CN115869946A - Preparation method of ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction - Google Patents
Preparation method of ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction Download PDFInfo
- Publication number
- CN115869946A CN115869946A CN202211417687.XA CN202211417687A CN115869946A CN 115869946 A CN115869946 A CN 115869946A CN 202211417687 A CN202211417687 A CN 202211417687A CN 115869946 A CN115869946 A CN 115869946A
- Authority
- CN
- China
- Prior art keywords
- ruthenium
- palladium
- salt
- catalyst
- salt solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- -1 phenylphosphine compound Chemical class 0.000 title claims abstract description 40
- 229910001252 Pd alloy Inorganic materials 0.000 title claims abstract description 33
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 37
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 150000002940 palladium Chemical class 0.000 claims abstract description 21
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 16
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 14
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000004321 preservation Methods 0.000 claims abstract description 14
- 150000003657 tungsten Chemical class 0.000 claims abstract description 13
- 150000003681 vanadium Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 24
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical group [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical group [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- HDULBKVLSJEMGN-UHFFFAOYSA-N dicyclohexylphosphane Chemical compound C1CCCCC1PC1CCCCC1 HDULBKVLSJEMGN-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- FRZKYCBWRQUFDF-UHFFFAOYSA-N dicyclohexylphosphane;lithium Chemical compound [Li].C1CCCCC1PC1CCCCC1 FRZKYCBWRQUFDF-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical class PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Abstract
The invention discloses a preparation method of a ruthenium palladium alloy carrier catalyst for phenylphosphine compound hydrogenation reduction reaction, which comprises the following steps: dissolving ruthenium salt in deionized water, and obtaining ruthenium salt solution after the ruthenium salt is dissolved; dissolving palladium salt in deionized water, and obtaining a palladium salt solution after dissolving; mixing the ruthenium salt solution and the palladium salt solution to obtain a ruthenium-palladium salt solution; pulping coconut shell activated carbon and water to prepare carbon pulp, then adding vanadium salt and tungsten salt, and performing ultrasound by using an ultrasonic device; and dripping the ruthenium palladium salt solution into the carbon slurry for heat preservation reaction, and then carrying out reduction aging to obtain the ruthenium palladium alloy carrier catalyst. The catalyst can reduce the diphenyl phosphine based compound to dicyclohexylphosphine based compound by hydrogenation, and has high catalytic efficiency.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a ruthenium palladium alloy carrier catalyst for phenylphosphine compound hydrogenation reduction reaction.
Background
A currently common method for synthesizing bis (dicyclohexylphosphine) alkanebis (tetrafluoroborate) is to prepare dicyclohexylphosphine lithium by reacting dicyclohexylphosphine with n-butyllithium, followed by reaction with an inactive dihaloalkane (Organometallics, 39 (10), 1688-1699,2020, wo 2018008510. However, dicyclohexylphosphine in this method is very easily oxidized and spontaneously ignited in air, making the reaction difficult to control. In addition, the method has more by-products due to higher activity of lithium dicyclohexylphosphine, so that the yield of the target product bis (dicyclohexylphosphine) alkane bis (tetrafluoroborate) is lower. In addition, in the process of preparing dicyclohexylphosphine, lithium aluminum hydride and other dangerous materials which are extremely easy to combust and explode are needed, and the production safety limits the industrial application of the dicyclohexylphosphine.
The research shows that the bis (diphenylphosphino) alkane bidentate phosphine ligand and the bis (dicyclohexylphosphine) alkane bidentate phosphine ligand are very similar in structure, only a benzene ring on the bis (diphenylphosphino) alkane bidentate phosphine ligand needs to be hydrogenated and reduced into cyclohexyl to form the latter, while the noble metal hydrogenation catalysts in various specifications only can reduce compounds such as benzoic acid into cyclohexanoic acid and cannot complete the reduction from diphenylphosphino to dicyclohexylphosphine.
Disclosure of Invention
The invention aims to provide a preparation method of a ruthenium palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction, which can be used for hydrogenation reduction of a diphenylphosphine compound into a dicyclohexylphosphino compound and has high catalytic efficiency.
The technical scheme adopted by the invention is as follows: the preparation method of the ruthenium palladium alloy carrier catalyst for the phenylphosphine compound hydrogenation reduction reaction is implemented according to the following steps:
step 1, dissolving ruthenium salt in deionized water, and obtaining ruthenium salt solution after the solution is clear;
step 2, dissolving palladium salt in deionized water, and obtaining a palladium salt solution after the palladium salt is dissolved;
step 3, mixing the ruthenium salt solution and the palladium salt solution to obtain a ruthenium-palladium salt solution;
step 4, pulping coconut shell activated carbon and water to prepare carbon pulp, then adding vanadium salt and tungsten salt, and performing ultrasound by using an ultrasonic device;
and step 5, dropwise adding the ruthenium palladium salt solution into the carbon slurry for heat preservation reaction, and then carrying out reduction aging to obtain the ruthenium palladium alloy carrier catalyst.
The present invention is also characterized in that,
in step 1, the mass ratio of ruthenium ions contained in the ruthenium salt to deionized water is 1:10 to 20; the ruthenium salt is ruthenium trichloride.
In the step 2, the mass ratio of palladium ions contained in the palladium salt to deionized water is 1:10 to 20; the palladium salt is palladium nitrate.
In the step 3, during mixing, the mass ratio of ruthenium ions to palladium ions is 1:0.1 to 1.
In the step 4, the mass ratio of the coconut shell activated carbon to the water is 1:10 to 20; the addition amount of the vanadium salt and the tungsten salt is 0.1 to 1 percent of the mass of the coconut shell activated carbon, and the vanadium salt is sodium metavanadate, ammonium metavanadate or potassium metavanadate; the tungsten salt is sodium tungstate, sodium phosphotungstate or sodium metatungstate.
In step 5, the method specifically comprises the following steps:
dropwise adding the ruthenium palladium salt solution into the carbon slurry obtained in the step (4), wherein the dropwise adding time is 30-120 min, and the ultrasonic state is always kept in the dropwise adding process; after the dripping is finished, regulating the pH value of the system to 7-9 by using alkali, then heating to 60-100 ℃, and preserving heat for 1h; and after the heat preservation is finished, placing the catalyst in a tubular furnace, reducing the catalyst for 2 hours at the temperature of 200-300 ℃ in the hydrogen atmosphere, switching to the argon atmosphere, heating to 800-1200 ℃, aging at the high temperature for 3 hours, reducing and aging, gradually and slowly cooling until the temperature is reduced to below 40 ℃, washing the catalyst by deionized water until no chloride ion exists, and thus obtaining the ruthenium-palladium alloy carrier catalyst.
The alkali is any one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate.
The beneficial effects of the invention are: the ruthenium palladium alloy catalyst has the characteristic that active center unit cells are distributed in a stepped mode, and a small amount of vanadium and tungsten are doped into the active center unit cells, so that the poisoning resistance and high temperature resistance of the catalyst are improved. The preparation method of the traditional catalyst is mostly a traditional impregnation method, and then reduction is carried out by adopting a chemical reduction method, the traditional impregnation method is adopted in the adsorption link, but hydrogen reduction is carried out by adopting a high-temperature tube furnace in the reduction link, so that the unit cells of the active center of the catalyst can form a step distribution characteristic, and an aging process with higher temperature is added, and the aim is to ensure that the added trace vanadium and tungsten can better enter the unit cells of the active center of the ruthenium-palladium alloy catalyst, thereby achieving the characteristics of poisoning resistance and high temperature resistance.
Drawings
FIG. 1 is a schematic representation of the unit cell characteristics of a ruthenium palladium alloy supported catalyst of the invention;
FIG. 2 is a graph showing the results of the energy spectrum analysis of the ruthenium palladium alloy supported catalyst of the present invention;
Detailed Description
The present invention will be described in detail with reference to the following detailed description and accompanying drawings.
The preparation method of the ruthenium palladium alloy carrier catalyst for the phenylphosphine compound hydrogenation reduction reaction is implemented according to the following steps:
step 1, dissolving ruthenium salt in deionized water, and obtaining ruthenium salt solution after the solution is clear;
wherein the mass ratio of ruthenium ions contained in the ruthenium salt to deionized water is 1:10 to 20; the ruthenium salt is ruthenium trichloride;
step 2, dissolving palladium salt in deionized water, and obtaining a palladium salt solution after the palladium salt is dissolved;
wherein the mass ratio of palladium ions contained in the palladium salt to deionized water is 1:10 to 20; the palladium salt is palladium nitrate;
step 3, mixing the ruthenium salt solution and the palladium salt solution to obtain a ruthenium-palladium salt solution;
wherein, when mixing, the mass ratio of ruthenium to palladium is 1:0.1 to 1.
Step 4, pulping coconut shell activated carbon and water to prepare carbon pulp, then adding vanadium salt and tungsten salt, and performing ultrasonic treatment at 40 Hz for 30 minutes by using an ultrasonic device;
wherein, the mass ratio of the coconut shell activated carbon to the water is 1:10 to 20;
the addition amount of the vanadium salt and the tungsten salt is 0.1 to 1 percent of the mass of the coconut shell activated carbon, and the vanadium salt is sodium metavanadate, ammonium metavanadate or potassium metavanadate; the tungsten salt is sodium tungstate, sodium phosphotungstate or sodium metatungstate;
step 5, dropwise adding the ruthenium-palladium salt solution into the carbon slurry obtained in the step 4 for 30-120 minutes, wherein the dropwise adding process is always kept in a 40 Hz ultrasonic state; after the dripping is finished, regulating the pH value of the system to 7-9 by using alkali, then heating to 60-100 ℃, and preserving heat for 1 hour; after the heat preservation is finished, placing the catalyst in a tubular furnace, reducing the catalyst for 2 hours at 200-300 ℃ in a hydrogen atmosphere, switching to an argon atmosphere, heating to 800-1200 ℃, carrying out high-temperature aging for 3 hours, after the reduction aging is finished, carrying out stepped slow cooling until the temperature is reduced to below 40 ℃, washing the catalyst with deionized water until no chlorine ion exists, and thus obtaining the ruthenium-palladium alloy carrier catalyst;
the alkali is any one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate;
according to the catalyst, two noble metal salts of palladium nitrate and ruthenium trichloride are used, then a small amount of metal vanadium salt and tungsten salt are added as auxiliary agents in the adsorption process, the poisoning resistance of the ruthenium palladium alloy catalyst to phosphorus in a phenylphosphine compound can be improved by adding a certain amount of vanadium salt, and the high temperature resistance of the ruthenium palladium alloy catalyst can be improved by adding a certain amount of tungsten salt. Finally, after reduction by a tubular furnace, the ruthenium-palladium alloy catalyst with the stepped unit cell characteristic is prepared by the working procedures of high-temperature sintering aging, washing and the like, and is used for hydrogenation reaction of benzene rings in phenylphosphine compounds. The schematic diagram of the unit cell characteristics of the ruthenium palladium alloy carrier catalyst prepared by the invention is shown in figure 1, and the catalyst with the active center having the stepped unit cell characteristic is particularly favorable for adsorbing substances with benzene ring structures and reducing the activation energy of substrates. Therefore, a catalyst having such a unit cell characteristic has higher catalytic activity.
The energy spectrum analysis result chart of the ruthenium palladium alloy carrier catalyst of the invention is shown in figure 2 and table 1; the energy spectrum analysis data shows that the vanadium and the tungsten which are added as main components in the vanadium salt and the tungsten salt are well blended into the ruthenium palladium alloy unit cell of the active center of the ruthenium palladium alloy catalyst, so that the active center forms an organic whole.
TABLE 1 energy spectrum analysis results of ruthenium palladium alloy supported catalyst
Note: calculated according to the weight percentage
Example 1, catalyst: ru5Pd2;
firstly, 92.0g of coconut shell activated carbon is taken, 1000.0g of deionized water is added for pulping, and then 0.5g of sodium metavanadate and 0.5g of sodium tungstate are added for ultrasonic standby;
ruthenium trichloride containing 5.0g of ruthenium is additionally taken, 50.0g of deionized water is added, and stirring is carried out to ensure that ruthenium trichloride is completely dissolved for later use. Then, 20.0g of deionized water was added to 2.0g of palladium nitrate, and the mixture was stirred to completely dissolve the palladium nitrate. And (3) uniformly mixing the two metal solutions, slowly dripping the metal solutions into the carbon slurry, controlling the dripping time to be 60 minutes, and keeping the 40 Hz ultrasonic state in the dripping process. After the dripping is finished, 10 percent sodium hydroxide solution is used for adjusting the pH value of the system to 7, the temperature is raised to 60 ℃, and the stirring is carried out for 1 hour under the heat preservation condition. After the heat preservation is finished, the mixture is reduced in a rotary tube furnace for 2 hours at 300 ℃ in a hydrogen atmosphere, then switched to an argon atmosphere, heated to 800 ℃ and aged at high temperature for 3 hours. After the reduction and aging are finished, the temperature is slowly reduced to below 40 ℃ in a stepped manner, and the mixture is washed by deionized water until no chloride ion exists.
Example 2, catalyst: ru5Pd5;
firstly, 89.2g of coconut shell activated carbon is taken, 1000.0g of deionized water is added for pulping, and then 0.3g of ammonium metavanadate and 0.5g of sodium phosphotungstate are added for ultrasonic standby.
And adding 25.0g of deionized water into ruthenium trichloride containing 2.5g of ruthenium, and stirring to completely dissolve the ruthenium trichloride for later use. Then, 25.0g of deionized water was added to 2.5g of palladium nitrate, and the mixture was stirred to completely dissolve the palladium nitrate. And (3) uniformly mixing the two metal solutions, slowly dripping the mixture into the carbon slurry, controlling the dripping time to be 60 minutes, and keeping the 40 Hz ultrasonic state in the dripping process. After the dripping is finished, 10% sodium carbonate solution is used for adjusting the pH value of the system to be 8, the temperature is raised to 60 ℃, and the stirring is carried out for 1 hour under the condition of heat preservation. After the heat preservation is finished, the mixture is reduced in a rotary tube furnace for 2 hours at 250 ℃ under the hydrogen atmosphere, then switched to the argon atmosphere, heated to 900 ℃ and aged for 3 hours at high temperature. After the reduction and aging are finished, slowly reducing the temperature to be below 40 ℃ in a stepped mode, and washing the product by deionized water until no chloride ions exist.
Example 3, catalyst: ru8Pd2;
firstly, 89.2g of coconut shell activated carbon is taken, 1000.0g of deionized water is added for pulping, 0.5g of potassium metavanadate and 0.3g of sodium metatungstate are added, and ultrasonic treatment is carried out for standby.
Ruthenium trichloride containing 8.0g of ruthenium is taken, 80.0g of deionized water is added, and stirring is carried out to ensure that ruthenium trichloride is completely dissolved for later use. Then 20.0g deionized water was added to the palladium nitrate containing 2.0g palladium, and the mixture was stirred to completely dissolve the palladium nitrate for further use. And (3) uniformly mixing the two metal solutions, slowly dripping the mixture into the carbon slurry, controlling the dripping time to be 30 minutes, and keeping the 40 Hz ultrasonic state in the dripping process. After the dripping is finished, 10 percent potassium hydroxide solution is used for adjusting the pH value of the system to 9, the temperature is raised to 80 ℃, and the stirring is carried out for 1 hour under the heat preservation condition. After the heat preservation is finished, the mixture is reduced in a rotary tube furnace for 2 hours at 200 ℃ under the hydrogen atmosphere, then switched to the argon atmosphere, heated to 1200 ℃, and aged for 3 hours at high temperature. After the reduction and aging are finished, the temperature is slowly reduced to below 40 ℃ in a stepped manner, and the mixture is washed by deionized water until no chloride ion exists.
Example 4, catalyst: ru6Pd3;
firstly, 90.2g of coconut shell activated carbon is taken, 1000.0g of deionized water is added for pulping, and then 0.4g of sodium metavanadate and 0.4g of sodium tungstate are added for standby ultrasonic treatment.
60.0g of deionized water is added into ruthenium trichloride containing 6.0g of ruthenium, and the mixture is stirred to completely dissolve the ruthenium trichloride for later use. Then, 30.0g of deionized water was added to 3.0g of palladium nitrate, and the mixture was stirred to completely dissolve the palladium nitrate. And (3) uniformly mixing the two metal solutions, slowly dripping the mixture into the carbon slurry, controlling the dripping time to be 120 minutes, and keeping the 40 Hz ultrasonic state in the dripping process. After the dripping is finished, 10 percent lithium hydroxide solution is used for adjusting the pH value of the system to 7.5, the temperature is raised to 90 ℃, and the stirring is carried out for 1 hour under the condition of heat preservation. After the heat preservation is finished, the mixture is reduced in a rotary tube furnace for 2 hours at 280 ℃ under the hydrogen atmosphere, then switched to the argon atmosphere, heated to 1000 ℃, and subjected to high-temperature aging for 3 hours. After the reduction and aging are finished, slowly reducing the temperature to be below 40 ℃ in a stepped mode, and washing the product by deionized water until no chloride ions exist.
The catalyst prepared by the method is used in actual reaction, and the reaction equation is as follows:
the raw materials are as follows: bis (diphenylphosphino) alkane bidentate phosphine ligand series;
the product is: bis (dicyclohexylphosphino) alkane bidentate phosphine ligands or bis tetrafluoroborate series thereof;
the solvent is as follows: alcohols such as methanol, ethanol, propanol, and isopropanol;
the reaction conditions are as follows: the temperature is above 220 ℃, the pressure is above 15MPa, and the reaction time is above 4.0 h;
TABLE 2 catalytic reaction results
Table 2 shows the results of the catalytic reaction with the catalyst of the present invention, it can be seen that the catalyst has a high yield, because the active center unit cell of the ruthenium palladium alloy catalyst is doped with vanadium and tungsten, and because of the presence of tungsten, the hydrogenation reaction can be carried out at a temperature of more than 200 ℃, thereby accelerating the reaction and shortening the reaction time. And the anti-poisoning performance of the catalyst is greatly enhanced due to the existence of vanadium, so that the conversion rate of the whole reaction is generally higher.
Claims (7)
1. The preparation method of the ruthenium palladium alloy carrier catalyst for the phenylphosphine compound hydrogenation reduction reaction is characterized by comprising the following steps:
step 1, dissolving ruthenium salt in deionized water, and obtaining ruthenium salt solution after the ruthenium salt is dissolved;
step 2, dissolving palladium salt in deionized water, and obtaining a palladium salt solution after the palladium salt is dissolved;
step 3, mixing the ruthenium salt solution and the palladium salt solution to obtain a ruthenium-palladium salt solution;
step 4, pulping coconut shell activated carbon and water to prepare carbon pulp, then adding vanadium salt and tungsten salt, and performing ultrasound by using an ultrasonic device;
and step 5, dropwise adding the ruthenium palladium salt solution into the carbon slurry for heat preservation reaction, and then carrying out reduction aging to obtain the ruthenium palladium alloy carrier catalyst.
2. The method for preparing a ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction according to claim 1, wherein in step 1, the mass ratio of ruthenium ions contained in the ruthenium salt to deionized water is 1:10 to 20; the ruthenium salt is ruthenium trichloride.
3. The method for preparing a ruthenium palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction according to claim 1, wherein in step 2, the mass ratio of palladium ions contained in the palladium salt to deionized water is 1:10 to 20; the palladium salt is palladium nitrate.
4. The method for preparing a ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction according to claim 1, wherein in the step 3, the mass ratio of ruthenium ions to palladium ions in the mixing is 1:0.1 to 1.
5. The method for preparing a ruthenium palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction according to claim 1, wherein in step 4, the mass ratio of coconut shell activated carbon to water is 1:10 to 20; the addition amount of the vanadium salt and the tungsten salt is 0.1 to 1 percent of the mass of the coconut shell activated carbon, and the vanadium salt is sodium metavanadate, ammonium metavanadate or potassium metavanadate; the tungsten salt is sodium tungstate, sodium phosphotungstate or sodium metatungstate.
6. The method for preparing a ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction according to claim 1, wherein in step 5, specifically:
dropwise adding the ruthenium-palladium salt solution into the carbon slurry obtained in the step (4), wherein the dropwise adding time is 30-120 min, and the ultrasonic state is always kept in the dropwise adding process; after the dripping is finished, regulating the pH value of the system to 7-9 by using alkali, then heating to 60-100 ℃, and preserving heat for 1h; and after the heat preservation is finished, placing the catalyst in a tubular furnace, reducing the catalyst for 2 hours at the temperature of 200-300 ℃ in the hydrogen atmosphere, switching to the argon atmosphere, heating to 800-1200 ℃, aging at the high temperature for 3 hours, reducing and aging, gradually and slowly cooling until the temperature is reduced to below 40 ℃, washing the catalyst by deionized water until no chloride ion exists, and thus obtaining the ruthenium-palladium alloy carrier catalyst.
7. The method for preparing a ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction according to claim 6, wherein the base is any one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate and lithium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211417687.XA CN115869946A (en) | 2022-11-11 | 2022-11-11 | Preparation method of ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211417687.XA CN115869946A (en) | 2022-11-11 | 2022-11-11 | Preparation method of ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115869946A true CN115869946A (en) | 2023-03-31 |
Family
ID=85759789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211417687.XA Pending CN115869946A (en) | 2022-11-11 | 2022-11-11 | Preparation method of ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115869946A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1153300A (en) * | 1955-05-10 | 1958-03-04 | Du Pont | Catalytic hydrogenation process for organic nitro compounds |
| CN101549292A (en) * | 2009-05-08 | 2009-10-07 | 西安凯立化工有限公司 | Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof |
| CN104039446A (en) * | 2012-01-06 | 2014-09-10 | 国际人造丝公司 | Precious metal, active metal and modified support - containing hydrogenation catalysts and acetic acid hydrogenation process using the same |
| CN106540690A (en) * | 2016-10-24 | 2017-03-29 | 厦门大学 | A kind of load type palladium ruthenium bimetallic catalyst and preparation method thereof |
| CN106582634A (en) * | 2016-11-16 | 2017-04-26 | 盘锦格林凯默科技有限公司 | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof |
| CN107684930A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of preparation method for phenol hydrogenation preparing cyclohexanone catalyst |
-
2022
- 2022-11-11 CN CN202211417687.XA patent/CN115869946A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1153300A (en) * | 1955-05-10 | 1958-03-04 | Du Pont | Catalytic hydrogenation process for organic nitro compounds |
| CN101549292A (en) * | 2009-05-08 | 2009-10-07 | 西安凯立化工有限公司 | Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof |
| CN104039446A (en) * | 2012-01-06 | 2014-09-10 | 国际人造丝公司 | Precious metal, active metal and modified support - containing hydrogenation catalysts and acetic acid hydrogenation process using the same |
| CN107684930A (en) * | 2016-08-05 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of preparation method for phenol hydrogenation preparing cyclohexanone catalyst |
| CN106540690A (en) * | 2016-10-24 | 2017-03-29 | 厦门大学 | A kind of load type palladium ruthenium bimetallic catalyst and preparation method thereof |
| CN106582634A (en) * | 2016-11-16 | 2017-04-26 | 盘锦格林凯默科技有限公司 | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109136973B (en) | Non-noble metal doped molybdenum carbide hydrogen evolution electrode and preparation method and application thereof | |
| CN103203232B (en) | High dispersion supported nano noble metal catalyst and preparation method and application thereof | |
| EP3825443A1 (en) | Method of preparing catalyst for pem water electrolysis and catalyst for pem water electrolysis | |
| CN109772336A (en) | A kind of porous double-metal hydroxide catalyst and its preparation method and application for the oxidation of electro-catalysis alcohols selectivity | |
| CN111589454A (en) | High-temperature preparation method of binary alloy catalyst of proton exchange membrane fuel cell | |
| CN111013615A (en) | Preparation method of CoP catalyst with hydrogen precipitation and oxygen precipitation high-efficiency dual functions | |
| CN110586159A (en) | Method for preparing full-hydrolysis catalyst with nickel monoatomic double-active-site | |
| CN110681404A (en) | Flaky molybdenum carbide catalyst for electrolytic water cathode hydrogen evolution reaction and preparation method and application thereof | |
| CN110350213B (en) | High-efficiency PtRu/C bifunctional fuel cell anode catalyst and preparation method thereof | |
| CN105195147A (en) | Dehydrogenation catalyst with copper nanoparticles loaded inside carbon nano tube and preparation method of dehydrogenation catalyst | |
| CN115869946A (en) | Preparation method of ruthenium-palladium alloy supported catalyst for phenylphosphine compound hydrogenation reduction reaction | |
| CN102861573B (en) | Carrier type platinum-ruthenium catalyst and application to hydrogenation of halide-containing nitro compound | |
| CN1979930A (en) | Preparing method for noble metal catalyst for proton exchanging film fuel cell | |
| CN113926477A (en) | Ruthenium-loaded phosphorus-doped activated carbon catalyst, preparation method thereof, electrode and application thereof | |
| CN109806904B (en) | Ni-Ag/SBA-15 supported bimetallic catalyst and preparation method and application thereof | |
| CN114621097B (en) | Method for preparing 2, 4-difluoroaniline by catalytic hydrogenation of 2, 4-difluoronitrobenzene | |
| CN114054055B (en) | Carrier material for loading noble metal catalyst and preparation method thereof | |
| CN113937305A (en) | Graphite carbon-coated platinum-cobalt alloy oxygen reduction electrocatalyst and preparation method thereof | |
| KR20100005946A (en) | Platinum-ruthenium binuclear complex for electrode catalyst of fuel cell and preparation method thereof | |
| WO2019114767A1 (en) | Catalyst and preparation method thereof for catalytic selective hydrogenation of chloroaromatic nitro compounds | |
| CN110075851A (en) | A kind of application of nickel-base catalyst and its catalysis furfural hydrogenation reaction | |
| CN115491700B (en) | Electrochemical synthesis method of spice 2-propionyl thiazole | |
| CN113903928B (en) | Preparation method and application of Sb/NC electrocatalyst | |
| CN113097499B (en) | FeNi/NiFe 2 O 4 @ NC composite material and preparation method and application thereof | |
| CN117810469A (en) | Preparation method of high-temperature polymer electrolyte membrane fuel cell catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |