CN106944082B - 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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- CN106944082B CN106944082B CN201610003114.0A CN201610003114A CN106944082B CN 106944082 B CN106944082 B CN 106944082B CN 201610003114 A CN201610003114 A CN 201610003114A CN 106944082 B CN106944082 B CN 106944082B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 168
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000002407 reforming Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 48
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002699 waste material Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 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 22
- 229910052720 vanadium Inorganic materials 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 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 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 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
- 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
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- FTWGTNVTSDGLFG-UHFFFAOYSA-N nitric acid zirconium Chemical compound [Zr].O[N+]([O-])=O FTWGTNVTSDGLFG-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 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
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 9
- 229910015234 MoCo 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
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 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
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005245 sintering Methods 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 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
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 150000001722 carbon compounds Chemical group 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 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 compound [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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- LBPYPRXFFYUUSI-UHFFFAOYSA-N furan-2-carbaldehyde;hydrate Chemical compound O.O=CC1=CC=CO1 LBPYPRXFFYUUSI-UHFFFAOYSA-N 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
- 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000002243 precursor 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
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
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 includes the following steps: to prepare catalyst precarsor A first, then reduction treatment is carried out to catalyst precarsor A, it is uniformly mixed with furfural aqueous solution by auxiliary agent presoma is soluble in water, then it is added in autoclave together with catalyst precarsor A, it is reacted after solution C is added, filtering obtained 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, not only reduces metal consumption, but also improve the selectivity of product.
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 technique
Methane and carbon dioxide is carbon compound cheap and resourceful in nature, utilizes methane and carbon dioxide
Reforming reaction producing synthesis gas, for alleviating energy crisis, mitigate due to greenhouse gases discharge caused by global gas
Time, which warms, to be of great significance.Methane and the synthesis gas of CO 2 reformation preparation have H2The characteristics of/CO≤1, can be applicable in
In F- T synthesis, the high chemicals of added values such as higher hydrocarbon are produced.
Currently, for synthesizing gas by reforming methane with co 2 catalyst mostly based on metal supported catalyst, mainly
It is divided into two major classes: noble metal and non-precious metal catalyst.For noble metal catalyst although having excellent reactivity worth, price is high
It is expensive, it is also easy to sintering under hot conditions and is lost.Non-precious metal catalyst is nickel or cobalt be carried on aluminium oxide, silica, magnesia,
On the carriers such as zirconium oxide, titanium oxide, the advantages of this system is that reactivity worth is good, and catalyst preparation is at low cost, but catalyst
Carbon accumulation resisting ability is low, can cause to inactivate 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 modification2O3
For carrier, using mass percent be 1% ~ 20% Ni and 1% ~ 20% Co as active component, prepared using infusion process.But the system
Standby technics comparing is complicated, higher cost.
CN 102658145A discloses a kind of MgO(111) preparation methods of supported nickel based catalysts, first step carrier closes
At, dehydrated alcohol is dissolved in by magnesium rod, sequentially adds methoxy benzyl alcohol, methanol, in autoclave react, roast obtain
Carrier；Carrier impregnation is obtained metallic catalyst by second step in nickel acetylacetonate solution.But the preparation cost of the catalyst is too
Height, and preparation process is not easy to control.
CN 1280882A discloses a kind of nickel-base catalyst of nano-crystal oxide load.The catalyst is by nickel nitrate
Aqueous solution be added in nanocrystal oxide, stirring, dry, roasting are made.The reaction of gained catalyst lasts a long time, but
This method preparation process is complicated, higher cost.
Although it is anti-that catalyst made from above-mentioned patented method obtains preferable synthesizing gas by reforming methane with co 2
Answer performance, but the problems such as carbon distribution easy there are still higher cost, catalyst.Reactant molecule in catalyst granules when mass transfer, by
In the difference of diffusion velocity, two kinds of reactant molecule ratios is caused gradient, methane inside particle radially occur in catalyst granules
It is much larger than stoichiometry with carbon dioxide ratio, therefore is easier to carbon distribution inside catalyst granules.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides one kind to synthesize for methane carbon dioxide reformation system
The preparation method of gas catalyst, the catalyst of this method preparation have low in cost, metal component utilization rate height and selectivity
Good feature.
The present invention provides a kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst, the catalysis
Agent includes active component, auxiliary agent and carrier, active component Ni, one or more of auxiliary agent Zr, La, Ce, Co, Mo or V,
Carrier is aluminium oxide；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component is
The content of 10wt%~20wt%, auxiliary agent are 7wt%~15wt%, and surplus is carrier；The preparation method of the catalyst includes as follows
Step:
(1) waste residue oil hydrogenating treatment catalyst is extracted into the oil on removal catalyst surface, after 80~150 DEG C are dry,
High-temperature roasting processing is carried out, catalyst precarsor A is obtained, wherein maturing temperature is 300 ~ 600 DEG C, and calcining time is 2~6h；
(2) reduction treatment is carried out to the catalyst precarsor A that step (1) obtains using reducing atmosphere；
(3) auxiliary agent presoma is soluble in water, obtain solution B, and be uniformly mixed with furfural aqueous solution, then with step
(2) the catalyst precarsor A obtained is added in autoclave together；
(4) water soluble polymer, active component presoma is soluble in water, obtain solution C；Solution C is added
It into autoclave described in step (3), is replaced 2~5 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 2~4MPa,
1~3h is reacted at 100~200 DEG C；
(5) solidliquid mixture obtained to step (4) is down to 20~30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added,
1~2h is placed, is then filtered, obtained 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, as described in step (1)
For waste residue oil hydrogenating treatment catalyst using aluminium oxide as carrier, active metal component contains Mo and Co, is that former reaction has been not achieved to want
It asks, or the residual oil hydrocatalyst due to gradation without being used on the fixed bed of complete deactivation or ebullated bed；It is described
Dead catalyst as being hydrotreating catalyst used in hydrogenation process, so generally being had in hydrogenation process
Part metals Ni and V deposition；The content of Mo is 5wt% ~ 10wt% in the catalyst precarsor A, the content of Co be 1wt% ~
The content of 3wt%, V are 1wt% ~ 3wt%, and the content of Ni is 1wt% ~ 5wt%.Extracting solvent described in step (1) can be petroleum
One or both of ether, toluene.
The present invention is used in the preparation method of synthesizing gas by reforming methane with co 2 catalyst, described in step (2)
Reducing atmosphere is the mixed gas of hydrogen or hydrogen and nitrogen, in the mixed gas hydrogen volume percentage composition be 10%~
95%.Specific reduction treatment process is as follows: catalyst precarsor being warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen
The mixed gas of gas or hydrogen and nitrogen, in 0.1~0.5MPa(absolute pressure) processing 4~8h after, be down to room temperature in a nitrogen atmosphere.
The present invention is used in the preparation method of synthesizing gas by reforming methane with co 2 catalyst, described in step (3)
Auxiliary agent presoma is one of zirconium nitrate, cerous nitrate, lanthanum nitrate or a variety of, preferably zirconium nitrate；
In the solution B, based on the element, the mass fraction in solution B is 1%~10% to auxiliary agent；The furfural aqueous solution
The mass fraction of middle furfural is 30%~50%；Furfural aqueous solution described in step (3) and the mass ratio of solution B are 3 ~ 5, described molten
The mass ratio for the reduction rear catalyst precursor A that the gross mass of liquid B and furfural aqueous solution and step (2) obtain is 3~6.
The present invention is used in the preparation method of synthesizing gas by reforming methane with co 2 catalyst, water described in step (4)
Soluble macromolecular polymer is one of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) or several
Kind；The active component presoma is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of, preferably nitric acid
Nickel；In the solution C, in active component presoma the nickeliferous mass fraction in solution C based on the element be 0.5%~3%, water
Mass fraction of the soluble macromolecular polymer in solution C is 3~6 times of Ni element mass fraction.
The present invention described in step (5) for adding in the preparation method of synthesizing gas by reforming methane with co 2 catalyst
The mass ratio of the quality and water soluble polymer that enter dehydrated alcohol or citric acid is 2 ~ 4；The aqueous citric acid solution
Mass fraction 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 maturing temperature is 350~650 DEG C, and preferably 400~600 DEG C, calcining time is 2~12h, preferably
4~8h.
The catalyst of the method for the present invention preparation can be applied to synthesizing gas by reforming methane with co 2 reaction.Catalyst exists
Using it is preceding in a hydrogen atmosphere, 600~800 DEG C of 2~5h of prereduction.The catalyst of the method for the present invention preparation is applied to methane dioxy
Change the reaction of carbon preparing synthetic gas by reforming, preferable process conditions are as follows: the composition CH of unstripped gas4/CO2Molar ratio is 1~1.5, unstripped gas
In can contain Ar, N2Or the dilution property gas such as He, 2000~6000h of unstripped gas air speed-1, reaction pressure is 0.1~2Mpa, instead
Answering temperature is 700~900 DEG C.
Compared with prior art, a kind of available active metal outer layer distribution of the preparation method being related to through the invention
Catalyst for synthesizing gas by reforming methane with co 2.In the present invention, it is carried out using waste residue oil hydrogenating treatment catalyst
Furfural water phase hydrogenation reaction.Active metal predecessor and water soluble polymer polymerization is added simultaneously in the system of furfural hydrogenation
On the one hand object hinders active metal to the diffusion inside catalyst granules using furfural hydrogenation product；On the other hand, activity is utilized
Coordination between metal precursor and water soluble polymer, reduce solution in active metallic ion in catalyst particles
Concentration difference outside intragranular slows down active metal to the diffusion velocity inside catalyst granules.This method takes full advantage of waste residue oil
Hydrotreating catalyst has saved cost, and the catalyst reaction activity of preparation is high, not only reduces metal consumption, but also improve production
The selectivity of object.Catalyst precarsor processing simultaneously is completed with one step of catalyst preparation, and preparation process is simple, is conducive to industry and puts
Greatly.
Specific embodiment
Technology contents and effect of the invention are further illustrated below with reference to embodiment, but are not so limited the present invention.
Evaluation condition: it is used hydrogen reducing 4 hours at 700 DEG C before catalyst reaction of the present invention.In continuous sample introduction fixed bed
It is reacted in quartz reactor, 700 DEG C of reaction temperature, unstripped gas forms CH4/CO2/ Ar=1/1/4(molar ratio), air speed
4000h-1, product is after condensation water removal with gas-chromatography on-line analysis.Reaction started sampling analysis, evaluation result after 1 ~ 3 hour
It is shown in Table 1.Reaction result in table 1 is average activity of the catalyst after 800 DEG C of work 50h.
The metal element content in catalyst is determined using XRF analysis technology.Using scanning electron microscope analysis institute of the present invention
The distribution situation of active component on a catalyst in the catalyst of preparation.Catalyst activity obtained by the embodiment of the present invention and comparative example
The scanning electron microscope analysis of component nickel the results are shown in Table 2.
Embodiment 1
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is taken out by petroleum ether
The oil on removal catalyst surface is mentioned, in 110 DEG C of dry 8 h, gained catalyst obtains catalyst precarsor in 450 DEG C of roasting 4h
A, wherein Mo accounts for catalyst precarsor A weight 6.1wt%, Co based on the element and accounts for catalyst precarsor A weight 1.8wt%, Ni based on the element
Catalyst precarsor A weight 2.3wt%, V are accounted for based on the element accounts for catalyst precarsor A weight 1.9wt% based on the element；By 20g catalyst
Precursor A is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C,
0.2MPa(absolute pressure), recovery time 4h；2.54g zirconium nitrate is dissolved in 16mL deionized water, obtains solution B, and with its 4 times of matter
The furfural aqueous solution that the mass fraction of amount is 40% is uniformly mixed, and is then added to together with the catalyst precarsor A after reduction activation
In autoclave；15g polyethylene glycol, 16.3g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；By solution C
It is added in autoclave, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, reacted at 150 DEG C
2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 45g dehydrated alcohol is added, and places 1.5h, then mistake
Filter, obtained solid sample are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for and urge
Agent percentage composition is 13.7%Ni, 1.9%Zr, 4.4%Mo, and the catalyst of 1.1%Co, 1.2%V are denoted as C-1.
Embodiment 2
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is taken out by petroleum ether
The oil on removal catalyst surface is mentioned, in 110 DEG C of dry 8 h, gained catalyst obtains catalyst precarsor in 450 DEG C of roasting 4h
A, wherein Mo accounts for catalyst precarsor A weight 5.2wt%, Co based on the element and accounts for catalyst precarsor A weight 1.2wt%, Ni based on the element
Catalyst precarsor A weight 1.5wt%, V are accounted for based on the element accounts for catalyst precarsor A weight 1.3wt% based on the element；By 20g catalyst
Precursor A is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C,
0.2MPa(absolute pressure), recovery time 4h；0.99g zirconium nitrate is dissolved in 16mL deionized water, obtains solution B, and with its 4 times of matter
The furfural aqueous solution that the mass fraction of amount is 40% is uniformly mixed, and is then added to together with the catalyst precarsor A after reduction activation
In autoclave；10g polyethylene glycol, 10.9g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；By solution C
It is added in autoclave, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, reacted at 150 DEG C
2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 30g dehydrated alcohol is added, and places 1.5h, then mistake
Filter, obtained solid sample are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for and urge
Agent percentage composition is 8.8%Ni, 0.3%Zr, 3.6%Mo, and the catalyst of 0.7%Co, 0.8%V are denoted as C-2.
Embodiment 3
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is taken out by petroleum ether
The oil on removal catalyst surface is mentioned, in 110 DEG C of dry 8 h, gained catalyst obtains catalyst precarsor in 450 DEG C of roasting 4h
A, wherein Mo accounts for catalyst precarsor A weight 6.1wt%, Co based on the element and accounts for catalyst precarsor A weight 1.8wt%, Ni based on the element
Catalyst precarsor A weight 2.3wt%, V are accounted for based on the element accounts for catalyst precarsor A weight 1.9wt% based on the element；By 20g catalyst
Precursor A is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C,
0.2MPa(absolute pressure), recovery time 4h；7.25g zirconium nitrate is dissolved in 20mL deionized water, obtains solution B, and with its 4 times of matter
The furfural aqueous solution that the mass fraction of amount is 40% is uniformly mixed, and is then added to together with the catalyst precarsor A after reduction activation
In autoclave；21g polyethylene glycol, 22.5g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；By solution C
It is added in autoclave, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, reacted at 150 DEG C
2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 62g dehydrated alcohol is added, and places 1.5h, then mistake
Filter, obtained solid sample are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for and urge
Agent percentage composition is 17.3%Ni, 5.4%Zr, 4.2%Mo, and the catalyst of 1.2%Co, 1.1%V are denoted as C-3.
Embodiment 4
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is taken out by petroleum ether
The oil on removal catalyst surface is mentioned, in 110 DEG C of dry 8 h, gained catalyst obtains catalyst precarsor in 450 DEG C of roasting 4h
A, wherein Mo accounts for catalyst precarsor A weight 6.1wt%, Co based on the element and accounts for catalyst precarsor A weight 1.8wt%, Ni based on the element
Catalyst precarsor A weight 2.3wt%, V are accounted for based on the element accounts for catalyst precarsor A weight 1.9wt% based on the element；By 20g catalyst
Precursor A is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C,
0.2MPa(absolute pressure), recovery time 4h；1.68g lanthanum nitrate is dissolved in 16mL deionized water, obtains solution B, and with its 3 times of matter
The furfural aqueous solution that the mass fraction of amount is 30% is uniformly mixed, and is then added to together with the catalyst precarsor A after reduction activation
In autoclave；15g polyethylene glycol, 16.3g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；By solution C
It is added in autoclave, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, reacted at 150 DEG C
2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 45g dehydrated alcohol is added, and places 1.5h, then mistake
Filter, obtained solid sample are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for and urge
Agent percentage composition is 13.3%Ni, 1.8%La, 4.5%Mo, and the catalyst of 1.1%Co, 1.1%V are denoted as C-4.
Embodiment 5
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is taken out by petroleum ether
The oil on removal catalyst surface is mentioned, in 110 DEG C of dry 8 h, gained catalyst obtains catalyst precarsor in 450 DEG C of roasting 4h
A, wherein Mo accounts for catalyst precarsor A weight 6.1wt%, Co based on the element and accounts for catalyst precarsor A weight 1.8wt%, Ni based on the element
Catalyst precarsor A weight 2.3wt%, V are accounted for based on the element accounts for catalyst precarsor A weight 1.9wt% based on the element；By 20g catalyst
Precursor A is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C,
0.2MPa(absolute pressure), recovery time 4h；1.67g cerous nitrate is dissolved in 16mL deionized water, obtains solution B, and with its 5 times of matter
The furfural aqueous solution that the mass fraction of amount is 50% is uniformly mixed, and is then added to together with the catalyst precarsor A after reduction activation
In autoclave；15g polyvinyl alcohol, 16.3g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；By solution C
It is added in autoclave, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, reacted at 150 DEG C
2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 45g dehydrated alcohol is added, and places 1.5h, then mistake
Filter, obtained solid sample are put into baking oven at 110 DEG C dry 6h, roast 6h at 700 DEG C, obtain quality based on the element and account for and urge
Agent percentage composition is 13.5%Ni, 1.7%Ce, 4.3%Mo, and the catalyst of 0.9%Co, 1.0%V are denoted as C-5.
Embodiment 6
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is taken out by petroleum ether
The oil on removal catalyst surface is mentioned, in 110 DEG C of dry 8 h, gained catalyst obtains catalyst precarsor in 450 DEG C of roasting 4h
A, wherein Mo accounts for catalyst precarsor A weight 6.1wt%, Co based on the element and accounts for catalyst precarsor A weight 1.8wt%, Ni based on the element
Catalyst precarsor A weight 2.3wt%, V are accounted for based on the element accounts for catalyst precarsor A weight 1.9wt% based on the element；By 20g catalyst
Precursor A is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C,
0.2MPa(absolute pressure), recovery time 4h；2.67g cobalt nitrate is dissolved in 16mL deionized water, obtains solution B, and with its 4 times of matter
The furfural aqueous solution that the mass fraction of amount is 40% is uniformly mixed, and is then added to together with the catalyst precarsor A after reduction activation
In autoclave；15g polyethylene glycol, 16.3g nickel nitrate are dissolved in 200mL deionized water, solution C is obtained；By solution C
It is added in autoclave, is replaced 3 times after sealing with hydrogen, then adjust Hydrogen Vapor Pressure to 3MPa, reacted at 150 DEG C
2h；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and it is water-soluble that the citric acid that 300g mass fraction is 15% is added
Liquid is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, that is, makes
Obtaining quality based on the element and accounting for catalyst percentage composition is 13.1%Ni, 3.1%Co, 4.5%Mo, and the catalyst of 1.1%V is denoted as C-6.
Embodiment 7
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is taken out by petroleum ether
The oil on removal catalyst surface is mentioned, in 110 DEG C of dry 8 h, gained catalyst obtains catalyst precarsor in 450 DEG C of roasting 4h
A, wherein Mo accounts for catalyst precarsor A weight 6.1wt%, Co based on the element and accounts for catalyst precarsor A weight 1.8wt%, Ni based on the element
Catalyst precarsor A weight 2.3wt%, V are accounted for based on the element accounts for catalyst precarsor A weight 1.9wt% based on the element；By 20g catalyst
Precursor A is activated in the mixed atmosphere of hydrogen, and hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C,
0.2MPa(absolute pressure), recovery time 4h；1.24g ammonium metavanadate is dissolved in 16mL deionized water, obtains solution B, and with its 4 times
The furfural aqueous solution that the mass fraction of quality is 40% is uniformly mixed, and is then added together with the catalyst precarsor A after reduction activation
Into autoclave；15g polyvinylpyrrolidone (k30), 16.3g nickel nitrate are dissolved in 200mL deionized water, obtained molten
Liquid C；Solution C is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa,
2h is reacted at 150 DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and it is 15% that 300g mass fraction, which is added,
Aqueous citric acid solution, place 1.5h, then filter, obtained solid sample is put into baking oven at 110 DEG C dry 6h, 700 DEG C
Lower roasting 6h, obtaining quality based on the element and accounting for catalyst percentage composition is 13.9%Ni, 2.9%V, 4.3%Mo, and 1.2%Co's urges
Agent is denoted as C-7.
Comparative example
Select the useless hydrotreating catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant2O3), it is taken out by petroleum ether
The oil on removal catalyst surface is mentioned, in 110 DEG C of dry 8 h, gained catalyst obtains catalyst precarsor in 450 DEG C of roasting 4h
A, wherein Mo accounts for catalyst precarsor A weight 6.1wt%, Co based on the element and accounts for catalyst precarsor A weight 1.8wt%, Ni based on the element
Catalyst precarsor A weight 2.3wt%, V are accounted for based on the element accounts for catalyst precarsor A weight 1.9wt% based on the element；By 20g catalyst
Precursor A is added in the aqueous solution containing 2.54g zirconium nitrate and 16.3g nickel nitrate, is evaporated in 80 DEG C of stirrings to solution, is put into baking
12h is dried in case at 110 DEG C, roasts 4h at 400 DEG C, obtaining quality based on the element and accounting for catalyst percentage composition is 14.3%
The catalyst of Ni, 2.1%Zr, 4.6%Mo, 1.3%Co, 1.2%V, are denoted as D-1.
The reactivity worth of 1 catalyst of table
2 catalyst activity component Ni content distribution (wt%) of table
Claims (19)
1. a kind of preparation method for synthesizing gas by reforming methane with co 2 catalyst, the catalyst include active group
Divide, auxiliary agent and carrier, active component Ni, one or more of auxiliary agent Zr, La, Ce, Co, Mo or V, carrier are oxidation
Aluminium；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component be 10wt%~
The content of 20wt%, auxiliary agent are 7wt%~15wt%, and surplus is carrier；The preparation method of the catalyst includes the following steps:
(1) waste residue oil hydrogenating treatment catalyst the oil on removal catalyst surface is extracted to carry out after 80~150 DEG C dry
High-temperature roasting processing, obtains catalyst precarsor A, wherein maturing temperature is 300 ~ 600 DEG C, and calcining time is 2~6h；
(2) reduction treatment is carried out to the catalyst precarsor A that step (1) obtains using reducing atmosphere；
(3) auxiliary agent presoma is soluble in water, solution B is obtained, and be uniformly mixed with furfural aqueous solution, is then obtained with step (2)
To catalyst precarsor A be added in autoclave together；
(4) water soluble polymer, active component presoma is soluble in water, obtain solution C；Solution C is added to step
Suddenly it in autoclave described in (3), is replaced 2~5 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 2~4MPa,
1~3h is reacted at 100~200 DEG C, the water soluble polymer is polyethylene glycol, polyvinylpyrrolidone, polyethylene
One or more of alcohol；
(5) solidliquid mixture obtained to step (4) is down to 20~30 DEG C, and dehydrated alcohol or aqueous citric acid solution is added, and places 1
~2h, is then filtered, and obtained solid sample after drying, calcination process, obtains catalyst again.
2. according to the method for claim 1, it is characterised in that: waste residue oil hydrogenating treatment catalyst as described in step (1)
Using aluminium oxide as carrier, active metal component contains Mo and Co.
3. according to the method for claim 1, it is characterised in that: the content of Mo in catalyst precarsor A as described in step (1)
For 5wt% ~ 10wt%, the content of Co is 1wt% ~ 3wt%, and the content of V is 1wt% ~ 3wt%, and the content of Ni is 1wt% ~ 5wt%.
4. according to the method for claim 1, it is characterised in that: reducing atmosphere described in step (2) is hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
5. according to the method for claim 1, it is characterised in that: auxiliary agent presoma described in step (3) is zirconium nitrate, nitre
One of sour cerium, lanthanum nitrate are a variety of.
6. according to method described in claim 1 or 5, it is characterised in that: auxiliary agent presoma described in step (3) is nitric acid
Zirconium.
7. according to the method for claim 1, it is characterised in that: in solution B described in step (3), auxiliary agent based on the element,
Mass fraction in solution B is 1%~10%.
8. according to the method for claim 1, it is characterised in that: the quality of furfural in furfural aqueous solution described in step (3)
Score is 30%~50%.
9. according to the method for claim 1, it is characterised in that: the quality of furfural aqueous solution and solution B described in step (3)
Than being 3 ~ 5.
10. according to the method for claim 1, it is characterised in that: solution B described in step (3) and furfural aqueous solution it is total
The mass ratio for the reduction rear catalyst precursor A that quality and step (2) obtain is 3~6.
11. according to the method for claim 1, it is characterised in that: active component presoma described in step (4) is nitric acid
One of nickel, nickel acetate, nickel sulfate, nickel chloride are a variety of.
12. according to the method for claim 1, it is characterised in that: active component presoma described in step (4) is nitric acid
Nickel.
13. according to the method for claim 1, it is characterised in that: in solution C described in step (4), active component presoma
Middle the nickeliferous mass fraction in solution C based on the element is 0.5%~3%, matter of the water soluble polymer in solution C
Measure 3~6 times that score is Ni element mass fraction.
14. according to the method for claim 1, it is characterised in that: addition dehydrated alcohol or citric acid described in step (5)
The mass ratio of quality and water soluble polymer is 2 ~ 4.
15. according to the method for claim 1, it is characterised in that: the mass fraction of aqueous citric acid solution described in step (5)
It is 10%~20%.
16. according to the method for claim 1, it is characterised in that: drying temperature described in step (5) is 70~150 DEG C, is done
The dry time is 2~12h.
17. according to method described in claim 1 or 16, it is characterised in that: drying temperature described in step (5) is 80~120
DEG C, drying time is 4~8h.
18. according to the method for claim 1, it is characterised in that: maturing temperature described in step (5) is 350~650 DEG C,
Calcining time is 2~12h.
19. according to method described in claim 1 or 18, it is characterised in that: maturing temperature described in step (5) is 400~600
DEG C, calcining time is 4~8h.
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