Membrane reactor for H2S, CO2 and H2 separation

Information

  • Patent Application
  • 20070240565
  • Publication Number
    20070240565
  • Date Filed
    August 28, 2006
    18 years ago
  • Date Published
    October 18, 2007
    17 years ago
Abstract
A system for the selective removal of CO2, H2S, and H2 from a gaseous fluid mixture comprising said CO2, H2S, and H2, which system includes a first membrane section having a nonporous metal oxide membrane, a second membrane section having a CO2-selective membrane, and a third membrane section having an H2-selective membrane. Each membrane section has a feed side and a permeate side and the membrane sections are arranged in series whereby the gaseous fluid mixture contacts the feed side, in sequence, of the first membrane section, the second membrane section and the third membrane section, resulting first in the separation or removal of H2S, second in the separation or removal of CO2, and third in the separation or removal of H2. The process can be used to process synthesis gas generated from the gasification or reforming of carbonaceous materials for hydrogen production and carbon dioxide capture.
Description

BRIEF DESCRIPTION OF THE DRAWINGS

These and other objects and features of this invention will be better understood from the following detailed description taken in conjunction with the drawings wherein:



FIG. 1 is a schematic diagram of a conventional process for production of hydrogen in a process for gasification or reforming of a carbonaceous material;



FIG. 2 is a schematic diagram of a complementary membrane configuration for CO2 and H2 separation with H2S removal; and



FIG. 3 is a schematic diagram of a gasification system for hydrogen production using the complementary membrane reactor configuration in accordance with one embodiment of this invention.





DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS

As used herein, the term “selective” when used in reference to membranes describes the propensity of the membrane to permit the transfer through the membrane of one component of a mixture to which the membrane is exposed relative to other components of the mixture. Thus, a CO2-selective membrane is one which preferentially permits the transfer of CO2 through the membrane relative to the transfer of other components, e.g. H2S and H2, of the mixture.


As used herein, the terms “membrane” and “membrane section” are used interchangeably and, thus, unless otherwise stated, statements made with respect to “membranes” are equally applicable to “membrane sections”.


The crux of the invention disclosed and claimed herein is the use of gas permeation membranes or membrane sections to separate H2S, CO2, and H2 individually along with the water-gas-shift reaction within a single membrane module. The three membranes or membrane sections are arranged in such a way that the feed (the gaseous fluid mixture) and the retentate (that portion of the gaseous fluid mixture remaining after the separation or removal of one of the components of interest by the respective selective membrane) contact the feed sides of the three membranes or membrane sections in series while the individual permeates, H2S, CO2, and H2, are obtained separately. In addition to being selective to H2S, CO2, and H2, respectively, the three membranes or membrane sections are able to operate at substantially the same temperature and pressure, thereby allowing them to be housed in a single reactor vessel in accordance with one embodiment of this invention, reducing the floor plan and simplifying the overall operation compared to conventional systems performing the same separations.


Each of the three membranes or membrane sections is comprised of a material which renders the membrane or membrane section selective for the removal of one of H2S, CO2 and H2. The membranes are arranged such that the first of the components removed from the gaseous fluid mixture is H2S, the second of the components is CO2, and the third of the components is H2. FIG. 2 shows the membrane configuration in accordance with one embodiment of this invention. As shown therein, in accordance with a particularly preferred embodiment of this invention, the membrane sections are joined into a single tubular membrane suitable for disposition in a single reactor vessel. The membrane comprises, in sequence, H2S-selective membrane section 20, CO2-selective membrane section 21, and H2-selective membrane section 22. The membrane sections, in accordance with a particularly preferred embodiment of this invention, are dense, nonporous membranes with close to 100% selectivity. Each membrane section comprises a feed side 25, 26, 27, which, in the embodiment shown, is the inside surface of the tubular membrane, and an opposite permeate side from which the permeate of interest is removed. In the embodiment shown, the gaseous fluid mixture is a synthesis gas which is introduced into an inlet end 23 of the tubular membrane and a retentate gas stream, from which H2S, CO2, and H2 have been separated out, is exhausted from an outlet end 24 for transfer to a gas clean up process. It will be apparent to those skilled in the art that other membrane configurations exist, for example, planar membranes with suitable spacing between each membrane to enable the flow of the gaseous fluid mixture to contact the feed side of each membrane, in sequence, and to enable removal of the separated gaseous components from the respective permeate sides of the membranes, and such embodiments are deemed to be within the scope of this invention. It will also be apparent to those skilled in the art that the process and system of this invention, in addition to synthesis gases, may also be used in connection with other gaseous fluid mixtures comprising H2S, CO2, and H2.


Membranes suitable for use in the method and system of this invention, in addition to being H2S—, CO2— and H2-selective, must also be capable of operating under the conditions, i.e. temperature and pressure, at which the gaseous fluid mixture is introduced into the system. For synthesis gas produced in a gasification process, the operational temperatures are in the range of about 600° C. to about 1000° C. For gaseous fluid mixtures derived from a fuel reforming process, the operational temperatures are typically in the range of about 500° C. to about 900° C. The operational pressures are in the range of about 10 to about 100 atm., preferably in the range of about 20 to about 60 atm.


Membranes suitable for use in the separation of H2S from the gaseous fluid mixture in accordance with one embodiment of this invention are nonporous (dense) membranes comprising at least one metal oxide. For gaseous fluid streams having temperatures in the range of about 600° C. to about 1000° C., the preferred metal oxides are calcium-based, such as CaO. In accordance with another embodiment of this invention, the membrane comprises CaS. For temperatures in the range of about 300° C. to about 600° C., the preferred metal oxides are zinc-based, such as ZnO.


For CO2 separation, the preferred membrane comprises at least one of a dense metal carbonate and a dense metal oxide wherein the metal is selected from the group consisting of Ca, Mg, Ba, Sr, Cd, Mn, Fe, Zn, Co, Ni, and combinations thereof. In accordance with one particularly preferred embodiment of this invention, the at least one dense metal carbonate is selected from the group consisting of CaCO3, MgCO3, Ca—Mg(CO3)2 and combinations thereof. Of the gaseous components remaining in the gaseous fluid mixture following removal of H2S therefrom, the dense carbonate membranes allow only CO2 in the form of carbonate ions to diffuse through and exclude all other gas species present in the gaseous mixture, including hydrogen. Thus, the method of this invention can achieve 100% selectivity for CO2 on the permeate side of the membranes. The membranes can operate at higher temperatures (greater than 200° C.) than conventional membranes to enable higher diffusion flux for the carbonate (CO32−) ions. Thus, the membranes of this invention are suitable for use in applications for CO2 separation from fuel/flue gas or synthesis gas at higher temperatures without the need of gas cooling. They can be used as a membrane reactor with the water-gas-shift reaction to increase hydrogen production by removing the equilibrium limitation. The catalysts of the water-gas-shift reaction may be eliminated if the membrane reactor is operated at sufficiently high temperatures (greater than about 500° C.).


For hydrogen separation, ceramic materials of the perovskite type are known to have virtually infinite selectivity to hydrogen in the temperature range of about 600° C. to about 1000° C. and, thus, are well suited for the third membrane section of the system in accordance with one embodiment of this invention. When operating at above about 600° C., the water gas shift reaction can take place without the need for catalysts in accordance with the following equation:





CO+H2O═CO2+H2+41 KJ/mole   (1)


As indicated by Equation (1) herein above, the water-gas-shift reaction is exothermic. Thus, equilibrium CO conversion is higher at lower operating temperatures, e.g. 200° C. to 300° C. While both CO2 and H2 are removed from the syngas by the two complementary membrane sections of this invention, the water-gas-shift reaction is more favorable for the production of H2 and CO2. Thus, the conversion of CO can be increased without being limited by its reaction equilibrium, even at temperatures between about 600° C. to about 1000° C. If necessary, catalysts can be added to the inside of the membrane module to promote further the steam-methane reforming reaction of CH4 to H2 in accordance with the following equation:





CH4+2H2O═CO2+4H2−200 KJ/mole   (2)


For temperatures in the range of about 300° C. to about 600° C., magnesium-based metal carbonates or oxide dense membranes are particularly suitable for CO2 separation. Palladium or its alloy materials, which have infinite selectivity to hydrogen, can be used for the third membrane section of the process and system of this invention for the separation of H2. For operating temperatures less than about 600° C., catalysts may be needed to facilitate the water-gas-shift reaction.


EXAMPLE

An Illinois #6 coal is gasified in a gasifier at a rate of about 100,000 lbs/hr, operating at a temperature of about 1000° C. and a pressure of about 30 atm. Steam is provided to the gasifier at a steam/carbon mole ratio of about 0.66 and oxygen is provided to the gasifier at a rate so as to provide an oxygen/carbon mole ratio of about 0.42. Based on the assumptions of thermodynamic equilibrium for all chemical reactions in the system, calculations were performed for four different process schemes: (A) the conventional process without the use of any membrane unit as shown in FIG. 1; (B) the current invention process in which a complementary membrane reactor configuration is employed as shown in FIGS. 2 and 3; (C) the same process as in process (B) but without the use of the H2 membrane in the membrane reactor configuration of FIG. 2; and (D) the same process as the process (B) except without the use of the CO2 membrane in the membrane reactor configuration of FIG. 2. The Ca-based membrane is used for the CO2 separation and the perovskite membrane is used for the hydrogen separation. The membrane reactors are operating at temperatures of about 760° C. without the use of any catalyst.


The pressures of the feed side of the membrane sections are at about 30 atm. For the hydrogen-selective membranes, the pressure of the permeate side is maintained at about 1 atm. Therefore, to maintain a positive pressure gradient across the membrane, the non-permeate synthesis gas stream exiting the H2 membrane has a H2 partial pressure of about 1 atm. For the CO2-selective membranes, the partial pressure of the CO2 at the permeate side needs to be below about 0.1 atm to ensure calcination of the CaCO3 on the permeate side according to the CO2 equilibrium pressure for the carbonation reaction. The non-permeate synthesis gas stream exiting from the CO2 membrane will have a partial pressure of about 0.3 atm for CO2 to prevent calcination of the membrane material. Additional steam is added to the water-gas-shift reactor for the membrane shift reactors at a steam/carbon mole ratio of 0.4. The hydrogen recovery for the PSA unit in the conventional coal to H2 process is assumed to be 80%.


The raw synthesis gas generated from gasification of the Illinois #6 coal also contains about 0.8% by weight of H2S. The use of a CaO membrane with a complementary membrane reactor as in process B also reduces the H2S down to about a 100 ppm level according to a thermodynamic equilibrium calculation.


The following table compares the results for the above four processes in terms of the number of moles for the hydrogen and carbon dioxide products. Also shown in the table are the amounts and the compositions of the gas that need downstream gas cleanup or further gas conditioning. The numbers in the table are all normalized to the hydrogen product for the process A.




















C.
D.



A.
B.
CO2
H2



Conventional
Complementary
Membrane
membrane



Coal to H2
Membrane
only
only




















H2, moles
100
130
112
116


CO2, moles

81
81


To gas cleanup,
201
27
157
115


moles


H2 %
33.1
3.6
79.2
3.6


CH4 %
0.5
4.0
0.7
0.9


CO
32.3
1.7
4.7
9.1


CO2 %
12.1
31.5
1.0
64.7


H2O %
22.0
59.2
14.5
21.7









As can be seen, the conventional process (A) needs to handle the largest amount of gas in the downstream separation units. Process B, which uses the complementary membrane reactor process of this invention, can produce the highest amount of H2 product with an additional pure CO2 byproduct ready for sequestration. After both H2 and CO2 have been separated from the raw synthesis gas stream, only about 15% of the gas volume remaining requires further conditioning, such as for removal of trace amounts of sulfur or other heavy metals. Use of the CO2 membrane reactor without the complementary use of the H2 membrane, as in Process C, results in pure CO2 product and a H2 enriched stream that requires further purification. If 90% of the H2 can be recovered from this purification process, the total H2 product is about 12% higher than the conventional coal to H2 process. On the other hand, the use of the H2 membrane reactor without the complementary use of the CO2 membrane, as in Process D, results in a pure H2 product that is about 10% lower in quantity than the complementary membrane reactor process of this invention. The advantage of the process and system of this invention can clearly be seen from its high hydrogen production rate and the low residual gas flow that needs further conditioning.


While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for the purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of this invention.

Claims
  • 1. A system for selective removal of CO2, H2S, and H2 from a fluid mixture comprising said CO2, H2S, and H2, the system comprising: a first membrane section comprising a nonporous metal oxide membrane;a second membrane section comprising a CO2-selective membrane;a third membrane section comprising an H2-selective membrane;each said membrane section having a feed side and a permeate side; andsaid membrane sections arranged in series whereby said fluid mixture contacts said feed side, in sequence, of said first membrane section, said second membrane section and said third membrane section.
  • 2. A system in accordance with claim 1, wherein said nonporous metal oxide membrane comprises a metal selected from the group consisting of Ca, Mg, Ba, Sr, Cd, Mn, Fe, Zn, Co, Ni, and combinations thereof.
  • 3. A system in accordance with claim 1, wherein said CO2-selective membrane is a nonporous metal carbonate membrane.
  • 4. A system in accordance with claim 3, wherein said nonporous metal carbonate membrane comprises a metal selected from the group consisting of Ca, Mg, Ba, Sr, Cd, Mn, Fe, Zn, Co, Ni, and combinations thereof.
  • 5. A system in accordance with claim 1, wherein said membrane sections are disposed within a single reactor vessel.
  • 6. A system in accordance with claim 4, wherein said nonporous metal carbonate is one of disposed on a surface of a porous substrate and disposed within an interior of said porous substrate.
  • 7. A system in accordance with claim 6, wherein substantially all pores of said porous substrate have pore sizes one of less than and equal to about 1000 nm in diameter.
  • 8. A system in accordance with claim 7, wherein said pore sizes are one of less than and equal to about 20 nm in diameter.
  • 9. A system in accordance with claim 1, wherein each said membrane section has a tubular shape.
  • 10. A method for separation of CO2, H2S, and H2 from a fluid mixture comprising said CO2, H2S, and H2, the method comprising the steps of: contacting a first membrane section feed side of a first membrane section comprising a nonporous metal oxide membrane with said fluid mixture;passing said H2S from said first membrane section feed side to a permeate side of said first membrane section, forming a reduced H2S fluid mixture;contacting a second membrane section feed side of a second membrane section comprising a CO2-selective membrane with said reduced H2S fluid mixture;passing said CO2 from said second membrane section feed side to a permeate side of said second membrane section, forming a reduced CO2 fluid mixture;contacting a third membrane section feed side of a third membrane section comprising an H2-selective membrane with said reduced CO2 fluid mixture; andpassing said H2 from said third membrane section feed side to a permeate side of said third membrane section, forming a reduced H2 fluid mixture.
  • 11. A method in accordance with claim 10, wherein said nonporous metal oxide membrane comprises a metal selected from the group consisting of Ca, Mg, Ba, Sr, Cd, Mn, Fe, Zn, Co, Ni, and combinations thereof.
  • 12. A method in accordance with claim 10, wherein said CO2-selective membrane is a nonporous metal carbonate membrane.
  • 13. A method in accordance with claim 12, wherein said nonporous metal carbonate membrane comprises a metal selected from the group consisting of Ca, Mg, Ba, Sr, Cd, Mn, Fe, Zn, Co, Ni, and combinations thereof.
  • 14. A method in accordance with claim 10, wherein said membrane sections are disposed within a single reactor vessel.
  • 15. A method in accordance with claim 12, wherein said nonporous metal carbonate is one of disposed on a surface of a porous substrate and disposed within an interior of said porous substrate.
  • 16. A method in accordance with claim 15, wherein substantially all pores of said porous substrate have pore sizes one of less than and equal to about 1000 nm in diameter.
  • 17. A method in accordance with claim 16, wherein said pore sizes are one of less than and equal to about 20 nm in diameter.
  • 18. A method in accordance with claim 10, wherein each said membrane section has a tubular shape.
Continuation in Parts (1)
Number Date Country
Parent 11406695 Apr 2006 US
Child 11511057 US