CN101300706A - Process and catalyst for hydrogenation of carbon oxides - Google Patents
Process and catalyst for hydrogenation of carbon oxides Download PDFInfo
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- CN101300706A CN101300706A CNA200680041258XA CN200680041258A CN101300706A CN 101300706 A CN101300706 A CN 101300706A CN A200680041258X A CNA200680041258X A CN A200680041258XA CN 200680041258 A CN200680041258 A CN 200680041258A CN 101300706 A CN101300706 A CN 101300706A
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- oxycarbide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 42
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 229910002090 carbon oxide Inorganic materials 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 8
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 16
- 229910020068 MgAl Inorganic materials 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 36
- 229910052751 metal Inorganic materials 0.000 description 34
- 239000002184 metal Substances 0.000 description 34
- 229910002091 carbon monoxide Inorganic materials 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 10
- 229960004424 carbon dioxide Drugs 0.000 description 8
- 239000000446 fuel Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910003271 Ni-Fe Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910017061 Fe Co Inorganic materials 0.000 description 2
- 101000852483 Homo sapiens Interleukin-1 receptor-associated kinase 1 Proteins 0.000 description 2
- 102100036342 Interleukin-1 receptor-associated kinase 1 Human genes 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052773 Promethium Inorganic materials 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical class [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
A process for hydrogenation of carbon oxides comprising contacting a gas mixture containing carbon oxides and of hydrogen with a catalyst comprising bimetallic iron-nickel or iron-cobalt alloys as the active catalytic material supported on a carrier of an oxide. The carrier is preferably formed to have a surface area greater than 20 m<2>/g.
Description
Background of invention
The present invention relates to the method for hydrotreating and the catalyst of oxycarbide (carbon monoxide and carbon dioxide).More particularly, the present invention relates to by use comprise carrier and with the catalyst of the active material of oxidation or reduction Ni, Fe of form and Co metal alloy composition by the hydrogenation reaction or the method for removing oxycarbide.
The existence of carbon monoxide is unwelcome in the fuel gas in some technologies.
In fuel cell (for example polymer dielectric film fuel cell), the existence of carbon monoxide is very crucial, because it can make noble metal electrode used in the fuel cell poison and reduce its validity thus.
Preferably, the CO concentration of fuel cell charging should be more preferably less than 50ppm less than 100ppm.Yet the initial concentration of the CO that obtains from fuel processor may surpass 1wt%.Therefore, need further to reduce CO concentration.Some methods that are generally used for reducing CO concentration are gating catalytic oxidations, transformation absorption of CO, by the Hydrogen Separation of film and the methanation of CO.
Similarly, in the ammonia preparation facilities, the existence of CO also is very unwelcome in ammonia synthesis reactor, and carbonomonoxide concentration is used usually and is reduced to the numerical value that is low to moderate 5～10ppmv.
The reaction of carbon monoxide and carbon dioxide and hydrogen also can be used for separation of methane/synthetic natural gas (SNG).SNG can be prepared by methanation then by biomass or coal gasification.
Methanation is in the presence of catalyst oxycarbide and hydrogen to be carried out prepared in reaction methane and other lower hydrocarbon of possibility less amount and the method for water.In known methanation method, at for example Al
2O
3, SiO
2Or TiO
2Carrier on the noble metal of load as the catalyst (U.S. Patent number 3615164 and WO 01/64337) of CO methanation.These catalyst can be reduced to CO concentration the numerical value of about 500～800ppm usually.The nickel-alumina catalyst that is used for conventional methanation method at present comprises the nickel of vast scale, surpasses about 20wt% usually.This demand has now been decided the actual fabrication method of this catalyst to a certain extent.In ammonia device, methanation mainly under 250 ℃～350 ℃ temperature at Ni/Al
2O
3Catalyst carries out under existing.Need carry out modification to realize reduction and reaction under the temperature lower in than conventional design to this catalyst.
The alloy of reactive metal and second activity or inactive metal can change this catalytic performance greatly.For example for monometallic iron catalyst and bimetallic copper-iron catalyst (A.M.van der Kraan, J.W.Geus, Appl Catal.A 171 (1998) 333 for E.Boellard, F.Th.Van Scheur).Further proof has substantially changed reduction form, carbon monoxide chemisorbed character and fischer-tropsch activity by add copper in iron phase.
French patent application FR 863473-A discloses the method by the hydrogenation preparing hydrocarbon of carbon monoxide, and wherein to comprise atomic ratio be 1: 1 iron and nickel to catalyst.
Patent application US 2005/0096211 discloses the catalyst that is used for fuel cells applications, and methanation has higher selectivity to CO for it, prevents CO
2Be converted into CO, and suppress CO
2Methanation.This catalyst package is contained in and is selected from ruthenium, nickel, iron, cobalt, lead, tin, silver, iridium, gold, copper, manganese, zinc, zirconium, molybdenum, other metal of formation metal carbonyl part and the metal of composition thereof on the load.
Summary of the invention
We find by improving in carbon monoxide and the carbon dioxide activity in the methanation of methane with nickel and ferroalloy in the special metal scope.
According to aforementioned discovery, the invention provides process for hydrogenation of carbon oxides, comprise that the admixture of gas that will comprise oxycarbide and hydrogen contacts with comprising the catalyst as the bimetallic Fe-Ni alloy of active catalytic material that loads on the oxide carrier, wherein this iron-nickle atom ratio is 0.1～0.8.
In the wideest scope, the present invention includes this new catalyst product.Therefore, we provide the hydrogenation catalyst of oxycarbide, comprise loading on the oxide carrier as the bimetallic Fe-Ni alloy of active catalytic material, and wherein this iron-nickle atom ratio is 0.1～0.8.
In preferred implementation of the present invention, this iron-nickle atom ratio is 0.1～0.7, for example 0.1～0.6, and preferred 0.1～0.5, more preferably 0.2～0.5, it produces wonderful high CO hydrogenation activity (methanation activity), therefore higher oxycarbide conversion ratio.Most preferably, this iron-nickle atom is than for about 0.3, and for example 0.35, such methanation activity that reaches even higher.
We find also and can improve in carbon monoxide and the carbon dioxide activity in the methanation of methane by make iron and cobalt alloy in the special metal scope.Therefore, we also provide process for hydrogenation of carbon oxides, comprise that the admixture of gas that will comprise oxycarbide and hydrogen contacts with comprising the catalyst as the bimetallic iron-cobalt alloy of active catalytic material that loads on the oxide carrier, wherein this iron-cobalt atom ratio is 0.05～2.
The present invention also comprises this new catalyst product.Therefore, we provide the hydrogenation catalyst of oxycarbide, comprise loading on the oxide carrier as the bimetallic Fe-Ni alloy of active catalytic material, and wherein this iron-cobalt atom ratio is 0.05～2.
In preferred implementation of the present invention, this iron-cobalt atom ratio is 0.1～1, for example 0.1～0.9, or 0.1～0.8, preferred 0.1～0.5, more preferably 0.2～0.5, it produces wonderful high CO hydrogenation activity (methanation activity), therefore higher oxycarbide conversion ratio.Most preferably, this iron-cobalt atom is than for about 0.3, and for example 0.35, such methanation activity that reaches even higher.
We also find the influence that the methane selectively in oxycarbide hydrogenation process and methanation activity are subjected to pressure used in reaction when catalyst comprises bimetallic iron-nickel, cobalt-nickel or iron-cobalt alloy.Therefore we also provide process for hydrogenation of carbon oxides, comprise the admixture of gas that will comprise oxycarbide and hydrogen and comprise the catalyst that loads on the oxide carrier and contact as bimetallic iron-nickel, cobalt-nickel or the iron-cobalt alloy of active catalytic material, wherein this total pressure is greater than 20 crust, more preferably 20～80 cling to, most preferably 30～60 crust for example 30 cling to.
This nickel-cobalt atom ratio is preferably 0.3～3.
Be preferably formed as the oxide carrier of this catalysis material load (this carrier) and have greater than 20m
2The surface area of/g.
In this specification, term carrier and load are used interchangeably.
Preferably, in the described admixture of gas that comprises oxycarbide and hydrogen, there is the excessive hydrogen of stoichiometry, substantially exceeds this stoichiometry usually.Stoichiometry is meant according to reaction CO+3H
2→ CH
4+ H
2O and CO
2+ 4H
2→ CH
4+ 2H
2O, oxycarbide carbon monoxide or carbon dioxide transform the accurate amount of required hydrogen fully.
Term oxycarbide used herein is used to comprise component carbon monoxide, carbon dioxide or both mixtures.
Be used for catalyst of the present invention and comprise having the regular lattice structure and be selected from oxide and (be generally MgAl
2O
4, Al
2O
3, SiO
2, ZrO
2And composition thereof) load on the element that is selected from nickel, iron and cobalt.Other load that is fit to comprises cerium oxide and magnesium oxide, its can with MgAl
2O
4, Al
2O
3, SiO
2, ZrO
2Combine or be not used in combination.Resulting bimetallic catalyst is catalyst based or according to Ni, the Fe of prior art and the alloy phase ratio of Co metal with traditional monometallic Ni, can more effectively use H
2To the oxycarbide hydrogenation.
Obtained extra high oxycarbide conversion ratio according to another embodiment of the present invention, wherein iron-nickel or iron-cobalt atom ratio is 0.1～0.8, for example 0.1～0.7, or 0.1～0.6, preferred 0.2～0.5, most preferably from about 0.3, this method is to carry out under the pressure greater than about 20 crust, more preferably 20～80 the crust, most preferably 30～60 the crust between pressure, for example about 30 the crust.Therefore, by the present invention, we also provide process for hydrogenation of carbon oxides, comprise that the admixture of gas that will comprise oxycarbide and hydrogen loads on contacting as the bimetallic Fe-Ni alloy of active catalytic material or the catalyst of iron-cobalt alloy on the oxide carrier with comprising, wherein this total pressure is clung to greater than 20, and this iron-nickle atom ratio is 0.1～0.8.In preferred embodiment, we provide process for hydrogenation of carbon oxides, comprise that the admixture of gas that will comprise oxycarbide and hydrogen loads on contacting as the bimetallic Fe-Ni alloy of active catalytic material or the catalyst of iron-cobalt alloy on the oxide carrier with comprising, wherein this total pressure is about 30 crust, and this iron-nickle atom ratio is about 0.3.
Be applicable in the methanation that (for example (is being used to prepare hydrocarbon) under the fischer-tropsch conditions) under the higher CO pressure and is particularly hanging down oxycarbide under the CO pressure according to method of the present invention, wherein for the reduction of carbon monoxide in polymer dielectric film (PEM) fuel cells applications and the synthesis gas that in the preparation process of ammonia, uses, must remove carbon monoxide, the removal of oxycarbide is also quite important in the preparation process of synthetic natural gas (SNG).In the latter,, oxycarbide is removed from this gas gradually by it is passed through a plurality of tactic reactors.Usually the gas that enters first reactor comprises about 50 volume %H
2With 16～17 volume % oxycarbides, and in last reactor (common the 4th reactor), enter H in the gas
2Content be about 4 volume % usually, the content of oxycarbide is low to moderate 1.2 volume %.Therefore in the end need methanation activity especially in the reactor, wherein must removal still remain in the small amount of carbon oxide in the gas.
Therefore, method of the present invention and catalyst under low CO pressure condition especially effectively (higher methanation activity), wherein the content of oxycarbide is lower than 5 volume %, and hydrogen content is in 1～10 volume % scope, common about 4 volume % hydrogen are for example in the preparation synthetic natural gas.Method of the present invention and catalyst also are effective under low CO pressure condition usually, wherein the content of oxycarbide is lower than 5 volume %, hydrogen content is greater than 40 volume %, for example in the preparation of ammonia synthesis gas from synthesis gas reduction carbon monoxide and/or in fuel cells applications, remove in the oxycarbide.
The accompanying drawing summary
Fig. 1 be according to the mixing Ni-Fe catalyst of the present invention preparation with have containing of same metal content of pure Ni or the diagram of the catalyst of the Fe CO methanation activity of comparing.
Fig. 2 is the diagram that different metal mixes the CO hydrogenation activity of iron-Raney nickel of forming that has according to the present invention's preparation.Total content of metal for the catalyst of all demonstrations is identical, all be about 2.5wt%, but it can easily be brought up to greater than 25wt%.
Fig. 3 is the diagram of the CO hydrogenation activity of iron-Co catalysts.Total content of metal for the catalyst of all demonstrations is identical, all is about 7.5wt%.
Detailed Description Of The Invention
By exemplary embodiment, figure and embodiment the present invention is described herein. Shown here Any embodiment, figure, embodiment and related data all only provide for principle of the present invention is advanced The row example is not limited to scope of the present invention.
Can metal be added on the carrier with the method that suppresses in any prior art, for example but also Non-limiting dipping, incipient wetness impregnation, immerse and spray. Metal nitrate used herein Can in air, will be decomposed into the water-soluble of oxide once heating with any in the prior art Salt or complex compound replace. Therefore, in another embodiment of the present invention, use in air one The precursor that will be converted into oxide through heating is immersed in this bimetallic catalyst on this carrier. Gold Belonging to component also can be in wide region with the order that obtains bimetallic catalyst to the dipping of load Change.
Comprising methane, hydrogen, two in exemplary for removal or the substantive oxycarbide that reduces Can use this catalysis in the method for the amount in the admixture of gas of carbonoxide, carbon monoxide and water Agent. The method can be used for admixture of gas in the temperature that is lower than the generation water shift reaction and occurred frequently Give birth under the temperature of temperature of selective methanation of carbon monoxide by on the catalyst.
In this catalyst, total content of metal of the content restriction of bimetallic active catalytic material is arranged Be preferably about 2.5wt%, but its also can bring up to 10,20,25,30,35,40wt%, Even high to 50wt%. Therefore, according to the present invention, the content of bimetallic active catalytic material is 2 Wt%～50wt%. Higher content of metal can access higher methanation activity.
Preferred load (carrier) is spinel-type MgAl2O
4, its can be in this area The spheroidal pelle of knowing or extrude the form of cylinder ring particle. Extrude the external diameter that ring has 5mm usually With the internal diameter of 2.5mm, aspect ratio is 2～10. Therefore, the particle diameter of this particle can be from 0.10mm Change to 10mm, preferred size (external diameter) is about 5mm. The particle diameter of this load also can 0.10mm in～1mm the scope, more preferably 0.25mm～0.5mm, pore volume is at 0.1cm3/g～
1.0cm
3In/g the scope, preferred about 0.7cm3/ g. Above-mentioned surface area is preferably greater than 20m2/ g, more preferably from about 70m2/ g. Another preferred load is Al2O
3, it also can be as known in the art Spheroidal pelle or extrude the form of cylinder ring particle. Extrude the external diameter and 2.5 that ring has 5mm usually The internal diameter of mm, aspect ratio are 2～10. Therefore, the particle diameter of this particle can become from 0.10mm Change to 10mm, preferred size (external diameter) is about 5mm. The particle diameter of this load also can 0.10mm in～1mm the scope, more preferably 0.25mm～0.5mm, pore volume is at 0.1cm3/g～
1.0cm
3In/g the scope, preferred about 0.7cm3/ g. Surface area is at 100～200m2In/g the scope, preferred 150m2/ g. Another preferred load is to have and MgAl2O
4And Al2O
3Same particle size and pore volume and surface area are at 200～400m2In/g the scope, preferred 300m2The silica SiO of/g2 Use Al2O
3Replace MgAl2O
4Usually can have higher methane selectively, but use MgAl2O
4CO conversion ratio (methanation activity) is usually higher during as carrier. In order to find first Selective and the CO conversion ratio of alkane is sufficiently high carrier all, can prepare MgAl2O
4And Al2O
3 Suitable mixture.
Method of the present invention and catalyst can carry out under the temperature of wide region, but in reaction temperature Be 200～600 ℃, preferred 200～400 ℃, more preferably greater than 250 ℃, for example 275 or 300 Or this catalyst particularly suitable under 350 ℃ the condition. Higher temperature can obtain higher CO Conversion ratio (higher methanation activity).
For comprising the bimetallic iron-nickel as active catalytic material that loads on the catalyst carrier The catalyst of alloy is obtaining best performance aspect methanation activity and the methane selectively, wherein This iron-nickle atom ratio is 0.1～0.5, and gross pressure is greater than 20 bar, and total metal content is greater than 20wt %, reaction temperature is greater than 225 ℃. In special embodiment, this carrier is Al2O
3, iron-nickel Atomic ratio is about 0.3, and gross pressure is about 30 bar, and total metal contents in soil is greater than 20～25wt%, and is anti-Answering temperature is about 300 ℃. Obtain CO up to 95% according to these enforcement of regulations the method2Transform Rate, 100% methane selectively does not generate higher hydrocarbon.
Can be selected from lanthanide series (rare earth element) with one or more, be preferably selected from cerium (Ce), The oxidation of the element of praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm) and composition thereof Thing promotes this catalyst. Therefore, this catalyst can further comprise the short of about 3wt% Advance agent, for example 5,7,10,15wt% or higher, wherein this promoter is one or more choosings Oxide from the element of cerium, praseodymium, neodymium, promethium, samarium and composition thereof.
Embodiment
In an embodiment, under different technology conditions, tested according to iron-Raney nickel of the present invention and be converted into activity and selectivity in the methanation of methane at carbon monoxide.Embodiment 1～21 and 23 carries out under the total pressure of about 1 crust, and in embodiment 22, pressure is 31 crust.
Embodiment 1
Use nickel nitrate (Ni (NO
3)
2) aqueous solution is that 0.25mm～0.5mm and pore volume are about 0.7cm to particle diameter
3/ g and surface area are about 70m
2The spinel-type MgAl of/g
2O
4Load carries out the comparative catalyst that the incipient wetness impregnation preparation contains Ni, makes resulting catalyst have the Ni of about 2.5wt%.Before dipping, in drying oven under 200 ℃ to dry 5 hours of this load.For being filled in the hole of this carrier, salting liquid needs about 4 hours time.At room temperature to dry 12 hours of the spinelle of this dipping, the rate of heat addition with 2.5 ℃/minute is heated to 500 ℃ in air then, keeps 5 hours at 500 ℃ then.
Embodiment 2
The method of following embodiment 1 prepares the comparative catalyst, only is to use ferric nitrate Fe (NO
3)
3Replace nickel nitrate, obtain comprising the catalyst of the Fe of about 2.5wt%.
Embodiment 3
Use the incipient wetness impregnation of carrier to prepare catalyst as shown in Example 1, just reduce Ni (NO
3)
2Concentration in resulting catalyst, to obtain the Ni of 2.1875wt%.Behind dipping, at room temperature, use Fe (NO then to this sample drying 12 hours
3)
3Solution impregnation obtains the concentration of iron of about 0.3125wt% in resulting catalyst.At room temperature to the catalyst of dipping dry 12 hours then, the rate of heat addition with 2 ℃/minute was heated to 500 ℃ in air then, keeps 5 hours at 500 ℃.
Embodiment 4
The method of following embodiment 3 prepares catalyst, just reduces Ni (NO
3)
2Concentration in resulting catalyst, to obtain the Ni of 1.875wt%, improve Fe (NO simultaneously
3)
3Concentration in resulting catalyst, to obtain the Fe of 0.625wt%.Fig. 1 has shown the performance of this catalyst under different temperatures.
Embodiment 5
The method of following embodiment 3 prepares catalyst, just reduces Ni (NO
3)
2Concentration in resulting catalyst, to obtain the Ni of 1.5625wt%, improve Fe (NO simultaneously
3)
3Concentration in resulting catalyst, to obtain the Fe of 0.9375wt%.
Embodiment 6
The method of following embodiment 3 prepares catalyst, just reduces Ni (NO
3)
2Concentration in resulting catalyst, to obtain the Ni of 1.25wt%, improve Fe (NO simultaneously
3)
3Concentration in resulting catalyst, to obtain the Fe of 1.25wt%.
Embodiment 7
The method of following embodiment 3 prepares catalyst, just reduces Ni (NO
3)
2Concentration in resulting catalyst, to obtain the Ni of 0.625wt%, improve Fe (NO simultaneously
3)
3Concentration in resulting catalyst, to obtain the Fe of 1.875wt%.
Embodiment 8
Prepare a series of catalyst similarly with embodiment 1～7, just the metal total concentration high 4 times (10wt%) in resulting catalyst.
Embodiment 9
With a series of catalyst of preparation similarly described in the embodiment 4, just the total concentration of the Ni+Fe metal in resulting catalyst is 2.5,5.0,10 and 20wt%.
Embodiment 10
Prepare a series of catalyst similarly with those catalyst of being discussed among the embodiment 1～7, only being to use specific area is about 150m
2/ g and particle diameter are the aluminium oxide Al of 0.25～0.5mm
2O
3Replace MgAl
2O
4Spinelle is as load.
Embodiment 11
Prepare a series of catalyst similarly with embodiment 1～7, just the metal total concentration higher (10wt%) in resulting catalyst.
Embodiment 12
Prepare a series of catalyst similarly with the catalyst series among the embodiment 10, just comprise the metal of 22～24wt%, and the nickel content in the metal is 99.4～67.2%, remain and be iron.
Embodiment 13
Prepare a series of catalyst similarly with embodiment 1～7, only being to use specific area is about 300m
2/ g and particle diameter are the silicon oxide sio of 0.25～0.5mm
2Replace MgAl
2O
4Spinelle is as load.
Embodiment 14
Prepare a series of catalyst, just the total content of metal high four times (10wt%) in resulting catalyst similar to Example 10ly.
Embodiment 15
The performance of the catalyst of preparation in the test implementation example 1～7 in the quartzy U-shaped pipe reactor of fixed bed.(part 0.25～0.50mm) is placed in this quartz U-shaped pipe reactor between two quartzy batts with the 150mg catalyst.Then with about 40000h
-1Space-time speed and the air-flow that under the reaction pressures of 1.1～1.3 crust, comprises 2vol%CO in H2 introduce in this reactor.Before determination of activity, this catalyst was reduced 4 hours at 500 ℃ in hydrogen, reduce temperature then, monitor the concentration of CO methane and other product simultaneously.
Embodiment 16
Measure blank CO hydrogenation activity as shown in Example 15, just loading catalyst not in reactor.Do not transforming to detecting CO under the stable condition and under 500 ℃ temperature.
Embodiment 17
The result who has provided in the table 1 as the methanation activity of several catalyst of preparation among the embodiment 1～7 compares.Obviously to close traditional monometallic Ni catalyst based better for visible preferred bimetallic Fe-Ni catalyst from these data, at iron-nickle atom than (approximating weight ratio; Atomic ratio=weight ratio * 1.05) obtained extra high methanation activity (test is as CO conversion ratio %) in the time of between 0.1～0.5.
Embodiment 18
Provided in the table 2 as the methanation activity of several catalyst of preparation among the embodiment 8 and optionally result's comparison.Obviously visible Fe from the data of table 1 and table 2: the Ni ratio is that the bimetallic Fe-Ni catalyst of 1: 1 and 1: 3 is catalyst based better than traditional monometallic Ni.Especially, find Fe: the Ni ratio is that the bimetallic Fe-Ni catalyst of 1: 3 (iron-nickle atom is than being about 0.3) has higher methanation activity.
Embodiment 19
Provided for Ni in the table 3
3Fe catalyst (be Fe: the Ni ratio is 1: 3 (iron-nickle atom is than being about 0.3)) as the methanation activity of the catalyst of preparation among the embodiment 9 and optionally result's comparison.From these data, obviously as seen when higher total content of metal, reached best catalytic performance.
Provided in the table 2 as the methanation activity of several catalyst of preparation among the embodiment 10 and optionally result's comparison.From these data obviously as seen at Al
2O
3Under the situation of carrier, Fe: the Ni ratio is that the bimetallic Fe-Ni catalyst of 1: 1 and 1: 3 also has the catalyst based higher activity than traditional monometallic Ni, and the data in also higher table 4 of selectivity and the table 3 show when using Al in this case
2O
3The time with use MgAl
2O
4Compare during as carrier, realized higher methane selectively.
Embodiment 21
The performance of catalyst of preparation in the test implementation example 12 in fixed bed tubular steel reactor under low pressure.With 40mg catalyst (part 0.25～0.5mm) and the 260mg inert material (MgAl described in the embodiment 1
2O
4Material) is placed in this reactor.Then with about 440000h
-1Space-time speed and 1.0～1.1 the crust reaction pressures under with H
2In comprise 9vol%CO
2Admixture of gas introduce in this reactor.Before determination of activity, this catalyst 550 ℃ of reduction 4 hours, is reduced temperature then, use gas chromatography monitoring CO simultaneously
2, CO, methane and other product concentration.Provided the comparison of the methanation activity of four kinds of catalyst of preparation among the embodiment 12 in the table 5.Obviously visible bimetallic Fe-Ni catalyst more has an activity than traditional monometallic Ni is catalyst based from these data.Especially, find Fe: the Ni ratio is that the bimetallic Fe-Ni catalyst of 1: 3 (iron-nickle atom is than being about 0.3) has higher methanation activity (CO2 conversion ratio %).
Embodiment 22
The performance of two kinds of catalyst of preparation in the test implementation example 12 in fixed bed tubular steel reactor under high pressure.(part 0.25～0.5mm) is placed in this reactor with the 300mg catalyst.Then with about 800000h
-1Space-time speed and 31 the crust reaction pressures under with H
2In comprise 4vol%CO
2Admixture of gas introduce in this reactor.Before determination of activity, this catalyst 550 ℃ of reduction 4 hours, is reduced temperature then, use gas chromatography monitoring CO simultaneously
2, CO, methane and other product concentration.The result who has provided the methanation activity of two kinds of catalyst of preparation among the embodiment 12 in the table 6 compares.Obviously as seen under high pressure bimetallic Fe-Ni catalyst than traditional monometallic Ni is catalyst based activity arranged more.In addition, the generation of higher hydrocarbon is negligible (higher selectivity).Especially, find Fe: the Ni ratio is that the bimetallic Fe-Ni catalyst of 1: 3 (iron-nickle atom is than being about 0.3) has higher methanation activity (CO
2Conversion ratio %).Used more much higher air speed although the data of table 5 and table 6 show in the catalyst in table 6, pressure is being realized obviously higher methanation activity when about 1 crust is brought up to about 30 crust.This effect even more obvious when reaction temperature is brought up to about 300 ℃.
Embodiment 23
Be similar to the activity of such catalysts of preparation in the embodiment 15 test implementation examples 11, just in reactant mixture, add the CO of 2 volume %
2Methanation activity and optionally result's comparison have been provided in the table 7.The alloy of obviously visible metal is compared with traditional catalyst and caused activity of such catalysts to significantly improve, and finds Fe especially: the Ni ratio is that the bimetallic Fe-Ni catalyst of 1: 3 (iron-nickle atom is than being about 0.3) has higher methanation activity.
Embodiment 24
Prepare a series of catalyst similarly with those catalyst of being discussed among the embodiment 1～7, only being to use specific area is about 150m
2/ g and particle diameter are the aluminium oxide Al of 0.25～0.5mm
2O
3Replace MgAl
2O
4Spinelle is as load, and use Co (NO
3)
2Replace Ni (NO
3)
2, and total content of metal is 7.5wt%.The result who has shown this iron-Co catalysts among table 8 and Fig. 3.Find that especially iron cobalt atom ratio is (to approximate weight ratio at 1: 3; Atomic ratio=weight ratio * 1.05) bimetallic Fe-Co catalyst has higher methanation activity.
The total content of metal of table 1. be 2.5wt% at MgAl
2O
4The catalytic performance of the monometallic of last load and bimetallic Ni-Fe catalyst.Gas composition: 2%CO, all the other are H
2GHSV＝40000h
-1(40.000h
-1)。
Table 1
The total content of metal of table 2. be 10wt% at MgAl
2O
4The catalytic performance of the monometallic of last load and bimetallic Ni-Fe catalyst.Gas composition: 2%CO, all the other are H
2GHSV＝40000h
-1(40.000h
-1)。
Table 2
Table 3. have different total content of metal at MgAl
2O
4The bimetallic Ni of last load
3The catalytic performance of Fe catalyst.Gas composition: 2%CO, all the other are H
2GHSV＝40000h
-1(40.000h
-1)。
Table 3
The total content of metal of table 4. be 10wt% at Al
2O
3The catalytic performance of the monometallic of last load and bimetallic Ni-Fe catalyst.Gas composition: 2%CO, all the other are H
2GHSV＝40000h
-1(40.000h
-1)。
Table 4
The total content of metal of table 5. be 22～24wt% at Al
2O
3The catalytic performance of the monometallic of last load and bimetallic Ni-Fe catalyst.Gas composition: 9%CO, all the other are H
2GHSV＝440000(440.000h
-1)h
-1。In these experiments, do not study selectivity.
Table 5
The total content of metal of table 6. be 22～24wt% at Al
2O
3The catalytic performance of the monometallic of last load and bimetallic Ni-Fe catalyst.Gas composition: 4%CO
2, all the other are H
2GHSV=780000h
-1(780.000h
-1), pressure is 31 crust.Methane is unique product after testing.
Table 6
The total content of metal of table 7. be 10wt% at Al
2O
3The catalytic performance of the monometallic of last load and bimetallic Ni-Fe catalyst.Gas composition: 2%CO, 2%CO
2, all the other are H
2GHSV＝40000h
-1(40.000h
-1)。
Table 7
The total content of metal of table 8. be 7.5wt% at Al
2O
3The catalytic performance of the monometallic of last load and bimetallic Fe-Co catalyst.Gas composition: 2%CO, all the other are H
2
Table 8
Claims (13)
1. process for hydrogenation of carbon oxides, comprise that the admixture of gas that will comprise oxycarbide and hydrogen contacts with comprising the catalyst as the bimetallic Fe-Ni alloy of active catalytic material that loads on the oxide carrier, wherein this iron-nickle atom ratio is 0.1～0.8.
2. process for hydrogenation of carbon oxides, comprise that the admixture of gas that will comprise oxycarbide and hydrogen contacts with comprising the catalyst as bimetallic iron-nickel, cobalt-nickel or the iron-cobalt alloy of active catalytic material that loads on the oxide carrier, wherein this total pressure is greater than 20 crust.
3. claim 1 or 2 method, wherein this carrier forms and has greater than 20m
2The surface area of/g.
4. claim 1 or 2 method wherein use in air the precursor that will be converted into oxide once heating that this bimetallic catalyst is immersed on this carrier.
5. claim 1 or 2 method, wherein this carrier is selected from MgAl
2O
4, Al
2O
3, SiO
2, ZrO
2, TiO
2And composition thereof.
6. claim 1 or 2 method, wherein the content of this bimetallic active catalytic material is 2wt%～50wt%.
7. claim 1 or 2 method, wherein this iron-nickle atom ratio is 0.2～0.5.
8. the method for claim 7, wherein this iron-nickle atom is than being about 0.3.
9. the method for claim 7, wherein this carrier is Al
2O
3
10. the method for claim 9, wherein this reaction temperature is 200 ℃～400 ℃.
11. the method for claim 10, wherein the concentration of this oxycarbide is less than 5 volume %, and this density of hydrogen is greater than 40 volume %.
12. the method for claim 2, wherein this stagnation pressure is in 20～80 crust scopes.
13. the hydrogenation catalyst of oxycarbide comprises loading on the oxide carrier as the bimetallic Fe-Ni alloy of active catalytic material that wherein this iron-nickle atom ratio is 0.1～0.8.
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| DKPA200600854 | 2006-06-24 | ||
| DK200600854A DK200600854A (en) | 2005-09-02 | 2006-06-24 | Process and catalyst for hydrogenation of carbon oxides |
| PCT/EP2006/008395 WO2007025691A1 (en) | 2005-09-02 | 2006-08-28 | Process and catalyst for hydrogenation of carbon oxides |
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| CN102247861A (en) * | 2011-05-11 | 2011-11-23 | 神华集团有限责任公司 | Coal gas high-temperature methanation catalyst and preparation method thereof |
| CN104209127A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Nickel iron bimetallic methanation catalyst and preparation and application thereof |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3876557A (en) * | 1973-06-29 | 1975-04-08 | Jackie Lou Bland | Metallic catalyst |
| US3933883A (en) * | 1975-04-14 | 1976-01-20 | W. R. Grace & Co. | Methanation catalyst and process of use |
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2006
- 2006-08-28 ZA ZA200802815A patent/ZA200802815B/en unknown
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| US11021809B2 (en) | 2015-02-06 | 2021-06-01 | Ecotricity Group Limited | Method of producing a synthetic diamond |
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| ZA200802815B (en) | 2009-09-30 |
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