CN109433214A - A kind of porous catalysts supported on carbon of Ni/Zn and its application in phenyl ring catalytic hydrogenation - Google Patents
A kind of porous catalysts supported on carbon of Ni/Zn and its application in phenyl ring catalytic hydrogenation Download PDFInfo
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- CN109433214A CN109433214A CN201811374521.8A CN201811374521A CN109433214A CN 109433214 A CN109433214 A CN 109433214A CN 201811374521 A CN201811374521 A CN 201811374521A CN 109433214 A CN109433214 A CN 109433214A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
The present invention relates to a kind of porous catalysts supported on carbon of Ni/Zn and its applications in phenyl ring catalytic hydrogenation, the preparation method of the porous catalysts supported on carbon of Ni/Zn includes the following steps: the preparation of (1) porous carbon: dry ginkgo leaf is placed in tube furnace, in the presence of ammonia, it is warming up to 800 DEG C, after heat preservation 2 hours, room temperature is down to up to the porous carbon；(2) Ni/Zn is loaded: deionized water is added in the porous carbon for taking step (1) to obtain, after ultrasonic disperse 5min, nickel nitrate solution, zinc nitrate solution is added, continue ultrasound 10min, sodium borohydride solution is added, after continuing ultrasound 20min, filtering, precipitating are washed with water, are dried in vacuo up to the porous catalysts supported on carbon of the Ni/Zn.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of porous catalysts supported on carbon of Ni/Zn and its urge in phenyl ring
Change the application added in hydrogen.
Background technique
Phenyl ring catalytic hydrogenation reaction is the important reaction of industrial production chemical industry, medicine intermediate, such as the phenyl ring of benzoic acid
Hydrogenation products naphthenic acid is to synthesize praziquantel, caprolactam, the important intermediate for pacifying trienine.However, due to phenyl ring
Big pi bond there is high stability, therefore hydrogenation need to be existing for high temperature and pressure, metallic catalyst under the conditions of, carries out, this
The harsh reaction condition of kind significantly limits its application, while causing high energy consumption and environmental pollution.The present invention provides a kind of new
Type porous carbon, and obtain a kind of porous catalysts supported on carbon of Ni/Zn using porous carbon load Ni/Zn, the catalyst can be with
Naphthenic acid is converted by benzoic acid under without using organic solvent, condition of normal pressure.
Summary of the invention
The present invention provides a kind of porous catalysts supported on carbon of Ni/Zn, it is characterised in that the Ni/Zn is porous carbon-supported
The preparation method of catalyst includes the following steps:
(1) preparation of porous carbon: dry ginkgo leaf is placed in tube furnace, in the presence of ammonia, is warming up to 800 DEG C,
After heat preservation 2 hours, room temperature is down to up to the porous carbon.
(2) Ni/Zn is loaded: the porous carbon addition deionized water for taking step (1) to obtain, and after ultrasonic disperse 5min, nitre is added
Sour nickel solution, zinc nitrate solution continue ultrasound 10min, and sodium borohydride solution is added, after continuing ultrasound 20min, filtering, precipitating
It is washed with water, is dried in vacuo up to the porous catalysts supported on carbon of the Ni/Zn.
The preferably 10 DEG C/min of heating rate described in step (1), rate of temperature fall preferably 10 DEG C/min.
The concentration of Ni is 5mg/mL in nickel nitrate solution in step (2), and the concentration of Zn is 5mg/mL, boron in zinc nitrate solution
The concentration of sodium hydride solution is 2mg/mL, and every gram of porous carbon is molten using nickel nitrate solution 2mL, zinc nitrate solution 2mL, sodium borohydride
Liquid 25mL.The dosage of deionized water is advisable with the fully dispersed porous carbon of energy, and preferably the mass ratio of porous carbon and deionized water is 1:
25-30；The preferred deionized water of water or redistilled water used when washing precipitating；Supersonic frequency is 20-30KHz.
Another embodiment of the present invention provides the above-mentioned Ni/Zn preparation method of porous catalysts supported on carbon, feature
It is to include the following steps:
(1) preparation of porous carbon: dry ginkgo leaf is placed in tube furnace, in the presence of ammonia, is warming up to 800 DEG C,
After heat preservation 2 hours, room temperature is down to up to the porous carbon.
(2) Ni/Zn is loaded: the porous carbon addition deionized water for taking step (1) to obtain, and after ultrasonic disperse 5min, nitre is added
Sour nickel solution, zinc nitrate solution continue ultrasound 10min, and sodium borohydride solution is added, after continuing ultrasound 20min, filtering, precipitating
It is washed with water, is dried in vacuo up to the porous catalysts supported on carbon of the Ni/Zn.
The preferably 10 DEG C/min of heating rate described in step (1), rate of temperature fall preferably 10 DEG C/min.
The concentration of Ni is 5mg/mL in nickel nitrate solution in step (2), and the concentration of Zn is 5mg/mL, boron in zinc nitrate solution
The concentration of sodium hydride solution is 2mg/mL, and every gram of porous carbon is molten using nickel nitrate solution 2mL, zinc nitrate solution 2mL, sodium borohydride
Liquid 25mL.The dosage of deionized water is advisable with the fully dispersed porous carbon of energy, and preferably the mass ratio of porous carbon and deionized water is 1:
25-30；The preferred deionized water of water or redistilled water used when washing precipitating；Supersonic frequency is 20-30KHz.
Another embodiment of the present invention provides the porous catalysts supported on carbon of above-mentioned Ni/Zn and adds in hydrogen in catalysis aromatic ring
Using.Especially add the application in hydrogen in catalysis benzene and benzene derivative.Preferred catalytic benzoic acid hydrogenation is converted into naphthenic acid
In application.
Another embodiment of the present invention provides a kind of method for preparing naphthenic acid by benzoic acid, it is characterised in that packet
Include following steps:
Benzoic acid, the porous catalysts supported on carbon of Ni/Zn are added in deionized water, after ultrasonic disperse is uniform, under normal pressure,
After being passed through hydrogen and being warming up to 80 DEG C -90 DEG C, reaction 12-16 hours, naphthenic acid can be obtained.
Every mM of benzoic acid uses the porous catalysts supported on carbon 100mg of Ni/Zn, uses deionized water 60mL.
Sodium borohydride solution of the present invention is the sodium borohydride aqueous solution of matching while using.
Compared with the prior art, the advantages of the present invention are as follows: (1) present invention using ginkgo leaf as raw material be prepared porous
Carbon；(2) porous carbon load Ni/Zn of the present invention obtains the porous catalysts supported on carbon of novel Ni/Zn, which can not make
With under organic solvent, normal pressure, phenyl ring hydrogen is restored, high energy consumption and environmental pollution are avoided, it is environmentally protective.
Detailed description of the invention
Fig. 1 is the electronic scanner microscope figure that the embodiment of the present invention 1 prepares porous carbon, A: side, B: cross section；
Fig. 2 is the nitrogen adsorption desorption curve phenogram that the embodiment of the present invention 1 prepares porous carbon.
Specific embodiment
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.But
It is that these embodiments are only not supposed to be a limitation to the present invention or implementation principle for better understanding invention, reality of the invention
The mode of applying is not limited to the following contents.The preferred 20-30KHz of supersonic frequency used in the embodiment of the present invention.
The preparation of 1 porous carbon of embodiment
Dry ginkgo leaf (100g) is placed in tube furnace, in the presence of ammonia, is warming up to the rate of 10 DEG C/min
After 800 DEG C, heat preservation 2 hours, room temperature is down to get the porous carbon with the rate of 10 DEG C/min.
Embodiment 2
Deionized water (25mL) is added in porous carbon (1.0g) prepared by Example 1, and after ultrasonic disperse 5min, nitric acid is added
Nickel solution (2mL, wherein the concentration of Ni is 5mg/mL), zinc nitrate solution (2mL, wherein the concentration of Zn is 5mg/mL), continue to surpass
Sound 10min is added sodium borohydride solution (25mL, 2mg/mL now match), and after continuing ultrasound 20min, filtering, precipitating use deionization
Water washing is dried in vacuo up to the porous catalysts supported on carbon of the Ni/Zn (hereinafter referred to as product A).
Embodiment 3
Deionized water (25mL) is added in porous carbon (1.0g) prepared by Example 1, and after ultrasonic disperse 5min, nitric acid is added
Nickel solution (2mL, wherein the concentration of Ni is 5mg/mL), continuation ultrasound 10min, addition sodium borohydride solution (25mL, 2mg/mL,
Now match), after continuing ultrasound 20min, filtering, precipitating are washed with deionized, are dried in vacuo up to Ni porous carbon supported catalyst
Agent (hereinafter referred to as product B).
Embodiment 4
Deionized water (25mL) is added in porous carbon (1.0g) prepared by Example 1, and after ultrasonic disperse 5min, nitric acid is added
Zinc solution (2mL, wherein the concentration of Zn is 5mg/mL), continuation ultrasound 10min, addition sodium borohydride solution (25mL, 2mg/mL,
Now match), after continuing ultrasound 20min, filtering, precipitating are washed with deionized, are dried in vacuo up to Zn porous carbon supported catalyst
Agent (hereinafter referred to as products C).
Embodiment 5
Benzoic acid (0.5mmol), product A (50mg) is taken to be added in deionized water (30mL), after ultrasonic disperse is uniform, normal pressure
Under, after being passed through hydrogen and being warming up to 80 DEG C, reaction 16 hours, reaction solution is extracted with ethyl acetate, ethyl acetate phase is through GC-MS
Analysis, benzoic acid are converted into the high conversion rate of naphthenic acid up to 96.7%.
Embodiment 6
According to the method that embodiment 5 is recorded, respectively with etc. product B, C of quality, commercially available 10%Pd-C, Raney's nickel replacement produce
Product A, GC-MS analysis, the conversion ratio that benzoic acid is converted into naphthenic acid see the table below.
| Catalyst | Conversion ratio |
| Product B | 18.5% |
| Products C | - |
| 10%Pd-C | - |
| Raney's nickel | - |
"-" indicates that conversion ratio is 0.
Claims (10)
1. a kind of porous catalysts supported on carbon of Ni/Zn, it is characterised in that the preparation of the porous catalysts supported on carbon of Ni/Zn
Method includes the following steps:
(1) preparation of porous carbon: dry ginkgo leaf is placed in tube furnace, in the presence of ammonia, is warming up to 800 DEG C, heat preservation 2
After hour, room temperature is down to up to the porous carbon；
(2) Ni/Zn is loaded: the porous carbon addition deionized water for taking step (1) to obtain, and after ultrasonic disperse 5min, nickel nitrate is added
Solution, zinc nitrate solution continue ultrasound 10min, and sodium borohydride solution is added, and after continuing ultrasound 20min, filtering, precipitating use water
It washs, be dried in vacuo up to the porous catalysts supported on carbon of the Ni/Zn.
2. the porous catalysts supported on carbon of Ni/Zn described in claim 1, it is characterised in that heating rate described in step (1)
It is preferred that 10 DEG C/min, rate of temperature fall preferably 10 DEG C/min.
3. the porous catalysts supported on carbon of the described in any item Ni/Zn of claim 1-2, it is characterised in that nitric acid in step (2)
The concentration of Ni is 5mg/mL in nickel solution, and the concentration of Zn is 5mg/mL in zinc nitrate solution, and the concentration of sodium borohydride solution is
2mg/mL, every gram of porous carbon use nickel nitrate solution 2mL, zinc nitrate solution 2mL, sodium borohydride solution 25mL.
4. the porous catalysts supported on carbon of the described in any item Ni/Zn of claim 1-3, it is characterised in that porous carbon and deionization
The mass ratio of water is 1:25-30；The preferred deionized water of water or redistilled water used when washing precipitating；Supersonic frequency is 20-
30KHz。
5. the preparation method of the porous catalysts supported on carbon of the described in any item Ni/Zn of claim 1-4.
6. the porous catalysts supported on carbon of the described in any item Ni/Zn of claim 1-4 adds the application in hydrogen in catalysis aromatic ring.
7. application as claimed in claim 6, it is characterised in that preferably add the application in hydrogen in catalysis benzene and benzene derivative.
8. application as claimed in claim 6, it is characterised in that preferred catalytic benzoic acid hydrogenation is converted into answering in naphthenic acid
With.
9. a kind of method for preparing naphthenic acid by benzoic acid, it is characterised in that include the following steps:
Benzoic acid, the porous catalysts supported on carbon of the described in any item Ni/Zn of claim 1-4 are added in deionized water, surpassed
After sound is uniformly dispersed, under normal pressure, after being passed through hydrogen and being warming up to 80 DEG C -90 DEG C, reaction 12-16 hours, hexamethylene can be obtained
Formic acid.
10. method as claimed in claim 9, it is characterised in that every mM of benzoic acid uses Ni/Zn porous carbon supported catalyst
Agent 100mg uses deionized water 60mL.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114236023A (en) * | 2021-11-29 | 2022-03-25 | 澳门科技大学 | Porous carbon carrier, preparation method thereof and application thereof in ligand fishing |
| CN114588910A (en) * | 2022-03-15 | 2022-06-07 | 福州大学 | Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114236023A (en) * | 2021-11-29 | 2022-03-25 | 澳门科技大学 | Porous carbon carrier, preparation method thereof and application thereof in ligand fishing |
| CN114588910A (en) * | 2022-03-15 | 2022-06-07 | 福州大学 | Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization |
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