CN110743544B - Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof - Google Patents
Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof Download PDFInfo
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- acetophenone
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 title abstract description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 51
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 12
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000012065 filter cake Substances 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000000889 atomisation Methods 0.000 claims description 9
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004280 Sodium formate Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002941 palladium compounds Chemical class 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 4
- 235000019254 sodium formate Nutrition 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 239000010949 copper Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- -1 aromatic ketone compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910010276 inorganic hydride Inorganic materials 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002699 waste material 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/399—
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/18—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part
- C07C33/20—Monohydroxylic alcohols containing only six-membered aromatic rings as cyclic part monocyclic
- C07C33/22—Benzylalcohol; phenethyl alcohol
Abstract
The invention discloses a palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone, which consists of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is at least one of lanthanum, copper, cerium, neodymium and nickel, and the carrier is activated carbon; the contents of the components are as follows according to the weight percentage of 100 percent: 1-5% of palladium, 0.1-0.5% of auxiliary agent and the balance of carrier; meanwhile, the invention also discloses a preparation method of the catalyst and a method for preparing alpha-phenethyl alcohol by acetophenone selective hydrogenation. The catalyst provided by the invention has good catalytic activity and selectivity; when the catalyst is used for preparing alpha-phenethyl alcohol by selective catalytic hydrogenation of acetophenone, the product yield is over 90 percent, the selectivity is more than 94 percent, and the catalyst has stable service life and can be used repeatedly, thereby belonging to the high-efficiency green environmental protection technology.
Description
Technical Field
The invention belongs to the technical field of noble metal catalysts, and particularly relates to a palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone, and a preparation method and application thereof.
Background
Acetophenone is a byproduct of a plurality of production processes of oxidizing ethylbenzene into styrene and the like, and the preparation of a product with high added value by using the acetophenone as a raw material meets the requirements of atom economy and green chemistry. Alpha-phenethyl alcohol is an important chemical productThe alpha-phenethyl alcohol is widely applied to the industries of medicine and spice, and has wide application in the industries of medicine and spice. The alpha-phenethyl alcohol synthesis method comprises a microbial fermentation method and an organic synthesis method. The microbial fermentation method generally takes phenylalanine and fluorophenylalanine as raw materials, and prepares the alpha-phenethyl alcohol through microbial fermentation and conversion. The method has the advantages of high price of raw materials, high production cost and unsuitability for industrial production. At present, the industry mainly adopts an organic synthesis method using acetophenone as a raw material. The traditional acetophenone reduction process uses expensive inorganic hydride (LiAlH) 4 , NaBH 4 ) As a metering reduction method of a reducing agent, the process generates a large amount of waste liquid containing metal ions, thereby not only increasing the separation difficulty of products, but also causing environmental pollution. The environment-friendly catalytic reduction technology is a main method for preparing aromatic alcohol from aromatic ketone compounds. The homogeneous catalytic reduction technology has higher hydrogenation activity and selectivity, but the catalyst is difficult to recover and the like, which influences the industrial application of the homogeneous catalytic reduction technology, and the preparation of the alpha-phenethyl alcohol by using acetophenone hydrogenation has good application prospect. When the noble metal catalyst is used for acetophenone hydrogenation reaction, the selectivity of alpha-phenylethyl alcohol is often low, or higher acetophenone conversion rate and alpha-phenylethyl alcohol selectivity cannot be obtained at the same time.
At present, the supported noble metal catalyst for acetophenone hydrogenation is mainly an activated carbon-supported nano palladium and lanthanum metal catalyst, and the ubiquitous problem of the catalysts is how to further improve the activity and selectivity of the catalyst on the basis of the existing level, and the key point of how to improve the service life of the catalyst is that the high cost of the noble metal is taken into consideration.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone, and a preparation method and application thereof.
A palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is at least one of lanthanum, copper, cerium, neodymium and nickel, and the carrier is activated carbon; the content of each component is as follows according to the weight percentage of 100 percent: 1 to 5 percent of palladium, 0.1 to 0.5 percent of auxiliary agent and the balance of carrier.
Preferably, the particle size of the carrier is 200-800 meshes, and the specific surface area is 800-1500 m 2 /g。
Preferably, the palladium has an average particle size of 10 to 30nm.
Preferably, the content of the palladium is 5%, the content of the auxiliary agent is 0.5%, and the balance is the carrier.
The preparation method of the palladium-carbon catalyst for preparing alpha-phenethyl alcohol by acetophenone selective hydrogenation comprises the following steps:
(1) Adding the carrier into 5-10mol/L nitric acid water solution, boiling for 0.5-2h, naturally cooling, washing with deionized water until the pH of washing liquor is neutral, and filtering to obtain a pretreated carrier;
(2) Dissolving soluble palladium compound and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution, wherein the solvent is water or alcohol;
(3) Carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring and dipping to obtain slurry, adjusting the pH of the slurry to 8-10 by using alkali liquor, continuously stirring for 3-5h and filtering to obtain a filter cake, washing the filter cake by using deionized water until the pH of washing liquor is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) Pulping the filter cake washed in the step (3) by pure water to obtain slurry, adjusting the pH of the slurry to 6-9 by alkali liquor, adding a reducing agent, carrying out reduction treatment at 60-100 ℃ for 0.5-6h, and then filtering, washing, drying and drying.
Preferably, the soluble palladium compound is palladium trichloride.
Preferably, the soluble salt of the auxiliary agent is chloride of the auxiliary agent or nitrate of the auxiliary agent.
Preferably, the reducing agent is any one of sodium hypophosphite, sodium borohydride, potassium borohydride, hydrazine hydrate, formic acid or sodium formate; the molar weight of the reducing agent is 3-10 times of that of the palladium.
Preferably, the drying temperature is 60-100 ℃ and the drying time is 5-12h.
A method for preparing alpha-phenylethyl alcohol by selectively hydrogenating acetophenone by using the catalyst comprises the following steps: adding acetophenone, catalyst and solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 1-5h at the temperature of 60-100 ℃ under the pressure of 0.5-2 MPa to obtain a product alpha-phenethyl alcohol; the addition amount of the catalyst is 0.5-5% of the mass of the acetophenone, and the solvent is absolute ethyl alcohol or methanol.
Preferably, adding acetophenone, a catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 3 hours at the temperature of 80 ℃ under the pressure of 1 MPa to obtain a product alpha-phenethyl alcohol; the adding amount of the catalyst is 1 percent of the mass of the acetophenone.
The invention has the advantages that:
1. according to the catalyst provided by the invention, after the carrier activated carbon is boiled in a nitric acid water solution for pretreatment, metal components are uniformly dispersed on the carrier, the particle size of palladium metal ions in the catalyst is 10-30nm, and the catalyst has good catalytic activity and selectivity;
2. the metal components are uniformly dispersed on the carrier by ultrasonic atomization treatment, so that the dispersibility and the activity of the catalyst are improved;
3. the preparation method of the catalyst provided by the invention is easy to operate, raw materials are easy to obtain, large-scale industrial production is easy to realize, the prepared catalyst is convenient to recover after being used, the production-recovery-reproduction of noble metals can be realized, the loss in the recovery process is less, and the production cost of the catalyst is greatly reduced;
4. when the catalyst provided by the invention is used for preparing alpha-phenethyl alcohol by selective catalytic hydrogenation of acetophenone, the steps are simple, the conditions are mild, the product yield exceeds 90%, the selectivity is greater than 94%, the product yield is greatly improved, the production cost is greatly reduced, the catalyst belongs to an efficient green environment-friendly technology, and favorable conditions are provided for large-scale application of the catalyst;
5. the catalyst prepared by the method has stable service life, can be reused for many times, reduces the cost problem of using the catalyst for one time, and is easy to realize industrialization.
Detailed Description
Example 1
1. A palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is neodymium, and the carrier is activated carbon; the content of each component is as follows according to the weight percentage of 100 percent: 5% of palladium, 0.5% of an auxiliary agent and the balance of a carrier;
wherein the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 1200 m 2 (iv) g; the average particle size of the palladium is 10-30nm.
2. The preparation method of the palladium-carbon catalyst for preparing alpha-phenethyl alcohol by acetophenone selective hydrogenation comprises the following steps:
(1) Adding 10g of carrier into 6mol/L nitric acid water solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) Dissolving palladium trichloride and neodymium chloride in water, and uniformly stirring to obtain a precursor solution;
(3) Carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, then soaking for 2 hours to obtain slurry, adjusting the pH of the slurry to 10 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, then filtering to obtain a filter cake, washing the filter cake by using deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) Adding the filter cake washed in the step (3) into pure water with the mass of 20 times, pulping to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, adding sodium borohydride, carrying out reduction treatment for 3 hours at 80 ℃, then filtering, washing, drying for 5 hours at 100 ℃ to obtain the filter cake; the molar weight of the sodium borohydride is 3 times of that of the palladium.
Example 2
1. A palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and a metal component loaded on the carrier, wherein the metal component comprises palladium and an auxiliary agent, the auxiliary agent is lanthanum, and the carrier is activated carbon; the content of each component is as follows according to the weight percentage of 100 percent: 5% of palladium, 0.5% of auxiliary agent and the balance of carrier;
wherein the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 1200 m 2 (ii)/g; the average particle size of the palladium is 10-30nm.
2. The preparation method of the palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) Adding 10g of carrier into 6mol/L nitric acid water solution, boiling for 1h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) Dissolving palladium trichloride and lanthanum chloride in water, and uniformly stirring to obtain a precursor solution;
(3) Carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 6 hours to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 5 hours, filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) Adding the filter cake washed in the step (3) into pure water with the mass of 20 times, pulping to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution with the mass concentration of 1%, adding potassium borohydride, carrying out reduction treatment at 100 ℃ for 2h, then filtering, washing, and drying at 90 ℃ for 4h to obtain the filter cake; the molar weight of the potassium borohydride is 3 times of that of palladium.
Example 3
1. A palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is lanthanum, neodymium and nickel, and the carrier is activated carbon; the content of each component is as follows according to the weight percentage of 100 percent: 5% of palladium, 0.5% of assistant, equal lanthanum, neodymium and nickel, and the balance of carrier;
wherein the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 1200 m 2 (ii)/g; the average particle size of the palladium is 10-30nm.
2. The preparation method of the palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) Adding 10g of carrier into 10mol/L nitric acid water solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) Dissolving palladium trichloride, lanthanum chloride, neodymium nitrate and nickel nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) Carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 3h to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 5h, filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) Adding the filter cake washed in the step (3) into pure water with the mass of 20 times, pulping to obtain slurry, adjusting the pH of the slurry to 6 by using a sodium hydroxide solution with the mass concentration of 1%, adding sodium hypophosphite, carrying out reduction treatment for 3h at 90 ℃, filtering, washing, and drying for 12h at 60 ℃ to obtain the filter cake; the molar weight of the sodium hypophosphite is 3 times of the molar weight of the palladium.
Example 4
1. A palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is copper and cerium, and the carrier is active carbon; the contents of the components are as follows according to the weight percentage of 100 percent: 5% of palladium, 0.5% of assistant, equal content of copper and cerium and the balance of carrier;
wherein the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 1200 m 2 (iv) g; the average particle size of the palladium is 10-30nm.
2. The preparation method of the palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone comprises the following steps:
(1) Adding 10g of carrier into 5mol/L nitric acid water solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) Dissolving palladium trichloride, copper nitrate and cerous nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) Carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, then soaking for 4 hours to obtain slurry, adjusting the pH of the slurry to 10 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, then filtering to obtain a filter cake, washing the filter cake by using deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) Adding the filter cake washed in the step (3) into pure water with the mass 30 times that of the filter cake, pulping to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, adding formic acid, carrying out reduction treatment at 60 ℃ for 6 hours, then filtering, washing, drying at 100 ℃ for 5 hours, and thus obtaining the filter cake; the molar amount of formic acid is 5 times of the molar amount of palladium.
Example 5
1. A palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is lanthanum, copper, cerium, neodymium and nickel, and the carrier is activated carbon; the contents of the components are as follows according to the weight percentage of 100 percent: 1% of palladium, 0.2% of an auxiliary agent, equal mass of lanthanum, copper, cerium, neodymium and nickel, and the balance of a carrier;
wherein the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 1500 m 2 (ii)/g; the average particle size of the palladium is 10-30nm.
2. The preparation method of the palladium-carbon catalyst for preparing alpha-phenethyl alcohol by acetophenone selective hydrogenation comprises the following steps:
(1) Adding 10g of carrier into 6mol/L nitric acid water solution, boiling for 2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) Dissolving palladium trichloride, lanthanum chloride, copper nitrate, cerium nitrate, neodymium chloride and nickel nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) Carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, dipping for 4 hours to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) Adding the filter cake washed in the step (3) into pure water with the mass 30 times that of the filter cake, pulping to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution with the mass concentration of 1%, adding sodium formate, carrying out reduction treatment at 100 ℃ for 0.5h, then filtering, washing, and drying at 100 ℃ for 5h to obtain the filter cake; the molar weight of the sodium formate is 4 times of that of the palladium.
Example 6
1. A palladium-carbon catalyst for preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise palladium and an auxiliary agent, the auxiliary agent is copper, cerium, neodymium and nickel, and the carrier is activated carbon; the content of each component is as follows according to the weight percentage of 100 percent: 3% of palladium, 0.1% of auxiliary agent, equal mass of copper, cerium, neodymium and nickel, and the balance of carrier;
wherein the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 800 m 2 (ii)/g; the average particle size of the palladium is 10-30nm.
2. The preparation method of the palladium-carbon catalyst for preparing alpha-phenethyl alcohol by acetophenone selective hydrogenation comprises the following steps:
(1) Adding 10g of carrier into 10mol/L nitric acid water solution, boiling for 0.5h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain the pretreated carrier;
(2) Dissolving palladium trichloride, copper nitrate, cerium nitrate, neodymium chloride and nickel nitrate in water, and uniformly stirring to obtain a precursor solution;
(3) Carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring, then soaking for 2 hours to obtain slurry, adjusting the pH of the slurry to 8 by using a sodium hydroxide solution with the mass concentration of 1%, continuously stirring for 3 hours, then filtering to obtain a filter cake, washing the filter cake with deionized water until the pH of a washing liquid is neutral, and keeping the filter cake for later use; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) Adding the filter cake washed in the step (3) into pure water with the mass 30 times that of the filter cake, pulping to obtain slurry, adjusting the pH of the slurry to 9 by using a sodium hydroxide solution with the mass concentration of 1%, adding hydrazine hydrate, carrying out reduction treatment for 1h at 90 ℃, then filtering, washing, drying for 5h at 100 ℃ to obtain the finished product; the molar amount of hydrazine hydrate is 5 times of the molar amount of palladium.
Example 7
The assistant is neodymium, the palladium content is 1%, the corresponding soluble salt in the preparation method is neodymium chloride, and the rest is the same as the example 1.
Example 8
The auxiliary agent is neodymium, the corresponding soluble salt in the preparation method with 3% of palladium content is neodymium chloride, and the rest is the same as example 1.
Example 9
The auxiliary agent is cerium, the corresponding soluble salt in the preparation method is cerium nitrate, and the rest is the same as example 1.
Example 10
The auxiliaries are copper, cerium and nickel, the corresponding soluble salts in the preparation method are copper nitrate, cerium nitrate and nickel nitrate, and the rest is the same as in example 3.
Comparative example 1
The palladium/activated carbon catalyst obtained by a commercially available method is used as a comparative example 1, the mass percentage of palladium in the catalyst is 5%, and the activated carbon carrier is 95%, the particle size of the carrier is 200-800 meshes, and the specific surface area is 1200 m 2 The particle diameter of the palladium metal is 10-30nm.
Example 11
The method for preparing the alpha-phenethyl alcohol by selectively hydrogenating the acetophenone by using the catalyst comprises the following steps: adding acetophenone, catalyst and solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 1-5h at the temperature of 60-100 ℃ under the pressure of 0.5-2 MPa to obtain a product alpha-phenethyl alcohol; the addition amount of the catalyst is 0.5-5% of the mass of the acetophenone, and the solvent is absolute ethyl alcohol or methanol.
Example 12
The catalyst of examples 1-6 and comparative example 1 is used for preparing alpha-phenethyl alcohol by selectively hydrogenating acetophenone, and the specific method comprises the following steps: adding acetophenone, a catalyst and a solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 3 hours at the temperature of 80 ℃ under the pressure of 1 MPa to obtain a product alpha-phenethyl alcohol; the addition amount of the catalyst is 1 percent of the mass of the acetophenone, and the solvent is absolute ethyl alcohol;
1. 5mL of the reaction product of example 12 was collected, filtered, diluted to 50mL with methanol, and analyzed by Shimadzu gas chromatography GC-2014, the results of which are shown in Table 1.
TABLE 1 test results of the selective hydrogenation of acetophenone by different catalysts
As can be seen from Table 1, the catalyst provided by the invention has high raw material conversion rate and high product yield when catalyzing acetophenone to prepare alpha-phenethyl alcohol.
2. Stability testing of the catalysts
The catalyst was recovered and recycled as described in example 12, with the test results shown in Table 2.
TABLE 2 recycle of different catalysts
As can be seen from Table 2, the catalyst provided by the invention has stable catalytic performance, high repeated use frequency and recycling property.
Claims (9)
1. A method for preparing alpha-phenethyl alcohol by acetophenone selective hydrogenation is characterized in that: the method comprises the following steps: adding acetophenone, catalyst and solvent into a high-pressure reaction kettle, introducing hydrogen into the high-pressure reaction kettle, and carrying out catalytic hydrogenation reaction for 1-5h at the temperature of 60-100 ℃ under the pressure of 0.5-2 MPa to obtain a product alpha-phenethyl alcohol; the addition amount of the catalyst is 0.5-5% of the mass of the acetophenone, and the solvent is absolute ethyl alcohol or methanol;
the catalyst consists of a carrier and a metal component loaded on the carrier, wherein the metal component comprises palladium and an auxiliary agent, the auxiliary agent is at least one of lanthanum, cerium, neodymium and nickel, and the carrier is activated carbon; the contents of the components are as follows according to the weight percentage of 100 percent: 1 to 5 percent of palladium, 0.1 to 0.5 percent of additive and the balance of carrier.
2. The method for preparing alpha-phenylethyl alcohol by selectively hydrogenating acetophenone according to claim 1, characterized in that: the particle diameter of the carrier is 200-800 meshes, and the specific surface area is 800-1500 m 2 /g。
3. The method for preparing alpha-phenylethyl alcohol by selectively hydrogenating acetophenone according to claim 1, characterized in that: the average particle size of the palladium is 10-30nm.
4. The method for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone according to any one of claims 1 to 3, characterized in that: the content of the palladium is 5 percent, the content of the auxiliary agent is 0.5 percent, and the balance is the carrier.
5. A process for the preparation of α -phenylethyl alcohol by selective hydrogenation of acetophenone as claimed in any one of claims 1 to 3, characterized in that: the catalyst is prepared by the following method: the method comprises the following steps:
(1) Adding the carrier into 5-10mol/L nitric acid water solution, boiling for 0.5-2h, naturally cooling, washing with deionized water until the pH value of washing liquor is neutral, and filtering to obtain a pretreated carrier;
(2) Dissolving soluble palladium compound and soluble salt of an auxiliary agent in a solvent, and uniformly stirring to obtain a precursor solution, wherein the solvent is water or alcohol;
(3) Carrying out ultrasonic atomization on the precursor solution to obtain atomized dropping liquid, introducing the atomized dropping liquid into a reactor containing the pretreated carrier, uniformly stirring and then dipping to obtain slurry, adjusting the pH of the slurry to 8-10 by using alkali liquor, continuously stirring for 3-5 hours and then filtering to obtain a filter cake, washing the filter cake by using deionized water until the pH of washing liquor is neutral, and reserving the filter cake; correspondingly adding 20mL of precursor solution into each gram of the pretreated carrier;
(4) And (4) pulping the filter cake washed in the step (3) by using pure water to obtain slurry, adjusting the pH of the slurry to 6-9 by using alkali liquor, adding a reducing agent, carrying out reduction treatment at the temperature of 60-100 ℃ for 0.5-6h, and then filtering, washing, drying and drying the slurry.
6. The method for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone according to claim 5, characterized in that: the soluble palladium compound is palladium trichloride.
7. The method for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone according to claim 5, characterized in that: the soluble salt of the auxiliary agent is chloride of the auxiliary agent or nitrate of the auxiliary agent.
8. The method for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone according to claim 5, characterized in that: the reducing agent is any one of sodium hypophosphite, sodium borohydride, potassium borohydride, hydrazine hydrate, formic acid or sodium formate; the molar weight of the reducing agent is 3-10 times of the molar weight of the palladium.
9. The method for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone according to claim 5, characterized in that: the drying temperature is 60-100 deg.C, and the drying time is 5-12h.
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| CN112642441B (en) * | 2020-12-10 | 2022-12-02 | 西安凯立新材料股份有限公司 | Catalyst for preparing 1,2, 4-butanetriol through catalytic hydrogenation and preparation method and application thereof |
| CN113522279A (en) * | 2021-07-16 | 2021-10-22 | 西安海望能源科技有限公司 | Gold palladium catalyst for hydrogen desorption of dodecahydroethylcarbazole and preparation method thereof |
| CN114345325B (en) * | 2021-12-31 | 2022-11-22 | 河北海力香料股份有限公司 | Reactivation method of palladium/carbon catalyst |
| CN115400750A (en) * | 2022-09-29 | 2022-11-29 | 西安凯立新材料股份有限公司 | Catalyst for preparing saturated ketone by hydrogenation of multi-double-bond unsaturated ketone and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4324222A1 (en) * | 1992-07-28 | 1994-02-03 | Inst Francais Du Petrole | Process for the production of aromatic alcohol by selective hydrogenation of aromatic ketone |
| CN1305981A (en) * | 2000-01-12 | 2001-08-01 | 住友化学工业株式会社 | Method of preparing alpha-phenyl ethyl alcohol |
| CN105749936A (en) * | 2016-04-05 | 2016-07-13 | 宁夏蓝丰精细化工有限公司 | Metal composite catalyst for selective dechloridation and preparation method thereof |
| CN106732564A (en) * | 2016-12-03 | 2017-05-31 | 西安凯立新材料股份有限公司 | The preparation method and application of aromatic hydrogenation rhodium/activated-carbon catalyst |
| CN107715870A (en) * | 2017-10-13 | 2018-02-23 | 西安凯立新材料股份有限公司 | A kind of preparation method and application for preparing L aminopropanol ruthenium Pd/carbon catalysts |
| CN109320398A (en) * | 2018-08-28 | 2019-02-12 | 浙江工业大学 | A method of benzhydrol is synthesized by benzophenone catalytic hydrogenation |
| CN110227487A (en) * | 2019-06-24 | 2019-09-13 | 西安凯立新材料股份有限公司 | A kind of preparation method and application of carbonyl hydrogen catalyst |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1543372A1 (en) * | 1966-10-18 | 1971-04-01 | Boehringer Sohn Ingelheim | Process for the preparation of o-substituted 3,4-dioxyphenylalkanolamines |
| DE3431687A1 (en) * | 1984-08-29 | 1986-03-13 | Bayer Ag, 5090 Leverkusen | 2,4-DICHLOR-3-ALKYL-6-NITROPHENOLS AND A METHOD FOR THE PRODUCTION THEREOF |
| JP3582337B2 (en) * | 1997-12-18 | 2004-10-27 | 住友化学工業株式会社 | Hydrogenation reaction method |
| CN1151876C (en) * | 2001-11-14 | 2004-06-02 | 中国石油化工股份有限公司 | Catalyst for prepn. of m-dimethyl amino benzoic acid |
| CN102441405B (en) * | 2011-10-31 | 2013-07-24 | 河南煤业化工集团研究院有限责任公司 | Catalyst used for gas-phase synthesis of oxalate ester and its preparation method |
| CN103754883B (en) * | 2014-01-02 | 2015-05-06 | 河南科技大学 | Catalyst for transforming silicon tetrachloride into trichlorosilane through hydrodechlorination and preparation method of catalyst |
| CN104689832B (en) * | 2015-03-20 | 2017-02-01 | 西安凯立新材料股份有限公司 | Preparation method for modified palladium-carbon catalyst for Suzuki coupling reaction |
| CN106622229B (en) * | 2017-01-10 | 2019-06-28 | 湘潭大学 | The preparation method and phenol selectivity of hydrogenation catalyst add the method for hydrogen preparing cyclohexanone |
| CN108187730A (en) * | 2018-01-26 | 2018-06-22 | 昆山普瑞凯纳米技术有限公司 | A kind of support type composition metal-acid bifunctional catalyst |
-
2019
- 2019-11-07 CN CN201911080016.7A patent/CN110743544B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4324222A1 (en) * | 1992-07-28 | 1994-02-03 | Inst Francais Du Petrole | Process for the production of aromatic alcohol by selective hydrogenation of aromatic ketone |
| CN1305981A (en) * | 2000-01-12 | 2001-08-01 | 住友化学工业株式会社 | Method of preparing alpha-phenyl ethyl alcohol |
| CN105749936A (en) * | 2016-04-05 | 2016-07-13 | 宁夏蓝丰精细化工有限公司 | Metal composite catalyst for selective dechloridation and preparation method thereof |
| CN106732564A (en) * | 2016-12-03 | 2017-05-31 | 西安凯立新材料股份有限公司 | The preparation method and application of aromatic hydrogenation rhodium/activated-carbon catalyst |
| CN107715870A (en) * | 2017-10-13 | 2018-02-23 | 西安凯立新材料股份有限公司 | A kind of preparation method and application for preparing L aminopropanol ruthenium Pd/carbon catalysts |
| CN109320398A (en) * | 2018-08-28 | 2019-02-12 | 浙江工业大学 | A method of benzhydrol is synthesized by benzophenone catalytic hydrogenation |
| CN110227487A (en) * | 2019-06-24 | 2019-09-13 | 西安凯立新材料股份有限公司 | A kind of preparation method and application of carbonyl hydrogen catalyst |
Non-Patent Citations (1)
| Title |
|---|
| "对甲基-α-苯乙醇合成条件的改进";郭小群等;《四川理工学院学报》;20070630;第20卷(第3期);第46页第1.2.1节加氢 * |
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