CN105642290B - A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst - Google Patents
A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst Download PDFInfo
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- CN105642290B CN105642290B CN201410732119.8A CN201410732119A CN105642290B CN 105642290 B CN105642290 B CN 105642290B CN 201410732119 A CN201410732119 A CN 201410732119A CN 105642290 B CN105642290 B CN 105642290B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000002407 reforming Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- 230000032683 aging Effects 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims description 72
- 229910052739 hydrogen Inorganic materials 0.000 claims description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 46
- 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 38
- 239000000203 mixture Substances 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 29
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229930195725 Mannitol Natural products 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000594 mannitol Substances 0.000 claims description 3
- 235000010355 mannitol Nutrition 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 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
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 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
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- -1 sorbierite Chemical compound 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 56
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 19
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000003426 co-catalyst Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 239000011148 porous material Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 238000002386 leaching Methods 0.000 description 16
- 238000007789 sealing Methods 0.000 description 15
- 230000004913 activation Effects 0.000 description 14
- 238000011084 recovery Methods 0.000 description 14
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 12
- 239000000600 sorbitol Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UKKGMDDPINLFIY-UHFFFAOYSA-N [C+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] UKKGMDDPINLFIY-UHFFFAOYSA-N 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, the catalyst includes active component, the first auxiliary agent, the second auxiliary agent and carrier, the preparation method is soluble in water by active component presoma and the first auxiliary agent presoma first, obtains solution A；Then carrier is added, catalyst precarsor B is obtained after aging, drying, calcination process；Reduction treatment is carried out to catalyst precarsor B using reducing atmosphere；Catalyst precarsor B after reduction and polyhydric alcohol solutions are added in reactor and carry out hydrogenation reaction, reaction effluent is placed, then filtration drying obtains catalyst precarsor C；Active component presoma and the second auxiliary agent presoma is soluble in water, solution D is obtained, catalyst precarsor C is then added, after drying, calcination process, obtains catalyst.The inventive method promotes more multiple active components and disperseed in carrier surface, had both improved the utilization rate of active metal, and had improved the conversion ratio of methane and the selectivity of product again.
Description
Technical field
The present invention relates to a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, more particularly, to one kind
The preparation method of synthesizing gas by reforming methane with co 2 loading type nickel-based catalyst.
Background technology
Methane and carbon dioxide is cheap in nature and resourceful carbon compound, utilizes methane and carbon dioxide
Reforming reaction producing synthesis gas, for alleviating energy crisis, mitigate caused by the discharge of greenhouse gases global gas
Time warms significant.The synthesis gas that methane is prepared with CO 2 reformation has H2The characteristics of/CO≤1, it can be applicable
In F- T synthesis, the high chemicals of added value such as production higher hydrocarbon.
It is more based on metal supported catalyst to be presently used for the catalyst of synthesizing gas by reforming methane with co 2, mainly
It is divided into two major classes：Noble metal and non-precious metal catalyst.Although noble metal catalyst is held high with excellent reactivity worth, price
It is expensive, sintering is also easy under hot conditions and is lost in.Non-precious metal catalyst is nickel or cobalt be carried on aluminum oxide, silica, magnesia,
It is that reactivity worth is good the advantages of this system, catalyst preparation cost is low, but catalyst on the carriers such as zirconium oxide, titanium oxide
Carbon accumulation resisting ability is low, can cause to inactivate because of carbon distribution, sintering.
CN 101352687A disclose a kind of bimetallic catalyst of modification, and the catalyst is with a kind of γ-Al of modification2O3
For carrier, it is 1% ~ 20% Ni and 1% ~ 20% Co for active component using mass percent, is prepared using infusion process.But the system
Standby technics comparing is complicated, and cost is higher.
CN 102658145A disclose a kind of MgO（111）The preparation method of supported nickel based catalysts, first step carrier close
Into, absolute ethyl alcohol is dissolved in by magnesium rod, sequentially adds methoxy benzyl alcohol, methanol, in autoclave react, be calcined obtain
Carrier；Carrier impregnation is obtained metallic catalyst by second step in nickel acetylacetonate solution.But the preparation cost of the catalyst is too
Height, and preparation process is difficult to control.
CN 1280882A disclose a kind of nickel-base catalyst of nano-crystal oxide load.The catalyst is by nickel nitrate
The aqueous solution be added in nanocrystal oxide, stirring, dry, roasting be made.The reaction of gained catalyst lasts a long time, but
This method preparation process is complicated, and cost is higher.
Although it is anti-to obtain preferable synthesizing gas by reforming methane with co 2 for catalyst made from above-mentioned patented method
Performance is answered, but catalyst all has the problem of cost is higher, and synthesizing gas by reforming methane with co 2 reaction or one
Fast reaction（This fast reaction is typically at what is carried out under conditions of mass transport limitation）, reactant is in arrival catalyst appearance
Reaction has been completed while face, thus the inner surface of catalyst is contributed goal response less, and this has resulted in carrier duct
Interior relatively low rate of metal, catalyst cost is added, while can also accelerate the deep oxidation of product.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of synthesizing gas by reforming methane with co 2 to urge
The preparation method of agent, catalyst prepared by this method have that cost is cheap, metal component utilization rate is high, good, the anti-product of selectivity
Charcoal ability is strong and the characteristics of stability is good.
The present invention provides a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, and the catalyst includes
Active component, the first auxiliary agent, the second auxiliary agent and carrier, active component Ni；First auxiliary agent is Co, the second auxiliary agent is Na, K, Mg,
One or more in Ca, Sr, Ba, Zr, Ce or La, carrier are any one in aluminum oxide, silica, SBA-15；To urge
Each element quality is accounted on the basis of the percentage of carrier quality in agent, and the content of active component is 10wt%~30wt%, preferably
15wt%~25wt%, the content of the first auxiliary agent are 1wt%~5wt%, preferably 1wt%~3wt%, the content of the second auxiliary agent for 5wt%~
10wt%, preferably 5wt%~8wt%, surplus are carrier；The preparation method of the catalyst comprises the following steps：
（1）Active component presoma and the first auxiliary agent presoma is soluble in water, obtain solution A；
（2）Carrier is added to step（1）In obtained solution A, after aging, drying, calcination process, catalyst is obtained
Precursor B；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）By step（3）Catalyst precarsor B after obtained reduction is added in autoclave with polyhydric alcohol solutions,
Replaced 2~5 times with hydrogen after sealing, then adjust Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C；
（5）By step（4）Obtained reaction effluent places 1~3h, then filters, gained solid sample enters at room temperature
Row drying, until sample surfaces without liquid phase, obtain catalyst precarsor C；
（6）Active component presoma and the second auxiliary agent presoma is soluble in water, solution D is obtained, then adds step（5）
Obtained catalyst precarsor C, after drying, calcination process, obtains catalyst.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（1）And step（6）Middle institute
Active component presoma is stated as the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride, preferably nickel nitrate or acetic acid
Nickel.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（1）Described in first help
Agent presoma is the soluble-salt of cobalt, is specifically as follows cobalt nitrate, cobalt chloride, preferably cobaltous sulfate, cobalt nitrate；The solution A
The concentration of middle active component nickel is 0.15~1.15mol/L, and the first auxiliary agent Co concentration is 0.1~1.1mol/L.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（2）Described in aging temperature
Spend for 10~90 DEG C, preferably 20~60 DEG C, ageing time is 1~24h, preferably 4~12h；The drying temperature be 70~
150 DEG C, preferably 80~120 DEG C, drying time are 2~12h, preferably 4~8h；The sintering temperature is 500~900 DEG C,
Preferably 600~800 DEG C, roasting time is 2~12h, preferably 4~8h.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（2）Described carrier is
One kind in aluminum oxide, silica, SBA-15；The carrier can use commercially available product, can also be by well known in the art
It is prepared by method；In the catalyst precarsor B, nickel counts weight content in the carrier as 1wt%~5wt% using element.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（3）Described in reduction
Atmosphere is hydrogen, or the mixed gas of hydrogen and nitrogen, and hydrogen volume percentage composition is 10%~95% in the mixed gas.
Specific reduction treatment process is as follows：Catalyst precarsor is warming up to 300~600 DEG C under nitrogen atmosphere, then pass to hydrogen or
The mixed gas of hydrogen and nitrogen, in 0.1~0.5MPa（Absolute pressure）After handling 4~8h, room temperature is down in a nitrogen atmosphere.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（4）Described in it is polynary
Alcohol can be the one or more in xylitol, sorbierite, mannitol, arabite；The mass concentration of polyhydric alcohol solutions is 5%
~10%；Polyhydric alcohol solutions and step（3）Obtained reduction rear catalyst precursor B volume ratio is 5~10.
In the preparation method of synthesizing gas by reforming methane with co 2 catalyst of the present invention, step（6）Described in second help
Agent presoma is sodium nitrate, potassium nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, strontium nitrate, barium nitrate, zirconium nitrate, chlorine oxygen
Change the one or more in zirconium, cerous nitrate, lanthanum nitrate, preferably magnesium nitrate；The concentration of active component nickel is 0.8 in the solution D
~6.5mol/L, the concentration of the second promoter metal is 0.3~3mol/L.Auxiliary agent and the specific dipping process of active component are use
Method well known to those skilled in the art.
Catalyst prepared by the inventive method can also need to be made suitable particle shape according to what is used, and bar is such as made
Shape, piece shape, cylindricality etc..
Catalyst prepared by the inventive method can apply to synthesizing gas by reforming methane with co 2 reaction.Catalyst exists
Using it is preceding in a hydrogen atmosphere, 600~800 DEG C of 2~5h of prereduction.Catalyst prepared by the inventive method is applied to methane dioxy
Change the reaction of carbon preparing synthetic gas by reforming, preferable process conditions are：The composition CH of unstripped gas4/CO2Mol ratio is 1~1.5, unstripped gas
In can contain Ar, N2Or the dilution such as He property gas, 2000~6000h of unstripped gas air speed-1, reaction pressure is 0.1~2Mpa, instead
It is 700~900 DEG C to answer temperature.
Catalyst of the present invention, using aluminum oxide, silica or SBA-15 carriers, first load a small amount of active metal
Component Ni and the first auxiliary agent Co, obtained catalyst precarsor is after reduction treatment, the catalytic polyol water in autoclave
Mutually it is hydrogenated with, the product C of generation5And C6Liquid alkane can be used as atent solvent to the further processing of catalyst precarsor；By processing
Catalyst precarsor afterwards load active component and adjuvant component again, preferably control the active metal loaded in carrier duct
Amount, promote more multiple active components in the scattered of carrier surface, both improved the utilization rate of active metal, reduce catalyst into
This, accelerates the adsorption desorption speed of reactant and product in catalyst surface and hole, so as to avoid the further of product again
Oxidation, improves the conversion ratio of methane and the selectivity of product.
Embodiment
The technology contents and effect of the present invention are further illustrated with reference to embodiment, but are not so limited the present invention.
Appreciation condition：With hydrogen reducing 4 hours at 700 DEG C before catalyst reaction of the present invention.In continuous sample introduction fixed bed
Reacted in quartz reactor, 700 DEG C of reaction temperature, unstripped gas composition CH4/CO2/Ar =1/1/4（Mol ratio）, air speed
4000h-1, gas-chromatography on-line analysis is used after the condensed water removal of product.Reaction starts sampling analysis, evaluation result after 1 ~ 3 hour
It is shown in Table 1.Average activity of the reaction result for catalyst after 800 DEG C of 50h that work in table 1.
Using the distribution situation of active component on a catalyst in the catalyst prepared by the scanning electron microscope analysis present invention.This
The scanning electron microscope analysis of catalyst activity component nickel the results are shown in Table 2 in inventive embodiments.
Embodiment 1
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 13.7g magnesium nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
Mg, 2%Co catalyst, are designated as C-1.
Embodiment 2
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g silica（Pore volume is 1.06ml/g, specific surface area 387m2/ g, spherical, equivalent diameter 0.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 13.7g magnesium nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
Mg, 2%Co catalyst, are designated as C-2.
Embodiment 3
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20gSBA-15（Pore volume is 1.23ml/g, specific surface area 701m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 13.7g magnesium nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
Mg, 2%Co catalyst, are designated as C-3.
Embodiment 4
Weigh 0.99g nickel nitrates and 0.99g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
1%, Co account for vehicle weight 1% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 13.86g nickel nitrates and 10.54g magnesium nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 15%Ni, 5%Mg,
1%Co catalyst, is designated as C-4.
Embodiment 5
Weigh 4.95g nickel nitrates and 2.97g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
5%, Co account for vehicle weight 3% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 19.8g nickel nitrates and 16.86g magnesium nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 25%Ni, 8%Mg,
3%Co catalyst, is designated as C-5.
Embodiment 6
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 7.66g calcium nitrate, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
Ca, 2%Co catalyst, are designated as C-6.
Embodiment 7
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 6.12g zirconium nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
Zr, 2%Co catalyst, are designated as C-7.
Embodiment 8
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 4.03g cerous nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
Ce, 2%Co catalyst, are designated as C-8.
Embodiment 9
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 4.05g lanthanum nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
La, 2%Co catalyst, are designated as C-9.
Embodiment 10
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The xylitol solution that body B and 400mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 13.7g magnesium nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
Mg, 2%Co catalyst, are designated as C-10.
Embodiment 11
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The mannitol solution that body B and 200mL mass concentrations are 10% is added in autoclave, replaces 3 times with hydrogen after sealing, so
Hydrogen Vapor Pressure is adjusted afterwards to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtered,
Gained solid sample is dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to
In the aqueous solution containing 16.83g nickel nitrates and 13.7g magnesium nitrates, it is evaporated, is put into baking oven in 110 to solution in 80 DEG C of stirrings
12h is dried at DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni, 6.5%
Mg, 2%Co catalyst, are designated as C-11.
Embodiment 12
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
Body B is added in autoclave with the arabite solution that 300mL mass concentrations are 10%, is replaced 3 times with hydrogen after sealing,
Then Hydrogen Vapor Pressure is adjusted to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, mistake
Filter, gained solid sample are dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added
Into the aqueous solution containing 16.83g nickel nitrates and 13.7g magnesium nitrates, be evaporated in 80 DEG C of stirrings to solution, be put into baking oven in
12h is dried at 110 DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni,
6.5%Mg, 2%Co catalyst, are designated as C-12.
Embodiment 13
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 5% is added in autoclave, replaces 3 times with hydrogen after sealing, then
Hydrogen Vapor Pressure is adjusted to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, institute
Solid sample is obtained to be dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to and contained
In the aqueous solution for having 16.83g nickel nitrates and 13.7g magnesium nitrates, it is evaporated, is put into baking oven in 110 DEG C to solution in 80 DEG C of stirrings
Lower dry 12h, 6h is calcined at 700 DEG C, is molded, that is, be made and quality is counted using element account for carrier percentage composition as 20%Ni, 6.5%Mg,
2%Co catalyst, is designated as C-13.
Embodiment 14
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is activated in the mixed atmosphere of hydrogen, hydrogen in mixed gas
Volume content is 80%, and reducing condition is 450 DEG C, 0.2MPa（Absolute pressure）, recovery time 4h；Before the catalyst after reduction activation
The sorbitol solution that body B and 300mL mass concentrations are 8% is added in autoclave, replaces 3 times with hydrogen after sealing, then
Hydrogen Vapor Pressure is adjusted to 3MPa, reacts 4h at 220 DEG C；Reacted mixture in above-mentioned autoclave is placed into 2h, filtering, institute
Solid sample is obtained to be dried at room temperature for obtaining catalyst precarsor C without liquid phase to sample surfaces；Catalyst precarsor C is added to and contained
In the aqueous solution for having 16.83g nickel nitrates and 13.7g magnesium nitrates, it is evaporated, is put into baking oven in 110 DEG C to solution in 80 DEG C of stirrings
Lower dry 12h, 6h is calcined at 700 DEG C, is molded, that is, be made and quality is counted using element account for carrier percentage composition as 20%Ni, 6.5%Mg,
2%Co catalyst, is designated as C-14.
Comparative example 1
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is added to 50mLC6In alkane solvent, 20min is impregnated, then
Filtering, is dried at room temperature for, until catalyst precarsor C is made without liquid phase in catalyst precursor surface；Catalyst precarsor C is added
Into the aqueous solution containing 16.83g nickel nitrates and 13.7g magnesium nitrates, be evaporated in 80 DEG C of stirrings to solution, be put into baking oven in
12h is dried at 110 DEG C, is calcined 6h at 700 DEG C, is molded, that is, is made and quality is counted using element is accounted for carrier percentage composition as 20%Ni,
6.5%Mg, 2%Co catalyst, are designated as D-1.
Comparative example 2
Weigh 2.97g nickel nitrates and 1.98g cobalt nitrates are dissolved in appropriate amount of deionized water, obtain solution A；Using isometric leaching
Stain method is carried on 20g aluminum oxide（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter 1.5mm）Carrier,
Aging 4h at room temperature, 80 DEG C of dry 12h, 700 DEG C of roasting 4h, are made catalyst precarsor B, wherein Ni and vehicle weight are accounted in terms of element
3%, Co account for vehicle weight 2% in terms of element；Catalyst precarsor B is added to the sorbitol solution that 300mL mass concentrations are 10%
In, 20min is impregnated, then filters, is dried at room temperature for, until catalyst precarsor C is made without liquid phase in catalyst precursor surface；
Catalyst precarsor C is added in the aqueous solution containing 16.83g nickel nitrates and 13.7g magnesium nitrates, steamed in 80 DEG C of stirrings to solution
It is dry, it is put into baking oven at 110 DEG C and dries 12h, 6h is calcined at 700 DEG C, be molded, that is, the quality in terms of element is made and accounts for carrier percentage
Content is 20%Ni, 6.5%Mg, 2%Co catalyst, is designated as D-2.
Comparative example 3
Weigh 19.8g nickel nitrates, 1.98g cobalt nitrates and 14.2g magnesium nitrates to be dissolved in deionized water, the aqueous solution is made；Adopt
20g aluminum oxide is carried on equi-volume impregnating（Pore volume is 0.72ml/g, specific surface area 242m2/ g, bar shaped, equivalent diameter
1.5mm）Carrier, aging 6h, 100 DEG C of dry 12h, 700 DEG C of roasting 6h, that is, be made the quality in terms of element and account for carrier percentage at room temperature
Content is 20%Ni, 6.5%Mg, 2%Co catalyst, is designated as D-3.
The reactivity worth of the catalyst of table 1
The catalyst activity component nickel content of table 2 is distributed（wt%）
Claims (18)
1. a kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst, the catalyst includes active component, the
One auxiliary agent, the second auxiliary agent and carrier, active component Ni；First auxiliary agent is Co, the second auxiliary agent is Na, K, Mg, Ca, Sr, Ba,
One or more in Zr, Ce or La, carrier are any one in aluminum oxide, silica, SBA-15；With each member in catalyst
Quality amount is accounted on the basis of the percentage of carrier quality, and the content of active component is 10wt%~30wt%, and the content of the first auxiliary agent is
1wt%~5wt%, the content of the second auxiliary agent is 5wt%~10wt%, and surplus is carrier；The preparation method of the catalyst is included such as
Lower step：
（1）Active component presoma and the first auxiliary agent presoma is soluble in water, obtain solution A；
（2）Carrier is added to step（1）In obtained solution A, after aging, drying, calcination process, catalyst precarsor is obtained
B；
（3）Using reducing atmosphere to step（2）Obtained catalyst precarsor B carries out reduction treatment；
（4）By step（3）Catalyst precarsor B after obtained reduction is added in autoclave with polyhydric alcohol solutions, is sealed
Replaced 2~5 times with hydrogen afterwards, then adjust Hydrogen Vapor Pressure to 2~4MPa, 2~5h is reacted at 200~300 DEG C, described is more
First alcohol is the one or more in xylitol, sorbierite, mannitol, arabite；
（5）By step（4）Obtained reaction effluent places 1~3h, then filters, gained solid sample is done at room temperature
It is dry, until sample surfaces without liquid phase, obtain catalyst precarsor C；
（6）Active component presoma and the second auxiliary agent presoma is soluble in water, solution D is obtained, then adds step（5）Obtain
Catalyst precarsor C, after drying, calcination process, obtain catalyst.
2. according to the preparation method described in claim 1, it is characterised in that：Carrier quality is accounted for each element quality in catalyst
On the basis of percentage, the content of active component is 15wt%~25wt%, and the content of the first auxiliary agent is 1wt%~3wt%, the second auxiliary agent
Content be 5wt%~8wt%.
3. according to the preparation method described in claim 1, it is characterised in that：Step（1）And step（6）Described in before active component
Drive body is the one or more in nickel nitrate, nickel acetate, nickel sulfate or nickel chloride.
4. according to the preparation method described in claim 1, it is characterised in that：Step（1）And step（6）Described in before active component
It is nickel nitrate or nickel acetate to drive body.
5. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in the first auxiliary agent presoma be cobalt
Soluble-salt.
6. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in the first auxiliary agent presoma be nitre
Sour cobalt, cobalt chloride, cobaltous sulfate.
7. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in the first auxiliary agent presoma be nitre
Sour cobalt.
8. according to the preparation method described in claim 1, it is characterised in that：Step（1）Described in active component nickel in solution A
Concentration is 0.15~1.15mol/L, and the first auxiliary agent Co concentration is 0.1~1.1mol/L.
9. according to the preparation method described in claim 1, it is characterised in that：Step（2）Described in aging temperature be 10~90 DEG C,
Ageing time is 1~24h, and the drying temperature is 70~150 DEG C, and drying time be 2~12h, the sintering temperature for 500~
900 DEG C, roasting time is 2~12h.
10. according to the preparation method described in claim 9, it is characterised in that：Step（2）Described in aging temperature be 20~60
DEG C, ageing time is 4~12h, and the drying temperature is 80~120 DEG C, and drying time is 4~8h, and the sintering temperature is 600
~800 DEG C, roasting time is 4~8h.
11. according to the preparation method described in claim 1, it is characterised in that：Step（2）In the catalyst precarsor B, nickel is with member
The weight content of element meter in the carrier is 1%~5%.
12. according to the preparation method described in claim 1, it is characterised in that：Step（3）Described in reducing atmosphere be hydrogen,
Or the mixed gas of hydrogen and nitrogen, hydrogen volume percentage composition is 10%~95% in the mixed gas.
13. according to the preparation method described in claim 1, it is characterised in that：Step（4）Described in reduction treatment process it is as follows：
Catalyst precarsor B is warming up to 300~600 DEG C under nitrogen atmosphere, then passes to the mixed gas of hydrogen or hydrogen and nitrogen,
After 0.1~0.5MPa of absolute pressure handles 4~8h, room temperature is down in a nitrogen atmosphere.
14. according to the preparation method described in claim 1, it is characterised in that：Step（4）Described in polyhydric alcohol solutions quality it is dense
Spend for 5%~10%.
15. according to the preparation method described in claim 1, it is characterised in that：Step（4）Middle polyhydric alcohol solutions and step（3）
The reduction rear catalyst precursor B arrived volume ratio is 5~10.
16. according to the preparation method described in claim 1, it is characterised in that：Step（6）Described in the second auxiliary agent presoma be nitre
Sour sodium, potassium nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, calcium chloride, strontium nitrate, barium nitrate, zirconium nitrate, basic zirconium chloride, cerous nitrate,
One or more in lanthanum nitrate.
17. according to the preparation method described in claim 1, it is characterised in that：Step（6）Described in the second auxiliary agent presoma be nitre
Sour magnesium.
18. according to the preparation method described in claim 1, it is characterised in that：Step（6）Described in active component nickel in solution D
Concentration be 0.8~6.5mol/L, the concentration of the second promoter metal is 0.3~3mol/L.
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