CN116196964A - Levulinate hydrogenation catalyst, preparation method and application - Google Patents
Levulinate hydrogenation catalyst, preparation method and application Download PDFInfo
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- CN116196964A CN116196964A CN202310223238.XA CN202310223238A CN116196964A CN 116196964 A CN116196964 A CN 116196964A CN 202310223238 A CN202310223238 A CN 202310223238A CN 116196964 A CN116196964 A CN 116196964A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229940058352 levulinate Drugs 0.000 title claims abstract description 49
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 title claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 238000001914 filtration Methods 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 claims description 23
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 claims description 10
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 6
- ISBWNEKJSSLXOD-UHFFFAOYSA-N Butyl levulinate Chemical compound CCCCOC(=O)CCC(C)=O ISBWNEKJSSLXOD-UHFFFAOYSA-N 0.000 claims description 5
- 229940005460 butyl levulinate Drugs 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 abstract description 16
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- -1 levulinate ester Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 61
- 238000001816 cooling Methods 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000004817 gas chromatography Methods 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 229910002441 CoNi Inorganic materials 0.000 description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 229910003321 CoFe Inorganic materials 0.000 description 6
- 229910002520 CoCu Inorganic materials 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000004730 levulinic acid derivatives Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
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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
- 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
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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
- 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
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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 dripping a precursor solution containing Co into a precursor solution containing another metal M under the condition of stirring at room temperature, standing, filtering and collecting precipitate, drying and then adding the precipitate into H 2 Pyrolysis is carried out in Ar mixed gas, cooled to room temperature and cooled in O 2 Passivating in 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 prepare levulinate ester in the reaction of preparing gamma-valerolactone by levulinate ester hydrogenationThe conversion rate of 100 percent is realized, the selectivity of gamma-valerolactone reaches more than 97 percent, and the gamma-valerolactone has higher stability and is not inactivated after being recycled for 6 times.
Description
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, applied catalysis A: general,2014, 470, 215-220) reported that Ru/ZSM-5 gave a 96% yield of gamma valerolactone in the hydrogenation of methyl levulinate to gamma valerolactone. Guan et al (Enhancedhydrogenationofethyl levulinatebyPd-ACdopedwithnb) 2 O 5 GreenChemistry,2014, 16, 3951-3957) incorporating an auxiliary Nb in the Pd/C catalyst 2 O 5 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 (Nb) 2 O 5 Plays a role of synergistic catalysis in the reaction process, on one hand, the catalyst can disperse and stabilize Pd nano particles, and on the other hand, nb 2 O 5 Is also an acid catalyst per se. Lin et al (StableandefficienccuCrcat catalyst for the solvent-freehydrogenationofbiomass derivedethyllevulinateto gamma-valeroactiondevice candidiate, fuel,2016,175,232-239) convert ethyl levulinate for hydrogenation using a CuCr catalyst that is reduced in situ during the reaction. The calcination temperature of the CuCr precursor greatly affects the reactivity of the CuCr catalyst. CuCr fired at 350 ℃ at 250 ℃ and 4MPaH 2 The best reaction performance is obtained, the conversion rate of ethyl levulinate is 85.6%, and the selectivity of gamma-valerolactone is as high as 98.6%. Increasing the roasting temperature to form CuCrO which is difficult to reduce 2 The conversion of ethyl levulinate is greatly reduced.
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 process for preparing the catalyst used for hydrogenating levulinate includes such steps as dripping the precursor solution containing Co to the precursor solution containing another metal M while stirring at room temp, laying aside, filtering, collecting deposit, drying and drying in H 2 Pyrolysis is carried out in Ar mixed gas, cooled to room temperature and cooled in O 2 The mixture of Ar and Ar is passivated, treated by sulfuric acid, filtered and dried to obtain the catalyst (the catalyst is named 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 K 3 [Co[(CN) 6 ]And Na (Na) 3 [Co[(CN) 6 ]When the Co precursor comprises two of the above substances, there is no special requirement on the proportion of each Co precursor, as long as the total concentration requirement of the Co precursor-containing solution in the solution can be satisfied.
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 at H 2 The pyrolysis is carried out in Ar mixed gas at 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 ℃; reaction H 2 The pressure 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 invention has the advantages thatThe hydrogenation reaction is carried out in a high-pressure reaction kettle.
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 used prior to the reactionIn a tube furnace H 2 Preactivation for 2h at 300℃in an Ar atmosphere.
Example 1
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of nickel nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 20 hours, the precipitate was collected by filtration, dried, and then purified by filtration under H 2 Pyrolyzing in Ar gas mixture at 800 ℃ for 6h, cooling to room temperature and cooling in O 2 Passivating in Ar mixed gas for 30min, treating the sample with sulfuric acid solution (1.5 mol/L) for 10h, filtering and drying to obtain the 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
Into a batch reactor, 0.1g of the CoNi@NC catalyst synthesized in example 1, 1g of ethyl levulinate, 10g of water, and 4MPaH were added 2 And sealed, the temperature was raised to 100 ℃, and the reaction was continued for 6 hours 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
Will 100mLNa 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of nitric acid with stirring at room temperatureNickel solution (0.03 mol/L), then standing for 20H, collecting precipitate by filtration, drying, and then adding H 2 Pyrolyzing in Ar mixture at 600 ℃ for 6h, cooling to room temperature and cooling in O 2 Passivating in Ar mixed gas for 30min, treating the sample with sulfuric acid solution (1.5 mol/L) for 10h, filtering and drying to obtain the CoNi@NC catalyst.
Application example 2
0.1g of the CoNi@NC catalyst synthesized in example 2, 1g of methyl levulinate, 10g of water and 4MPaH were added to a batch reactor 2 And sealed, the temperature was raised to 120 ℃, and the reaction was continued for 5 hours 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
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of nickel nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 20 hours, the precipitate was collected by filtration, dried, and then purified by filtration under H 2 Pyrolyzing in Ar gas mixture at 1000 ℃ for 6h, cooling to room temperature and cooling in O 2 Passivating in Ar mixed gas for 30min, treating the sample with sulfuric acid solution (1.5 mol/L) for 10h, filtering and drying to obtain the CoNi@NC catalyst.
Application example 3
Into a batch reactor, 0.05g of the CoNi@NC catalyst synthesized in example 3, 0.6g of ethyl levulinate, 10g of water, and 3MPaH were added 2 And sealed, the temperature was raised to 110 ℃, and the reaction was 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
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of nickel nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 20 hours, the precipitate was collected by filtration, dried, and then purified by filtration under H 2 Pyrolyzing in Ar mixture at 800 ℃ for 5h, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar gas mixture, and using sulfuric acid solution (0).8 mol/L) was treated for 5 hours, filtered and dried to give a CoNi@NC catalyst.
Application example 4
Into a batch reactor, 0.15g of the CoNi@NC catalyst synthesized in example 4, 1.2g of propyl levulinate, 10g of water, and 6MPaH were added 2 And sealed, the temperature was raised to 120 ℃, and the reaction was continued for 8 hours 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
Will 100mLNa 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of nickel nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 20 hours, the precipitate was collected by filtration, dried, and then purified by filtration under H 2 Pyrolyzing in Ar mixture at 1000 ℃ for 10h, cooling to room temperature and cooling in O 2 Passivating in Ar mixed gas for 30min, treating the sample with sulfuric acid solution (0.5 mol/L) for 20h, filtering and drying to obtain the CoNi@NC catalyst.
Application example 5
Into a batch reactor, 0.1g of the CoNi@NC catalyst synthesized in example 5, 1.1g of butyl levulinate, 10g of water and 5MPaH were added 2 And sealed, the temperature was raised to 120 ℃, and the reaction was continued for 6 hours 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
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of copper nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, and then purified by filtration under H 2 Pyrolyzing in Ar/600 ℃ for 10 hours, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar mixed gas, treating the sample with sulfuric acid solution (1 mol/L) for 10h, filtering and drying to obtain the CoCu@NC catalyst.
Application example 6
Into a batch reactor was added 0.1g of the synthesis of example 6CoCu@NC catalyst, 1g of methyl levulinate, 10g of water, and 4MPaH flushing 2 And sealed, the temperature was raised to 110 ℃, and the reaction was continued for 6 hours 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
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of copper nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, and then purified by filtration under H 2 Pyrolyzing in Ar mixture at 800 ℃ for 5h, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar mixed gas, treating the sample with sulfuric acid solution (1 mol/L) for 10h, filtering and drying to obtain the CoCu@NC catalyst.
Application example 7
Into a batch reactor, 0.08g of the CoCu@NC catalyst synthesized in example 7, 1.1g of ethyl levulinate, 10g of water, and 5MPaH were added 2 And sealed, the temperature was raised to 130 ℃, and the reaction was continued for 8 hours 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
Will 100mLNa 3 [Co(CN) 6 ]The solution (0.03 mol/L) was added dropwise to 100mL of copper nitrate solution (0.05 mol/L) with stirring at room temperature, and then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, and then purified by filtration under H 2 Pyrolyzing in Ar mixture at 1000 ℃ for 4h, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar mixed gas, treating the sample with sulfuric acid solution (1 mol/L) for 10h, filtering and drying to obtain the CoCu@NC catalyst.
Application example 8
Into a batch reactor, 0.15g of the CoCu@NC catalyst synthesized in example 8, 1.5g of butyl levulinate, 10g of water and 4MPaH were added 2 And sealed, the temperature was raised to 130 ℃, and the reaction was continued for 10 hours under magnetic stirring. After stopping the reaction, collecting the reaction liquid obtained by centrifugal separationAnalysis was performed by gas chromatography. Under the reaction conditions, the conversion of ethyl levulinate was 100%, and the gamma valerolactone selectivity was 98.2%.
Example 9
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of ferric nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 24 hours, the precipitate was collected by filtration, dried and then purified by filtration under H 2 Pyrolyzing in Ar/600 ℃ for 10 hours, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar mixed gas, treating the sample with sulfuric acid solution (1 mol/L) for 10h, filtering and drying to obtain the CoFe@NC catalyst.
Application example 9
Into a batch reactor, 0.15g of the CoFe@NC catalyst synthesized in example 9, 1g of ethyl levulinate, 10g of water, and 5MPaH were added 2 And sealed, the temperature was raised to 110 ℃, and the reaction was continued for 8 hours 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
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of ferric nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 24 hours, the precipitate was collected by filtration, dried and then purified by filtration under H 2 Pyrolyzing in Ar mixture at 800 ℃ for 5h, cooling to room temperature and cooling in O 2 Passivating in Ar mixed gas for 30min, treating the sample with sulfuric acid solution (1.5 mol/L) for 8h, filtering and drying to obtain the CoFe@NC catalyst.
Application example 10
0.1g of the CoFe@NC catalyst synthesized in example 10, 1g of methyl levulinate, 10g of water and 6MPaH were added to a batch reactor 2 And sealed, the temperature was raised to 130 ℃, and the reaction was continued for 5 hours 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
Will 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of ferric nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 24 hours, the precipitate was collected by filtration, dried and then purified by filtration under H 2 Pyrolyzing in Ar gas mixture at 1000 ℃ for 6h, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar mixed gas, treating the sample with sulfuric acid solution (2 mol/L) for 10h, filtering and drying to obtain the CoFe@NC catalyst.
Application example 11
Into a batch reactor, 0.08g of the CoFe@NC catalyst synthesized in example 11, 1.2g of ethyl levulinate, 10g of water, and 6MPaH were added 2 And sealed, the temperature was raised to 90 ℃, and the reaction was continued for 10 hours 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
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.02 mol/L) was added dropwise to 100mL of zinc nitrate solution (0.03 mol/L) with stirring at room temperature, and then allowed to stand for 24 hours, the precipitate was collected by filtration, dried, and then purified by filtration under H 2 Pyrolyzing in Ar/600 ℃ for 10 hours, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar mixed gas, treating the sample with sulfuric acid solution (1 mol/L) for 10h, filtering and drying to obtain the CoZn@NC catalyst.
Application example 12
0.1g of the CoZn@NC catalyst synthesized in example 12, 1g of methyl levulinate, 10g of water and 4MPaH were added to a batch reactor 2 And sealed, the temperature was raised to 120℃and the reaction was 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
Will be 100mLK 3 [Co(CN) 6 ]And Na (Na) 3 [Co(CN) 6 ]Solution ([ Co (CN)) 6 ] 3+ Total concentration 0.02 mol/L) was added dropwise to 100mL of zinc nitrate solution (0.03 mol/L) with stirring at room temperatureThen standing for 30H, filtering to collect precipitate, drying, and standing in H 2 Pyrolyzing in Ar mixture at 800 ℃ for 5h, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar mixed gas, treating the sample with sulfuric acid solution (1 mol/L) for 20h, filtering and drying to obtain the CoZn@NC catalyst.
Application example 13
Into a batch reactor, 0.1g of the CoZn@NC catalyst synthesized in example 13, 1g of ethyl levulinate, 10g of water and flushing with 6MPaH were added 2 And sealed, the temperature was raised to 90 ℃, and the reaction was continued for 10 hours 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
Will be 100mLK 3 [Co(CN) 6 ]The solution (0.05 mol/L) was added dropwise to 100mL of zinc nitrate solution (0.08 mol/L) with stirring at room temperature, and then allowed to stand for 30 hours, the precipitate was collected by filtration, dried and then purified by filtration under H 2 Pyrolyzing in Ar gas mixture at 1000 ℃ for 8h, cooling to room temperature and cooling in O 2 Passivating for 30min in Ar mixed gas, treating the sample with sulfuric acid solution (1 mol/L) for 20h, filtering and drying to obtain the CoZn@NC catalyst.
Application example 14
Into a batch reactor, 0.15g of the CoZn@NC catalyst synthesized in example 14, 1.6g of propyl levulinate, 10g of water, and 6MPaH were added 2 And sealed, the temperature was raised to 110 ℃, and the reaction was continued for 6 hours 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 (10)
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%.
2. A levulinate hydrogenation catalyst according to claim 1, characterised in that: the other metal M is one of Ni, fe, cu and Zn.
3. A levulinate hydrogenation catalyst according to claim 1, characterised in that: the specific surface area of the catalyst is 50-150 m 2 /g。
4. 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.
5. A process for preparing a levulinate hydrogenation catalyst according to claim 1, wherein: dropwise adding the precursor solution containing Co into the precursor solution containing the other metal M at room temperature under stirring, standing, filtering and collecting precipitateDrying and then in H 2 Pyrolysis is carried out in Ar mixed gas, cooled to room temperature and cooled in O 2 Passivating in Ar mixed gas, treating with sulfuric acid, filtering and drying to obtain the catalyst.
6. The method for preparing the levulinate hydrogenation catalyst according to claim 5, wherein: 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.
7. The method for preparing the levulinate hydrogenation catalyst according to claim 5, wherein: the standing time is 5-30 h; the at H 2 The pyrolysis temperature in the Ar mixed gas is 400-1000 ℃, and the pyrolysis time is 4-20 h.
8. Use of the levulinate hydrogenation catalyst according to claim 1 in the preparation of gamma valerolactone by levulinate hydrogenation.
9. The use of a levulinate hydrogenation catalyst according to claim 8, characterised in that: the levulinate is one or more of methyl levulinate, ethyl levulinate, propyl levulinate or butyl levulinate.
10. The use of a levulinate hydrogenation catalyst according to claim 8, characterised 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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