Method and system for producing hydrogen using an oxygen transport membrane based reforming system with secondary reforming

• US 9,556,027 B2
• Filed: 12/01/2014
• Issued: 01/31/2017
• Est. Priority Date: 12/02/2013
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Chakravarti, Shrikar, Drnevich, Raymond F., Stuckert, Ines C., Shah, Minish M.
• Primary Examiner(s): Silverman, Stanley
• Assistant Examiner(s): IQBAL, SYED TAHA
• Application Number:
  US14/556,833
• Publication Number:
  US 20160152469A1
• Time in Patent Office: 792 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 19/245 placed in series
• CPC Class Codes: B01J 19/2475 Membrane reactors
• CPC Class Codes: B01J 2219/00051 Controlling the temperature
• CPC Class Codes: B01J 2219/00157 by means of a burner
• CPC Class Codes: B01J 2219/24 Stationary reactors without moving elements inside
• CPC Class Codes: B01J 8/067 Heating or cooling the reactor B01J8/062 takes precedence
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0244 the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• CPC Class Codes: C01B 2203/0261 containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/042 Purification by adsorption on solids
• CPC Class Codes: C01B 2203/0811 by combustion of fuel
• CPC Class Codes: C01B 2203/0838 by heat exchange with exothermic reactions, other than by combustion of fuel
• CPC Class Codes: C01B 2203/0844 the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
• CPC Class Codes: C01B 2203/1235 Hydrocarbons
• CPC Class Codes: C01B 2203/142 At least two reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/143 Three or more reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/1623 Adjusting the temperature
• CPC Class Codes: C01B 3/382 Multi-step processes
• CPC Class Codes: C01B 3/48 followed by reaction of water vapour with carbon monoxide

Abstract

A method and system for producing hydrogen using an oxygen transport membrane based reforming system is disclosed that carries out a primary reforming process within a reforming reactor, and a secondary reforming process within a reactively driven and catalyst containing oxygen transport membrane reactor with or without an auxiliary source of heat to support primary reforming process within the reforming reactor to first form a synthesis gas product. The auxiliary source of heat is disposed within the oxygen transport membrane based reforming system proximate to the reforming reactors and comprises an auxiliary oxygen transport membrane reactor or a ceramic burner. The synthesis gas product is further treated in a separate high temperature water gas shift reactor and optionally in a separate low temperature water gas shift reactor. Hydrogen is produced from the resulting hydrogen-enriched gas using hydrogen PSA.

Claims

1. A method for hydrogen production utilizing an oxygen transport membrane based reforming system, the method comprising the steps of:

reforming a hydrocarbon containing feed stream in a reforming reactor in the presence of a reforming catalyst disposed in the reforming reactor and heat to produce a reformed synthesis gas stream comprising hydrogen, carbon monoxide, and unreformed hydrocarbon gas;

feeding the reformed synthesis gas stream to a reactant side of a reactively driven and catalyst containing oxygen transport membrane reactor, wherein the oxygen transport membrane reactor includes at least one oxygen transport membrane element configured to separate oxygen from an oxygen containing stream at the oxidant side of the reactively driven and catalyst containing oxygen transport membrane reactor and permeate separated oxygen to the reactant side through oxygen ion transport when subjected to an elevated operational temperature and a difference in oxygen partial pressure across the at least one oxygen transport membrane element;

reacting a portion of the reformed synthesis gas stream with oxygen permeated through the at least one oxygen transport membrane element to produce the difference in oxygen partial pressure across the at least one oxygen transport membrane element and generate reaction products and heat, including a first portion of the heat required for the reforming of the hydrocarbon containing feed stream in the reforming reactor;

reforming unreformed hydrocarbon gas in the reformed synthesis gas stream in the presence of one or more catalysts contained in the oxygen transport membrane reactor, the reaction products and the heat to produce a synthesis gas product stream;

treating at least a portion of the synthesis gas product stream in a separate high temperature shift reactor to form a hydrogen-enriched synthesis gas stream; and

treating the hydrogen-enriched synthesis gas stream in a hydrogen PSA and recovering a hydrogen product stream and a tail gas stream;

wherein a second portion of the heat required for the reforming of the hydrocarbon containing feed in the reforming reactor is transferred from an auxiliary heat source disposed proximate to the reforming reactor.

2. The method of claim 1 wherein the heat generated as a result of the reaction of the reformed synthesis gas stream with permeated oxygen is transferred:

(i) to the reformed synthesis gas stream present in the reactively driven, catalyst containing oxygen transport membrane reactor;

(ii) to the reforming reactor; and

(iii) to an oxygen depleted retentate stream.

3. The method of claim 1 wherein the auxiliary heat source provides from about 15% to about 85% of the heat required for the reforming of the hydrocarbon containing feed stream in the reforming reactor.

4. The method of claim 1 wherein the auxiliary heat source comprises one or more auxiliary oxygen transport membrane reactors wherein the auxiliary oxygen transport membrane reactor comprises a plurality of reactively driven oxygen transport membrane elements disposed proximate the reforming reactor and configured to:

(i) separate oxygen from the oxygen containing stream contacting the oxidant side of the oxygen transport membrane element and permeate separated oxygen to the reactant side of the oxygen transport membrane element through oxygen ion transport;

(ii) receive a hydrogen containing stream at the reactant side at a pressure of about 3 bar or less; and

(iii) react the hydrogen containing stream with the permeated oxygen at the reactant side to produce the difference in oxygen partial pressure across the oxygen transport membrane element and to produce an auxiliary reaction product stream and heat.

5. The method of claim 1 wherein the auxiliary heat source utilizes all of a portion of the tail gas or a portion of the synthesis gas product or a light hydrocarbon containing gas or mixtures thereof.

6. The method of claim 2 further comprising the step of reheating the oxygen depleted stream to a temperature of from about 1050°

C. to about 1200°

C. using a duct burner disposed within or proximate to the oxygen transport membrane based reforming system, where the duct burner is configured to combust a fuel stream to heat the incoming oxygen containing stream via indirect heat exchange.

7. The method of claim 1 wherein the auxiliary heat source is one or more ceramic burners disposed proximate the reforming reactor and the reactively driven and catalyst containing oxygen transport membrane reactor, the one or more ceramic burners configured to burn a light hydrocarbon containing gas using air or enriched air as the oxidant.

8. The method of claim 1 wherein the hydrogen to carbon monoxide ratio (H₂/CO) of the synthesis gas product stream is greater than 2.8 and is dependent on the reforming temperature and the amount of heat supplied to the reforming reactor from the auxiliary heat source.

9. A hydrogen production system comprising:

an oxygen transport membrane based reactor housing comprising;

a reforming reactor disposed in the reactor housing and configured to reform a hydrocarbon containing feed stream in the presence of a reforming catalyst disposed in the reforming reactor and heat to produce a reformed synthesis gas stream;

a reactively driven, catalyst containing oxygen transport membrane reactor disposed in the reactor housing proximate the reforming reactor and configured to receive the reformed synthesis gas stream and react a portion of the reformed synthesis gas stream with permeated oxygen and generate a first reaction product and heat, including a first portion of the heat required by the reforming reactor;

wherein the reactively driven, catalyst containing oxygen transport membrane reactor is further configured to reform any unreformed hydrocarbon gas in the reformed synthesis gas stream in the presence of reforming catalyst, some of the heat and the first reaction product generated by the reaction of the reformed synthesis gas stream and permeated oxygen to produce a synthesis gas product stream; and

an auxiliary heat source disposed in the reactor housing proximate the reforming reactor and configured to supply a second portion of the heat required by the reforming reactor to produce the reformed synthesis gas stream;

the oxygen transport membrane based hydrogen production system further comprising;

a water gas shift reactor unit; and

a hydrogen PSA unit.

10. The system of claim 9 wherein the reactively driven, catalyst containing oxygen transport membrane reactor further comprises a plurality of reforming catalyst containing oxygen transport membrane tubes defining an oxidant side and a reactant side and configured to separate oxygen from an oxygen containing stream contacting the oxidant side and permeate separated oxygen to the reactant side through oxygen ion transport when subjected to the elevated operational temperature and the difference in oxygen partial pressure across the at least one oxygen transport membrane tube.

11. The system of claim 9 wherein the hydrogen to carbon monoxide ratio (H₂/CO) of the synthesis gas product stream is greater than 2.8 and is dependent on the reforming temperature and the amount of heat supplied to the reforming reactor from the auxiliary heat source.

12. The system of claim 9 wherein the auxiliary heat source comprises one or more auxiliary oxygen transport membrane reactors configured to provide from about 15% to about 85% of the heat required for the reforming of the hydrocarbon containing feed stream in the reforming reactor.

13. The system of claim 9 wherein the auxiliary heat source comprises one or more ceramic burners configured to burn a light hydrocarbon containing stream using air or enriched air as the oxidant and provide from about 15% to about 85% of the heat required for the reforming of the hydrocarbon containing feed stream in the reforming reactor.

14. A method for hydrogen production utilizing an oxygen transport membrane based reforming system, the method comprising the steps of:

reforming a hydrocarbon containing feed stream in a reforming reactor in the presence of a reforming catalyst disposed in the reforming reactor and heat to produce a reformed synthesis gas stream comprising hydrogen, carbon monoxide, and unreformed hydrocarbon gas;

feeding the reformed synthesis gas stream to a reactant side of a reactively driven and catalyst containing oxygen transport membrane reactor, wherein the oxygen transport membrane reactor includes at least one oxygen transport membrane element configured to separate oxygen from an oxygen containing stream at the oxidant side of the reactively driven and catalyst containing oxygen transport membrane reactor and permeate separated oxygen to the reactant side through oxygen ion transport when subjected to an elevated operational temperature and a difference in oxygen partial pressure across the at least one oxygen transport membrane element;

reacting a portion of the reformed synthesis gas stream with oxygen permeated through the at least one oxygen transport membrane element to produce the difference in oxygen partial pressure across the at least one oxygen transport membrane element and generate reaction products and heat, including the heat required for the reforming of the hydrocarbon containing feed stream in the reforming reactor;

reforming unreformed hydrocarbon gas in the reformed synthesis gas stream in the presence of one or more catalysts contained in the oxygen transport membrane reactor, the reaction products and the heat to produce a synthesis gas product stream;

treating at least a portion of the synthesis gas product stream in a separate high temperature shift reactor followed by a low temperature shift reactor to form a hydrogen-rich synthesis gas stream; and

treating the hydrogen-rich synthesis gas stream in a hydrogen PSA and recovering a hydrogen product stream and a tail gas stream.

15. The method of claim 14 wherein the reactively driven oxygen transport membrane reactor further comprises a plurality of reforming catalyst containing oxygen transport membrane tubes defining an oxidant side and a reactant side and configured to separate oxygen from an oxygen containing stream contacting the oxidant side to the reactant side through oxygen ion transport when subjected to the elevated operational temperature and the difference in oxygen partial pressure across the at least one oxygen transport membrane tube.

16. The method of claim 14 wherein the hydrogen to carbon monoxide ratio (H₂/CO) of the synthesis gas product stream is from about 2.5 to about 3.5.

17. The method of claim 14 wherein the tail gas stream has a lower heating value of less than 100 Btu/Scf.