CN109320398B - Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone - Google Patents

Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone Download PDF

Info

Publication number
CN109320398B
CN109320398B CN201810985584.0A CN201810985584A CN109320398B CN 109320398 B CN109320398 B CN 109320398B CN 201810985584 A CN201810985584 A CN 201810985584A CN 109320398 B CN109320398 B CN 109320398B
Authority
CN
China
Prior art keywords
solution
containing compound
benzophenone
catalyst
deionized water
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.)
Active
Application number
CN201810985584.0A
Other languages
Chinese (zh)
Other versions
CN109320398A (en
Inventor
张群峰
周媛
马磊
卢春山
丰枫
李小年
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN201810985584.0A priority Critical patent/CN109320398B/en
Publication of CN109320398A publication Critical patent/CN109320398A/en
Application granted granted Critical
Publication of CN109320398B publication Critical patent/CN109320398B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B01J23/8966—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 germanium, tin or lead

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone, which comprises the following steps: the method adopts a supported multi-component catalyst and adds a protective agent into a reaction system; the supported multi-component catalyst is Pd-Cu-Sn/C, the carrier of the supported multi-component catalyst is activated carbon, the active component is Pd, and the auxiliary agents are Cu and Sn, wherein the load capacity of Pd is 1-10 wt%, the load capacity of Cu is 1-5 wt%, and the load capacity of Sn is 1-5 wt%; the protective agent is sodium acetate. The method can improve the conversion rate of the benzophenone and the selectivity of the benzhydryl alcohol.

Description

Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone
(I) technical field
The invention relates to a method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone.
(II) background of the invention
Benzhydrol, also known as alpha-phenyl benzyl alcohol, is an important organic intermediate, and is mainly used for synthesizing diphenhydramine (antihistamine), dimenhydrinate (antihistaminic, dimenhydrinate), cyclizine (antihistamine), diphenhydramine (antihistamine), phentoline (anticholinergic), modafinil (antidepressant), cinnarizine (vasodilator), and adrafil (central nervous stimulant).
The synthesis of the benzhydryl alcohol is mainly obtained by the reduction of the benzophenone. The earliest production process of benzhydrol is zinc powder reduction and then aluminum powder reduction, and the two methods have the disadvantages of more three wastes, less capacity, poor quality and high energy consumption. The existing production process is mainly a sodium borohydride reduction method, and although the process is relatively low in energy consumption and good in product quality, more wastewater, waste residues and the like are still discharged.
The catalytic hydrogenation process is a green synthesis process, but when benzophenone is hydrogenated to synthesize the benzhydryl alcohol, excessive hydrogenation is often easy to generate the diphenyl methane, and the catalytic hydrogenation process for synthesizing the diphenyl methanol cannot be realized in industry all the time.
Therefore, it is very meaningful to find a method for synthesizing benzhydrol by high-activity and high-selectivity catalytic hydrogenation.
Disclosure of the invention
The invention aims to provide a method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone, so as to improve the conversion rate of the benzophenone and the selectivity of the benzhydryl alcohol.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone is as follows: the method adopts a supported multi-component catalyst and adds a protective agent into a reaction system; the supported multi-component catalyst is Pd-Cu-Sn/C, the carrier of the supported multi-component catalyst is activated carbon, the active component is Pd, and the auxiliary agents are Cu and Sn, wherein the load capacity of Pd is 1-10 wt%, the load capacity of Cu is 1-5 wt%, and the load capacity of Sn is 1-5 wt%; the protective agent is sodium acetate.
Further, the method is implemented according to the following steps: adding benzophenone, an organic solvent, a protective agent and a supported multi-component catalyst into a reaction kettle, introducing hydrogen, and reacting for 1-10h under the conditions of 0.2-5.0 MPa and 40-120 ℃ (preferably 50-100 ℃); filtering the obtained reaction liquid to remove the supported multi-component catalyst, and distilling or rectifying the filtrate to obtain the benzhydrol; the addition amount of the protective agent is 0.001-0.005 g/g based on the mass of the benzophenone.
Further, the organic solvent is methanol or ethanol. The adding amount of the organic solvent is 0.5-3.0 ml/g based on the mass of the benzophenone.
Further, the hydrogenation reaction temperature is preferably 50 to 100 ℃.
Furthermore, the dosage of the supported multi-component catalyst is 0.005-0.05 g/g, preferably 0.005-0.01 g/g, calculated by the mass of the benzophenone.
Further, the Pd-Cu-Sn/C catalyst is prepared by the following method: adding deionized water into active carbon as a carrier to prepare slurry with the concentration of 4-40 wt% at 25-100 ℃, slowly dropwise adding a soluble palladium-containing compound solution, a soluble copper-containing compound solution and a soluble tin-containing compound solution according to metal loading, and fully and uniformly stirring; after dipping for 0.5-10 h, adding an alkaline solution to adjust the pH value of the solution to 7.5-10.0, continuously stirring for 0.5-5 h, cooling the temperature to room temperature, filtering, and washing a filter cake to be neutral by deionized water; and preparing the filter cake into slurry by using deionized water at the temperature of 20-95 ℃, dropwise adding a liquid-phase reducing agent, stirring for 0.5-4h, filtering, washing the filter cake to be neutral by using the deionized water, and drying in vacuum at the temperature of 70-120 ℃ to obtain the Pd-Cu-Sn/C catalyst.
Still further, the soluble palladium-containing compound is H2PdCl4、K2PdCl4Or Na2PdCl4。
Still further, the soluble copper-containing compound is CuCl2Or Cu (NO)3)2。
Still further, the soluble tin-containing compound is SnCl2Or SnCl4。
Furthermore, the particle size of the active carbon is 100-1000 meshes, and the specific surface area is 800-2000 m2(ii)/g, ash content is less than or equal to 5.0 wt%.
Still further, the alkaline solution is an aqueous solution of NaOH or KOH or ammonia water. The mass fraction of the alkaline solution is 2-20 wt%.
Still further, the liquid-phase reducing agent is hydrazine hydrate, formic acid, formaldehyde or sodium formate.
Still further, the ratio of the amount of the liquid-phase reducing agent to the amount of the substance containing a palladium compound is 10 to 200: 1.
still further, the vacuum drying time is 1-10 h.
Compared with the prior art, the invention has the following advantages:
1) the Pd-Cu-Sn/C catalyst prepared by the invention utilizes the modification of Cu and Sn on Pd, reduces active sites for promoting the hydrogenolysis of the benzhydryl alcohol, can obviously inhibit the side reaction of generating the diphenylmethane by the hydrogenolysis of the benzhydryl alcohol, and is beneficial to improving the selectivity of the benzhydryl alcohol; meanwhile, the hydrogenation activity of the catalyst can be further improved through the synergistic effect of three metals of Pd, Cu and Sn.
2) According to the method for synthesizing the benzhydryl alcohol by hydrogenation, a small amount of sodium acetate is added as a protective agent, so that the benzhydryl alcohol can be further prevented from being excessively hydrogenated, the high-yield benzhydryl alcohol can be obtained, and the sodium acetate can be easily separated from the benzhydryl alcohol in the subsequent rectification or distillation link.
(IV) detailed description of the preferred embodiments
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example one
10g of active carbon with the granularity of 1000 meshes and the specific surface area of 1500m is weighed2(g), ash content 3.5 wt%, in 100ml deionized water to prepare 25 deg.C slurry, slowly dropping 10ml H2PdCl4Solution (Pd content 0.05g/ml), 10ml of Cu (NO)3)2Solution (Cu content 0.03g/ml), 10ml SnCl4Stirring the solution (with Sn content of 0.03g/ml) for 0.5 h; adjusting the pH value of the solution to 8 by using 10 wt% KOH solution, continuously stirring for 0.5h, cooling to room temperature, filtering, and washing filter residues to be neutral by using deionized water to obtain filter cakes; and preparing the filter cake into 80ml of slurry at 80 ℃, dropwise adding 0.9g of 85 wt% hydrazine hydrate solution, stirring for 2.5h, filtering, washing the filter cake to be neutral by using deionized water, and drying in vacuum at 100 ℃ for 2h to obtain the 5% Pd-3% Cu-3% Sn/C catalyst.
Example two
10g of active carbon is weighed, the granularity is 800 meshes, and the specific surface area is 800m2(1.2 wt%) in 100ml deionized water, and slowly adding 10ml Na dropwise2PdCl4Solution (Pd content 0.01g/ml), 10ml of Cu (NO)3)2Solution (Cu content 0.01g/ml), 10ml SnCl2Stirring the solution (the Sn content is 0.01g/ml) for 2 hours; adjusting the pH value of the solution to 8.5 by using 10 wt% NaOH solution, continuously stirring for 2.5h, cooling to room temperature, filtering, and washing filter residues to be neutral by using deionized water; preparing the filter cake into 50ml of slurry at 100 ℃, dropwise adding 14g of 40 wt% formaldehyde, stirring for 0.5h, filtering, washing the filter cake to be neutral by deionized water, and cooling to 90 DEG CVacuum drying for 1h to obtain the catalyst of 1 percent Pd-1 percent Cu-1 percent Sn/C.
EXAMPLE III
10g of active carbon is weighed, the granularity is 100 meshes, and the specific surface area is 2000m2(g), ash content 3.0 wt%, in 100ml deionized water to prepare 40 deg.C slurry, slowly dropping 4ml H2PdCl4Solution (Pd content 0.2g/ml), 4ml of CuCl2Solution (Pd content 0.1g/ml), 4ml SnCl4Stirring the solution (the Pd content is 0.1g/ml) for 10 hours; adjusting the pH value of the solution to 9 by using 10 wt% of ammonia water, continuously stirring for 3h, cooling the temperature to room temperature, filtering, and washing filter residues to be neutral by using deionized water to obtain filter cakes; and preparing the filter cake into 100ml of slurry at the temperature of 20 ℃, dropwise adding 30g of 30 wt% formic acid, stirring for 50h, filtering, washing the filter cake to be neutral by using deionized water, and performing vacuum drying at the temperature of 80 ℃ for 10h to obtain the 8% Pd-4% Cu-4% Sn/C catalyst.
Example four
10g of active carbon is weighed, the granularity is 200 meshes, and the specific surface area is 1800m2(5 wt%) in 100ml deionized water to obtain 90 deg.C slurry, and slowly adding 10ml K2PdCl4Solution (Pd content 0.03g/ml), 10ml of CuCl2Solution (Cu content 0.02g/ml), 10ml SnCl2Stirring the solution (the Sn content is 0.01g/ml) for 1 h; adjusting the pH value of the solution to 9.5 by using 10 wt% KOH solution, continuously stirring for 1h, cooling to room temperature, filtering, and washing filter residues to be neutral by using deionized water to obtain filter cakes; and preparing the filter cake into 60ml of slurry at 70 ℃, dropwise adding 15g of 20 wt% sodium formate, stirring for 4h, filtering, washing the filter cake to be neutral by using deionized water, and drying in vacuum for 4h at 100 ℃ to obtain the 3% Pd-2% Cu-1% Sn/C catalyst.
EXAMPLE five
10g of activated carbon with the granularity of 600 meshes and the specific surface area of 1300m is weighed20.5 wt% ash content in 100ml deionized water to prepare slurry with 70 deg.C, slowly dropping 10ml Na2PdCl4Solution (Pd content 0.06g/ml), 10ml of Cu (NO)3)2Solution (Cu content 0.02g/ml), 10ml SnCl4Stirring the solution (the Sn content is 0.04g/ml) for 2 hours; adjusting the pH value of the solution to 8.5 by using 10 wt% NaOH solution, continuously stirring for 4h, cooling to room temperature, filtering, and washing filter residues to be neutral by using deionized water to obtain filter cakes; and preparing the filter cake into 150ml of slurry at 90 ℃, dropwise adding 3g of 85 wt% hydrazine hydrate (77.8mmol), stirring for 4h, filtering, washing the filter cake to be neutral by deionized water, and drying in vacuum at 110 ℃ for 4h to obtain the 6% Pd-2% Cu-4% Sn/C catalyst.
EXAMPLE six
10g of active carbon is weighed, the granularity is 400 meshes, and the specific surface area is 1500m2(g), ash content 2.5 wt%, in 100ml deionized water to prepare 70 deg.C slurry, slowly dropping 10ml H2PdCl4Solution (Pd content 0.07g/ml), 5ml of CuCl2Solution (Cu content 0.06g/ml), 10ml SnCl2Stirring the solution (the Sn content is 0.02g/ml) for 2 hours; adjusting the pH value of the solution to 8.5 by using 10 wt% NaOH solution, continuously stirring for 2h, cooling to room temperature, filtering, and washing filter residues to be neutral by using deionized water to obtain filter cakes; and preparing the filter cake into 200ml of slurry at 50 ℃, dropwise adding 3g of 85 wt% hydrazine hydrate (77.8mmol), stirring for 4h, filtering, washing the filter cake to be neutral by deionized water, and drying in vacuum at 110 ℃ for 6h to obtain the 7% Pd-3% Cu-2% Sn/C catalyst.
Examples seven to twelve
Examples seven to twelve examined the use of different Pd-Cu-Sn/C catalysts prepared in examples one to six in the catalytic hydrogenation to benzhydrol.
Adding 100g of benzophenone, 180ml of methanol, 0.2g of sodium acetate and 1.0g of the prepared Pd-Cu-Sn/C catalyst into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and then replacing with hydrogen for three times; heating to 75 ℃ and hydrogen pressure of 1.2MPa, starting stirring at the stirring speed of 900r/min, and reacting for 2 h; stopping reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The results of the experiment are shown in table 1.
TABLE 1 catalytic hydrogenation Performance of different Pd-Cu-Sn/C
Examples Catalyst and process for preparing same Conversion (wt%) Selectivity (wt%)
7 Example one 100 97.5
8 Example two 100 96.4
9 EXAMPLE III 100 97.1
10 Example four 100 98.0
11 EXAMPLE five 100 96.9
12 EXAMPLE six 100 97.3
Examples thirteen to seventeen
The thirteen to seventeen examples examine the reaction performance of the Pd-Cu-Sn/C catalyst for preparing the benzhydrol under different hydrogenation reaction conditions.
Adding 100g of benzhydryl alcohol, 150ml of ethanol and 0.5g of the catalyst prepared in the fourth embodiment into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and then replacing with hydrogen for three times; after the temperature and the hydrogen pressure are increased to the range required by the reaction, stirring is started, the stirring speed is 900r/min, and the reaction is carried out for 3 hours; stopping reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The results of the experiment are shown in table 2.
TABLE 2 catalytic performance of nitrogen-doped mesoporous carbon supported palladium catalysts under different hydrogenation reaction conditions
Examples Reaction conditions Conversion (wt%) Selectivity (wt%)
13 0.4g of sodium acetate, 45 ℃ and 3MPa 100 98.6
14 0.3g of sodium acetate, 90 ℃ and 1.4MPa 100 97.3
15 0.2g of sodium acetate, 70 ℃ and 0.5MPa 100 96.8
16 0.1g of sodium acetate, 110 ℃ and 0.2MPa 100 96.5
17 0.4g of sodium acetate, 80 ℃ and 4MPa 100 97.1
Comparative example 1
Comparative example one investigates the reaction performance of Pd/C in the preparation of benzhydrol by catalytic hydrogenation.
10g of active carbon with the granularity of 1000 meshes and the specific surface area of 1500m is weighed20.2g of sodium acetate and 3.5 percent of ash content in 100ml of deionized water to prepare slurry with the temperature of 25 ℃, and slowly dripping 10ml of H2PdCl4Stirring the solution (Pd content is 0.05g/ml) for 0.5 h; adjusting the pH value of the solution to 8 by using 10 wt% KOH solution, cooling the temperature to room temperature, filtering, and washing filter residues to be neutral by using deionized water to obtain filter cakes; preparing the filter cake into 80ml slurry at 80 ℃, dropwise adding 0.9g of 85 wt% hydrazine hydrate solution, stirring for 2.5h, filtering, washing the filter cake with deionized water until the filter cake is washedAnd (4) neutralizing, and drying for 2 hours in vacuum at 100 ℃ to obtain the 5% Pd/C catalyst.
Adding 100g of benzophenone, 180ml of methanol and 1.0g of the prepared Pd-Cu-Sn/C catalyst into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and replacing with hydrogen for three times; heating to 75 ℃ and hydrogen pressure of 1.2MPa, starting stirring at the stirring speed of 900r/min, and reacting for 2 h; stopping reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The results of the experiment were 99.2 wt% conversion and 58.2 wt% selectivity.
Comparative example No. two
Comparative example II investigates the reaction performance of Pd-Cu/C in the preparation of benzhydrol by catalytic hydrogenation.
10g of active carbon with the granularity of 1000 meshes and the specific surface area of 1500m is weighed2(g), ash content 3.5 wt%, in 100ml deionized water to prepare 25 deg.C slurry, slowly dropping 10ml H2PdCl4Solution (Pd content 0.05g/ml), 10ml of Cu (NO)3)2Stirring the solution (the Cu content is 0.03g/ml) for 0.5 h; adjusting the pH value of the solution to 8 by using 10 wt% KOH solution, cooling the temperature to room temperature, filtering, and washing filter residues to be neutral by using deionized water to obtain filter cakes; and preparing the filter cake into 80ml of slurry at 80 ℃, dropwise adding 0.9g of 85 wt% hydrazine hydrate solution, stirring for 2.5h, filtering, washing the filter cake to be neutral by using deionized water, and drying in vacuum at 100 ℃ for 2h to obtain the 5% Pd-3% Cu/C catalyst.
Adding 100g of benzophenone, 180ml of methanol, 0.2g of sodium acetate and 1.0g of the prepared Pd-Cu-Sn/C catalyst into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and then replacing with hydrogen for three times; heating to 75 ℃ and hydrogen pressure of 1.2MPa, starting stirring at the stirring speed of 900r/min, and reacting for 2 h; stopping reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The results of the experiment were 98.9 wt% conversion and 75.9 wt% selectivity.
Comparative example No. three
And the third comparative example investigates the reaction performance of the Pd-Sn/C in the preparation of the benzhydryl alcohol by catalytic hydrogenation.
10g of active carbon with the granularity of 1000 meshes and the specific surface area of 1500m is weighed2(g), ash content 3.5 wt%, in 100ml deionized water to prepare 25 deg.C slurry, slowly dropping 10ml H2PdCl4Solution (Pd content 0.05g/ml), 10ml SnCl4Stirring the solution (with Sn content of 0.03g/ml) for 0.5 h; adjusting the pH value of the solution to 8 by using 10 wt% KOH solution, cooling the temperature to room temperature, filtering, and washing filter residues to be neutral by using deionized water to obtain filter cakes; and preparing the filter cake into 80ml of slurry at 80 ℃, dropwise adding 0.9g of 85 wt% hydrazine hydrate solution, stirring for 2.5h, filtering, washing the filter cake to be neutral by using deionized water, and drying in vacuum at 100 ℃ for 2h to obtain the 5% Pd-3% Sn/C catalyst.
Adding 100g of benzophenone, 180ml of methanol, 0.2g of sodium acetate and 1.0g of the prepared Pd-Cu-Sn/C catalyst into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and then replacing with hydrogen for three times; heating to 75 ℃ and hydrogen pressure of 1.2MPa, starting stirring at the stirring speed of 900r/min, and reacting for 2 h; stopping reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The results of the experiment were 98.6 wt% conversion and 81.5 wt% selectivity.
Comparative example No. four
Comparative example four the reaction performance of Pd-Cu-Sn/C in the preparation of benzhydryl alcohol by catalytic hydrogenation without adding sodium acetate was investigated.
Adding 100g of benzophenone, 180ml of methanol and 1.0g of the Pd-Cu-Sn/C catalyst prepared in the first embodiment into a 500ml stainless steel reaction kettle, closing the reaction kettle, replacing air in the reaction kettle with nitrogen for three times, and replacing with hydrogen for three times; heating to 75 ℃ and hydrogen pressure of 1.2MPa, starting stirring at the stirring speed of 900r/min, and reacting for 2 h; stopping reaction, cooling to room temperature, taking out the reaction solution, filtering to remove the catalyst, and analyzing the filtrate by liquid chromatography. The results of the experiment were 100 wt% conversion and 90.8 wt% selectivity.

Claims (11)

1. A method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone is as follows: the method adopts a supported multi-component catalyst and adds a protective agent into a reaction system; the supported multi-component catalyst is Pd-Cu-Sn/C, the carrier of the supported multi-component catalyst is activated carbon, the active component is Pd, and the auxiliary agents are Cu and Sn, wherein the load capacity of Pd is 1-10 wt%, the load capacity of Cu is 1-5 wt%, and the load capacity of Sn is 1-5 wt%; the protective agent is sodium acetate;
the method is implemented according to the following steps: adding benzophenone, an organic solvent, a protective agent and a supported multi-component catalyst into a reaction kettle, introducing hydrogen, and reacting for 1-10h under the conditions of 0.2-5.0 MPa and 40-120 ℃; filtering the obtained reaction liquid to remove the supported multi-component catalyst, and distilling or rectifying the filtrate to obtain the benzhydrol; the dosage of the supported multi-component catalyst is 0.005-0.05 g/g calculated by the mass of the benzophenone; the addition amount of the protective agent is 0.001-0.005 g/g based on the mass of the benzophenone;
the Pd-Cu-Sn/C catalyst is prepared by the following method: adding deionized water into active carbon as a carrier to prepare slurry with the concentration of 4-40 wt% at 25-100 ℃, slowly dropwise adding a soluble palladium-containing compound solution, a soluble copper-containing compound solution and a soluble tin-containing compound solution according to metal loading, and fully and uniformly stirring; after dipping for 0.5-10 h, adding an alkaline solution to adjust the pH value of the solution to 7.5-10.0, continuously stirring for 0.5-5 h, cooling the temperature to room temperature, filtering, and washing a filter cake to be neutral by deionized water; and preparing the filter cake into slurry by using deionized water at the temperature of 20-95 ℃, dropwise adding a liquid-phase reducing agent, stirring for 0.5-4h, filtering, washing the filter cake to be neutral by using the deionized water, and drying in vacuum at the temperature of 70-120 ℃ to obtain the Pd-Cu-Sn/C catalyst.
2. The method of claim 1, wherein: the organic solvent is methanol or ethanol.
3. The method of claim 1, wherein: the dosage of the supported multi-component catalyst is 0.005-0.01 g/g based on the mass of the benzophenone; the adding amount of the organic solvent is 0.5-3.0 ml/g based on the mass of the benzophenone.
4. The method of claim 1, wherein: the hydrogenation reaction temperature is 50-100 ℃.
5. The method of claim 1, wherein: the particle size of the active carbon is 100-1500 meshes, and the specific surface area is 800-2000 m2(ii)/g, ash content is less than or equal to 5.0 wt%.
6. The method of claim 1, wherein: the soluble palladium-containing compound is H2PdCl4、K2PdCl4Or Na2PdCl4(ii) a The soluble copper-containing compound is CuCl2Or Cu (NO)3)2(ii) a The soluble tin-containing compound is SnCl2Or SnCl4。
7. The method of claim 5, wherein: the soluble palladium-containing compound is H2PdCl4、K2PdCl4Or Na2PdCl4(ii) a The soluble copper-containing compound is CuCl2Or Cu (NO)3)2(ii) a The soluble tin-containing compound is SnCl2Or SnCl4。
8. The method of claim 1, wherein: the alkaline solution is NaOH or KOH aqueous solution or ammonia water.
9. The method of claim 2, wherein: the alkaline solution is NaOH or KOH aqueous solution or ammonia water.
10. The method of claim 1, wherein: the liquid-phase reducing agent is hydrazine hydrate, formic acid, formaldehyde or sodium formate, and the amount ratio of the liquid-phase reducing agent to the palladium-containing compound is 10-200: 1.
11. the method of claim 2, wherein: the liquid-phase reducing agent is hydrazine hydrate, formic acid, formaldehyde or sodium formate, and the amount ratio of the liquid-phase reducing agent to the palladium-containing compound is 10-200: 1.
CN201810985584.0A 2018-08-28 2018-08-28 Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone Active CN109320398B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810985584.0A CN109320398B (en) 2018-08-28 2018-08-28 Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810985584.0A CN109320398B (en) 2018-08-28 2018-08-28 Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone

Publications (2)

Publication Number Publication Date
CN109320398A CN109320398A (en) 2019-02-12
CN109320398B true CN109320398B (en) 2022-03-18

Family

ID=65264295

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810985584.0A Active CN109320398B (en) 2018-08-28 2018-08-28 Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone

Country Status (1)

Country Link
CN (1) CN109320398B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110743544B (en) * 2019-11-07 2023-02-24 西安凯立新材料股份有限公司 Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof
CN111233626B (en) * 2020-01-21 2023-05-16 浙江师范大学 Method for preparing benzhydrol by diphenyl ketone hydrogenation
CN112206786B (en) * 2020-08-31 2023-04-07 浙江工业大学 Multi-metal nanoparticle catalyst and preparation and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101544571A (en) * 2009-05-13 2009-09-30 南通海迪化工有限公司 A method for preparing o-chloro PPD
CN102202788A (en) * 2008-08-04 2011-09-28 斯里赛科公司 Metal-containing organosilica catalyst
CN102241566A (en) * 2011-05-09 2011-11-16 中山奕安泰医药科技有限公司 Method for preparing diphenyl carbinol and derivatives thereof
CN102274734A (en) * 2010-06-13 2011-12-14 中化蓝天集团有限公司 Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof
CN102924236A (en) * 2012-10-30 2013-02-13 武汉怡兴化工有限公司 Preparation method of diphenylmethanol
EP2966081A1 (en) * 2013-03-04 2016-01-13 National University Corporation Nagoya University Ligand, metal complex containing ligand, and reaction using metal complex containing ligand

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102202788A (en) * 2008-08-04 2011-09-28 斯里赛科公司 Metal-containing organosilica catalyst
CN101544571A (en) * 2009-05-13 2009-09-30 南通海迪化工有限公司 A method for preparing o-chloro PPD
CN102274734A (en) * 2010-06-13 2011-12-14 中化蓝天集团有限公司 Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof
CN102241566A (en) * 2011-05-09 2011-11-16 中山奕安泰医药科技有限公司 Method for preparing diphenyl carbinol and derivatives thereof
CN102924236A (en) * 2012-10-30 2013-02-13 武汉怡兴化工有限公司 Preparation method of diphenylmethanol
EP2966081A1 (en) * 2013-03-04 2016-01-13 National University Corporation Nagoya University Ligand, metal complex containing ligand, and reaction using metal complex containing ligand

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
An efficient and sustainable catalytic reduction of carbon-carbon multiple bonds, aldehydes, and ketones using a Cu nanoparticle decorated metal organic framework;Ashish Kumar Kar 等;《New J. Chem》;20180423;第9557-9567页 *
Chemoselective control of hydrogenation among aromatic carbonyl and benzyl alcohol derivatives using Pd/C(en) catalyst;Kazuyuki Hattori 等;《Tetrahedron》;20011231;第4817-4824页 *
Commutative reduction of aromatic ketones to arylmethylenes/alcohols by hypophosphites catalyzed by Pd/C under biphasic conditions;Carole Guyon 等;《Tetrahedron》;20141231;第2088-2095页 *
Easy and partial hydrogenation of aromatic carbonyls to benzyl alcohols using Pd/C(en)-catalyst;Hironao Sajiki 等;《J. Chem. Soc., Perkin Trans. 1》;19981231;第4043-4044页 *
Hydrodeoxygenation of benzophenone on Pd catalysts;Martina Bejblova 等;《Applied Catalysis A: General》;20051231;第169-175页 *
Liquid-phase catalytic hydrogenation of p-chlorobenzophenone to p-chlorobenzhydrol over a 5 % Pd/C catalyst;Sunil P. Bawane 等;《Chem. Eng. Technol.》;20041231;第914-920页 *
Specific Inhibition of the Hydrogenolysis of Benzylic C-O Bonds Using Palladium Nanoparticles Supported on Nitrogen-Doped Carbon Nanofibers;Yukihiro Motoyama 等;《CHEMCATCHEM Communications》;20180207;第505-509页 *
二苯甲醇的相转移催化合成研究;王树清 等;《南通大学学报（自然科学版）》;20090930;第58-61页 *
改进Zagoumenny还原法制备二苯甲醇;张珍明 等;《兰州理工大学学报》;20130228;第54-57页 *
水相中二苯甲醇的简便绿色合成方法的研究;孙孟展 等;《山东化工》;20081231;第15-16,25页 *
相转移催化法合成二苯甲醇;王勤;《湖北化工》;19981231;第14,24页 *
超声波法合成二苯甲醇;石川 等;《厦门大学学报（自然科学版）》;20081231;第196-197,200页 *

Also Published As

Publication number Publication date
CN109320398A (en) 2019-02-12

Similar Documents

Publication Publication Date Title
CN109053380B (en) Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone
CN109320398B (en) Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone
CN109046430B (en) Nitrogen-doped activated carbon-supported palladium-iron catalyst for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone and application thereof
CN101347737B (en) Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid
CN108218718B (en) Method for efficiently preparing N, N-dibenzyl ethylenediamine through catalytic hydrogenation
CN110743544A (en) Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof
CN102125838B (en) Method for preparing high-selectivity Pd/TiO2-C hydrogenation catalyst
CN111233626A (en) Method for preparing benzhydryl alcohol by hydrogenation of benzophenone
EP3299088B1 (en) Metal complex catalyst, preparation method thereof, and use thereof in preparing d,l-menthol
CN112661585A (en) Method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha dimethyl benzyl alcohol and application
CN111167515B (en) Monomolecular heteropoly acid inlaid honeycomb-shaped carbon material loaded nano metal catalyst and preparation method and application thereof
CN111589464B (en) Boron nitride-loaded rhodium-gallium-tin liquid alloy catalyst and preparation method and application thereof
CN109772291B (en) Selective hydrogenation and dealkynization catalyst and preparation method and application thereof
CN114369006B (en) Method for preparing isohexide and methyl isobutyl carbinol
CN114950505B (en) Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide, and preparation method and application thereof
CN113735688B (en) Recycling method of waste liquid of butanol device
CN110743567B (en) Iridium-carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof
CN112121848B (en) Modified hierarchical pore molecular sieve catalyst, preparation method thereof and production method of 3-methyl-2-butene-1-ol
CN113617352B (en) Crude terephthalic acid hydrofining catalyst and preparation method thereof
US4769500A (en) Process for preparation of 2,3,5-trimethylhydroquinone
CN110743590B (en) High-selectivity catalyst for synthesizing vitamin A intermediate and preparation method thereof
EP1207146B1 (en) Process for the conversion of 1,4 butynediol to 1, 4 butenediol
CN110624571B (en) Catalyst for synthesizing 3, 5-dichloroaniline and preparation method and application thereof
CN115400750B (en) Catalyst for preparing saturated ketone by hydrogenating multi-double bond unsaturated ketone, and preparation method and application thereof
CN116116442B (en) Preparation method and application of low-load sub-nanometer noble metal 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
GR01 Patent grant
GR01 Patent grant