CN105727944B - A kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst - Google Patents
A kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst Download PDFInfo
- Publication number
- CN105727944B CN105727944B CN201610175982.7A CN201610175982A CN105727944B CN 105727944 B CN105727944 B CN 105727944B CN 201610175982 A CN201610175982 A CN 201610175982A CN 105727944 B CN105727944 B CN 105727944B
- Authority
- CN
- China
- Prior art keywords
- zro
- catalyst
- nanometer sheet
- preparation
- hydro
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 9
- 150000003303 ruthenium Chemical class 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 48
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 14
- 239000006185 dispersion Substances 0.000 abstract description 6
- OSKSAMGBRKRQOZ-UHFFFAOYSA-N benzene cyclohexene Chemical compound C1CCC=CC1.C1CCC=CC1.C1=CC=CC=C1 OSKSAMGBRKRQOZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 32
- 239000002002 slurry Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 12
- 238000011068 loading method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 229910006219 ZrO(NO3)2·2H2O Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 241000370738 Chlorion Species 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 add methanol Chemical compound 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 235000013490 limbo Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
- C07C13/20—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexene ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst, the catalyst are carried on ZrO by metal Ru2In nanometer sheet, 1 10 wt.% of Ru load capacity（With ZrO2On the basis of）, preparation method is：It is prepared using hydrothermal deposition method, active component Ru is anchored to ZrO2Nanometer sheet（ZrO2‑NS）Nano-composite catalyst is prepared, the soluble salt solutions of Ru and Zr are mixed and obtain catalyst precursor nucleus through hydro-thermal reaction；Then by introducing precipitating reagent, ZrO is made through drying, reduction2Nanometer sheet supported ruthenium catalyst（Ru/ZrO2‑NS）Catalyst.Compared with other support type benzene hydrogenating catalysts, the catalyst Ru prepared by the present invention is uniformly distributed in ZrO2In nanometer sheet, dispersion degree is high, and preparation process is simple；It is reacted for partial hydrogenation of benzene cyclohexene, has the advantages that high conversion rate, selectivity are good and stability is high.
Description
Technical field
The present invention relates to a kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst, metal catalyst preparing technical field.
Background technology
Cyclohexene is a kind of extremely important chemical intermediate, is widely used in medicine, agricultural chemicals, feed, polyester
The production of material and other fine chemical products.Cyclohexene is typically to be made by dehydration of cyclohexanol, and traditional preparation methods include halogen
Take off halocarbon method and Brich reduction methods for hexamethylene, but all there are complex process, byproduct is more, energy consumption is big and environment is dirty
Contaminate the shortcomings of serious.In comparison, there is Atom economy by partial hydrogenation of benzene cyclohexene, energy consumption can be reduced, improve warp
Ji benefit.However, in terms of thermodynamics, the standard Gibbs free energy changes of partial hydrogenation of benzene generation cyclohexene are -23 KJmol-1,
And the free energy change of benzene complete hydrogenation generation hexamethylene is -98 KJmol-1, illustrate the reaction of partial hydrogenation of benzene cyclohexene in heat
It is totally unfavorable on mechanics.Thus, high performance catalyst is researched and developed, the catalyst particularly with high cyclohexene selectivity seems
It is particularly important.
The double bond of cyclohexene is more active than the big pi bond of phenyl ring, and cyclohexene is easily further hydrogenated to hexamethylene, and reaction is difficult
Rest on the generation cyclohexene stage.Hartog in 1963 only obtains 0.18 in benzene liquid-phase hydrogenatin process by catalyst of ruthenium black
The cyclohexene of mol%.Nineteen sixty-five Stamicarbon N.V companies deliver patent 660,742 in Belgium and propose by adding C1-
The low-carbon alcohols of C4 can improve the selectivity of benzene liquid phase selective Hydrogenation cyclohexene, particularly add methanol, and selectivity is reachable
20%.1972, DuPont was pointed out in Deutsche Bundespatent 2,221,137 with RuCl3For precursor, with titanium trichloride, two
Chromium chloride, sodium borohydride or hydrogen etc. are reducing agent, and in alkaline aqueous solution, benzene hydrogenation process cyclohexene yield is up to 30 %.
1975, for alkaline aqueous solution system is avoided to improve the stability of catalyst, Philip to carrier and reaction equipment etching problem
Oil company Gerhard etc. is open using metal Ru as catalyst in patent US 3,912,787, Al2O3Or zinc aluminate is carrier,
VIB, group VIIIB element of Fe, Cr, Co, Ni, W, Mo are auxiliary agent, in pH<Cyclohexene yield is realized in 7.5 water solution system
20.2 %.1988, Japanese Asahi companies Nagahara etc. proposed to use on patent US 4,734,536 small with crystallite dimension
It is catalyst in the metal Ru of 20 nm, auxiliary agent ZnSO is introduced in reacting slurry4·7H2O and dispersant ZrO2Or HfO2, reaction
About 26 % of 20 min cyclohexene yield reacts 65 min or so cyclohexene yield close to 50 %.1989, Japanese Asahi companies
The industrialization of partial hydrogenation of benzene cyclohexene is realized using non-loading type RuZn catalyst.But non-loading type nanometer Ru catalyst
During the reaction because particles collision is easy to cause growing up for Ru crystallites, cause irreversible inactivation, exist simultaneously reaction product and
Catalyst is difficult to detach and lose problem.
Last century the nineties rise, and during solving partial hydrogenation of benzene, non-loading type Ru catalyst is easily because colliding grain
Son, which is grown up, leads to Catalysts Deactivation Problems, and domestic and international many researchers are dedicated to the preparation of support type Ru base catalyst.US 4,
678,861 disclose a kind of method for preparing cycloolefin, and this method used catalyst is carried on La or La-Zn etc. by infusion process
On rare earth element composition bimetallic complex carrier, and prepared by hydrogen reduction method.US 5,569,803 disclose it is a kind of with
ZrO2Modified SiO2For carrier, dip loading Ru catalyst.US 5,414,171 discloses one kind with La2O3Modified SiO2Or
Al2O3For complex carrier, dip loading Ru catalyst.US 6,060,423 is disclosed using Ga-Zn bimetallics as complex carrier
Ru catalyst prepares supported Ru catalysts by incipient impregnation and liquid-phase reduction.Patent CN1424293A discloses one kind
Support type Ru base catalyst is prepared using coprecipitation, by ZrOCl2·8H2O and ammonium hydroxide are added dropwise to RuCl simultaneously3·xH2O is carried
Body exists with colloid or amorphous state, and support type Ru/ZrO is obtained by liquid-phase reduction2·xH2O catalyst.Patent
CN101219391A discloses a kind of Ru base catalyst using preparation MCM-41, HMS, the SBA-15 load of solvent pairs infusion process.
103480393 A of patent CN disclose a kind of using surfactant-modified precipitation method synthesis Zr-Al-O composite oxides loads
Body prepares support type Ru base catalyst after roasting through deposition sedimentation and liquid-phase reduction.
Above-mentioned supported Ru catalysts mainly use conventional infusion process or coprecipitation preparation or cumbersome there are process,
Or the problem of ruthenium dispersion degree is low or catalytic activity selectivity is insufficient, industrialization is not implemented.
Invention content
The purpose of the present invention is to provide a kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst.It is prepared by simplification
Journey optimizes the texture of catalyst, promotes reaction mass transfer process, solution catalyst non-loading type noble metal Ru dosages are big, are easy to roll into a ball
The problem of poly- inactivation.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of ZrO2Nanometer sheet supported ruthenium catalyst is carried on ZrO by metal Ru2In nanometer sheet, wherein ZrO2With the matter of Ru
Amount is than being 100:1-10（That is Ru load capacity 1-10 wt.%, with ZrO2On the basis of）, preparation method is：Using hydro-thermal-precipitation method
It prepares, active component Ru is anchored to ZrO2Nanometer sheet（ZrO2-NS）Surface forms nano-composite catalyst, i.e., first by activearm
Point（Ruthenium salting liquid）With carrier salting liquid（Soluble zirconates）Hydro-thermal forms nucleus, then makes its precipitation by introducing precipitating reagent,
And ZrO is made through drying, reduction roasting2Nanometer sheet loads ruthenium（Ru/ZrO2-NS）Catalyst；Specific preparation process is as follows：
(1) at room temperature, it weighs soluble zirconates and ruthenium salt is made into the mixed solution of 150-160 mL, it is poly- to be transferred to band
Hydro-thermal process is carried out in tetrafluoroethene liner reaction kettle, 130-200 DEG C of hydrothermal temperature, hydro-thermal time control is in 3-18 h；It is preferred that
Hydrothermal temperature for 170 DEG C, the hydro-thermal time is 6 h, and product is khaki suspension；
(2) precipitating reagent is slowly added drop-wise in above-mentioned suspension under stirring, 6-20 h are aged at 40 DEG C -90 DEG C；
(3) by the sediment that step (2) obtains through centrifuge washing, vacuum drying, the H in tube furnace2In 150 under atmosphere
DEG C -450 DEG C of reduction roasting 4-8h are to get Ru/ZrO2- NS catalyst.
Soluble zirconates described in above-mentioned preparation method step (1) is ZrOCl2·8H2O and ZrO (NO3)2·2H2In O
It is one or more of；Soluble ruthenium salt is RuCl3·3H2O、C14H27O18Ru3、KRuO4With RuNO (NO3)3One or more of.
When with KRuO4During for precursor, step (1) can add a small amount of ethyl alcohol, and the mixing ratio of second alcohol and water is (1-10):100.Due to
In acidity, water-heat process part metals salt forms the nucleus of precursor for zirconates and ruthenium mixed salt solution.
It is 9-13 that precipitation, which terminates pH value, in rate-determining steps (2), and all metal salts is made to turn on the basis of the nucleus of precursor
Hydroxide precipitation is melted into, forms flaky nanometer structure；In step (2) precipitating reagent be urea, one in NaOH, KOH and ammonium hydroxide
Kind or a variety of, 40-90 DEG C of Aging Temperature, digestion time 6-20 h, gained is precipitated as blackish green.It is excellent when precipitating reagent is urea
The Aging Temperature of choosing is 90 DEG C, and the digestion time of optimization is 20 h.When selecting other precipitating reagents, preferred Aging Temperature is 60
DEG C, the digestion time of optimization is 4 h.
Washing solution is one or more of deionized water, weak aqua ammonia and acetone solvent in step (3), and washing times are
4-6 times.When zirconates is ZrOCl2·8H2O, ruthenium salt are RuCl3·3H2During O, preferred washing medium is acetone or deionized water
Or their mixture washing；When zirconates is ZrO (NO3)2·2H2O, ruthenium salt are KRuO4Or RuNO (NO3)3During solution, selection
Deionized water or weak aqua ammonia washing.Due to Ru (OH)4Solubility product（~1.0×10-44）Less than Ru (OH)3Solubility product（~1.0×
10-38）, when selecting ruthenium salt as trivalent ruthenium（RuCl3·3H2O or C14H27O18Ru3）When, 1 mL, 30 wt.% are added dropwise before washing
H2O2Solution converts it into tetravalence ruthenium Ru (IV), to reduce washing process Ru losses.
Catalyst reduction described in above-mentioned preparation method step (3) is that heating restores under an atmosphere of hydrogen, preferred temperature
It it is 200 DEG C, the recovery time is 6 h.
A kind of ZrO as described above2Nanometer sheet supported ruthenium catalyst is applied to catalysis partial hydrogenation of benzene cyclohexene, by institute
It states catalyst to be added in autoclave, adds one or more of soluble sulphate of Zn, Fe and Cd and catalyst is carried out
It is passivated to improve catalyst choice.
The present invention has built a homogeneous environment by presoma of the hydro-thermal for active component and carrier, due to the zirconium of use
Salt and ruthenium mixed salt solution are acidity, and water-heat process part metals salt forms tiny nucleus, and the formation of these nucleus determines
Precipitation process obtains the ZrO of laminated structure2Presoma.It utilizes Zr (OH)4Solubility product 6.4 × 10-49Less than Ru (OH)3And Ru
(OH)4The characteristic of solubility product makes Ru precursor uniform depositions on carrier, and the catalyst Ru dispersion degrees of preparation are high.
The beneficial effects of the present invention are：
(1) loaded catalyst prepared by the present invention, with nano-sheet ZrO2As carrier, Ru catalyst can be uniform
Ground is carried on carrier, is distributed in island；When Ru contents are 5 wt.%, the dispersion degree of Ru is up to 14.7 %, far above non-negative
Load type Ru catalyst（The dispersion degree of Ru is only 2.9 %）, the active force enhancing between Ru and carrier；
(2) using the unique texturizing properties of nano-sheet, be conducive to improve reaction process H2Interior diffusion, cyclohexene
Liquid is spread admittedly, promotes gas-solid-four phase reaction of water-oil in partial hydrogenation of benzene reaction process；ZrO is utilized simultaneously2The abundant hydroxyl in surface
Base promotes the desorption of cyclohexene, improves the activity, selectivity and stability of catalyst；
(3) non-loading type Ru catalyst contents industrially（With ZrO2On the basis of dispersant, generally in 18 wt.%
Left and right）, by improving the dispersion degrees of Ru metals in the present invention, when obtaining catalytic performance comparable with industrial catalyst, can drop
The usage amount of low Ru saves catalyst cost, has very high industrial application value.
Description of the drawings
Fig. 1 X-ray powder diffraction figures；(a) non-loading types Ru catalyst；(b)) carrier ZrO2-NS；(c) this hair of
Ru/ZrO made from bright embodiment 12- NS nanocatalysts；
Fig. 2 scanning electron microscope (SEM) photographs；(a) carriers ZrO2-NS；(b) 1 samples of comparative example of the present invention；(c) 1 sample of embodiments；
Fig. 3 is the graph of pore diameter distribution of catalyst that the embodiment of the present invention 1 obtains；
Fig. 4 scanning electron microscope (SEM) photographs；(a) embodiments 1, (b) embodiments 2, (c) embodiments 3 and (d) embodiments 4 obtain
Catalyst.
Specific embodiment
It for the present invention is furture elucidated, is elaborated below with embodiment, and provides prepared by the attached drawing description present invention
Specificity of catalyst characterizes, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
Weigh 1.3 g RuNO (NO3)3、17.1 g ZrO(NO3)2·2H2O is dissolved in 156 mL deionized waters, transfer
In the water heating kettle for being 200 mL to volume, in 170 DEG C of 6 h of hydro-thermal, cooled to room temperature obtains khaki slurries；It takes
Go out slurries, using 10 wt.% NaOH solutions as precipitating reagent, precipitated in 60 DEG C, it is 9 that control precipitation, which terminates pH, is stood old
Change 4 h；By gained sediment deionized water centrifuge washing to neutrality；By sediment after 80 DEG C are dried in vacuo 12 h, in hydrogen
Atmosphere encloses 6 h of lower 200 DEG C of roastings.
Embodiment 2
Weigh 0.48 g KRuO4、17.1 g ZrO(NO3)2·2H2O is dissolved in the alcoholic solution of 156 mL, 10 vol.%
In, it is transferred in the water heating kettle that volume is 200 mL, in 130 DEG C of 18 h of hydro-thermal, cooled to room temperature obtains khaki
Slurries；Slurries to be taken out, using 10 wt.% KOH solutions as precipitating reagent, are precipitated in 70 DEG C, it is 13 that control precipitation, which terminates pH,
Still aging 12 h；By gained sediment deionized water centrifuge washing to neutrality；Sediment is dried in vacuo 12 h in 80 DEG C
Afterwards, under an atmosphere of hydrogen 450 DEG C roasting 4 h.
Embodiment 3
Weigh 2.14 g RuCl3·3H2O、20.6 g ZrOCl2·8H2O is dissolved in 150 mL deionized waters, transfer
In the water heating kettle for being 200 mL to volume, in 150 DEG C of 12 h of hydro-thermal, cooled to room temperature obtains khaki slurries；It takes
Go out slurries, using 10 wt.% NaOH solutions as precipitating reagent, precipitated in 80 DEG C, it is 10 that control precipitation, which terminates pH, is stood old
Change 12 h, 1 mL of addition, 30 wt.% H2O2Solution；By gained sediment acetone and deionized water（Volume ratio 1:5）Mixing
Liquid centrifuge washing is to using AgNO3Solution detection exists without chlorion；By sediment after 80 DEG C are dried in vacuo 12 h, in hydrogen
4 h of the lower 300 DEG C of roastings of atmosphere.
Embodiment 4
Weigh 5.33 g C14H27O18Ru3、17.1 g ZrO(NO3)2·2H2O is dissolved in 156 mL deionized waters, is turned
It moves in the water heating kettle that volume is 200 mL, in 200 DEG C of 6 h of hydro-thermal, cooled to room temperature obtains khaki slurries；
Slurries are taken out, using 10 wt.% ammonia spirits as precipitating reagent, are precipitated in 60 DEG C, it is 9 that control precipitation, which terminates pH, is stood
It is aged 6 h, 1 mL of addition, 30 wt.% H2O2Solution；By gained sediment deionized water centrifuge washing to neutrality；It will precipitation
Object roasts 6 h for 200 DEG C under an atmosphere of hydrogen after 80 DEG C are dried in vacuo 12 h.
Embodiment 5
Weigh 0.25 g RuNO (NO3)3、17.1 g ZrO(NO3)2·2H2O is dissolved in 156 mL deionized waters, transfer
In the water heating kettle for being 200 mL to volume, in 200 DEG C of 18 h of hydro-thermal, cooled to room temperature obtains khaki slurries；It takes
Go out slurries, using 1.2 M urea liquids as precipitating reagent, precipitated in 90 DEG C, it is 10 that control precipitation, which terminates pH, still aging
20 h, gained sediment weak aqua ammonia centrifuge washing；By sediment after 80 DEG C are dried in vacuo 12 h, under an atmosphere of hydrogen 200
DEG C roasting 8 h.
Embodiment 6
Weigh 0.4 g RuCl3·3H2O、20.6 g ZrOCl2·8H2O is dissolved in 150 mL deionized waters, is transferred to
Volume is in the water heating kettle of 200 mL, and in 150 DEG C of 10 h of hydro-thermal, cooled to room temperature obtains khaki slurries；It takes out
Slurries using 10 wt.% ammonia spirits as precipitating reagent, are precipitated in 40 DEG C, and it is 10, still aging 6 that control precipitation, which terminates pH,
30 wt.% H of h, 1 mL of addition2O2Solution, by gained sediment acetone and deionized water（Volume ratio 1:5）Mixed liquor from
The heart is washed to using AgNO3Solution detection exists without chlorion；By sediment after 80 DEG C are dried in vacuo 12 h, in atmosphere of hydrogen
8 h of lower 150 DEG C of roastings.
Comparative example 1
Weigh 20.6 g ZrOCl2·8H2O is dissolved in 152 mL deionized waters, is transferred to the hydro-thermal that volume is 200 mL
In kettle, in 150 DEG C of 12 h of hydro-thermal, cooled to room temperature is up to milky slurries；Slurries are taken out, it is molten with 10 wt.% NaOH
Liquid is precipitated, it is 10 that control precipitation, which terminates pH, still aging 12 h as precipitating reagent in 80 DEG C；By gained sediment with third
Ketone and deionized water（Volume ratio 1:5）Mixed liquor centrifuge washing to using AgNO3Solution detection exists without chlorion；By sediment
After 80 DEG C are dried in vacuo 12 h, 300 DEG C of 4 h of roasting, both obtain ZrO under an atmosphere of hydrogen2-NS。
Weigh 1.07 g RuCl3·3H2O is dissolved in 150 mL deionized waters, using 10 wt.% NaOH solutions as heavy
Shallow lake agent is precipitated in 80 DEG C, and it is 10, still aging 12 h that control precipitation, which terminates pH, adds few drops of H2O2Solution；Gained is sunk
Starch acetone and deionized water（Volume ratio 1:5）Mixed liquor centrifuge washing to using AgNO3Solution detection exists without chlorion；
By sediment in autoclave 5.0 MPa H2Pressure restores 4 h to get non-loading type Ru catalyst under the conditions of 150 DEG C.
Take 0.1g non-loading type Ru catalyst and 0.5 g ZrO2- NS is used for estimation of stability.
Performance test
Catalyst activity evaluation method of the present invention is comparable with domestic and foreign literature data.Liquid phase benzene is partial to add hydrogen
Reaction carries out in Buchiglasuster companies limbo high-pressure mini reaction kettles, 0.6 g Ru/ZrO2- NS is nano combined to be urged
Agent, 80 mL H2O, 0.035 mol ZnSO4·7H2O；140 DEG C, 900 rmin of stir speed (S.S.)-1With Hydrogen Vapor Pressure 4.5
Prereduction under the conditions of MPa；150 DEG C of 40 mL benzene of addition are risen to, adjust rotating speed to 1200 rmin-1Start to react timing.Using
GC-2010 chromatographics product forms, fid detector, obtains benzene conversion ratio and cyclohexene selectivity.
Conversion ratio, the hexamethylene of benzene when catalyst prepared by 1 embodiment 1-6 of table reacts 25 min for partial hydrogenation of benzene
The selectivity and yield of alkene
2 embodiment 1 of table and the partial hydrogenation of benzene reaction stability of comparative example 1 compare
Note：For test condition with activity rating method, it is 25 min often to take turns the reaction time, is detached before loop test organic
Phase, no prereduction rejoin benzene and carry out test evaluation.
The diffraction maximum of active component Ru is not observed in Fig. 1 c, illustrates that Ru is highly dispersed in carrier surface；Compared with Fig. 1 b,
Its ZrO2Characteristic diffraction peak wideization, relative intensity are also varied from, illustrate Ru and ZrO2There are certain interactions.
As can be seen that working as ZrO from Fig. 2 b2Catalyst can not adequately disperse during as dispersant, and using hydro-thermal
Ru/ZrO prepared by coprecipitation2-NS（Fig. 2 c）It can hardly see isolated Ru particles, Ru is mainly dispersed in ZrO2On, Cheng Dao
Shape is distributed.
From figure 3, it can be seen that the Ru/ZrO of hydro-thermal-precipitation method one-step synthesis2The pore size distribution of-NS catalyst is in 3 nm and 40
Near nm, pore size distribution in pairs, this be beneficial to gas-solid in partial hydrogenation of benzene reaction process-four phase reaction mass transfer of water-oil into
Row.
From fig. 4, it can be seen that the catalyst obtained is two-dimensional nano chip architecture.
The foregoing is merely the more typical embodiment of the present invention, all equivalent changes done according to scope of the present invention patent
With modification, the covering scope of the present invention is come under.
Claims (6)
1. a kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst, it is characterised in that：ZrO is carried on by metal Ru2Nanometer sheet
On, wherein ZrO2Mass ratio with Ru is 100:1-10；It is prepared, included the following steps using hydro-thermal-precipitation method：
(1) at room temperature, it weighs soluble zirconates and ruthenium salt is made into the mixed solution of 150-160 mL, move to band polytetrafluoroethyl-ne
Alkene liner reaction kettle carries out hydro-thermal reaction, obtains khaki suspension；
(2) precipitating reagent is slowly dropped in above-mentioned suspension under stirring, is aged 6-20 hours at 40 DEG C -90 DEG C；
(3) by the sediment that step (2) obtains through centrifuge washing 4-6 times, vacuum drying, in H2Under atmosphere in 150-450 DEG C also
4-8h is to get the catalyst for original roasting.
2. a kind of ZrO according to claim 12The preparation method of nanometer sheet supported ruthenium catalyst, it is characterised in that：Step
(1) hydrothermal temperature described in is 130-200 DEG C, hydro-thermal time 3-18 h.
3. according to the method described in claim 1, it is characterized in that：Soluble zirconates described in step (1) is ZrOCl2·8H2O
With ZrO (NO3)2·2H2One or both of O；Soluble ruthenium salt is RuCl3·3H2O、C14H27O18Ru3、KRuO4And RuNO
(NO3)3One or more of.
4. according to the method described in claim 1, it is characterized in that：It is 9-13 that precipitation, which terminates pH value, in rate-determining steps (2)；Precipitation
Agent is urea, one or more of NaOH, KOH and ammonium hydroxide.
5. according to the method described in claim 1, it is characterized in that：When ruthenium salt is RuCl3·3H2O or C14H27O18Ru3When, step
Suddenly 1 mL, 30 wt.% H are added in precipitated product before washing in (3)2O2Solution.
6. according to the method described in claim 1, it is characterized in that：In step (3) washing solution be deionized water, weak aqua ammonia and
One or more of acetone solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610175982.7A CN105727944B (en) | 2016-03-25 | 2016-03-25 | A kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610175982.7A CN105727944B (en) | 2016-03-25 | 2016-03-25 | A kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105727944A CN105727944A (en) | 2016-07-06 |
| CN105727944B true CN105727944B (en) | 2018-06-15 |
Family
ID=56251514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610175982.7A Active CN105727944B (en) | 2016-03-25 | 2016-03-25 | A kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105727944B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107096532B (en) * | 2017-05-16 | 2019-12-10 | 嘉兴学院 | Au-ZrO 2 catalyst and application thereof |
| CN108405881A (en) * | 2018-02-02 | 2018-08-17 | 贵研铂业股份有限公司 | A kind of preparation method of high pure spherical ruthenium powder |
| CN108689431B (en) * | 2018-07-26 | 2020-05-19 | 北京化工大学 | Preparation method of aqueous phase nano zirconium oxide particle dispersoid |
| CN110961100B (en) * | 2018-09-30 | 2022-12-20 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof |
| CN110479259B (en) * | 2019-08-23 | 2020-12-29 | 福州大学 | Supported Ru-based catalyst with molybdenum oxide-zinc oxide-zirconium oxide composite oxide as carrier |
| CN112774674A (en) * | 2019-11-08 | 2021-05-11 | 中国科学院大连化学物理研究所 | Supported ruthenium cluster catalyst for ammonia synthesis, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424293A (en) * | 2002-12-12 | 2003-06-18 | 复旦大学 | Benzene selective hydrogenation carried ruthenium based catalyst and its preparation |
| CN102974342A (en) * | 2012-12-05 | 2013-03-20 | 同济大学 | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof |
| CN103288132A (en) * | 2013-06-07 | 2013-09-11 | 中国矿业大学 | Preparation method of graded monoclinic phase ZrO2 nanosheet |
| CN103599778A (en) * | 2013-11-13 | 2014-02-26 | 福州大学 | Cu-Zr binary oxide low-temperature water-gas shift catalyst and preparation method thereof |
| CN104028267A (en) * | 2014-05-23 | 2014-09-10 | 中国海洋石油总公司 | Method for preparing cyclohexane precious metal Ru catalyst by benzene selective hydrogenation |
-
2016
- 2016-03-25 CN CN201610175982.7A patent/CN105727944B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424293A (en) * | 2002-12-12 | 2003-06-18 | 复旦大学 | Benzene selective hydrogenation carried ruthenium based catalyst and its preparation |
| CN102974342A (en) * | 2012-12-05 | 2013-03-20 | 同济大学 | Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof |
| CN103288132A (en) * | 2013-06-07 | 2013-09-11 | 中国矿业大学 | Preparation method of graded monoclinic phase ZrO2 nanosheet |
| CN103599778A (en) * | 2013-11-13 | 2014-02-26 | 福州大学 | Cu-Zr binary oxide low-temperature water-gas shift catalyst and preparation method thereof |
| CN104028267A (en) * | 2014-05-23 | 2014-09-10 | 中国海洋石油总公司 | Method for preparing cyclohexane precious metal Ru catalyst by benzene selective hydrogenation |
Non-Patent Citations (2)
| Title |
|---|
| The significant role of oxygen vacancy in Cu/ZrO2 catalyst for enhancing wateregas-shift performance;Chongqi Chen et al.;《International Journal Of Hydroogen Energy》;20131116;第39卷;317-324 * |
| 低温水煤气变换催化剂CuO/ZrO2的制备、表征与性能;阮春晓等;《催化学报》;20121231;第33卷(第5期);842-849 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105727944A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105727944B (en) | A kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst | |
| WO2020082410A1 (en) | Supported bimetal core-shell structure catalyst and preparation method therefor | |
| CN102946994B (en) | Nanometer-sized copper-based catalyst, production method thereof, and alcohol production method using the same through direct hydrogenation of carboxylic acid | |
| CN113145155B (en) | Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof | |
| CN109126823A (en) | Nitrobenzene selective hydrogenation prepares the catalyst and preparation method, application of aniline | |
| CN109201059A (en) | A kind of dimethyl oxalate selective hydrogenation methyl glycollate catalyst and its preparation method and application | |
| CN110102313B (en) | Preparation of ruthenium-nickel core-shell bimetallic nano-catalyst with limited domain structure and application of ruthenium-nickel core-shell bimetallic nano-catalyst in catalyzing selective hydrogenation of dimethyl terephthalate | |
| CN111715226A (en) | Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof | |
| CN114829004A (en) | Method for preparing Ni-X-based oxide catalyst and application thereof in transfer hydrogenation | |
| CN109225190A (en) | A kind of self-supporting hydrogenation catalyst and its preparation method and application | |
| Ma et al. | Au/Mg (OH) 2: Highly efficient for selective oxidation of 1, 2-propanediol to lactic acid with molecular oxygen | |
| CN107597119A (en) | Anti-carbon type cobalt-based low temperature methane carbon dioxide reformation catalyst and preparation method thereof | |
| CN106669681A (en) | Ni/Cu/Al/Fe hydrotalcite precursor catalyst with magnetism and preparation method and application thereof | |
| CN111514889A (en) | Ruthenium-based carbon dioxide hydromethanation catalyst and preparation method thereof | |
| CN111282575A (en) | Catalyst for methanol steam reforming hydrogen production and preparation method and application thereof | |
| CN113952960A (en) | Co-CeO for preparing low-carbon alcohol from synthetic gas2Catalyst, preparation method and application | |
| CN109876804A (en) | A kind of titanium dioxide loaded ruthenium catalyst and preparation method thereof adding hydrogen cyclohexene for benzene selective | |
| CN109092321B (en) | Catalyst system for preparing low-carbon olefin by synthesis gas one-step method | |
| CN105582957B (en) | Cobalt-based Fischer-Tropsch synthesis catalyst loaded on spherical carrier and preparation method thereof | |
| EA015831B1 (en) | Fischer-tropsch process | |
| CN110368953A (en) | A kind of composite oxide supported platinum catalyst and its preparation and application | |
| CN115138359B (en) | Supported single-atom synergistic nanoparticle bimetallic catalyst and preparation and application thereof | |
| CN112023963B (en) | Catalyst for synthesizing 1, 4-butynediol and application | |
| CN113649049A (en) | Maleic anhydride selective hydrogenation catalyst, and preparation method and application method thereof | |
| CN116196937A (en) | Supported monoatomic alloy catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |