Process For The Production Of Hydrogen And Carbon Dioxide Utilizing Dry Magnesium Based Sorbents In A Fixed Bed

• US 20130011325A1
• Filed: 07/05/2011
• Published: 01/10/2013
• Est. Priority Date: 07/05/2011
• Status: Abandoned Application

• Current Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Original Assignee: L'Air Liquide Societe Anonyme Pour L'Etude et L'Exploitation Des Procedes Georges Claude (L'Air Liquide SA)
• Inventors: Grover, Bhadra S.
• Application Number:
  US13/176,566
• Publication Number:
  US 20130011325A1
• Time in Patent Office: Days
• US Class Current: 423/437.1
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• 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: C01B 2203/02 Processes for making hydrogen or synthesis gas
• CPC Class Codes: C01B 2203/0266 containing a decomposition step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/04 containing a purification step for the hydrogen or the synthesis gas
• CPC Class Codes: C01B 2203/042 Purification by adsorption on solids
• 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 2203/1235 Hydrocarbons
• CPC Class Codes: C01B 2203/148 involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 3/12 by reaction of water vapour with carbon monoxide
• CPC Class Codes: C01B 3/24 of hydrocarbons
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/48 followed by reaction of water vapour with carbon monoxide
• CPC Class Codes: C01B 3/50 Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification C01B3/14 takes precedence
• 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
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The present invention relates to a process for recovering hydrogen along with high temperature high pressure carbon dioxide from one or more hydrocarbon gas streams by incorporating a carbon dioxide recovery unit which utilizes a magnesium based sorbent into a process that includes a gasification unit, an optional sulfur removal unit, a water gas shift reactor and a hydrogen pressure swing adsorption unit.

Claims

1. A process for recovering hydrogen and high temperature and high pressure carbon dioxide from one or more hydrocarbon feed streams, said process comprising:

a) introducing the one or more hydrocarbon feed streams into a high pressure gasification unit to produce a sour syngas stream that contains at least hydrogen, carbon monoxide, carbon dioxide, sulfur containing compounds, methane and water vapor;

b) subjecting the sour syngas stream to desulfurization in a sulfur removal unit to obtain an essentially sulfur free syngas stream;

c) subjecting the essentially sulfur free syngas stream to water gas shift in a water gas shift reactor to obtain a water gas shift effluent;

d) subjecting the water gas shift effluent to treatment in a carbon dioxide removal unit that contains one or more fixed sorbent beds, each fixed sorbent bed containing a sorbent that is highly selective for carbon dioxide and is selected from magnesium based sorbents, the treatment involving;

i) a sorption phase in which the water gas shift effluent is introduced into the one or more fixed sorbent beds at a temperature from 100°

C. to 315°

C. and a pressure from 10 bar to 60 bar thereby allowing for the carbon dioxide in the water gas shift effluent to selectively react with the sorbent as the effluent passes through the one or more fixed sorbent bed while a portion of the remaining components of the water gas shift effluent are nonspecifically trapped in the void spaces in the sorbent and the remaining portion of the components of the water gas shift effluent is discharged from the one or more fixed sorbent bed as a carbon dioxide depleted stream,

ii) a purge phase in which the one or more fixed sorbent bed is purged of the components of the water gas shift effluent that are nonspecifically trapped in the void spaces in the sorbent by introducing a high pressure superheated steam to produce a purge effluent gas that is discharged from the one or more fixed sorbent bed;

iii) a carbon dioxide release in which the temperature of the one or more fixed sorbent bed is increased to a temperature of between 350°

C. and 420°

C. using superheated steam and indirect heat to allow for the release of the carbon dioxide from the sorbent thereby producing a wet, high temperature carbon dioxide rich stream that is discharged from the one or more fixed sorbent bed; and

iv) a rehydroxylation phase in which the temperature of the one or more fixed sorbent bed is reduced to from about 200°

C. to 300°

C. while at the same time contacting the one or more fixed sorbent bed with steam or any other moisture containing stream to allow for the rehydroxylation of the sorbent;

e) recycling the purge effluent gas along with the high pressure superheated steam to the syngas stream that is to be introduced into the water gas shift reactor unit;

f) passing the wet, high pressure carbon dioxide rich stream on for further use; and

g) introducing the carbon dioxide depleted stream obtained into a pressure swing adsorption unit to allow for the recovery of a high purity gaseous hydrogen stream.

2. The process of claim 1, wherein the gasification unit is a coal gasification unit.

3. The process of claim 1, wherein the carbon dioxide removal unit contains more than one fixed sorbent bed wherein the beds are configured in such a manner that there is always at least one bed in each phase at a given time.

4. The process of claim 1, wherein the carbon dioxide removal unit contains multiple sorbent beds in each phase.

5. The process of claim 1, wherein the sorbent used in the one or more fixed sorbent beds is magnesium hydroxide.

6. The process of claim 1, wherein the purge phase pressure is higher than the pressure in the water gas shift reactor, enabling the purge stream to feed into the water gas shift reactor without further compression.

7. The process of claim 1, wherein during the release of the carbon dioxide during the release phase, the temperature of the fixed sorbent bed is from about 375°

C. to about 420°

C.

8. The process of claim 1, wherein each of the fixed sorbent beds includes a means for heating and cooling the fixed sorbent bed.

9. The process of claim 8, wherein the means for heating and cooling the fixed sorbent bed comprises a set of heat transfer surfaces imbeded in each sorbent bed, the heat transfer surfaces having disposed therein a heat transfer media which becomes heated due to the heat generated during sorption and rehydroxylation, or cooled due to heat required during carbon dioxide release.

10. The process of claim 9, wherein the heat transfer media is used to generate high pressure steam for the carbon dioxide removal unit or as a source of heat for the high pressure gasification unit.

11. The process of claim 9, wherein the heat transfer media is used to transfer heat from high pressure gasification unit or water gas shift to heat the sorbent bed in carbon dioxide release phase.

12. The process of claim 9, wherein the heat transfer media is molten carbonate salt mixture.

13. The process of claim 9, wherein the heat transfer media is an inorganic or organic compound with a boiling point that ranges about 250°

C. to about 350°

C.

14. A process for recovering hydrogen and high temperature and high pressure carbon dioxide from one or more hydrocarbon feed streams, said process comprising:

a) introducing the one or more hydrocarbon feed streams into a high pressure gasification unit to produce a syngas stream that contains at least hydrogen, carbon monoxide, carbon dioxide, methane and water vapor;

b) subjecting the syngas stream to water gas shift in a water gas shift reactor to obtain a water gas shift effluent;

c) subjecting the water gas shift effluent to treatment in a carbon dioxide removal unit that contains one or more fixed sorbent beds, each fixed sorbent bed containing a sorbent that is highly selective for carbon dioxide and is selected from magnesium based sorbents, the treatment involving;

i) a sorption phase in which the water gas shift effluent is introduced into the one or more fixed sorbent beds at a temperature from 100°

C. to 315°

C. and a pressure from 10 bar to 60 bar thereby allowing for the carbon dioxide in the water gas shift effluent to selectively react with the sorbent as the effluent passes through the one or more fixed bed while a portion of the remaining components of the water gas shift effluent are nonspecifically trapped in the void spaces in the sorbent and the remaining portion of the components of the water gas shift effluent is discharged from the one or more fixed bed as a carbon dioxide depleted stream,

ii) a purge phase in which the one or more fixed bed is purged of the components of the water gas shift effluent that are nonspecifically trapped in the void spaces in the sorbent by introducing a high pressure superheated steam to produce a purge effluent gas that is discharged from the one or more fixed bed;

iii) a carbon dioxide release in which the temperature of the one or more fixed bed is increased to a temperature of between 350°

C. and 420°

C. using superheated steam and indirect heat to allow for the release of the carbon dioxide from the sorbent thereby producing a wet, high temperature carbon dioxide rich stream that is discharged from the one or more fixed bed; and

iv) a rehydroxylation phase in which the temperature of the one or more fixed bed is reduced to from about 200°

C. to 300°

C. while at the same time contacting the one or more fixed bed with steam or any other moisture containing stream to allow for the rehydroxylation of the sorbent;

d) recycling the purge effluent gas along with the high pressure superheated steam to the syngas stream that is to be introduced into the water gas shift reactor unit;

e) passing the wet, high pressure carbon dioxide rich stream on for further use; and

f) introducing the carbon dioxide depleted stream obtained into a pressure swing adsorption unit to allow for the recovery of a high purity gaseous hydrogen stream.

15. The process of claim 14, wherein the gasification unit is a coal gasification unit.

16. The process of claim 14, wherein the carbon dioxide removal unit contains more than one fixed sorbent bed wherein the beds are configured in such a manner that there is always at least one bed in each phase at a given time.

17. The process of claim 14, wherein the carbon dioxide removal unit contains multiple sorbent beds in each phase.

18. The process of claim 14, wherein the sorbent used in the one or more fixed sorbent beds is magnesium hydroxide.

19. The process of claim 14, wherein the purge phase pressure is higher than the pressure in the water gas shift reactor, enabling the purge stream to feed into the water gas shift reactor without further compression.

20. The process of claim 14, wherein during the release of the carbon dioxide during the release phase, the temperature of the one or more fixed bed is from about 375°

C. to about 420°

C.

21. The process of claim 14, wherein each of the one or more fixed beds includes a means for heating and cooling the one or more fixed bed.

22. The process of claim 21, wherein the means for heating and cooling the one or more fixed bed comprises a set of heat transfer surfaces imbeded in each sorbent bed, the heat transfer surfaces having disposed therein a heat transfer media which becomes heated due to the heat generated during sorption and rehydroxylation, or cooled due to heat required during carbon dioxide release.

23. The process of claim 22, wherein the heat transfer media is used to generate high pressure steam for the carbon dioxide removal unit or as a source of heat for the gasifier process.

24. The process of claim 22, wherein the heat transfer media is used to transfer heat from gasifier or water gas shift to heat the sorbent bed in carbon dioxide release phase.

25. The process of claim 22, wherein the heat transfer media is molten carbonate salt mixture.

26. The process of claim 22, wherein the heat transfer media is an inorganic or organic compound with a boiling point that ranges about 250°

C. to about 350°

C.