Claims
- 1. A process for removing sulphur-containing compounds from a residual gas issued from a CLAUS sulphur plant with recovery of said compounds in the form of sulphur, which comprises:
- a) subjecting the residual gas to a combined hydrogenation and hydrolysis treatment, thereby converting the sulphur-containing compounds to H.sub.2 S and forming a gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and water vapor,
- b) cooling said gaseous effluent, thereby condensing the water vapor contained therein and producing water-lean gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and less than 10% by volume of water vapor,
- c) feeding essentially all of said water-lean gaseous effluent and a controlled and limited quantity of an oxidizing gas containing free oxygen to a H.sub.2 S oxidation catalyst and partially oxidizing the H.sub.2 S in said gaseous effluent to sulphur and SO.sub.2, while operating said catalyst at a temperature higher than about 150.degree. C. and producing a gaseous stream containing elemental sulphur, and H.sub.2 S and SO.sub.2 in a H.sub.2 S to SO.sub.2 molar ratio of about 2:1,
- d) maintaining said molar ratio by continuously adjusting the flow-rate of the oxidizing gas,
- e) cooling the whole gaseous stream which contains elemental sulphur resulting from said partial oxidation to a temperature below 160.degree. C. and concurrently removing from the gaseous stream substantially all the sulphur contained therein by condensation,
- f) feeding essentially all of the cooled gaseous stream substantially free of sulphur to a CLAUS catalyst in a converter, contacting said cooled gaseous stream with the CLAUS catalyst, thereby depositing sulphur formed by reaction of the H.sub.2 S with SO.sub.2 on the catalyst, said catalyst operating at a temperature between about 120.degree. C. and 140.degree. C. to retain the sulphur produced, and obtaining a purified residual gas substantially free of sulphur compounds,
- g) exhausting the purified gas,
- h) periodically regenerating the CLAUS catalyst by sweeping the sulphur-laden CLAUS catalyst with a non-oxidizing gas mixture containing a fraction of the residual gas to be treated at a temperature between 200.degree. C. and 500.degree. C., vaporizing the sulphur retained on the catalyst, thereby regenerating said catalyst, and
- i) cooling the regenerated catalyst to the catalyst operating temperature of step f) with an inert gas having a temperature less than about 160.degree. C.
- 2. The process of claim 1 wherein the water-lean gaseous effluent of step b) is heated prior to being fed to the oxidation catalyst in step c).
- 3. The process of claim 2 wherein the heating of said gas is performed by indirect heat exchange with the gaseous effluent of step a).
- 4. The process of claim 1 wherein the regenerating gas is laden with water vapor.
- 5. The process of claim 1 wherein the cooling gas for the regenerated catalyst is an inert gas selected from the group consisting of methane, nitrogen, CO.sub.2 or a mixture thereof.
- 6. The process of claim 1 wherein the cooling gas in step i) contains water vapor.
- 7. The process of claim 6 wherein the content of water in the cooling gas is from 1 to 50% by volume.
- 8. The process of claim 1 in which steps a) through g) are being repeated while steps h) and i) also are being repeated.
- 9. The process of claim 1, wherein the H.sub.2 S oxidation catalyst comprises at least one compound of a metal selected from the group consisting of Fe, Ni, Co, Cu and Zn in contact with a support consisting of at least one member selected from the group consisting of alumina and silica.
- 10. The process of claim 1, wherein the H.sub.2 S oxidation catalyst is titanium oxide based.
- 11. The process of claim 1, wherein the H.sub.2 S oxidation catalyst comprises at least one compound of a metal selected from the group consisting of Fe, Cu, Cd, Zn, Cr, Mo, W, Co, Ni and Bi in contact with a support consisting of at least one member selected from the group consisting of silica and titanium oxide.
- 12. The process of claim 1, wherein the H.sub.2 S oxidation catalyst comprises at least one compound selected from the group consisting of Fe, Cu, Cd, Zn, Cr. Mo, W, Co, Ni and Bi in contact with a support consisting of active alumina thermally stabilized.
- 13. The process of claim 9, wherein the H.sub.2 S oxidation temperature on the oxidation catalyst is between about 150.degree. C. and 400.RTM. C.
- 14. The process of claim 10, wherein the H.sub.2 S oxidation catalyst is between about 150.degree. C. and 500.degree. C.
- 15. The process of claim 11, wherein the H.sub.2 S oxidation catalyst is between about 150.degree. C. and 700.degree. C.
- 16. The process of claim 12, wherein the H.sub.2 S oxidation catalyst is between about 150.degree. C. and 1000.degree. C.
- 17. The process of claim 1, wherein the CLAUS catalyst comprises at least one member selected from the group consisting of alumina, bauxite , silica and zeolite.
- 18. The process of claim 10, wherein the H.sub.2 S oxidation catalyst comprises a second catalyst surface layer made of a material consisting of at least one compound of a metal selected from the group consisting of Fe, Ni, Co, Cu and Zn in contact with a support consisting of at least one member selected from the group consisting of alumina and silica.
- 19. The process of claim 11, wherein the H.sub.2 S oxidation catalyst comprises a second catalyst surface layer made of a material consisting of at least one compound of a metal selected from the group consisting of Fe, Ni, Co, Cu and Zn in contact with a support consisting of at least one member selected from the group consisting of alumina and silica.
- 20. The process of claim 12, wherein the H.sub.2 S oxidation catalyst comprises a second catalyst surface layer made of a material consisting of at least one compound of a metal selected from the group consisting of Fe, Ni, Co, Cu and Zn in contact with a support consisting of at least one member selected from the group consisting of alumina and silica.
- 21. The process of claim 18, wherein the H.sub.2 S oxidation temperature on the oxidation catalyst is between 150.degree. C. and 400.degree. C.
- 22. The process of claim 19, wherein the H.sub.2 S oxidation temperature on the oxidation catalyst is between 150.degree. C. and 400.degree. C.
- 23. The process of claim 20, wherein the H.sub.2 S oxidation temperature on the oxidation catalyst is between 150.degree. C. and 400.degree. C.
- 24. The process of claim 10, wherein the H.sub.2 S oxidation catalyst comprises titanium oxide with an alkaline-earth metal sulfate.
- 25. The process of claim 24, wherein the H.sub.2 S oxidation catalyst comprises titanium oxide with calcium sulfate.
- 26. The process of claim 11, wherein the supported H.sub.2 S oxidation catalyst further comprises Pd, Pt, Ir or Rh.
- 27. The process of claim 12, wherein the H.sub.2 S oxidation catalyst further comprises Pd, Pt, Ir or Rh.
- 28. The process of claim 12, wherein the active alumina support is stabilized by at least one rare earth oxide.
- 29. The process of claim 1 in which steps a) through g) are being repeated while steps h) and i) also are being repeated.
- 30. A process for removing sulphur-containing compounds from a residual gas issued from a CLAUS sulphur plant with recovery of said compounds in the form of sulphur, in which at least two alternating CLAUS converters are used wherein while CLAUS conversion takes place in at least one converter, regeneration and cooling takes place in one of the other converters, which process comprises:
- a) subjecting the residual gas to a combined hydrogenation and hydrolysis treatment converting the sulphur-containing compounds to H.sub.2 S and forming a gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and water vapor,
- b) cooling said gaseous effluent, thereby condensing the water vapor contained therein and producing water-lean gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and less than 10% by volume of water vapor,
- c) feeding essentially all of said water-lean gaseous effluent and a controlled and limited quantity of an oxidizing gas containing free oxygen to a H.sub.2 S oxidation catalyst and partially oxidizing the H.sub.2 S in said gaseous effluent to sulphur and SO.sub.2, while operating said catalyst at a temperature higher than about 150.degree. C. and producing a gaseous stream containing elemental sulphur, and H.sub.2 S and SO.sub.2 in a H.sub.2 S to SO.sub.2 molar ratio of about 2:1,
- d) maintaining said molar ratio by continuously adjusting the flow-rate of the oxidizing gas,
- e) cooling the whole gaseous stream which contains elemental sulphur resulting from said partial oxidation to a temperature below 160.degree. C. and concurrently removing from the gaseous stream substantially all the sulphur contained therein by condensation,
- f) feeding essentially all of the cooled gaseous stream substantially free of sulphur to a CLAUS catalyst in at least one of the CLAUS converters which is in the conversion mode, contacting said cooled gaseous stream with the CLAUS catalyst, thereby depositing sulphur formed by reaction of H.sub.2 S with SO.sub.2 on the catalyst, said catalyst operating at a temperature between about 120.degree. C. and 140.degree. C. to retain the sulphur produced, and obtaining a purified residual gas substantially free of sulphur compounds,
- g) exhausting the purified gas,
- h) periodically regenerating the sulphur-laden CLAUS catalyst in the CLAUS converter which is in the regeneration mode by sweeping it with a non-oxidizing gas mixture containing a fraction of the residual gas to be treated at a temperature between 200.degree. C. and 500.degree. C., vaporizing the sulphur retained on the catalyst, and thereby regenerating said catalyst, and
- i) cooling the regenerated catalyst to the catalyst operating temperature of step f) with the same gas which is used to regenerate the CLAUS catalyst and having a temperature less than about 160.degree. C., and wherein the conversion on one hand, and the regeneration and cooling on the other hand, in the respective CLAUS converters takes place alternatingly downstream of the partial oxidation referred to in step c).
- 31. The process of claim 30, wherein the CLAUS catalyst comprises a material consisting of at least one compound of a metal selected from the group consisting of Fe, Ni, Co, Cu and Zn in contact with a support comprising a material selected from the group consisting of silica and alumina.
- 32. A process for removing sulphur-containing compounds from a residual gas issued from a CLAUS sulphur plant with recovery of said compounds in the form of sulphur, which comprises:
- a) subjecting the residual gas to a combined hydrogenation and hydrolysis treatment, thereby converting the sulphur-containing compounds to H.sub.2 S and forming a gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and water vapor,
- b) cooling said gaseous effluent, thereby condensing the water vapor contained therein and producing water-lean gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and less than 10% by volume of water vapor,
- c) feeding essentially all of said water-lean gaseous effluent and a controlled and limited quantity of an oxidizing gas containing free oxygen to a H.sub.2 S oxidation catalyst and partially oxidizing the H.sub.2 S in said gaseous effluent to sulphur and SO.sub.2, while operating said catalyst at a temperature higher than about 150.degree. C. and producing a gaseous stream containing elemental sulphur, and H.sub.2 S and SO.sub.2 in a H.sub.2 S to SO.sub.2 molar ratio of about 2:1,
- d) maintaining said molar ratio by continuously adjusting the flow-rate of the oxidizing gas,
- e) cooling the whole gaseous stream which contains elemental sulphur resulting from said partial oxidation to a temperature below 160.degree. C. and concurrently removing from the gaseous stream substantially all the sulphur contained therein by condensation,
- f) feeding essentially all of the cooled gaseous stream substantially free of sulphur to a CLAUS catalyst in a converter, contacting said cooled gaseous stream with the CLAUS catalyst, thereby depositing sulphur formed by reaction of the H.sub.2 S with SO.sub.2 on the catalyst, said catalyst operating at a temperature between about 120.degree. C. and 140.degree. C. to retain the sulphur produced, and obtaining a purified residual gas substantially free of sulphur compounds,
- g) exhausting the purified gas,
- h) periodically regenerating the CLAUS catalyst by sweeping the sulphur-laden CLAUS catalyst with a non-oxidizing gas at a temperature between 200.degree. C. and 500.degree. C., vaporizing the sulphur retained on the catalyst and thereby regenerating said catalyst, and
- i) cooling the regenerated catalyst to the catalyst operating temperature of step f) with an inert gas having a temperature less than about 160.degree. C.
- j) repeating step h), and when the regeneration gas contains essentially no more sulphur from the catalyst, mixing a fraction of the H.sub.2 S-containing residual gas to be treated with the regeneration gas and repeating Step h.
- 33. A process for removing sulphur-containing compounds from a residual gas issued from a CLAUS sulphur plant with recovery of said compounds in the form of sulphur, which comprises:
- a) subjecting the residual gas to a combined hydrogenation and hydrolysis treatment, thereby converting the sulphur-containing compounds to H.sub.2 S and forming a gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and water vapor,
- b) cooling said gaseous effluent, thereby condensing the water vapor contained therein and producing water-lean gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and less than 10% by volume of water vapor,
- c) feeding essentially all of said water-lean gaseous effluent and a controlled and limited quantity of an oxidizing gas containing free oxygen to a H.sub.2 S oxidation catalyst and partially oxidizing the H.sub.2 S in said gaseous effluent to sulphur and SO.sub.2, while operating said catalyst at a temperature higher than about 150.degree. C. and producing a gaseous stream containing elemental sulphur, and H.sub.2 S and SO.sub.2 in a H.sub.2 S to SO.sub.2 molar ratio of about 2:1,
- d) maintaining said molar ratio by continuously adjusting the flow-rate of the oxidizing gas,
- e) cooling the whole gaseous stream which contains elemental sulphur resulting from said partial oxidation to a temperature below 160.degree. C. and concurrently removing from the gaseous stream substantially all the sulphur contained therein by condensation,
- f) feeding essentially all of the cooled gaseous stream substantially free of sulphur to a CLAUS catalyst in a converter, contacting said cooled gaseous stream with the CLAUS catalyst, thereby depositing sulphur formed by reaction of the H.sub.2 S with SO.sub.2 on the catalyst, said catalyst operating at a temperature between about 120.degree. C. and 140.degree. C. to retain the sulphur produced, and obtaining a purified residual gas substantially free of sulphur compounds,
- g) exhausting the purified gas,
- h) periodically regenerating the CLAUS catalyst by sweeping the sulphur-laden CLAUS catalyst with a non-oxidizing gas mixture containing a fraction of the residual gas to be treated at a temperature between 200.degree. C. and 500.degree. C., vaporizing the sulphur retained on the catalyst, thereby regenerating said catalyst, and
- i) cooling the regenerated catalyst to the catalyst operating temperature of step f) with an inert gas having a temperature less than about 160.degree. C.
- 34. The process of claim 33 wherein the water-lean gaseous effluent of step b) is heated prior to being fed to the oxidation catalyst in step c).
- 35. The process of claim 34 wherein the heating of said gas is performed by indirect heat exchange with the gaseous effluent of step a).
- 36. The process of claim 33 wherein the regenerating gas is laden with H.sub.2 S.
- 37. The process of claim 33 wherein the cooling gas for the regenerated catalyst is an inert gas selected from the group consisting of methane, nitrogen, CO.sub.2 or a mixture thereof.
- 38. The process of claim 33 wherein the cooling gas contains a fraction of the residual gas to be treated.
- 39. The process of claim 33 wherein the cooling gas in step i) contains water vapor.
- 40. The process of claim 39 wherein the content of water in the cooling gas is from 1 to 50% by volume.
- 41. The process of claim 33 wherein the regeneration gas after vaporization of the greatest portion of the sulphur deposited on the catalyst, is made to contain a reducing gas selected from the group consisting of H.sub.2, CO and H.sub.2 S.
- 42. The process of claim 41 wherein the concentration of the reducing gas is from 0.5 to 25% by volume of the regeneration gas.
- 43. A process for removing sulphur-containing compounds from a residual gas issued from a CLAUS sulphur plant with recovery of said compounds in the form of sulphur, in which at least two alternating CLAUS converters are used wherein while CLAUS conversion takes place in at least one converter, regeneration and cooling takes place in one of the other converters, which process comprises:
- a) subjecting the residual gas to a combined hydrogenation and hydrolysis treatment converting the sulphur-containing compounds to H.sub.2 S and forming a gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and water vapor,
- b) cooling said gaseous effluent, thereby condensing the water vapor contained therein and producing water-lean gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and less than 10% by volume of water vapor,
- c) feeding essentially all of said water-lean gaseous effluent and a controlled and limited quantity of an oxidizing gas containing free oxygen to a H.sub.2 S oxidation catalyst and partially oxidizing the H.sub.2 S in said gaseous effluent to sulphur and SO.sub.2, while operating said catalyst at a temperature higher than about 150.degree. C. and producing a gaseous stream containing elemental sulphur, and H.sub.2 S and SO.sub.2 in a H.sub.2 S to SO.sub.2 molar ratio of about 2:1,
- d) maintaining said molar ratio by continuously adjusting the flow-rate of the oxidizing gas,
- e) cooling the whole gaseous stream which contains elemental sulphur resulting from said partial oxidation to a temperature below 160.degree. C. and concurrently removing from the gaseous stream substantially all the sulphur contained therein by condensation,
- f) feeding essentially all of the cooled gaseous stream substantially free of sulphur from step e) to a CLAUS catalyst in at least one of the CLAUS converters which is in the conversion mode, contacting said cooled gaseous stream with the CLAUS catalyst, thereby depositing sulphur formed by reaction of H.sub.2 S with SO.sub.2 on the catalyst, said catalyst operating at a temperature between about 120.degree. C. and 140.degree. C. to retain the sulphur produced, and obtaining a purified residual gas substantially free of sulphur compounds,
- g) exhausting the purified gas,
- h) periodically regenerating the sulphur-laden CLAUS catalyst in the CLAUS converter which is in the regeneration mode by sweeping it with a non-oxidizing gas mixture containing a fraction of the purified residual gas at a temperature between about 200.degree. C. and 500.degree. C., vaporizing the sulphur retained on the catalyst, thereby regenerating said catalyst, and
- i) cooling the regenerated catalyst to the catalyst operating temperature of step f) with the same gas which is used to regenerate the CLAUS catalyst and having a temperature less than about 160.degree. C., and wherein the conversion on one hand, and the regeneration and cooling on the other hand, in the respective CLAUS converters takes place alternatingly downstream of the partial oxidation referred to in step c).
- 44. A process for removing sulphur-containing compounds from a residual gas issued from a CLAUS sulphur plant with recovery of said compounds in the form of sulphur, which comprises:
- a) subjecting the residual gas to a combined hydrogenation and hydrolysis treatment, thereby converting the sulphur-containing compounds to H.sub.2 S and forming a gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and water vapor,
- b) cooling said gaseous effluent, thereby condensing the water vapor contained therein and producing water-lean gaseous effluent containing H.sub.2 S essentially as the sole sulphur-containing compound and less than 10% by volume of water vapor,
- c) feeding essentially all of said water-lean gaseous effluent and a controlled and limited quantity of an oxidizing gas containing free oxygen to a H.sub.2 S oxidation catalyst and partially oxidizing the H.sub.2 S in said gaseous effluent to sulphur and SO.sub.2, while operating said catalyst at a temperature higher than about 150.degree. C. and producing a gaseous stream containing elemental sulphur, and H.sub.2 S and SO.sub.2 in a H.sub.2 S to SO.sub.2 molar ratio of about 2:1,
- d) maintaining said molar ratio by continuously adjusting the flow-rate of the oxidizing gas,
- e) cooling the whole gaseous stream which contains elemental sulphur resulting from said partial oxidation to a temperature below 160.degree. C. and concurrently removing from the gaseous stream substantially all the sulphur contained therein by condensation,
- f) feeding essentially all of the cooled gaseous stream substantially free of sulphur to a CLAUS catalyst in a converter, contacting said cooled gaseous stream with the CLAUS catalyst, thereby depositing sulphur formed by reaction of the H.sub.2 S with SO.sub.2 on the catalyst, said catalyst operating at a temperature between about 120.degree. C. and 140.degree. C. to retain the sulphur produced, and obtaining a purified residual gas substantially free of sulphur compounds,
- g) exhausting the purified gas,
- h) periodically regenerating the CLAUS catalyst by sweeping the sulphur-laden CLAUS catalyst with a non-oxidizing gas mixture containing a fraction of the residual gas to be treated at a temperature between 200.degree. C. and 500.degree. C., vaporizing the sulphur retained on the catalyst, thereby regenerating said catalyst, and
- i) cooling the regenerated catalyst to the catalyst operating temperature of step f) with an inert gas having a temperature less than about 160.degree. C., wherein the cooling gas contains a fraction of the residual gas to be treated.
Priority Claims (1)
Number |
Date |
Country |
Kind |
85 15906 |
Oct 1985 |
FRX |
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Parent Case Info
This is a division of application Ser. No. 07/075,749, filed filed as PCT/FR86/00365, Oct. 24, 1986, now U.S. Pat. No. 4,980,146.
US Referenced Citations (5)
Foreign Referenced Citations (1)
Number |
Date |
Country |
1307716 |
Feb 1973 |
GBX |
Non-Patent Literature Citations (2)
Entry |
Lauer et al., Chemical Engineering Techniques, Reinhold Publishing Corp., 1952, pp. 220-222. |
Olsen, Unit Processes and Principles of Chemical Engineering, Van Nostrand Co., Inc., 1932, pp. 1-3. |
Divisions (1)
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Number |
Date |
Country |
Parent |
75749 |
Jun 1987 |
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