CN101322942A - Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications - Google Patents
Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications Download PDFInfo
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- CN101322942A CN101322942A CN 200810045665 CN200810045665A CN101322942A CN 101322942 A CN101322942 A CN 101322942A CN 200810045665 CN200810045665 CN 200810045665 CN 200810045665 A CN200810045665 A CN 200810045665A CN 101322942 A CN101322942 A CN 101322942A
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- Prior art keywords
- oxygen
- coal bed
- bed gas
- containing coal
- oxide
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- 239000007789 gas Substances 0.000 title claims abstract description 99
- 239000001301 oxygen Substances 0.000 title claims abstract description 96
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 96
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003245 coal Substances 0.000 title claims description 81
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000010457 zeolite Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000292 calcium oxide Substances 0.000 claims abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004927 clay Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 14
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 abstract 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 abstract 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 abstract 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 229910052680 mordenite Inorganic materials 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- 239000000571 coke Substances 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 8
- 229960004643 cupric oxide Drugs 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 102100035353 Cyclin-dependent kinase 2-associated protein 1 Human genes 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a deoxidizing catalyst for a coal-seam gas containing oxygen and a preparation method as well as an application thereof. The deoxidizing catalyst of the invention consists of an active component, an active auxiliary and a porous carrier. The active component is the compound of Co; the active auxiliary is one or more compounds of Mn, Fe, Zn and Cu; the porous carrier is one or more of aluminum oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, silicon oxide, a phosphor-aluminium molecular sieve, an A-typed molecular sieve, an X-typed molecular sieve, a Y-typed molecular sieve, a mordenite, a ZSM-5 zeolite, diatomaceous earth, kaolinite, natural clay, aluminum silicate and magnesium silicate; calculated by oxide, the weight percentage of the active component is 1 to 60 percent; the weight percentage of the active auxiliary is 1 to 50 percent; the rest is the carrier. The catalyst of the invention has certain sulfur-resistance performance, is applicable to the deoxidization treatment of coal-seam gas with an oxygen content of 3 to 6 percent (V/V) and is capable of causing the oxygen content in the coal-seam gas to be lower than 0.5 percent by deoxidization.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of oxygen-containing coal bed gas deoxidation catalyst and preparation method thereof and the application in oxygen-containing coal bed gas deoxidation thereof.
Background technology
Coal bed gas is present in the coal seam in a large number, belongs to unconventional natural gas; It is the one of the main reasons that causes the colliery down-hole accident.In fact coal bed gas is a kind of calorific value height, and free of contamination new forms of energy can be used as fuel used to generate electricity, process fuel, industrial chemicals and resident living fuel etc.China causes the huge environmental pressure and the wasting of resources to about 300 billion cubic meters of airborne release coal bed gas every year.Coal bed gas is rationally fully utilized, can remedy China's energy shortage.The recycling of coal bed gas simultaneously also helps the protection ring border, and the greenhouse effects of methane are CO
2More than 20 times, a large amount of coal bed gas enters atmosphere and has aggravated Global Greenhouse Effect.Therefore, the poor efficiency of coal bed gas had both caused the significant wastage of resource, had increased the weight of environmental pollution again.
Southnest China Chemical Engineering Inst., Ministry of Chemical Industry discloses a kind of method of utilizing pressure swing adsorption method separation and concentration methane from coal bed gas in the Chinese patent ZL85103557 " methane in the pressure swing adsorption method enrichment coal mine mash gas " of application in 1985.Generally speaking, the oxygen content of methane discharging waste gas in concentrating purification process also is concentrated raising, owing to inevitably contain 5～15% methane in the waste gas, cause exhaust gas discharged to be in the explosion limit scope of methane, in the discharging waste gas pipe, all the time exist the danger of blast, this makes this The Application of Technology be restricted, thereby to carry out deoxidation treatment before coal bed gas comprehensive utilization be very necessary.
Present adoptable coal bed gas deoxidation method mainly contains catalytic deoxidation method (ZL02113628.9) and coke deoxidization method (ZL02113627.0,200610021720.1) etc., these two kinds of methods all can effectively be reduced to the oxygen content in the coal bed gas below 0.5%, propose the safety operation of dense process to guarantee subsequent technique.
Employed catalyst was noble metal catalysts such as Pt or Pd during Chinese patent ZL02113628.9 " produced the catalytic combustion deoxidization process of methyl alcohol with coal mine mash gas ", the advantage of this type of catalyst is the catalytic activity height, reaction temperature is lower, oxygen after the deoxidation in the gas can eliminate substantially, technological operation is easy, equipment is simple, is convenient to automatic control.Weak point is that catalyst costs an arm and a leg, contain sulfide in the coal bed gas simultaneously, thereby toxic effect causes catalysqt deactivation and sulphur is to noble metal, therefore will carry out desulfurization before deoxidation earlier carries out deoxygenation again, cause the deoxidation cost to increase like this, caused the disposal cost of coal bed gas catalytic deoxidation higher.
Coal bed gas coke method deoxidation (ZL02113627.0,200610021720.1) is under hot conditions, is rich in oxygen and coke gasification reaction in the methane gas, thereby while part methane and oxygen reaction reach the purpose of deoxidation.The advantage of coke method deoxidation is about 70% oxygen and coke gasification reaction, 30% oxygen and methane reaction, so the loss of methane is less.The disposal cost of this method is lower than precious metal catalyst deoxidation method.But shortcoming is this method and wants the coke resource of consume valuable that the consuming cost of coke is about about 50% of whole service expense.In addition the deoxidation of coke method its add Jiao, the labour intensity of slagging tap is big, ambient dust is bigger, and has the sulfide of variform in the coke.
In view of precious metal catalyst deoxidation and coke method deoxidation shortcoming separately, develop a kind of base metal oxygen-containing coal bed gas deoxidation catalyst and be undoubtedly a kind of optimal selection, have very big market prospects simultaneously.
Summary of the invention
The objective of the invention is in order to overcome above shortcomings in the prior art, a kind of new base metal oxygen-containing coal bed gas deoxidation catalyst is provided.
Another object of the present invention provides the preparation method of above-mentioned oxygen-containing coal bed gas deoxidation catalyst.
The 3rd purpose of the present invention provides the application of this oxygen-containing coal bed gas deoxidation catalyst in oxygen-containing coal bed gas deoxidation, making coalbed methane containing oxygen need not to carry out earlier desulfurization handles, can directly enter deoxidation in the deoxidation reactor, thereby reduce disposal cost, and simplify processing step.
Dehydrogenation catalyst of the present invention is by active component, coagent and porous carrier are formed, described active component is the compound of cobalt, described coagent is a manganese, iron, zinc, in the copper compound one or more, described porous carrier is selected from aluminium oxide, titanium oxide, zirconia, magnesia, calcium oxide, silica, phosphate aluminium molecular sieve, A type molecular sieve, X type molecular sieve, Y zeolite, modenite, the ZSM-5 zeolite, diatomite, kaolin, natural clay, alumina silicate, in the magnesium silicate one or more, in oxide, the weight percentage of active component is 1～60%, the weight percentage of coagent is 1～50%, and all the other are carrier.
Described active component is any one in cobalt oxide, cobalt acetate, cobalt nitrate, cobalt chloride or the cobaltous sulfate.
Described coagent is selected from the oxide of manganese, iron, zinc, copper or in the soluble-salt one or more.
Described coagent is selected from any one or a few in nitrate, chloride or the sulfate of manganese, iron, zinc, copper.
The preparation method of oxygen-containing coal bed gas deoxidation catalyst of the present invention may further comprise the steps:
(1) active component and coagent are mixed with the aqueous solution;
(2) porous carrier is immersed in the aqueous solution of step (1) preparation, flooded 6～12 hours down in normal temperature;
(3) with the mixture of step (2) gained by roller forming or extruded moulding, in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours can make oxygen-containing coal bed gas deoxidation catalyst of the present invention.
Coalbed methane containing oxygen catalyst of the present invention also can be prepared as follows:
(1) coagent compound and porous carrier are mixed in proportion;
(2) mixture with step (1) passes through compressing tablet, spin or extruded moulding, makes the oxygen-containing coal bed gas deoxidation catalyst precursor;
(3) active component is made into the aqueous solution, with this solution impregnation or the oxygen-containing coal bed gas deoxidation catalyst precursor that makes of spraying step (2), in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make oxygen-containing coal bed gas deoxidation catalyst.
Coalbed methane containing oxygen of the present invention also can be prepared as follows:
(1) active constituent compound and porous carrier are mixed in proportion;
(2) mixture that step (1) is made makes the oxygen-containing coal bed gas deoxidation catalyst precursor by compressing tablet, spin or extruded moulding;
(3) coagent is mixed with the aqueous solution, with the catalyst precarsor of this solution impregnation or spraying step (2), in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make oxygen-containing coal bed gas deoxidation catalyst.
The moulding of above-mentioned oxygen-containing coal bed gas deoxidation catalyst can be made multiple shapes such as spherical, strip, column, sheet, ring-type.
Oxygen-containing coal bed gas deoxidation catalyst of the present invention is the deoxidation treatment of the coal bed gas of 1～12% (V/V) applicable to oxygen content, be specially adapted to oxygen content and be the deoxidation treatment of 3～6% coal bed gas, can regulate the oxygen content that enters reactor, unstripped gas air speed 1000～6000h during deoxidation treatment by regulating circulating air
-1, reaction temperature is 200～750 ℃, reaction temperature is preferably 300～650 ℃, the oxygen content in the coal bed gas can be taken off after the reaction to less than 0.5%.
Key reaction in the deoxidation process of coalbed methane containing oxygen is:
CH
4+2O
2→CO
2+2H
2O
A small amount of methane generation cracking under the high temperature:
CH
4→C+2H
2
Following reaction further takes place again in charcoal and hydrogen that methane cracking produces:
2C+O
2→2CO
2CO+O
2→2CO
2
2H
2+O
2→2H
2O
Because methane and oxygen reaction are strong exothermal reactions, the adiabatic temperature rise of per 1% oxygen and methane reaction heat release is at 90～100 ℃, when oxygen content is higher in the raw material coal bed gas, can be by in the unstripped gas of the cooled gas of cyclic part deoxidation to the deoxidation, adjusting enters the oxygen content of reactor to optimum range, thereby effectively reaction temperature is controlled in the optimum range, coalbed methane containing oxygen catalytic deoxidation range of reaction temperature is 200～750 ℃.
Reaction velocity in the above-mentioned deoxidation reactor can be preferably 1000～6000h
-1
Compared with prior art, the invention has the beneficial effects as follows:
(1) compare with noble metal catalyst catalytic deoxidation method, coalbed methane containing oxygen catalytic deoxidation process of the present invention is owing to select non-precious metal catalyst for use, and the catalyst price declines to a great extent; The used coalbed methane containing oxygen catalyst of the present invention simultaneously has certain sulfur tolerance, the coal bed gas sulfur content≤10mg/m in general colliery
3, can be with the method without pre-desulfurization, thereby saved the expense of pre-desulfurization link;
(2) compare with the coke deoxidization method, because coalbed methane containing oxygen catalytic deoxidation process of the present invention does not need to consume coke resource owing to the methane reaction in oxygen and the coal bed gas, but energy savings; And technological process of the present invention is easier, and easy and simple to handle, equipment is simple, is convenient to automatic control, and its operating cost descends about 1/3rd than coke method;
(3) compare with the coke deoxidization method, though coalbed methane containing oxygen catalytic deoxidation process of the present invention will consume a small amount of methane, thereby the methane total amount slightly reduces after making deoxidation, but the oxygen content after the deoxidation in the coal bed gas has reduced to below 0.5%, the total gas flow in back that dewaters reduces to some extent, thus after the deoxidation in the gas component relative amount of methane change little; Simultaneously, though methane is lost, generate CO owing to behind the methane oxidation
2And H
2O can obtain heat, produces the part waste hot steam, can make other purposes.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, in the embodiment of the invention in the oxygen-containing coal bed gas deoxidation catalyst percentage composition of each component be weight percentage.
Embodiment 1
The strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 1% active component, 50% coagent and 49% carrier, active component is that to be equivalent to cobalt oxide in the catalyst be 1% cobalt nitrate, coagent is that to be equivalent to manganese dioxide be that 10% manganese nitrate, zinc oxide are that 10% zinc chloride and cupric oxide are that 30% copper sulphate is formed, carrier is 49% aluminium oxide, is named doc1.
The preparation method of the oxygen-containing coal bed gas deoxidation catalyst of present embodiment is:
(1) 3.9g cobalt nitrate hexahydrate (being equivalent to the 1g cobalt oxide), 29g four water manganese nitrates (being equivalent to 10g manganese dioxide), 16.8g anhydrous zinc chloride (being equivalent to 10g zinc oxide) and 94g cupric sulfate pentahydrate (being equivalent to the 30g cupric oxide) are dissolved in the 100g water, are made into the aqueous solution;
(2) the 49g aluminium oxide is immersed in the aqueous solution of step (1) configuration, normal temperature flooded 6 hours down;
(3) with the mixture extruded moulding of step (2), 120 ℃ dry 1 hour down, 500 ℃ of following roastings 4 hours can make the strip oxygen-containing coal bed gas deoxidation catalyst doc1 of present embodiment.
Embodiment 2
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 60% active component, 1% coagent and 39% carrier, active component is that to be equivalent to cobalt oxide content in the catalyst be 60% cobalt acetate, coagent is that to be equivalent to ferric oxide content be 1% ferrous sulfate, carrier is that the zirconia of 20% titanium oxide and 19% is formed, and is named doc2.
(1) 199g Cobalt diacetate tetrahydrate (being equivalent to the 60g cobalt oxide), 20g titanium oxide and 19g zirconia are fully mixed, extruded moulding, 120 ℃ dry 2 hours down, 400 ℃ of following roastings 5 hours promptly make catalyst precarsor;
(2) 3.5g ferrous sulfate heptahydrate (being equivalent to the 1g di-iron trioxide) is dissolved in the 50g water, is made into the aqueous solution;
(3) catalyst precarsor that step (1) made immerses in the solution of step (2) preparation, and normal temperature is dipping 12 hours down, 120 ℃ dry 1 hour down, 500 ℃ of following roastings 4 hours can make the strip oxygen-containing coal bed gas deoxidation catalyst doc2 of present embodiment.
Embodiment 3
The oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 30% active component, 30% coagent and 40% carrier, active component is that to be equivalent to cobalt oxide be 30% cobalt chloride, coagent is that to be equivalent to manganese dioxide be 5% manganese chloride and to be equivalent to zinc oxide be that 25% zinc nitrate is formed, carrier is formed by the A type molecular sieve of 10% magnesia, 10% calcium oxide, 10% silica and 10%, is named doc3.
(1) A type molecular sieve with 11.4g tetrahydrate manganese chloride (being equivalent to 5g manganese dioxide), 91.7g zinc nitrate hexahydrate (being equivalent to 25g zinc oxide) and 10g magnesia, 10g calcium oxide, 10g silica and 10g fully mixes, roller forming, drying is 1.5 hours under 120 ℃, 450 ℃ of following roastings 4.5 hours make catalyst precarsor;
(2) 95.2g CoCL2 (being equivalent to the 30g cobalt oxide) is dissolved in the 150g water, is made into the aqueous solution;
(3) catalyst precarsor of step (1) is immersed in the solution of step (2), normal temperature is dipping 10 hours down, 120 ℃ dry 2 hours down, 480 ℃ of following roastings 4 hours can make the strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment.
Embodiment 4
The strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 6% active component, 45% coagent and 49% carrier, active component is a cobalt oxide, coagent is that 5% manganese nitrate, zinc oxide are that 10% zinc chloride and cupric oxide are that 30% copper sulphate is formed by being equivalent to manganese dioxide, carrier is made up of 9% phosphate aluminium molecular sieve, 10%X type molecular sieve, 10%Y type molecular sieve, 10% modenite, 10% diatomite, is named doc4.
The preparation method of the oxygen-containing coal bed gas deoxidation catalyst of present embodiment is:
(1) 6g cobalt oxide, 9g phosphate aluminium molecular sieve, 10g X type molecular sieve, 10g Y zeolite, 10g modenite, 10g diatomite are mixed;
(2) with the mixture extruded moulding, 120 ℃ dry 2 hours down, catalyst precarsor is made in 500 ℃ of following roastings 1.5 hours;
(3) 14.5g four water manganese nitrates (being equivalent to 5g manganese dioxide), 16.8g anhydrous zinc chloride (being equivalent to 10g zinc oxide) and 94g cupric sulfate pentahydrate (being equivalent to the 30g cupric oxide) are dissolved in the 100g water, be made into the aqueous solution, the catalyst precarsor that makes with this solution spraying step (2), drying is 2 hours under 120 ℃, 480 ℃ of following roastings 4 hours promptly make oxygen-containing coal bed gas deoxidation catalyst doc4.
Embodiment 5
The strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 16% active component, 40% coagent and 44% carrier, active component is that to be equivalent to cobalt oxide be 16% cobaltous sulfate, coagent is that to be equivalent to manganese dioxide be that 10% manganese nitrate, zinc oxide are that 10% zinc chloride and cupric oxide are that 20% copper sulphate is formed, carrier is 44% alumina silicate, is named doc5.
The preparation method of the oxygen-containing coal bed gas deoxidation catalyst of present embodiment is:
(1) 59.9g cobalt sulfate (being equivalent to the 16g cobalt oxide), 29g four water manganese nitrates (being equivalent to 10g manganese dioxide), 16.8g anhydrous zinc chloride (being equivalent to 10g zinc oxide) and 62.5g cupric sulfate pentahydrate (being equivalent to the 20g cupric oxide) are dissolved in the 150g water, are made into the aqueous solution;
(2) the 44g alumina silicate is immersed in the aqueous solution of step (1) configuration, normal temperature flooded 6 hours down;
(3) with the mixture extruded moulding of step (2), 120 ℃ dry 1 hour down, 400 ℃ of following roastings 5 hours can make the strip oxygen-containing coal bed gas deoxidation catalyst doc5 of present embodiment.
Embodiment 6
The strip oxygen-containing coal bed gas deoxidation catalyst of present embodiment, form by 20% active component, 40% coagent and 40% carrier, active component is that to be equivalent to cobalt oxide be 20% cobalt nitrate, coagent is that to be equivalent to manganese dioxide be that 10% manganese nitrate, zinc oxide are that 10% zinc chloride and cupric oxide are that 20% copper sulphate is formed, carrier is made up of 10%ZSM-5 zeolite, 10% kaolin, 10% natural clay, 10% magnesium silicate, is named doc6.
The preparation method of the oxygen-containing coal bed gas deoxidation catalyst of present embodiment is:
(1) 29g four water manganese nitrates (being equivalent to 10g manganese dioxide), 16.8g anhydrous zinc chloride (being equivalent to 10g zinc oxide) and 62.5g cupric sulfate pentahydrate (being equivalent to the 20g cupric oxide), 10g ZSM-5 zeolite, 10g kaolin, 10g natural clay, 10g magnesium silicate are mixed;
(2) with the mixture extruded moulding, 120 ℃ dry 2 hours down, catalyst precarsor is made in 500 ℃ of following roastings 2 hours;
(3) 78g cobalt nitrate hexahydrate (being equivalent to the 20g cobalt oxide) is dissolved in the 100g water, be made into the aqueous solution, with the catalyst precarsor that this solution spraying step (2) makes, drying is 1 hour under 120 ℃, 1500 ℃ of following roastings 4 hours promptly make oxygen-containing coal bed gas deoxidation catalyst doc6.
Embodiment 7
Present embodiment is the application of oxygen-containing coal bed gas deoxidation catalyst of the present invention in the deoxidation treatment of coalbed methane containing oxygen.
Directly send in deoxidation reactor after by the preheater preheating raw material coalbed methane containing oxygen, under normal pressure, uniform temperature and air speed condition, in beds, methane in the coal bed gas and oxygen reaction generate carbon dioxide and water, simultaneously a spot of methane generation cracking produces charcoal and hydrogen, charcoal that cracking produces and hydrogen react with oxygen again, thereby reach the purpose of effectively removing oxygen in the coal bed gas.
Methane and oxygen reaction are strong exothermal reaction, and per 1% oxygen and methane reaction liberated heat adiabatic temperature rise are 95～100 ℃, therefore, for the unlikely too high methane cracking loss that causes of control reaction temperature, need the unstripped gas Control for Oxygen Content 3～6%.When raw material coal bed gas oxygen content is higher than 6%, can be by in the raw material coal bed gas of the cooled coal bed gas of cyclic part deoxidation to the deoxidation, regulate enter reactor oxygen content to optimum range, thereby reach the purpose of deoxidation and temperature control.
Different model catalyst activity property testing concrete outcome sees Table 1, and the unstripped gas oxygen content is 3～6% (V/V), sulfur content 3～10mg/m
3, methane content is 70～85%, all the other are nitrogen, unstripped gas air speed 1000～6000h
-1, the catalytic deoxidation reaction temperature is 300～650 ℃, loaded catalyst 100ml.
Table 1
| The catalyst numbering | Unstripped gas oxygen content % | Unstripped gas total sulfur content mg/m 3 | Deoxidation temperature ℃ | Unstripped gas air speed h -1 | Tail gas oxygen content % |
| doc1 | 3.01 | 3.0 | 650 | 4000 | 0.35 |
| doc2 | 6.02 | 6.4 | 300 | 6000 | 0.22 |
| doc3 | 3.52 | 3.5 | 500 | 3000 | 0.15 |
| doc4 | 4.62 | 7.5 | 450 | 4000 | 0.18 |
| doc5 | 4.05 | 4.2 | 380 | 3000 | 0.12 |
| doc6 | 5.15 | 10.0 | 495 | 1000 | 0.08 |
Claims (8)
1, a kind of oxygen-containing coal bed gas deoxidation catalyst, by active component, coagent and porous carrier are formed, it is characterized in that: described active component is the compound of cobalt, described coagent is a manganese, iron, zinc, in the copper compound one or more, described porous carrier is selected from aluminium oxide, titanium oxide, zirconia, magnesia, calcium oxide, silica, phosphate aluminium molecular sieve, A type molecular sieve, X type molecular sieve, Y zeolite, modenite, the ZSM-5 zeolite, diatomite, kaolin, natural clay, alumina silicate, in the magnesium silicate one or more, in oxide, the weight percentage of active component is 1～60%, the weight percentage of coagent is 1～50%, and all the other are carrier.
2, oxygen-containing coal bed gas deoxidation catalyst according to claim 1 is characterized in that: described active component is any one in cobalt oxide, cobalt acetate, cobalt nitrate, cobalt chloride or the cobaltous sulfate.
3, oxygen-containing coal bed gas deoxidation catalyst according to claim 1 is characterized in that: described coagent is selected from the oxide of manganese, iron, zinc, copper or in the soluble-salt one or more.
4, oxygen-containing coal bed gas deoxidation catalyst according to claim 3 is characterized in that: described coagent is selected from any one or a few in nitrate, chloride or the sulfate of manganese, iron, zinc, copper.
5, a kind of preparation method of each described oxygen-containing coal bed gas deoxidation catalyst of claim 4 is characterized in that may further comprise the steps:
(1) active component and coagent are mixed with the aqueous solution;
(2) porous carrier is immersed in the aqueous solution of step (1) preparation, flooded 6～12 hours down in normal temperature;
(3) with the mixture of step (2) gained by roller forming or extruded moulding, in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make oxygen-containing coal bed gas deoxidation catalyst.
6, the preparation method of any described oxygen-containing coal bed gas deoxidation catalyst of a kind of claim 1～4 is characterized in that may further comprise the steps:
(1) coagent compound and porous carrier are mixed in proportion;
(2) mixture with step (1) passes through compressing tablet, spin or extruded moulding, makes the oxygen-containing coal bed gas deoxidation catalyst precursor;
(3) active component is made into the aqueous solution, with this solution impregnation or the oxygen-containing coal bed gas deoxidation catalyst precursor that makes of spraying step (2), in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make oxygen-containing coal bed gas deoxidation catalyst.
7, the preparation method of any described oxygen-containing coal bed gas deoxidation catalyst of a kind of claim 1～4 is characterized in that may further comprise the steps:
(1) active constituent compound and porous carrier are mixed in proportion;
(2) mixture that step (1) is made makes the oxygen-containing coal bed gas deoxidation catalyst precursor by compressing tablet, spin or extruded moulding;
(3) coagent is mixed with the aqueous solution, with the coalbed methane containing oxygen catalyst precarsor of this solution impregnation or spraying step (2), in 120 ℃ dry 1～2 hour down, 400～500 ℃ of following roastings 4～5 hours make oxygen-containing coal bed gas deoxidation catalyst.
8, according to the application of the described oxygen-containing coal bed gas deoxidation catalyst of claim 1～4 in coalbed methane containing oxygen, it is characterized in that: described oxygen-containing coal bed gas deoxidation catalyst is applied to the deoxidation treatment that oxygen content is 3～6% coal bed gas, the unstripped gas air speed is 1000～6000h-1, and the temperature of catalytic deoxidation reaction is 300～650 ℃.
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