CN105727944A - Preparation method of ZrO2 nanosheet supported ruthenium catalyst - Google Patents
Preparation method of ZrO2 nanosheet supported ruthenium catalyst Download PDFInfo
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- CN105727944A CN105727944A CN201610175982.7A CN201610175982A CN105727944A CN 105727944 A CN105727944 A CN 105727944A CN 201610175982 A CN201610175982 A CN 201610175982A CN 105727944 A CN105727944 A CN 105727944A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 29
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002135 nanosheet Substances 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract 2
- 239000002244 precipitate Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 230000009467 reduction Effects 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
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 7
- 150000003303 ruthenium Chemical class 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 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
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 51
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000011068 loading method Methods 0.000 abstract description 12
- 239000012266 salt solution Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000004873 anchoring Methods 0.000 abstract 1
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 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
- 239000007791 liquid phase Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910006219 ZrO(NO3)2·2H2O Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- OSKSAMGBRKRQOZ-UHFFFAOYSA-N benzene cyclohexene Chemical compound C1CCC=CC1.C1CCC=CC1.C1=CC=CC=C1 OSKSAMGBRKRQOZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000009826 distribution Methods 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
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- -1 cyclohexane halide Chemical class 0.000 description 3
- 230000029087 digestion Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002245 particle 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
- 239000003643 water by type Substances 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial 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
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 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 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid 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
- 238000012546 transfer 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 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
- 230000033228 biological regulation Effects 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete 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
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 238000010335 hydrothermal treatment Methods 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
- 230000003993 interaction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 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
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 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
- 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
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc 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
-
- B01J35/396—
-
- 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
Abstract
The invention discloses a preparation method of a ZrO2 nanosheet supported ruthenium catalyst. The catalyst is characterized in that metal Ru is supported on a ZrO2 nanosheet and the loading volume of Ru is 1wt%-10wt% (subjected to ZrO2). The preparation method comprises the following steps: with a hydrothermal-precipitation method, anchoring the active component Ru on the ZrO2 nanosheet (ZrO2-NS) for preparing a nanometer compound catalyst; mixing Ru and Zr soluble salt solutions and conducting hydrothermal reaction, thereby acquiring a catalyst precursor crystal nucleus; and introducing a precipitator, drying and reducing, thereby acquiring the ZrO2 nanosheet supported ruthenium catalyst (Ru/ZrO2-NS). Compared with other supported type benzene hydrogenation catalyst, the catalyst prepared according to the method provided by the invention has the advantages that Ru is uniformly distributed on the ZrO2 nanosheet, the dispersity is high and the preparation process is simple, when applied to reaction for local benzene hydrogenation for preparing cyclohexene, the catalyst has the advantages of high conversion rate, excellent selectivity and high stability.
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 the production of medicine, agricultural chemicals, feedstuff, polyester material and other fine chemical products.Cyclohexene is typically to be prepared by dehydration of cyclohexanol, and traditional preparation methods includes that cyclohexane halide takes off halocarbon method and Brich reducing process, but all there is complex process, the shortcoming such as side-product is many, energy resource consumption is big and environmental pollution is serious.Comparatively speaking, partial hydrogenation of benzene cyclohexene there is Atom economy, it is possible to decrease energy consumption, increase economic efficiency.But, in terms of thermodynamics, it is-23 KJ mol that partial hydrogenation of benzene generates the standard Gibbs free energy change of cyclohexene-1, and the free energy change that benzene complete hydrogenation generates hexamethylene is-98 KJ mol-1, illustrate that the reaction of partial hydrogenation of benzene cyclohexene is thermodynamically totally unfavorable.Thus, research and develop high performance catalyst, particularly there is the selective catalyst of high cyclohexene and seem particularly important.
The double bond of cyclohexene is more active than the big π key of phenyl ring, and cyclohexene is hydrogenated to hexamethylene the most further, and reaction is difficult to rest on the generation cyclohexene stage.Hartog in 1963 only obtains 0.18 in benzene liquid-phase hydrogenatin process with ruthenium black for catalyst
The cyclohexene of mol%.Nineteen sixty-five Stamicarbon
N.V company delivers patent 660 in Belgium, and 742 propose can be improved the selectivity of benzene liquid phase selective Hydrogenation cyclohexene by the low-carbon alcohols adding C1-C4, particularly add methanol, and selectivity is up to 20%.1972, DuPont, at Deutsche Bundespatent 2, was pointed out with RuCl in 221,1373For precursor, with titanous chloride., chromium dichloride, sodium borohydride or hydrogen etc. as reducing agent, in alkaline aqueous solution, benzene hydrogenation process cyclohexene yield reaches 30 %.1975, for avoiding alkaline aqueous solution system to carrier and reaction equipment etching problem, improving the stability of catalyst, Philip oil company Gerhard etc. is in patent US 3, and 912,787 is open with metal Ru as catalyst, Al2O3Or 23K-S is carrier, VIB, group VIIIB element of Fe, Cr, Co, Ni, W, Mo are auxiliary agent, realize cyclohexene yield 20.2 % in the water solution system of pH < 7.5.1988, Japan Asahi company Nagahara etc., in patent US 4, proposed on 734,536 to use with the crystallite dimension metal Ru less than 20 nm as catalyst, introduces auxiliary agent ZnSO in reacting slurry4·7H2O and dispersant ZrO2Or HfO2, react 20
Min cyclohexene yield about 26 %, reacts 65
Min right and left rings hexene yield is close to 50 %.1989, Asahi company of Japan utilized non-loading type RuZn catalyst to achieve the industrialization of partial hydrogenation of benzene cyclohexene.But non-loading type nanometer Ru catalyst is easily caused growing up of Ru crystallite because of particles collision in course of reaction, cause irreversible inactivation, there is product simultaneously and catalyst is difficult to separate and loss problem.
Last century, the nineties rose, and during solving partial hydrogenation of benzene, non-loading type Ru catalyst is easily grown up because of impingment particle and caused Catalysts Deactivation Problems, and the most many researcheres are devoted to the preparation of support type Ru base catalyst.US 4,678,861 discloses a kind of method preparing cycloolefin, and the method used catalyst is carried on by infusion process on the rare earth element composition bimetallic complex carriers such as La or La-Zn, and is prepared by hydrogen reduction method.US
5,569,803 disclose one with ZrO2Modified SiO2For carrier, dip loading Ru catalyst.US 5,414,171 discloses a kind of with La2O3Modified SiO2Or Al2O3For complex carrier, dip loading Ru catalyst.US 6,060,423 discloses the Ru catalyst with Ga-Zn bimetallic as complex carrier, prepares supported Ru catalysts by incipient impregnation and liquid-phase reduction.Patent CN1424293A discloses a kind of employing coprecipitation and prepares support type Ru base catalyst, by ZrOCl2·8H2O and ammonia are simultaneously added dropwise to RuCl3·xH2O, carrier exists with colloid or amorphous state, obtains support type Ru/ZrO by liquid-phase reduction2·xH2O catalyst.Patent CN101219391A discloses a kind of employing solvent pairs infusion process and prepares MCM-41, the Ru base catalyst of HMS, SBA-15 load.Patent CN 103480393 A discloses and a kind of uses surfactant-modified sedimentation method synthesis Zr-Al-O composite oxide carrier, prepares support type Ru base catalyst through deposition sedimentation and liquid-phase reduction after roasting.
Above-mentioned supported Ru catalysts mainly uses the infusion process of routine or coprecipitation to prepare, or it is loaded down with trivial details to there is process, or ruthenium dispersion is low, or the problem that catalysis active selectable is not enough, the most unrealized industrialization.
Summary of the invention
It is an object of the invention to provide a kind of ZrO2The preparation method of nanometer sheet supported ruthenium catalyst.Simplify preparation process, optimize the texture of catalyst, promote reaction mass transfer process, solve catalyst non-loading type noble metal Ru consumption big, it is easy to the problem of inactivation of reuniting.
For achieving 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 ZrO2It is 100:1-10(i.e. Ru load capacity 1-10 wt.% with the mass ratio of Ru, with ZrO2On the basis of), its preparation method is: use hydro-thermal-sedimentation method to prepare, active component Ru is anchored to ZrO2Nanometer sheet (ZrO2-NS) surface forms nano-composite catalyst, and the most first active component (ruthenium saline solution) and supporting electrolyte solution (solubility zirconates) hydro-thermal are formed nucleus, then makes it precipitate by introducing precipitant, and drying, reduction roasting prepare ZrO2Nanometer sheet load ruthenium (Ru/ZrO2-NS) catalyst；Concrete preparation process is as follows:
(1) at room temperature, weighing solubility zirconates and ruthenium salt is made into the mixed solution of 150-160 mL, be transferred in band polytetrafluoroethyllining lining reactor carry out hydrothermal treatment consists, hydrothermal temperature 130-200 DEG C, the hydro-thermal time controls at 3-18 h；Preferably hydrothermal temperature is 170 DEG C, and the hydro-thermal time is 6 h, and product is khaki suspension；
(2) under stirring, precipitant is added drop-wise in above-mentioned suspension slowly, at 40 DEG C-90 DEG C, is aged 6-20 h；
(3) precipitate that step (2) obtains is washed by centrifugation, vacuum drying, H in tube furnace2In 150 DEG C-450 DEG C reduction roasting 4-8h under atmosphere, obtain Ru/ZrO2-NS catalyst.
Described in above-mentioned preparation method step (1), solubility zirconates is ZrOCl2·8H2O and ZrO (NO3)2·2H2One or more in O；Solubility ruthenium salt is RuCl3·3H2O、C14H27O18Ru3、KRuO4With RuNO (NO3)3In one or more.When with KRuO4During for precursor, step (1) can add a small amount of ethanol, and the mixing ratio of second alcohol and water is (1-10): 100.Owing to zirconates and ruthenium mixed salt solution are acidity, the nucleus of water-heat process part metals salt formation precursor.
In rate-determining steps (2), precipitation terminates pH value is 9-13, makes all of slaine change into hydroxide precipitation on the basis of the nucleus of precursor, forms flaky nanometer structure；In step (2), precipitant is one or more in carbamide, NaOH, KOH and ammonia, Aging Temperature 40-90 DEG C, digestion time 6-20
H, gained is precipitated as blackish green.When precipitant is carbamide, preferred Aging Temperature is 90 DEG C, and the digestion time of optimization is 20 h.When selecting other precipitant, preferred Aging Temperature is 60 DEG C, and the digestion time of optimization is 4 h.
In step (3), wash solution is one or more in deionized water, weak ammonia and acetone solvent, and washing times is 4-6 time.When zirconates is ZrOCl2·8H2O, ruthenium salt is RuCl3·3H2During O, preferred washing medium is acetone or deionized water or the washing of their mixture；When zirconates is ZrO (NO3)2·2H2O, ruthenium salt is KRuO4Or RuNO (NO3)3During solution, select deionized water or weak ammonia washing.Due to Ru (OH)4Solubility product (~ 1.0 × 10-44) less than Ru (OH)3Solubility product (~ 1.0 × 10-38), it is trivalent ruthenium (RuCl when selecting ruthenium salt3·3H2O or C14H27O18Ru3) time, drip 1 mL 30 wt.% H before washing2O2Solution so that it is change into tetravalence ruthenium Ru (IV), to reduce washing process Ru loss.
Catalyst reduction described in above-mentioned preparation method step (3) is to add thermal reduction under an atmosphere of hydrogen, and preferred temperature is 200 DEG C, and the recovery time is 6 h.
A kind of ZrO as above2Nanometer sheet supported ruthenium catalyst is applied to be catalyzed partial hydrogenation of benzene cyclohexene, joins in autoclave by described catalyst, and catalyst is passivated improving catalyst choice by one or more added in the soluble sulphate of Zn, Fe and Cd.
The present invention has built a homogeneous environment by the presoma that hydro-thermal is active component and carrier, owing to the zirconates used and ruthenium mixed salt solution are acid, the nucleus that water-heat process part metals salt formation is tiny, the formation of these nucleus determines precipitation process and obtains the ZrO of laminated structure2Presoma.Utilize Zr (OH)4Solubility product 6.4 × 10-49Less than Ru (OH)3With Ru (OH)4The characteristic of solubility product, makes Ru precursor uniform deposition on carrier, and the catalyst Ru dispersion of preparation is high.
The beneficial effects of the present invention is:
(1) loaded catalyst prepared by the present invention, with nano-sheet ZrO2As carrier, Ru catalyst can be carried on carrier equably, is distributed in island；When Ru content is 5 wt.%, the dispersion of Ru reaches 14.7 %, and far above non-loading type Ru catalyst (dispersion of Ru is only 2.9 %), the active force between Ru and carrier strengthens；
(2) utilize the texturizing properties that nano-sheet is unique, be conducive to improving course of reaction H2Internal diffusion, the liquid-solid diffusion of cyclohexene, promote gas-solid-water-oily four phase reactions in partial hydrogenation of benzene course of reaction；Utilize ZrO simultaneously2The hydroxyl that surface is abundant, promotes the desorption of cyclohexene, improves the activity of catalyst, selectivity and stability；
(3) industrial non-loading type Ru catalyst content is (with ZrO2On the basis of dispersant, typically at about 18 wt.%), by improving the dispersion of Ru metal in the present invention, when obtaining the catalytic performance suitable with industrial catalyst, it is possible to decrease the usage amount of Ru, save catalyst cost, there is the highest industrial application value.
Accompanying drawing explanation
Fig. 1 X-ray powder diagram；(a). non-loading type Ru catalyst；(b) .) carrier ZrO2-NS； (c)
. the Ru/ZrO that the embodiment of the present invention 1 prepares2-NS nanocatalyst；
Fig. 2 scanning electron microscope (SEM) photograph；(a). carrier ZrO2-NS；(b). comparative example 1 sample of the present invention；(c). embodiment 1 sample；
Fig. 3 is the graph of pore diameter distribution of the catalyst that the embodiment of the present invention 1 obtains；
Fig. 4 scanning electron microscope (SEM) photograph；(a). embodiment 1, (b). embodiment 2, (c). embodiment 3 and (d). the catalyst that embodiment 4 obtains.
Detailed description of the invention
For being further elucidated with the present invention, elaborate with embodiment below, and provide accompanying drawing and describe specificity of catalyst prepared by the present invention and characterize, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Weigh 1.3 g RuNO (NO3)3、17.1 g ZrO(NO3)2·2H2O is dissolved in 156
In mL deionized water, it is transferred in the water heating kettle that volume is 200 mL, in 170 DEG C of hydro-thermal 6 h, naturally cools to room temperature and i.e. obtain khaki serosity；Taking out serosity, using 10 wt.% NaOH solution as precipitant, precipitate in 60 DEG C, controlling precipitation and terminating pH is 9, still aging 4 h；By gained precipitate with deionized water centrifuge washing to neutral；By precipitate after 80 DEG C of vacuum drying 12 h, 200 DEG C of roasting 6 h under an atmosphere of hydrogen.
Embodiment 2
Weigh 0.48 g KRuO4、17.1 g ZrO(NO3)2·2H2O is dissolved in 156
In the alcoholic solution of mL 10 vol.%, it is transferred in the water heating kettle that volume is 200 mL, in 130 DEG C of hydro-thermal 18 h, naturally cools to room temperature and i.e. obtain khaki serosity；Taking out serosity, using 10 wt.% KOH solution as precipitant, precipitate in 70 DEG C, controlling precipitation and terminating pH is 13, still aging 12 h；By gained precipitate with deionized water centrifuge washing to neutral；By precipitate after 80 DEG C of vacuum drying 12 h, 450 DEG C of roasting 4 h under an atmosphere of hydrogen.
Embodiment 3
Weigh 2.14 g RuCl3·3H2O、20.6
g ZrOCl2·8H2O is dissolved in 150 mL deionized waters, is transferred in the water heating kettle that volume is 200 mL, in 150 DEG C of hydro-thermal 12 h, naturally cools to room temperature and i.e. obtains khaki serosity；Taking out serosity, using 10 wt.% NaOH solution as precipitant, precipitate in 80 DEG C, controlling precipitation and terminating pH is 10, and still aging 12 h add 1 mL 30 wt.% H2O2Solution；By the mixed liquor centrifuge washing of gained precipitate acetone and deionized water (volume ratio 1:5) to using AgNO3Solution detection exists without chloride ion；By precipitate after 80 DEG C of vacuum drying 12 h, 300 DEG C of roasting 4 h under an atmosphere of hydrogen.
Embodiment 4
Weigh 5.33 g C14H27O18Ru3、17.1 g ZrO(NO3)2·2H2O is dissolved in 156
In mL deionized water, it is transferred in the water heating kettle that volume is 200 mL, in 200 DEG C of hydro-thermal 6 h, naturally cools to room temperature and i.e. obtain khaki serosity；Taking out serosity, using 10 wt.% ammonia spirits as precipitant, precipitate in 60 DEG C, controlling precipitation and terminating pH is 9, and still aging 6 h add 1 mL 30 wt.% H2O2Solution；By gained precipitate with deionized water centrifuge washing to neutral；By precipitate after 80 DEG C of vacuum drying 12 h, 200 DEG C of roasting 6 h under an atmosphere of hydrogen.
Embodiment 5
Weigh 0.25 g RuNO (NO3)3、17.1 g ZrO(NO3)2·2H2O is dissolved in 156
In mL deionized water, it is transferred in the water heating kettle that volume is 200 mL, in 200 DEG C of hydro-thermal 18 h, naturally cools to room temperature and i.e. obtain khaki serosity；Taking out serosity, using 1.2 M urea liquids as precipitant, precipitate in 90 DEG C, controlling precipitation and terminating pH is 10, still aging 20 h, gained precipitate weak ammonia centrifuge washing；By precipitate after 80 DEG C of vacuum drying 12 h, 200 DEG C of roasting 8 h under an atmosphere of hydrogen.
Embodiment 6
Weigh 0.4 g RuCl3·3H2O、20.6
g ZrOCl2·8H2O is dissolved in 150 mL deionized waters, is transferred in the water heating kettle that volume is 200 mL, in 150 DEG C of hydro-thermal 10 h, naturally cools to room temperature and i.e. obtains khaki serosity；Taking out serosity, using 10 wt.% ammonia spirits as precipitant, precipitate in 40 DEG C, controlling precipitation and terminating pH is 10, and still aging 6 h add 1 mL 30 wt.% H2O2Solution, by the mixed liquor centrifuge washing of gained precipitate acetone and deionized water (volume ratio 1:5) to using AgNO3Solution detection exists without chloride ion；By precipitate after 80 DEG C of vacuum drying 12 h, 150 DEG C of roasting 8 h under an atmosphere of hydrogen.
Comparative example 1
Weigh 20.6 g ZrOCl2·8H2O is dissolved in 152
In mL deionized water, it is transferred in the water heating kettle that volume is 200 mL, in 150 DEG C of hydro-thermal 12 h, naturally cools to room temperature and i.e. obtain milky serosity；Taking out serosity, using 10 wt.% NaOH solution as precipitant, precipitate in 80 DEG C, controlling precipitation and terminating pH is 10, still aging 12 h；By the mixed liquor centrifuge washing of gained precipitate acetone and deionized water (volume ratio 1:5) to using AgNO3Solution detection exists without chloride ion；By precipitate after 80 DEG C of vacuum drying 12 h, 300 DEG C of roasting 4 h under an atmosphere of hydrogen, both obtained ZrO2-NS。
Weigh 1.07 g RuCl3·3H2O is dissolved in 150 mL deionized waters, using 10 wt.% NaOH solution as precipitant, precipitates in 80 DEG C, and controlling precipitation and terminating pH is 10, and still aging 12 h add few drops H2O2Solution；By the mixed liquor centrifuge washing of gained precipitate acetone and deionized water (volume ratio 1:5) to using AgNO3Solution detection exists without chloride ion；By precipitate in autoclave 5.0
MPa H2Pressure, reduces 4 h under the conditions of 150 DEG C, obtain non-loading type Ru catalyst.
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 methodology of the present invention and domestic and foreign literature data have comparability.The partial hydrogenation reaction of liquid phase benzene is carried out in Buchiglasuster company limbo high-pressure mini reactor, 0.6 g Ru/ZrO2-NS nano-composite catalyst, 80 mL H2O, 0.035
mol ZnSO4·7H2O；140 DEG C, stir speed (S.S.) 900 r min-1With Hydrogen Vapor Pressure 4.5
Prereduction under the conditions of MPa；Rise to 150 DEG C and add 40 mL benzene, regulation rotating speed to 1200 r min-1Start to react timing.Use GC-2010 chromatographic product composition, fid detector, it is thus achieved that benzene conversion ratio and cyclohexene selectivity.
Catalyst prepared by table 1 embodiment 1-6 is the conversion ratio of benzene, the selectivity of cyclohexene and yield when partial hydrogenation of benzene reacts 25 min
Table 2 embodiment 1 contrasts with the partial hydrogenation of benzene reaction stability of comparative example 1
Note: test condition, with activity rating method, is often taken turnsResponse time is 25 min, separates organic facies, without prereduction, rejoin benzene and carry out test evaluation before loop test.
Fig. 1 c does not observes the diffraction maximum of active component Ru, illustrates that Ru is highly dispersed in carrier surface；Compared with Fig. 1 b, its ZrO2Characteristic diffraction peak wideization, relative intensity is also varied from, Ru and ZrO is described2There is certain interaction.
It can be seen that work as ZrO from Fig. 2 b2Can not sufficiently disperse as catalyst during dispersant, and use Ru/ZrO prepared by hydrothermal co-precipitation method2-NS(Fig. 2 c) it is little to see isolated Ru particle, Ru is mainly dispersed in ZrO2On, become island distribution.
From figure 3, it can be seen that the Ru/ZrO of hydro-thermal-sedimentation method one-step synthesis2The pore size distribution of-NS catalyst, near 3 nm and 40 nm, becomes diplopore distribution, and this is beneficial to the carrying out of gas-solid in partial hydrogenation of benzene course of reaction-water-oily four phase reaction mass transfers.
From fig. 4, it can be seen that the catalyst obtained is two-dimensional nano chip architecture.
The foregoing is only the more typically embodiment of the present invention, all impartial changes done according to scope of the present invention patent and modification, come under the covering scope of the present invention.
Claims (6)
1. a ZrO2The preparation method of nanometer sheet supported ruthenium catalyst, it is characterised in that: it is carried on ZrO by metal Ru2In nanometer sheet, wherein ZrO2It is 100:1-10 with the mass ratio of Ru；Use hydro-thermal-sedimentation method to prepare, comprise the steps:
(1) at room temperature, weigh solubility zirconates and ruthenium salt is made into 150-160
The mixed solution of mL, moves to band polytetrafluoroethyllining lining reactor, carries out hydro-thermal reaction, it is thus achieved that khaki suspension；
(2) under stirring, precipitant is slowly dropped in above-mentioned suspension, is aged 6-20 hour at 40 DEG C-90 DEG C；
(3) being washed 4-6 time by centrifugation by the precipitate that step (2) obtains, vacuum drying, at H2In 150-450 DEG C of reduction roasting 4-8h under atmosphere, obtain described catalyst.
A kind of ZrO the most according to claim 12The preparation method of nanometer sheet supported ruthenium catalyst, it is characterised in that: described in step (1), hydrothermal temperature is 130-200 DEG C, hydro-thermal time 3-18 h.
Method the most according to claim 1, it is characterised in that: described in step (1), solubility zirconates is ZrOCl2·8H2O and ZrO (NO3)2·2H2One or both in O；Solubility ruthenium salt is RuCl3·3H2O、C14H27O18Ru3、KRuO4With RuNO (NO3)3In one or more.
Method the most according to claim 1, it is characterised in that: in rate-determining steps (2), precipitation terminates pH value is 9-13；Precipitant is one or more in carbamide, NaOH, KOH and ammonia.
Method the most according to claim 1, it is characterised in that: when ruthenium salt is RuCl3·3H2O or C14H27O18Ru3Time, step (3) adds 1 mL 30 wt.% H in precipitated product before washing2O2Solution.
Method the most according to claim 1, it is characterised in that: in step (3), wash solution is one or more in deionized water, weak ammonia and acetone solvent.
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