CN106944078A - A kind of preparation method for catalyst for hydrogen production from methane vapor reforming - Google Patents
A kind of preparation method for catalyst for hydrogen production from methane vapor reforming Download PDFInfo
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- CN106944078A CN106944078A CN201610003103.2A CN201610003103A CN106944078A CN 106944078 A CN106944078 A CN 106944078A CN 201610003103 A CN201610003103 A CN 201610003103A CN 106944078 A CN106944078 A CN 106944078A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 159
- 239000001257 hydrogen Substances 0.000 title claims abstract description 70
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000002407 reforming Methods 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 50
- 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 26
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 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
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 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 12
- 229920003169 water-soluble polymer Polymers 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 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
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 238000005245 sintering Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 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
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 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 10
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- 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 16
- 239000003643 water by type Substances 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- 229910015234 MoCo Inorganic materials 0.000 description 8
- 239000003426 co-catalyst Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 238000005516 engineering process Methods 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
- 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
- 238000009826 distribution Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 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
- 238000009792 diffusion process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- -1 methane hydrogen Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 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
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/8871—Rare earth metals or actinides
-
- 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
- B01J23/8872—Alkali or alkaline earth metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation method for catalyst for hydrogen production from methane vapor reforming, 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 catalyst for hydrogen production from methane vapor reforming, more particularly, to a kind of loading type nickel-based catalyst preparation method for hydrogen production from methane vapor reforming.
Background technology
Methane is hydrogen-carbon ratio highest hydrocarbon molecules in nature, and its abundance can be used as excellent hydrogen feedstock.At present, the hydrogen producing technology using methane as raw material mainly has hydrogen production from methane vapor reforming, partial oxidation of methane hydrogen, self-heating reforming hydrogen manufacturing etc..This several technology typically all obtains synthesis gas first（H2With CO gaseous mixture）, then pass through transformationreation（WGS）And pressure-variable adsorption（PSA）Obtain hydrogen.Wherein hydrogen production from methane vapor reforming can obtain hydrogen-carbon ratio（H2/CO）For 3 synthesis gas, therefore it is more suitable for for hydrogen manufacturing.Hydrogen production from methane vapor reforming is a kind of ripe industrialization hydrogen producing technology, and process is highly endothermic, generally in high temperature（800~1100 DEG C）Under the conditions of carry out, using high steam/hydrocarbons ratio operate（VH2O/VCH4>3）, to prevent catalyst carbon deposit.At present, the research of hydrogen production from methane vapor reforming is laid particular emphasis under the conditions of low steam carbon ratio high activity and the catalyst preparation of high stability, to seek the investment and the technical scheme of production cost that reduce natural gas steam reforming process.
Conventional SMR catalyst be loaded catalyst, carrier be aluminum oxide, zirconium oxide, cerium oxide, magnesia, lanthana, niobium oxide, zeolite, perovskite, silica clay, yittrium oxide, cobalt oxide, iron oxide and its mixture or one of.In group VIII non-radioactive metal can as SMR catalyst active metal.Research shows, by group VIII noble metals Ru, Rh, Pd even load when on suitable carrier, all with higher reactivity and anti-carbon performance, but noble metal shortcoming be that it is expensive；In group VIII base metal, Raney nickel has higher reactivity, typically using Ni/Al2O3Catalyst, reaction condition is 1.5 ~ 3MPa, 850 ~ 900 DEG C, the H of generation2The ratio between/CO is about 3.
Although existing catalyst can obtain preferable hydrogen production from methane vapor reforming reactivity worth, still suffer from that cost is higher, catalyst easy carbon distribution the problems such as.Particularly work as reactant（Methane and water）Molecule during mass transfer, due to the difference of diffusion velocity, causes two kinds of reactant molecule ratios gradient radially occur in catalyst granules, particle inside steam/hydrocarbons ratio, which is much smaller than inside stoichiometry, therefore catalyst granules, is more easy to carbon distribution in catalyst granules.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of preparation method for catalyst for hydrogen production from methane vapor reforming, 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 catalyst for hydrogen production from methane vapor reforming, the catalyst includes active component, auxiliary agent and carrier, active component is Ni, and auxiliary agent is the one or more in Mg, Ca, Mo, Co, Zr, La or Ce, 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 15wt%~25wt%, and the content of auxiliary agent is 8wt%~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 catalyst for hydrogen production from methane vapor reforming, 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 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 catalyst for hydrogen production from methane vapor reforming, 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 catalyst for hydrogen production from methane vapor reforming, step（3）Described in auxiliary agent presoma be one or more in magnesium nitrate, calcium nitrate, zirconium nitrate, cerous nitrate, lanthanum nitrate, preferably magnesium nitrate；In the solution B, auxiliary agent is in terms of element, and the mass fraction in solution B is 3%~12%；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 catalyst for hydrogen production from methane vapor reforming, 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 1%~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 catalyst for hydrogen production from methane vapor reforming, 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 hydrogen production from methane vapor reforming reaction.Catalyst using before in a hydrogen atmosphere, 700~800 DEG C of 2~5h of prereduction.Catalyst prepared by the inventive method reacts applied to hydrogen production from methane vapor reforming, and preferable process conditions are：The composition H of unstripped gas2O/CH4Mol ratio is 1~4, can contain Ar, N in unstripped gas2Or the dilution such as He property gas, 1000~3000h of unstripped gas air speed-1, reaction pressure is 0.2~3Mpa, and reaction temperature is 600~800 DEG C.
Compared with prior art, the catalyst reacted for hydrogen production from methane vapor reforming 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 3 hours at 700 DEG C before catalyst reaction of the present invention.Reacted in continuous sample introduction fixed-bed quartz reactor, 750 DEG C of reaction temperature, unstripped gas composition H2O/CH4/N2=6.75/2.25/1（Mol ratio）, air speed 2000h-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 750 DEG C of 100h 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, obtain catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element catalyst precarsor A weight 1.8wt%, Ni are accounted in terms of element accounts for catalyst precarsor A weight 2.3wt% 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；19.02g magnesium nitrates are dissolved in 30mL 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；24g polyethylene glycol, 25.47g 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 70g absolute ethyl alcohols, 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 18.4%Ni, 5.9%Mg, 3.8%Mo, 0.9%Co catalyst, is 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, obtain catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 5.2wt%, Co in terms of element catalyst precarsor A weight 1.2wt%, Ni are accounted in terms of element accounts for catalyst precarsor A weight 1.5wt% 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；10.26g magnesium nitrates are dissolved in 25mL 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；18g polyethylene glycol, 19.32g 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 53g absolute ethyl alcohols, 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 12.7%Ni, 2.9%Mg, 3.3%Mo, 0.6%Co catalyst, is 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, obtain catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element catalyst precarsor A weight 1.8wt%, Ni are accounted in terms of element accounts for catalyst precarsor A weight 2.3wt% 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；27.99g magnesium nitrates are dissolved in 40mL 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；30g polyethylene glycol, 32.41g 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 90g absolute ethyl alcohols, 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 23.2%Ni, 8.8%Mg, 3.9%Mo, 1.0%Co catalyst, is 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, obtain catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element catalyst precarsor A weight 1.8wt%, Ni are accounted in terms of element accounts for catalyst precarsor A weight 2.3wt% 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；10.51g calcium nitrate is dissolved in 20mL deionized waters, solution B is obtained, and is well mixed with the mass fraction of its 3 times of quality for 30% furfural aqueous solution, is then added to together with the catalyst precarsor A after reduction activation in autoclave；24g polyethylene glycol, 25.47g 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 70g absolute ethyl alcohols, 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 17.9%Ni, 5.3%Ca, 3.9%Mo, 1.1%Co catalyst, is 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, obtain catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element catalyst precarsor A weight 1.8wt%, Ni are accounted in terms of element accounts for catalyst precarsor A weight 2.3wt% 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；8.79g cobalt nitrates are dissolved in 20mL 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；24g polyvinyl alcohol, 25.47g 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 70g absolute ethyl alcohols, 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 18.1%Ni, 5.6%Co, 3.9%Mo, 0.9%Co catalyst, is designated as C-5.
Embodiment 6
From the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）The oil on catalyst surface is removed by extracting, in 110 DEG C of dry 8 h, gained catalyst is calcined 4h at 450 DEG C, obtain catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element catalyst precarsor A weight 1.8wt%, Ni are accounted in terms of element accounts for catalyst precarsor A weight 2.3wt% 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；8.38g zirconium nitrates are dissolved in 30mL deionized waters, solution B is obtained, and are well mixed with the mass fraction of its 4 times of quality for 50% furfural aqueous solution, are then added to together with the catalyst precarsor A after reduction activation in autoclave；24g polyethylene glycol, 25.47g 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 20 DEG C in above-mentioned autoclave, add the aqueous citric acid solution that 467g 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 18.2%Ni, 5.2%Zr, 4.1%Mo, 1.1%Co 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, obtain catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element catalyst precarsor A weight 1.8wt%, Ni are accounted in terms of element accounts for catalyst precarsor A weight 2.3wt% 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；5.55g lanthanum 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；By 24g polyvinylpyrrolidones（k30）, 25.47g 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 30 DEG C in above-mentioned autoclave, add the aqueous citric acid solution that 466g 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 18.7%Ni, 6.1%La, 4.1%Mo, 1.1%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, obtain catalyst precarsor A, wherein Mo is accounted for catalyst precarsor A weight 6.1wt%, Co in terms of element catalyst precarsor A weight 1.8wt%, Ni are accounted in terms of element accounts for catalyst precarsor A weight 2.3wt% in terms of element；20g catalyst precarsors A is added in the aqueous solution containing 19.02g magnesium nitrates and 25.473g 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, it is made and quality is counted using element accounts for catalyst percentage composition as 19.1%Ni, 6.2%Mg, 4.2%Mo, 1.1%Co catalyst, is 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 catalyst for hydrogen production from methane vapor reforming, the catalyst includes active component, auxiliary agent and carrier, active component is Ni, and auxiliary agent is the one or more in Mg, Ca, Mo, Co, Zr, La or Ce, 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 15wt%~25wt%, and the content of auxiliary agent is 8wt%~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 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 magnesium nitrate, calcium nitrate, zirconium nitrate, cerous nitrate, lanthanum nitrate, preferably magnesium 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 3%~12%.
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 1%~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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| CN111841550A (en) * | 2020-08-18 | 2020-10-30 | 中国科学技术大学 | Application of Bimetallic Alloys in Anti-Carbon Catalyst for Methane Steam Reforming |
| CN113289630A (en) * | 2021-05-19 | 2021-08-24 | 哈尔滨工业大学（深圳） | Catalyst for diesel reforming reaction, preparation method thereof, hydrogen production reformer and system |
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| EP0669163B1 (en) * | 1994-02-02 | 1997-10-29 | Degussa Aktiengesellschaft | Formed copper catalyst for the selective hydrogenation of furfural to furfuryl-alcohol |
| CN103203240A (en) * | 2013-03-11 | 2013-07-17 | 中国石油大学(华东) | Preparation method and application of fixed bed framework metal catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0669163B1 (en) * | 1994-02-02 | 1997-10-29 | Degussa Aktiengesellschaft | Formed copper catalyst for the selective hydrogenation of furfural to furfuryl-alcohol |
| CN103203240A (en) * | 2013-03-11 | 2013-07-17 | 中国石油大学(华东) | Preparation method and application of fixed bed framework metal catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111841550A (en) * | 2020-08-18 | 2020-10-30 | 中国科学技术大学 | Application of Bimetallic Alloys in Anti-Carbon Catalyst for Methane Steam Reforming |
| CN113289630A (en) * | 2021-05-19 | 2021-08-24 | 哈尔滨工业大学（深圳） | Catalyst for diesel reforming reaction, preparation method thereof, hydrogen production reformer and system |
| CN113289630B (en) * | 2021-05-19 | 2022-11-22 | 哈尔滨工业大学（深圳） | Catalyst for diesel reforming reaction, preparation method thereof, hydrogen production reformer and system |
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