CN106944085B - A kind of preparation method of synthesis gas full methanation preparing natural gas catalyst - Google Patents
A kind of preparation method of synthesis gas full methanation preparing natural gas catalyst Download PDFInfo
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- CN106944085B CN106944085B CN201610003118.9A CN201610003118A CN106944085B CN 106944085 B CN106944085 B CN 106944085B CN 201610003118 A CN201610003118 A CN 201610003118A CN 106944085 B CN106944085 B CN 106944085B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 183
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000007789 gas Substances 0.000 title claims abstract description 46
- 239000003345 natural gas Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 41
- 239000007787 solid Substances 0.000 claims abstract description 29
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 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 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution 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 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 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 7
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 238000000465 moulding Methods 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
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000001914 filtration Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 229910052593 corundum Inorganic materials 0.000 description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 10
- 239000003245 coal Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 229910015234 MoCo Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 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
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 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
- 238000002156 mixing Methods 0.000 description 2
- -1 nickel nitrates Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 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
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 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
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 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
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-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
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization 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
-
- B01J35/396—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/12—Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel
Abstract
The present invention relates to a kind of preparation methods of synthesis gas full methanation preparing natural gas catalyst, and the catalyst includes active component, auxiliary agent and carrier；The preparation method of the catalyst includes the following steps：Catalyst precarsor A is prepared 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 with 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, the catalyst reaction activity of preparation is high, not only reduces metal consumption, but also improve the selectivity of methane.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst of synthesis gas full methanation preparing natural gas, more particularly, to one kind
The support type catalyst with base of molybdenum preparation method of synthesis gas full methanation preparing natural gas.
Background technology
Methanation refers to CO/CO2With H2Under certain temperature, pressure and catalyst action, CH is generated4Process, mesh
Before, this reaction is widely used in synthesizing the removing of trace carbon, gas employing methanation of coke oven, natural gas from coal in ammonia or hydrogen production process
Etc. among techniques.Methanation is a kind of important catalysis technique, especially in fuel applications field, can be used for improving combustion gas heat
Value allows coke-stove gas, coal or biomass to the conversion of natural gas.In recent years, with China's coal substitute natural gas industry
Fast development, the methanation as one of core technology is of increased attention.
China is one, and the country of " rich coal, oil-poor, few gas " passes through coal based synthetic gas using abundant coal resources
Methanation production natural gas is with good economic efficiency in Waste Era of Oil, to solving the problem of complex utilization of coal resources,
The present situation for alleviating Chinese postman problem algorithm shortage safeguards energy security, realizes CO2Emission reduction, environmental protection all have important strategy
Meaning.
From basic research result and the relevant information of open report it is found that being reacted for synthesis gas preparing natural gas by methanation,
Ni base catalyst（High Ni contents, 20%~70%）For main fluid catalyst；The easy coking deactivation of Fe base catalyst；Co base catalyst is resistant to
Property is strong, but poor selectivity；Ru base catalyst activities are higher than Ni base catalyst, but its is of high cost；The auxiliary agent or carrier material of use
There are aluminium oxide, titanium oxide, silica, cerium oxide, lanthana, zirconium oxide, calcium oxide, magnesia etc..In short, to natural gas from coal
The requirement of industrial catalyst is mainly：Low temperature, efficiently（I.e. reaction temperature is low, and the hydrogen-carbon ratio range of unstripped gas is wide, CO and CO2's
Hydrogenation conversion is high, CH4High selectivity）, stability is good（It is i.e. wear-resisting, heatproof, anti-carbon deposit, anti-poisoning）, service life is long, at
This is low.Reach these requirements, the compositing formula of catalyst and the reasonable selection of fabricating technology are crucial.
Methanation catalyst is with Al disclosed in Chinese patent CN1043639A2O3For carrier, nickel is active component, with rare earth
Metal or alkaline-earth metal or alkali metal are auxiliary agent.Methanation catalyst is with high-purity gamma-disclosed in United States Patent (USP) US3933883
Al2O3For carrier, load active component nickel oxide and cobalt oxide.Methanation catalyst disclosed in Chinese patent CN1043449A, nickel
For active component, rare earth metal and magnesium are co-catalyst, remaining is aluminium oxide.
Although catalyst made from above-mentioned patented method obtains preferable synthesis gas methanation reaction performance, due to
The reaction is a fast reaction（This fast reaction, which is typically at, to be carried out under conditions of mass transport limitation）, reactant to
It is completed up to reaction while catalyst external surface, thus the inner surface of catalyst contributes less goal response, this just makes
At lower rate of metal in carrier duct, the manufacturing cost of catalyst is increased.
Invention content
In order to overcome shortcoming in the prior art, the present invention provides a kind of synthesis gas full methanation preparing natural gas
The preparation method of catalyst.Mo, Co and alumina support in useless hydrotreating catalyst, Er Qiechong is not only utilized in this method
Divide and the Ni and V deposited on useless hydrotreating catalyst is utilized, solves the pollution problem of dead catalyst, and economize on resources,
It improves benefit, is technically easy to implement, the synthesis gas methanation catalyst of gained has of low cost, metal component utilization rate
Feature high and that selectivity is good.
The present invention provides a kind of preparation method of synthesis gas full methanation preparing natural gas catalyst, the catalyst packets
Include active component, auxiliary agent and carrier；The active component is Mo, one or more of auxiliary agent Ni, Co, V, and carrier is oxidation
Aluminium；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst, the content of active component Mo be 10wt%~
The content of 20wt%, auxiliary agent are 1wt%~8wt%, and surplus is carrier；The preparation method of the catalyst includes the following steps：
（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, calcination temperature is 300~600 DEG C, and roasting time is 2~6h；
（2）By step（1）Obtained waste residue oil hydrogenating treatment catalyst is ground；
（3）To step（2）Strong inorganic acid is added in catalyst after obtained crushing, after dead catalyst dissolving, filtering
Remove solid insoluble；
（4）To step（3）The presoma containing Ni is added in obtained filtrate, organic acid is added after dissolving；
（5）Boehmite is added to step（4）In obtained solution, heating stirring to solution is evaporated, and obtains solid
Object；
（6）Step（5）Obtained solids obtains catalyst precarsor A by dry, roasting, molding；
（7）Using reducing atmosphere to step（6）Obtained catalyst precarsor A carries out reduction treatment；
（8）High molecular weight water soluble polymer, active component presoma is soluble in water, solution B is obtained, and water-soluble with furfural
Liquid be uniformly mixed, then with step（7）Obtained catalyst precarsor A is added in autoclave together, and hydrogen is used after sealing
Displacement 2~5 times, then Hydrogen Vapor Pressure is adjusted to 2~4MPa, 1~3h is reacted at 100~200 DEG C；
（9）Wait for step（8）Obtained solidliquid mixture is down to 20~30 DEG C, and absolute ethyl 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.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（1）Described in waste residue
For oil hydrogenating treatment catalyst using aluminium oxide as carrier, active metal component contains Mo and Co, be former reaction has been not achieved to require, or
Residual oil hydrocatalyst of the person due to grading without being used on the fixed bed of complete deactivation or ebullated bed；It is described useless to urge
Agent, so in hydrogenation process, generally has part gold due to being hydrotreating catalyst used in hydrogenation process
Belong to Ni and V depositions；The content of Mo is 3wt%~5wt% in the catalyst precarsor A, and the content of Co is 0.1wt%~1wt%, V
Content be 0.1wt%~1wt%, the content of Ni is 1wt%~5wt%.Step（1）Described in extracting solvent can be petroleum ether,
One or both of toluene.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（2）In give up hydrotreating
Catalyst is ground to more than 120 mesh, more than preferably 200 mesh.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（3）Described in strong nothing
Machine acid is one or more mixed acid in concentrated nitric acid, the concentrated sulfuric acid, concentrated hydrochloric acid, and the preferably concentrated sulfuric acid, concentrated nitric acid and concentrated hydrochloric acid is mixed
Close acid or concentrated nitric acid and concentrated sulfuric acid mixed acid.The concentration of strong inorganic acid is generally 30wt%~100wt%, and wherein concentrated hydrochloric acid is dense
Degree is in 30wt% or more, and the concentration of concentrated nitric acid is in 50wt% or more, and the concentration of the concentrated sulfuric acid is in 50wt% or more.Dead catalyst and strong nothing
The volume ratio of machine acid is 1:1~1:10；Step（3）Described in need to heat in dead catalyst course of dissolution, temperature is 40~80
DEG C, strong stirring is needed in course of dissolution.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（4）Described in containing Ni's
Presoma is the soluble-salt of Ni, is specifically as follows one or more in nickel nitrate, nickel chloride, nickel sulfate, preferably nitric acid
Nickel；The organic acid is citric acid, tartaric acid, one or more in malic acid, is rubbed with Mo in useless hydrotreating catalyst
You are than being 0.5~1.5.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（5）Described in intend thin water
Aluminium stone is added to step（4）In obtained solution, at 50~80 DEG C of temperature stirring be all evaporated to solution.It is described to intend thin water aluminium
The addition of stone is added according to the requirement of dead catalyst and final catalyst.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（6）Described in drying
Condition is dry 4~12h at 60~120 DEG C, and roasting condition is that 2~6h is roasted at 400~700 DEG C.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（7）Described in reduction
Atmosphere is the mixed gas of hydrogen or hydrogen and nitrogen, and hydrogen volume percentage composition is 10%~95% in the gaseous mixture.Tool
The reduction treatment process of body is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen or hydrogen
The mixed gas of gas and nitrogen, in 0.1~0.5MPa（Absolute pressure）After handling 4~8h, it is down to room temperature in a nitrogen atmosphere.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（8）Described in it is water-soluble
High molecular polymer is polyethylene glycol（PEG）, polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）One or more of；
The active component presoma is the soluble-salt of Mo, is specifically as follows ammonium tetramolybdate and/or ammonium molybdate, preferably ammonium molybdate；
In the solution B, the mass fraction in solution B is 0.5%~5% to contained molybdenum based on the element in active component presoma, water-soluble
Property mass fraction of the high molecular polymer in solution B be 2~5 times of Mo element mass fractions；Chaff in the furfural aqueous solution
The mass fraction of aldehyde is 30%~50%；Step（8）Described in furfural aqueous solution and step（7）The matter of obtained catalyst precarsor A
Amount is than being 2~4.
In the preparation method of synthesis gas full methanation preparing natural gas catalyst of the present invention, step（9）Described in nothing is added
The mass ratio of the quality and high molecular weight water soluble polymer of water-ethanol or citric acid is 2~4；The quality of the aqueous citric acid solution
Score is 10%~20%；The drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably
For 4~8h；The calcination temperature be 350~650 DEG C, preferably 400~600 DEG C, roasting time be 2~12h, preferably 4~
8h。
Catalyst prepared by the method for the present invention can be applied to the reaction of synthesis gas preparing natural gas by methanation.Catalyst is reacting
Before use 2%（Volume fraction）H2S/H2Gaseous mixture 3~6h of presulfurization, preferably 4h；Curing temperature is 400~600 DEG C, and vulcanization is completed
After be passed through unstripped gas and reacted.Catalyst prepared by the method for the present invention is reacted applied to synthesis gas preparing natural gas by methanation, tool
There are the appropriate resistant to sulfur ability, preferable process conditions to be：H in unstripped gas2/ CO molar ratios are 1.0~4.0, sulfur content 0.5%
~1.5%, Ar, N can be contained in unstripped gas2Or the dilution property gas such as He, 2000~20000h of unstripped gas air speed-1, reaction pressure
For 0.1~6Mpa, reaction temperature is 250~650 DEG C.
Compared with prior art, the preparation method being related to through the invention can obtain a kind of distribution of active metal outer layer
Synthesis gas preparing natural gas by methanation catalyst.In the present invention, waste residue oil hydrogenating treatment catalyst is utilized
Carry out furfural water phase hydrogenation reaction.Active metal predecessor and water solubility is added simultaneously in the system of furfural hydrogenation
On the one hand high molecular polymer utilizes furfural hydrogenation product to hinder active metal to the diffusion inside catalyst granules；Another party
Face, using the coordination between active metal predecessor and high molecular weight water soluble polymer, reduce in solution active metal from
Concentration difference of the son inside and outside catalyst granules slows down active metal to the diffusion velocity inside catalyst granules.This method is abundant
Waste residue oil hydrogenating treatment catalyst is utilized, has saved cost, the catalyst reaction activity of preparation is high, has both reduced metal use
Amount, and improve the selectivity of methane.Catalyst precarsor processing simultaneously is completed with one step of catalyst preparation, and preparation process is simple,
Be conducive to industrial amplification.
Specific implementation mode
The technology contents and effect further illustrated the present invention with reference to embodiment, but it is not so limited the present invention.
Evaluation condition：With 2% at 450 DEG C before catalyst reaction of the present invention（Volume fraction）H2S/H2Gaseous mixture presulfurization
4h.It is reacted in continuous sample introduction fixed-bed quartz reactor, 300 DEG C, reaction pressure 2MPa of reaction temperature, unstripped gas composition
H2/CO/N2/H2S= 67.5/22.5/9/1（Volume ratio）, air speed 5000h-1, online with gas-chromatography after the condensed water removal of product
Analysis, reaction result are shown in Table 1.Reaction result shown in table 1 is that catalyst works the average activity of 20h at 300 DEG C.
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 molybdenum the results are shown in Table 2.
Embodiment 1
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8h, gained catalyst roasts 4h at 450 DEG C, catalysis of giving up after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground to
200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C,
So that solid is dissolved, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid 27.31g is added
（The molar ratio of citric acid and Mo in useless agent are 1）, all dissolving after be added boehmite 300.32g, stirred at 70 DEG C to
Solution is evaporated, and by obtained solid in 100 DEG C of dry 8h, 4 h is roasted at 600 DEG C to get catalyst precarsor A, wherein Mo is with member
Element meter accounts for catalyst precarsor A weight 4wt%, Ni and accounts for catalyst precarsor A weight 3wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；10.33g polyethylene glycol, 5.43g ammonium molybdates are dissolved in 200mL deionized waters, obtain solution B, and with
The furfuryl aldehyde solution that 60g mass fractions are 40% is uniformly mixed, and is then added to height with together with the catalyst precarsor A after reduction activation
It presses in reaction kettle, is replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；It waits for above-mentioned
Solidliquid mixture after being reacted in autoclave is down to 25 DEG C, and 31g absolute ethyl alcohols are added, and places 1.5h, then filters, obtained solid
Sample is put into baking oven at 110 DEG C dry 6h, and 6h is roasted at 700 DEG C, obtains quality based on the element and accounts for catalyst percentage and contains
Amount is 2.6%Ni, 13.4%Mo, 0.6%Co, and the catalyst of 0.6%V is denoted as C-1.
Embodiment 2
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8h, gained catalyst roasts 4h at 450 DEG C, catalysis of giving up after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground to
200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, the mixing that the 98 wt% concentrated sulfuric acids and 65 wt% concentrated nitric acids are added is molten
Liquid 300mL, volume ratio 2:1, constant temperature stirs at 50 DEG C, so that solid is dissolved, filtrate is collected by filtration, be added into filtrate
After stirring and dissolving, citric acid 40.98g is added in 11.73g nickel nitrates（The molar ratio of citric acid and Mo in useless agent are 1.5）, all
Boehmite 462.37g is added after dissolving, stirring to solution is evaporated at 70 DEG C, and obtained solid is dried 8 h at 100 DEG C,
4h is roasted at 600 DEG C and accounts for catalyst precarsor A weight 3wt% based on the element to get catalyst precarsor A, wherein Mo, and Ni is with element
Meter accounts for catalyst precarsor A weight 1wt%；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；；By 6.65g polyethylene glycol, 3.5g
Ammonium molybdate is dissolved in 200mL deionized waters, obtains solution B, and the furfuryl aldehyde solution for being 40% with 60g mass fractions is uniformly mixed, so
It is added in autoclave with together with the catalyst precarsor A after reduction activation afterwards, is replaced 3 times with hydrogen after sealing, then adjusted
Hydrogen Vapor Pressure is saved to 3MPa, reacts 2h at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, adds
Enter 20g absolute ethyl alcohols, place 1.5h, then filter, obtained solid sample, which is put into baking oven at 110 DEG C, dries 6h, at 700 DEG C
6h is roasted, it is 0.8%Ni, 8.7%Mo, 0.5%Co, the catalysis of 0.5%V to obtain quality based on the element and account for catalyst percentage composition
Agent is denoted as C-2.
Embodiment 3
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8h, gained catalyst roasts 4h at 450 DEG C, catalysis of giving up after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground to
200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, the mixing that 35 wt% concentrated hydrochloric acids and 65 wt% concentrated nitric acids are added is molten
Liquid 450mL, volume ratio 1:1, constant temperature stirs at 50 DEG C, so that solid is dissolved, filtrate is collected by filtration, be added into filtrate
After stirring and dissolving, citric acid 13.66g is added in 54.01g nickel nitrates（The molar ratio of citric acid and Mo in useless agent are 0.5）, all
Boehmite 203.08g is added after dissolving, stirring to solution is evaporated at 70 DEG C, and obtained solid is dried 8 h at 100 DEG C,
4h is roasted at 600 DEG C and accounts for catalyst precarsor A weight 5wt% based on the element to get catalyst precarsor A, wherein Mo, and Ni is with element
Meter accounts for catalyst precarsor A weight 5wt%；20g catalyst precarsors A is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Air volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；；By 14g polyethylene glycol, 7.36g
Ammonium molybdate is dissolved in 200mL deionized waters, obtains solution B, and the furfuryl aldehyde solution for being 40% with 60g mass fractions is uniformly mixed, so
It is added in autoclave with together with the catalyst precarsor A after reduction activation afterwards, is replaced 3 times with hydrogen after sealing, then adjusted
Hydrogen Vapor Pressure is saved to 3MPa, reacts 2h at 150 DEG C；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, adds
Enter 42g absolute ethyl alcohols, place 1.5h, then filter, obtained solid sample, which is put into baking oven at 110 DEG C, dries 6h, at 700 DEG C
6h is roasted, it is 4.1%Ni, 18.2%Mo, 0.7%Co, the catalysis of 0.5%V to obtain quality based on the element and account for catalyst percentage composition
Agent is denoted as C-3.
Embodiment 4
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8h, gained catalyst roasts 4h at 450 DEG C, catalysis of giving up after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground to
200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C,
So that solid is dissolved, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid 27.31g is added
（The molar ratio of citric acid and Mo in useless agent are 1）, all dissolving after be added boehmite 300.32g, stirred at 70 DEG C to
Solution is evaporated, and by obtained solid in 100 DEG C of dry 8h, 4 h is roasted at 600 DEG C to get catalyst precarsor A, wherein Mo is with member
Element meter accounts for catalyst precarsor A weight 4wt%, Ni and accounts for catalyst precarsor A weight 3wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；10.33g polyethylene glycol, 5.43g ammonium molybdates are dissolved in 200mL deionized waters, obtain solution B, and with
The furfuryl aldehyde solution that 40g mass fractions are 30% is uniformly mixed, and is then added to height with together with the catalyst precarsor A after reduction activation
It presses in reaction kettle, is replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；It waits for above-mentioned
Solidliquid mixture after being reacted in autoclave is down to 20 DEG C, and 21g absolute ethyl alcohols are added, and places 1.5h, then filters, obtained solid
Sample is put into baking oven at 110 DEG C dry 6h, and 6h is roasted at 700 DEG C, obtains quality based on the element and accounts for catalyst percentage and contains
Amount is 2.4%Ni, 12.8%Mo, 0.6%Co, and the catalyst of 0.6%V is denoted as C-4.
Embodiment 5
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8h, gained catalyst roasts 4h at 450 DEG C, catalysis of giving up after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground to
200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C,
So that solid is dissolved, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid 27.31g is added
（The molar ratio of citric acid and Mo in useless agent are 1）, all dissolving after be added boehmite 300.32g, stirred at 70 DEG C to
Solution is evaporated, and by obtained solid in 100 DEG C of dry 8h, 4 h is roasted at 600 DEG C to get catalyst precarsor A, wherein Mo is with member
Element meter accounts for catalyst precarsor A weight 4wt%, Ni and accounts for catalyst precarsor A weight 3wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；10.33g polyvinyl alcohol, 5.43g ammonium molybdates are dissolved in 200mL deionized waters, obtain solution B, and with
The furfuryl aldehyde solution that 80g mass fractions are 50% is uniformly mixed, and is then added to height with together with the catalyst precarsor A after reduction activation
It presses in reaction kettle, is replaced 3 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；It waits for above-mentioned
Solidliquid mixture after being reacted in autoclave is down to 30 DEG C, and 31g absolute ethyl alcohols are added, and places 1.5h, then filters, obtained solid
Sample is put into baking oven at 110 DEG C dry 6h, and 6h is roasted at 700 DEG C, obtains quality based on the element and accounts for catalyst percentage and contains
Amount is 2.7%Ni, 13.1%Mo, 0.5%Co, and the catalyst of 0.6%V is denoted as C-5.
Embodiment 6
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8h, gained catalyst roasts 4h at 450 DEG C, catalysis of giving up after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground to
200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C,
So that solid is dissolved, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid 27.31g is added
（The molar ratio of citric acid and Mo in useless agent are 1）, all dissolving after be added boehmite 300.32g, stirred at 70 DEG C to
Solution is evaporated, and by obtained solid in 100 DEG C of dry 8h, 4 h is roasted at 600 DEG C to get catalyst precarsor A, wherein Mo is with member
Element meter accounts for catalyst precarsor A weight 4wt%, Ni and accounts for catalyst precarsor A weight 3wt% based on the element；20g catalyst precarsors A is existed
It is activated in the mixed atmosphere of hydrogen, hydrogen volume content is 80% in mixed gas, and reducing condition is 450 DEG C, 0.2MPa（Absolutely
Pressure）, recovery time 4h；By 10.33g polyvinylpyrrolidones（k30）, 5.43g ammonium molybdates be dissolved in 200mL deionized waters, obtain
To solution B, and with 60g mass fractions be 40% furfuryl aldehyde solution be uniformly mixed, then with the catalyst precarsor A after reduction activation
It is added in autoclave, is replaced 3 times with hydrogen after sealing together, then adjust Hydrogen Vapor Pressure to 3MPa, at 150 DEG C instead
Answer 2h；Solidliquid mixture after being reacted in above-mentioned autoclave is down to 25 DEG C, and the citric acid water that 207g mass fractions are 15% is added
Solution 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, i.e.,
It is 2.8%Ni, 13.7%Mo, 0.6%Co that quality based on the element, which is made, and accounts for catalyst percentage composition, and the catalyst of 0.6%V is denoted as C-
6。
Comparative example
Select the useless hydrotreating catalyst of fixed bed residual hydrogenation commercial plant（MoCo/Al2O3）, taken out by petroleum ether
The oil on removal catalyst surface is carried, in 110 DEG C of dry 8h, gained catalyst roasts 4h at 450 DEG C, catalysis of giving up after being handled
Agent（Containing Mo：12.8wt%, Co：2.3 wt%, V：2.5wt%, Ni：1.9 wt%, Al2O3：71.2 wt%）, catalyst is ground to
200 mesh（Refer to and is sieved by 200 mesh）, powder weight 100g is weighed, 98 wt% concentrated sulfuric acid 260mL are added, constant temperature stirs at 50 DEG C,
So that solid is dissolved, filtrate is collected by filtration, 38.15g nickel nitrates are added into filtrate, after stirring and dissolving, citric acid 27.31g is added
（The molar ratio of citric acid and Mo in useless agent are 1）, all dissolving after be added boehmite 300.32g, stirred at 70 DEG C to
Solution is evaporated, and by obtained solid in 100 DEG C of dry 8h, 4 h is roasted at 600 DEG C to get catalyst precarsor A, wherein Mo is with member
Element meter accounts for catalyst precarsor A weight 4wt%, Ni and accounts for catalyst precarsor A weight 3wt% based on the element；20g catalyst precarsors A is added
Enter into the aqueous solution containing 5.43g ammonium molybdates, be evaporated to solution in 80 DEG C of stirrings, is put into baking oven at 110 DEG C dry
12h roasts 4h at 400 DEG C, and it is 2.7% Ni, 14.3%Mo, 0.6%Co to obtain quality based on the element and account for catalyst percentage composition,
The catalyst of 0.6%V, is denoted as D-1.
The reactivity worth of 1 catalyst of table
The active component Mo content distributions of 2 catalyst of table（wt%）
Claims (28)
1. a kind of preparation method of synthesis gas full methanation preparing natural gas catalyst, the catalyst include active component, help
Agent and carrier；The active component is Mo, auxiliary agent Ni, Co and V, and carrier is aluminium oxide；It is accounted for each element quality in catalyst
On the basis of the percentage of catalyst quality, the content of active component Mo is 10wt%~20wt%, the content of auxiliary agent be 1wt%~
8wt%, surplus are carrier；The preparation method of the catalyst includes the following steps：
（1）Waste residue oil hydrogenating treatment catalyst is extracted into the oil on removal catalyst surface, after 80~150 DEG C dry, is carried out
High-temperature roasting is handled, and calcination temperature is 300~600 DEG C, and roasting time is 2~6h；
（2）By step（1）Obtained waste residue oil hydrogenating treatment catalyst is ground；
（3）To step（2）Strong inorganic acid is added in catalyst after obtained crushing, after dead catalyst dissolving, is filtered to remove
Solid insoluble；
（4）To step（3）The presoma containing Ni is added in obtained filtrate, organic acid is added after dissolving；
（5）Boehmite is added to step（4）In obtained solution, heating stirring to solution is evaporated, and obtains solids；
（6）Step（5）Obtained solids obtains catalyst precarsor A by dry, roasting, molding；
（7）Using reducing atmosphere to step（6）Obtained catalyst precarsor A carries out reduction treatment；
（8）High molecular weight water soluble polymer, active component presoma is soluble in water, solution B is obtained, and mixed with furfural aqueous solution
Close it is uniform, then with step（7）Obtained catalyst precarsor A is added in autoclave together, and 2 are replaced with hydrogen after sealing
~5 times, then Hydrogen Vapor Pressure is adjusted to 2~4MPa, 1~3h, the high molecular weight water soluble polymer are reacted at 100~200 DEG C
For polyethylene glycol（PEG）, polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）One or more of；
（9）Wait for step（8）Obtained solidliquid mixture is down to 20~30 DEG C, and absolute ethyl 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：Step（1）Described in waste residue oil hydrogenating treatment catalyst
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：Step（6）Described in catalyst precarsor A in Mo content
For 3wt%~5wt%, the content of Co is 0.1wt%~1wt%, and the content of V is 0.1wt%~1wt%, the content of Ni be 1wt%~
5wt%。
4. according to the method for claim 1, it is characterised in that：Step（2）In give up hydrotreating catalyst grind to
It is more than 120 mesh.
5. according to the method described in claim 1 or 4, it is characterised in that：Step（2）In give up hydrotreating catalyst grind
To more than 200 mesh.
6. according to the method for claim 1, it is characterised in that：Step（3）Described in strong inorganic acid be concentrated nitric acid, dense sulphur
One or more mixed acid in acid, concentrated hydrochloric acid.
7. according to the method described in claim 1 or 6, it is characterised in that：Step（3）Described in strong inorganic acid be the concentrated sulfuric acid,
Concentrated nitric acid and concentrated hydrochloric acid mixed acid or concentrated nitric acid and concentrated sulfuric acid mixed acid.
8. according to the method for claim 1, it is characterised in that：Step（3）Described in strong inorganic acid a concentration of 30wt%
~100wt%.
9. according to the method for claim 6, it is characterised in that：Step（3）Described in concentrated hydrochloric acid concentration 30wt% with
On, the concentration of concentrated nitric acid is in 50wt% or more, and the concentration of the concentrated sulfuric acid is in 50wt% or more.
10. according to the method for claim 1, it is characterised in that：Step（3）Described in dead catalyst and strong inorganic acid
Volume ratio is 1:1~1:10.
11. according to the method for claim 1, it is characterised in that：Step（4）Described in the presoma containing Ni be Ni it is solvable
Property salt.
12. according to the method described in claim 1 or 11, it is characterised in that：Step（4）Described in the presoma containing Ni be nitric acid
It is one or more in nickel, nickel chloride, nickel sulfate.
13. according to the method for claim 12, it is characterised in that：Step（4）Described in the presoma containing Ni be nickel nitrate.
14. according to the method for claim 1, it is characterised in that：Step（4）Described in organic acid be citric acid, tartaric acid,
One or more in malic acid, the molar ratio of the organic acid and Mo in useless hydrotreating catalyst are 0.5~1.5.
15. according to the method for claim 1, it is characterised in that：Step（6）Described in drying be at 60~120 DEG C
Dry 4~12h is roasted to 2~6h of roasting at 400~700 DEG C.
16. according to the method for claim 1, it is characterised in that：Step（7）Described in reducing atmosphere be hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
17. according to the method for claim 1, it is characterised in that：Step（8）Described in active component presoma be Mo can
Soluble.
18. according to the method described in claim 1 or 17, it is characterised in that：Step（8）Described in active component presoma be four
Ammonium molybdate.
19. according to the method described in claim 1 or 17, it is characterised in that：Step（8）Described in active component presoma be molybdenum
Sour ammonium.
20. according to the method for claim 1, it is characterised in that：Step（8）Described in solution B, active component presoma
In contained molybdenum based on the element the mass fraction in solution B be 0.5%~5%, matter of the high molecular weight water soluble polymer in solution B
Measure 2~5 times that score is Mo element mass fractions.
21. according to the method for claim 1, it is characterised in that：Step（8）Described in furfural aqueous solution furfural quality
Score is 30%~50%.
22. according to the method for claim 1, it is characterised in that：Step（8）Described in furfural aqueous solution and step（7）?
The mass ratio of the catalyst precarsor A arrived is 2~4.
23. according to the method for claim 1, it is characterised in that：Step（9）Described in absolute ethyl alcohol or citric acid is added
The mass ratio of quality and high molecular weight water soluble polymer is 2~4.
24. according to the method for claim 1, it is characterised in that：Step（9）Described in aqueous citric acid solution mass fraction
It is 10%~20%.
25. according to the method for claim 1, it is characterised in that：Step（9）Described in drying temperature be 70~150 DEG C, do
The dry time is 2~12h.
26. according to the method described in claims 1 or 25, it is characterised in that：Step（9）Described in drying temperature be 80~120
DEG C, drying time is 4~8h.
27. according to the method for claim 1, it is characterised in that：Step（9）Described in calcination temperature be 350~650 DEG C,
Roasting time is 2~12h.
28. according to the method described in claims 1 or 27, it is characterised in that：Step（9）Described in calcination temperature be 400~600
DEG C, roasting time is 4~8h.
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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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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