WO2000045940A1 - Hydrogen-selective silica based membrane - Google Patents
Hydrogen-selective silica based membrane Download PDFInfo
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- WO2000045940A1 WO2000045940A1 PCT/US2000/002075 US0002075W WO0045940A1 WO 2000045940 A1 WO2000045940 A1 WO 2000045940A1 US 0002075 W US0002075 W US 0002075W WO 0045940 A1 WO0045940 A1 WO 0045940A1
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- membrane
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- porous material
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- membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
- B01D2323/081—Heating
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Definitions
- the present invention generally relates to hydrogen generation, purification, and recovery and, more particularly, to a method for preparing a porous glass membrane having selectivity for hydrogen while retaining permeability.
- Ceramic membranes are receiving considerable attention. Over the last ten years it has been demonstrated that membrane-based separation processes are commercially viable in a wide variety of applications. However, polymer-based membranes are used in the majority of these processes, and thus, there are inherent limitations in the operating temperatures and pressures that can be used. It is felt that ceramic-based membranes would offer significant improvements in the range of operating temperatures and pressures available. The question is how to make ceramic membranes with high selectivity and high permeability.
- the dehydrogenation of methanol and n- butane in alumina membrane reactors was studied with 50% improvement in conversions obtained in the membrane mode of operation as compared to the fixed-bed mode of operation.
- the methane steam reforming reaction in metal dispersed alumina membrane reactors has resulted in conversions twice as high as equilibrium.
- the same reaction in an alumina membrane reactor has provided conversions 20% higher than the equilibrium level.
- a membrane is formed by chemical vapor deposition (CND) of tetraethyl orthosilicate (TEOS) at high temperature in the absence of oxygen or steam.
- CND chemical vapor deposition
- TEOS tetraethyl orthosilicate
- This membrane has selectivities of 100% with respect to CH 4 , CO, CO 2 and H 2 O.
- the invention can be practiced with other silica precursors such as tetraethyl silicates, tetra isopropyl silicates, chloro-, dichloro-, and trichloromethylsilanes, and other silicon compounds.
- An important feature of the invention is that the silica precursor be decomposed in an inert atmosphere (lacking oxygen or steam). Decomposition can be accomplished by high temperature exposure, laser exposure, or other means.
- Figure 1 is a schematic of the experimental apparatus as used in the preparation of the Nanosil membrane of the present invention.
- Figure 2 is a bar graph comparing permeabilities of the untreated Nycor membrane to several Nanosil membranes;
- Figure 3 is a schematic showing the experimental apparatus used for the isotopic exchange determinations;
- Figure 4 is a stability plot for the Nanosil membrane on exposure to moisture (10% H 2 O in Ar) at 873 K;
- Figure 5 is a schematic showing the experimental apparatus used in the polymerization of a silica precursor
- Figure 6 is a bar graph comparing H 2 /CH 4 separation ratios for different membranes
- Figure 7 is a graph showing the adsorption and desorption isotherms for fresh and used samples of the membranes of the present invention
- Figure 8 is a graph of the pore size distributions of the untreated Nycor glass and the Nanosil membrane.
- Figure 9 is a schematic of the experimental apparatus used in the catalyst reactivity studies.
- Figure 10 is a bar graph comparing the methane conversions in three reactor configurations.
- the Nanosil membrane of the present invention is formed by the deposition of a thin layer of silica in the mouth of the pores of the porous glass substrate.
- the layer is sufficient to impede passage of species other than hydrogen to the pores.
- the Nanosil membrane is prepared as follows: A porous substrate, in this case Nycor glass (Corning 7930 glass), is modified in the experimental setup shown in Figure 1.
- the reactor assembly 101 including tube 102 and shell 103 with a 4 cm porous glass (Nycor) section 104 is heated to 873 K with Ar flow on both the shell (20 ⁇ mol s "1 ) and the tube (8 ⁇ mol s " ') side.
- Tetraethyl orthosilicate (TEOS, Aldrich, 98%) is introduced through a bubbler at 298 K using Ar (3 ⁇ mol s " ') as the carrier gas.
- the stream is premixed with the tube stream Ar before introduction in the tube side.
- the TEOS-Ar stream is allowed to flow for different time periods (12 h, 24 h, 48 h) after which the reactor is cooled in Ar.
- the experimental H 2 permeability coefficient Q H2 was 4 x 10 "8 cm 3 cm “2 s " ' Pa " ' at 873 K, which is typical for this material. Separation factors were obtained from individual permeability coefficients and are listed in Table 1 (for a temperature range 300-973 K). The separation factors obtained with the unmodified Nycor membrane were close to that predicted by the Knudsen equation and the temperature coefficient for diffusion was T ' ° 56 . A good match between the experimental and theoretical results strongly indicates that the mode of transport of all species was molecular. Table 1 : Knudsen selectivities
- the modified porous glass membrane was prepared by the chemical vapor deposition of TEOS at 873 K as described above. The deposition was conducted on different samples for 48, 24, and 12 h.
- Figure 2 compares the permeabilities of these Nanosil membranes, subject of the present invention, with the original porous glass membrane. It is evident from the temperature dependency that the diffusion changed from Knudsen to an activated mode.
- the 48, and 24 h deposited membranes had lower permeability than the support Nycor material.
- the 12 h deposited membrane had permeability comparable to the support material.
- Table 2 compares the selectivities of the porous glass membrane with that of the 12 h membrane.
- the modified membrane offered unprecedented selectivity (100%) to hydrogen with HJCH 4 , HJCO, and H 2 /CO 2 separation factors of at least 27000, 87000, and 8200 respectively, while retaining a high permeability, comparable to the support material.
- HJCH 4 , HJCO, and H 2 /CO 2 separation factors of at least 27000, 87000, and 8200 respectively, while retaining a high permeability, comparable to the support material.
- the Nanosil membrane is completely different from the substrate material.
- Table 2 Selectivity factors for porous glass and Nanosil membranes
- FIG. 3 shows the experimental setup for the isotope exchange studies.
- the experimental apparatus consists of concentric quartz tubes; the inner one hereinafter referred to as the tube 301 and the outer one referred to as the shell 302.
- the tube 301 incorporates the membrane subject of t his invention 303.
- the tube 301 and shell 302 portion of the apparatus is within a furnace 304.
- the intake 305 to the shell 302 is connected to Ar, D 2 , and H 2 supplies 311.
- the shell 302 also has a vent 306.
- the intake 307 to the tube 301 is connected to N 2 .
- the outlet 308 of the tube 301 is connected to a mass spectrometer 309 which also has vent 310.
- the mass spectrometer 309 analyzes for the presence of gases which permeate the membrane 303.
- An equimolar mixture of H 2 and D 2 (5 ⁇ mol s '1 ) premixed with Ar (7 ⁇ mol s "1 ) was passed through the shell side of the reactor.
- N 2 (29 ⁇ mol s' 1 ) was used as the sweep gas on the tube side.
- a sample from the tube side was analyzed online using the mass spectrometer (Dycor) for masses 1 , 2, 3, and 4. This was repeated for several temperatures.
- Table 3 lists the results of the studies with a hydrogen deuterium mixture.
- the top section shows the results of reference measurements carried out with the mesoporous Nycor glass membrane.
- the observation of mass 1 and mass 3 species in this case where only molecular hydrogen transport occurred was due to the fragmentation and recombination of hydrogen species in the mass spectrometer ionizer, and can be considered as a blank level for these species.
- the bottom section summarizes the results for the Nanosil membrane. The most important result is that the ratio of mass 3/mass 4 is substantially above the blank level indicating that HD (mass 3) has been formed by passage through the membrane. Meanwhile the ratio mass 1/mass 2 remains substantially unchanged since any fragmentation of HD contributes equal quantities of H and D.
- the Nanosil membrane can be distinguished from other membranes by its stability.
- a wide variety of the latter were prepared using published techniques. This included membranes made by the sol-gel, polymerization, silica sol, and decomposition methods. In a first example, the sol-gel method was reproduced from the work of
- Kitao et al. Gas separation by thin porous silica membrane prepared by sol-gel and CVD methods, Materials 61 & 62(1991)267) and involved the preparation of three solutions, A, B, and C with TEOS, H 2 O and HNO 3 in the ratio 1 : 10:0.1, 1 :50:0.05 and 1 :100:0.005 respectively.
- Polymer A was obtained by boiling solution A for 0.33 h and polymer B by boiling solution B for 0.16 h.
- Solution C was used as prepared.
- the polymerization of a silica precursor involved the polymerization of a silica precursor, trichioromethylsilane (Aldrich 97 %) within the pores of the Nycor tube.
- the shell 502 and tube 501 sides were isolated from each other using stoppers 503 and mounted as shown in Figure 5.
- the membrane section (outer tube 501 side) was wrapped with absorbent tissue and held together with elastic bands.
- the assembly was rotated using a motor 504 at 4 rpm while being maintained at 265 K using a constant temperature bath (prepared by dissolving NaCl in ice + water). After 10 h, the inner tube was removed, dried in O 2 for 12 h at 343 K, followed by heating to 693 K and maintaining this temperature for 8 h.
- a silica sol processing method was adopted from de Lange (Microporous sol-gel derived ceramic membranes for gas separation, Ph.D. dissertation, University of Twente, The Netherlands, 1993), which involved refluxing a solution of TEOS, H 2 O, C 2 H 5 OH, and HNO 3 (in the ratio 1 :1 :26:11.76) at 353K for 2 h.
- a sample of the solution was diluted with C 2 H 5 OH (1 : 18) and the membrane dipped (with ends sealed to prevent the solution from coating the inner side of the tube) for a few seconds. It was then dried at 393 K for 3 h and calcined at 673 K for 3 h.
- TEOS tetraethoxysilane
- J. Membr. Sci. 42 (1989) 109 The method was similar to the description of the present invention except that the TEOS was decomposed at a low temperature (473 K).
- the TEOS was also introduced through a bubbler at room temperature using Ar (3 ⁇ mol s "1 ) as the carrier gas, but was premixed with 0 2 (5 ⁇ mol s "1 ) to facilitate the decomposition of TEOS at the lower temperature.
- the TEOSAr-O 2 stream was introduced on the tube side and was allowed to flow for 80 h after which the reactor was cooled in Ar.
- the porous glass membrane modified by the various methods described above was tested for permeability.
- Figure 6 compares the H 2 /CH 4 separation ratios for the membranes prepared by the modification of the original porous glass membrane by polymerization, dip coating, silica sols and decomposition of TEOS (at 473 K). There was no enhancement in selectivities by modifying the porous membrane by any of these methods (compare to table 2).
- the H 2 permeabilities were at or lower than the permeability of the original support material. It was also observed that the membranes would often fracture during thermal treatment particularly, those made by the sol-gel and silica sol methods. Also, with silica sol processing and polymerization, it was extremely difficult to ensure repeatability due to the inherent nature of these processes.
- the membranes described in this invention were characterized by N, physisorption conducted in a volumetric unit (Micromeritics ASAP 2000) using 0.4-0.6 g of the sample.
- the desorption isotherm was obtained by retracing the above steps. A total of 156 points was used to obtain the adsorption desorption isotherms.
- the Barrett, Joyner and Halenda (B JH) method was used to determine the pore size distribution from the desorption isotherm (because of the fact that the desorption curve represents the thermodynamically stable adsorbate).
- Figure 9 shows the reactor used for the catalysis studies which was of a concentric shell 901 and tube 902 type with a central 4 cm catalyst bed 903 packed on the shell 902 side.
- the nominal diameters of the outer 902 and inner 901 tubes were 16 mm and 10 mm respectively, with a thickness of 1 mm.
- a quartz tube with a central 4 cm porous glass section (glass blown to the tube) was incorporated.
- the ends of the reactor were sealed with Swagelock fittings 904 equipped with lines for introducing feed gases and removing products. Inlet flow was controlled using mass flow controllers (not shown) (Brooks model 5850E) and shell and tube side pressures were monitored using pressure gauges (not shown).
- the inlet 905 to the shell side was a mixture of Ar, CH 4 and CO 2 .
- Ar was also introduced in the tube side inlet 906 as a sweep gas (only for membrane experiments).
- the central part of the reactor was heated using a furnace.
- the specific surface area (Sg) of the catalyst and support (Al 2 O 3 ) was determined using a five-point N 2 BET (Brumauer, Emmett, and Teller) analysis and the number of active sites was obtained by titrating with CO.
- Tables 4 and 5 provide results from physisorption and chemisorptron measurements for the 1% Rh/Al 2 O 3 catalyst.
- the BET surface area measurements indicated a high surface area for the alumina support. Surface areas decreased moderately after reaction.
- the number of active sites was determined by titrating with CO. The value of 60 ⁇ mol g "1 for the fresh sample corresponded to a dispersion of 72%, while the value of 48 ⁇ mol g-1 for the spent sample indicated a dispersion of 58%.
- Table 4 Nitrogen Physisorption results
- a typical experimental procedure involved mixing 0.5 g of catalyst (30/120 mesh) with an appropriate amount of quartz chips (30/120 mesh) to make up the 4 cm bed on the shell side. The ends of the reactor were then sealed with the fittings after checking for the absence of leaks the catalyst was heated to 723 K in Ar flow (27 ⁇ mol s -1 ), reduced in H 2 (24 ⁇ mol s '1 ) for 0.5 h, and then heated to the reaction temperature with only the Ar flow.
- the dry reforming reaction (1) of methane with carbon dioxide is highly endothermic and two moles of reactants produce four moles of products. Hence, the reaction is favored by high temperatures and low pressures.
- the stoichiometry of (I) indicates that the expected HJCO ratio in the product stream to be 1.0. Experimentally, this ratio was less than 1.0 and can be attributed to the occurrence of the reverse water-gas shift reaction, RWGS) (2),
- Figure 10 compares the methane conversions in the three reactor configurations: fixed-bed, porous glass membrane, and Nanosil membrane. Both the membrane configurations provided methane conversions that were higher than equilibrium conversion levels. The Nanosil membrane reactor however, provided conversions higher than the Vycor reactor configuration. Experimental observations indicated that H 2 separation by the Nanosil membrane was comparable to the porous glass membrane with the added advantage of providing almost 190% pure H 2 separation. While the invention has been described in terms of a single preferred embodiment, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the appended claims.
- the method of preparation which involves the deposition of a thin layer of silica over a porous glass substrate (e.g., Vycor) should be applicable to any porous substrate such as alumina, titania, zirconia, or zeolit,e, by themselves or in combination with each other or other supports such as anodized alumina or stainless steel or other metal filters.
- the reaction studied in the present example is that of the dry reforming of method to produce a mixture of H 2 and CO.
- any reaction that produces H 2 should be enhanced by using the membrane in this invention.
- the silica coatings of this invention which are formed in an inert atmosphere lacking oxygen or steam, are preferably thin (e.g., on the o order of 10-100 A) such that the support retains a high permeability.
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Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00913269A EP1154836B1 (en) | 1999-02-02 | 2000-01-31 | Hydrogen-selective silica based membrane |
US09/890,020 US6527833B1 (en) | 1999-02-02 | 2000-01-31 | Hydrogen-selective silica based membrane |
AU34743/00A AU766490B2 (en) | 1999-02-02 | 2000-01-31 | Hydrogen-selective silica based membrane |
DE60031245T DE60031245D1 (en) | 1999-02-02 | 2000-01-31 | SILICON-BASED DIAPHRAGNETICALLY SELECTED AGAINST HYDROGEN |
CA002361504A CA2361504A1 (en) | 1999-02-02 | 2000-01-31 | Hydrogen-selective silica based membrane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US11843399P | 1999-02-02 | 1999-02-02 | |
US60/118,433 | 1999-02-02 |
Publications (1)
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WO2000045940A1 true WO2000045940A1 (en) | 2000-08-10 |
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PCT/US2000/002075 WO2000045940A1 (en) | 1999-02-02 | 2000-01-31 | Hydrogen-selective silica based membrane |
Country Status (7)
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US (1) | US6527833B1 (en) |
EP (1) | EP1154836B1 (en) |
AT (1) | ATE342119T1 (en) |
AU (1) | AU766490B2 (en) |
CA (1) | CA2361504A1 (en) |
DE (1) | DE60031245D1 (en) |
WO (1) | WO2000045940A1 (en) |
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US6503298B1 (en) | 2001-04-30 | 2003-01-07 | Battelle Memorial Institute | Apparatus and methods for hydrogen separation/purification utilizing rapidly cycled thermal swing sorption |
US6508862B1 (en) | 2001-04-30 | 2003-01-21 | Battelle Memorial Institute | Apparatus and methods for separation/purification utilizing rapidly cycled thermal swing sorption |
US6630012B2 (en) | 2001-04-30 | 2003-10-07 | Battelle Memorial Institute | Method for thermal swing adsorption and thermally-enhanced pressure swing adsorption |
WO2003101593A1 (en) * | 2002-06-04 | 2003-12-11 | Conocophillips Company | Hydrogen-selective silica-based membrane |
US6680044B1 (en) | 1999-08-17 | 2004-01-20 | Battelle Memorial Institute | Method for gas phase reactant catalytic reactions |
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KR101880769B1 (en) * | 2009-12-11 | 2018-07-20 | 스미토모덴키고교가부시키가이샤 | Silica-based hydrogen separation material and manufacturing method therefor, as well as hydrogen separation module and hydrogen production apparatus having the same |
US8900344B2 (en) * | 2010-03-22 | 2014-12-02 | T3 Scientific Llc | Hydrogen selective protective coating, coated article and method |
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- 2000-01-31 CA CA002361504A patent/CA2361504A1/en not_active Abandoned
- 2000-01-31 US US09/890,020 patent/US6527833B1/en not_active Expired - Lifetime
- 2000-01-31 EP EP00913269A patent/EP1154836B1/en not_active Expired - Lifetime
- 2000-01-31 WO PCT/US2000/002075 patent/WO2000045940A1/en active IP Right Grant
- 2000-01-31 AT AT00913269T patent/ATE342119T1/en not_active IP Right Cessation
- 2000-01-31 AU AU34743/00A patent/AU766490B2/en not_active Expired
- 2000-01-31 DE DE60031245T patent/DE60031245D1/en not_active Expired - Lifetime
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US6680044B1 (en) | 1999-08-17 | 2004-01-20 | Battelle Memorial Institute | Method for gas phase reactant catalytic reactions |
EP1920818A3 (en) * | 2001-03-16 | 2008-08-13 | The Robert Gordon University | Apparatus and method for separating gases |
US6974496B2 (en) | 2001-04-30 | 2005-12-13 | Battelle Memorial Institute | Apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption |
US6508862B1 (en) | 2001-04-30 | 2003-01-21 | Battelle Memorial Institute | Apparatus and methods for separation/purification utilizing rapidly cycled thermal swing sorption |
US6630012B2 (en) | 2001-04-30 | 2003-10-07 | Battelle Memorial Institute | Method for thermal swing adsorption and thermally-enhanced pressure swing adsorption |
US6503298B1 (en) | 2001-04-30 | 2003-01-07 | Battelle Memorial Institute | Apparatus and methods for hydrogen separation/purification utilizing rapidly cycled thermal swing sorption |
US6814781B2 (en) | 2001-04-30 | 2004-11-09 | Battelle Memorial Institute | Methods for separation/purification utilizing rapidly cycled thermal swing sorption |
US6824592B2 (en) | 2001-04-30 | 2004-11-30 | Battelle Memorial Institute | Apparatus for hydrogen separation/purification using rapidly cycled thermal swing sorption |
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US6854602B2 (en) | 2002-06-04 | 2005-02-15 | Conocophillips Company | Hydrogen-selective silica-based membrane |
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EP1720634A4 (en) * | 2004-02-10 | 2007-08-15 | Virginia Polytechnic Inst | Hydrogen-selective silica-based membrane |
JP2018159699A (en) * | 2017-03-23 | 2018-10-11 | 株式会社住化分析センター | Kit for thickening impurities in hydrogen gas, method for thickening impurities in hydrogen gas and method for managing quality of hydrogen gas |
CN108187507A (en) * | 2017-12-22 | 2018-06-22 | 中国矿业大学(北京) | Reactive electrochemical membrane that a kind of surface is modified and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
EP1154836A4 (en) | 2002-08-28 |
AU3474300A (en) | 2000-08-25 |
US6527833B1 (en) | 2003-03-04 |
ATE342119T1 (en) | 2006-11-15 |
EP1154836A1 (en) | 2001-11-21 |
CA2361504A1 (en) | 2000-08-10 |
DE60031245D1 (en) | 2006-11-23 |
AU766490B2 (en) | 2003-10-16 |
EP1154836B1 (en) | 2006-10-11 |
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