CN116273051A - Gamma-Al 2 O 3 Supported ruthenium-nickel catalyst and application thereof in phenol hydrogenation reaction - Google Patents
Gamma-Al 2 O 3 Supported ruthenium-nickel catalyst and application thereof in phenol hydrogenation reaction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910018072 Al 2 O 3 Inorganic materials 0.000 title claims abstract description 57
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 46
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 62
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 40
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 claims abstract description 40
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 31
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 12
- 238000005580 one pot reaction Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000003223 protective agent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- 239000013543 active substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical group O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a gamma-Al 2 O 3 Ruthenium-nickel-loaded catalyst and application thereof in phenol hydrogenation reaction, and solution formed by dissolving ruthenium chloride trihydrate and nickel chloride hexahydrate through N, N-dimethylformamide is helpful to the reaction with a reducing agent benzoic acid, a protective agent polyvinylpyrrolidone and a carrier gamma-Al 2 O 3 More thoroughly dispersed through stirring and ultrasonic vibration to form a uniform precursor solution; the preparation method has the advantages that the precursor solution is heated by a one-pot method to react at a constant temperature to prepare the catalyst slurry, the preparation process and the used equipment are simple, the process parameters are easy to control, the cost is low, the mass production is easy, and the catalyst after filtering, washing and drying has active catalytic centers formed by bimetal, has better crystallinity and is between ruthenium and nickelThe electron transfer exists, and the synergic action between the bimetallic elements enhances the catalytic activity; gamma-Al 2 O 3 When the supported ruthenium-nickel catalyst is used for the hydrogenation reaction of phenol, the sodium hydroxide solution is used for adjusting the pH of the phenol to be 10-12, so that part of phenol can form sodium phenolate, and the hydrogenation reaction can be facilitated.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a gamma-Al catalyst 2 O 3 The supported ruthenium-nickel catalyst and the application thereof in sodium phenolate hydrogenation reaction.
Background
With the continuous acceleration of the global industrialization process, the consumption of fossil fuels is increasing, and serious pollution is caused to the environment, such as greenhouse effect, acid rain, ozone layer cavity and the like, and the key to solving the problems is to reduce the dependence on fossil energy and develop an environment-friendly and sustainable renewable alternative energy. The hydrogen energy has the characteristics of high energy density, abundant reserves, wide sources, various storage forms, environmental friendliness and the like, and is regarded as the green secondary energy with the most development potential in the 21 st century.
Hydrogen storage and transportation are key links for limiting the large-scale application of hydrogen energy, and developing hydrogen storage technologies based on certain materials, including adsorbents capable of meeting the hydrogen storage targets, chemical hydrogen storage materials and the like, are long-term targets of the hydrogen storage technologies. Among a plurality of hydrogen storage materials, the liquid organic hydride hydrogen storage has the advantages of low cost of organic liquid, high hydrogen storage density, large hydrogen storage amount, convenient transportation, high safety, convenient operation, recycling and the like, and has bright application prospect.
The phenol and the cyclohexanol can be interconverted through reversible hydrogenation dehydrogenation, the reversible hydrogen absorption and desorption amount is about 6wt%, and the phenol-cyclohexanol can be used as a hydrogen storage material. The material needs high-efficiency catalyst in the hydrogenation reaction to overcome kinetic resistance, but the reported research only screens partial commercialized catalyst such as Pt/C, pd/C and the like, which is not only expensive, but also is not ideal in catalytic activity and selectivity. Therefore, the development of efficient, low cost metal organic hydride hydrogenation/dehydrogenation catalysts is a highly desirable problem.
Disclosure of Invention
The technical proposal of the patent provides a gamma-Al 2 O 3 The supported ruthenium-nickel catalyst can be used for preparing cyclohexanol by phenol hydrogenation, and the synergistic effect between ruthenium-nickel nano alloys in the catalyst can effectively improve the hydrogenation performance of a single metal catalyst, reduce the dosage of noble metal ruthenium and compare with single metal Ru/Al 2 O 3 The catalyst has obvious advantages. The catalyst has the advantages of simple preparation method, easy control of technological parameters and easy mass production.
In order to solve the problems in the background art, the invention provides the following technical scheme:
Gamma-Al 2 O 3 The supported ruthenium-nickel catalyst is characterized by being prepared by the following steps:
s1: adding ruthenium chloride trihydrate and nickel chloride hexahydrate into N, N-dimethylformamide according to the molar ratio of 1:0.5-2, and stirring until all the materials are dissolved to obtain ruthenium-nickel solution;
s2: sequentially adding polyvinylpyrrolidone and benzoic acid into the ruthenium-nickel solution, and then adding gamma-Al 2 O 3 The powder is stirred and dispersed by ultrasonic vibration to obtain a precursor solution;
s3: putting the precursor solution into an autoclave, sealing the autoclave, heating to the reaction temperature, carrying out heat preservation reaction, cooling, and opening the autoclave to obtain catalyst slurry;
s4: filtering the catalyst slurry, washing a filter cake with deionized water, and vacuum drying to obtain gamma-Al 2 O 3 Ruthenium nickel catalyst is supported.
Further, the mass ratio of the total dosage of the ruthenium chloride trihydrate and the nickel chloride hexahydrate to the dosage of the N, N-dimethylformamide in the S1 is 1:200-2000.
Further, the gamma-Al described in S2 2 O 3 Powder amount and ruthenium nickel foldThe mass ratio of the hundred amounts is 10-100:1.
Further, the molar ratio of the amount of benzoic acid to the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate in S2 is 5-20:1.
Further, the mass ratio of the polyvinylpyrrolidone usage amount to the benzoic acid usage amount in the S2 is 2:1.
Further, the reaction condition in the step S3 is that the reaction temperature is 120-230 ℃ and the reaction time is 8-20 h.
The invention also provides the following technical scheme:
Gamma-Al 2 O 3 The application of the supported ruthenium-nickel catalyst in the phenol hydrogenation reaction is characterized in that the gamma-Al prepared by the method 2 O 3 The supported ruthenium nickel catalyst is a hydrogenation catalyst.
Further, the conditions for the hydrogenation reaction of phenol also include adjusting phenol to ph=10 to 12 using sodium hydroxide solution.
The beneficial effects of the invention are as follows:
the invention provides a gamma-Al 2 O 3 Ruthenium-nickel-loaded catalyst and application thereof in phenol hydrogenation reaction, and solution formed by dissolving ruthenium chloride trihydrate and nickel chloride hexahydrate through N, N-dimethylformamide is helpful to the reaction with a reducing agent benzoic acid, a protective agent polyvinylpyrrolidone and a carrier gamma-Al 2 O 3 More thoroughly dispersed through stirring and ultrasonic vibration to form a uniform precursor solution; the precursor solution is heated and subjected to heat preservation reaction to prepare the catalyst slurry by a one-pot method, the preparation process and the used equipment are simple, the process parameters are easy to control, the cost is low, the mass production is easy, the catalyst after filtering, washing and drying has the active catalytic center formed by the bimetal, the catalyst has good crystallinity, the electron transfer exists between ruthenium and nickel, and the catalysis activity is enhanced by the synergic action between the bimetal; gamma-Al 2 O 3 When the supported ruthenium-nickel catalyst is used for the hydrogenation reaction of phenol, the sodium hydroxide solution is used for adjusting the pH of the phenol to be 10-12, so that part of phenol can form sodium phenolate, and the hydrogenation reaction can be facilitated.
gamma-Al of the invention 2 O 3 Compared with Ru/gamma-Al, the supported ruthenium-nickel catalyst 2 O 3 And the catalytic performance of Pt/C is obviously improved, the conversion rate and the selectivity of phenol hydrogenation are improved to a certain extent, and the catalyst can replace single noble metal catalysts such as Pt, ru and the like in a phenol-cyclohexanol hydrogen storage system, thereby being an ideal relatively cheap hydrogenation catalyst.
Drawings
FIG. 1 shows gamma-Al 2 O 3 Is RuNi/gamma-Al 2 O 3 、Ru/γ-Al 2 O 3 And Ni/gamma-Al 2 O 3 Comparison of catalytic effects of the three catalysts.
Detailed Description
In order to make the technical means, features and effects achieved by the present invention easier to understand, the technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the specific implementation and the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Gamma-Al 2 O 3 A supported ruthenium nickel catalyst prepared by the steps of:
s1: 20.7mg of ruthenium chloride trihydrate and 23.7mg of nickel chloride hexahydrate are put into 44.4g of N, N-dimethylformamide and stirred until the ruthenium and the nickel are completely dissolved, so as to obtain a ruthenium and nickel solution;
s2: 488mg polyvinylpyrrolidone and 244mg benzoic acid were added sequentially to the ruthenium nickel solution, followed by 320mg gamma-Al 2 O 3 The powder is stirred and dispersed by ultrasonic vibration to obtain a precursor solution;
s3: putting the precursor solution into an autoclave, sealing the autoclave, heating to the reaction temperature of 180 ℃, preserving heat for 12 hours, cooling, and opening the autoclave to obtain catalyst slurry;
s4: filtering the catalyst slurry, washing a filter cake with deionized water, and vacuum drying to obtain gamma-Al 2 O 3 Ruthenium nickel catalyst is supported.
gamma-Al prepared in example 1 2 O 3 The molar ratio of the ruthenium chloride trihydrate to the nickel chloride hexahydrate is 1:1, the mass ratio of the total consumption of the ruthenium chloride trihydrate and the nickel chloride hexahydrate to the consumption of the N, N-dimethylformamide is 1:1000, and the gamma-Al is the catalyst 2 O 3 The mass ratio of the powder to the ruthenium nickel folded percentage is 20:1, the molar ratio of the benzoic acid to the total of the ruthenium chloride trihydrate and the nickel chloride hexahydrate is 10:1, the mass ratio of the polyvinylpyrrolidone to the benzoic acid is 2:1, and after one-pot reaction, the slurry is filtered, washed by deionized water and dried in vacuum to obtain the gamma-Al with the load of 5 percent 2 O 3 Supported ruthenium nickel catalyst, designated RuNi/gamma-Al 2 O 3 (5％)。
RuNi/gamma-Al obtained in example 1 2 O 3 (5%) for hydrogenation of phenol, 10g of phenol was added to an autoclave, a 30% sodium hydroxide solution was added dropwise to adjust ph=11, and RuNi/γ -Al obtained in example 1 was added 2 O 3 (5%) 0.43g, filling hydrogen gas to pressurize to 20bar after sealing the kettle for replacement, heating to 100 ℃, stirring at 500rpm, reacting for 6h, keeping the pressure constant, and stopping the reaction.
After acidification of the feed liquid, extraction with methylene dichloride and sampling analysis of supernatant liquid, experimental data show that the conversion rate of phenol reaches 100%, GC shows no by-product, and the phenol hydrogenation product is cyclohexanol, and the selectivity is 100%.
In example 1, ruNi/gamma-Al 2 O 3 The molar ratio of active substance to phenol in (5%) was 1:400.
Comparative example 1
Gamma-Al 2 O 3 A supported ruthenium catalyst prepared by the steps of:
s1: 41.4mg of ruthenium chloride trihydrate is put into 41.4g of N, N-dimethylformamide and stirred until the ruthenium chloride is completely dissolved, so as to obtain ruthenium solution;
s2: 488mg polyvinylpyrrolidone and 244mg benzoic acid were added sequentially to the ruthenium solution followed by 404.4mg gamma-Al 2 O 3 PowderStirring and dispersing by ultrasonic vibration to obtain a precursor solution;
s3: putting the precursor solution into an autoclave, sealing the autoclave, heating to the reaction temperature of 180 ℃, preserving heat for 12 hours, cooling, and opening the autoclave to obtain catalyst slurry;
s4: filtering the catalyst slurry, washing a filter cake with deionized water, and vacuum drying to obtain gamma-Al 2 O 3 A supported ruthenium catalyst.
gamma-Al prepared in comparative example 1 2 O 3 The mass ratio of the ruthenium chloride trihydrate to the N, N-dimethylformamide is 1:1000, and the gamma-Al is supported on the catalyst 2 O 3 The mass ratio of the powder to the ruthenium folding percentage is 20:1, the molar ratio of the benzoic acid to the ruthenium chloride trihydrate is 10:1, the mass ratio of the polyvinylpyrrolidone to the benzoic acid is 2:1, and the gamma-Al with the loading capacity of 5% is obtained by filtering the slurry, washing with deionized water and vacuum drying after one-pot reaction 2 O 3 Supported ruthenium catalyst, designated Ru/gamma-Al 2 O 3 (5％)。
Ru/gamma-Al obtained in comparative example 1 2 O 3 (5%) for hydrogenation of phenol, 10g of phenol was added to an autoclave, a 30% sodium hydroxide solution was added dropwise to adjust ph=11, and Ru/γ -Al obtained in comparative example 1 was added 2 O 3 (5%) 0.54g, after the autoclave was replaced, hydrogen was charged to pressurize to 20bar, the temperature was raised to 100℃and the stirring speed was 500rpm, and the reaction was stopped for 6 hours.
After the feed liquid is acidified, layering and supernatant liquid sampling analysis are carried out, experimental data show that the conversion rate of phenol reaches 78.9%, GC shows that a small amount of byproducts are generated, and the phenol hydrogenation product is mainly cyclohexanol, and the selectivity is 94.9%.
In comparative example 1, ru/gamma-Al 2 O 3 The molar ratio of active substance to phenol in (5%) was 1:400.
Comparative example 2
Gamma-Al 2 O 3 A supported nickel catalyst prepared by the steps of:
s1: 47.4mg of nickel chloride hexahydrate is put into 47.4g of N, N-dimethylformamide and stirred until the nickel chloride is completely dissolved, so as to obtain a nickel solution;
s2: 488mg polyvinylpyrrolidone and 244mg benzoic acid were added sequentially to the nickel solution followed by 234.8mg gamma-Al 2 O 3 The powder is stirred and dispersed by ultrasonic vibration to obtain a precursor solution;
s3: putting the precursor solution into an autoclave, sealing the autoclave, heating to the reaction temperature of 180 ℃, preserving heat for 12 hours, cooling, and opening the autoclave to obtain catalyst slurry;
s4: filtering the catalyst slurry, washing a filter cake with deionized water, and vacuum drying to obtain gamma-Al 2 O 3 Nickel catalyst is supported.
gamma-Al prepared in comparative example 2 2 O 3 The mass ratio of the dosage of the nickel chloride hexahydrate to the dosage of the N, N-dimethylformamide is 1:1000, and the gamma-Al is carried out 2 O 3 The mass ratio of the powder to the nickel-folded hundred is 20:1, the molar ratio of the benzoic acid to the nickel chloride hexahydrate is 10:1, the mass ratio of the polyvinylpyrrolidone to the benzoic acid is 2:1, and the gamma-Al with the loading capacity of 5% is obtained by filtering slurry, washing with deionized water and vacuum drying after one-pot reaction 2 O 3 Supported Ni catalyst, designated Ni/gamma-Al 2 O 3 (5％)。
Ni/gamma-Al obtained in comparative example 2 2 O 3 (5%) for hydrogenation of phenol, 10g of phenol was added to an autoclave, a 30% sodium hydroxide solution was added dropwise to adjust ph=11, and Ni/γ -Al obtained in comparative example 2 was added 2 O 3 (5%) 0.31g, after the autoclave was replaced, hydrogen was charged to pressurize to 20bar, the temperature was raised to 100℃and the stirring speed was 500rpm, and the reaction was stopped for 6 hours.
After acidification of the feed solution, the layers are separated, and the supernatant liquid is sampled and analyzed, and experimental data show that phenol is not converted at all, and the conversion rate is 0.
In comparative example 2, ni/gamma-Al 2 O 3 The molar ratio of active substance to phenol in (5%) was 1:400.
As shown in FIG. 1, the catalysts obtained in example 1, comparative example 1 and comparative example 2 were used for the hydrogenation of phenolFrom the conversion data at different reaction times, it can be seen that RuNi/gamma-Al 2 O 3 The catalytic performance is obviously higher than Ru/gamma-Al 2 O 3 And Ni/gamma-Al 2 O 3 。
Examples 2 to 4
Unlike example 1, the molar ratio of ruthenium chloride trihydrate and nickel chloride hexahydrate was adjusted, the mass ratio of the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate to the amount of N, N-dimethylformamide was 1:1000, and gamma-Al 2 O 3 The mass ratio of the powder to the ruthenium nickel folded percentage is 20:1, the molar ratio of the benzoic acid to the total of the ruthenium chloride trihydrate and the nickel chloride hexahydrate is 10:1, the mass ratio of the polyvinylpyrrolidone to the benzoic acid is 2:1, and after one-pot reaction, the slurry is filtered, washed by deionized water and dried in vacuum to obtain the gamma-Al with the load of 5 percent 2 O 3 Ruthenium nickel catalyst is supported.
The molar ratio of ruthenium chloride trihydrate to nickel chloride hexahydrate in example 2 was 1:0.5; prepared gamma-Al 2 O 3 Supported ruthenium nickel catalyst, designated Ru 2 Ni/γ-Al 2 O 3 (5％)；
The molar ratio of ruthenium chloride trihydrate to nickel chloride hexahydrate in example 3 was 1:1.5, resulting in gamma-Al 2 O 3 Supported ruthenium nickel catalyst, designated Ru 2 Ni 3 /γ-Al 2 O 3 (5％)；
The molar ratio of ruthenium chloride trihydrate to nickel chloride hexahydrate in example 4 was 1:2; prepared gamma-Al 2 O 3 Supported ruthenium nickel catalyst, designated as RuNi 2 /γ-Al 2 O 3 (5％)；
Gamma-Al prepared in examples 2 to 4 2 O 3 The supported ruthenium-nickel catalyst is used for phenol hydrogenation reaction, and the molar ratio of the active substances in the catalyst to phenol is 1:400; the reaction conditions were the same as in example 1, and the experimental data are shown in Table 1.
TABLE 1 influence of the molar ratio of ruthenium chloride trihydrate and nickel chloride hexahydrate on the catalytic effect of the catalyst
Note that: the molar ratio of ruthenium chloride trihydrate to nickel chloride hexahydrate is designated N.
As can be seen from the data in Table 1, electron transfer exists between ruthenium and nickel, and the synergistic effect between the bimetallic elements enhances the catalytic activity, gamma-Al 2 O 3 The supported ruthenium-nickel catalyst can maintain higher conversion rate and selectivity in low-temperature hydrogenation of phenol.
Examples 5 to 7
Unlike example 1, the mass ratio of the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate to the amount of N, N-dimethylformamide was adjusted, the molar ratio of ruthenium chloride trihydrate and nickel chloride hexahydrate was 1:1, and γ -Al 2 O 3 The mass ratio of the powder to the ruthenium nickel folded percentage is 20:1, the molar ratio of the benzoic acid to the total of the ruthenium chloride trihydrate and the nickel chloride hexahydrate is 10:1, the mass ratio of the polyvinylpyrrolidone to the benzoic acid is 2:1, and after one-pot reaction, the slurry is filtered, washed by deionized water and dried in vacuum to obtain the gamma-Al with the load of 5 percent 2 O 3 Supported ruthenium nickel catalyst, designated RuNi/gamma-Al 2 O 3 (5％)。
Gamma-Al prepared in examples 5 to 7 2 O 3 The supported ruthenium-nickel catalyst is used for phenol hydrogenation reaction, and the molar ratio of the active substances in the catalyst to phenol is 1:400; the reaction conditions were the same as in example 1, and the experimental data are shown in Table 2.
TABLE 2 influence of the mass ratio of the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate to the amount of N, N-dimethylformamide on the catalytic effect of the catalyst
| Examples | M | Conversion (%) | Selectivity (%) |
| 1 | 1:1000 | 100 | 100 |
| 5 | 1:200 | 97.5 | 98.3 |
| 6 | 1:500 | 99.8 | 100 |
| 7 | 1:2000 | 100 | 100 |
Note that: the mass ratio of the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate to the amount of N, N-dimethylformamide is designated as M.
As can be seen from the data in Table 2, N, N-dimethylformamide as a solvent for the ruthenium-nickel solution, when the amount thereof is large, it is advantageous to disperse the catalyst precursor, gamma-Al 2 O 3 The supported ruthenium-nickel catalyst can be added at low temperature of phenolThe conversion rate and selectivity in hydrogen are kept high.
Examples 8 to 10
Unlike example 1, γ -Al was used 2 O 3 The mass ratio of the powder consumption to the ruthenium nickel fold and hundred consumption is adjusted, the molar ratio of the ruthenium chloride trihydrate to the nickel chloride hexahydrate is 1:1, the mass ratio of the total consumption of the ruthenium chloride trihydrate and the nickel chloride hexahydrate to the N, N-dimethylformamide consumption is 1:1000, the molar ratio of the benzoic acid consumption to the total consumption of the ruthenium chloride trihydrate and the nickel chloride hexahydrate is 10:1, the mass ratio of the polyvinylpyrrolidone consumption to the benzoic acid consumption is 2:1, and the gamma-Al with different loading amounts is obtained by filtering slurry, washing with deionized water and vacuum drying after the one-pot reaction 2 O 3 Ruthenium nickel catalyst is supported.
Gamma-Al prepared in examples 8 to 10 2 O 3 The supported ruthenium-nickel catalyst is used for phenol hydrogenation reaction, and the molar ratio of the active substances in the catalyst to phenol is 1:400; the reaction conditions were the same as in example 1, and the experimental data are shown in Table 3.
TABLE 3 gamma-Al 2 O 3 Influence of mass ratio of powder consumption to ruthenium-nickel folded hundred consumption on catalytic effect of catalyst
| Examples | P | Load (%) | Conversion (%) | Selectivity (%) |
| 1 | 20:1 | 5 | 100 | 100 |
| 8 | 10:1 | 10 | 100 | 95.5 |
| 9 | 50:1 | 2 | 96.6 | 100 |
| 10 | 100:1 | 1 | 90.5 | 100 |
Note that: gamma-Al 2 O 3 The mass ratio of the powder amount to the ruthenium nickel hundred amount was designated as P.
As can be seen from the data in Table 3, gamma-Al 2 O 3 When the dosage is smaller, the conversion rate is higher due to the unchanged dosage of the active center, but the selectivity is slightly lower along with gamma-Al 2 O 3 The amount was increased and the conversion was gradually decreased because 1% loading of catalyst was used and the total amount of catalyst reached about 20% of the substrate, and the effect of stirring using magnetons was poor in a small autoclave, which was unfavorable for the two-phase hydrogenation reaction, but in general, gamma-Al was used 2 O 3 The supported ruthenium-nickel catalyst can maintain higher conversion rate and selectivity in low-temperature hydrogenation of phenol.
Examples 11 to 13
Unlike example 1, the molar ratio of benzoic acid to the total of ruthenium chloride trihydrate and nickel chloride hexahydrate was adjusted, the molar ratio of ruthenium chloride trihydrate and nickel chloride hexahydrate was 1:1, the mass ratio of the total of ruthenium chloride trihydrate and nickel chloride hexahydrate to the amount of N, N-dimethylformamide was 1:1000, and gamma-Al 2 O 3 The mass ratio of the powder to the ruthenium nickel folding dosage is 20:1, the mass ratio of the polyvinylpyrrolidone to the benzoic acid dosage is 2:1, and after one-pot reaction, the slurry is filtered, washed by deionized water and dried in vacuum to obtain the gamma-Al with the load of 5 percent 2 O 3 Ruthenium nickel catalyst is supported.
Gamma-Al prepared in examples 11 to 13 2 O 3 The supported ruthenium-nickel catalyst is used for phenol hydrogenation reaction, and the molar ratio of the active substances in the catalyst to phenol is 1:400; the reaction conditions were the same as in example 1, and the experimental data are shown in Table 4.
TABLE 4 influence of the molar ratio of the amount of benzoic acid to the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate on the catalytic effect of the catalyst
| Examples | Q | Conversion (%) | Selectivity (%) |
| 1 | 10:1 | 100 | 100 |
| 11 | 5:1 | 98.6 | 94.3 |
| 12 | 15:1 | 100 | 100 |
| 13 | 20:1 | 100 | 100 |
Note that: the molar ratio of the amount of benzoic acid to the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate is designated Q.
As can be seen from the data in Table 4, benzoic acid as a reducing agent has a good reducing effect when used in a sufficient amount, and the molar ratio of the amount of benzoic acid to the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate is greater than 5:1, so that the prepared gamma-Al can be obtained 2 O 3 The supported ruthenium-nickel catalyst maintains higher conversion and selectivity in the low temperature hydrogenation of phenol.
Examples 14 to 16
Unlike example 1, the reaction temperature and reaction time in S3 were adjusted so that the molar ratio of ruthenium chloride trihydrate to nickel chloride hexahydrate was 1:1, the mass ratio of the total amount of ruthenium chloride trihydrate and nickel chloride hexahydrate to the amount of N, N-dimethylformamide was 1:1000, and gamma-Al 2 O 3 The mass ratio of the powder to the ruthenium nickel folded percentage is 20:1, the molar ratio of the benzoic acid to the total of the ruthenium chloride trihydrate and the nickel chloride hexahydrate is 10:1, the mass ratio of the polyvinylpyrrolidone to the benzoic acid is 2:1, and after one-pot reaction, the slurry is filtered, washed by deionized water and dried in vacuum to obtain the gamma-Al with the load of 5 percent 2 O 3 Ruthenium nickel catalyst is supported.
Will be implementedGamma-Al prepared in examples 14 to 16 2 O 3 The supported ruthenium-nickel catalyst is used for phenol hydrogenation reaction, and the molar ratio of the active substances in the catalyst to phenol is 1:400; the reaction conditions were the same as in example 1, and the experimental data are shown in Table 5.
The effect of the reaction temperature and the reaction time on the catalytic effect of the catalyst in Table 5S3
| Examples | Reaction temperature (. Degree. C.) | Reaction time (h) | Conversion (%) | Selectivity (%) |
| 1 | 180 | 12 | 100 | 100 |
| 11 | 120 | 20 | 94.2 | 95.5 |
| 12 | 160 | 16 | 98.8 | 100 |
| 13 | 230 | 8 | 100 | 100 |
As can be seen from the data in Table 5, when the reaction temperature in S3 is high, the reaction time is short, the reduction effect is good, and the prepared gamma-Al can be obtained 2 O 3 The supported ruthenium-nickel catalyst maintains higher conversion and selectivity in the low temperature hydrogenation of phenol.
Example 17
RuNi/gamma-Al prepared in example 1 2 O 3 (5%) for hydrogenation of phenol, 10g of phenol was added to an autoclave, and RuNi/gamma-Al obtained in example 1 was added 2 O 3 (5%) 0.43g, after the autoclave was replaced, hydrogen was charged to pressurize to 20bar, the temperature was raised to 100℃and the stirring speed was 500rpm, and the reaction was stopped for 6 hours.
Sample analysis shows that the conversion rate of phenol reaches 90.2%, GC shows no by-product, the hydrogenated product of phenol is cyclohexanol, and the selectivity is 100%.
Example 18
RuNi/gamma-Al prepared in example 1 2 O 3 (5%) for hydrogenation of phenol, 10g of phenol was added to an autoclave, and RuNi/gamma-Al obtained in example 1 was added 2 O 3 (5%) 0.43g, filling hydrogen gas to pressurize to 20bar after sealing the kettle for replacement, heating to 100 ℃, stirring at 500rpm, reacting for 10h, keeping the pressure constant, and stopping the reaction.
Sample analysis shows that the conversion rate of phenol reaches 100%, GC shows no by-product, the hydrogenated product of phenol is cyclohexanol, and the selectivity is 100%.
Example 19
RuNi/gamma-Al prepared in example 1 2 O 3 (5%) for phenol hydrogenation reactionTo this end, 10g of phenol was added to an autoclave, a 30% sodium hydroxide solution was added dropwise to adjust ph=10, and the RuNi/γ -Al obtained in example 1 was added 2 O 3 (5%) 0.43g, filling hydrogen gas to pressurize to 20bar after sealing the kettle for replacement, heating to 100 ℃, stirring at 500rpm, reacting for 6h, keeping the pressure constant, and stopping the reaction.
After acidification of the feed liquid, extraction with methylene dichloride and sampling analysis of supernatant liquid, experimental data show that the conversion rate of phenol reaches 99.2%, GC shows no by-product, and the phenol hydrogenation product is cyclohexanol, and the selectivity is 100%.
Example 20
RuNi/gamma-Al prepared in example 1 2 O 3 (5%) for hydrogenation of phenol, 10g of phenol was added to an autoclave, a 30% sodium hydroxide solution was added dropwise to adjust ph=12, and RuNi/γ -Al obtained in example 1 was added 2 O 3 (5%) 0.43g, filling hydrogen gas to pressurize to 20bar after sealing the kettle for replacement, heating to 100 ℃, stirring at 500rpm, reacting for 6h, keeping the pressure constant, and stopping the reaction.
After acidification of the feed liquid, extraction with methylene dichloride and sampling analysis of the supernatant liquid, experimental data show that the conversion rate of phenol reaches 100%, GC shows that a small amount of byproducts are generated, and the phenol hydrogenation product is mainly cyclohexanol, and the selectivity is 98.9%.
Examples 1 and 17 to 20 show that the gamma-Al provided by the present invention 2 O 3 The supported ruthenium-nickel catalyst is applied to phenol hydrogenation reaction, and the reaction time can be effectively shortened by adjusting the pH value of phenol to be 10-12 through sodium hydroxide solution, so that a better reaction effect is achieved.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. Gamma-Al 2 O 3 A ruthenium-nickel supported catalyst characterized by comprising the steps ofPreparation:
s1: adding ruthenium chloride trihydrate and nickel chloride hexahydrate into N, N-dimethylformamide according to the molar ratio of 1:0.5-2, and stirring until all the materials are dissolved to obtain ruthenium-nickel solution;
s2: sequentially adding polyvinylpyrrolidone and benzoic acid into the ruthenium-nickel solution, and then adding gamma-Al 2 O 3 The powder is stirred and dispersed by ultrasonic vibration to obtain a precursor solution;
s3: putting the precursor solution into an autoclave, sealing the autoclave, heating to the reaction temperature, carrying out heat preservation reaction, cooling, and opening the autoclave to obtain catalyst slurry;
s4: filtering the catalyst slurry, washing a filter cake with deionized water, and vacuum drying to obtain gamma-Al 2 O 3 Ruthenium nickel catalyst is supported.
2. gamma-Al according to claim 1 2 O 3 The supported ruthenium-nickel catalyst is characterized in that the mass ratio of the total consumption of the ruthenium chloride trihydrate and the nickel chloride hexahydrate to the consumption of the N, N-dimethylformamide in the S1 is 1:200-2000.
3. gamma-Al according to claim 1 2 O 3 A supported ruthenium nickel catalyst characterized in that the gamma-Al described in S2 2 O 3 The mass ratio of the powder consumption to the ruthenium nickel folding percentage is 10-100:1.
4. gamma-Al according to claim 1 2 O 3 The supported ruthenium-nickel catalyst is characterized in that the molar ratio of the using amount of benzoic acid to the total using amount of ruthenium chloride trihydrate and nickel chloride hexahydrate in S2 is 5-20:1.
5. gamma-Al according to claim 1 2 O 3 The supported ruthenium-nickel catalyst is characterized in that the mass ratio of the dosage of polyvinylpyrrolidone to the dosage of benzoic acid in S2 is 2:1.
6. gamma-Al according to claim 1 2 O 3 The ruthenium-nickel catalyst is loaded on the catalyst,the method is characterized in that the reaction condition in S3 is that the reaction temperature is 120-230 ℃ and the reaction time is 8-20 h.
7. Gamma-Al 2 O 3 Use of a supported ruthenium nickel catalyst for the hydrogenation of phenol, characterized in that a gamma-Al according to any one of claims 1 to 6 is used 2 O 3 The supported ruthenium nickel catalyst is a hydrogenation catalyst.
8. gamma-Al according to claim 7 2 O 3 The application of the supported ruthenium-nickel catalyst in phenol hydrogenation reaction is characterized in that the condition of the phenol hydrogenation reaction also comprises the step of adjusting the pH value of phenol to be 10-12 by using sodium hydroxide solution.
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