WO2014079142A1 - 一种复合氧化物、其制造方法及其应用 - Google Patents
一种复合氧化物、其制造方法及其应用 Download PDFInfo
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- WO2014079142A1 WO2014079142A1 PCT/CN2013/001217 CN2013001217W WO2014079142A1 WO 2014079142 A1 WO2014079142 A1 WO 2014079142A1 CN 2013001217 W CN2013001217 W CN 2013001217W WO 2014079142 A1 WO2014079142 A1 WO 2014079142A1
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- Prior art keywords
- composite oxide
- source
- hours
- water
- reaction
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- 239000002131 composite material Substances 0.000 title claims abstract description 204
- 238000002360 preparation method Methods 0.000 title abstract 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 239000000203 mixture Substances 0.000 claims abstract description 79
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 58
- 230000003647 oxidation Effects 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 120
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 96
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 88
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 84
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 84
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 82
- 239000007864 aqueous solution Substances 0.000 claims description 69
- 239000002243 precursor Substances 0.000 claims description 64
- -1 organic acid salt Chemical class 0.000 claims description 55
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 39
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 36
- 229910017604 nitric acid Inorganic materials 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 32
- 235000006408 oxalic acid Nutrition 0.000 claims description 32
- 229910021529 ammonia Inorganic materials 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 150000004679 hydroxides Chemical class 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 3
- 159000000021 acetate salts Chemical class 0.000 claims 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 132
- 239000000243 solution Substances 0.000 description 81
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 76
- 229910052720 vanadium Inorganic materials 0.000 description 60
- 239000008367 deionised water Substances 0.000 description 59
- 229910021641 deionized water Inorganic materials 0.000 description 59
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 56
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 53
- 235000011114 ammonium hydroxide Nutrition 0.000 description 53
- 239000011259 mixed solution Substances 0.000 description 44
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 33
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 32
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 32
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 26
- 238000006722 reduction reaction Methods 0.000 description 20
- 230000009467 reduction Effects 0.000 description 19
- 229910017052 cobalt Inorganic materials 0.000 description 18
- 239000010941 cobalt Substances 0.000 description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 229910003206 NH4VO3 Inorganic materials 0.000 description 13
- 101001012040 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Immunomodulating metalloprotease Proteins 0.000 description 13
- 229910052707 ruthenium Inorganic materials 0.000 description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 10
- 229910052797 bismuth Inorganic materials 0.000 description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 150000004677 hydrates Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- MVERHZLHVRAECL-UHFFFAOYSA-N [Mo].[V].[Y] Chemical compound [Mo].[V].[Y] MVERHZLHVRAECL-UHFFFAOYSA-N 0.000 description 2
- DQHHLDJPSFVUAI-UHFFFAOYSA-N [O-2].[Al+3].[V+5].[Y+3] Chemical compound [O-2].[Al+3].[V+5].[Y+3] DQHHLDJPSFVUAI-UHFFFAOYSA-N 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- TVLQHSJXFZLTMW-UHFFFAOYSA-N [Mo].[V].[La] Chemical compound [Mo].[V].[La] TVLQHSJXFZLTMW-UHFFFAOYSA-N 0.000 description 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 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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Definitions
- the present invention relates to a composite oxide, particularly a lanthanum vanadium molybdenum composite oxide, and to a process for producing the composite oxide and its use as a catalyst for selective oxidation of methane. Background technique
- the inventors of the present invention have found through diligent research that if a specific complex oxide is used as a catalyst, ethanol and acetaldehyde can be co-produced by selective oxidation reaction of decane, and thus the present invention has been completed.
- the invention relates primarily to the following aspects.
- Ni:Co 0.01 to 20:1, preferably 0.1 to 10:1, more preferably 1 to 3:1 in terms of a molar ratio.
- the composite oxide according to any of the preceding aspects, wherein the weight ratio of the composite oxide to the carrier is from 0.01 to 1:1, preferably from 0.1 to 0.5:1, more preferably from 0.1 to 0.3:1.
- the carrier is selected from one or more of the inorganic refractory oxides, preferably selected from the group consisting of SiO 2 , A 1 2 0 3 , MgO-SiO 2 , MgO-Al 2 O 3 , Al 2 0 3 -SiO 2 ,
- One or more of CaO-SiO 2 and CaO-MgO-SiO 2 are more preferably one or more selected from the group consisting of SiO 2 , A 1 2 3 3 , MgO-SiO 2 , and MgO-Al 2 0 3 .
- the composite oxide according to any of the preceding aspects which exhibits a crystalline state, preferably in its powder X-ray diffraction pattern, at least at a diffraction angle of 2 ⁇ 28.5 ⁇ 0.5. There is a diffraction peak, and more preferably at least a diffraction angle of 2 ⁇ 18.5 ⁇ 0.5. 28.5 ⁇ 0.5. , 31.5 ⁇ 0.5. And 34.5 ⁇ 0.5. There are diffraction peaks.
- a method for producing a composite oxide comprising the steps of: optionally providing a Rh source, a Mo source, a V source, and optionally a Ni source and/or optionally using in the presence of a carrier; Co source contact (preferably mixing), a reaction occurs to obtain a composite oxide, wherein a relative amount ratio of the Rh source, the Mo source, the V source, the Ni source, and the Co source is such that the obtained composite
- ⁇ is a positive number, representing the oxygen reaching price in the composite oxide
- the composite oxide is partially reduced such that ⁇ reaches greater than 0 to ⁇ /2, preferably greater than 0 to ⁇ /4.
- Rh source is one or more selected from the group consisting of oxides, hydroxides, inorganic acid salts and organic acid salts of Rh, preferably a water-soluble inorganic acid selected from Rh.
- the Ni source being selected from the group consisting of oxides and hydroxides of Ni, One or more of a mineral acid salt and an organic acid salt, preferably one or more selected from the group consisting of a water-soluble inorganic acid salt of Ni and a water-soluble organic acid salt, more preferably a nitrate and acetic acid selected from the group consisting of Ni
- the Co source being selected from one or more of the oxides, hydroxides, inorganic acid salts and organic acid salts of Co, preferably selected from the group consisting of water-soluble inorganic acid salts of Co and One or more of the water-soluble organic acid salts, more preferably one selected from the group consisting of nitrates and acetates of Co Or a plurality of, the Mo source is selected from one or more of the oxides, hydroxides
- Rh source, the Mo source, the V source, the Ni source, and the Co source are provided in the form of an aqueous solution by causing a coprecipitation reaction of the aqueous solution.
- An aqueous slurry is obtained, and then the aqueous slurry is dehydrated, dried and calcined to obtain the composite oxide.
- reaction conditions are: pH 3 - 10, preferably 5-9, under stirring, reaction temperature 60-90 ° C, preferably 70-80 ° C, reaction time 1-12 hours, preferably 3-10 hours;
- drying conditions are: drying temperature 60-150 ° C, preferably 100-120 ° C, drying time 4-48 hours, preferably 6-36 hours, more preferably 8 - 24 hours;
- the calcination conditions are: calcination temperature 400-900 ° C, preferably 500-700 ° C, more preferably 580-680 ° C, calcination time 3-10 hours, preferably 4-8 hours.
- aqueous solution of the Mo source further contains ammonia at a concentration of 1-3 mol/L
- the aqueous solution of the V source further contains a concentration of 0.1 - 0.5 mol/L.
- a method for co-producing ethanol and acetaldehyde by a selective oxidation reaction of methane characterized in that the composite oxide of any of the foregoing aspects or the composite oxide produced by the production method of any of the foregoing aspects is used as a catalyst
- the decane is selectively oxidized to co-produce ethanol and acetaldehyde.
- the present invention has the following advantages over the prior art.
- a catalyst suitable for co-production of ethanol and acetaldehyde by a selective oxidation reaction of methane is obtained for the first time.
- a molybdenum vanadium center having a methane selective oxidation function is bonded to a ruthenium center having a sterol carbonylation function in a crystalline form, and the crystalline active phase provides d electron holes on the one hand, and Providing lattice oxygen on the one hand, which has better decane activation and selective oxidation properties, thus achieving higher decane conversion (eg, up to 17% or more) and ethanol and acetaldehyde selectivity (ie total Selectivity, such as up to 78% or more).
- selective oxidation of methane can be achieved at a lower reaction pressure (e.g., below IMPa).
- the composite oxide according to the present invention is simple in its production method and is advantageous for industrial production.
- 1 to 8 are powder X-ray diffraction patterns of the composite oxides prepared in Examples 1, 5, 9, 11, 12, 19, 25 and 28, respectively.
- the phrase "the value at which the oxygen in the composite oxide reaches the equilibrium of the valence state" means that Rh is +3 valence, Mo is +6 valence, V is +5 valence, and Ni in the composite oxide.
- Rh is +3 valence
- Mo is +6 valence
- V is +5 valence
- Ni in the composite oxide.
- Co is +2
- 0 is -2
- a 0, a value required for the electrically neutral composite oxide is formed.
- x 0 to 3.0, preferably 0.01 to 3.0, more preferably 0.5 to 2.5, still more preferably 1.0 to 2.0.
- y 0.1 - 0.9, preferably 0.2 - 0.7, more preferably 0.4 - 0.6.
- z 0.1 - 0.9, preferably 0.2 - 0.9, more preferably 0.5 - 0.8.
- a 0 to ⁇ / 2, preferably 0 to ⁇ / 4, more preferably 0.
- Ni:Co 0.01 -20:1, preferably 0.1 - 10:1 , more preferably 1 -3:1, in terms of molar ratio.
- the composite oxide may be a supported composite oxide (also referred to as a composite oxide in the present specification for convenience of description), that is, a composite oxide is supported on a carrier.
- a supported composite oxide also referred to as a composite oxide in the present specification for convenience of description
- an inorganic refractory oxide is preferred as the carrier.
- the inorganic Refractory oxide such as may include Si0 2, A1 2 0 3, MgO-Si0 2, MgO-Al 2 0 3, Al 2 0 3 -Si0 2, CaO-Si0 2 and CaO-MgO-Si0 2 and the like, Among them, SiO 2 , A 1 2 0 3 , Mg ⁇ -SiO 2 , MgO-Al 2 ⁇ 3 or a combination thereof is preferable.
- the ratio of the composite oxide to the carrier is not particularly limited, and is usually 0.01 - 1 : 1 , preferably 0.1 - 0.5 : 1, more preferably 0.1 - 0.3 : 1 by weight.
- the composite oxide preferably exhibits a crystalline state. This crystalline state can be confirmed by powder X-ray diffraction measurement of the composite oxide (or supported composite oxide) and identification of a clear diffraction peak from the obtained powder X-ray diffraction pattern.
- the composite oxide when it is in a crystalline state, it is preferably at least 25.6 ⁇ 0.5 in the powder X-ray diffraction pattern at a diffraction angle of 2 ⁇ .
- a strongest diffraction peak also called a main diffraction peak
- main diffraction peak at a position (for example, near 28.8)
- soil 0.5 There are clear diffraction peaks.
- the diffraction angle 2 ⁇ is at least 18.80. 28.80. 31.47. And 34.60.
- diffraction peaks corresponding to the [101], [103], [004], and [200] crystal planes There are clear diffraction peaks corresponding to the [101], [103], [004], and [200] crystal planes, and the interplanar spacing and relative diffraction intensity have the following characteristics.
- the composite oxide can be produced by the following production method.
- the manufacturing method comprises the steps of contacting a Rh source, a Mo source, a V source, and optionally a Ni source and/or an optionally used Co source (sequentially or simultaneously) to react to obtain a composite oxide. .
- the relative amount ratio of the Rh source, the Mo source, the V source, the Ni source (optional), and the Co source (optional) is such that the composition of the obtained composite oxide is used
- ⁇ 0 - 3.0, preferably 0.01 - 3.0, more preferably 0.5 - 2.5, further preferably 1.0 - 2.0.
- y 0.1 - 0.9, preferably 0.2 - 0.7, more preferably 0.4 - 0.6.
- z 0.1 - 0.9, preferably 0.2 - 0.9, more preferably 0.5 - 0.8.
- ⁇ 0 to ⁇ /2, preferably 0 to ⁇ /4, more preferably 0.
- Ni:Co 0.01 -20:1, preferably 0.1-10:1, more preferably 1-3:1, in terms of molar ratio.
- the manner of the contact is not limited as long as the Rh source, the Mo source, the V source, and optionally the Ni source and/or the Co source optionally used can be made.
- the composite oxide A may be formed by reacting with each other to form a chemical reaction, and for example, a method of mixing these sources (sequentially or simultaneously) in a solution or in a molten form may be mentioned.
- the contacting can be carried out in the presence of a support, whereby a supported composite oxide A (also referred to as composite oxide A) is obtained.
- a supported composite oxide A also referred to as composite oxide A
- an inorganic refractory oxide or a precursor thereof is preferred as the carrier.
- the inorganic refractory oxide include SiO 2 , A1 2 0 3 , MgO-SiO 2 , MgO-Al 2 O 3 , Al 2 0 3 -SiO 2 , CaO-SiO 2 and CaO-MgO-.
- Si0 2 or the like among which, Si0 2 , A1 2 0 3 , MgO-SiO 2 , MgO-Al 2 O 3 or a combination thereof is preferable.
- the precursor of the inorganic refractory oxide has a general meaning in the art, and means that it can be converted into inorganic refractory oxidation during the process of the composite oxide production method of the present invention (for example, by a calcination step as described below).
- any material of the material for example, aluminum nitrate, aluminum chloride, aluminum silicate, aluminum isopropoxide, sodium silicate, ethyl orthosilicate, silica sol, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride Etc., preferably, aluminum nitrate, aluminum chloride, aluminum acid, sodium silicate, ethyl orthosilicate, nitric acid, calcium nitrate, more preferably aluminum nitrate, aluminum sulphate, sodium silicate, magnesium nitrate.
- the amount of the carrier used at this time is not particularly limited, but it is preferred that the carrier be used in an amount such that the weight ratio of the composite oxide A to the carrier (in terms of inorganic refractory oxide) is 0.01. -1 : 1 , preferably 0.1 - 0.5: 1 , more preferably 0.1 - 0.3: 1.
- examples of the Rh source include oxides, hydroxides, inorganic acid salts and organic acid salts of Rh (including hydrates of these compounds), among which water-soluble inorganic acid salts of Rh and water-soluble are preferred.
- the organic acid salt is more preferably a nitrate and an acetate selected from the group consisting of Rh, such as Rh(N0 3 ) 3 or a hydrate thereof.
- examples of the Ni source include oxides, hydroxides, inorganic acid salts, and organic acid salts of Ni (including hydrates of these compounds), among which water-soluble inorganic acid salts of Ni and water-soluble are preferable.
- Organic acid salt more preferably nitrate and acetate of Ni, For example, Ni(N0 3 ) 2 or a hydrate thereof.
- examples of the Co source include oxides, hydroxides, inorganic acid salts, and organic acid salts of Co (including hydrates of these compounds), among which water-soluble inorganic acid salts of Co and water-soluble are preferable.
- the organic acid salt is more preferably a nitrate or acetate of Co, such as Co(N0 3 ) 2 or a hydrate thereof.
- examples of the Mo source include oxides of Mo, hydroxides, inorganic acid salts, organic acid salts, and ammonium oxyacid salts (including hydrates of these compounds), of which water solubility of Mo is preferred.
- the inorganic mineral acid salt, the water-soluble organic acid salt and the ammonium oxyacid salt are more preferably an ammonium oxyacid salt of Mo, such as (NH 4 ) 6 Mo 7 0 24 or a hydrate thereof.
- examples of the V source include oxides of V, hydroxides, inorganic acid salts, organic acid salts, and ammonium oxyacid salts (including hydrates of these compounds), of which water solubility of V is preferred.
- the inorganic mineral acid salt, the water-soluble organic acid salt and the ammonium oxyacid salt are more preferably an ammonium oxyacid salt of V such as NH 4 V0 3 or a hydrate thereof.
- the Rh source, the Mo source, the V source, the Ni source (optional) and the Co source (optional) are provided in the form of an aqueous solution, optionally
- These composite oxides A are obtained by mixing these aqueous solutions (sequentially or simultaneously) in the presence of the carrier to cause a reaction.
- the aqueous solution of the Mo source when supplied in the form of an aqueous solution, further contains 1-3 mol/L of ammonia.
- the aqueous solution of the V source when provided in the form of an aqueous solution, further contains 0.1 to 0.5 mol/L of a C 2-6 polycarboxylic acid (preferably a C 2-6 dicarboxylic acid, Preferably oxalic acid).
- a C 2-6 polycarboxylic acid preferably a C 2-6 dicarboxylic acid, Preferably oxalic acid.
- the reaction of the Rh source, the Mo source, the V source, the Ni source (optional) and the Co source (optional) is preferably carried out in the presence of agitation.
- the Rh source, the Mo source, the V source, the Ni source (optional), and the Co source (optional), when the reaction is carried out are generally:
- the pH of the system is from 3 to 10, preferably from 5 to 9
- the reaction temperature is from 60 to 90 ° C, preferably from 70 to 8 CTC
- the reaction time is from 1 to 12 hours, preferably from 3 to 10 hours.
- the composite oxide A of the present invention can also be formed into a suitable particle form such as a strip shape, a sheet shape, a column shape or the like according to a technique known in the art as needed.
- the ratio of more than 0 to ⁇ /4 is selected, and the composite oxide at this time is also referred to as a composite oxide ruthenium.
- a part of the metal element in the composite oxide crucible may be present in a reduced valence state (such as ⁇ ⁇ , V 3+ or V Q , etc.).
- the present invention is also not specific to the type of metal element in which the partial reduction occurs.
- a composite oxide B represented by the formula RhR x Mo y V z O a can be obtained, wherein a is greater than 0 to ⁇ /2, preferably greater than 0 to ⁇ /4, and other symbols are the same Pre-description.
- the partial reduction method for example, a method in which the composite oxide ruthenium is brought into contact with a reducing agent (e.g., hydrogen) under appropriate reaction conditions to cause a reduction reaction.
- a reducing agent e.g., hydrogen
- the reaction conditions for example, a reaction temperature of 60 to 600 ° C, a reaction pressure of 15 to 1500 psia, and a portion sufficient to reduce the composite oxide A to ⁇ greater than 0 to ⁇ / 2 (preferably greater than 0 to ⁇ / 4) may be mentioned.
- Reaction time (such as 0.5-12 hours, but sometimes not limited to this).
- the composition of the composite oxide (including the composite oxide ruthenium and the composite oxide B) can be identified by atomic emission spectrometry (ICP) or X-ray fluorescence spectroscopy (XRF).
- ICP atomic emission spectrometry
- XRF X-ray fluorescence spectroscopy
- the Rh source, the Mo source, the V source, and optionally the Ni source and/or the Co source optionally used are generated by the contacting The coprecipitation reaction (neutralization reaction), thereby obtaining a crystalline composite oxide A (referred to as in situ crystallization).
- the Rh source, the Mo source, the V source, the Ni source (optional), and the Co source (optional) are provided in the form of an aqueous solution.
- These aqueous solutions are optionally mixed (sequentially or simultaneously) in the presence of the support to cause a coprecipitation reaction to obtain an aqueous slurry.
- the aqueous solution of the Mo source when supplied in the form of an aqueous solution, further contains ammonia at a concentration of 1-3 mol/L.
- the aqueous solution of the V source when provided in the form of an aqueous solution, further contains a C 2-6 polycarboxylic acid (preferably a C 2-6 dicarboxylic acid) having a concentration of 0.1 to 0.5 mol/L. Acid, more preferably oxalic acid).
- a C 2-6 polycarboxylic acid preferably a C 2-6 dicarboxylic acid having a concentration of 0.1 to 0.5 mol/L. Acid, more preferably oxalic acid).
- the Rh source, the Mo source, the V source, the Ni source (optional), and the Co source (optional) are respectively dissolved in water to prepare respective aqueous solutions.
- These aqueous solutions and optionally used carriers are added to the reaction system (such as a reaction vessel) in a predetermined amount, sequentially or simultaneously (preferably first added to the carrier, and/or finally added to the aqueous solution of the Mo source), and the mixture is adjusted.
- the pH of the reaction system is 3-10 (preferably 5-9, such as using nitric acid or aqueous ammonia solution), and the coprecipitation is carried out for 1-12 hours (preferably 3) at a reaction temperature of 60-9 CTC (preferably 70-80 ° C). -10 hours), thereby obtaining the aqueous slurry.
- the composite oxide A can be obtained by dehydrating, optionally forming, drying, and calcining the aqueous slurry.
- the dehydration can be carried out in a manner known in the art, and examples thereof include an evaporation water removal method or a filtration water removal method.
- the molding can be carried out in a manner known in the art (e.g., extrusion, granulation) to facilitate obtaining a composite oxide A having a suitable particle form (e.g., strip shape, sheet shape, column shape, etc.).
- a suitable particle form e.g., strip shape, sheet shape, column shape, etc.
- the drying can be carried out in a manner known in the art, and examples thereof include a spray drying method, a vacuum drying method, a hot oven drying method, and the like.
- the drying and the molding can be carried out as one step as needed.
- the drying conditions for example, a drying temperature of 60 to 150 ° C, preferably 100 to 120 ° C, and a drying time of 4 to 48 hours, preferably 6 to 36 hours, more preferably 8 to 24 hours are mentioned.
- the dried aqueous slurry is completely converted into the crystalline composite oxide A by the calcination, while the precursor of the inorganic refractory oxide (when used) is converted into inorganic refractory Oxide.
- the conditions for the calcination for example, a calcination temperature of 400 to 900 ° C, preferably 500 to 700 ° C, more preferably 580 to 680 ° C, and a calcination time of 3 to 10 hours, preferably 4 to 8 hours are mentioned.
- the calcination can be carried out in an oxygen-containing atmosphere (e.g., air) as needed.
- the present invention relates to a process for co-producing ethanol and acetaldehyde by selective oxidation of methane, comprising the co-production of ethanol and acetaldehyde by selective oxidation of methane using the composite oxide of the present invention as a catalyst. step.
- the reaction conditions of the methane selective oxidation reaction are: a reaction temperature of 300 to 800 ° C, preferably 400 to 700 ° C, more preferably 500 to 600 ° C; and a reaction pressure of 0.1 to 5.0 MPa (gauge pressure) It is preferably 0.2-2.0 MPa (gauge pressure), more preferably 0.5-1.0 MPa (gauge pressure);
- the space velocity of methane is 1200-3500 h" 1 , preferably 2000-2800! ⁇ 1 .
- Example 1 The invention is further illustrated by the following examples, but the invention is not limited to the examples.
- Example 1 The invention is further illustrated by the following examples, but the invention is not limited to the examples.
- Rh(N0 3 ) 3 .2H 2 0 was weighed and dissolved in 25 g of deionized water to prepare an aqueous solution of cerium nitrate.
- 0.9 g of NH 4 VO 3 was dissolved in 25 g of deionized water, and then treated with an equimolar amount of oxalic acid with NH 4 V 0 3 to prepare a dark blue homogenous solution of the vanadium-containing precursor, and uniformly mixed with the solution containing cerium nitrate. , heated to 75 ° C in a water bath.
- Example 2 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 1 is shown in Fig. 1, indicating that the composite oxide exhibited a crystalline state.
- Example 2 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 1 is shown in Fig. 1, indicating that the composite oxide exhibited a crystalline state.
- Rh(N0 3 ) 3 was weighed and dissolved in 25 g of deionized water to prepare an aqueous solution of cerium nitrate.
- 0.9 g of NH4VO3 was dissolved in 25 g of deionized water, and then treated with an equimolar amount of oxalic acid with NH 4 V0 3 to prepare a dark blue homogenous solution of the vanadium-containing precursor, and uniformly mixed with the solution containing cerium nitrate, water bath Heat to 75 °C.
- the composite oxide has a composition formula of RhV 9 Mo 0 . 4 O 5 .
- the conversion of decane was determined to be 8.8%, and the total selectivity of ethanol and acetaldehyde was 65.6%.
- Rh(N0 3 ) 3 , 2H 2 0 was weighed and dissolved in 25 g of deionized water to prepare an aqueous solution of cerium nitrate.
- the composite oxide of l.Og is used for selective oxidation of decane.
- the methane conversion was determined to be 7.3%, and the total selectivity of ethanol and acetaldehyde was 57.9%.
- the solution is slowly added dropwise to the above mixed solution containing cerium nitrate and a vanadium-containing precursor, and the pH is adjusted to about 9 with nitric acid or ammonia water. After stirring at 75 ° C for 6 hours, the stirring is stopped, and the temperature is kept constant until no.
- the clear water was dried at 100 ° C for 16 hours and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composite oxide has a composition formula of RhV 7 Mo. . 7 0 5 . 4 .
- the composite oxide of l.Og is used for selective oxidation of decane.
- the methane conversion was determined to be 12.9%, and the total selectivity of ethanol and acetaldehyde was 74.8%.
- Example 6 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 5 is shown in Fig. 2, indicating that the composite oxide exhibited a crystalline state.
- Example 6 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 5 is shown in Fig. 2, indicating that the composite oxide exhibited a crystalline state.
- Rh(N0 3 ) 3 was weighed and dissolved in 25 g of deionized water to prepare an aqueous solution of cerium nitrate. Dissolving 1.8 g of NH 4 V0 3 in 25 g of deionized water, and then treating with an equimolar amount of oxalic acid with NH 4 V0 3 to prepare a dark blue homogenous solution of the vanadium-containing precursor, and mixing with the solution containing cerium nitrate Evenly, heat in a water bath to 75 °C.
- the composite oxide of l.Og is used for the selective oxidation of decane.
- the conversion of decane was determined to be 12.4%, and the total selectivity of ethanol and acetaldehyde was 76.3%.
- Rh(N0 3 ) 3 was weighed and dissolved in 25 g of deionized water to prepare an aqueous solution of cerium nitrate.
- the composition of the composite oxide is RhV0.7Mo0.7O5 4/Al2O3.
- the selective oxidation of decane was carried out with 1.0 g of the composite oxide.
- the methane conversion was determined to be 10.6%, and the total selectivity of ethanol and acetaldehyde was 78.8%.
- Rh(N0 3 ) 3 was weighed and dissolved in 25 g of deionized water to prepare an aqueous solution of cerium nitrate.
- 1.8 g of NH 4 V0 3 was dissolved in 25 g of deionized water, and then treated with an equimolar amount of oxalic acid with NH 4 V 0 3 to obtain a dark blue homogeneous solution containing a vanadium precursor, and uniformly mixed with a solution containing cerium nitrate.
- 12.0 g of water-containing boehmite containing 5% by weight of MgO was added, and heated to 75 ° C in a water bath.
- Rh(N0 3 ) 3 was weighed and dissolved in 25 g of deionized water to prepare an aqueous solution of cerium nitrate.
- the composition of the composite oxide is RhVo.7Moo.7O54/MgO-S1O2.
- the methane conversion was determined to be 13.8%, and the total selectivity of ethanol and acetaldehyde was 73.7%.
- Example 10 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 9 is shown in Fig. 3, indicating that the composite oxide exhibited a crystalline state.
- Example 10 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 9 is shown in Fig. 3, indicating that the composite oxide exhibited a crystalline state.
- Rh(N0 3 ) 3 was weighed and dissolved in 25 g of deionized water to prepare an aqueous solution of cerium nitrate.
- 1.8 g of NH 4 V0 3 was dissolved in 25 g of deionized water, and then treated with an equimolar amount of oxalic acid with NH 4 V 0 3 to prepare a dark blue homogenous solution of the vanadium-containing precursor, and uniformly mixed with the solution containing cerium nitrate. , heated to 75 ° C in a water bath.
- the composite oxide has a composition formula of RhV. 6 Mo Q . 6 0 5 . 8 .
- the composite oxide obtained by hydrogen reduction has a reduction pressure of 0.1 MPa, a temperature of 350 ° C, a space velocity of 1000 h" 1 , a reduction time of lh, and a composition formula of the composite oxide after reduction is RhV 7 Moo 7 0 29 .
- the methane conversion rate was determined to be 7.3%, and the total selectivity of ethanol and acetaldehyde was 61.2%.
- the composition of the composite oxide is RhCo 5 V 7 Mo 2 0 4 . 4 .
- Selective oxidation of methane, the feed gas with a composite oxide l.Og molar composition of CH 4: 0 2: H 2 0 2: 1: 4, CH 4 200011-1 space velocity, and the reaction IMPa It was carried out at 550 ° C for 4 hours.
- the methane conversion was determined to be 12.7%, and the total selectivity of ethanol and acetaldehyde was 53.9%.
- Example 12 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 11 is shown in Fig. 4, indicating that the composite oxide exhibited a crystalline state.
- Example 12 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 11 is shown in Fig. 4, indicating that the composite oxide exhibited a crystalline state.
- the composition of the composite oxide is RhNi 07 V 07 Mo 9 O 6 . 7 .
- the conversion of decane was determined to be 8.9%, and the selectivity of ethanol and acetaldehyde was 57.6%.
- Example 13 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 12 is shown in Fig. 5, indicating that the composite oxide exhibited a crystalline state.
- Example 13 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 12 is shown in Fig. 5, indicating that the composite oxide exhibited a crystalline state.
- Rh(N0 3 )3'2H 2 0 was dissolved in 35 g of deionized water to prepare a mixed solution containing cobalt nitrate, nickel nitrate and cerium nitrate.
- 0.6g of NH4VO3 was added to 20g of deionized water, and then treated with oxalic acid equivalent to NH 4 V0 3 to obtain a dark blue homogenized solution containing vanadium precursor, and nitrated with nickel, cobalt and bismuth.
- the solution was mixed and hooked, and heated to 70 ° C in a water bath.
- 0.25 g of ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 was dissolved in 20 g of an 8% by weight aqueous solution of ammonia to form an aqueous solution of (NH 4 ) 6 Mo 7 0 2 4 in ammonia.
- the solution is slowly added dropwise to the above mixed solution containing nickel nitrate, cobalt nitrate, cerium nitrate and vanadium-containing precursor, and the pH is adjusted with nitric acid or ammonia water.
- the composition of the composite oxide is RhNi 1 C) Coo. 5 V 0 . 8 Mo 2 0 5 . 6 .
- the composite oxide of l.Og is used for selective oxidation of decane.
- the conversion of decane was determined to be 9.1%, and the selectivity of ethanol and acetaldehyde was 65.0%.
- Rh(N0 3 ) 3 *2H 2 dissolved in 35 g of deionized water, to prepare a mixed solution containing cobalt nitrate, nickel nitrate and cerium nitrate.
- 1.8g of NH4VO3 was added to 20g of deionized water, and then treated with oxalic acid equivalent to NH 4 V0 3 to obtain a dark blue homogenous solution containing vanadium precursor, and nitrated with nickel, cobalt and bismuth. The solution was mixed and heated to 75 ° C in a water bath.
- Og ( ⁇ 4 ) 6 ⁇ 7 ⁇ 24 ⁇ 4 ⁇ 2 0 was dissolved in 40 g of an 8% by weight aqueous ammonia solution to form an aqueous solution of (NH 4 ) 6 Mo 7 0 24 ammonia.
- the solution was slowly added dropwise to the above mixed solution containing nickel nitrate, cobalt nitrate, cerium nitrate and vanadium-containing precursor, and the pH was adjusted to 8 with nitric acid or ammonia water, and stirred at 75 ° C for 6 hours, and the stirring was stopped.
- the temperature was kept constant until there was no clear water, dried at 110 ° C for 24 hours, and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composition of the composite oxide is RhNiL5CoL5Vo.9Moo.9OK).
- the selective oxidation of decane is carried out by using 1.00 g of the composite oxide.
- the conversion of decane was determined to be 8.3%, and the selectivity of ethanol and acetaldehyde was 66.5%.
- the temperature was kept constant until there was no clear water, dried at 10 ° C for 24 hours, and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composition of the composite oxide is RhNi 8 CoQ. 2 V. . 3 Moo. 8 0 4 . 2 .
- the methane selective oxidation reaction is carried out by using the composite oxide of 1.0 g.
- the methane conversion was determined to be 12.7%, and the selectivity to ethanol and acetaldehyde was 68.5%.
- the temperature was kept constant until there was no clear water, dried at 10 ° C for 24 hours, and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composition of the composite oxide is RhNicMCowV sMocnO ⁇ a.
- the composite oxide is used for the selective oxidation of methane.
- the rate was 280011 - 1 and the reaction was carried out at 1 MPa and 550 ° C for 4 hours.
- the conversion of decane was determined to be 10.5%, and the selectivity of ethanol and acetaldehyde was 61.6%.
- Rh(N0 3 )3*2H 2 dissolved in 35 g of deionized water, to prepare a mixed solution containing cobalt nitrate, nickel nitrate and cerium nitrate.
- 1.4g of NH4VO3 was added to 20g of deionized water, and then treated with oxalic acid equivalent to NH 4 V0 3 to obtain a dark blue homogenized solution containing vanadium precursor, and nitrated with nickel, cobalt and bismuth. The solution was mixed and heated to 75 °C in a water bath.
- the temperature was kept constant until there was no clear water, dried at 10 ° C for 24 hours, and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composition of the composite oxide is RhNi 2 Coo. 2Vo.7Mo 6 0 5 . 5 .
- Example 20 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 19 is shown in Fig. 6, indicating that the composite oxide exhibited a crystalline state.
- Example 20 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 19 is shown in Fig. 6, indicating that the composite oxide exhibited a crystalline state.
- the solution was mixed and heated to 75 °C in a water bath.
- 0.8 g ( ⁇ 4 ) 6 ⁇ ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 was dissolved in 30 g of an 8% by weight aqueous ammonia solution to form an aqueous solution of (NH 4 ) 6 Mo 7 0 24 in ammonia.
- the solution was slowly added dropwise to the above mixed solution containing nickel nitrate, cobalt nitrate, cerium nitrate and vanadium-containing precursor, and the pH was adjusted to 6 with nitric acid or ammonia water, and stirred at 75 ° C for 6 hours, and the stirring was stopped.
- the temperature was kept constant until there was no clear water, dried at 10 ° C for 24 hours, and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composition of the composite oxide is RhNi 1 0 Co 0 . 5 V 5 Mo a 7O6.4.
- the composite oxide of l.Og is used for selective oxidation of decane.
- the conversion of decane was determined to be 15.1%, and the selectivity of ethanol and acetaldehyde was 73.2%.
- the temperature was kept constant until there was no clear water, dried at 110 ° C for 24 hours, and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composition of the composite oxide is RhNiLoCo ⁇ VcuMocnC ⁇
- the space velocity was SOOOh and the reaction was carried out at 2 MPa and 550 ° C for 4 hours.
- the methane conversion was determined to be 10.7%, and the selectivity of ethanol and acetaldehyde was 51.7%.
- the temperature was kept constant until there was no clear water, dried at U0 ° C for 24 hours, and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composition of the composite oxide is RhNiLoCoo.sVo.sMoojO.
- the composite oxide obtained by hydrogen reduction has a reduction pressure of 0.1 MPa, a temperature of 350 ° C, a space velocity of 1000 h, a reduction time of 0.5 h, and a composite oxide composition after reduction.
- RhNlL0Co0.5V0.5MO0.7O50 The methane selective oxidation reaction is carried out by using the reduced composite oxide of 1.0 g.
- the hydrochloric acid solution was mixed and hooked, and 7.0 g of pseudoboehmite was added, and the mixture was heated to 75 ° C in a water bath.
- 2.7 g ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 was dissolved in 30 g of an 8% by weight aqueous ammonia solution to form an aqueous solution of (NH 4 ) 6 Mo 7 0 24 ammonia.
- the solution is slowly added dropwise to the above mixed solution containing nickel nitrate, cobalt nitrate, cerium nitrate and vanadium-containing precursor, adjusted to pH 7 with nitric acid or ammonia water, stirred at 75 ° C for 6 hours, and stirred under water bath.
- Example 24 It was evaporated to dryness, dried at U 0 ° C for 24 hours, and calcined at 600 ° C for 8 hours to obtain a composite oxide.
- the composition of the composite oxide is RhNi 2 Coo. 2 Vo. 7 Mo 0 7 0 5 8 /Al 2 0 3 .
- Example 24 Example 24
- 1.8 g of NH 4 V0 3 was added to 20 g of deionized water, and then treated with an equimolar amount of oxalic acid with NH 4 V0 3 to obtain a dark blue homogeneous solution containing a vanadium precursor, and a nitric acid containing nickel, cobalt and ruthenium.
- the hydrochloric acid solution was mixed and hooked, and 7.0 g of pseudoboehmite was added, and the mixture was heated to 75 ° C in a water bath.
- 2.7 g ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0 was dissolved in 30 g of an 8% by weight aqueous ammonia solution to form an aqueous solution of (NH 4 ) 6 Mo 7 0 24 ammonia.
- the solution is slowly added dropwise to the above mixed solution containing nickel nitrate, cobalt nitrate, cerium nitrate and vanadium-containing precursor, adjusted to pH 7 with nitric acid or ammonia water, stirred at 75 ° C for 6 hours, and stirred under water bath.
- the composition of the composite oxide is RhNi 2 Coo. 2 Vo. 75 MoQ. 75 0 6 . 4 /Al 2 0 3 .
- the composite oxide obtained by hydrogen reduction has a reduction pressure of 0.1 MPa, a temperature of 350 ° C, a space velocity of 1000 h, a reduction time of 0.5 h, and a composite oxide composition after reduction. RhNi. . 2 Co. . 2 V 7 Mo 7 0 5 . 5 /Al 2 0 3 .
- the selective oxidation of decane was carried out by using 1.0 g of the reduced composite oxide.
- the composition of the composite oxide is RhNi 10 Co 10 V 0 . 5 Mo 06 O 64 /MgO-SiO 2 .
- Example 26 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 25 is shown in Fig. 7, indicating that the composite oxide exhibited a crystalline state.
- Example 26 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 25 is shown in Fig. 7, indicating that the composite oxide exhibited a crystalline state.
- the hydrochloric acid solution was mixed and hooked, and heated to 75 ° C in a water bath. Slowly add 8% by weight of aqueous ammonia solution to the above mixed solution containing nickel nitrate, cobalt nitrate, cerium nitrate and vanadium-containing precursor, and adjust the pH to 7, 7 °C with nitric acid or ammonia water. Stirring 6 In an hour, the stirring was stopped, the temperature was kept constant until there was no clear water, dried at 110 ° C for 24 hours, and air-fired at 600 ° C for 8 hours to obtain a Co, Ni, Rh, V composite oxide.
- the composite oxide composition is The composite oxide obtained by hydrogen reduction has a reduction pressure of 0.1 MPa, a temperature of 35 CTC, a space velocity of 1000 h, a reduction time of 0.5 h, and a composition formula of the composite oxide after reduction is RhNi 08 Co 12 V 07 Mo 05 O 37 .
- the selective oxidation of decane is carried out by using 1.00 g of the composite oxide.
- the conversion of decane was determined to be 5.5%, and the selectivity of ethanol and acetaldehyde was 0.7%.
- the yttrium-vanadium-aluminum oxide supported yttrium-vanadium-molybdenum composite oxide was produced by the impregnation method Weigh 6.9 g of Rh(N0 3 ) 3 «2H 2 0, dissolved in 10 g of deionized water to prepare an aqueous solution of cerium nitrate. 1.8 g of NH 4 V0 3 was dissolved in 10 g of deionized water and then treated with an equimolar amount of oxalic acid with NH 4 V ⁇ 3 to prepare a dark blue homogeneous solution containing the vanadium precursor.
- the methane selective oxidation reaction is carried out with 1.0 nm of the composite oxide.
- the conversion of decane was determined to be 8.6%, and the total selectivity of ethanol and acetaldehyde was 0.5%.
- Example 29 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 28 is shown in Fig. 8, indicating that the composite oxide does not have a crystalline state.
- Example 29 The powder X-ray diffraction spectrum of the composite oxide obtained in Example 28 is shown in Fig. 8, indicating that the composite oxide does not have a crystalline state.
- the yttrium-vanadium-aluminum oxide supported yttrium-vanadium-molybdenum composite oxide was produced by the impregnation method Weigh 1.2g of Co(N0 3 ) 2 *6H 2 0, 1.2 g of Ni(N0 3 ) 2 '6H 2 0 and 6.9g of Rh(N0 3 ) 3 '2H 2 0, dissolved in 10g of deionized water to prepare nitric acid An aqueous solution of cobalt, nickel nitrate, and cerium nitrate.
- the air atmosphere is 600 ° C for 8 hours.
- a composite oxide of the same composition and content as in Example 23 was obtained.
- the composition of the composite oxide is RhNio. 2 Coo. 2 V 0 . 7 Mo 0 . 7 0 5 . 8 /Al 2 0 3 .
- the composite oxide of l.Og is used for the selective oxidation of decane.
- the methane conversion was determined to be 10.9%, and the total selectivity of ethanol and acetaldehyde was 0.3%.
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EP13857060.1A EP2915582B1 (en) | 2012-11-01 | 2013-10-10 | Composite oxide, preparation method for same, and application thereof |
US14/440,096 US9314776B2 (en) | 2012-11-01 | 2013-10-10 | Composite oxide, preparation method for same, and application thereof |
KR1020157014527A KR101880623B1 (ko) | 2012-11-01 | 2013-10-10 | 복합 산화물, 그의 제조 방법 및 그의 용도 |
PL13857060T PL2915582T3 (pl) | 2012-11-01 | 2013-10-10 | Złożony tlenek, sposób jego wytwarzania i jego zastosowanie |
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US20230257334A1 (en) * | 2020-06-30 | 2023-08-17 | Japan Science And Technology Agency | Method for Partially Oxidizing Alkane |
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WO2010133461A1 (de) * | 2009-05-20 | 2010-11-25 | Basf Se | Anlage und verfahren zur herstellung von höherwertigen kohlenwasserstoffen aus methan |
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US5220080A (en) * | 1992-06-29 | 1993-06-15 | Sun Company, Inc. (R&M) | Chromia on metal oxide catalysts for the oxidation of methane to methanol |
US5702838A (en) * | 1995-08-18 | 1997-12-30 | Matsushita Electric Industrial Co., Ltd. | Fuel cell device equipped with catalyst material for removing carbon monoxide and method for removing carbon monoxide |
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US20050107252A1 (en) * | 2003-11-17 | 2005-05-19 | Gaffney Anne M. | Process for preparing mixed metal oxide catalyst |
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CN101146753A (zh) * | 2005-02-24 | 2008-03-19 | 罗伊·A·佩里亚纳 | 用于将烃转化成官能化产物的新型催化体系 |
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WO2014079142A8 (zh) | 2015-05-28 |
KR20150103664A (ko) | 2015-09-11 |
CN103801327A (zh) | 2014-05-21 |
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PL2915582T3 (pl) | 2018-06-29 |
EP2915582A4 (en) | 2016-07-13 |
TW201431824A (zh) | 2014-08-16 |
TWI605030B (zh) | 2017-11-11 |
EP2915582A1 (en) | 2015-09-09 |
US9314776B2 (en) | 2016-04-19 |
CN103801327B (zh) | 2016-01-06 |
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US20150321179A1 (en) | 2015-11-12 |
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