Method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that is free of metal dusting corrosion

• US 9,611,144 B2
• Filed: 11/26/2013
• Issued: 04/04/2017
• 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, Burgers, Kenneth L.
• Primary Examiner(s): Mayes, Melvin C
• Assistant Examiner(s): CALL, DOUGLAS BRYANT
• Application Number:
  US14/090,289
• Publication Number:
  US 20140319426A1
• Time in Patent Office: 1,225 Days
• CPC Class Codes: B01J 2219/00006 Large-scale industrial plants
• 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 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• 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 2203/0822 the fuel containing hydrogen
• CPC Class Codes: C01B 2203/0827 at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/142 At least two reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 3/382 Multi-step processes
• CPC Class Codes: C01B 3/384 the catalyst being continuously externally heated
• CPC Class Codes: Y02P 20/10 Process efficiency

Abstract

A method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that utilizes a combined feed stream having a steam to carbon ratio between about 1.6 and 3.0 and a temperature between about 500° C. and 750° C. The combined feed stream is comprised a pre-reformed hydrocarbon feed, superheated steam, and a reaction product stream created by the reaction of a hydrogen containing stream reacted with the permeated oxygen at the permeate side of the oxygen transport membrane elements and wherein the oxygen transport membrane based reforming system and associated synthesis production process equipment are substantially free of carbon formation and metal dusting corrosion.

Claims

1. A method for producing synthesis gas in an oxygen transport membrane based reforming system, wherein said system comprises two distinct reactors:

at least one catalyst containing reforming reactor comprising a plurality of catalytic reforming tubes, wherein said reforming reactor is configured to produce a synthesis gas stream by reacting a combined feed stream in the presence of the catalyst and heat; and

a reactively driven oxygen transport membrane reactor proximate to said at least one catalyst containing reforming reactor, the reactively driven oxygen transport membrane reactor comprising a plurality of oxygen transport membrane elements 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 and an oxygen depleted retentate stream at a retentate side of the oxygen transport membrane elements, the method comprising the steps of;

separating an oxygen containing stream into an oxygen permeate and an oxygen depleted retentate stream using a plurality of oxygen transport membrane elements disposed in the oxygen transport membrane based reforming system;

reacting a hydrogen containing stream contacting a permeate side of the oxygen transport membrane elements with the oxygen permeate to generate a reaction product stream and heat;

pre-heating a hydrocarbon containing feed stream and combining the pre-heated hydrocarbon containing feed stream with a portion of the reaction product stream and steam to produce a combined feed stream having a temperature between about 500°

C. and 750°

C.;

reforming the combined feed steam in the at least one catalyst containing reforming reactor in the presence of the catalyst and heat, wherein said heat is generated said oxygen transport membrane reactor by the reaction of the hydrogen containing stream and permeated oxygen, to produce a synthesis gas stream, the at least one catalyst based reforming reactor disposed proximate the oxygen transport membrane elements;

cooling the synthesis gas stream exiting the oxygen transport membrane based reforming system in a heat exchange network fluidly coupled to the reforming reactor and the oxygen transport membrane reactor, wherein said network comprises one or more coils disposed in an oxygen depleted retentate stream duct, wherein steam is superheated via indirect heat exchange between the oxygen depleted retentate stream as the steam is directed through the one or more coils disposed in the oxygen depleted retentate stream duct, wherein said heat exchange network is configured to;

(i) cool the synthesis gas stream exiting the at least one catalyst containing reforming reactor to a temperature of less than about 400°

C.;

(ii) produce steam, and (iii) optionally pre-heat a hydrocarbon containing feed stream; and

feeding a portion of the cooled synthesis gas stream to the permeate side of the plurality of oxygen transport membrane elements to form all or a portion of the hydrogen containing stream;

wherein the oxygen transport membrane based reforming system and associated synthesis production process equipment are substantially free of carbon formation and metal dusting corrosion.

2. The method of claim 1 further comprising the step of superheating the steam by heating the steam via indirect heat exchange with the heated retentate stream and feeding a portion of the superheated steam to the hydrocarbon containing feed stream to adjust the steam to carbon ratio and temperature of the combined feed stream.

3. The method of claim 2 wherein the superheated steam is between about 15 bar to 80 bar and between about 300°

C. and 600°

C.

4. The method of claim 1 wherein the step of pre-heating the hydrocarbon feed stream further comprises pre-heating the hydrocarbon containing feed stream via indirect heat exchange with the synthesis gas stream or via indirect heat exchange with the oxygen depleted retentate stream or both.

5. The method of claim 1 further wherein the step of combining the pre-heated hydrocarbon containing feed stream with a portion of the reaction product stream and steam to produce the combined feed stream further comprises mixing the hydrocarbon feed stream with superheated steam and heating the mixed stream via indirect heat exchange with the oxygen depleted retentate stream.

6. The method of claim 1 wherein the step of feeding a portion of the cooled synthesis gas stream to the permeate side of the plurality of oxygen transport membrane elements further comprises:

compressing the portion of the cooled synthesis gas stream while maintaining the temperature of the cooled, compressed portion of the synthesis gas stream at a temperature less than about 400°

C.; and

directing the cooled, compressed portion of the synthesis gas stream to the permeate side of the oxygen transport membrane elements to react with the oxygen permeate to generate the reaction product stream and heat.

7. The method of claim 1 further comprising the steps of:

Feeding the oxygen depleted retentate stream to a duct burner where it reacts with a source of supplemental fuel to produce a heated exhaust stream; and

heating the oxygen containing stream via indirect heat exchange with the heated exhaust stream using a continuously rotating ceramic regenerator disposed in operative association with the oxygen containing stream and the heated retentate stream.

8. The method of claim 1 further comprising the steps of further cooling the synthesis gas stream with one or more of the following streams:

a boiler feed water stream in an economizer to produce heated boiler feedwater;

a feed water stream in a feed water heater to heat the feed water;

or a cooling water stream in a cooling water heat exchanger.

9. An oxygen transport membrane based reforming system for producing synthesis gas which comprises two distinct reactors, said system comprising:

a reactor housing;

at least one catalyst containing reforming reactor comprising a plurality of catalytic reforming tubes disposed in the reactor housing and configured to produce a synthesis gas stream by reacting a combined feed stream in the presence of the catalyst and heat; and

a reactively driven oxygen transport membrane reactor disposed in the reactor housing proximate the at least one catalyst containing reforming reactor, the reactively driven oxygen transport membrane reactor comprising a plurality of oxygen transport membrane elements 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 and an oxygen depleted retentate stream at a retentate side of the oxygen transport membrane elements;

a hydrogen containing stream in contact with the permeate side of the plurality of oxygen transport membrane elements, wherein the permeated oxygen reacts with the hydrogen containing stream to reactively drive the separation of oxygen from the oxygen containing feed stream and to generate a reaction product stream and heat that is transferred to the oxygen depleted retentate stream and to at least one catalyst containing reforming reactor; and

a heat exchange network fluidly coupled to the reforming reactor and the oxygen transport membrane reactor, the heat exchange network comprising one or more coils disposed in an oxygen depleted retentate stream duct, wherein steam is superheated via indirect heat exchange between the oxygen depleted retentate stream as the steam is directed through the one or more coils disposed in the oxygen depleted retentate stream duct, said heat exchange network configured to;

(i) cool the synthesis gas stream exiting the at least one catalyst containing reforming reactor to a temperature of less than about 400°

C.;

(ii) produce steam, and (iii) optionally pre-heat a hydrocarbon containing feed stream;

wherein the pre-heated hydrocarbon feed and steam are mixed with the reaction product stream upstream of the at least one catalyst containing reforming reactor to produce the combined feed stream having a temperature between 500°

C. and 750°

C.; and

wherein the oxygen transport membrane based reforming system and associated synthesis production process equipment are substantially free of carbon formation and metal dusting corrosion.

10. The system of claim 9 wherein the heat exchange network further comprises:

a first heat exchanger configured to cool the synthesis gas stream via indirect heat exchange with a process gas boiler feed stream and wherein the steam is produce from the indirect heat exchange between the synthesis gas stream and the process gas boiler feed water stream; and

optionally, a second heat exchanger configured to pre-heat the hydrocarbon containing feed stream via indirect heat exchange with the cooled synthesis gas stream.

11. The system of claim 9 wherein the superheated steam is between about 15 bar to 80 bar and between about 300°

C. and 600°

C.

12. The system of claim 9 wherein the hydrocarbon containing feed stream is further pre-heated via indirect heat exchange with the oxygen depleted retentate stream as the hydrocarbon containing feed stream is directed through the one or more coils disposed in the oxygen depleted retentate stream duct or a combined stream of the hydrocarbon containing feed stream and superheated steam is directed through the one or more coils disposed in the oxygen depleted retentate stream duct.

13. The system of claim 9 wherein the combined feed stream has a steam to carbon ratio between about 1.6 and 3.0 and a temperature between about 500°

C. and 750°

C.

14. The system of claim 9 further comprising a synthesis gas recycle circuit between the heat exchange network and the oxygen transport membrane reactor to recirculate a portion of the cooled synthesis gas to the permeate side of the oxygen transport membrane elements as all or a portion of the hydrogen containing stream.

15. The system of claim 14 wherein the synthesis gas recycle circuit further comprises a compressor configured to compress the cooled synthesis gas stream while maintaining the temperature of the cooled, compressed portion of the synthesis gas stream at a temperature less than about 400°

C.

16. The system of claim 9 further comprising:

a burner disposed in the oxygen depleted retentate stream duct and configured to produce a heated exhaust stream using the oxygen depleted retentate stream and a source of supplemental fuel; and

a continuously rotating ceramic regenerator configured to transfer heat from the heated exhaust stream to the oxygen containing feed stream.

17. The system of claim 9 further comprising a burner disposed in an air intake duct and configured to produce a heated oxygen containing stream using the oxygen containing stream and a source of supplemental fuel.