CN106944062B - A kind of preparation method of synthesis gas preparing natural gas catalyst - Google Patents
A kind of preparation method of synthesis gas preparing natural gas catalyst Download PDFInfo
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- CN106944062B CN106944062B CN201610003124.4A CN201610003124A CN106944062B CN 106944062 B CN106944062 B CN 106944062B CN 201610003124 A CN201610003124 A CN 201610003124A CN 106944062 B CN106944062 B CN 106944062B
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- catalyst
- solution
- auxiliary agent
- active component
- nickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000007789 gas Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003345 natural gas Substances 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 51
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 22
- 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 20
- 230000032683 aging Effects 0.000 claims description 19
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 229910052759 nickel Inorganic materials 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 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 229920003169 water-soluble polymer Polymers 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 claims 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-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
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 239000003245 coal Substances 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 5
- 235000005979 Citrus limon Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 244000248349 Citrus limon Species 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 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
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009792 diffusion process 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 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
- 239000011260 aqueous acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000006555 catalytic reaction Methods 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 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
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 229920000642 polymer Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of synthesis gas preparing natural gas catalyst, the catalyst includes active component, auxiliary agent and carrier, the preparation method of the catalyst includes the following steps: to prepare catalyst precarsor B first, then reduction treatment is carried out to catalyst precarsor B, 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 B, it is reacted after solution D is added, filtering obtained solid sample obtains catalyst again after drying, calcination process after obtained solidliquid mixture processing separation.The catalyst reaction activity of this method 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 preparation methods of synthesis gas preparing natural gas catalyst, more particularly, to a kind of synthesis gas day
The preparation method of right gas loading type nickel-based catalyst.
Background technique
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 to improve 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 receive more and more attention.
China is one, and the country of " rich coal, oil-poor, few gas " passes through coal based synthetic gas using coal resources abundant
Methanation produce natural gas it is with good economic efficiency in Waste Era of Oil, to solve coal resources problem of complex utilization,
Alleviate the status of Chinese postman problem algorithm shortage, safeguard energy security, realizes CO2Emission reduction, protection environment 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 content, 20% ~ 70%) is main fluid catalyst；The easy coking deactivation of Fe base catalyst；The tolerance of Co base catalyst
Property is strong, but poor selectivity；Ru base catalyst activity is higher than Ni base catalyst, but its is at 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, CH4Selectivity it is high), stability is good (i.e. wear-resisting, heatproof, anti-carbon deposit, anti-poisoning), long service life, at
This is low.Reach these requirements, the compositing formula of catalyst and the reasonable selection of fabricating technology are crucial.
Methanation catalyst disclosed in Chinese patent CN1043639A is with Al2O3For carrier, nickel is active component, with rare earth
Metal or alkaline-earth metal or alkali metal are auxiliary agent.Methanation catalyst disclosed in United States Patent (USP) US3933883 is with high-purity gamma-
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 carries out under conditions of being typically at mass transport limitation), and reactant arrives
Reaction is completed while up to catalyst external surface, thus the inner surface of catalyst contributes less goal response, this just makes
At lower metal utilization in carrier duct, the preparation cost of catalyst is increased.
Summary of the invention
Place in order to overcome the shortcomings in the prior art, the present invention provides a kind of preparations of synthesis gas preparing natural gas catalyst
Method, the catalyst of this method preparation have the characteristics that low in cost, metal component utilization rate is high and selectivity is good.
The present invention provides a kind of preparation method of synthesis gas preparing natural gas catalyst, the catalyst includes active group
Point, the first auxiliary agent, the second auxiliary agent and carrier, active component Ni, the first auxiliary agent is Fe, the second auxiliary agent be Ca, Mg, Zr, Ce or
One or more of La, carrier are any one of aluminium oxide, silica；Catalyst matter is accounted for each element quality in catalyst
On the basis of the percentage of amount, the content of active component is 10wt%~20wt%, and the content of the first auxiliary agent is 1wt%~3wt%, second
The content of auxiliary agent is 1wt%~3wt%, and surplus is carrier；The preparation method of the catalyst includes the following steps:
(1) active component presoma and the first auxiliary agent presoma is soluble in water, obtain solution A；
(2) carrier is added in the solution A that step (1) obtains, after dipping, aging, drying, calcination process, is obtained
Catalyst precarsor B；
(3) reduction treatment is carried out to the catalyst precarsor B that step (2) obtains using reducing atmosphere；
(4) the second auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step
Suddenly the catalyst precarsor B that (3) obtain is added in autoclave together；
(5) water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added
It into autoclave described in step (4), 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；
(6) solidliquid mixture obtained to step (5) 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.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, active component presoma described in step (1) is
One of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride are a variety of, preferably nickel nitrate；The first auxiliary agent presoma is iron
Soluble-salt, be specifically as follows one or more of ferric nitrate, iron chloride, ferric sulfate, preferably ferric nitrate；The solution
In A, based on the element, mass fraction in solution A A is 1%~7% to active component, the first adjuvant component based on the element, in solution
Mass fraction in A is 1%~5%.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, dipping described in step (2) is isometric leaching
Stain, dip time are 1~3h；The aging can aging at room temperature, can also the aging under certain steady temperature, aging temperature
It is 10~90 DEG C, preferably 20~60 DEG C, ageing time is 1~for 24 hours, preferably 4~12h；Institute in step (2) and step (6)
Stating drying temperature is 70~150 DEG C, and preferably 80~120 DEG C, drying time is 2~12h, preferably 4~8h；Step (2) with
Maturing temperature described in step (6) be 350~650 DEG C, preferably 400~600 DEG C, calcining time be 2~12h, preferably 4~
8h。
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, carrier described in step (2) is aluminium oxide, oxygen
Any one of SiClx, the carrier can use commercially available product, can also prepare by method well known in the art；It is described to urge
In agent precursor B, the nickel of load is 1wt%~5wt% of final catalyst, the iron of load is with element wt in terms of element wt
Meter is 1wt%~3wt% of final catalyst.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, reducing atmosphere described in step (3) is hydrogen
Or the mixed gas of hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.Specific reduction
Treatment process is as follows: catalyst precarsor being warming up to 300~600 DEG C under nitrogen atmosphere, then passes to hydrogen or hydrogen and nitrogen
Mixed gas, in 0.1~0.5MPa(absolute pressure) processing 4~8h after, be down to room temperature in a nitrogen atmosphere.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, auxiliary agent presoma described in step (4) is nitre
One of sour calcium, calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate are a variety of, preferably
Zirconium nitrate；In the solution C, based on the element, the mass fraction in solution C is 1%~4% to the second auxiliary agent；The furfural is water-soluble
The mass fraction of furfural is 30%~50% in liquid；Furfural aqueous solution described in step (4) and the mass ratio of solution C are 3 ~ 5, described
The mass ratio for the reduction rear catalyst precursor B that solution C and the gross mass of furfural aqueous solution and step (3) obtain is 3~6.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, the polymerization of water soluble polymer described in step (5)
Object is one or more of polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA)；The active group
Dividing presoma is one of nickel nitrate, nickel acetate, nickel sulfate, nickel chloride or a variety of, preferably nickel nitrate；In the solution D,
In active component presoma the nickeliferous mass fraction in solution D based on the element be 0.4%~2%, water soluble polymer polymerization
Mass fraction of the object in solution D is 3~6 times of Ni element mass fraction.
In the preparation method of synthesis gas preparing natural gas catalyst of the present invention, addition dehydrated alcohol or lemon described in step (6)
The quality of lemon acid and the mass ratio of water soluble polymer are 2 ~ 4；The mass fraction of the aqueous citric acid solution be 10%~
20%。
The catalyst of the method for the present invention preparation can be applied to the reaction of synthesis gas preparing natural gas by methanation.Catalyst is using
It is preceding in a hydrogen atmosphere, 400~600 DEG C of 2~6h of prereduction, preferably 4h.The catalyst of the method for the present invention preparation is applied to synthesis
The reaction of gas preparing natural gas by methanation, preferable process conditions are as follows: the composition H of unstripped gas2/ CO molar ratio is 1.0~4.0, raw material
Ar, N can be contained in gas2Or the dilution property gas such as He, 2000~20000h of unstripped gas air speed-1, reaction pressure be 0.1~
5Mpa, reaction temperature are 250~650 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
Synthesis gas preparing natural gas catalyst.In the present invention, pre-soaked a part of active metal is to carry out furfural water phase hydrogenation reaction.
Active metal predecessor and water soluble polymer is added simultaneously in the system of furfural hydrogenation, is on the one hand added using furfural
Hydrogen product hinders active metal to the diffusion inside catalyst granules；On the other hand, active metal predecessor and water solubility are utilized
Coordination between high molecular polymer reduces concentration difference of the active metallic ion inside and outside catalyst granules in solution, subtracts
Delay active metal to the diffusion velocity inside catalyst granules.The catalyst reaction activity of this method preparation is high, both reduces gold
Belong to dosage, and improves the selectivity of methane.Catalyst precarsor processing simultaneously is completed with one step of catalyst preparation, preparation process letter
It is single, be conducive to industrial amplification.
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 450 DEG C before catalyst reaction of the present invention.In continuous sample introduction fixed bed
It is reacted in quartz reactor, 270 DEG C of reaction temperature, reaction pressure 2MPa, unstripped gas forms H2/CO/N2 = 67.5/
22.5/10(molar ratio), air speed 3200h-1, product uses gas-chromatography on-line analysis after condensation water removal, and reaction result is shown in Table 1.
Reaction result shown in table 1 is average activity of the catalyst in 270 DEG C of work 6h, including CO conversion ratio and CH4Selectivity.
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
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B
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
(absolute pressure), recovery time 4h；1.88g zirconium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, institute
It obtains solid sample and is 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 catalyst
Percentage composition is 12.4%Ni, and the catalyst of 1.5%Fe, 1.6%Zr are denoted as C-1.
Embodiment 2
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.1g silica support (Kong Rongwei 0.97mL/g, specific surface area 372m2/ g, spherical, equivalent diameter
0.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B
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
(absolute pressure), recovery time 4h；1.88g zirconium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, institute
It obtains solid sample and is 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 catalyst
Percentage composition is 12.1%Ni, and the catalyst of 1.7%Fe, 1.4%Zr are denoted as C-2.
Embodiment 3
Weigh 0.99g nickel nitrate, 1.44g ferric nitrate is dissolved in 16mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 16.9g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, is the 1% of final catalyst, and the Fe of load is the 1% of final catalyst in terms of element wt；Catalyst precarsor B
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
(absolute pressure), recovery time 4h；0.94g zirconium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；8.1g polyethylene glycol, 8.92g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
It into autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；To
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 25g dehydrated alcohol is added, and places 1.5h, then filters, gained
Solid sample is put into baking oven at 110 DEG C dry 6h, roasts 6h at 700 DEG C, obtains quality based on the element and account for catalyst hundred
Dividing content is 8.6%Ni, and the catalyst of 0.8%Fe, 0.7%Zr are denoted as C-3.
Embodiment 4
Weigh 4.96g nickel nitrate, 4.33g ferric nitrate is dissolved in 10mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 13.3g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, is the 5% of final catalyst, and the Fe of load is the 3% of final catalyst in terms of element wt；Catalyst precarsor B
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
(absolute pressure), recovery time 4h；2.82g zirconium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；13.5g polyethylene glycol, 14.87g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 41g dehydrated alcohol is added, and places 1.5h, then filters, institute
It obtains solid sample and is 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 catalyst
Percentage composition is 16.9%Ni, and the catalyst of 2.2%Fe, 2.4%Zr are denoted as C-4.
Embodiment 5
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B
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
(absolute pressure), recovery time 4h；1.25g lanthanum nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 4 times of quality are obtained
It measures the furfural aqueous solution that score is 40% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；10.8g polyethylene glycol, 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, institute
It obtains solid sample and is 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 catalyst
Percentage composition is 12.2%Ni, and the catalyst of 1.8%Fe, 1.7%La are denoted as C-5.
Embodiment 6
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 15.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B
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
(absolute pressure), recovery time 4h；2.36g calcium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 3 times of quality are obtained
It measures the furfural aqueous solution that score is 30% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；10.8g polyvinylpyrrolidone (k30), 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；
Solution D is also added in autoclave, is replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, 150
2h is reacted at DEG C；Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and the lemon that 220g mass fraction is 15% is added
Lemon aqueous acid is placed 1.5h, is then filtered, and obtained solid sample is put into baking oven at 110 DEG C dry 6h, roasts at 700 DEG C
6h is burnt, obtaining quality based on the element and accounting for catalyst percentage composition is 12.6%Ni, and the catalyst of 1.2%Fe, 1.4%Ca are denoted as C-
6。
Embodiment 7
Weigh 2.97g nickel nitrate, 2.89g ferric nitrate is dissolved in 12mL deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 14.9g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m2/ g, bar shaped, equivalent diameter
1.5mm), impregnate 2h, aging 4h, 80 DEG C of dry 12h, 700 DEG C of roasting 4h at room temperature, be made catalyst precarsor B, the Ni of load with
Element wt meter, is the 3% of final catalyst, and the Fe of load is the 2% of final catalyst in terms of element wt；Catalyst precarsor B
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
(absolute pressure), recovery time 4h；4.27g magnesium nitrate is dissolved in 16mL deionized water, solution C, and the matter with its 5 times of quality are obtained
It measures the furfural aqueous solution that score is 50% to be uniformly mixed, it is anti-to be then added to high pressure together with the catalyst precarsor B after reduction activation
It answers in kettle；10.8g polyvinyl alcohol, 11.89g nickel nitrate are dissolved in 200mL deionized water, solution D is obtained；Solution D is also added
Enter into autoclave, replaced 3 times after sealing with hydrogen, then adjusts Hydrogen Vapor Pressure to 3MPa, react 2h at 150 DEG C；
Solidliquid mixture after reacting in above-mentioned autoclave is down to 25 DEG C, and 33g dehydrated alcohol is added, and places 1.5h, then filters, institute
It obtains solid sample and is 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 catalyst
Percentage composition is 12.5%Ni, and the catalyst of 1.7%Fe, 1.8%Mg are denoted as C-7.
Comparative example
It weighs 14.87g nickel nitrate, 2.89g ferric nitrate, 1.88g zirconium nitrate to be dissolved in deionized water, aqueous solution is made；It adopts
15.1g alumina support (Kong Rongwei 0.73mL/g, specific surface area 253m are carried on equi-volume impregnating2/ g, bar shaped, when
Measure diameter 1.5mm), 2h is impregnated at room temperature, and aging 6h, 110 DEG C of dry 6h, 700 DEG C of roasting 6h obtain quality based on the element and account for
Catalyst percentage composition is 14.1%Ni, and the catalyst of 1.5%Fe, 1.7%Zr are denoted as D-1.
The reactivity worth of 1 catalyst of table
The distribution results of the active component Ni of 2 catalyst of table, wt%
Claims (26)
1. a kind of preparation method of synthesis gas preparing natural gas catalyst, the catalyst includes active component, the first auxiliary agent, second
Auxiliary agent and carrier, active component Ni, the first auxiliary agent are Fe, and the second auxiliary agent is one or more of Ca, Mg, Zr, Ce or La,
Carrier is any one of aluminium oxide, silica；On the basis of each element quality accounts for the percentage of catalyst quality in catalyst,
The content of active component is 10wt%~20wt%, and the content of the first auxiliary agent is 1wt%~3wt%, and the content of the second auxiliary agent is 1wt%
~3wt%, surplus are carrier；The preparation method of the catalyst includes the following steps:
(1) active component presoma and the first auxiliary agent presoma is soluble in water, obtain solution A；
(2) carrier is added in the solution A that step (1) obtains, after dipping, aging, drying, calcination process, is catalyzed
Agent precursor B；
(3) reduction treatment is carried out to the catalyst precarsor B that step (2) obtains using reducing atmosphere；
(4) the second auxiliary agent presoma is soluble in water, obtain solution C, and be uniformly mixed with furfural aqueous solution, then with step
(3) the catalyst precarsor B obtained is added in autoclave together；
(5) water soluble polymer, active component presoma is soluble in water, obtain solution D；Solution D is added to step
Suddenly it in autoclave described in (4), 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 (PEG), polyvinylpyrrolidone
(PVP), one or more of polyvinyl alcohol (PVA)；
(6) solidliquid mixture obtained to step (5) 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: active component presoma described in step (1) be nickel nitrate,
One of nickel acetate, nickel sulfate, nickel chloride are a variety of.
3. method according to claim 1 or 2, it is characterised in that: active component presoma described in step (1) is nitric acid
Nickel.
4. according to the method for claim 1, it is characterised in that: the first auxiliary agent presoma described in step (1) can for iron
One or more of soluble, specially ferric nitrate, iron chloride, ferric sulfate.
5. according to method described in claim 1 or 4, it is characterised in that: the first auxiliary agent presoma described in step (1) is nitric acid
Iron.
6. according to the method for claim 1, it is characterised in that: in solution A described in step (1), active component is with element
Meter, mass fraction in solution A are 1%~7%, the first adjuvant component based on the element, the mass fraction in solution A is 1%~
5%。
7. according to the method for claim 1, it is characterised in that: dipping described in step (2) is incipient impregnation, dipping
Time is 1~3h.
8. according to the method for claim 1, it is characterised in that: aging temperature described in step (2) is 10~90 DEG C, aging
Time be 1~for 24 hours.
9. according to method described in claim 1 or 8, it is characterised in that: aging temperature described in step (2) is 20~60 DEG C,
Ageing time is 4~12h.
10. according to the method for claim 1, it is characterised in that: drying temperature described in step (2) and step (6) is 70
~150 DEG C, drying time is 2~12h.
11. according to method described in claim 1 or 10, it is characterised in that: drying temperature described in step (2) and step (6)
It is 80~120 DEG C, drying time is 4~8h.
12. according to the method for claim 1, it is characterised in that: maturing temperature described in step (2) and step (6) is 350
~650 DEG C, calcining time is 2~12h.
13. according to method described in claim 1 or 12, it is characterised in that: maturing temperature described in step (2) and step (6)
It is 400~600 DEG C, calcining time is 4~8h.
14. according to the method for claim 1, it is characterised in that: in catalyst precarsor B described in step (2), the nickel of load
It is 1wt%~5wt% of final catalyst in terms of element wt, the iron of load is the 1wt% of final catalyst in terms of element wt
~3wt%.
15. according to the method for claim 1, it is characterised in that: reducing atmosphere described in step (3) is hydrogen or hydrogen
The mixed gas of gas and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
16. according to the method for claim 1, it is characterised in that: auxiliary agent presoma described in step (4) be calcium nitrate,
One of calcium chloride, magnesium nitrate, magnesium chloride, zirconium nitrate, basic zirconium chloride, cerous nitrate, lanthanum nitrate are a variety of.
17. according to method described in claim 1 or 16, it is characterised in that: auxiliary agent presoma described in step (4) is nitric acid
Zirconium.
18. according to the method for claim 1, it is characterised in that: in solution C described in step (4), the second auxiliary agent is with element
Meter, the mass fraction in solution C are 1%~4%.
19. according to the method for claim 1, it is characterised in that: the quality of furfural in furfural aqueous solution described in step (4)
Score is 30%~50%.
20. according to the method for claim 1, it is characterised in that: the matter of furfural aqueous solution and solution C described in step (4)
Amount is than being 3 ~ 5.
21. according to the method for claim 1, it is characterised in that: solution C described in step (4) and furfural aqueous solution it is total
The mass ratio for the reduction rear catalyst precursor B that quality and step (3) obtain is 3~6.
22. according to the method for claim 1, it is characterised in that: active component presoma described in step (5) is nitric acid
One of nickel, nickel acetate, nickel sulfate, nickel chloride are a variety of.
23. according to method described in claims 1 or 22, it is characterised in that: active component presoma described in step (5) is nitre
Sour nickel.
24. according to the method for claim 1, it is characterised in that: in solution D described in step (5), active component presoma
Middle the nickeliferous mass fraction in solution D based on the element is 0.4%~2%, matter of the water soluble polymer in solution D
Measure 3~6 times that score is Ni element mass fraction.
25. according to the method for claim 1, it is characterised in that: addition dehydrated alcohol or citric acid described in step (6)
The mass ratio of quality and water soluble polymer is 2 ~ 4.
26. according to the method for claim 1, it is characterised in that: the mass fraction of aqueous citric acid solution described in step (6)
It is 10%~20%.
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| CN106944062A (en) | 2017-07-14 |
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