CN116196964B - Levulinate hydrogenation catalyst, preparation method and application - Google Patents

Levulinate hydrogenation catalyst, preparation method and application Download PDF

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CN116196964B
CN116196964B CN202310223238.XA CN202310223238A CN116196964B CN 116196964 B CN116196964 B CN 116196964B CN 202310223238 A CN202310223238 A CN 202310223238A CN 116196964 B CN116196964 B CN 116196964B
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levulinate
catalyst
hydrogenation
reaction
valerolactone
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CN116196964A (en
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高晓庆
朱善辉
郑洪岩
牛宇岚
王峰
薛彦峰
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Taiyuan Institute of Technology
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/398—Egg yolk like
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a levulinate hydrogenation catalyst, a preparation method and application thereof, and belongs to the technical field of catalytic hydrogenation. The method comprises the steps of dropwise adding a precursor solution containing Co into a precursor solution containing another metal M under the condition of stirring at room temperature, standing, filtering, collecting a precipitate, drying, pyrolyzing in H 2/Ar mixed gas, cooling to room temperature, passivating in O 2/Ar mixed gas, treating with sulfuric acid, filtering and drying to obtain the catalyst. The catalyst is in a core-shell structure and comprises an N-doped carbon carrier and active components of a Co-containing bimetallic alloy coated by the carrier; specifically, the mass content of Co and M (one of Ni, fe, cu and Zn) is 5-30%. The catalyst provided by the invention can realize 100% conversion rate of levulinate in the levulinate hydrogenation reaction for preparing gamma-valerolactone, has gamma-valerolactone selectivity reaching more than 97%, and has higher stability, and the levulinate can be recycled for 6 times without inactivation.

Description

Levulinate hydrogenation catalyst, preparation method and application
Technical Field
The invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a levulinate hydrogenation catalyst, a preparation method and application thereof.
Background
With the rapid development of biomass conversion, significant progress has also been made in the synthesis of levulinate esters from lignocellulose. For this reason, there is a need to develop new processes to convert the utilization of increasing levulinate esters to produce high value added downstream products.
The gamma-valerolactone has very wide application, and is especially used in synthesizing basic chemical material 1, 4-pentanediol, 2-methyltetrahydrofuran, etc. The gamma-valerolactone can be used as a raw material for synthesizing high-grade transportation and aviation fuels. In addition, gamma valerolactone has been found to be useful in dissolving cellulose, lignin and humus, a good solvent for biomass conversion. With the increasing interest in the potential use of gamma valerolactone, the direct production of gamma valerolactone from biomass has gained increasing attention. The preparation method has the advantages that the process route for preparing the gamma-valerolactone by catalytic hydrogenation of the levulinate is simple, the yield of the target product gamma-valerolactone is high, the reaction condition is mild, the levulinate does not contain acidity, the acid resistance requirement on the catalyst is low, and the method is very suitable for large-scale industrial application.
At present, levulinate hydrogenation catalysts mainly comprise noble metals such as Ru, pd and the like, non-noble metals such as Cu, ni and the like. Nadgeri et al (Liquidphasehydrogenationofmethyllevulinateoverthe mixtureofsupportedrutheniumcatalystandzeoliteinwater,AppliedCatalysisA:General,2014,470,215-220) report that Ru/ZSM-5 produced a 96% yield of gamma valerolactone in the reaction of methyl levulinate hydrogenation to gamma valerolactone. The Guan et al (Enhancedhydrogenationofethyl levulinatebyPd–ACdopedwithNb2O5,GreenChemistry,2014,16,3951-3957) introduces an auxiliary Nb 2O5 into the Pd/C catalyst, so that the conversion rate of ethyl levulinate is improved from 38% to 87%, and the selectivity of gamma-valerolactone is improved from 74% to 93%. Nb 2O5 plays a synergistic catalytic role in the reaction process, on the one hand it can disperse and stabilize Pd nanoparticles, on the other hand Nb 2O5 itself is also an acid catalyst. Lin et al (StableandefficientCuCrcatalystforthesolvent-freehydrogenationofbiomass derivedethyllevulinatetoγ-valerolactoneaspotentialbiofuelcandidate,Fuel,2016,175,232-239) used in situ reduction of CuCr catalyst during the reaction to convert ethyl levulinate for hydrogenation to prepare gamma valerolactone. The calcination temperature of the CuCr precursor greatly affects the reactivity of the CuCr catalyst. The optimal reaction performance of CuCr baked at 350 ℃ is obtained at 250 ℃ and 4MPaH 2, the conversion rate of ethyl levulinate is 85.6%, and the selectivity of gamma-valerolactone is as high as 98.6%. Increasing the firing temperature to form the more difficult-to-reduce CuCrO 2 greatly reduces the conversion of ethyl levulinate.
The noble metal Ru catalyst used in the method has high gamma-valerolactone yield, but has high price, so that the economic value of the levulinate hydrogenation process is reduced. The non-noble metal catalyst Cu is used to obtain higher levulinate conversion rate and gamma-valerolactone selectivity at a very high reaction temperature. However, biomass itself contains water, and Cu catalyst in aqueous solution is easily lost to deactivate the catalyst, which is not suitable for industrial use.
Disclosure of Invention
Aiming at the problems of high price, harsh reaction conditions, poor stability and the like of the existing catalyst for preparing the levulinate by hydrogenation, the invention aims to provide the levulinate hydrogenation catalyst, and the preparation method and application thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
a levulinate hydrogenation catalyst which has a core-shell structure and comprises a carrier and an active component coated by the carrier; the carrier is N-doped carbon; the active component is a bimetal alloy containing Co; the Co-containing bimetallic alloy is specifically metal Co and another metal M, and the mass content of the Co-containing bimetallic alloy is 5-30%; preferably 10 to 20%, more preferably 10 to 15%. The mass content of N element in the catalyst is 0.5-10%.
The other metal M is one of Ni, fe, cu and Zn.
The specific surface area of the catalyst is 50-150 m 2/g.
The average grain diameter of the bimetallic alloy of the catalyst is 5-30 nm.
The invention adopts the nitrogen-doped carbon to coat the CoM alloy to form a core-shell structure, which can greatly inhibit the loss of CoM alloy components and can greatly improve the stability of the catalyst. In addition, strong electronic interaction exists between the two components of the CoM alloy catalyst, and the CoM alloy can form strong chemical adsorption with carbonyl of levulinate, so that the levulinate can be activated, and the activity of the catalyst is improved. In addition, the shell N doped with carbon has a finite field function, and can allow levulinate and gamma-valerolactone to pass through, and prevent 4-hydroxyvalerate serving as an intermediate product with larger molecular diameter from passing through, so that the selectivity of target gamma-valerolactone can be improved.
A preparation method of levulinate hydrogenation catalyst comprises the steps of dropwise adding a precursor solution containing Co into a precursor solution containing another metal M under the condition of stirring at room temperature, standing, filtering, collecting precipitate, drying, pyrolyzing in H 2/Ar mixed gas, cooling to room temperature, passivating in O 2/Ar mixed gas, treating with sulfuric acid, filtering and drying to obtain the catalyst (the catalyst is named as CoM@NC).
Further, the molar ratio of the metal Co to the other metal in the precursor solution containing Co and the precursor solution containing the other metal M is 1:0.5-1.4. According to the hydrogenation catalyst provided by the invention, the non-noble metal is adopted as an active component to replace the traditional noble metal catalyst, so that the catalyst cost can be greatly saved. In addition, the product gamma-valerolactone adsorbed on the surface of the CoM alloy can timely pass through the shell carbon micropores, and can inhibit the excessive hydrogenation reaction of the gamma-valerolactone, so that the selectivity of the gamma-valerolactone is further improved. In the present invention, the molar ratio of the metal Co to the metal M in the bimetal alloy is preferably 1:1 to 1:2.
The metal Co precursor preferably comprises one or two of K 3[Co[(CN)6 and Na 3[Co[(CN)6, and when the Co precursor comprises two of the above substances, no special requirement is imposed on the proportion of each Co precursor, so long as the total concentration requirement of the Co precursor-containing solution in the solution can be met.
The other metal M precursor is one of nickel nitrate, copper nitrate, ferric nitrate and zinc nitrate.
Further, the standing time is 5-30 hours; the pyrolysis temperature in the H 2/Ar mixed gas is 400-1000 ℃, preferably 500-600 ℃; more preferably 500 to 550 ℃; the pyrolysis time is 4 to 20 hours, preferably 5 to 6 hours.
Further, the concentration of the sulfuric acid is 0.3 mol/L-3 mol/L, and the treatment time of the sulfuric acid is 5-30 h. The purpose of the sulfuric acid treatment is to etch away the CoM metal component that is not coated by the carbon support.
During the pyrolysis process, the metal framework material formed by the Co and M precursors may decompose to form the metals Co and M, and ultimately form the CoM alloy.
An application of a levulinate hydrogenation catalyst in preparing gamma-valerolactone by levulinate hydrogenation.
Further, the levulinate is one or more of methyl levulinate, ethyl levulinate, propyl levulinate or butyl levulinate.
Further, the reaction temperature of levulinate hydrogenation is 60-150 ℃, preferably 80-130 ℃; the pressure of the reaction H 2 is 2-6 MPa, preferably 3-5 MPa; the mass of the catalyst is 0.03-5% of that of levulinate, and is preferably 1-2%. The reaction time is 3 to 15 hours, preferably 5 to 8 hours; the levulinate hydrogenation reaction is preferably carried out by taking water as a reaction solvent. The hydrogenation reaction is preferably carried out in an autoclave.
Compared with the prior art, the invention has the following advantages:
The active components in the levulinate hydrogenation catalyst provided by the invention are non-noble metals Co and M, so that the catalyst cost can be greatly saved. The invention adopts the nitrogen-doped carbon to coat the CoM alloy to form a core-shell structure, which can greatly inhibit the loss of CoM alloy components and can greatly improve the stability of the catalyst. In addition, strong electronic interaction exists between the two components of the CoM alloy catalyst, and the CoM alloy can form strong chemical adsorption with carbonyl of levulinate, so that the levulinate can be activated, and the catalyst has higher activity. In addition, the shell N doped with carbon has a finite field function, and allows levulinate and gamma-valerolactone to pass through, and prevents 4-hydroxyvalerate, an intermediate product with larger molecular diameter, from passing through, so that the selectivity of target gamma-valerolactone can be improved. In addition, the product gamma-valerolactone desorbed from the surface of the CoM alloy can timely pass through the shell carbon micropores, and can inhibit the excessive hydrogenation reaction of the gamma-valerolactone, thereby further improving the selectivity of the gamma-valerolactone.
The results of the examples show that the catalyst provided by the invention can realize 100% conversion rate of levulinate in the reaction of preparing gamma-valerolactone by hydrogenating levulinate, has gamma-valerolactone selectivity reaching more than 97%, and has higher stability (recycling is performed for 6 times without deactivation).
The catalyst of the invention is used for catalyzing levulinate hydrogenation to prepare gamma-valerolactone, and has the advantages of taking water as a green solvent and mild reaction conditions.
Drawings
FIG. 1 is a High Resolution Transmission Electron Microscope (HRTEM) image of the CoNi@NC catalyst prepared in example 1.
Detailed Description
The levulinate catalysts, methods for their preparation and use provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
The catalyst in the examples below was preactivated for 2 hours in a tube furnace at 300℃in an atmosphere of H 2/Ar prior to the reaction.
Example 1
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of nickel nitrate solution (0.03 mol/L) under stirring at room temperature, then left to stand for 20 hours, the precipitate was collected by filtration, dried, pyrolyzed at 800℃in H 2/Ar mixture for 6 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1.5 mol/L) for 10 hours, filtered and dried to give CoNi@NC catalyst. The high-resolution transmission electron microscope test result of the catalyst is shown in figure 1, and as can be seen from figure 1, all CoNi alloy nano particles are coated by a carbon carrier, so that a good core-shell structure is formed.
Application example 1
To a batch reactor was added 0.1g of the CoNi@NC catalyst synthesized in example 1, 1g of ethyl levulinate, 10g of water, flushed with 4MPaH 2 and sealed, and the reaction was warmed to 100℃and continued for 6h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 100%, and the gamma valerolactone selectivity was 98.5%. After the catalyst is recycled for 6 times, the conversion rate of ethyl levulinate is 100%, and the selectivity of gamma-valerolactone is 98.3%, which proves that the catalyst has high stability.
Comparative example 1
Comparative example commercial Ru/C catalyst was used with a Ru mass content of 5%.
The catalyst of comparative example 1 was subjected to performance test according to the reaction conditions of application example 1, and the evaluation result of the Ru/C catalyst showed that the ethyl levulinate conversion was 97.5% and the gamma valerolactone selectivity was 87.1%. After the catalyst is recycled for 3 times, the conversion rate of ethyl levulinate is reduced to 94.1%, and the selectivity of gamma-valerolactone is reduced to 40.3%, which indicates that the Ru/C catalyst is deactivated after being recycled for 3 times.
Example 2
100MLNa 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of nickel nitrate solution (0.03 mol/L) under stirring at room temperature, then left to stand for 20 hours, the precipitate was collected by filtration, dried, pyrolyzed at 600℃in H 2/Ar mixture for 6 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1.5 mol/L) for 10 hours, filtered and dried to give CoNi@NC catalyst.
Application example 2
To a batch reactor was added 0.1g of the CoNi@NC catalyst synthesized in example 2, 1g of methyl levulinate, 10g of water, flushed with 4MPaH 2 and sealed, and the reaction was warmed to 120℃and continued for 5h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of methyl levulinate was 100%, and the gamma valerolactone selectivity was 99.1%.
Example 3
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of nickel nitrate solution (0.03 mol/L) under stirring at room temperature, then left to stand for 20 hours, the precipitate was collected by filtration, dried, pyrolyzed at 1000℃in H 2/Ar mixture for 6 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1.5 mol/L) for 10 hours, filtered and dried to give CoNi@NC catalyst.
Application example 3
To a batch reactor was added 0.05g of the CoNi@NC catalyst synthesized in example 3, 0.6g of ethyl levulinate, 10g of water, flushed with 3MPaH 2 and sealed, and the reaction was warmed to 110℃and continued for 7h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 100% and the gamma valerolactone selectivity was 97.2%.
Example 4
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) is added dropwise to 100mL nickel nitrate solution (0.03 mol/L) under stirring at room temperature, then the mixture is kept stand for 20H, the precipitate is collected by filtration, dried and pyrolyzed in H 2/Ar mixed gas at 800 ℃ for 5H, cooled to room temperature and passivated in O 2/Ar mixed gas for 30min, the sample is treated with sulfuric acid solution (0.8 mol/L) for 5H, and the CoNi@NC catalyst is obtained by filtration and drying.
Application example 4
To a batch reactor was added 0.15g of the CoNi@NC catalyst synthesized in example 4, 1.2g of propyl levulinate, 10g of water, flushed with 6MPaH 2 and sealed, and the reaction was warmed to 120℃and continued for 8h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of propyl levulinate was 99.5% and the gamma valerolactone selectivity was 97.9%.
Example 5
100MLNa 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of nickel nitrate solution (0.03 mol/L) under stirring at room temperature, then left to stand for 20 hours, the precipitate was collected by filtration, dried, pyrolyzed at 1000℃in H 2/Ar mixture for 10 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (0.5 mol/L) for 20 hours, filtered and dried to obtain the CoNi@NC catalyst.
Application example 5
To a batch reactor was added 0.1g of the CoNi@NC catalyst synthesized in example 5, 1.1g of butyl levulinate, 10g of water, flushed with 5MPaH 2 and sealed, and the reaction was warmed to 120℃and continued for 6h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of butyl levulinate was 100% and the gamma valerolactone selectivity was 98.1%.
Example 6
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of copper nitrate solution (0.03 mol/L) under stirring at room temperature, then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, pyrolyzed at 600℃in H 2/Ar mixture for 10 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1 mol/L) for 10 hours, filtered and dried to give CoCu@NC catalyst.
Application example 6
To a batch reactor was added 0.1g of the CoCu@NC catalyst synthesized in example 6, 1g of methyl levulinate, 10g of water, flushed with 4MPaH 2 and sealed, and the reaction was warmed to 110℃and continued for 6h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of methyl levulinate was 100%, and the gamma valerolactone selectivity was 99.1%.
Example 7
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of copper nitrate solution (0.03 mol/L) under stirring at room temperature, then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, pyrolyzed at 800℃in a H 2/Ar mixture for 5 hours, cooled to room temperature and passivated in an O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1 mol/L) for 10 hours, filtered and dried to give a CoCu@NC catalyst.
Application example 7
To a batch reactor was added 0.08g of the CoCu@NC catalyst synthesized in example 7, 1.1g of ethyl levulinate, 10g of water, flushed with 5MPaH 2 and sealed, and the reaction was warmed to 130℃and continued for 8h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 100% and the gamma valerolactone selectivity was 97.8%.
Example 8
100MLNa 3[Co(CN)6 ] solution (0.03 mol/L) was added dropwise to 100mL of copper nitrate solution (0.05 mol/L) under stirring at room temperature, then left to stand for 24 hours, the precipitate was collected by filtration, dried, pyrolyzed in H 2/Ar gas mixture at 1000℃for 4 hours, cooled to room temperature and passivated in O 2/Ar gas mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1 mol/L) for 10 hours, filtered and dried to obtain CoCu@NC catalyst.
Application example 8
To a batch reactor was added 0.15g of the CoCu@NC catalyst synthesized in example 8, 1.5g of butyl levulinate, 10g of water, flushed with 4MPaH 2 and sealed, and the reaction was warmed to 130℃and continued for 10h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 100%, and the gamma valerolactone selectivity was 98.2%.
Example 9
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of ferric nitrate solution (0.03 mol/L) under stirring at room temperature, then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, pyrolyzed at 600℃in H 2/Ar mixture for 10 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1 mol/L) for 10 hours, filtered and dried to give CoFe@NC catalyst.
Application example 9
To a batch reactor was added 0.15g of the CoFe@NC catalyst synthesized in example 9, 1g of ethyl levulinate, 10g of water, flushed with 5MPaH 2 and sealed, and the reaction was warmed to 110℃and continued for 8h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 100%, and the gamma valerolactone selectivity was 99.5%.
Example 10
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of ferric nitrate solution (0.03 mol/L) under stirring at room temperature, then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, pyrolyzed at 800℃in H 2/Ar mixture for 5 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1.5 mol/L) for 8 hours, filtered and dried to give CoFe@NC catalyst.
Application example 10
To a batch reactor was added 0.1g of the CoFe@NC catalyst synthesized in example 10, 1g of methyl levulinate, 10g of water, flushed with 6MPaH 2 and sealed, and the reaction was warmed to 130℃and continued for 5h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of methyl levulinate was 100%, and the gamma valerolactone selectivity was 97.8%.
Example 11
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of ferric nitrate solution (0.03 mol/L) under stirring at room temperature, then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, pyrolyzed at 1000℃in H 2/Ar mixture for 6 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (2 mol/L) for 10 hours, filtered and dried to give CoFe@NC catalyst.
Application example 11
To a batch reactor was added 0.08g of the CoFe@NC catalyst synthesized in example 11, 1.2g of ethyl levulinate, 10g of water, flushed with 6MPaH 2 and sealed, and the reaction was warmed to 90℃and continued for 10h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 100%, and the gamma valerolactone selectivity was 99.3%.
Example 12
100MLK 3[Co(CN)6 ] solution (0.02 mol/L) was added dropwise to 100mL of zinc nitrate solution (0.03 mol/L) under stirring at room temperature, then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, pyrolyzed at 600℃in H 2/Ar mixture for 10 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1 mol/L) for 10 hours, filtered and dried to give CoZn@NC catalyst.
Application example 12
To a batch reactor was added 0.1g of the CoZn@NC catalyst synthesized in example 12, 1g of methyl levulinate, 10g of water, flushed with 4MPaH 2 and sealed, and the temperature was raised to 120℃and the reaction continued for 7h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 99.8% and the gamma valerolactone selectivity was 98.2%.
Example 13
100MLK 3[Co(CN)6 ] and Na 3[Co(CN)6 ] solutions ([ Co (CN) 6]3+ total concentration of 0.02 mol/L) were added dropwise to 100mL of zinc nitrate solution (0.03 mol/L) under stirring at room temperature, then left to stand for 30 hours, the precipitate was collected by filtration, dried, pyrolyzed in a H 2/Ar mixture at 800℃for 5 hours, cooled to room temperature and passivated in an O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1 mol/L) for 20 hours, filtered and dried to obtain a CoZn@NC catalyst.
Application example 13
To a batch reactor was added 0.1g of the CoZn@NC catalyst synthesized in example 13, 1g of ethyl levulinate, 10g of water, flushed with 6MPaH 2 and sealed, and the reaction was warmed to 90℃and continued for 10h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 100% and the gamma valerolactone selectivity was 97.8%.
Example 14
100MLK 3[Co(CN)6 ] solution (0.05 mol/L) was added dropwise to 100mL of zinc nitrate solution (0.08 mol/L) under stirring at room temperature, then left to stand for 30 hours, the precipitate was collected by filtration, dried and pyrolyzed at 1000℃in H 2/Ar mixture for 8 hours, cooled to room temperature and passivated in O 2/Ar mixture for 30 minutes, the above sample was treated with sulfuric acid solution (1 mol/L) for 20 hours, filtered and dried to obtain CoZn@NC catalyst.
Application example 14
To a batch reactor was added 0.15g of the CoZn@NC catalyst synthesized in example 14, 1.6g of propyl levulinate, 10g of water, flushed with 6MPaH 2 and sealed, and the reaction was warmed to 110℃and continued for 6h under magnetic stirring. After stopping the reaction, the reaction solution obtained by centrifugal separation was analyzed by gas chromatography. Under the reaction conditions, the conversion of propyl levulinate was 99.9% and the gamma valerolactone selectivity was 97.4%.
From the above examples and comparative examples, the present invention provides a levulinate hydrogenation catalyst, a preparation method and application thereof, wherein noble metals are not used in the catalyst, the catalyst preparation cost is saved, the catalyst has very high activity in the levulinate hydrogenation reaction for preparing gamma-valerolactone, and meanwhile, the selectivity and stability of gamma-valerolactone can be improved.
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.

Claims (8)

1. A levulinate hydrogenation catalyst, characterized by: the levulinate hydrogenation catalyst has a core-shell structure and comprises a carrier and an active component coated by the carrier; the carrier is N-doped carbon; the active component is a bimetal alloy containing Co; the Co-containing bimetallic alloy specifically comprises an active component Co and another metal M, and the mass contents of the active component Co and the another metal M are 5-30%; the mass content of N element in the catalyst is 0.5% -10%;
The other metal M is one of Ni, fe, cu and Zn;
The preparation method of the levulinate hydrogenation catalyst comprises the following steps: dropwise adding a precursor solution containing Co into a precursor solution containing another metal M under the condition of stirring at room temperature, standing, filtering, collecting a precipitate, drying, pyrolyzing in H 2/Ar mixed gas, cooling to room temperature, passivating in O 2/Ar mixed gas, treating with sulfuric acid, filtering and drying to obtain a catalyst;
The Co-containing precursor is one or two of K 3 [Co[(CN)6 and Na 3 [Co[(CN)6.
2. A levulinate hydrogenation catalyst according to claim 1, characterised in that: the specific surface area of the catalyst is 50-150 m 2/g.
3. A levulinate hydrogenation catalyst according to claim 1, characterised in that: the average grain diameter of the bimetallic alloy of the catalyst is 5-30 nm.
4. A levulinate hydrogenation catalyst according to claim 1, characterised in that: the molar ratio of the metal Co to the other metal in the precursor solution containing Co to the precursor solution containing the other metal M is 1:0.5-1.4.
5. A levulinate hydrogenation catalyst according to claim 1, characterised in that: the standing time is 5-30 hours; the pyrolysis temperature in the H 2/Ar mixed gas is 400-1000 ℃, and the pyrolysis time is 4-20H.
6. Use of the levulinate hydrogenation catalyst according to claim 1 in the preparation of gamma valerolactone by levulinate hydrogenation.
7. The use according to claim 6, characterized in that: the levulinate is one or more of methyl levulinate, ethyl levulinate, propyl levulinate or butyl levulinate.
8. The use according to claim 6, characterized in that: the reaction temperature of levulinate hydrogenation is 60-150 ℃, the reaction pressure is 2-6 MPa, and the mass of the catalyst is 0.03-5% of the mass of levulinate.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106378449A (en) * 2016-10-11 2017-02-08 中国科学技术大学 Ruthenium-cobalt alloy nanoparticle as well as preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111097470A (en) * 2018-10-25 2020-05-05 中国科学院金属研究所 Preparation method of Fe-Ni alloy nano square electrocatalyst coated by nitrogen-doped graphite carbon layer
CN110548505A (en) * 2019-08-20 2019-12-10 青岛科技大学 Core-shell type catalyst, synthesis method thereof and method for preparing gamma-valerolactone by catalyzing levulinic acid by core-shell type catalyst
CN113828339B (en) * 2020-06-08 2023-08-29 中国石油大学(北京) M-Co monoatomic alloy catalyst and preparation method and application thereof
CN114308094B (en) * 2020-10-10 2023-09-29 中国石油大学(北京) Cobalt monoatomic/nitrogen doped mesoporous carbon fiber material, and preparation method and application thereof
CN112371153B (en) * 2020-11-03 2022-06-03 湖北大学 Bimetallic CoNi-ZIF derived CoNi @ CN catalyst, preparation method and catalytic hydrogenation application thereof
CN113976879B (en) * 2021-10-27 2023-04-25 电子科技大学 Carbon layer coated ferrocobalt nano core-shell structure and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106378449A (en) * 2016-10-11 2017-02-08 中国科学技术大学 Ruthenium-cobalt alloy nanoparticle as well as preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Efficient formation of γ-valerolactone in the vapor-phase hydrogenation of levulinic acid over Cu-Co/alumina catalyst;Daichi Yanase等;Catalysis Communications;20200220;第139卷;105967 *
Exploring the Zn-regulated function in Co-Zn catalysts for efficient hydrogenation of ethyl levulinate to γ-valerolactone;Jie Chu等;Catal. Sci. Technol.;20220513;第12卷;4325-4338 *
MOF-derived bimetallic NiCo nanoalloys for the hydrogenation of biomass-derived levulinic acid to γ-valerolactone;Hong Xu等;AIChE J.;20221123;第69卷;17973 *
The Relationship between Structure and Catalytic Activity-Stability of Non-Precious Metal-Based Catalysts towards Levulinic Acid Hydrogenation to γ-Valerolactone:A Review;Ying Yang等;Energies;20221031;第15卷;8093 *

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