Method and device for separating hydrogen sulfide and hydrogen production system using the same

• US 9,365,423 B2
• Filed: 10/29/2012
• Issued: 06/14/2016
• Est. Priority Date: 12/08/2011
• Status: Expired due to Fees

• Current Assignee: Kawasaki Jukogyo Kabushiki Kaisha (Kawasaki Heavy Industries Limited)
• Original Assignee: Kawasaki Jukogyo Kabushiki Kaisha (Kawasaki Heavy Industries Limited)
• Inventors: Nakamoto, Takashi, Muraoka, Toshinori, Kumada, Norihiko, Okajima, Shigenobu, Hirokawa, Masatoshi, Shoji, Takatoshi
• Primary Examiner(s): LAWRENCE JR, FRANK M
• Application Number:
  US14/363,423
• Publication Number:
  US 20140360368A1
• Time in Patent Office: 1,324 Days
• Field of Search: 961/21, 961/26, 961/31, 961/32, 961/53, 951/36, 951/39, 423/230
• US Class Current: 1/1
• CPC Class Codes: B01D 2252/20431 Tertiary amines
• CPC Class Codes: B01D 2253/20 Organic adsorbents
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/0462 Temperature swing adsorption
• CPC Class Codes: B01D 53/52 Hydrogen sulfide
• CPC Class Codes: B01D 53/82 with stationary reactants
• CPC Class Codes: B01J 2219/00 Chemical, physical or physico-chemical processes in general; Their relevant apparatus
• CPC Class Codes: C01B 17/167 Separation
• CPC Class Codes: C01B 2203/043 Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0485 the impurity being a sulfur compound
• CPC Class Codes: C01B 2203/146 At least two purification steps in series
• CPC Class Codes: C01B 2203/147 Three or more purification steps in series
• CPC Class Codes: C01B 3/508 by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions the appropriate mediums per se C01B3/0005
• CPC Class Codes: C01B 3/56 by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: C01B 32/50 Carbon dioxide
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

The system includes adsorbent-packed towers 11 and 21 filled with H₂S adsorbent which triethanolamine is supported by activated carbon. Mixed gas derived from a synthesis gas containing CO₂ and H₂S at about 40° C. is supplied to the adsorbent-packed towers 11 and 21 through a line. Valves 12 and 13 are opened, valves 22 and 23 are closed, valves 14 and 15 are closed, and valves 24 and 25 are opened to perform adsorption of H₂S contained in the gas to be treated in the adsorbent-packed tower 11 in a dry state and to perform desorption of H₂S in the adsorbent-packed tower 21. When adsorption of H₂S contained in the gas to be treated is performed in the adsorbent-packed tower 21 and desorption of H₂S is performed in the adsorbent-packed tower 11, the valves 12, 13, 24, and 25 are closed and the valves 22, 23, 14, and 15 are opened.

Claims

1. A system for producing hydrogen from a raw material gas that is a gas to be treated containing hydrogen sulfide, carbon dioxide, and hydrogen, the system comprising:

a hydrogen sulfide separation device

a carbon dioxide separation device that is provided downstream of the hydrogen sulfide separation device to separate carbon dioxide from a gas obtained by removing hydrogen sulfide from the raw material gas; and

a hydrogen purification device that is provided downstream of the carbon dioxide separation device to separate hydrogen from a gas obtained by removing hydrogen sulfide and carbon dioxide from the raw material gas;

wherein the hydrogen sulfide separation device is a device for selectively separating hydrogen sulfide from a gas to be treated containing hydrogen sulfide and carbon dioxide using a hydrogen sulfide adsorbent in which an amine compound is supported by a porous material, the device comprising;

an adsorbent-packed tower filled with the hydrogen sulfide adsorbent;

means for supplying the gas to be treated to the adsorbent-packed tower to bring the hydrogen sulfide adsorbent and the gas to be treated into contact with each other; and

means for supplying a heated gas flow for desorbing hydrogen sulfide from the hydrogen sulfide adsorbent after adsorption of hydrogen sulfide to the adsorbent-packed tower,

wherein the amine compound is a tertiary amine, and the contact between the hydrogen sulfide adsorbent and the gas to be treated in the adsorbent-packed tower is made in a dry state.

3. The hydrogen production system according to claim 1, wherein the hydrogen sulfide separation device and the carbon dioxide separation device are provided on a high-pressure gas treatment line.

9. The hydrogen production system according to claim 1, wherein the carbon dioxide separation device separates carbon dioxide using a carbon dioxide adsorbent in which an amine compound is supported by a porous material.

11. The hydrogen production system according to claim 1, wherein combustible off-gas after separation of hydrogen by the hydrogen purification device is used to generate a heated gas flow for desorbing hydrogen sulfide from the hydrogen sulfide adsorbent in the hydrogen sulfide separation device.

13. The hydrogen production system according to claim 9, wherein combustible off-gas after separation of hydrogen by the hydrogen purification device is used to generate a heated gas flow for desorbing carbon dioxide from the carbon dioxide adsorbent in the carbon dioxide separation device.

17. The hydrogen production system according to claim 1, wherein the tertiary amine is a tertiary alkanolamine.

2. A system for producing hydrogen from a raw material gas that is a gas to be treated containing hydrogen sulfide, carbon dioxide, and hydrogen, the system comprising:

a hydrogen sulfide separation device

a carbon dioxide separation device that is provided downstream of the hydrogen sulfide separation device to separate carbon dioxide from a gas obtained by removing hydrogen sulfide from the raw material gas; and

a hydrogen purification device that is provided downstream of the carbon dioxide separation device to separate hydrogen from a gas obtained by removing hydrogen sulfide and carbon dioxide from the raw material gas;

wherein the hydrogen sulfide separation device is a device for selectively separating hydrogen sulfide from a gas to be treated containing hydrogen sulfide and carbon dioxide using a hydrogen sulfide adsorbent in which an amine compound is supported by a porous material, the device comprising;

a plurality of adsorbent-packed towers filled with the hydrogen sulfide adsorbent;

a plurality of means for supplying the gas to be treated to the adsorbent-packed towers, respectively, to bring the hydrogen sulfide adsorbent and the gas to be treated into contact with each other; and

a plurality of means for supplying a heated gas flow for desorbing hydrogen sulfide from the hydrogen sulfide adsorbent after adsorption of hydrogen sulfide to the adsorbent-packed towers, respectively,

wherein the amine compound is a tertiary amine, and the contact between the hydrogen sulfide adsorbent and the gas to be treated in each of the adsorbent-packed towers is made in a dry state, and

wherein the gas to be treated is supplied from the gas supplying means to one or more of the adsorbent-packed towers, respectively, to selectively adsorb hydrogen sulfide, and the heated gas flow is supplied from the heated gas flow supplying means to another of the adsorbent-packed towers or one or more of the other adsorbent-packed towers, respectively, to desorb hydrogen sulfide.

4. The hydrogen production system according to claim 2, wherein the hydrogen sulfide separation device and the carbon dioxide separation device are provided on a high-pressure gas treatment line.

10. The hydrogen production system according to claim 2, wherein the carbon dioxide separation device separates carbon dioxide using a carbon dioxide adsorbent in which an amine compound is supported by a porous material.

12. The hydrogen production system according to claim 2, wherein combustible off-gas after separation of hydrogen by the hydrogen purification device is used to generate a heated gas flow for desorbing hydrogen sulfide from the hydrogen sulfide adsorbent in the hydrogen sulfide separation device.

14. The hydrogen production system according to claim 10, wherein combustible off-gas after separation of hydrogen by the hydrogen purification device is used to generate a heated gas flow for desorbing carbon dioxide from the carbon dioxide adsorbent in the carbon dioxide separation device.

16. The hydrogen production system according to claim 2, comprising a carbon dioxide recovery device for recovering finally-separated carbon dioxide.

18. The hydrogen production system according to claim 2, wherein the tertiary amine is a tertiary alkanolamine.

5. A system for producing hydrogen from a raw material gas that is a gas to be treated containing hydrogen sulfide, carbon dioxide, and hydrogen, the system comprising:

a carbon dioxide separation device that separates hydrogen sulfide and carbon dioxide from the raw material gas;

a hydrogen purification device that is provided downstream of the carbon dioxide separation device to separate hydrogen from a gas obtained by removing hydrogen sulfide and carbon dioxide from the raw material gas; and

a hydrogen sulfide separation device;

wherein the hydrogen sulfide separating device is a device for selectively separating hydrogen sulfide from a gas to be treated containing hydrogen sulfide and carbon dioxide using a hydrogen sulfide adsorbent in which an amine compound is supported by a porous material, the device comprising;

an adsorbent packed tower filled with the hydrogen sulfide adsorbent;

means for supplying the gas to be treated to the adsorbent packed tower to bring the hydrogen sulfide adsorbent and the gas to be treated into contact with each other; and

means for supplying a heated gas flow for desorbing hydrogen sulfide from the hydrogen sulfide adsorbent after adsorption of hydrogen sulfide to the adsorbent-packed tower,

wherein the amine compound is a tertiary amine, and the contact between the hydrogen sulfide adsorbent and the gas to be treated in the adsorbent-packed tower is made in a dry state.

7. The hydrogen production system according to claim 5, wherein the carbon dioxide separation device is provided on a high-pressure gas treatment line and the hydrogen sulfide separation device is provided on an ordinary-pressure gas treatment line.

15. The hydrogen production system according to claim 7, comprising a carbon dioxide recovery device for recovering finally-separated carbon dioxide.

19. The hydrogen production system according to claim 5, wherein the tertiary amine is a tertiary alkanolamine.

6. A system for producing hydrogen from a raw material gas that is a gas to be treated containing hydrogen sulfide, carbon dioxide, and hydrogen, the system comprising:

a carbon dioxide separation device that separates hydrogen sulfide and carbon dioxide from the raw material gas;

a hydrogen purification device that is provided downstream of the carbon dioxide separation device to separate hydrogen from a gas obtained by removing hydrogen sulfide and carbon dioxide from the raw material gas; and

a hydrogen sulfide separation device;

wherein the hydrogen sulfide separation device is a device for selectively separating hydrogen sulfide from a gas to be treated containing hydrogen sulfide and carbon dioxide using a hydrogen sulfide adsorbent in which an amine compound is supported by porous material, the device comprising;

a plurality of adsorbent-packed towers filled with the hydrogen sulfide adsorbent;

a plurality of means for supplying the gas to be treated to the adsorbent-packed towers, respectively, to bring the hydrogen sulfide adsorbent and the gas to be treated into contact with each other; and

a plurality of means for supplying a heated gas flow for desorbing hydrogen sulfide from the hydrogen sulfide adsorbent after adsorption of hydrogen sulfide to the adsorbent-packed towers, respectively,

wherein the amine compound is a tertiary amine, and the contact between the hydrogen sulfide adsorbent and the gas to be treated in each of the adsorbent-packed towers is made in a dry state, and

wherein the gas to be treated is supplied from the gas supplying means to one or more of the adsorbent-packed towers, respectively, to selectively adsorb hydrogen sulfide, and the heated gas flow is supplied from the heated gas flow supplying means to another of the adsorbent-packed towers or one or more of the other adsorbent-packed towers, respectively, to desorb hydrogen sulfide.

8. The hydrogen production system according to claim 6, wherein the carbon dioxide separation device is provided on a high-pressure gas treatment line and the hydrogen sulfide separation device is provided on an ordinary-pressure gas treatment line.

20. The hydrogen production system according to claim 6, wherein the tertiary amine is a tertiary alkanolamine.