 0.3079 0.3597 0.3614 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0934 0.0048 0.0003 0.0000 0.0001 0.0000 0.0000 S3_Vapor 0.0000 0.0005 0.0008 0.0001 0.0000 0.0000 0.0000 0.0000 S4_Vapor 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0000 0.0015 0.0006 0.0000 0.0000 0.0001 0.0000 S6_Vapor 0.0000 0.0000 0.0110 0.0083 0.0002 0.0004 0.0013 0.0001 S7_Vapor 0.0000 0.0000 0.0077 0.0063 0.0001 0.0002 0.0008 0.0000 S8_Vapor 0.0000 0.0000 0.0074 0.0130 0.0006 0.0003 0.0029 0.0003 Other gases** 0.0094 0.0372 0.0397 0.0399 0.0411 0.0411 0.0413 0.0414 To to to to to to to to Stream Name CV-2 CD-3 DH-2 CV-3 CD-4 DH-3 Hy HE-2 Vapour/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temperature [F.] 410 470 324 390 401 265 1203 230 Pressure [psig] 3.5 2.4 1.9 1.4 1.4 1.2 1.2 1.2 Molar Flow 26.0 25.8 25.7 26.1 26.1 26.1 39.0 39.0 [MMSCFD] Mol Fraction Nitrogen 0.5319 0.5354 0.4432 0.4472 0.4476 0.4480 0.4554 0.4561 CO.sub.2 0.0467 0.0471 0.2130 0.2108 0.2110 0.2112 0.2071 0.2173 H.sub.2S 0.0294 0.0076 0.0059 0.0058 0.0028 0.0028 0.0027 0.0049 COS 0.0001 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 SO.sub.2 0.0149 0.0039 0.0031 0.0030 0.0015 0.0015 0.0015 0.0000 CS.sub.2 0.0000 0.0000 0.0001 0.0001 0.0001 0.0001 0.0001 0.0000 H.sub.2O 0.3355 0.3597 0.3022 0.3009 0.3042 0.3045 0.3020 0.2956 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S3_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S6_Vapor 0.0001 0.0013 0.0001 0.0001 0.0003 0.0000 0.0000 0.0000 S7_Vapor 0.0001 0.0008 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 S8_Vapor 0.0003 0.0029 0.0003 0.0003 0.0006 0.0001 0.0000 0.0000 Other gases** 0.0410 0.0413 0.0322 0.0318 0.0318 0.0318 0.0310 0.0261 **Other gases: hydrocarbons, argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(131) TABLE-US-00002 TABLE 1-2 Air to FG to Stream Name Air Air-1 Air-2 TOX FG-1 FG-2 TOX Vapour/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temperature [F.] 120 120 120 120 100 100 100 Pressure [psig] 9 9 9 9 50 50 50 Molar Flow 18.4 0.473 0.41 12.54 0.06 0.06 0.06 [MMSCFD] Mol Fraction Argon 0.0088 0.0088 0.0088 0.0088 Oxygen 0.1964 0.1964 0.1964 0.1964 Nitrogen 0.732 0.732 0.732 0.732 0.03 0.03 0.03 CO.sub.2 0.0003 0.0003 0.0003 0.0003 0.02 0.02 0.02 H.sub.2O 0.0626 0.0626 0.0626 0.0626 Hydrogen 0.07 0.07 0.07 Methane 0.76 0.76 0.76 Ethane 0.07 0.07 0.07 Propane 0.05 0.05 0.05
(132) TABLE-US-00003 TABLE 1-3 Stream Name S1 S2 S3 S4 Vapour/Phase 0 0 0 0 Fraction Temperature [F.] 355 332 324 265 Pressure [psig] 5.1 3.5 1.9 1.2 Molar Flow 570.9 129 95.2 25.3 [lbmol/hr] Mol Fraction H.sub.2S 0.0005 0.0002 0.0000 0.0000 S_Liquid 0.9995 0.9998 1.0000 1.0000
Example 2. SSMTGT H.SUB.2.S Route
(133) This example illustrates the integration of the SSMTGT with SRU according to
(134) Table 2-1 through Table 2-3 provide the material balance around the SRU and TOX. The details of the fuel gas and air required by the process are detailed in Table 2-2. The recovered liquid sulfur is detailed in Table 2-3. On the other hand, Table 2-4 provides the material balance of the SSMTGT.
(135) Table 2-5 provides the performance of the 1.sup.st stage (e.g. Facilitated Transport Membrane (FTM)) and the second stage pressure driven H.sub.2S-selective membrane. Table 2-6 provides the membrane units size and compression power. The first stage of the membrane process is swept with about 47 MMSCFD of steam at 245° F., from which about 43.4 MMSCFD is recovered as liquid water from its permeate stream (P1). As a result, the H.sub.2S in the remaining gas is concentrated from about (0.0031) in (P1) to about (0.0234) in the feed to the 2.sup.nd stage H.sub.2S-selective membrane unit.
(136) The sulfur recovery of the overall SRU+SSMTGT is:
% SRU recovery=(547.5*0.9997+164.1*0.9998+99.2*1.0+25.8*1.0)/(1098*0.7623)*100=99.91%
(137) TABLE-US-00004 TABLE 2-1 Acid Gas Acid Gas To To CD-1 To To To To To Stream Name Feed Recycled FR HE-1 CD-1 out CV-1 CD-2 DH-1 CV-2 CD-3 Vapor/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temp [F.] 131 140 1949 800 620 355 593 663 332 410 457 Pressure 9.0 15.0 6.6 5.6 5.6 5.1 4.7 4 3.5 3.5 2.4 [psig] Molar Flow 10.0 6.0 34.9 33.2 33.1 32.4 32.4 32.1 31.9 32.6 32.4 [MMSCFD] Mol Fraction Nitrogen 0.0000 0.0015 0.3964 0.4165 0.4184 0.4277 0.4276 0.431 0.4341 0.4391 0.4415 CO.sub.2 0.1304 0.9473 0.1936 0.2035 0.2044 0.2089 0.2089 0.2121 0.2136 0.211 0.2122 H.sub.2S 0.7623 0.0268 0.0467 0.0491 0.0493 0.0503 0.0503 0.0243 0.0245 0.024 0.0058 COS 0.0000 0.0000 0.0003 0.0003 0.0003 0.0003 0.0003 0.0001 0.0001 0.0001 0.0001 SO.sub.2 0.0000 0.0000 0.0248 0.026 0.0261 0.0267 0.0267 0.0123 0.0124 0.0121 0.0031 CS.sub.2 0.0000 0.0000 0.0013 0.0013 0.0013 0.0014 0.0014 0.0001 0.0001 0.0001 0.0001 H.sub.2O 0.098 0.0238 0.2335 0.2454 0.2465 0.2519 0.2519 0.2803 0.2823 0.2812 0.301 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0000 0.0734 0.0045 0.0003 0.0000 0.0001 0.0005 0.0000 0.0000 0.0000 S3_Vapor 0.0000 0.0000 0.0006 0.0007 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0000 0.0000 0.0012 0.0005 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 S6_Vapor 0.0000 0.0000 0.0000 0.0088 0.0068 0.0002 0.0004 0.0028 0.0001 0.0001 0.0011 S7_Vapor 0.0000 0.0000 0.0000 0.0059 0.0049 0.0001 0.0002 0.0017 0.0000 0.0001 0.0006 S8_Vapor 0.0000 0.0000 0.0000 0.0055 0.0098 0.0006 0.0003 0.0023 0.0004 0.0003 0.0025 Other gases** 0.0094 0.0006 0.0296 0.0311 0.0312 0.0319 0.0319 0.0321 0.0324 0.0319 0.032 to to to to to to to To To Stream Name DH-2 CV-3 CD-4 DH-3 to Hy HE-2 SSMTGT TOX WHB-2 Stck Vapour/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temperature 324 390 398 265 390 428 230 240 1206 230 [F.] Pressure 1.9 1.4 1.4 1.2 1.2 1.2 1.2 1.0 0 0 [psig] Molar Flow 32.3 32.9 32.8 32.8 34 33.9 33.9 26.24 39.85 39.85 [MMSCFD] Mol Fraction Nitrogen 0.4432 0.4472 0.4476 0.448 0.4554 0.4561 0.4561 0.5889 0.627 0.627 CO.sub.2 0.213 0.2108 0.211 0.2112 0.2071 0.2173 0.2173 0.0636 0.062 0.062 H.sub.2S 0.0059 0.0058 0.0028 0.0028 0.0027 0.0049 0.0049 0.0002 0.0000 0.0000 COS 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 SO.sub.2 0.0031 0.003 0.0015 0.0015 0.0015 0.0000 0.0000 0.0000 0.0001 0.0001 CS.sub.2 0.0001 0.0001 0.0001 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2O 0.3022 0.3009 0.3042 0.3045 0.302 0.2956 0.2956 0.3138 0.2746 0.2746 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S3_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S6_Vapor 0.0001 0.0001 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S7_Vapor 0 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S8_Vapor 0.0003 0.0003 0.0006 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 Other gases** 0.0322 0.0318 0.0318 0.0318 0.031 0.0261 0.0261 0.0336 0.0162 0.0162 **Other gases: hydrocarbons, argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(138) TABLE-US-00005 TABLE 2-2 Air to FG to Stream Name Air Air-1 Air-2 Air-3 TOX FG-1 FG-2 FG-3 TOX Vapour/ 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Phase Fraction Temperature 120 120 120 120 120 100 100 100 100 [F.] Pressure 9 9 9 9 9 50 50 50 50 [psig] Molar Flow 18.9 0.63 0.53 1.03 12.98 0.06 0.05 0.1 0.78 [MMSCFD] Mol Fraction Argon 0.0088 0.0088 0.0088 0.0088 0.0088 Oxygen 0.1964 0.1964 0.1964 0.1964 0.1964 Nitrogen 0.732 0.732 0.732 0.732 0.732 0.03 0.03 0.03 0.03 CO2 0.0003 0.0003 0.0003 0.0003 0.0003 0.02 0.02 0.02 0.02 H2O 0.0626 0.0626 0.0626 0.0626 0.0626 Hydrogen 0.07 0.07 0.07 0.07 Methane 0.76 0.76 0.76 0.76 Ethane 0.07 0.07 0.07 0.07 Propane 0.05 0.05 0.05 0.05
(139) TABLE-US-00006 TABLE 2-3 Stream Name S1 S2 S3 S4 Vapour/Phase Fraction 0 0 0 0 Temperature [F.] 355 332 324 265 Pressure [psig] 5.1 3.5 1.9 1.2 Molar Flow [lbmol/hr] 547.5 164.1 99.16 25.78 Mol Fraction H.sub.2S 0.0005 0.0002 0 0 S_Liquid 0.9995 0.9998 1 1
(140) TABLE-US-00007 TABLE 2-4 Rej-1 to Snd Rej-2 1st stg to stg Water 2nd P2 to to To Stream Name fd TOX Swp P1 Comp Recycled Stg Fd SRU TOX TOX Vapour/Phase 1.00 1.00 1.00 1.00 1.00 0.00 1.00 1.00 1.00 1.00 Fraction Temperature 245 245 245 245 140 140 140 140 140 240 [F.] Pressure 30 30 0 0 0 0 125 15 125 30 [psig] Molar Flow 30.6 25.3 47 51.9 8.5 43.4 6.95 6.02 0.93 26.2 [MMSCFD] Mol Fraction Nitrogen 0.506 0.605 0.0000 0.003 0.0183 0.0000 0.0223 0.0015 0.1565 0.5889 CO.sub.2 0.241 0.0349 0.0002 0.1252 0.7647 0.0003 0.9324 0.9473 0.8362 0.0636 H.sub.2S 0.0054 0.0002 0.0000 0.0031 0.0192 0.0000 0.0234 0.0268 0.0014 0.0002 H.sub.2O 0.2187 0.3254 0.9998 0.8685 0.1968 0.9997 0.0206 0.0238 0.0002 0.3138 Other gases* 0.0289 0.0345 0.0000 0.0002 0.001 0.0000 0.0013 0.0006 0.0057 0.0336 *Other gases: include argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(141) TABLE-US-00008 TABLE 2-5 H.sub.2S- FTM selective Membrane Gas Component (Gas/Nitrogen) (Gas/Nitrogen) Nitrogen 1.0 1.0 CO.sub.2 250 44.7 H.sub.2S 500 161 H.sub.2O 2190 323 Other Gases ** 1.0 3.2 Gas Permeance H.sub.2S Permeance (GPU) 500 161 ** Other gases: include argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(142) TABLE-US-00009 TABLE 2-6 1st Stage (FTM) Membrane size (m.sup.2) 19,681 TG-Comp (MW)*** 1.88 2nd Stage H.sub.2S-Selective Membrane size (m.sup.2) 1505 TG-Comp-2 (MW)*** 1.02 ***Polytropic efficiency~77.6%
Example 3. SSMTGT H.SUB.2.S Route
(143) This example constructs comparison with Example 2 to illustrate the impact of using pressure driven membrane in the first stage, replacing the steam swept facilitated transport membrane. As well, the impact of the feed pressure to the first stage on the size of the membrane units and compression power requirement is illustrated. Both membrane stages have performance factors similar to the second stage membrane unit in Example 2, i.e. H.sub.2S-Selective Membrane performance factors shown in Table 2-5. The pressure of the feed and permeate streams of the second stage is maintained similar to that in Example 2, i.e. 125 psig and 15 psig, respectively. Table 3-1 shows the impact of the first stage feed pressure on the overall membrane process size and compression.
(144) TABLE-US-00010 TABLE 3-1 1st Stage 1st 2nd Feed 1st Stage Stage 2nd Stage Stage Pressure feed Size feed Size TG- TG- (psig) (MMSCFD) (m2) (MMSCFD) (m2) Comp-1 Comp-2 30 26.8 175,300 11.9 6,600 1.69 1.61 60 24.9 46,700 8.8 3,700 2.34 1.16 90 23.9 21,500 7.4 2,800 2.76 0.96
(145) It is clear from comparing Table 3-1 and Table 2-6 that the pressure-driven H.sub.2S selective membrane requires higher 1.sup.st stage feed pressure, about 90 psig, to have comparable membrane size to that of the SSMTGT illustrated in Table 2-6, where about 30% more compression is required.
Example 4. SSMTGT H.SUB.2.S Route
(146) As noted in Example 2, the 1.sup.st stage of SSMTGT is swept with about 47.0 MMSCFD of low-pressure steam at (0.0 psig and 245° F.). This steam can be produced by a utility boiler.
Example 5. SSMTGT H.SUB.2.S Route
(147) As noted in Example 2, the 1.sup.st stage of SSMTGT is swept with about 47.0 MMSCFD of low-pressure steam at (0.0 psig and 245° F.). This steam can be produced (fully) by integrating with the SRU WHB and/or condensers and TOX WHB-2.
(148)
(149) TABLE-US-00011 TABLE 5-1 Water to Stream Water Water Steam Name Recycled Make-UP Generation St-1 St-2 St-3 Vapour/ 0.00 0.00 0.00 1.00 1.00 1.00 Phase Fraction Temp. [F.] 140 120 218 715 250 250 Pressure 0 0 500 500 5 5 [psig] Molar Flow 16.3 4.4 5 [MMSCFD] Mass Flow 85,912 11,007 96,919 32,137 8,784 9,965 [lb/hr] Stream Blow Name St-4 St-5 St-6 St-7 Swp Down Vapour/ 1.00 1.00 1.00 1.00 1.00 1.00 Phase Fraction Temp. [F.] 250 250 250 250 250 250 Pressure 5 5 5 500 0 0 [psig] Molar Flow 2 2 4.1 15.2 47.0 2.0 [MMSCFD] Mass Flow 4,025 4,024 8,031 30,082 92,972 3,873 [lb/hr]
(150) TABLE-US-00012 TABLE 5-2 Turbine Power Produced (MW)** T-1 1.84 T-2 1.72 **Polytropic efficiency~72%.
Example-6. SSMTGT H.SUB.2.S Route
(151) In this example, the SSMTGT consists of two stages that are swept with low pressure steam, as illustrated in
(152) Table 6-1 provides the mass balance around the SRU and TOX. Table 6-2 details Air and Fuel Gas streams of the SRU and TOX. Table 6-3 details the liquid sulfur produced in the condensers of the SRU. Table 6-4 material balance around the SSMTGT process. Table 6-5 details steam production integrating with the waste heat boilers and condensers of the SRU and TOX. Table 6-6 performance of FTM and H.sub.2S-selective membranes. Table 6-6 membrane unit size and compression power required by the SSMTGT.
(153) TABLE-US-00013 TABLE 6-1 Acid Stream Gas Acid Gas to to CD-1 to To to To to Name Feed Recycled FR HE-1 CD-1 out CV-1 CD-2 DH-1 CV-2 CD-3 Vapor/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temp [F.] 131 270 1959 800 620 355 592 664 332 410 460 Pressure 9.0 15.0 6.6 5.6 5.6 5.1 4.7 4.0 3.5 3.5 2.4 [psig] Molar Flow 10.0 6.1 35 33.4 33.2 32.5 32.5 32.3 32 32.7 32.5 [MMSCFD] Mol Fraction Nitrogen 0.0000 0.0001 0.3952 0.4148 0.4167 0.4256 0.4256 0.429 0.4322 0.4372 0.4397 CO.sub.2 0.1304 0.775 0.1667 0.175 0.1758 0.1796 0.1796 0.1823 0.1837 0.1817 0.1828 H.sub.2S 0.7623 0.0282 0.049 0.0515 0.0517 0.0527 0.0527 0.0259 0.0261 0.0255 0.0063 COS 0.0000 0.0000 0.0002 0.0002 0.0002 0.0002 0.0002 0.0001 0.0001 0.0001 0.0000 SO.sub.2 0.0000 0.0000 0.0261 0.0274 0.0275 0.0281 0.0281 0.0134 0.0135 0.0132 0.0036 CS.sub.2 0.0000 0.0000 0.0012 0.0012 0.0013 0.0013 0.0013 0.0001 0.0001 0.0001 0.0001 H.sub.2O 0.098 0.1968 0.2591 0.2719 0.2732 0.2791 0.279 0.3085 0.3108 0.3091 0.3303 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0000 0.0716 0.0044 0.0003 0.0000 0.0001 0.0005 0.0000 0.0000 0.0000 S3_Vapor 0.0000 0.0000 0.0006 0.0007 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0000 0.0000 0.0012 0.0005 0.0000 0.0000 0.0003 0.0000 0.0000 0.0001 S6_Vapor 0.0000 0.0000 0.0000 0.0086 0.0066 0.0002 0.0004 0.0029 0.0001 0.0001 0.0011 S7_Vapor 0.0000 0.0000 0.0000 0.0057 0.0048 0.0001 0.0002 0.0017 0.0000 0.0001 0.0007 S8_Vapor 0.0000 0.0000 0.0000 0.0053 0.0095 0.0006 0.0003 0.0024 0.0004 0.0003 0.0026 Other gases** 0.0094 0.0000 0.0303 0.0318 0.0319 0.0326 0.0326 0.0329 0.0331 0.0326 0.0328 Stream to to to to to to to to To Name DH-2 CV-3 CD-4 DH-3 Hy HE-2 SSMTGT TOX WHB-2 To Stck Vapour/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1 1 1 Fraction Temperature 324 390 399 265 390 430 230 245 1200 230 [F.] Pressure 1.9 1.4 1.4 1.2 1.2 1.2 1.2 30 30 30 [psig] Molar Flow 32.4 33.0 32.9 32.9 34.0 34.0 34.0 26.41 39.95 39.95 [MMSCFD] Mol Fraction Nitrogen 0.4415 0.4455 0.4459 0.4464 0.4538 0.4546 0.4546 0.5848 0.6241 0.6241 CO.sub.2 0.1836 0.1819 0.182 0.1822 0.1792 0.1882 0.1882 0.0595 0.0593 0.0593 H.sub.2S 0.0063 0.0062 0.0029 0.0029 0.0028 0.0052 0.0052 0.0003 0.0000 0.0000 COS 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 SO.sub.2 0.0036 0.0035 0.0019 0.0019 0.0018 0.0000 0.0000 0.0000 0.00018 0.00018 CS.sub.2 0.0001 0.0001 0.0001 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2O 0.3317 0.3299 0.3335 0.3339 0.3305 0.326 0.326 0.3221 0.2803 0.2803 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S3_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S6_Vapor 0.0001 0.0001 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S7_Vapor 0 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S8_Vapor 0.0003 0.0003 0.0007 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 Other gases** 0.0329 0.0325 0.0325 0.0326 0.0318 0.0259 0.0259 0.0333 0.0161 0.0161 **Other gases: hydrocarbons, argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(154) TABLE-US-00014 TABLE 6-2 Air to FG to Stream Name Air Air-1 Air-2 Air-3 TOX FG-1 FG-2 FG-3 TOX Vapour/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temperature 120 120 120 120 120 100 100 100 100 [F.] Pressure 9 9 9 9 9 50 50 50 50 [psig] Molar Flow 18.85 0.63 0.53 1.03 12.92 0.06 0.05 0.10 0.77 [MMSCFD] Mol Fraction Argon 0.0088 0.0088 0.0088 0.0088 0.0088 Oxygen 0.1964 0.1964 0.1964 0.1964 0.1964 Nitrogen 0.732 0.732 0.732 0.732 0.732 0.03 0.03 0.03 0.03 CO.sub.2 0.0003 0.0003 0.0003 0.0003 0.0003 0.02 0.02 0.02 0.02 H.sub.2O 0.0626 0.0626 0.0626 0.0626 0.0626 Hydrogen 0.07 0.07 0.07 0.07 Methane 0.76 0.76 0.76 0.76 Ethane 0.07 0.07 0.07 0.07 Propane 0.05 0.05 0.05 0.05
(155) TABLE-US-00015 TABLE 6-3 Stream Name S1 S2 S3 S4 Vapour/Phase Fraction 0.0 0.0 0.0 0.0 Temperature [F.] 355 332 324 265 Pressure [psig] 5.1 3.5 1.9 1.2 Molar Flow 534.6 168.2 105.9 27.82 Mol Fraction H.sub.2S 0.0005 0.0002 0.0000 0.0000 S_Liquid 0.9995 0.9998 1.0000 1.0000
(156) TABLE-US-00016 TABLE 6-4 1 st Rej-1 to 2nd stg Water Stream Name stg fd to TOX Swp P1 Comp Recycled Vapour/Phase 1.00 1.00 1.00 1.00 1.00 0.00 Fraction Temperature 245 245 245 245 140 140 [F.] Pressure [psig] 30 30 0 0 0 0 Molar Flow 37.3 26.4 47 57.4 13.9 43.5 [MMSCFD] Mol Fraction Nitrogen 0.4184 0.5847 0 0.0027 0.0111 0.0000 CO.sub.2 0.3321 0.0598 0 0.1869 0.7731 0.0003 H.sub.2S 0.00703 0.0003 0 0.0045 0.0184 0.0000 H.sub.2O 0.2187 0.3221 1.0000 0.8058 0.1968 0.9997 Other gases* 0.0237 0.0332 0.0000 0.0002 0.0006 0.0000 Water 2nd Stg Utility Rej-2 To Recy to P2 to Stream Name Fd SWP P2 Recycled TOX Utility SRU Vapour/Phase 1.00 1.00 1.00 1.00 1.00 0.00 1.00 Fraction Temperature 245 245 245 245 240 140 270 [F.] Pressure [psig] 30 0 0 30 30 0 15 Molar Flow 13.86 18 22.34 9.37 26.2 16.2 6.1 [MMSCFD] Mol Fraction Nitrogen 0.0111 0.0000 0.0000 0.0163 0.5889 0 0.0001 CO.sub.2 0.7731 0.0000 0.2121 0.64 0.0636 0.0003 0.775 H.sub.2S 0.01841 0.0000 0.00772 0.0089 0.0002 0.0000 0.02818 H.sub.2O 0.1968 1.0000 0.7802 0.3338 0.3138 0.9997 0.1968 Other gases* 0.0006 0.0000 0.0000 0.0009 0.0336 0.0000 0.0000 *Other gases: include argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(157) TABLE-US-00017 TABLE 6-5 FTM Gas Component (Gas/Nitrogen) Nitrogen 1.0 CO.sub.2 250 H.sub.2S 500 H.sub.2O 2190 Other Gases ** 1.0 H.sub.2S Permeance (GPU) 500 ** Other gases: include argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(158) TABLE-US-00018 TABLE 6-6 1st Stage (FTM) Membrane size (m.sup.2) 21,356 TG-Comp (MW)*** 2.155 2nd Stage (FTM) Membrane size (m.sup.2) 2,022 TG-Comp-2 (MW)*** 0.886 ***Polytropic efficiency~77.6%
(159) As noted, the 2.sup.nd stage membrane is swept with steam on the permeate side. For this, the pressure of the feed to the 2.sup.nd stage membrane unit is kept at low pressure (30 psig). The lower pressure ratio is compensated for by sweeping the permeate side with steam. Nevertheless, the H.sub.2S in the stream recycled to feed the SRU (P2 to SRU) is concentrated to a mole fraction of 0.028, which is comparable to the H.sub.2S concentration obtained when a H.sub.2S-selective membrane is deployed where higher feed pressure is needed (up to 125 psig) to achieve the same result as in Example 2.
(160) The sulfur recovery of the overall process SRU+SSMTGT:
% SRU recovery=(534.6*0.9997+168.2*0.9998+105.9*1.0+27.82*1.0)/(1098*0.7623)*100=99.91%
Example 7. SSMTGT H.SUB.2.S Route
(161) This example illustrates the utilization of the SRU to produce part of the sweeping steam required by the SSMTGT, while the utility boiler of the plant is used to complement the sweeping steam requirement not produced by the SRU.
(162) As noted in Example 6, the 1.sup.st stage unit of the SSMTGT is swept with about 47 MMSCFD of low-pressure steam (0 psig, 245° F.). This steam is produced by integrating with the SRU and TOX waste heat boilers and condensers, as illustrated in
(163) Table 7-1 details the steam flow produced by the SRU and TOX waste heat boilers and condensers. Table 7-2 provides the power that can be produced in turbines T-1 and T-2 by expanding the high-pressure steam produced in the SRU and TOX waste heat boilers.
(164) TABLE-US-00019 TABLE 7-1 Water to Water Water Steam Stream Name Recycled Make-UP Generation St-1 St-2 St-3 Vapor/Phase 0.00 0.00 0.00 1.00 1.00 1.00 Fraction Temp. [F.] 140 120 218 715 250 250 Pressure [psig] 0 0 500 500 5 5 Molar Flow 16.4 4.4 5.0 [MMSCFD] Mass Flow 86,170 10,039 96,209 32,440 8,793 9,975 [lb/hr] Stream Name St-4 St-5 St-6 St-7 Swp Blow Down Vapor/Phase 1.00 1.00 1.00 1.00 1.00 1.00 Fraction Temp. [F.] 250 250 250 250 245 245 Pressure [psig] 5 5 5 500 0 0 Molar Flow 2.0 2.0 4.0 14.7 47.0 1.6 [MMSCFD] Mass Flow 4,021 4,017 7,869 29,094 92,973 3,180 [lb/hr]
(165) TABLE-US-00020 TABLE 7-2 Turbine Power Produced (MW)** T-1 1.84 T-2 1.72 **Polytropic efficiency~72%
Example 8. SSMTGT SO.SUB.2 .Route
(166) This example illustrates the integration of the SSMTGT with SRU according to
(167) Table 8-1 provides the mass balance around the SRU. Table 8-2 details Air and Fuel Gas streams of the SRU and TOX. Table 8-3 details the liquid sulfur produced in the condensers of the SRU. Table 8-4 shows material balance around the SSMTGT process. Table 8-5 shows integrated steam production in SRU waste heat boiler and condensers. Table 8-6 shows performance of SO.sub.2-selective membrane. Table 8-7 shows membrane unit size and compression power required by the SSMTGT.
(168) TABLE-US-00021 TABLE 8-1 Acid Gas Acid Gas to to CD-1 to To to Stream Name Feed Recycled FR HE-1 CD-1 out CV-1 CD-2 DH-1 Vapor/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temp [F.] 131 339 2062 800 620 355 595 679 332 Pressure 9.0 12.0 6.6 5.6 5.6 5.1 4.7 4.0 3.5 [psig] Molar Flow 10 4.2 31.9 30.3 30.1 29.5 29.5 29.2 29 [MMSCFD] Mol Fraction Nitrogen 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 CO.sub.2 0.0000 0.0079 0.4075 0.4290 0.4310 0.4408 0.4408 0.4446 0.4482 H.sub.2S 0.1304 0.0742 0.0466 0.0491 0.0493 0.0504 0.0504 0.0543 0.0547 COS 0.7623 0.0000 0.0567 0.0597 0.0600 0.0613 0.0613 0.0346 0.0348 SO.sub.2 0.0000 0.0000 0.0016 0.0017 0.0017 0.0018 0.0018 0.0001 0.0001 CS.sub.2 0.0000 0.0478 0.0307 0.0323 0.0325 0.0332 0.0332 0.0173 0.0175 H.sub.2O 0.0000 0.0000 0.0016 0.0017 0.0017 0.0018 0.0018 0.0001 0.0001 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0000 0.0757 0.0045 0.0003 0.0000 0.0001 0.0006 0.0000 S3_Vapor 0.0000 0.0000 0.0005 0.0007 0.0001 0.0000 0.0000 0.0001 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0000 0.0000 0.0013 0.0005 0.0000 0.0000 0.0004 0.0000 S6_Vapor 0.0000 0.0000 0.0000 0.0090 0.0069 0.0002 0.0004 0.0031 0.0001 S7_Vapor 0.0000 0.0000 0.0000 0.0061 0.0051 0.0001 0.0002 0.0019 0.0000 S8_Vapor 0.0000 0.0000 0.0000 0.0057 0.0101 0.0006 0.0003 0.0024 0.0004 Other gases** 0.0094 0.0027 0.0290 0.0306 0.0307 0.0314 0.0314 0.0317 0.0319 Acid Gas from To to to to to To to to Water Stream Name CV-2 CD-3 DH-2 CV-3 CD-4 COX HE-2 SSMTGT Treatment Vapor/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temp [F.] 410 477 324 390 404 265 743 230 180 Pressure [psig] 3.5 2.4 1.9 1.4 1.4 1.2 0.7 0.7 0 Molar Flow 29.6 29.4 29.2 29.7 29.7 29.6 38.4 38.4 0.03 [MMSCFD] Mol Fraction Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0200 0.0200 0.0000 CO.sub.2 0.4527 0.4560 0.4584 0.4620 0.4627 0.4634 0.5188 0.5188 0.0000 H.sub.2S 0.0554 0.0559 0.0562 0.0567 0.0568 0.0569 0.0535 0.0535 0.0000 COS 0.0341 0.0093 0.0094 0.0092 0.0041 0.0041 0.0000 0.0000 0.0000 SO.sub.2 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.4893 CS.sub.2 0.0171 0.0047 0.0047 0.0046 0.0021 0.0021 0.0053 0.0053 0.0000 H.sub.2O 0.0001 0.0001 0.0001 0.0001 0.0001 0.0001 0.0000 0.0000 0.5017 S1_Vapor 0.0000 0.0000 0.4389 0.4354 0.4411 0.4418 0.3745 0.3745 0.0000 S2_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S3_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S6_Vapor 0.0001 0.0014 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S7_Vapor 0.0001 0.0009 0.0001 0.0001 0.0004 0.0000 0.0000 0.0000 0.0000 S8_Vapor 0.0003 0.0032 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 Other gases** 0.0315 0.0317 0.0318 0.0315 0.0315 0.0316 0.0279 0.0279 0.0000 **Other gases: hydrocarbons, argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(169) TABLE-US-00022 TABLE 8-2 Air-3 Stream Name Air Air-1 Air-2 (COX Heater) FG-1 FG-2 FG COX Vapor/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temperature 120 120 120 120 100 100 100 [F.] Pressure [psig] 9 9 9 9 50 50 50 Molar Flow 17.7 0.55 0.47 8.44 0.054 0.046 0.354 [MMSCFD] Mol Fraction Argon 0.0088 0.0088 0.0088 0.0088 Oxygen 0.1964 0.1964 0.1964 0.1964 Nitrogen 0.7320 0.7320 0.7320 0.7320 0.03 0.03 0.03 CO.sub.2 0.0003 0.0003 0.0003 0.0003 0.02 0.02 0.02 H.sub.2O 0.0626 0.0626 0.0626 0.0626 Hydrogen 0.07 0.07 0.07 Methane 0.76 0.76 0.76 Ethane 0.07 0.07 0.07 Propane 0.05 0.05 0.05
(170) TABLE-US-00023 TABLE 8-3 Stream Name S1 S2 S3 S4 Vapor/Phase Fraction 0.0 0.0 0.0 0.0 Temperature [F.] 355 332 324 265 Pressure [psig] 5.1 3.5 1.9 1.2 Molar Flow [lbmol/hr] 515.4 164.4 122.9 33.79 Mol Fraction H.sub.2S 0.0006 0.0002 0.0001 0.0000 S_Liquid 0.9994 0.9998 0.9999 1.0000
(171) TABLE-US-00024 TABLE 8-4 1 st Rej-1 to Recycle Water to Stream Name stg fd Stck Swp P1 to FR Treatment Vapor/Phase 1.0 1.0 1 1 1.0 0.0 Fraction Temperature 245 245 245 245 339 205 [F.] Pressure [psig] 30 30 0 0 12 0 Molar Flow 38.2 34.7 37 40.5 4.1 36.4 [MMSCFD] Volumetric 4939 Flow (Barrel/day) Mol Fraction Nitrogen 0.5210 0.5726 0.0000 0.0008 0.0080 0.0000 CO.sub.2 0.0537 0.0496 0.0002 0.0077 0.0745 0.0000 SO.sub.2 0.0054 0.0002 0.0000 0.0049 0.0446 0.0014 H.sub.2O 0.3762 0.3300 0.9998 0.9862 0.8693 0.9986 Other gases* 0.0236 0.0257 0.0000 0.0003 0.0027 0.0000 *Other gases: include argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(172) TABLE-US-00025 TABLE 8-5 Water to Steam Blow Stream Name Generation St-1 St-2 St-3 St-4 St-5 St-6 Swp Down Vapour/Phase 0.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Fraction Temp. [F.] 218 715 250 250 250 250 250 245 245 Pressure [psig] 500 500 5 5 5 5 5 0 0 Molar Flow 15.6 4.08 4.81 2.13 1.92 9.49 37.0 1.01 [MMSCFD] Mass Flow 75,190 30,870 8,070 9,519 4,204 3,798 18,770 73,190 2,000 [lb/hr]
(173) TABLE-US-00026 TABLE 8-6 Membrane Selectivity Gas Component (Gas/Nitrogen) Nitrogen 1.0 CO.sub.2 100 SO.sub.2 3000 H.sub.2O 3000 Other Gases ** 1.0 Membrane Permeance (GPU) SO.sub.2 Permeance (GPU) 1500 ** Other gases: include argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(174) TABLE-US-00027 TABLE 8-7 1.sup.st Stage SO.sub.2-Selective Membrane Unit Membrane size (m.sup.2) 17,375 TG-Comp (MW)*** 2.46 TG-Comp-2*** 0.15 ***Polytropic efficiency~76.4%
(175) TABLE-US-00028 TABLE 8-8 Turbine Power Produced (MW)** T-1 1.77 **Polytropic efficiency~72%
(176) As noted in Table 8-4 that the water precipitated in WKD at about 205° F. to maintain the majority of the SO.sub.2 in the gas stream directed to the FR. However, the SO.sub.2 dissolved in the water will be claimed later in the water treatment unit and recycled back to the FR (as noted in
(177) The sulfur recovery of the overall process SRU+SSMTGT
(178)
Example 9. SSMTGT SO.SUB.2 .Route
(179) This example illustrates the integration of the SSMTGT with SRU according to
(180) Table 9-1 provides the mass balance around the SRU. Table 9-2 details Air and Fuel Gas streams of the SRU and TOX. Table 9-3 details the liquid sulfur produced in the condensers of the SRU. Table 9-4 shows material balance around the SSMTGT process. Table 9-5 shows integrated steam production in SRU waste heat boiler and condensers. Table 9-6 shows membrane unit size and compression power required by the SSMTGT. Table 9-7 shows power produced by expanding high pressure steam produced in WHB of SRU.
(181) TABLE-US-00029 TABLE 9-1 Acid Acid Gas Gas to to CD-1 to To to Stream Name Feed Recycled FR HE-1 CD-1 out CV-1 CD-2 DH-1 Vapor/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temp [F.] 131 339 2062 800 620 355 595 679 332 Pressure [psig] 9.0 12.0 6.6 5.6 5.6 5.1 4.7 4.0 3.5 Molar Flow 10.0 4.2 31.9 30.3 30.1 29.5 29.5 29.2 29.0 [MMSCFD] Mol Fraction Oxygen Nitrogen 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 CO.sub.2 0.0000 0.0001 0.4516 0.4819 0.4844 0.4983 0.4982 0.5021 0.5059 H.sub.2S 0.1304 0.0502 0.0404 0.0431 0.0433 0.0446 0.0446 0.0483 0.0487 COS 0.7623 0.0000 0.0516 0.0550 0.0553 0.0568 0.0568 0.0316 0.0318 SO.sub.2 0.0000 0.0000 0.0026 0.0027 0.0028 0.0028 0.0028 0.0001 0.0001 CS.sub.2 0.0000 0.1781 0.0275 0.0293 0.0295 0.0303 0.0303 0.0157 0.0158 H.sub.2O 0.0000 0.0000 0.0006 0.0006 0.0006 0.0006 0.0006 0.0000 0.0000 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0000 0.0931 0.0048 0.0003 0.0000 0.0001 0.0006 0.0000 S3_Vapor 0.0000 0.0000 0.0005 0.0008 0.0001 0.0000 0.0000 0.0001 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0000 0.0000 0.0015 0.0006 0.0000 0.0000 0.0003 0.0000 S6_Vapor 0.0000 0.0000 0.0000 0.0110 0.0083 0.0002 0.0004 0.0029 0.0001 S7_Vapor 0.0000 0.0000 0.0000 0.0077 0.0063 0.0001 0.0002 0.0018 0.0000 S8_Vapor 0.0000 0.0000 0.0000 0.0074 0.0129 0.0006 0.0003 0.0022 0.0004 Other gases* 0.0094 0.0002 0.0343 0.0366 0.0368 0.0379 0.0379 0.0382 0.0384 Acid Gas from To to to to to To to to Water Stream Name CV-2 CD-3 DH-2 CV-3 CD-4 COX HE-2 SSMTGT Treatment Vapor/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temp [F.] 410 477 324 390 404 265 743 230 180 Pressure [psig] 3.5 2.4 1.9 1.4 1.4 1.2 0.7 0.7 0.0 Molar Flow 29.6 29.4 29.2 29.7 29.7 29.6 38.4 38.4 0.0 [MMSCFD] Mol Fraction Oxygen 0.0000 0.0000 0.0000 0.0000 0.0200 0.0200 0.0000 Nitrogen 0.0000 0.0000 0.5151 0.5177 0.5184 0.5191 0.5610 0.5610 0.0000 CO.sub.2 0.5092 0.5127 0.0501 0.0508 0.0509 0.0509 0.0489 0.0489 0.0000 HS.sub.2 0.0495 0.0499 0.0083 0.0081 0.0037 0.0037 0.0000 0.0000 0.0000 COS 0.0312 0.0082 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 SO.sub.2 0.0001 0.0000 0.0041 0.0040 0.0018 0.0018 0.0047 0.0047 0.4893 CS.sub.2 0.0155 0.0040 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 H.sub.2O 0.0000 0.0000 0.3836 0.3811 0.3860 0.3865 0.3325 0.3325 0.5107 S1_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S2_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S3_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S4_Vapor 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S5_Vapor 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 S6_Vapor 0.0001 0.0013 0.0001 0.0001 0.0003 0.0000 0.0000 0.0000 0.0000 S7_Vapor 0.0001 0.0008 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 S8_Vapor 0.0003 0.0030 0.0003 0.0003 0.0008 0.0001 0.0000 0.0000 0.0000 Other gases* 0.0378 0.0381 0.0383 0.0378 0.0379 0.0379 0.0328 0.0328 0.0000 *Other gases: hydrocarbons, argon (Ar), carbon monoxide (CO), hydrogen (H.sub.2)
(182) TABLE-US-00030 TABLE 9-2 Air-3 (COX FG Stream Name Air Air-1 Air-2 Heater) FG-1 FG-2 COX Vapour/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Fraction Temperature [F.] 120 120 120 120 100 100 100 Pressure [psig] 9 9 9 9 50 50 50 Molar Flow 17.75 0.48 0.41 7.32 0.047 0.04 0.309 [MMSCFD] Mol Fraction Argon 0.0088 0.0088 0.0088 0.0088 Oxygen 0.1964 0.1964 0.1964 0.1964 Nitrogen 0.7320 0.7320 0.7320 0.7320 0.03 0.03 0.03 CO.sub.2 0.0003 0.0003 0.0003 0.0003 0.02 0.02 0.02 H.sub.2O 0.0626 0.0626 0.0626 0.0626 Hydrogen 0.07 0.07 0.07 Methane 0.76 0.76 0.76 Ethane 0.07 0.07 0.07 Propane 0.05 0.05 0.05
(183) TABLE-US-00031 TABLE 9-3 Stream Name S1 S2 S3 S4 Vapor/Phase 0.0 0.0 0.0 0.0 Fraction Temperature [F.] 355 332 324 265 Pressure [psig] 5.1 3.5 1.9 1.2 Molar Flow 575.2 133.7 100.5 26.91 [lbmol/hr] Mol Fraction H.sub.2S 0.0005 0.0002 0.0000 0.0000 S_Liquid 0.9995 0.9998 1.0000 1.0000
(184) TABLE-US-00032 TABLE 9-4 Water Rej-1 2nd Rej-2 P2 to to Stream Name 1st stg fd to Stek Swp-1 P1 StgFd Recycled Swp-2 P2 FR Treatment Vapour/Phase 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.0 1.0 0.0 Fraction Temperature 245 245 245 245 245 245 245 205 200 207 [F.] Pressure [psig] 30 30 0 0 30 30 0 0 12 0 Molar Flow 34.2 33.1 33 34.3 1.4 0.557 3.5 3.8 0.86 35.92 [MMSCFD] Volumetric Flow 4867 (Barrel/day) Mol Fraction Nitrogen 0.5568 0.5749 0.0000 0.0011 0.0267 0.0656 0.0000 0.0000 0.0001 0.0000 CO.sub.2 0.0569 0.0493 0.0002 0.0098 0.2438 0.5188 0.0002 0.0119 0.0526 0.0000 SO.sub.2 0.0048 0.0002 0.0000 0.0047 0.1072 0.0043 0.0000 0.0380 0.1633 0.0006 H.sub.2O 0.3357 0.3287 0.9998 0.9840 0.6101 0.3815 0.9998 0.9500 0.7838 0.9994 Other gases* 0.0458 0.0469 0.0000 0.0005 0.0122 0.0298 0.0000 0.0001 0.0002 0.0000 *Other gases: include argon (Ar), carbon monoxice (CO), hydrogen (H.sub.2), oxygen (O.sub.2)
(185) TABLE-US-00033 TABLE 9-5 Water to Steam Blow Stream Name Generation St-1 St-2 St-3 St-4 St-5 St-6 Swp Swp-1 Swp-2 Down Vapour/Phase 0.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Fraction Temp. [F.] 224 715 250 250 250 250 250 245 245 245 245 Pressure [psig] 500 500 5 5 5 5 5 0 0 0 0 Molar Flow 17.0 3.6 4.3 1.8 1.7 8.2 36.66 33.0 3.0 0.66 [MMSCFD] Mass Flow 72,619 33,648 7,174 8,474 3,598 3,321 16,235 72,449 65,279 5,934 2,000 [lb/hr]
(186) TABLE-US-00034 TABLE 9-6 1st Stage SO.sub.2-Selective Membrane Unit Membrane size (m.sup.2) 16,428 TG-Comp (MW)*** 2.17 2nd Stage SO.sub.2-Selective Membrane Unit Membrane size (m.sup.2) 316 TG-Comp-2*** 0.27 TG-Comp-3 *** 0.032 ***Polytropic efficiency~76.4%
(187) TABLE-US-00035 TABLE 9-7 Turbine Power Produced (MW)** T-1 1.93 **Polytropic efficiency~72%
% SRU recovery=(575.2*0.9995+133.7*0.9998+100.5*1.0+26.91*1.0)/(1098*0.7623)*100=99.90%
(188) A number of implementations have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the disclosure.