CN109320398A - A method of benzhydrol is synthesized by benzophenone catalytic hydrogenation - Google Patents
A method of benzhydrol is synthesized by benzophenone catalytic hydrogenation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
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- 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
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Abstract
The invention discloses a kind of method for synthesizing benzhydrol by benzophenone catalytic hydrogenation, the methods are as follows: the method is using support type multicomponent catalyst and protective agent is added in the reaction system；The support type multicomponent catalyst is Pd-Cu-Sn/C, and carrier is active carbon, and active component Pd, auxiliary agent is Cu and Sn, and wherein the load capacity of Pd is 1~10wt%, and the load capacity of Cu is 1~5wt%, and the load capacity of Sn is 1~5wt%；The protective agent is sodium acetate.The conversion ratio of benzophenone and the selectivity of benzhydrol can be improved in the method for the invention.
Description
(1) technical field
The present invention relates to a kind of methods for synthesizing benzhydrol by benzophenone catalytic hydrogenation.
(2) background technique
Benzhydrol is also known as α-phenyl benzil alcohol, is a kind of important organic intermediate, is mainly used for synthesizing diphenhydramine
(antihistamine), dramamine (antihistamine, dramamine), marezine (antihistamine), Diphenylpyraline (antihistamine), benzene
First tropine (anticholinergic agent), modafinil (antidepressants), cinnarizine (vasodilator agent), adrafinil (central nervous excitation
Medicine) etc. drugs synthesis.
The synthesis of benzhydrol is mainly obtained by the reduction of benzophenone.The earliest production technology of benzhydrol is zinc
Powder reduction, then development is aluminum reduction, this two methods three wastes is more, production capacity is few, poor quality, energy consumption is high.Existing production technology master
More waste water, waste residue are still remained although this technique relative energy consumption is low, good product quality for sodium borohydride reduction
Deng discharge.
Catalytic hydrogenation process is a kind of green synthesis process, but when for benzophenone hydrogenation synthesis benzhydrol, often
It is easy to happen excessive hydrogenation and generates diphenyl-methane, catalytic hydrogenation synthesis benzhydrol technique industrially cannot achieve always.
Therefore, a kind of high activity is sought, the method for highly selective catalytic hydrogenation synthesis benzhydrol is significantly.
(3) summary of the invention
The purpose of the present invention is to provide a kind of methods for synthesizing benzhydrol by benzophenone catalytic hydrogenation, to improve two
The conversion ratio of Benzophenone and the selectivity of benzhydrol.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A method of benzhydrol, the method being synthesized by benzophenone catalytic hydrogenation are as follows: the method is using load
Simultaneously protective agent is added in type multicomponent catalyst in the reaction system；The support type multicomponent catalyst is Pd-Cu-Sn/C,
Its carrier is active carbon, and active component Pd, auxiliary agent is Cu and Sn, and wherein the load capacity of Pd is 1~10wt%, the load capacity of Cu
For 1~5wt%, the load capacity of Sn is 1~5wt%；The protective agent is sodium acetate.
Further, the method is implemented in accordance with the following steps: in a kettle, benzophenone, organic solvent, guarantor is added
Agent and support type multicomponent catalyst are protected, hydrogen is passed through, in 0.2~5.0MPa, 40~120 DEG C (preferably 50~100 DEG C)
Under the conditions of react 1~10h；Obtained reaction solution is filtered to remove support type multicomponent catalyst, filtrate is after distillation or rectifying
Up to benzhydrol；Protectant additional amount is calculated as 0.001~0.005g/g with the quality of benzophenone.
Further, the organic solvent is methanol or ethyl alcohol.The additional amount of the organic solvent is with benzophenone
Quality is calculated as 0.5~3.0ml/g.
Further, preferred 50-100 DEG C of hydrogenation reaction temperature.
Further, the dosage of the support type multicomponent catalyst is calculated as 0.005~0.05g/ with benzophenone quality
G, preferably 0.005~0.01g/g.
Further, the Pd-Cu-Sn/C catalyst is prepared via a method which: using active carbon as carrier, adding deionization
It is 4~40wt% slurries that water, which is configured to concentration at 25~100 DEG C, and soluble chemical combination containing palladium is slowly added dropwise respectively by content of metal
The solution of the solution of object, the solution of soluble copper-containing compound and soluble sn-containing compound, stirs；Dipping 0.5
After~10h, addition alkaline solution adjusting solution ph to 7.5~10.0 cools the temperature to room temperature after continuing 0.5~5h of stirring,
Filtering, filter cake are washed with deionized to neutrality；Filter cake is configured to slurries, dropping liquid with deionized water at 20~95 DEG C again
Phase reducing agent stirs 0.5-4h, and filtering, filter cake is washed with deionized to neutrality, be dried in vacuo at 70~120 DEG C to get
The Pd-Cu-Sn/C catalyst.
Again further, the soluble containing palladium compound is H2PdCl4、K2PdCl4Or Na2PdCl4。
Again further, the soluble copper-containing compound is CuCl2Or Cu (NO3)2。
Again further, the soluble sn-containing compound is SnCl2Or SnCl4。
Again further, the granularity of activated carbon is 100~1000 mesh, and specific surface area is 800~2000m2/ g, ash content
Content≤5.0wt%.
Again further, the alkaline solution is the aqueous solution or ammonium hydroxide of NaOH or KOH.The matter of the alkaline solution
Amount score is 2~20wt%.
Again further, the liquid-phase reduction agent is hydrazine hydrate, formic acid, formaldehyde or sodium formate.
Again further, the ratio between described amount of substance of liquid-phase reduction agent and containing palladium compound is 10~200:1.
Again further, vacuum drying time 1-10h.
Compared with prior art, the present invention having the advantage that
1) Pd-Cu-Sn/C catalyst prepared by the present invention, the modification using Cu and Sn to Pd reduce and promote hexichol first
The active site of alcohol hydrogenolysis can significantly inhibit the side reaction that benzhydrol hydrogenolysis generates diphenyl-methane, be conducive to improve hexichol first
The selectivity of alcohol；Meanwhile it is living by tri- kinds of Pd, Cu, Sn intermetallic the can further improve catalyst plus hydrogen that act synergistically
Property.
2) a small amount of sodium acetate is added in the method for hydrogenation synthesis benzhydrol of the present invention as protective agent, it can be into
One step ensures that benzhydrol avoids excessive hydrogenation, help to obtain the benzhydrol of high yield, and sodium acetate is in subsequent essence
Link is evaporated or distilled, can easily be separated with benzhydrol.
(4) specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto:
Embodiment one
10g active carbon is weighed, granularity is 1000 mesh, specific surface area 1500m2/ g, content of ashes 3.5wt%, by it
It is configured to 25 DEG C of temperature of slurries in 100ml deionized water, the H of 10ml is slowly added dropwise2PdCl4(Pd content is 0.05g/ to solution
Ml), the Cu (NO of 10ml3)2The SnCl of solution (Cu content is 0.03g/ml), 10ml4Solution (Sn content is 0.03g/ml), is stirred
Mix 0.5h；Solution ph is adjusted to 8 with the KOH solution of 10wt%, is continued to cool the temperature to room temperature after stirring 0.5h, be filtered, filter
Slag is washed with deionized to neutrality and obtains filter cake；Again filter cake is configured to 80ml slurries at 80 DEG C, is added dropwise 0.9g's
85wt% hydrazine hydrate solution stirs 2.5h, filtering, and filter cake is washed with deionized to neutrality, is dried in vacuo 2h at 100 DEG C,
Up to 5%Pd-3%Cu-3%Sn/C catalyst.
Embodiment two
10g active carbon is weighed, granularity is 800 mesh, specific surface area 800m2/ g, content of ashes 1.2wt%, by its in
It is configured to 100 DEG C of temperature of slurries in 100ml deionized water, the Na of 10ml is slowly added dropwise2PdCl4(Pd content is 0.01g/ to solution
Ml), the Cu (NO of 10ml3)2The SnCl of solution (Cu content is 0.01g/ml), 10ml2Solution (Sn content is 0.01g/ml), is stirred
Mix 2h；Solution ph is adjusted to 8.5 with the NaOH solution of 10wt%, is continued to cool the temperature to room temperature after stirring 2.5h, be filtered, filter
Slag is washed with deionized to neutrality；Again filter cake is configured to 50ml slurries at 100 DEG C, the 40wt% formaldehyde of 14g is added dropwise, stirs
0.5h is mixed, is filtered, filter cake is washed with deionized to neutrality, is dried in vacuo 1h at 90 DEG C to get 1%Pd-1%Cu-1%
Sn/C catalyst.
Embodiment three
10g active carbon is weighed, granularity is 100 mesh, specific surface area 2000m2/ g, content of ashes 3.0wt%, by its in
It is configured to 40 DEG C of temperature of slurries in 100ml deionized water, the H of 4ml is slowly added dropwise2PdCl4Solution (Pd content is 0.2g/ml),
The CuCl of 4ml2The SnCl of solution (Pd content is 0.1g/ml), 4ml4Solution (Pd content is 0.1g/ml), stirs 10h；With
The ammonium hydroxide of 10wt% adjusts solution pH value to 9, continues to cool the temperature to room temperature after stirring 3h, filter, filter residue is washed with deionized water
It washs to neutrality and obtains filter cake；Again filter cake is configured to 100ml slurries at 20 DEG C, the 30wt% formic acid of 30g is added dropwise, stirs 50h,
Filtering, filter cake are washed with deionized to neutrality, are dried in vacuo 10h at 80 DEG C to get 8%Pd-4%Cu-4%Sn/C catalysis
Agent.
Example IV
10g active carbon is weighed, granularity is 200 mesh, specific surface area 1800m2/ g, content of ashes 5wt%, by its in
It is configured to 90 DEG C of temperature of slurries in 100ml deionized water, the K of 10ml is slowly added dropwise2PdCl4(Pd content is 0.03g/ to solution
Ml), the CuCl of 10ml2The SnCl of solution (Cu content is 0.02g/ml), 10ml2Solution (Sn content is 0.01g/ml), stirring
1h；Solution ph is adjusted to 9.5 with the KOH solution of 10wt%, is continued to cool the temperature to room temperature after stirring 1h, be filtered, filter residue is used
Deionized water washs to neutrality and obtains filter cake；Again filter cake is configured to 60ml slurries at 70 DEG C, the 20wt% formic acid of 15g is added dropwise
Sodium stirs 4h, filtering, and filter cake is washed with deionized to neutrality, is dried in vacuo 4h at 100 DEG C to get 3%Pd-2%Cu-
1%Sn/C catalyst.
Embodiment five
10g active carbon is weighed, granularity is 600 mesh, specific surface area 1300m2/ g, content of ashes 0.5wt%, by its in
It is configured to the slurries of temperature 70 C in 100ml deionized water, the Na of 10ml is slowly added dropwise2PdCl4(Pd content is 0.06g/ to solution
Ml), the Cu (NO of 10ml3)2The SnCl of solution (Cu content is 0.02g/ml), 10ml4Solution (Sn content is 0.04g/ml), is stirred
Mix 2h；Solution ph is adjusted to 8.5 with the NaOH solution of 10wt%, is continued to cool the temperature to room temperature after stirring 4h, be filtered, filter residue
It is washed with deionized to neutrality and obtains filter cake；Again filter cake is configured to 150ml slurries at 90 DEG C, is added dropwise the 85wt%'s of 3g
Hydrazine hydrate (77.8mmol) stirs 4h, filtering, and filter cake is washed with deionized to neutrality, 4h is dried in vacuo at 110 DEG C, i.e.,
Obtain 6%Pd-2%Cu-4%Sn/C catalyst.
Embodiment six
10g active carbon is weighed, granularity is 400 mesh, specific surface area 1500m2/ g, content of ashes 2.5wt%, by its in
It is configured to the slurries of temperature 70 C in 100ml deionized water, the H of 10ml is slowly added dropwise2PdCl4(Pd content is 0.07g/ to solution
Ml), the CuCl of 5ml2The SnCl of solution (Cu content is 0.06g/ml), 10ml2Solution (Sn content is 0.02g/ml), stirs 2h；
Solution ph is adjusted to 8.5 with the NaOH solution of 10wt%, is continued to cool the temperature to room temperature after stirring 2h, be filtered, filter residue is spent
Ion water washing to neutrality obtains filter cake；Again filter cake is configured to 200ml slurries at 50 DEG C, the hydration of the 85wt% of 3g is added dropwise
Hydrazine (77.8mmol) stirs 4h, filtering, and filter cake is washed with deionized to neutrality, is dried in vacuo 6h at 110 DEG C to get 7%
Pd-3%Cu-2%Sn/C catalyst.
Embodiment seven to 12
Embodiment seven to 12 has investigated the different Pd-Cu-Sn/C catalyst of the preparation of embodiment one to six in catalytic hydrogenation
Prepare the application in benzhydrol reaction.
In 500ml stainless steel cauldron, it is above-mentioned that 100g benzophenone, 180ml methanol, 0.2g sodium acetate, 1.0g is added
The Pd-Cu-Sn/C catalyst of preparation is closed reaction kettle, three times, then with hydrogen is replaced with the air in nitrogen replacement reaction kettle
Three times；By temperature rise to 75 DEG C, hydrogen press as 1.2MPa, start to stir, stirring rate 900r/min, react 2h；Stop reaction,
It is cooled to room temperature to temperature, takes out reaction solution, Filtration of catalyst, filtrate liquid-phase chromatographic analysis.Experimental result such as 1 institute of table
Show.
The catalytic hydrogenation property of 1 difference Pd-Cu-Sn/C of table
| Embodiment | Catalyst | Conversion ratio (wt%) | Selectivity (wt%) |
| 7 | Embodiment one | 100 | 97.5 |
| 8 | Embodiment two | 100 | 96.4 |
| 9 | Embodiment three | 100 | 97.1 |
| 10 | Example IV | 100 | 98.0 |
| 11 | Embodiment five | 100 | 96.9 |
| 12 | Embodiment six | 100 | 97.3 |
Embodiment 13 to 17
Embodiment 13 to 17 has investigated Pd-Cu-Sn/C catalyst and has prepared hexichol first under different hydrogenation conditions
The reactivity worth of alcohol.
In 500ml stainless steel cauldron, prepared by addition 100g benzhydrol, 150ml ethyl alcohol, 0.5g example IV is urged
Agent closes reaction kettle, three times with the air in nitrogen replacement reaction kettle, then three times with hydrogen displacement；Temperature and hydrogen pressure are risen
After the range to needed for reacting, start to stir, stirring rate 900r/min, reacts 3h；Stop reaction, be cooled to room temperature to temperature,
Take out reaction solution, Filtration of catalyst, filtrate liquid-phase chromatographic analysis.Experimental result is as shown in table 2.
Catalytic performance of the 2 N doping mesoporous carbon-loaded palladium catalyst of table under different hydrogenation conditions
| Embodiment | Reaction condition | Conversion ratio (wt%) | Selectivity (wt%) |
| 13 | 0.4g sodium acetate, 45 DEG C, 3MPa | 100 | 98.6 |
| 14 | 0.3g sodium acetate, 90 DEG C, 1.4MPa | 100 | 97.3 |
| 15 | 0.2g sodium acetate, 70 DEG C, 0.5MPa | 100 | 96.8 |
| 16 | 0.1g sodium acetate, 110 DEG C, 0.2MPa | 100 | 96.5 |
| 17 | 0.4g sodium acetate, 80 DEG C, 4MPa | 100 | 97.1 |
Comparative example one
Comparative example one has investigated Pd/C and has prepared reactivity worth in benzhydrol in catalytic hydrogenation.
10g active carbon is weighed, granularity is 1000 mesh, specific surface area 1500m2/ g, 0.2g sodium acetate, content of ashes are
It is configured to 25 DEG C of temperature of slurries in 100ml deionized water, the H of 10ml is slowly added dropwise by 3.5wt%2PdCl4Solution (Pd
Content is 0.05g/ml), stir 0.5h；Solution ph is adjusted to 8 with the KOH solution of 10wt%, and cools the temperature to room temperature, mistake
Filter, filter residue are washed with deionized to neutrality and obtain filter cake；Again filter cake is configured to 80ml slurries at 80 DEG C, is added dropwise 0.9g's
85wt% hydrazine hydrate solution stirs 2.5h, filtering, and filter cake is washed with deionized to neutrality, is dried in vacuo 2h at 100 DEG C,
Up to 5%Pd/C catalyst.
In 500ml stainless steel cauldron, be added 100g benzophenone, 180ml methanol, the above-mentioned preparation of 1.0g Pd-Cu-
Sn/C catalyst closes reaction kettle, three times with the air in nitrogen replacement reaction kettle, then three times with hydrogen displacement；By temperature liter
Pressing to 75 DEG C, hydrogen is 1.2MPa, starts to stir, stirring rate 900r/min, reacts 2h；Stop reaction, is down to room temperature to temperature
Afterwards, reaction solution, Filtration of catalyst, filtrate liquid-phase chromatographic analysis are taken out.Experimental result is conversion ratio 99.2wt%, selects
Property 58.2wt%.
Comparative example two
Comparative example two has investigated Pd-Cu/C and has prepared reactivity worth in benzhydrol in catalytic hydrogenation.
10g active carbon is weighed, granularity is 1000 mesh, specific surface area 1500m2/ g, content of ashes 3.5wt%, by it
It is configured to 25 DEG C of temperature of slurries in 100ml deionized water, the H of 10ml is slowly added dropwise2PdCl4(Pd content is 0.05g/ to solution
Ml), the Cu (NO of 10ml3)2Solution (Cu content is 0.03g/ml), stirs 0.5h；PH value of solution is adjusted with the KOH solution of 10wt%
Value cools the temperature to room temperature to 8, filters, and filter residue is washed with deionized to neutrality and obtains filter cake；Again by filter cake at 80 DEG C
Be configured to 80ml slurries, be added dropwise the 85wt% hydrazine hydrate solution of 0.9g, stir 2.5h, filtering, filter cake be washed with deionized to
Neutrality is dried in vacuo 2h at 100 DEG C to get 5%Pd-3%Cu/C catalyst.
In 500ml stainless steel cauldron, it is above-mentioned that 100g benzophenone, 180ml methanol, 0.2g sodium acetate, 1.0g is added
The Pd-Cu-Sn/C catalyst of preparation is closed reaction kettle, three times, then with hydrogen is replaced with the air in nitrogen replacement reaction kettle
Three times；By temperature rise to 75 DEG C, hydrogen press as 1.2MPa, start to stir, stirring rate 900r/min, react 2h；Stop reaction,
It is cooled to room temperature to temperature, takes out reaction solution, Filtration of catalyst, filtrate liquid-phase chromatographic analysis.Experimental result is conversion
Rate 98.9wt%, selectivity 75.9wt%.
Comparative example three
Comparative example three has investigated Pd-Sn/C and has prepared reactivity worth in benzhydrol in catalytic hydrogenation.
10g active carbon is weighed, granularity is 1000 mesh, specific surface area 1500m2/ g, content of ashes 3.5wt%, by it
It is configured to 25 DEG C of temperature of slurries in 100ml deionized water, the H of 10ml is slowly added dropwise2PdCl4(Pd content is 0.05g/ to solution
Ml), the SnCl of 10ml4Solution (Sn content is 0.03g/ml), stirs 0.5h；Solution ph is adjusted with the KOH solution of 10wt%
To 8, and room temperature is cooled the temperature to, filtered, filter residue is washed with deionized to neutrality and obtains filter cake；Filter cake is matched at 80 DEG C again
80ml slurries are set to, the 85wt% hydrazine hydrate solution of 0.9g is added dropwise, stir 2.5h, filtering, filter cake is washed with deionized into
Property, 2h is dried in vacuo at 100 DEG C to get 5%Pd-3%Sn/C catalyst.
In 500ml stainless steel cauldron, it is above-mentioned that 100g benzophenone, 180ml methanol, 0.2g sodium acetate, 1.0g is added
The Pd-Cu-Sn/C catalyst of preparation is closed reaction kettle, three times, then with hydrogen is replaced with the air in nitrogen replacement reaction kettle
Three times；By temperature rise to 75 DEG C, hydrogen pressure be 1.2 MPa, start to stir, stirring rate 900r/min, react 2h；Stop reaction,
It is cooled to room temperature to temperature, takes out reaction solution, Filtration of catalyst, filtrate liquid-phase chromatographic analysis.Experimental result is conversion
Rate 98.6wt%, selectivity 81.5wt%.
Comparative example four
Pd-Cu-Sn/C is prepared anti-in benzhydrol in catalytic hydrogenation when comparative example four has been investigated without addition sodium acetate
Answer performance.
In 500ml stainless steel cauldron, 100g benzophenone, 180ml methanol, 1.0g embodiment one is added and prepares
Pd-Cu-Sn/C catalyst closes reaction kettle, three times with the air in nitrogen replacement reaction kettle, then three times with hydrogen displacement；It will
Temperature rise to 75 DEG C, hydrogen pressure be 1.2MPa, start to stir, stirring rate 900r/min, react 2h；Stop reaction, is dropped to temperature
To room temperature, reaction solution, Filtration of catalyst, filtrate liquid-phase chromatographic analysis are taken out.Experimental result is conversion ratio
100wt%, selectivity 90.8wt%.
Claims (10)
1. a kind of method for synthesizing benzhydrol by benzophenone catalytic hydrogenation, the method are as follows: the method uses support type
Simultaneously protective agent is added in multicomponent catalyst in the reaction system；The support type multicomponent catalyst is Pd-Cu-Sn/C,
Carrier is active carbon, and active component Pd, auxiliary agent is Cu and Sn, and wherein the load capacity of Pd is 1~10wt%, and the load capacity of Cu is
The load capacity of 1~5wt%, Sn are 1~5wt%；The protective agent is sodium acetate.
2. the method as described in claim 1, it is characterised in that the method is implemented in accordance with the following steps: in a kettle,
Benzophenone, organic solvent, protective agent and support type multicomponent catalyst is added, is passed through hydrogen, 0.2~5.0MPa, 40~
1~10h is reacted under conditions of 120 DEG C；Obtained reaction solution is filtered to remove support type multicomponent catalyst, filtrate through distillation or
Up to benzhydrol after rectifying；Protectant additional amount is calculated as 0.001~0.005g/g with the quality of benzophenone.
3. method according to claim 2, it is characterised in that: the organic solvent is methanol or ethyl alcohol.
4. method according to claim 2, it is characterised in that: the dosage of the support type multicomponent catalyst is with benzophenone
Quality is calculated as 0.005~0.05g/g, preferably 0.005~0.01g/g；The additional amount of the organic solvent is with benzophenone
Quality is calculated as 0.5~3.0ml/g.
5. method according to claim 2, it is characterised in that: hydrogenation reaction temperature is 50-100 DEG C.
6. the method as described in one of Claims 1 to 5, it is characterised in that the Pd-Cu-Sn/C catalyst is by the following method
Preparation: using active carbon as carrier, adding deionized water to be configured to concentration at 25~100 DEG C is 4~40wt% slurries, by Metal Supported
The solution and soluble sn-containing compound of the solution of soluble containing palladium compound, soluble copper-containing compound is slowly added dropwise in amount respectively
Solution, stir；After impregnating 0.5~10h, addition alkaline solution adjusts solution ph to 7.5~10.0, continues to stir
Room temperature is cooled the temperature to after mixing 0.5~5h, is filtered, filter cake is washed with deionized to neutrality；Again by filter cake at 20~95 DEG C
Slurries are configured to deionized water, liquid phase reducing agent is added dropwise, stir 0.5-4h, filtering, filter cake is washed with deionized to neutrality,
Vacuum drying is at 70~120 DEG C to get the Pd-Cu-Sn/C catalyst.
7. method as claimed in claim 6, it is characterised in that: the granularity of activated carbon is 100~1500 mesh, specific surface area
For 800~2000m2/ g, content of ashes≤5.0wt%.
8. method according to claim 6 or 7, it is characterised in that: the soluble containing palladium compound is H2PdCl4、
K2PdCl4Or Na2PdCl4；The soluble copper-containing compound is CuCl2Or Cu (NO3)2；The stanniferous chemical combination of solubility
Object is SnCl2Or SnCl4。
9. method according to claim 6 or 7, it is characterised in that: the alkaline solution be NaOH or KOH aqueous solution or
Person's ammonium hydroxide.
10. method according to claim 6 or 7, it is characterised in that: the liquid-phase reduction agent is hydrazine hydrate, formic acid, formaldehyde
Or sodium formate, the ratio between the liquid-phase reduction agent and the amount of substance of containing palladium compound are 10~200:1.
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| CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
| CN111233626A (en) * | 2020-01-21 | 2020-06-05 | 浙江师范大学 | Method for preparing benzhydryl alcohol by hydrogenation of benzophenone |
| CN112206786A (en) * | 2020-08-31 | 2021-01-12 | 浙江工业大学 | Multi-metal nanoparticle catalyst and preparation and application thereof |
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