CN100435945C - Method for preparing nickel catalyst carried in ion liquid - Google Patents
Method for preparing nickel catalyst carried in ion liquid Download PDFInfo
- Publication number
- CN100435945C CN100435945C CNB2006100522543A CN200610052254A CN100435945C CN 100435945 C CN100435945 C CN 100435945C CN B2006100522543 A CNB2006100522543 A CN B2006100522543A CN 200610052254 A CN200610052254 A CN 200610052254A CN 100435945 C CN100435945 C CN 100435945C
- Authority
- CN
- China
- Prior art keywords
- nickel
- ionic liquid
- salt
- catalyst
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims description 22
- 239000007788 liquid Substances 0.000 title claims description 18
- 239000000243 solution Substances 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 150000002815 nickel Chemical class 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 150000003608 titanium Chemical class 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 17
- -1 silicon ester Chemical class 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000002608 ionic liquid Substances 0.000 claims description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 25
- 150000002148 esters Chemical class 0.000 claims description 25
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- 241001502050 Acis Species 0.000 claims description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 150000001340 alkali metals Chemical group 0.000 claims description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 15
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003426 co-catalyst Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 11
- 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 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- GOMPLJOPYGQBPL-UHFFFAOYSA-K [F-].[F-].[F-].F.[B+3] Chemical compound [F-].[F-].[F-].F.[B+3] GOMPLJOPYGQBPL-UHFFFAOYSA-K 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- MNYOKDIIUJDYBM-UHFFFAOYSA-N 1-benzyl-3-methyl-2h-imidazole Chemical class C1=CN(C)CN1CC1=CC=CC=C1 MNYOKDIIUJDYBM-UHFFFAOYSA-N 0.000 claims description 4
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 229940078494 nickel acetate Drugs 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
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- BKAFBBWDHTZFSB-UHFFFAOYSA-N 2-(3-methyl-2h-imidazol-1-yl)ethanol Chemical class CN1CN(CCO)C=C1 BKAFBBWDHTZFSB-UHFFFAOYSA-N 0.000 claims description 2
- MDPWQIVUHBASSL-UHFFFAOYSA-K CCCCN1C(C=CC=C2)=C2N(CC)C1.[B+3].[F-].[F-].[F-].F Chemical compound CCCCN1C(C=CC=C2)=C2N(CC)C1.[B+3].[F-].[F-].[F-].F MDPWQIVUHBASSL-UHFFFAOYSA-K 0.000 claims description 2
- LTVZAACKNHHMKU-UHFFFAOYSA-K CCN1C(C=CC=C2)=C2N(CC2=CC=CC=C2)C1.[B+3].[F-].[F-].[F-].F Chemical compound CCN1C(C=CC=C2)=C2N(CC2=CC=CC=C2)C1.[B+3].[F-].[F-].[F-].F LTVZAACKNHHMKU-UHFFFAOYSA-K 0.000 claims description 2
- HBHGASIVUOOWTF-UHFFFAOYSA-K CCN1C(C=CC=C2)=C2N(CCO)C1.[B+3].[F-].[F-].[F-].F Chemical compound CCN1C(C=CC=C2)=C2N(CCO)C1.[B+3].[F-].[F-].[F-].F HBHGASIVUOOWTF-UHFFFAOYSA-K 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract 3
- 239000006193 liquid solution Substances 0.000 abstract 3
- VXPFEVUAMVPPQU-UHFFFAOYSA-N dioxosilane nickel Chemical group [Ni].O=[Si]=O VXPFEVUAMVPPQU-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 108010010803 Gelatin Proteins 0.000 abstract 1
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229920000159 gelatin Polymers 0.000 abstract 1
- 239000008273 gelatin Substances 0.000 abstract 1
- 235000019322 gelatine Nutrition 0.000 abstract 1
- 235000011852 gelatine desserts Nutrition 0.000 abstract 1
- 239000002923 metal particle Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 235000013985 cinnamic acid Nutrition 0.000 description 7
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 7
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 6
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 229930016911 cinnamic acid Natural products 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003980 solgel method Methods 0.000 description 5
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a preparation method of a load type nickel catalyst. The catalyst is Ni-SiO2 or Ni-TiO2 or Ni-SiO2 with auxiliary agent modification or Ni-TiO2. Nickel salt, soluble salt of the auxiliary agent, and silicon ester or titanium salt are respectively dissolved in ionic solution and are uniformly mixed; the ion liquid solution of the nickel salt, the ion liquid solution of the auxiliary agent and dilute acid solution (the pH value of the solution is regulated between 2 and 6) are simultaneously dripped into the ion liquid solution of the silicate ester or the titanium salt and are uniformly mixed; the evenly mixed solution is stirred at the temperature of 40 to 100 DEG C to obtain gelatin and is aged for 12 to 48 hours; the mixed solution is dried at the temperature of 80 to 150 DEG C, calcined at the temperature of 300 to 1000 DEG C for 2 to 6 hours, and finally reduced at the temperature of 300 to 800 DEG C for 1 to 10 hours. The catalyst has simple preparation processes and no environmental pollution, can effectively protect nickel metal particles from agglomeration in the preparation processes, and is suitable for catalytic hydrogenation reaction with high selectivity.
Description
(1) technical field
The present invention relates to a kind of nickel catalyst carried preparation method, particularly in ion liquid medium, prepare the method for Raney nickel.
(2) background technology
Advantages such as loading type nickel-based catalyst is inexpensive with it, be easy to get, high activity are widely used in all kinds of catalytic hydrogenation reactions.The Preparation of catalysts method is very big to its catalytic performance influence.Nickel-base catalyst preparation method commonly used has infusion process, ion-exchange, sol-gel process etc.Wherein sol-gel process has demonstrated huge superiority and application prospects because of preparation condition gentleness, specific area are big, particle diameter is evenly distributed, is not subjected to advantages such as influence, activity of such catalysts and the selection performance of stoichiometric composition are greatly improved as a kind of new method for preparing catalysis material.Traditional process for preparing sol-gel is solvent with the alcohol-water mixture, can cause the hole in the gel to subside owing to the solvent evaporation in the Preparation of catalysts process, and then influence the catalytic performance of catalyst.The ion liquid Preparation of catalysts that appears as provides new approaches.Ionic liquid is compared with traditional organic solvent as a kind of green solvent, has wideer liquid scope and almost negligible vapour pressure, and is not volatile; A large amount of inorganic and organic substances is all shown good dissolving ability; By regulating its many special natures and performance such as dissolubility, become the important component part of Green Chemistry as solvent to inorganic matter, water, organic matter and polymer to the appropriate design of yin, yang ion.Ion liquid just above-mentioned special nature makes it can be used as the active solvent that sol-gel process prepares nano catalytic material.Ionic liquid as solvent in the sol-gel preparation process, its negligible vapour pressure can be avoided the solvent evaporation, curing time of can extending is tended towards stability gel network structure, can guarantee that again gel network does not crack, and can not cause the contraction of gel inner duct and subsides.Research in this respect at present also is in the starting stage, except several pieces about being that solvent adopts sol-gel technology preparing SiO with the ionic liquid
2And TiO
2Outside the research of the nano-porous materials report, rarely reporting only have people such as Anderson to adopt the method successfully must prepare Pd/SiO aspect the research of preparation load type metal catalyst
2Catalyst is also used it for catalytic hydrogenation reaction, and this catalyst demonstrates very high activity and selectivity.And be solvent with the ionic liquid, adopt sol-gel process to prepare loading type nickel-based catalyst and do not see the patent documentation report both at home and abroad so far.
(3) summary of the invention
The purpose of this invention is to provide a kind of is solvent with the ionic liquid, adopts sol-gel process to prepare the method for loading type nickel-based catalyst.
The technical solution used in the present invention is as follows:
With nickel salt, esters of silicon acis or titanium salt are dissolved in the ionic liquid respectively and mix separately, the ionic liquid solution and the dilute acid soln of nickel salt are added drop-wise in the ionic liquid solution of esters of silicon acis or titanium salt simultaneously, the amount that adds diluted acid is advisable at 2～6 with regulator solution pH value, mix back being stirred to and obtain gel and aging 12～48h at 40～100 ℃, in 80～150 ℃ of dryings, again in 300～1000 ℃ of roasting 2～6h, at last in 300～800 ℃ of reduction 1～10h, described nickel salt is one of following at least nickel salt: nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate, citric acid nickel, described esters of silicon acis is methyl silicate or ethyl orthosilicate, described titanium salt is a titanium tetrachloride, titanium sulfate or butyl titanate, described ionic liquid is a glyoxaline ion liquid, and described ionic liquid is 1: 0.3～1 with the amount of substance ratio of esters of silicon acis or titanium salt.
Further, described glyoxaline ion liquid is preferred one of following: 1-methyl-3-butyl-imidazoles tetrafluoride boron ([BmIm] BF
4), 1-methyl-3-benzyl-imidazoles tetrafluoride boron ([BzmIm] BF
4), 1-methyl-3-(2-hydroxyethyl)-imidazoles tetrafluoride boron ([C
2OHmIm] BF
4), 1-ethyl-3-butyl-benzimidazole tetrafluoride boron ([BeBIm] BF
4), 1-ethyl-3-benzyl-benzimidazole tetrafluoride boron ([BzeBIm] BF
4) or 1-ethyl-3-(2-hydroxyethyl)-benzimidazole tetrafluoride boron ([C
2OHeBIm] BF
4), these ionic liquids can synthesize as required, general method is two step synthetic methods, specifically: at first methylimidazole and the halogenated alkane of selecting for use that has the particular functional group are prepared the halogen ([cation] X type ionic liquid) that contains glyoxaline cation by quaterisation, use target anion Y then
-Displace X
-Ion obtains specific ionic liquid.With [BmIm] BF
4Synthetic method be example: the first step, [BmIm] Br's is synthetic: N-methylimidazole and the bromination of n-butane of getting 0.3mol place three mouthfuls of round-bottomed flasks of 250ml, react in 140 ℃ of oil baths, generate white milk and very fast disappearance in the flask, solution becomes light yellow, treats milk complete obiteration recession baths of deoiling, and cooling condition is continuation stirring reaction 10min down, and then placing continuation reaction 15min under 140 ℃ of oil baths, product obtains [BmIm] Br behind 100-120 ℃ of following vacuum drying 2h; Second step, displacement anion: [BmIm] Br is dissolved in the 100ml distilled water, adds 0.3molNaBF
4, at room temperature stir 5h.Gained solution is told the ionic liquid phase with washed with dichloromethane, removes minor amount of water with anhydrous magnesium sulfate drying, and the decompression distillation ionic liquid is removed carrene mutually and promptly obtained product [BmIm] BF then
4
Further again, described diluted acid is nitric acid, acetate, hydrochloric acid or sulfuric acid solution, and generally selecting amount of substance concentration for use is the dilute acid soln of 0.1mol/L.Consumption is advisable 2～6 for regulator solution pH value.
When preparation is nickel catalyst carried, the loading of general selection nickel is 1～50wt%, in order to improve catalyst activity or at specific reaction, the co-catalyst that may also contain 0～20wt% in the Raney nickel, here 0 implication is that co-catalyst can be infinitely close to 0, described co-catalyst is an alkali metal, the oxide of alkaline-earth metal or rare earth element, described alkali metal, alkaline-earth metal or rare earth element are potassium, calcium, magnesium, zirconium, titanium, cerium, lanthanum or samarium, described preparation method can followingly carry out, loading according to nickel in the catalyst is the nickel salt that 1～50wt% takes by weighing respective amount, content according to co-catalyst is alkali metal or alkaline-earth metal or the corresponding soluble-salt of rare earth element that 0～20wt% takes by weighing respective amount, esters of silicon acis or titanium salt are dissolved in the ionic liquid respectively and mix, ionic liquid solution with nickel salt, corresponding soluble-salt ionic liquid solution of alkali metal or alkaline-earth metal or rare earth element and dilute acid soln (regulator solution pH value 2～6 amount) are added drop-wise in the ionic liquid solution of esters of silicon acis or titanium salt simultaneously, mix back being stirred to and obtain gel and aging 12～48h at 40～100 ℃, in 80～150 ℃ of dryings, again in 300～1000 ℃ of roasting 2～6h, at last in 300～800 ℃ of reduction 1～10h, preferred nickel nitrate of described nickel salt or nickel chloride, described ionic liquid is a glyoxaline ion liquid, preferred 1-methyl-3-benzyl-imidazoles tetrafluoride boron, described ionic liquid as solvent is 1: 0.3～1 with the amount of substance ratio of esters of silicon acis or titanium salt.
The corresponding soluble-salt of described alkali metal or alkaline-earth metal or rare earth element recommends to use nitrate.
Concrete, preparation method nickel catalyst carried in the ionic liquid is: the loading according to nickel is 1～50wt%, the content of co-catalyst is that 0～20wt% takes by weighing the nickel salt of respective amount and alkali metal or alkaline-earth metal or the corresponding solubility nitrate of rare earth element and esters of silicon acis or titanium salt and is dissolved in the glyoxaline ion liquid respectively, described ionic liquid is 1: 0.5～1 with the amount of substance ratio of esters of silicon acis or titanium salt, behind the ionic liquid solution 10～30min of stir silicon acid esters or titanium salt, slowly drip ionic liquid solution and alkali metal or the alkaline-earth metal or the nitrate of rare earth element ionic liquid solution of nickel salt, the while dripping dilute acid, regulator solution pH value is 2～6, after dropwising mixed solution is fully mixed, under 40～80 ℃, be stirred to again and obtain gel, and aging 12～48h, 80～120 ℃ of drying 4～12h again, at 300～800 ℃ of following roasting 2～6h, at last in hydrogen atmosphere or hydrogen nitrogen mixture atmosphere 300～800 ℃ the reduction 1～10h.
The present invention compared with prior art, its advantage is embodied in:
This catalyst preparation process is simple, and is environmentally friendly, and can effectively prevent the reunion of nickel metallic in the preparation process, and the active component of catalyst own is even, has good catalytic activity, selectivity and service life, is applicable to the high selectivity catalytic hydrogenation reaction.
(4) specific embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
Press ethyl orthosilicate: ionic liquid=1: 2 (mol ratio), take by weighing 2.64 the gram nickel nitrates and 16.7 the gram ethyl orthosilicates be dissolved in respectively 18.1 the gram [BmIm] BF
4In the ionic liquid, [BmIm] BF of magnetic agitation ethyl orthosilicate
4Behind the solution 10min, slowly drip [BmIm] BF of nickel nitrate
4Drip several 0.1mol/L watery hydrochloric acid in the time of solution, treat [BmIm] BF of nickel nitrate
4After solution dropwises, stir down 34min at 60 ℃ again behind the magnetic agitation 20min and obtain the emerald green gel, then at 60 ℃ of down aging 48h, in 110 ℃ dry down, 500 ℃ of following roasting 4h, 500 ℃ of reduction 3h down make Ni-SiO in hydrogen atmosphere
2Catalyst.
Embodiment 2
Press ethyl orthosilicate: ionic liquid=1: 1 (amount of substance ratio), other conditions and operation are carried out Ni-SiO with embodiment 1
2Preparation of catalysts.
Embodiment 3～7
Divide in addition with [BzmIm] BF
4, [C
2OHmIm] BF
4, [BeBIm] BF
4, [BzeBIm] BF
4, [C
2OHeBIm] BF
4Ionic liquid is a reaction medium, and its colloidal sol stirs gelation time, the gel ageing time is as shown in table 1, and other conditions and operation make Ni-SiO with embodiment 1
2Catalyst.
Gel gelation time and gel ageing time in table 1, the different ionic liquid medium
Embodiment 8:
Press ethyl orthosilicate: ionic liquid=1: 2 (amount of substance ratio) takes by weighing [BeBIm] BF that 2.16 gram nickel chlorides and 16.7 gram ethyl orthosilicates are dissolved in 11.58 grams respectively
4In the ionic liquid, [BeBIm] BF of magnetic agitation ethyl orthosilicate
4Behind the solution 10min, slowly drip [BeBIm] BF of nickel chloride
4Slowly drip several 0.1mol/L dilute solution of acetic acid in the time of solution, treat [BeBIm] BF of nickel chloride
4Solution dropwises, and stirs 45min down at 60 ℃ behind the magnetic agitation 10min and obtains the limegreen gel, and is at 60 ℃ of down aging 48h, dry under 110 ℃ again, 500 ℃ of following roasting 4h, and 700 ℃ of following reductase 12 h in hydrogen atmosphere make Ni-SiO at last
2Catalyst.
Embodiment 9
Press ethyl orthosilicate: ionic liquid=1: 2 (mol ratio), take by weighing 2.64 the gram nickel nitrates and 0.46 the gram cerous nitrate be dissolved in 18.1 the gram [BmIm] BF
4Ionic liquid takes by weighing 16.7 gram ethyl orthosilicates and is dissolved in 18.1 gram [BmIm] BF
4In the ionic liquid, [BmIm] BF of magnetic agitation ethyl orthosilicate
4Behind the solution 10min, slowly drip nickel nitrate and cerous nitrate] [BmIm] BF
4Drip several 0.1mol/L watery hydrochloric acid in the time of solution, treat [BmIm] BF of nickel nitrate and cerous nitrate
4After solution dropwises, stir down 40min at 60 ℃ again behind the magnetic agitation 30min and obtain green gel, then at 60 ℃ of down aging 48h, in 110 ℃ dry down, 500 ℃ of following roasting 4h, 500 ℃ of reduction 3h down make Ni-CeO in hydrogen atmosphere
2-SiO
2Catalyst.
Embodiment 10
Ni-SiO with embodiment 1 preparation
2Catalyst is used for cinnamic acid selective hydrogenation synthetic styrene-acrylic aldehyde reaction.500 milligrams of catalyst, 5.0 gram cinnamic acids, 50 milliliters of etoh solvents are added 100 milliliters of autoclaves, 80 ℃ of reaction temperatures, reaction hydrogen pressure 2.0MPa, reaction time 3h, the conversion ratio of cinnamic acid are 87.7%, the selectivity of benzenpropanal is 100%.And be the Ni-SiO of solvent preparation with conventional alcohol-water mixed liquid
2The conversion ratio of catalyst cinnamic acid under same reaction conditions is 100%, but the selectivity of benzenpropanal has only 25.1%.
Embodiment 11
Ni-SiO with embodiment 4 preparations
2Catalyst is used for cinnamic acid selective hydrogenation synthetic styrene-acrylic aldehyde reaction.Reaction condition is with embodiment 10, and reaction time 3h, the conversion ratio of cinnamic acid are 97.5%, and the selectivity of benzenpropanal is 100%.And be the Ni-SiO of solvent preparation with conventional alcohol-water mixed liquid
2The conversion ratio of catalyst cinnamic acid under same reaction conditions is 100%, but the selectivity of benzenpropanal has only 25.1%.
Claims (11)
1. one kind prepares nickel catalyst carried method in ionic liquid, it is characterized in that being dissolved in nickel salt and esters of silicon acis or titanium salt in the ionic liquid respectively, mix separately, the ionic liquid solution and the dilute acid soln of nickel salt are added drop-wise in the ionic liquid solution of esters of silicon acis or titanium salt simultaneously, mix back being stirred to and obtain gel and aging 12～48h at 40～100 ℃, in 80～150 ℃ of dryings, again in 300～1000 ℃ of roasting 2～6h, at last in 300～800 ℃ of reduction 1～10h, described nickel salt is one of following at least nickel salt: nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate or citric acid nickel, described esters of silicon acis is methyl silicate or ethyl orthosilicate, described titanium salt is a titanium tetrachloride, titanium sulfate or butyl titanate, described ionic liquid is a glyoxaline ion liquid, and described total ionic liquid is 1: 0.3～1 with the amount of substance ratio of esters of silicon acis or titanium salt.
2. as claimed in claim 1 in ionic liquid the nickel catalyst carried method of preparation, it is characterized in that described glyoxaline ion liquid is one of following: 1-methyl-3-butyl-imidazoles tetrafluoride boron, 1-methyl-3-benzyl-imidazoles tetrafluoride boron, 1-methyl-3-(2-hydroxyethyl)-imidazoles tetrafluoride boron, 1-ethyl-3-butyl-benzimidazole tetrafluoride boron, 1-ethyl-3-benzyl-benzimidazole tetrafluoride boron or 1-ethyl-3-(2-hydroxyethyl)-benzimidazole tetrafluoride boron.
3. as claimed in claim 1 in ionic liquid the nickel catalyst carried method of preparation, it is characterized in that described nickel catalyst carried in the loading of nickel be 1～50wt%.
As one of claim 1～3 described in ionic liquid the nickel catalyst carried method of preparation, it is characterized in that described diluted acid is one of following: nitric acid, acetate, hydrochloric acid or sulfuric acid solution.
5. as claimed in claim 3 in ionic liquid the nickel catalyst carried method of preparation, describedly also contain in nickel catalyst carried＞0 and≤co-catalyst of 20wt%, described co-catalyst is an alkali metal, the oxide of alkaline-earth metal or rare earth element, described alkali metal is potassium, described alkaline-earth metal is calcium or magnesium, described rare earth element is a cerium, lanthanum or samarium, it is characterized in that described preparation method is, loading according to nickel in the catalyst is the nickel salt that 1～50wt% takes by weighing respective amount, according to the content of co-catalyst for＞0 and≤20wt% takes by weighing alkali metal or the alkaline-earth metal or the corresponding soluble-salt of rare earth element of respective amount, and esters of silicon acis or titanium salt are dissolved in the ionic liquid respectively and mix separately, ionic liquid solution with nickel salt, corresponding soluble-salt ionic liquid solution of alkali metal or alkaline-earth metal or rare earth element and dilute acid soln are added drop-wise in the ionic liquid solution of esters of silicon acis or titanium salt simultaneously, the amount that adds dilute acid soln is for to be adjusted in 2～6 amount with mixed solution pH value, mix back being stirred to and obtain gel and aging 12～48h at 40～100 ℃, dry down in 80～150 ℃, again in 300～1000 ℃ of following roasting 2～6h, at last in 300～800 ℃ of following reduction 1～10h, described nickel salt is one of following at least nickel salt: nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate, citric acid nickel, described ionic liquid is a glyoxaline ion liquid, and described total ionic liquid is 1: 0.3～1 with the amount of substance ratio of esters of silicon acis or titanium salt.
6. as claimed in claim 3 in ionic liquid the nickel catalyst carried method of preparation, describedly also contain in nickel catalyst carried＞0 and≤co-catalyst of 20wt%, described co-catalyst is zirconium or titanyl compound, it is characterized in that described preparation method is, loading according to nickel in the catalyst is the nickel salt that 1～50wt% takes by weighing respective amount, according to the content of co-catalyst for＞0 and≤20wt% takes by weighing the zirconium or the corresponding soluble-salt of titanium of respective amount, and esters of silicon acis or titanium salt are dissolved in the ionic liquid respectively and mix separately, ionic liquid solution with nickel salt, corresponding soluble-salt ionic liquid solution of zirconium or titanium and dilute acid soln are added drop-wise in the ionic liquid solution of esters of silicon acis or titanium salt simultaneously, the amount that adds dilute acid soln is for to be adjusted in 2～6 amount with mixed solution pH value, mix back being stirred to and obtain gel and aging 12～48h at 40～100 ℃, dry down in 80～150 ℃, again in 300～1000 ℃ of following roasting 2～6h, at last in 300～800 ℃ of following reduction 1～10h, described nickel salt is one of following at least nickel salt: nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate, citric acid nickel, described ionic liquid is a glyoxaline ion liquid, and described total ionic liquid is 1: 0.3～1 with the amount of substance ratio of esters of silicon acis or titanium salt.
7. as claimed in claim 5 in ionic liquid the nickel catalyst carried method of preparation, it is characterized in that the corresponding soluble-salt of described alkali metal or alkaline-earth metal or rare earth element is a nitrate.
8. as claimed in claim 7 in ionic liquid the nickel catalyst carried method of preparation, it is characterized in that described method is 1～50wt% for the loading according to nickel, the content of co-catalyst for＞0 and≤20wt% takes by weighing the nickel salt of respective amount and alkali metal or alkaline-earth metal or the corresponding solubility nitrate of rare earth element and esters of silicon acis or titanium salt and is dissolved in the glyoxaline ion liquid respectively, described total ionic liquid is 1: 0.5～1 with the amount of substance ratio of esters of silicon acis or titanium salt, behind the ionic liquid solution 10～30min of stir silicon acid esters or titanium salt, drip ionic liquid solution and alkali metal or the alkaline-earth metal or the nitrate of rare earth element ionic liquid solution of nickel salt, dripping dilute acid is regulated ionic liquid solution pH value 2～6 simultaneously, after dropwising mixed solution is mixed, under 40～80 ℃, be stirred to again and obtain gel, and aging 12～48h, again in 80～120 ℃ of drying 4～12h, at 300～800 ℃ of roasting 2～6h, 300～800 ℃ of following reduction 1～10h in hydrogen atmosphere or hydrogen nitrogen mixture atmosphere at last.
9. as claimed in claim 8 in ionic liquid the nickel catalyst carried method of preparation, it is characterized in that described diluted acid is nitric acid, acetate, hydrochloric acid or the sulfuric acid solution of 0.1mol/L for amount of substance concentration.
10. as claimed in claim 8 in ionic liquid the nickel catalyst carried method of preparation, it is characterized in that described method is 1～50wt% for the loading according to nickel, the content of co-catalyst for＞0 and≤20wt% takes by weighing the nickel salt of respective amount and alkali metal or alkaline-earth metal or the corresponding solubility nitrate of rare earth element and esters of silicon acis and is dissolved in respectively in the glyoxaline ion liquid, described total ionic liquid is 1: 0.5～1 with the amount of substance ratio of esters of silicon acis.
11. as claimed in claim 8 in ionic liquid the nickel catalyst carried method of preparation, it is characterized in that described glyoxaline ion liquid is: 1-methyl-3-benzyl-imidazoles tetrafluoride boron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100522543A CN100435945C (en) | 2006-07-03 | 2006-07-03 | Method for preparing nickel catalyst carried in ion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100522543A CN100435945C (en) | 2006-07-03 | 2006-07-03 | Method for preparing nickel catalyst carried in ion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1868588A CN1868588A (en) | 2006-11-29 |
| CN100435945C true CN100435945C (en) | 2008-11-26 |
Family
ID=37442449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100522543A Expired - Fee Related CN100435945C (en) | 2006-07-03 | 2006-07-03 | Method for preparing nickel catalyst carried in ion liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100435945C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009029284A1 (en) * | 2009-09-08 | 2011-03-10 | Evonik Oxeno Gmbh | Process for the oligomerization of olefins |
| CN102343278A (en) * | 2011-07-20 | 2012-02-08 | 北京工业大学 | Method for preparing heterogeneous catalyst used for epoxy cyclohexane and application thereof |
| CN105618147B (en) * | 2014-10-28 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of catalyst of Synthesis of dimethyl carbonate and its preparation method and application |
| CN105642343B (en) * | 2014-11-10 | 2018-09-04 | 中国石油天然气股份有限公司 | Silicon-loaded ionic liquid catalyst |
| CN104959149A (en) * | 2015-06-01 | 2015-10-07 | 常州大学 | Alpha, beta nonsaturated aldehyde selective hydrogenation catalyst and preparation method thereof |
| CN107899575B (en) * | 2017-11-20 | 2020-04-28 | 山东理工大学 | Nano-gold catalyst for generating ester by one-step oxidation esterification of aldehyde and alcohol and preparation method and application thereof |
| CN114074951B (en) * | 2020-08-17 | 2023-08-29 | 厦门稀土材料研究所 | Method for preparing rare earth fluoride by using fluorinated ionic liquid |
| CN117050218B (en) * | 2023-10-11 | 2024-02-13 | 传化智联股份有限公司 | Rare earth catalyst containing Nd-MIL-103 and method for preparing cis-polybutadiene based on catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210759A (en) * | 1997-09-05 | 1999-03-17 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
| WO2005123253A1 (en) * | 2004-06-17 | 2005-12-29 | Total Petrochemicals Research Feluy | Use of ionic liquids for simultaneous deposition of several single site catalyst components on a support to generate hybrid polymers |
| CN1782032A (en) * | 2004-12-01 | 2006-06-07 | 中国石油天然气股份有限公司 | By TiO2－SiO2Preparation method of diesel oil hydrofining catalyst with composite oxide as carrier |
-
2006
- 2006-07-03 CN CNB2006100522543A patent/CN100435945C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210759A (en) * | 1997-09-05 | 1999-03-17 | 中国石油化工总公司 | Low nickel content benzene hydrogenating catalyst and its preparing process |
| WO2005123253A1 (en) * | 2004-06-17 | 2005-12-29 | Total Petrochemicals Research Feluy | Use of ionic liquids for simultaneous deposition of several single site catalyst components on a support to generate hybrid polymers |
| CN1782032A (en) * | 2004-12-01 | 2006-06-07 | 中国石油天然气股份有限公司 | By TiO2－SiO2Preparation method of diesel oil hydrofining catalyst with composite oxide as carrier |
Non-Patent Citations (2)
| Title |
|---|
| 室温离子液体介质中尺寸、结构可控Ni 纳米微粒的制备及结构表征. 张晟卯，张春丽等.化学学报，第62卷第15期. 2004 |
| 室温离子液体介质中尺寸、结构可控Ni 纳米微粒的制备及结构表征. 张晟卯，张春丽等.化学学报，第62卷第15期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1868588A (en) | 2006-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100435945C (en) | Method for preparing nickel catalyst carried in ion liquid | |
| CN100409943C (en) | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use | |
| CN106966884B (en) | Method for preparing anthraquinone by oxidizing anthracene | |
| CN103586048B (en) | A kind of nano Pd particle magnetic catalyst, preparation and react for liquid-phase catalysis | |
| CN101157019A (en) | A catalyzer for preparing dimethyl ether by dewatering methanol as well as its preparing method | |
| CN104667913A (en) | Macroporous aluminum oxide assembled nano metal catalyst as well as preparation and application to methanol liquid-phase catalytic reaction | |
| CN105665018A (en) | Preparation method and application of composite solid superacid catalyst | |
| CN102416325A (en) | Preparation method of isobutyl ketone synthesis catalyst | |
| CN105797707A (en) | Method for preparing mesoporous titanic acid lanthanum zinc photocatalyst | |
| CN111686730A (en) | Preparation method and application of catalyst for synthesizing 2-phenylimidazole by Debus method | |
| CN104399460A (en) | Catalyst for industrial wastewater treatment and preparation method of catalyst | |
| CN104525183B (en) | A kind of mesoporous catalyst loading chromio and its preparation method and application | |
| CN110665505B (en) | Cu @ mZrO for efficiently catalyzing levulinic acid hydrogenation to prepare gamma-valerolactone2Core-shell catalyst and application | |
| CN101440040A (en) | Process for synthesizing p-aminophenol by catalytic hydrogenation of nitrobenzene | |
| CN102260359B (en) | Method for preparing chromium silica gel catalyst carrier with high specific surface area and large pore volume | |
| CN111747831A (en) | Method for preparing cyclopentanone | |
| CN111875493A (en) | Method for synthesizing borneol by using imidazole acidic ionic liquid | |
| CN106311201B (en) | It is a kind of using mesoporous carbon containing Sn as dehydrogenation of isobutane Pt bases catalyst, preparation method and its application of carrier | |
| CN114904587B (en) | Preparation method of cesium modified phosphotungstic acid@UiO-66/porous carbon-based composite material | |
| CN111841590B (en) | Method for controllably synthesizing vanadium phosphorus oxide catalyst by binary mixed solvent system | |
| CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof | |
| CN109201055A (en) | A kind of titanium nano tube catalyst of vanadium Ag doping and its preparation method and application | |
| CN109772337B (en) | Supported nickel-based nano catalyst and preparation method and application thereof | |
| CN107987023A (en) | A kind of method of solid acid catalysis synthesis 4-Hydroxyphenyl hydantoin | |
| CN105032400A (en) | Preparation method of graphene-loaded metal oxide catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081126 Termination date: 20110703 |