CN110479259B - Supported Ru-based catalyst with molybdenum oxide-zinc oxide-zirconium oxide composite oxide as carrier - Google Patents
Supported Ru-based catalyst with molybdenum oxide-zinc oxide-zirconium oxide composite oxide as carrier Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 10
- -1 molybdenum oxide-zinc oxide-zirconium oxide Chemical compound 0.000 title description 2
- 238000003756 stirring Methods 0.000 claims abstract description 37
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 150000002751 molybdenum Chemical class 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 239000011686 zinc sulphate Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 63
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 7
- 229910019891 RuCl3 Inorganic materials 0.000 description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 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
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000013490 limbo Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- 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
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention relates to the use of MoO3‑ZnO‑ZrO2The preparation method of the supported Ru-based catalyst with the composite oxide as the carrier comprises the active components of Ru and MoO3‑ZrO2-ZnO composite oxide carrier composition, and the preparation method comprises: prepared by adopting a dipping deposition precipitation-chemical reduction method, and ZrO is added under the stirring condition2Adding the carrier into the mixed aqueous solution of Mo salt and Zn salt, adding a precipitator, drying and roasting to obtain MoO3‑ZnO‑ZrO2Carrier, finally activating active component Ru by chemical reduction method to obtain MoO3‑ZnO‑ZrO2A Ru-based catalyst which is a support. The catalyst prepared by the invention has the advantages of simple preparation process, less consumption of the active component Ru, high activity, selectivity, stability and the like when being applied to the process of preparing cyclohexene by benzene selective hydrogenation.
Description
Technical Field
The invention relates to MoO3-ZnO-ZrO2A load type Ru-based catalyst with composite oxide as a carrier and a preparation method thereof belong to the technical field of catalyst preparation.
Background
As early as the last century, cyclohexene was produced primarily by dehydration of cyclohexanol, dehydrohalogenation of halogenated cyclohexane and Brich reduction. The traditional method has many disadvantages (such as complex process, high energy consumption, low yield, high cost, large pollution and the like), and the application range of the cyclohexene is limited. With the development of the synthesis industry, the demand of nylon-6 and nylon-66 is increasing, and the exploration of new processes for producing cyclohexene on a large scale is urgent. At present, the process widely adopted at home and abroad is a new method for preparing cyclohexene by catalytic selective hydrogenation by taking cheap benzene as a raw material. Compared with the traditional complete hydrogenation process route, the process route for preparing the nylon-6 and the nylon-66 by using the benzene as the raw material and then preparing the cyclohexanol by hydrating the cyclohexene has the advantages of low energy consumption and less hydrogen consumption of the new process; the effective utilization rate of carbon is as high as 99 percent; and one third less hydrogen is consumed. The development and application of the method for preparing cyclohexene by benzene selective hydrogenation obviously reduce the cost for generating cyclohexene, and can meet the requirement of industrial large-scale production of various important chemical products.
Benzene is a typical aromatic compound, contains conjugated large pi bonds and has high chemical stability. Relatively speaking, the carbon-carbon double bond of cyclohexene is extremely active and very easy to enterAnd (4) carrying out hydrogenation reaction. Although cyclohexene was a theoretical intermediate in the hydrogenation of benzene, it was long known to scholars, Anderson et al, until 1957, first experimentally confirmed the presence of trace amounts of cyclohexene in the hydrogenation of benzene. The rationality of the proposed benzene hydrogenation mechanism was demonstrated. Namely, the benzene in the adsorption state and the cyclohexane gradually generated by dispersing the hydrogen adsorbed on the catalyst. In 1963, Hartog and colleagues used ruthenium black as a catalyst and aromatic alcohol in the process of benzene liquid phase hydrogenation, and liquid phase benzene hydrogenation was carried out at normal temperature and normal pressure, and the yield of cyclohexene obtained was 2.2%. In 1972, Drinkard et al, DuPont, USA, made a breakthrough, and the cyclohexene yield increased to 32%. In 1988, Nagahara et al, Asahi, Japan, proposed the use of a ruthenium metal having a grain size of less than 20 nm as a catalyst and the introduction of a ZnSO auxiliary agent into the reaction slurry4·7H2O and a dispersant ZrO2Or HfO2The cyclohexene yield is about 26% after 20 min of reaction, and the cyclohexene yield is about 50% after 65 min of reaction. In 1990, the japan asahi chemical company has first achieved the industrial production of cyclohexene by the partial hydrogenation of benzene, and the asahi chemical company has been monopolized in the field of catalysts for the hydrogenation of benzene to cyclohexene.
At present, when the industrial operation index is 40 percent of benzene conversion, the selectivity of cyclohexene reaches more than 80 percent. However, the non-supported RuZn catalyst produced by Asahi formation has large use amount of Ru, high manufacturing cost, and irreversible inactivation caused by growth of Ru microcrystal due to particle collision in the reaction, and the separation of the nano-scale catalyst from the product is difficult. For this reason, the domestic patents mostly adopt ZrO2、Al2O3、SiO2SBA-15, composite oxides and other carriers to load metal Ru (CN 103785477A, CN 100496728C, CN 1978053B, CN 101219391A, CN 1015492925B), aiming at solving the problem that the catalyst and the product are difficult to separate. However, the noble metal Ru supported by the catalyst has larger dosage, which is not beneficial to reducing the production cost.
Disclosure of Invention
The invention aims to overcome the defects of large using amount of noble metal Ru and easy agglomeration and inactivation in a non-supported catalyst, and provides a supported Ru-based catalyst for preparing cyclohexene by benzene hydrogenation and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: para-ZrO2The supported Ru-based catalyst modified by carrier is prepared by supporting metal Ru on MoO3-ZnO-ZrO2On a support, wherein the loading of Ru is 5wt% (in MoO)3-ZnO-ZrO2Carrier is taken as benchmark), Mo is 0.1-0.5wt% of the carrier, Zn is 0.5-5wt% of the carrier, and the preparation method comprises the following steps: prepared by adopting a dipping deposition precipitation-chemical reduction method, firstly MoO3And ZnO is deposited on ZrO2Forming a composite oxide carrier on the surface of the carrier, and anchoring the active component Ru to MoO3-ZnO-ZrO2Forming a supported Ru-based catalyst on the surface; the preparation method comprises the following specific steps:
(1) under the condition of stirring, soluble Mo salt and Zn salt are dissolved in deionized water, and ZrO with a certain proportion is added2Stirring for reaction for 0.5-1 h, adding precipitant to adjust pH to 8-10, stirring for 1-2h, drying, and calcining to obtain MoO3-ZnO-ZrO2Carrier, product is MoO3-ZnO-ZrO2A white solid; (ii) a
(2) Dissolving the carrier prepared in the step (1) in deionized water according to the mass-to-volume ratio of 1:10-15 g/mL under the condition of stirring, simultaneously and respectively adding a Ru salt water solution and a 5wt% sodium hydroxide solution to adjust the pH to 6-10, preferably to 9.5 under the condition of stirring, continuously stirring for 1-5 h, slowly adding a sodium borohydride water solution, and stirring for 1 h; the volume ratio of the deionized water to the Ru salt water solution to the sodium borohydride water solution is 5:2: 1;
(3) centrifugally washing the precipitate obtained in the step (2) for 3-5 times, and drying in vacuum to obtain Ru-B/MoO3-ZnO-ZrO2A catalyst.
The soluble molybdenum salt in the step (1) is molybdenum salt (NH)4)6Mo7O24∙4H2O, soluble zinc salt being Zn (NO)3)2∙6H2O、ZnSO4∙H2O or Zn (CH)3COO)2At a precipitation stop pH of 8-10, converting all zinc salts to hydroxidesPrecipitating, and loading the molybdenum salt in a dipping and adsorbing form. .
Molybdenum salt, zinc salt and ZrO described in step (1)2The molar mass ratio of (1: 1-25: 300-.
The precipitator in the step (1) is any one of urea, ammonium bicarbonate and ammonia water, and the concentration of the precipitator is 10-15 wt%.
In the step (1), the drying temperature is 100 ℃, the drying time is 2 hours, the roasting temperature is 300 ℃, and the roasting time is 1 hour.
The mass ratio of the Ru salt to the carrier in the step (2) is 1: 1-10; the concentration of the sodium borohydride aqueous solution is 0.5-1.5 mol/L.
The pH is maintained at 6 to 10 in the step (2) of the above production method so that the supported ZrO becomes2The above ZnO is not dissolved by the acidity of ruthenium salt, and the reaction of adding sodium borohydride is milder.
The invention has the beneficial effects that:
the supported Ru-based catalyst prepared by the invention is used for ZrO by using an immersion deposition precipitation method2By calcining the obtained composite oxide MoO3-ZnO-ZrO2The catalyst is a carrier, so that the hydrophilicity of the catalyst is greatly improved, the selectivity of the catalyst is obviously improved, and the sulfur resistance of the catalyst is improved; meanwhile, the uniform loading and activation of the Ru precursor are realized in a parallel flow mode, the aggregation of an active component Ru is effectively inhibited, and the activity, selectivity and stability of the catalyst are obviously improved. When the content of Ru is 5wt%, the dispersion degree of Ru reaches 16.7%, which is much higher than that of non-load Ru-based catalyst (the dispersion degree of Ru is only 2.9%), the utilization rate of noble metal Ru as an active component is improved, and the use amount of noble metal Ru (MoO) is reduced3-ZnO-ZrO2An activity and industrial non-supported RuZn catalyst (taking ZrO) under the premise that the content of Ru on the basis of a carrier is 5wt percent2The dispersant is taken as a reference, and the amount of Ru is about 18 wt percent), thereby greatly reducing the production cost of the catalyst and leading the catalyst to have higher application prospect.
Drawings
FIG. 1 shows Ru-B/MoO3-ZnO-ZrO2CatalysisXRD pattern of the agent.
FIG. 2 shows Ru-B/MoO3-ZnO-ZrO2Pore size distribution of the catalyst.
Detailed Description
To further illustrate the present invention, the following examples are given as illustrations describing the characterization of the catalyst prepared according to the present invention.
Example 1
(1) Preparation of zirconia
To 125 g of 750 mL ZrOCl2·8H2And (3) gradually adding 12.5 wt% of ammonia water into the O aqueous solution until the pH value of the solution reaches 10, stirring and refluxing for 48 h at 100 ℃ to obtain a white precipitate, washing for 3 times by using deionized water, washing for 2 times by using absolute ethyl alcohol, drying the precipitate for 24 h at 60 ℃, and roasting for 5 h at 800 ℃ to obtain the zirconium oxide powder. ZrO (ZrO)2The characterization shows that: ZrO (ZrO)2The specific surface area is 83.7 m2Per g, pore volume 0.38 cm3/g-1Average pore diameter of 18.3 nm.
(2) Preparation of the catalyst
4.5 g of the above-mentioned ZrO were weighed2Dispersed in 0.029g (NH)4)6Mo7O24∙4H2O and 0.174 g Zn (NO)3 )2∙6H2Stirring the mixture for 0.5 h in 10 mL of aqueous solution prepared from O, adding 10wt% ammonium bicarbonate solution to adjust the pH value to 8, further stirring for 1h, drying the mixture for 2h in a drying box at the temperature of 100 ℃, and roasting the mixture for 1h in a muffle furnace at the temperature of 300 ℃. Weighing 4 g of the carrier, dissolving in 50 mL of deionized water, and stirring 0.602 g of 20 mL RuCl3·3H2The aqueous O solution and 5wt% NaOH solution were added together and the pH adjusted to 9.5, stirred for 3.5 h, and 0.315 g of 10 mL NaBH slowly added4The aqueous solution was stirred for 1 h. Centrifugally washing the obtained precipitate with deionized water to neutrality; the precipitate was dried under vacuum at 80 ℃ for 24 h.
Example 2
(1) Zirconium oxide example 1
(1) Preparation of the catalyst
4.5 g of ZrO were weighed2Dissolving in 0.029g (NH)4)6Mo7O24∙4H2O and 0.348 g Zn (NO)3 )2∙6H2Stirring the mixture for 0.5 h in 10 mL of aqueous solution prepared from O, adding 10wt% ammonium bicarbonate solution to adjust the pH value to 8, further stirring for 1h, drying the mixture for 2h in a drying box at the temperature of 100 ℃, and roasting the mixture for 1h in a muffle furnace at the temperature of 300 ℃. Weighing 4 g of the carrier, dissolving in 50 mL of deionized water, and stirring 0.602 g of 20 mL RuCl3·3H2The aqueous O solution and 5wt% NaOH solution were added together and the pH adjusted to 9.5, stirred for 3.5 h, and 0.315 g of 10 mL NaBH slowly added4The aqueous solution was stirred for 1 h. Centrifugally washing the obtained precipitate with deionized water to neutrality; the precipitate was dried under vacuum at 80 ℃ for 24 h.
Example 3
(1) Zirconium oxide example 1
(2) Preparation of the catalyst
4.5 g of ZrO were weighed2Dissolved in 0.015 g (NH)4)6Mo7O24∙4H2O and 0.523 g Zn (NO)3 )2∙6H2Stirring the mixture for 0.5 h in 10 mL of aqueous solution prepared from O, adding 10wt% ammonium bicarbonate solution to adjust the pH value to 8, further stirring for 1h, drying the mixture for 2h in a drying box at the temperature of 100 ℃, and roasting the mixture for 1h in a muffle furnace at the temperature of 300 ℃. Weighing 4 g of the carrier, dissolving in 50 mL of deionized water, and stirring 0.602 g of 20 mL RuCl3·3H2The aqueous O solution and 5wt% NaOH solution were added together and the pH adjusted to 9.5, stirred for 3.5 h, and 0.315 g of 10 mL NaBH slowly added4The aqueous solution was stirred for 1 h. Centrifugally washing the obtained precipitate with deionized water to neutrality; the precipitate was dried under vacuum at 80 ℃ for 24 h.
Example 4
(1) Zirconium oxide example 1
(2) Preparation of the catalyst
4.5 g of ZrO were weighed2Dissolved in 0.015 g (NH)4)6Mo7O24∙4H2O and 0.697 g Zn (NO)3 )2∙6H2O into 10 mL of aqueous solution, stirring for 0.5 h, adding 10wt% ammonium bicarbonateThe solution was adjusted to pH 8 and stirred for 1h, then dried in a drying oven at 100 ℃ for 2h and calcined in a muffle furnace at 300 ℃ for 1 h. Weighing 4 g of the carrier, dissolving in 50 mL of deionized water, and stirring 0.602 g of 20 mL RuCl3·3H2The aqueous O solution and 5wt% NaOH solution were added together and the pH adjusted to 9.5, stirred for 3.5 h, and 0.315 g of 10 mL NaBH slowly added4The aqueous solution was stirred for 1 h. Centrifugally washing the obtained precipitate with deionized water to neutrality; the precipitate was dried under vacuum at 80 ℃ for 24 h.
Example 5
(1) Zirconium oxide example 1
(2) Preparation of the catalyst
4.5 g of ZrO were weighed2Dissolving in 0.029g (NH)4)6Mo7O24∙4H2O and 0.215 g Zn (CH)3COO)2The prepared 10 mL of aqueous solution is stirred for 0.5 h, 10wt% ammonium bicarbonate solution is added to adjust the pH value to 8, the stirring is continued for 1h, then the mixture is dried for 2h in a drying box at the temperature of 100 ℃, and the mixture is roasted for 1h in a muffle furnace at the temperature of 300 ℃. Weighing 4 g of the carrier, dissolving in 50 mL of deionized water, and stirring 0.602 g of 20 mL RuCl3·3H2The aqueous O solution and 5wt% NaOH solution were added together and the pH adjusted to 9.5, stirred for 3.5 h, and 0.315 g of 10 mL NaBH slowly added4The aqueous solution was stirred for 1 h. Centrifugally washing the obtained precipitate with deionized water to neutrality; the precipitate was dried under vacuum at 80 ℃ for 24 h.
Example 6
(1) Zirconium oxide example 1
(2) Preparation of the catalyst
4.5 g of ZrO were weighed2Dissolving in 0.029g (NH)4)6Mo7O24∙4H2O and 0.337 g ZnSO4·7H2Stirring the mixture for 0.5 h in 10 mL of aqueous solution prepared from O, adding 10wt% ammonium bicarbonate solution to adjust the pH value to 8, continuing stirring for 1h, drying the mixture for 2h in a drying box at the temperature of 100 ℃, and roasting the mixture for 1h in a muffle furnace at the temperature of 300 ℃. Weighing 4 g of the carrier, dissolving in 50 mL of deionized water, and stirring 0.602 g of 20 mL RuCl3·3H2The aqueous O solution and 5wt% NaOH solution were added together and the pH adjusted to 9.5, stirred for 3.5 h, and 0.315 g of 10 mL NaBH slowly added4The aqueous solution was stirred for 1 h. Centrifugally washing the obtained precipitate with deionized water to neutrality; the precipitate was dried under vacuum at 80 ℃ for 24 h.
FIG. 1 shows Ru-B/MoO corresponding to example 6 and comparative example 53-ZnO-ZrO2The XRD pattern of the catalyst shows that no diffraction peaks of the active component Ru and the auxiliary agents Mo and Zn are observed, which indicates that Ru is MoO highly dispersed on the surface of the carrier3And ZnO is uniformly dispersed in the carrier; in addition, we synthesized tetragonal and monoclinic ZrO2The tetragonal phase has higher catalytic performance than the monoclinic phase.
FIG. 2 shows Ru-B/MoO corresponding to example 6 and comparative example 53-ZnO-ZrO2The pore size distribution of the catalyst shows that Ru-B/MoO synthesized by immersion deposition precipitation-chemical reduction method3-ZnO-ZrO2The (tetragonal phase) catalyst mostly has pore diameter mainly concentrated around 20.8 nm, and Ru-B/MoO synthesized by a hydrothermal method3- ZnO-ZrO2The (monoclinic phase) catalyst is a multi-stage hole, the most possible pore diameter is mainly concentrated at about 3.4 nm and 41.9 nm, and the larger pore diameter distribution is favorable for the gas-solid-water-oil four-phase reaction mass transfer in the hydrogenation reaction process of the benzene part.
Comparative example 1
This comparative example differs from example 1 only in that: step (2) is carried out without adding (NH)4)6Mo7O24∙4H2O。
Comparative example 2
This comparative example differs from example 6 only in that: when the performance is tested, ZnSO is not added4·7H2O。
Comparative example 3
0.3073 g of RuCl were added with stirring3·3H20、0.153 g ZnSO4·7H2O was dissolved in 35 mL of deionized water, and 2.0 g of ZrO was added2Stirring for 1h, adding 5 ml of NaOH (30 wt%), stirring and refluxing at 80 deg.C for 3 h, cooling to room temperature, and separating the upper layer liquid to obtain black precipitatePrecipitating, and washing with deionized water to neutrality. Putting the precursor into a high-pressure reaction kettle, adding 150 mL of NaOH solution (the mass fraction is 5 percent) under the hydrogen pressure of 5MPa and the stirring speed of 500 r-min-1Reducing at 150 deg.c for 5 hr, cooling to room temperature, and washing the black precipitate to neutrality. The precipitate was dried under vacuum at 80 ℃ for 24 h.
Comparative example 4
An industrial unsupported Ru-Zn catalyst.
Catalyst evaluation method
Comparative example 5
This comparative example differs from example 6 only in that: monoclinic phase ZrO prepared by hydrothermal method2Is a carrier.
The liquid phase benzene partial hydrogenation reaction was carried out in a limbo mini autoclave reactor of Buchiglaster corporation, 1.000 g of Ru-based catalyst (about 0.048 g of Ru), 58 mL of H2O，8.786 g ZnSO4·7H2O; stirring speed of 900 r ∙ min at 140 DEG C-1Pre-reducing under the condition of hydrogen pressure of 5 MPa; adding 29 mL of benzene which is heated to 140 ℃, and adjusting the rotating speed to 1200 r ∙ min-1The reaction timing was started. And analyzing the product composition by using a GC-2010 gas chromatograph FID detector to obtain the benzene conversion rate and the cyclohexene selectivity.
The Ru-based catalysts of examples 1 to 6 and comparative examples 1 to 5 were evaluated for benzene conversion, cyclohexene selectivity and yield, as shown in table 1. The benzene selectivity hydrogenation stability of example 1 was compared to that of comparative example 1 and is shown in table 2.
TABLE 1
TABLE 2
Note: the test conditions are the same as the activity evaluation method, the reaction time of each round is 20 min, the organic phase is separated before the cycle test, the pre-reduction is not carried out, and the benzene is added again for test evaluation.
Claims (6)
1. With MoO3-ZnO-ZrO2The supported Ru-based catalyst with the composite oxide as the carrier is characterized in that: the catalyst consists of active components of Ru and MoO3-ZnO-ZrO2The carrier is composed of MoO in mass fraction of Ru3-ZnO-ZrO25wt% of the carrier, the mass fraction of Mo being ZrO20.1-0.5wt% of carrier, and mass fraction of Zn is ZrO20.5-5wt% of the carrier;
the active component Ru is in a metal state, and the transition metal elements Mo and Zn are in an oxidation state.
2. The MoO of claim 13-ZnO-ZrO2The preparation method of the composite oxide carrier loaded Ru-based catalyst is characterized by comprising the following steps of: loaded on MoO by metal Ru3-ZnO-ZrO2The carrier is prepared by a chemical reduction method, and comprises the following steps:
(1) under the condition of stirring, dissolving soluble Mo salt and Zn salt in 10-20 mL deionized water, and adding ZrO at a certain proportion2Stirring for reaction for 0.5-1 h, adding precipitant to adjust pH to 8-10, stirring for 1-2h, drying, and calcining to obtain MoO3-ZnO-ZrO2A carrier;
(2) dissolving the carrier prepared in the step (1) in deionized water according to the mass-volume ratio of 1:10-15 g/mL under the condition of stirring, simultaneously and respectively adding a Ru salt water solution and a 5wt% sodium hydroxide solution to adjust the pH value to 6-10 under the condition of stirring, continuously stirring for 1-5 h, slowly adding a sodium borohydride water solution, and stirring for 1 h; the volume ratio of the deionized water to the Ru salt water solution to the sodium borohydride water solution is 5:2: 1;
(3) centrifugally washing the precipitate obtained in the step (2) for 3-5 times, and drying in vacuum to obtain the catalyst;
molybdenum salt, zinc salt and ZrO described in step (1)2The molar mass ratio of (1: 1-25: 300-.
3. The method of claim 2, wherein: the soluble molybdenum salt in the step (1) is molybdenum salt (NH)4)6Mo7O24∙4H2O, soluble zinc salt being Zn (NO)3)2∙6H2O、ZnSO4∙H2O or Zn (CH)3COO)2One or more of them.
4. The method of claim 2, wherein: the precipitator in the step (1) is any one of urea, ammonium bicarbonate and ammonia water, and the concentration of the precipitator is 10-15 wt%.
5. The method of claim 2, wherein: in the step (1), the drying temperature is 100 ℃, the drying time is 2 hours, the roasting temperature is 300 ℃, and the roasting time is 1 hour.
6. The method of claim 2, wherein: the mass ratio of the Ru salt to the carrier in the step (2) is 1: 1-10; the concentration of the sodium borohydride aqueous solution is 0.5-1.5 mol/L.
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