CN116651445A - Ruthenium-silver/carbon catalyst, preparation method and application - Google Patents
Ruthenium-silver/carbon catalyst, preparation method and application Download PDFInfo
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- CN116651445A CN116651445A CN202310599585.2A CN202310599585A CN116651445A CN 116651445 A CN116651445 A CN 116651445A CN 202310599585 A CN202310599585 A CN 202310599585A CN 116651445 A CN116651445 A CN 116651445A
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- ruthenium
- silver
- carbon
- catalyst
- phenol
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 87
- JMGVPAUIBBRNCO-UHFFFAOYSA-N [Ru].[Ag] Chemical compound [Ru].[Ag] JMGVPAUIBBRNCO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000011068 loading method Methods 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 238000009210 therapy by ultrasound Methods 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 23
- 229910021645 metal ion Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000006228 supernatant Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 15
- 239000002028 Biomass Substances 0.000 claims description 14
- 238000000855 fermentation Methods 0.000 claims description 13
- 230000004151 fermentation Effects 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000010806 kitchen waste Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000003303 ruthenium Chemical class 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 5
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- -1 ruthenium ions Chemical class 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 description 17
- 238000004817 gas chromatography Methods 0.000 description 15
- 238000005119 centrifugation Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 150000002431 hydrogen Chemical group 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000000527 sonication Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 101710134784 Agnoprotein Proteins 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VLWBWEUXNYUQKJ-UHFFFAOYSA-N cobalt ruthenium Chemical compound [Co].[Ru] VLWBWEUXNYUQKJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
-
- 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
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a ruthenium-silver/carbon catalyst, a preparation method and application thereof, and belongs to the technical field of catalyst preparation. The ruthenium-silver/carbon catalyst provided by the invention consists of a carrier and ruthenium-silver alloy nano particles loaded on the carrier, wherein the carrier is active carbon, the loading amount of ruthenium is 1-5wt%, and the loading ratio of ruthenium to silver is 1:1-1:4. the catalyst provided by the invention takes active biochar as a carrier, ruthenium-silver alloy nano particles are loaded on the carrier, and cheaper silver is used for dispersing catalytic active species ruthenium, and the catalyst is used for catalyzing phenol hydrogenation to prepare cyclohexanol and has the advantages of high efficiency, good selectivity, mild reaction conditions, reusability of the catalyst and the like.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a ruthenium-silver/carbon catalyst, a preparation method and application thereof.
Background
Cyclohexanol is an essential chemical intermediate in modern industry, and has wide application in the fields of rubber preparation, emulsifying agent, plasticizer, resin and other chemicals. The product is mainly used for producing adipic acid, hexamethylenediamine, cyclohexanone and caprolactam, can also be used as a stabilizer of soap, can be used for preparing disinfectant soap and detergent emulsion, and can be used as a solvent for rubber, resin, nitrocellulose, metal soap, oil, esters and ethers, an admixture for coating, a degreasing agent, a mold release agent, a dry cleaning agent and a polishing agent for leather. Cyclohexanol is also a raw material for fiber finishing agents, pesticides, plasticizers. The cyclohexanol production method mainly comprises a phenol hydrogenation method and a cyclohexane oxidation method.
Currently, nickel catalysts are generally used for the hydrogenation of phenol. The reaction temperature is 150 ℃, the pressure is 2.5MPa, the yield is close to the theoretical value, the product purity is high, and the reaction is stable. In view of the cost of raw materials, cyclohexane oxidation gradually replaces phenol hydrogenation. The cyclohexane oxidation reaction is relatively complex, which first generates cyclohexylhydroperoxide and then decomposes to cyclohexanol and cyclohexanone. Cyclohexanol and cyclohexanone oxidize more readily than cyclohexane; most of the cyclohexanone is formed by the oxidation of cyclohexanol, which in turn forms various oxidation byproducts.
In view of the foregoing, it is desirable to provide a ruthenium-silver/carbon catalyst and a method of preparation and use thereof.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a ruthenium-silver/carbon catalyst, a preparation method and application thereof.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a ruthenium-silver/carbon catalyst, which consists of a carrier and ruthenium-silver alloy nano particles loaded on the carrier, wherein the carrier is active carbon, the loading amount of ruthenium is 1-5wt%, and the loading ratio of ruthenium to silver is 1:1-1:4.
the invention also provides a preparation method of the ruthenium-silver/carbon catalyst, which comprises the following steps: and mixing the active carbon with a ruthenium salt solution and a silver salt solution, and reducing ruthenium metal ions and silver metal ions in the solution into ruthenium-silver alloy nano particles by adopting a reducing agent and loading the ruthenium-silver alloy nano particles on the active carbon to obtain the ruthenium-silver/carbon catalyst.
The invention also provides application of the ruthenium-silver/carbon catalyst in preparing cyclohexanol by phenol catalytic hydrogenation.
The invention has the following beneficial effects:
the ruthenium-silver/carbon catalyst provided by the invention consists of a carrier and ruthenium-silver alloy nano particles loaded on the carrier, the active carbon is used as the carrier, the active carbon carrier can play a role of dispersing and anchoring the ruthenium-silver alloy nano particles, meanwhile, cheaper silver is utilized to disperse a catalytic active center ruthenium species, the catalytic activity of the ruthenium species can be fully exerted, and the obtained ruthenium-silver/carbon catalyst has the advantages of high efficiency and selectivity, mild reaction conditions and repeated use of the catalyst when being used for producing cyclohexanol by phenol hydrogenation, and is obviously superior to the traditional cyclohexanol production method.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a TEM-mapping diagram of 2wt% ruthenium-6 wt% silver/kitchen waste fermentation residue activated carbon 。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The ruthenium-silver/carbon catalyst, the preparation method and the application provided by the embodiment of the invention are specifically described below.
In a first aspect, an embodiment of the present invention provides a ruthenium-silver/carbon catalyst, which is composed of a carrier and ruthenium-silver alloy nanoparticles supported on the carrier, wherein the carrier is activated carbon, the loading amount of ruthenium is 1wt% -5wt%, and the loading ratio of ruthenium to silver is 1:1-1:4.
the embodiment of the invention provides a ruthenium-silver/carbon catalyst, which consists of a carrier and ruthenium-silver alloy nano particles loaded on the carrier, wherein the catalyst provided by the invention can fully play the role of dispersing and anchoring the ruthenium-silver alloy nano particles by utilizing silver to disperse a catalytic active center ruthenium species, and the active carbon carrier can play the role of dispersing and anchoring the ruthenium-silver alloy nano particles, so that the obtained catalyst is used for producing cyclohexanol by phenol hydrogenation and has good catalytic activity.
In an alternative embodiment, the loading of ruthenium is 2wt% to 3wt%, and the ratio of ruthenium to silver loading is 1:1.5-1:2.
in an alternative embodiment, the activated carbon is obtained by the following method: roasting biomass to obtain biochar, and activating and roasting the biochar to obtain active carbon;
preferably, the biomass comprises any one of fermentation residues, plant biomass and animal biomass;
more preferably, the fermentation residues are mainly prepared by jointly anaerobic fermentation of kitchen waste and anaerobic sludge;
more preferably, the animal biomass is selected from the group consisting of hide powder;
more preferably, the plant biomass is selected from birch wood flour.
Illustratively, reference may be made to the patent already filed by the inventor for the preparation of activated carbon from fermentation residues: ZL202111564362.X, utilize carbon, nitrogen element in the kitchen garbage fermentation residue to prepare the porous active carbon carrier of nitrogen containing of high specific surface area, be favorable to the load and the attachment of metal particle.
In a second aspect, an embodiment of the present invention provides a method for preparing the ruthenium-silver/carbon catalyst, including: and mixing the active carbon with a ruthenium salt solution and a silver salt solution, and reducing ruthenium metal ions and silver metal ions in the solution into ruthenium-silver alloy nano particles by adopting a reducing agent and loading the ruthenium-silver alloy nano particles on the active carbon to obtain the ruthenium-silver/carbon catalyst.
In an alternative embodiment, the method comprises the steps of:
roasting and activating biomass to obtain active carbon, uniformly mixing the obtained active carbon with ruthenium salt, silver salt and deionized water in proportion, enabling the active carbon to uniformly adsorb metal ions by ultrasonic waves at room temperature, and after ultrasonic waves are finished, centrifugally washing to remove supernatant;
under the ultrasonic condition, adding a reducing agent to perform a reduction reaction, and after the reaction is completed, centrifugally washing and drying to obtain the ruthenium-silver/carbon catalyst.
In an alternative embodiment, the ruthenium salt comprises at least one of ruthenium chloride, ruthenium nitrate, potassium chlororuthenate, and the silver salt is silver nitrate.
In an alternative embodiment, the reducing agent comprises a member selected from the group consisting of NaBH 4 At least one of formaldehyde, glycine and ethylene glycol solution;
preferably, the reducing agent is selected from sodium borohydride, sodium borohydride and ruthenium and silver salts in a molar ratio of the total amount of metals used of 3:1.
in an alternative embodiment, the drying temperature is 60-110℃for a period of 6-24 hours.
In a third aspect, the present invention provides an application of the ruthenium-silver/carbon catalyst in preparing cyclohexanol by catalytic hydrogenation of phenol.
In an alternative embodiment, the catalytic hydrogenation comprises: phenol reacts in a water system under the action of hydrogen atmosphere and ruthenium-silver/carbon catalyst to obtain cyclohexanol.
In an alternative embodiment, the mass molar ratio of ruthenium-silver/carbon catalyst to phenol in the catalytic hydrogenation is from 25 to 150mg:1mmol; the ratio of phenol to water was 2.5mmol:25mL.
Preferably, the hydrogen pressure is 0.5-4MPa, more preferably 1-2MPa;
preferably, the reaction temperature is from 30 to 90 ℃, more preferably from 50 to 70 ℃; the reaction time is 0.5 to 4 hours, more preferably 1 to 2 hours.
From the above, it can be seen that the embodiment of the invention provides a ruthenium-silver/carbon catalyst, which is composed of a carrier and ruthenium-silver alloy nano particles loaded on the carrier, wherein, the carbon-based catalyst carrier is prepared by taking kitchen waste, tanning waste or agriculture and forestry waste as raw materials, so that the solid waste resource utilization can be realized, and the nitrogen-containing porous active carbon carrier with high specific surface area can be prepared without adding nitrogen source because of abundant carbon and nitrogen elements in the kitchen waste as raw materials, thereby playing the roles of dispersing and anchoring the ruthenium-silver metal nano particles. In addition, the active metal ruthenium is dispersed by cheaper silver, so that the catalytic activity of the ruthenium can be fully exerted, and the inventor also proves that after a plurality of experiments: when the catalyst is used for preparing cyclohexanol by phenol hydrogenation, the conditions are milder, the reaction time is shorter, the efficiency and the selectivity of cyclohexanol are good, the catalyst can be recycled, and the catalyst is obviously superior to the traditional cyclohexanol production method.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
The method provided by the invention mainly prepares a carbon-based catalyst carrier by using solid waste, loads ruthenium-silver alloy nano particles on the carrier, and disperses active center ruthenium by using silver to obtain a catalyst with a composition of ruthenium-silver/carbon, wherein the catalyst can efficiently reduce phenol into cyclohexanol under a mild condition.
Example 1
Activated carbon preparation: kitchen waste and anaerobic sludge are respectively crushed and adjusted to be 20g/L in TSS, and the ratio of 9: mixing in proportion, regulating pH value to 8 with sodium bicarbonate, anaerobic fermenting at room temperature for 8 days, washing for multiple times, centrifuging, and collecting to obtain kitchen waste fermentation residue with a fermentation residue yield of 42.8%. Roasting the fermentation residues in a tubular furnace at 450 ℃ in nitrogen atmosphere for 2 hours, and adding the obtained biochar into a KOH solution with the mass ratio of 4:1 soaking for 12 hours, drying the mixture, roasting the dried biochar in a tube furnace at 800 ℃ under nitrogen atmosphere for 2 hours, washing to be neutral, and drying to obtain the activated carbon.
(2) And (3) preparing a catalyst: taking (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.1mol/L AgNO) 3 1.670mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, adding the mixture into a centrifuge tubeNaBH 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 6.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 100mg and water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 2.0MPa, and reacted at 90℃for 30 minutes. The conversion of phenol was 99.9% by gas chromatography and the yield of cyclohexanol was 99.7%.
TEM-mapping of the ruthenium-silver/carbon catalyst prepared in example 1 above is shown in FIG. 1, and can be seen from FIG. 1: ruthenium and silver are uniformly dispersed on the active carbon carrier, signals of the ruthenium and the silver are overlapped to form ruthenium-silver alloy nano particles, and the catalytic activity of ruthenium species can be fully exerted by dispersing catalytic active center ruthenium species with cheaper silver.
Example 2
(1) The activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: taking (0.1 mol/L of chlororuthenic acid solution 0.300mL, 0.1mol/L of AgNO) 3 0.840mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 1.0wt% of ruthenium and 3.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 150mg and water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 3.0MPa, and reacted at 70℃for 120min. The conversion of phenol was 99.5% and the yield of cyclohexanol was 99.2% as measured by gas chromatography.
Example 3
(1) The activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: taking (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.1mol/L AgNO) 3 1.115mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 4.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 100mg and water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 2.0MPa, and reacted at 70℃for 90 minutes. The conversion of phenol was 99.7% by gas chromatography and the yield of cyclohexanol was 99.5%.
Example 4
(1) The activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: taking (0.1 mol/L of chlororuthenic acid solution 1.485mL, 0.1mol/L of AgNO) 3 1.390mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the solution is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with 5.0wt% of ruthenium and 5.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 25mg and water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 1.5MPa, and reacted at 70℃for 60 minutes. The conversion of phenol was 84.9% by gas chromatography and the yield of cyclohexanol was 84.5%.
Example 5
(1) The activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: taking (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.1mol/L AgNO) 3 2.225mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 8.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 75mg, water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 4.0MPa, and reacted at 50℃for 120min. The conversion of phenol was 99.9% by gas chromatography and the yield of cyclohexanol was 99.7%.
Example 6
(1) The activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: taking (0.1 mol/L of chlororuthenic acid solution 0.895mL, 0.1mol/L of AgNO) 3 1.255mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the solution is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 3.0wt% of ruthenium and 4.5wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 150mg, and water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 4.0MPa, and reacted at 30℃for 240 minutes. The conversion of phenol was 86.5% by gas chromatography and the yield of cyclohexanol was 86.1%.
Example 7
(1) The activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: taking (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.1mol/L AgNO) 3 1.115mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 4.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 100mg and water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 0.5MPa, and reacted at 70℃for 240min. The conversion of phenol was 96.5% by gas chromatography and the yield of cyclohexanol was 96.1%.
Example 8
(1) Activated carbon preparation: roasting birch wood powder in a tubular furnace at 450 ℃ in nitrogen atmosphere for 2 hours, and adding the obtained biochar into a KOH solution with the mass ratio of 4:1 soaking for 12 hours, drying the mixture, roasting the dried biochar in a tube furnace at 800 ℃ under nitrogen atmosphere for 2 hours, washing to be neutral, and drying to obtain the activated carbon.
(2) And (3) preparing a catalyst: taking (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.1mol/L AgNO) 3 1.115mL of solution, 0.3g of birch activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment at about 20 ℃ for 2 hours in an ultrasonic cleaner, so that the activated carbon and metal ions are uniformly mixed. After the end of the ultrasound treatment,and (3) centrifugally washing the supernatant with secondary water for three times in a high-speed refrigerated centrifuge to ensure that the supernatant is colorless. After the centrifugal washing is finished, 5mg/mL NaBH is added into a centrifuge tube 4 1.5mL of the solution, and carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing again for three times, and after finishing, drying moisture in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 4.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 100mg, water 25mL, hydrogen pressure 2.0MPa, temperature 70℃and reaction time 60min. The conversion of phenol was 99.9% by gas chromatography and the yield of cyclohexanol was 99.7%.
Example 9
(1) Activated carbon preparation: roasting leather waste powder in a tubular furnace at 450 ℃ in nitrogen atmosphere for 2 hours, and adding the obtained biochar into a KOH solution with the mass ratio of 4:1 soaking for 12 hours, drying the mixture, roasting the dried biochar in a tube furnace at 800 ℃ under nitrogen atmosphere for 2 hours, washing to be neutral, and drying to obtain the activated carbon.
(2) And (3) preparing a catalyst: taking (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.1mol/L AgNO) 3 1.115mL of solution, 0.3g of powdered activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment at about 20 ℃ for 2 hours in an ultrasonic cleaner, so that the activated carbon and metal ions are uniformly mixed. After the ultrasonic treatment, the supernatant is washed three times by secondary water centrifugation in a high-speed refrigerated centrifuge, and the colorless supernatant is ensured. After the centrifugal washing is finished, 5mg/mL NaBH is added into a centrifuge tube 4 1.5mL of the solution, and carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing again for three times, and after finishing, drying moisture in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 4.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 100mg, water 25mL, hydrogen pressure 2.0MPa, temperature 70℃and reaction time 60min. The conversion of phenol was 97.4% by gas chromatography and the yield of cyclohexanol was 97.1%.
TABLE 1
From the above table 1, it can be seen that the carbon-based catalyst carrier is prepared from kitchen waste (such as fermentation residues), leather-making waste (leather powder) or agricultural and forestry waste (such as birch wood powder), and ruthenium-silver alloy nanoparticles are loaded thereon, and when the catalyst carrier is used for catalytic hydrogenation of phenol, the phenol conversion rate and the cyclohexanol yield are very high, which are obviously superior to those of the conventional metal catalyst.
Comparative example 1
Similar to the procedure of example 1, the only difference is that: the activated carbon-loaded metal nanoparticles do not contain silver, only contain single ruthenium nanoparticles, and the experimental process and results are as follows:
(1) the activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: the solution (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.3g of activated carbon and 3mL of water) is added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment in an ultrasonic instrument at room temperature for 2 hours, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a 105 ℃ oven to obtain the ruthenium/carbon catalyst with the load of 2.0wt% of ruthenium.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium/carbon catalyst 100mg and water 25mL were placed in a high-pressure reaction vessel, the air in the reaction vessel was replaced with hydrogen, and the initial hydrogen pressure was maintained at 2.0MPa, and the reaction was carried out at 70℃for 60 minutes. The conversion of phenol was 41.5% by gas chromatography and the yield of cyclohexanol was 41.1%.
Comparative example 2
Similar to the procedure of comparative example 1, the only difference is that: the activated carbon-loaded metal nano particles are single palladium nano particles, and the experimental process and the experimental result are as follows:
(1) the activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: take (0.1 mol/L K) 2 PdCl 4 0.565mL of the solution, 0.3g of activated carbon, and 3mL of water) was added to a 50mL centrifuge tube, and the mixture was sonicated in an sonicator at room temperature for 2h to allow the activated carbon to fully adsorb metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the palladium/carbon catalyst with the load of 2.0wt% of palladium.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, palladium/carbon catalyst 100mg and water 25mL were placed in a high-pressure reaction vessel, the air in the reaction vessel was replaced with hydrogen, and the initial hydrogen pressure was kept at 2.0MPa, and the reaction was carried out at 70℃for 60 minutes. The conversion of phenol was 2.3% by gas chromatography and the yield of cyclohexanol was 1.9%.
Comparative example 3
Similar to the procedure of comparative example 1, the only difference is that: the activated carbon-loaded metal nanoparticles are single platinum nanoparticles, and the experimental process and the experimental result are as follows:
(1) the activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: taking (0.1 mol/L H) 2 PtCl 6 0.310mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the platinum/carbon catalyst with the platinum loading amount of 2.0 wt%.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, platinum/carbon catalyst 100mg and water 25mL were placed in a high-pressure reaction vessel, the air in the reaction vessel was replaced with hydrogen, and the initial hydrogen pressure was maintained at 2.0MPa, and the reaction was carried out at 70℃for 60 minutes. The conversion of phenol was 2.9% by gas chromatography and the yield of cyclohexanol was 2.5%.
Comparative example 4
Similar to the procedure of example 1, the only difference is that: the reaction condition parameters in the catalytic process are changed as follows: the ruthenium loading is 2.0wt%, the ruthenium silver loading ratio is 1/1, the temperature is 70 ℃, the hydrogen pressure is 2MPa, the time is 1h, and the experimental process and the results are as follows:
(1) the activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: taking (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.1mol/L AgNO) 3 0.560mL of solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-silver/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 2.0wt% of silver.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-silver/carbon catalyst 100mg and water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 2.0MPa, and reacted at 70℃for 60 minutes. The conversion of phenol was found to be 60.7% by gas chromatography and the yield of cyclohexanol was found to be 60.4%.
Comparative example 5
Similar to the procedure of comparative example 4, the only difference is that: the supported bimetal is changed from ruthenium silver bimetal to ruthenium cobalt bimetal, and the experimental process and the result are as follows:
(1) the activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: 0.595mL of a solution of 0.1mol/L of a solution of chlororuthenic acid, 0.1mol/L of Co (NO 3 ) 2 1.020mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the solution is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. Ultrasonic waveAfter the completion, the supernatant was removed by centrifugal washing with distilled water three times in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-cobalt/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 2.0wt% of cobalt.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-cobalt/carbon catalyst 100mg and water 25mL were placed in a high-pressure reaction kettle, the air in the reaction kettle was replaced with hydrogen, and the initial hydrogen pressure was kept at 2.0MPa, and the reaction was carried out at 70℃for 60min. The conversion of phenol was 45.5% by gas chromatography and the yield of cyclohexanol was 45.2%.
Comparative example 6
Similar to the procedure of comparative example 4, the only difference is that: the supported bimetal is changed from ruthenium silver bimetal to ruthenium nickel bimetal, and the experimental process and the result are as follows:
(1) the activated carbon preparation was the same as described in example 1.
(2) And (3) preparing a catalyst: the solution (0.595 mL of 0.1mol/L chlororuthenic acid solution, 0.1mol/L NiCl) was taken 2 1.025mL of the solution, 0.3g of activated carbon and 3mL of water) are added into a 50mL centrifuge tube, and the mixture is subjected to ultrasonic treatment for 2 hours at room temperature in an ultrasonic instrument, so that the activated carbon fully adsorbs metal ions. After the end of the sonication, the supernatant was removed by centrifugation three times with distilled water in a high-speed centrifuge. After centrifugal washing is finished, naBH is added into a centrifuge tube 4 Solution of NaBH 4 The molar ratio of the metal to the metal is 3:1, carrying out ultrasonic treatment again for 1h, after ultrasonic treatment is finished, carrying out centrifugal washing for three times, and after finishing, drying the solid in a drying oven at 105 ℃ to obtain the ruthenium-nickel/carbon catalyst with the loading amount of 2.0wt% of ruthenium and 2.0wt% of nickel.
(3) Catalytic hydrogenation of phenol: phenol 2.5mmol, ruthenium-nickel/carbon catalyst 100mg and water 25mL were placed in an autoclave, the air in the autoclave was replaced with hydrogen, and the initial hydrogen pressure was maintained at 2.0MPa, and reacted at 70℃for 60 minutes. The conversion of phenol was 47.3% by gas chromatography and the yield of cyclohexanol was 46.9%.
TABLE 2
As can be seen from table 2 above: the ruthenium-silver/carbon catalyst prepared in the comparative example is applied to the reaction of hydrogenating phenol into cyclohexanol, and although the effect of ruthenium is better than that of palladium and platinum, the effect of a single-metal catalyst is far lower than that of a double-metal ruthenium-silver catalyst, and meanwhile, the effect of dispersing ruthenium by silver by the double-metal catalyst is better. The ruthenium-silver/carbon catalyst prepared by the embodiment of the invention disperses active metal ruthenium with cheaper silver, and has the advantages of good efficiency and selectivity for catalyzing phenol hydrogenation into cyclohexanol, mild reaction condition and reusability.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The ruthenium-silver/carbon catalyst is characterized by comprising a carrier and ruthenium-silver alloy nano particles loaded on the carrier, wherein the carrier is active carbon, the loading of ruthenium is 1-5wt%, and the loading ratio of ruthenium to silver is 1:1-1:4.
2. the ruthenium-silver/carbon catalyst according to claim 1, wherein the loading of ruthenium is 2wt% to 3wt%, and the ratio of ruthenium to silver loading is 1:1.5-1:2.
3. ruthenium-silver/carbon catalyst according to claim 1, characterized in that the activated carbon is obtained by the following method: roasting biomass to obtain biochar, and activating and roasting the biochar to obtain the activated carbon;
preferably, the biomass includes any one of fermentation residues, plant biomass, and animal biomass;
more preferably, the fermentation residues are mainly prepared by jointly anaerobic fermentation of kitchen waste and anaerobic sludge;
more preferably, the animal biomass is selected from the group consisting of hide powder;
more preferably, the plant biomass is selected from birch wood flour.
4. A process for the preparation of a ruthenium-silver/carbon catalyst according to any one of claims 1 to 3, comprising: and mixing active carbon with a ruthenium salt solution and a silver salt solution, and reducing ruthenium ions and silver ions in the solution into ruthenium-silver alloy nano particles by adopting a reducing agent and loading the ruthenium-silver alloy nano particles on the active carbon to obtain the ruthenium-silver/carbon catalyst.
5. The method of manufacturing according to claim 4, comprising the steps of:
roasting and activating biomass to obtain active carbon, uniformly mixing the obtained active carbon with ruthenium salt, silver salt and deionized water in proportion, enabling the active carbon to uniformly adsorb metal ions by ultrasonic at room temperature, and after ultrasonic treatment, centrifugally washing to remove supernatant;
under the ultrasonic condition, adding a reducing agent to perform a reduction reaction, and after the reaction is completed, centrifugally washing and drying to obtain the ruthenium-silver/carbon catalyst.
6. The method according to claim 5, wherein the ruthenium salt comprises at least one of ruthenium chloride, ruthenium nitrate, chlororuthenic acid, and chlororuthenic acid potassium, and the silver salt is silver nitrate.
7. The method of claim 5, wherein the reducing agent comprises a member selected from the group consisting of NaBH 4 At least one of formaldehyde, glycine and glycol solutionOne of the two;
preferably, the reducing agent is selected from sodium borohydride, the molar ratio of the total amount of metal in the sodium borohydride and the ruthenium salt to the silver salt being 3:1.
8. use of the ruthenium-silver/carbon catalyst according to claim 1 or 2 for the catalytic hydrogenation of phenol to cyclohexanol.
9. The use according to claim 8, wherein the catalytic hydrogenation comprises: phenol reacts in a water system under the action of hydrogen atmosphere and the ruthenium-silver/carbon catalyst to obtain cyclohexanol.
10. The use according to claim 9, characterized in that in the catalytic hydrogenation the mass molar ratio of ruthenium-silver/carbon catalyst to phenol is 25-150mg:1mmol; the dosage ratio of the phenol to the water is 2.5 mmol/25 mL;
preferably, the hydrogen pressure is 0.5-4MPa, more preferably 1-2MPa;
preferably, the reaction temperature is from 30 to 90 ℃, more preferably from 50 to 70 ℃; the reaction time is 0.5 to 4 hours, more preferably 1 to 2 hours.
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