Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system

• US 9,938,145 B2
• Filed: 05/27/2016
• Issued: 04/10/2018
• Est. Priority Date: 04/26/2013
• Status: Active Grant

• Current Assignee: Praxair Technology Incorporated (Linde Plc)
• Original Assignee: Praxair Technology Incorporated (Linde Plc)
• Inventors: Chakravarti, Shrikar, Drnevich, Raymond Francis, Shah, Minish M., Stuckert, Ines C.
• Primary Examiner(s): Merkling, Matthew J
• Application Number:
  US15/166,735
• Publication Number:
  US 20160272493A1
• Time in Patent Office: 683 Days
• CPC Class Codes: B01J 2208/0053 Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
• CPC Class Codes: B01J 2219/00006 Large-scale industrial plants
• CPC Class Codes: B01J 2219/00495 Means for heating or cooling the reaction vessels
• CPC Class Codes: B01J 2219/00745 Inorganic compounds
• CPC Class Codes: B01J 8/009 Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
• CPC Class Codes: B01J 8/0457 the beds being placed in separate reactors
• CPC Class Codes: B01J 8/0496 Heating or cooling the reactor
• CPC Class Codes: C01B 13/0251 by making use of membranes
• 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 2203/04 containing a purification step for the hydrogen or the synthesis gas
• CPC Class Codes: C01B 2203/0495 the impurity being water
• CPC Class Codes: C01B 2203/0833 Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
• CPC Class Codes: C01B 2203/0838 by heat exchange with exothermic reactions, other than by combustion of fuel
• CPC Class Codes: C01B 2203/0883 by indirect heat exchange
• CPC Class Codes: C01B 2203/1205 Composition of the feed
• CPC Class Codes: C01B 2203/1235 Hydrocarbons
• CPC Class Codes: C01B 2203/127 Catalytic desulfurisation
• CPC Class Codes: C01B 2203/142 At least two reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/80 : Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
• CPC Class Codes: C01B 3/26 : using catalysts
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C01B 3/384 : the catalyst being continuously externally heated
• CPC Class Codes: C01B 3/386 : Catalytic partial combustion

Abstract

A method and system for producing a synthesis gas in an oxygen transport membrane based reforming system is disclosed that carries out an air heated pre-reforming process, a primary reforming process, a secondary reforming process.

Claims

1. A method for producing a synthesis gas in an oxygen transport membrane based reforming system, wherein said system comprises a reforming reactor, an oxygen transport membrane reactor and a heated pre-reformer, the method comprising the steps of:

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

feeding the partially 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 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 partially 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 a steam containing heated reaction product stream and heat;

transferring some of the heat generated as a result of the reaction;

(i) to the gas in the catalyst containing oxygen transport membrane reactor;

(ii) by radiation to the reforming reactor; and

(iii) by convection to the oxygen depleted stream; and

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

wherein prior to partially reforming said mixed feed stream in said reforming reactor said mixed feed stream is pre-reformed in a heated pre-reformer in the presence of a pre-reforming catalyst.

2. The method of claim 1 wherein the mixed feed stream has a steam to carbon ratio of from about 0.6 to about 3.0 and a temperature of from about 450°

C. and 750°

C.

3. The method of claim 1 further comprising the step of directly cooling the synthesis gas product stream to a temperature of about 400°

C. or less.

4. The method of claim 1 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, wherein the duct burner is configured to combust a supplemental fuel stream and residual oxygen in the oxygen depleted stream to heat the incoming oxygen containing stream via indirect heat exchange.

5. The method of claim 1 wherein the synthesis gas product stream has a module of greater than 2.0.

6. The method of claim 5 wherein the synthesis gas product stream has a module of from about 2.0 to about 2.2.

7. The method of claim 6 wherein the synthesis gas product stream has a module of from 2.0 to about 2.1.

8. The method of claim 7 wherein the synthesis gas product stream has a module of 2.0.

9. The method of claim 7 wherein the synthesis gas product stream has a module of 2.1.

10. An oxygen transport membrane based reforming system for producing synthesis gas comprising:

a reactor housing;

a plurality of catalyst containing and reactively driven oxygen transport membrane elements or tubes disposed in the reactor housing and configured to separate oxygen from an oxygen containing feed stream and produce an oxygen permeate at a permeate side of the oxygen transport membrane elements or tubes and an oxygen depleted stream, wherein one or more catalysts are disposed proximate the permeate side of the oxygen transport membrane tubes or elements;

a plurality of catalyst containing reformer tubes disposed in the reactor housing juxtaposed to the oxygen transport membrane elements or tubes, the catalyst containing reformer tubes configured to produce a partially reformed synthesis gas stream by reforming a hydrocarbon containing feed and steam in the presence of the catalyst contained in the reformer tubes and heat radiated from the juxtaposed oxygen transport membrane elements or tubes; and

a heated pre-reformer containing a pre-reforming catalyst, wherein said pre-reformer is configured to convert higher hydrocarbons in the mixed feed stream to methane, hydrogen, carbon monoxide and carbon dioxide;

wherein an outlet of the heated pre-reformer is coupled to an inlet to the catalyst containing reformer tubes, and an outlet of said catalyst containing reformer tubes is fluidically coupled to the permeate side of the oxygen transport membrane elements or tubes such that the partially reformed synthesis gas flows through the oxygen transport membrane elements or tubes,

wherein hydrogen, carbon monoxide and methane in the partially reformed synthesis gas reacts with the oxygen permeate at the permeate side of the oxygen transport membrane elements or tubes to reactively drive the separation of oxygen from the oxygen containing feed stream and to produce partial oxidation reaction products and heat; and

wherein the oxygen transport membrane elements and tubes are further configured to produce a synthesis gas product stream by the partial oxidation and by further reforming of the partially reformed synthesis gas stream fed to the permeate side of the oxygen transport membrane elements or tubes in the presence of the one or more catalyst(s) and the heat.

11. The oxygen transport membrane based reforming system of claim 10 further comprising a synthesis gas cooling subsystem configured to cool the synthesis gas product stream to a temperature of about 400°

C. or less.

12. The oxygen transport membrane based reforming system of claim 10 further comprising a duct burner disposed within or proximate to the oxygen transport membrane based reforming system housing and configured to combust a supplemental fuel stream and residual oxygen in the oxygen depleted stream to heat the oxygen containing feed stream via indirect heat exchange.