CN106944082A - A kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst - Google Patents
A kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst Download PDFInfo
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- CN106944082A CN106944082A CN201610003114.0A CN201610003114A CN106944082A CN 106944082 A CN106944082 A CN 106944082A CN 201610003114 A CN201610003114 A CN 201610003114A CN 106944082 A CN106944082 A CN 106944082A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 182
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000002407 reforming Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 51
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 229910052720 vanadium Inorganic materials 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- 229920003169 water-soluble polymer Polymers 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 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 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000003643 water by type Substances 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 9
- 229910015234 MoCo Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 230000004913 activation Effects 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- 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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- B01J35/396—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst, the catalyst includes active component, auxiliary agent and carrier；The preparation method of the catalyst comprises the following steps：Catalyst precarsor A is prepared first, then reduction treatment is carried out to catalyst precarsor A, it is well mixed auxiliary agent presoma is soluble in water with furfural aqueous solution, then it is added to together with catalyst precarsor A in autoclave, reacted after adding solution C, filtering gained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.This method takes full advantage of waste residue oil hydrogenating treatment catalyst, has saved cost, and the catalyst reaction activity of preparation is high, both reduces metal consumption, the selectivity of product is improved again.
Description
Technical field
The present invention relates to a kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst, more particularly, to a kind of preparation method for synthesizing gas by reforming methane with co 2 loading type nickel-based catalyst.
Background technology
Methane and carbon dioxide is cheap in nature and resourceful carbon compound; using the reforming reaction producing synthesis gas of methane and carbon dioxide, for alleviating energy crisis, mitigate due to caused by the discharge of greenhouse gases global climate warm it is significant.The synthesis gas that methane is prepared with CO 2 reformation has H2The characteristics of/CO≤1, go for F- T synthesis, the high chemicals of added value such as production higher hydrocarbon.
The catalyst for being presently used for synthesizing gas by reforming methane with co 2 is more based on metal supported catalyst, is broadly divided into two major classes：Noble metal and non-precious metal catalyst.Although noble metal catalyst is with excellent reactivity worth, expensive, sintering is also easy under hot conditions and is lost in.Non-precious metal catalyst is that nickel or cobalt are carried on the carriers such as aluminum oxide, silica, magnesia, zirconium oxide, titanium oxide, the advantage of this system is that reactivity worth is good, catalyst preparation low cost, but catalyst carbon accumulation resisting ability is low, can cause inactivation because of carbon distribution, sintering.
CN
101352687A discloses a kind of bimetallic catalyst of modification, and the catalyst is with a kind of γ-Al of modification2O3For carrier, the Co using mass percent as 1% ~ 20% Ni and 1% ~ 20% is prepared for active component using infusion process.But the preparation technology is more complicated, cost is higher.
CN
102658145A discloses a kind of MgO（111）The preparation method of supported nickel based catalysts, first step carrier synthesis, is dissolved in absolute ethyl alcohol by magnesium rod, sequentially adds methoxy benzyl alcohol, methanol, is reacted in autoclave, roasting obtains carrier；Carrier impregnation is obtained metallic catalyst by second step in nickel acetylacetonate solution.But the preparation cost of the catalyst is too high, and preparation process is whard to control.
CN
1280882A discloses a kind of nickel-base catalyst of nano-crystal oxide load.The catalyst is that the aqueous solution of nickel nitrate is added in nanocrystal oxide, and stirring, dry, roasting are made.The reaction of gained catalyst is lasted a long time, but this method preparation process is complicated, and cost is higher.
Although catalyst made from above-mentioned patented method obtains preferable synthesizing gas by reforming methane with co 2 reactivity worth, still suffer from that cost is higher, catalyst easy carbon distribution the problems such as.Reactant molecule is in catalyst granules during mass transfer, due to the difference of diffusion velocity, two kinds of reactant molecule ratios are caused gradient radially occur in catalyst granules, particle inside methane is much larger than inside stoichiometry, therefore catalyst granules with carbon dioxide ratio and is more easy to carbon distribution.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst, the characteristics of catalyst prepared by this method has with low cost, metal component utilization rate high and is selective good.
The invention provides a kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst, the catalyst includes active component, auxiliary agent and carrier, active component is Ni, and auxiliary agent is the one or more in Zr, La, Ce, Co, Mo or V, and carrier is aluminum oxide；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component is 10wt%~20wt%, and the content of auxiliary agent is 7wt%~15wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）Waste residue oil hydrogenating treatment catalyst is extracted to the oil removed on catalyst surface, after 80~150 DEG C are dried, high-temperature roasting processing is carried out, obtains catalyst precarsor A, wherein, sintering temperature is 300 ~ 600 DEG C, and roasting time is 2~6h；
（2）Using reducing atmosphere to step（1）Obtained catalyst precarsor A carries out reduction treatment；
（3）Auxiliary agent presoma is soluble in water, solution B is obtained, and be well mixed with furfural aqueous solution, then with step（2）Obtained catalyst precarsor A is added in autoclave together；
（4）High molecular weight water soluble polymer, active component presoma is soluble in water, obtain solution C；Solution C is added to step（3）In described autoclave, replaced 2~5 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 2~4MPa, 1~3h is reacted at 100~200 DEG C；
（5）Treat step（4）Obtained solidliquid mixture is down to 20~30 DEG C, adds absolute ethyl alcohol or aqueous citric acid solution, places 1~2h, then filters, gained solid sample after drying, calcination process, obtains catalyst again.
The present invention is used in the preparation method of synthesizing gas by reforming methane with co 2 catalyst, step（1）Described in waste residue oil hydrogenating treatment catalyst using aluminum oxide as carrier, active metal component contains Mo and Co, is not reached former reaction to require, or due to level with reason without the residual oil hydrocatalyst that is used in the fixed bed or ebullated bed of complete deactivation；Described dead catalyst is due to being hydrotreating catalyst used in hydrogenation process, so in hydrogenation process, typically having part metals Ni and V deposition；Mo content is 5wt% ~ 10wt% in described catalyst precarsor A, and Co content is 1wt% ~ 3wt%, and V content is 1wt% ~ 3wt%, and Ni content is 1wt% ~ 5wt%.Step（1）Described in extracting solvent can be petroleum ether, toluene in one or two.
The present invention is used in the preparation method of synthesizing gas by reforming methane with co 2 catalyst, step（2）Described in reducing atmosphere be the mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.Specific reduction treatment process is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, the mixed gas of hydrogen or hydrogen and nitrogen is then passed to, in 0.1~0.5MPa（Absolute pressure）Handle after 4~8h, room temperature is down in a nitrogen atmosphere.
The present invention is used in the preparation method of synthesizing gas by reforming methane with co 2 catalyst, step（3）Described in auxiliary agent presoma be one or more in zirconium nitrate, cerous nitrate, lanthanum nitrate, preferably zirconium nitrate；
In the solution B, auxiliary agent is in terms of element, and the mass fraction in solution B is 1%~10%；The mass fraction of furfural is 30%~50% in the furfural aqueous solution；Step（3）Described in furfural aqueous solution and the mass ratio of solution B be 3 ~ 5, the gross mass and step of the solution B and furfural aqueous solution（2）Obtained reduction rear catalyst precursor A mass ratio is 3~6.
The present invention is used in the preparation method of synthesizing gas by reforming methane with co 2 catalyst, step（4）Described in high molecular weight water soluble polymer be polyethylene glycol（PEG）, polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）In one or more；The active component presoma is the one or more in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, preferably nickel nitrate；In the solution C, in active component presoma it is nickeliferous mass fraction in solution C is counted as 0.5%~3% using element, mass fraction of the high molecular weight water soluble polymer in solution C is 3~6 times of Ni element mass fractions.
The present invention is used in the preparation method of synthesizing gas by reforming methane with co 2 catalyst, step（5）Described in add the quality of absolute ethyl alcohol or citric acid and the mass ratio of high molecular weight water soluble polymer be 2 ~ 4；The mass fraction of the aqueous citric acid solution is 10%~20%；The drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h；The sintering temperature is 350~650 DEG C, and preferably 400~600 DEG C, roasting time is 2~12h, preferably 4~8h.
Catalyst prepared by the inventive method can apply to synthesizing gas by reforming methane with co 2 reaction.Catalyst using before in a hydrogen atmosphere, 600~800 DEG C of 2~5h of prereduction.Catalyst prepared by the inventive method reacts applied to synthesizing gas by reforming methane with co 2, and preferable process conditions are：The composition CH of unstripped gas4/CO2Mol ratio is 1~1.5, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, 2000~6000h of unstripped gas air speed-1, reaction pressure is 0.1~2Mpa, and reaction temperature is 700~900 DEG C.
Compared with prior art, the catalyst for synthesizing gas by reforming methane with co 2 that a kind of active metal outer layer is distributed can be obtained by preparation method of the present invention.In the present invention, furfural aqueous phase hydrogenation reaction is carried out using waste residue oil hydrogenating treatment catalyst.Add active metal predecessor and high molecular weight water soluble polymer simultaneously in the system of furfural hydrogenation, on the one hand hinder active metal to the diffusion inside catalyst granules using furfural hydrogenation product；On the other hand, using the coordination between active metal predecessor and high molecular weight water soluble polymer, concentration difference of the active metallic ion inside and outside catalyst granules in reduction solution slows down active metal to the diffusion velocity inside catalyst granules.This method takes full advantage of waste residue oil hydrogenating treatment catalyst, has saved cost, and the catalyst reaction activity of preparation is high, both reduces metal consumption, the selectivity of product is improved again.Catalyst precarsor processing simultaneously is completed with the step of catalyst preparation one, and preparation technology is simple, is conducive to industrial amplification.
Embodiment
The technology contents and effect of the present invention are further illustrated with reference to embodiment, but are not so limited the present invention.
Appreciation condition：With hydrogen reducing 4 hours at 700 DEG C before catalyst reaction of the present invention.Reacted in continuous sample introduction fixed-bed quartz reactor, 700 DEG C of reaction temperature, unstripped gas composition CH4/CO2/Ar
=1/1/4（Mol ratio）, air speed 4000h-1, gas-chromatography on-line analysis is used after the condensed water removal of product.Reaction starts sampling analysis after 1 ~ 3 hour, and evaluation result is shown in Table 1.Average activity of the reaction result for catalyst after 800 DEG C of 50h that work in table 1.
The metal element content in catalyst is determined using XRF analysis technology.Using the distribution situation of active component on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.The scanning electron microscope analysis of catalyst activity component nickel the results are shown in Table 2 obtained by the embodiment of the present invention and comparative example.
Embodiment 1
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, catalyst precarsor A is obtained, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element and catalyst precarsor A weight 1.8wt% is accounted in terms of element, Ni is accounted for catalyst precarsor A weight 2.3wt%, V in terms of element and catalyst precarsor A weight 1.9wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；2.54g zirconium nitrates are dissolved in 16mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；15g polyethylene glycol, 16.3g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, 45g absolute ethyl alcohols are added, 1.5h is placed, then filters, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, that is, is made and quality is counted using element is accounted for catalyst percentage composition as 13.7%Ni, 1.9%Zr, 4.4%Mo, 1.1%Co, 1.2%V catalyst, are designated as C-1.
Embodiment 2
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, catalyst precarsor A is obtained, wherein Mo is accounted for catalyst precarsor A weight 5.2wt%, Co in terms of element and catalyst precarsor A weight 1.2wt% is accounted in terms of element, Ni is accounted for catalyst precarsor A weight 1.5wt%, V in terms of element and catalyst precarsor A weight 1.3wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；0.99g zirconium nitrates are dissolved in 16mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；10g polyethylene glycol, 10.9g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, 30g absolute ethyl alcohols are added, 1.5h is placed, then filters, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, that is, is made and quality is counted using element is accounted for catalyst percentage composition as 8.8%Ni, 0.3%Zr, 3.6%Mo, 0.7%Co, 0.8%V catalyst, are designated as C-2.
Embodiment 3
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, catalyst precarsor A is obtained, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element and catalyst precarsor A weight 1.8wt% is accounted in terms of element, Ni is accounted for catalyst precarsor A weight 2.3wt%, V in terms of element and catalyst precarsor A weight 1.9wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；7.25g zirconium nitrates are dissolved in 20mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；21g polyethylene glycol, 22.5g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, 62g absolute ethyl alcohols are added, 1.5h is placed, then filters, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, that is, is made and quality is counted using element is accounted for catalyst percentage composition as 17.3%Ni, 5.4%Zr, 4.2%Mo, 1.2%Co, 1.1%V catalyst, are designated as C-3.
Embodiment 4
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, catalyst precarsor A is obtained, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element and catalyst precarsor A weight 1.8wt% is accounted in terms of element, Ni is accounted for catalyst precarsor A weight 2.3wt%, V in terms of element and catalyst precarsor A weight 1.9wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.68g lanthanum nitrates are dissolved in 16mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 3 times of quality for 30% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；15g polyethylene glycol, 16.3g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, 45g absolute ethyl alcohols are added, 1.5h is placed, then filters, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, that is, is made and quality is counted using element is accounted for catalyst percentage composition as 13.3%Ni, 1.8%La, 4.5%Mo, 1.1%Co, 1.1%V catalyst, are designated as C-4.
Embodiment 5
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, catalyst precarsor A is obtained, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element and catalyst precarsor A weight 1.8wt% is accounted in terms of element, Ni is accounted for catalyst precarsor A weight 2.3wt%, V in terms of element and catalyst precarsor A weight 1.9wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.67g cerous nitrates are dissolved in 16mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 5 times of quality for 50% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；15g polyvinyl alcohol, 16.3g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, 45g absolute ethyl alcohols are added, 1.5h is placed, then filters, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, that is, is made and quality is counted using element is accounted for catalyst percentage composition as 13.5%Ni, 1.7%Ce, 4.3%Mo, 0.9%Co, 1.0%V catalyst, are designated as C-5.
Embodiment 6
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, catalyst precarsor A is obtained, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element and catalyst precarsor A weight 1.8wt% is accounted in terms of element, Ni is accounted for catalyst precarsor A weight 2.3wt%, V in terms of element and catalyst precarsor A weight 1.9wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；2.67g cobalt nitrates are dissolved in 16mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；15g polyethylene glycol, 16.3g nickel nitrates are dissolved in 200mL deionized waters, solution C is obtained；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, add the aqueous citric acid solution that 300g mass fractions are 15%, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 13.1%Ni, 3.1%Co, 4.5%Mo, 1.1%V catalyst, is designated as C-6.
Embodiment 7
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, catalyst precarsor A is obtained, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element and catalyst precarsor A weight 1.8wt% is accounted in terms of element, Ni is accounted for catalyst precarsor A weight 2.3wt%, V in terms of element and catalyst precarsor A weight 1.9wt% is accounted in terms of element；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；1.24g ammonium metavanadates are dissolved in 16mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 40% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；By 15g polyvinylpyrrolidones（k30）, 16.3g nickel nitrates be dissolved in 200mL deionized waters, obtain solution C；Solution C is also added in autoclave, replaced 3 times with hydrogen after sealing, Hydrogen Vapor Pressure is then adjusted to 3MPa, 2h is reacted at 150 DEG C；Treat that reacted solidliquid mixture is down to 25 DEG C in above-mentioned autoclave, add the aqueous citric acid solution that 300g mass fractions are 15%, 1.5h is placed, is then filtered, gained solid sample is put into baking oven in dry 6h at 110 DEG C, 6h is calcined at 700 DEG C, it is made and quality is counted using element accounts for catalyst percentage composition as 13.9%Ni, 2.9%V, 4.3%Mo, 1.2%Co catalyst, is designated as C-7.
Comparative example
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil removed on catalyst surface is extracted by petroleum ether, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, catalyst precarsor A is obtained, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element and catalyst precarsor A weight 1.8wt% is accounted in terms of element, Ni is accounted for catalyst precarsor A weight 2.3wt%, V in terms of element and catalyst precarsor A weight 1.9wt% is accounted in terms of element；20g catalyst precarsors A is added in the aqueous solution containing 2.54g zirconium nitrates and 16.3g nickel nitrates, it is evaporated in 80 DEG C of stirring to solution, it is put into baking oven in dry 12h at 110 DEG C, 4h is calcined at 400 DEG C, that is, is made and quality is counted using element is accounted for catalyst percentage composition as 14.3%Ni, 2.1%Zr, 4.6%Mo, 1.3%Co, 1.2%V catalyst, are designated as D-1.
The reactivity worth of the catalyst of table 1
The catalyst activity component Ni content distributions of table 2（wt%）
Claims (16)
1. a kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst, the catalyst includes active component, auxiliary agent and carrier, active component is Ni, and auxiliary agent is the one or more in Zr, La, Ce, Co, Mo or V, and carrier is aluminum oxide；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component is 10wt%~20wt%, and the content of auxiliary agent is 7wt%~15wt%, and surplus is carrier；The preparation method of the catalyst comprises the following steps：
（1）Waste residue oil hydrogenating treatment catalyst is extracted to the oil removed on catalyst surface, after 80~150 DEG C are dried, high-temperature roasting processing is carried out, obtains catalyst precarsor A, wherein, sintering temperature is 300 ~ 600 DEG C, and roasting time is 2~6h；
（2）Using reducing atmosphere to step（1）Obtained catalyst precarsor A carries out reduction treatment；
（3）Auxiliary agent presoma is soluble in water, solution B is obtained, and be well mixed with furfural aqueous solution, then with step（2）Obtained catalyst precarsor A is added in autoclave together；
（4）High molecular weight water soluble polymer, active component presoma is soluble in water, obtain solution C；Solution C is added to step（3）In described autoclave, replaced 2~5 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 2~4MPa, 1~3h is reacted at 100~200 DEG C；
（5）Treat step（4）Obtained solidliquid mixture is down to 20~30 DEG C, adds absolute ethyl alcohol or aqueous citric acid solution, places 1~2h, then filters, gained solid sample after drying, calcination process, obtains catalyst again.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in waste residue oil hydrogenating treatment catalyst using aluminum oxide as carrier, active metal component contain Mo and Co.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described in catalyst precarsor A in Mo content be 5wt% ~ 10wt%, Co content is 1wt% ~ 3wt%, and V content is 1wt% ~ 3wt%, and Ni content is 1wt% ~ 5wt%.
4. in accordance with the method for claim 1, it is characterised in that：Step（2）Described in reducing atmosphere be the mixed gas of hydrogen or hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
5. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in auxiliary agent presoma be one or more in zirconium nitrate, cerous nitrate, lanthanum nitrate, preferably zirconium nitrate.
6. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in solution B, auxiliary agent is in terms of element, and the mass fraction in solution B is 1%~10%.
7. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in furfural aqueous solution the mass fraction of furfural be 30%~50%.
8. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in furfural aqueous solution and the mass ratio of solution B be 3 ~ 5.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）Described in solution B and the gross mass and step of furfural aqueous solution（2）Obtained reduction rear catalyst precursor A mass ratio is 3~6.
10. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in high molecular weight water soluble polymer be polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol in one or more.
11. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in active component presoma be one or more in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, preferably nickel nitrate.
12. in accordance with the method for claim 1, it is characterised in that：Step（4）Described in solution C, in active component presoma it is nickeliferous mass fraction in solution C is counted as 0.5%~3% using element, mass fraction of the high molecular weight water soluble polymer in solution C is 3~6 times of Ni element mass fractions.
13. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in add the quality of absolute ethyl alcohol or citric acid and the mass ratio of high molecular weight water soluble polymer be 2 ~ 4.
14. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in aqueous citric acid solution mass fraction be 10%~20%.
15. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in drying temperature be 70~150 DEG C, preferably 80~120 DEG C, drying time be 2~12h, preferably 4~8h.
16. in accordance with the method for claim 1, it is characterised in that：Step（5）Described in sintering temperature be 350~650 DEG C, preferably 400~600 DEG C, roasting time be 2~12h, preferably 4~8h.
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