CN112892539A - Method for coupling hydrogenolysis of lignin by heterogeneous catalyst and homogeneous catalyst - Google Patents
Method for coupling hydrogenolysis of lignin by heterogeneous catalyst and homogeneous catalyst Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 61
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 28
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002815 homogeneous catalyst Substances 0.000 title claims abstract description 16
- 230000008878 coupling Effects 0.000 title claims abstract description 10
- 238000010168 coupling process Methods 0.000 title claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- -1 benzene alcohol compounds Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000012691 depolymerization reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B01J35/19—
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
- C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention discloses a method for coupling and hydrogenolyzing lignin by using a heterogeneous catalyst and a homogeneous catalyst. The method comprises the following steps: the method comprises the steps of taking lignin extracted by an organic solvent as a raw material, dissolving the lignin in an alcohol solvent, carrying out hydrogenolysis reaction on the lignin under the action of a homogeneous alkali catalyst and a heterogeneous catalyst to convert the lignin into an aromatic hydrocarbon compound, wherein the reaction temperature is 180-260 ℃, the reaction time is 0.5-15h, the hydrogen pressure in a reaction system is 1.0-4.0MPa, the solid-liquid ratio of the lignin to ethanol is 1:60, the mass ratio of the homogeneous alkali catalyst to the lignin is 2:5, and the mass ratio of the heterogeneous catalyst to the lignin is 1: 5. The homogeneous alkali catalyst and the heterogeneous Co/C catalyst provided by the invention have the advantages of rich raw materials, low price, mild preparation conditions, simple preparation method, excellent catalytic activity and high hydrodeoxygenation efficiency, and lignin can be efficiently converted into aromatic hydrocarbon compounds under the action of the catalyst.
Description
The technical field is as follows:
the invention belongs to the technical field of chemistry and chemical engineering, and particularly relates to a method for hydrogenolysis of lignin by coupling a heterogeneous catalyst and a homogeneous catalyst.
Background art:
lignocellulose biomass is a green clean energy source in nature, and mainly comes from plants and agricultural and forestry wastes, wherein the plants comprise various woods and herbaceous plants, and agricultural byproducts such as corn stalks, corn cobs, sorghum stalks, bagasse and the like. Most lignocellulosic biomass is composed primarily of three major components, cellulose, hemicellulose, and lignin. Lignin (lignin), is the only renewable resource in nature containing a large number of benzene rings. Therefore, the efficient conversion of lignin to aromatic hydrocarbon platform compounds is of great significance to improve the economic efficiency of biomass utilization.
At present, lignin depolymerization modes mainly comprise acid-base depolymerization, thermal cracking, oxidative depolymerization, hydrogenation depolymerization, a photocatalytic method and the like. Most of the acid-base depolymerization adopts homogeneous catalysts, the depolymerization reaction is easy to occur in the depolymerization process, carbon deposition is caused, products obtained by thermal cracking and oxidative cracking are complex and various, and contain higher oxygen and have lower heat value. The current depolymerization efficiency of the photocatalytic depolymerization is low. The lignin is depolymerized by hydrogenation, so that the thermal value is high, the product distribution is relatively concentrated, and the carbon deposition rate is low.
Metals such as Pt, Pd, Ru and the like have high catalytic hydrogenation activity, and can selectively break lignin to obtain aromatic hydrocarbon compounds under the mild hydrogenolysis condition. For example, lignin is selectively hydrogenolyzed to monophenolic compounds by the action of ZMS-5 supported Pt, Ru and Pd. However, such catalysts are very unstable and are easily deactivated; in addition, noble metal catalysts are expensive and not suitable for large-scale industrial production. In addition to precious metals, transition and other subgroup metals are also active in lignin depolymerization reactions. Oxides, nitrides and carbides of molybdenum have been used for hydrogenolysis of lignin and phenolic model compounds.
Therefore, the development of a catalyst with rich raw materials, mild preparation conditions and excellent catalytic activity certainly has a good application prospect.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide a method for hydrogenolysis of lignin by coupling a heterogeneous catalyst and a homogeneous catalyst, the method utilizes homogeneous alkali and heterogeneous Co/C as catalysts, lignin can be efficiently converted into hydrocarbon chemicals, and the catalysts have the advantages of rich raw materials, low price, mild preparation conditions, simple preparation method, excellent catalytic activity, high hydrogenolysis efficiency, low cost, high efficiency and large-scale popularization and application.
The invention aims to provide a method for hydrogenolysis of lignin by coupling a heterogeneous catalyst and a homogeneous catalyst, which comprises the following steps: the method comprises the steps of taking lignin extracted by an organic solvent as a raw material, dissolving the lignin in an alcohol solvent, carrying out hydrogenolysis reaction on the lignin under the action of a homogeneous base catalyst and a heterogeneous catalyst to convert the lignin into an aromatic hydrocarbon compound, wherein the reaction temperature is 180-260 ℃, the reaction time is 0.5-15h, the hydrogen pressure in a reaction system is 1.0-4.0MPa, the solid-liquid ratio of the lignin to the alcohol solvent is 1:60, the mass ratio of the homogeneous base catalyst to the lignin is 2:5, and the mass ratio of the heterogeneous catalyst to the lignin is 1: 5. The alcohol solvent is ethanol.
Preferably, the heterogeneous catalyst is a carbon-supported metal type heterogeneous catalyst, and is obtained by the following preparation method: dissolving metal salt in deionized water, adding active carbon under stirring condition, stirring at normal temperature for 10-16 hr, heating to 40-80 deg.C, stirring for 12 hr to obtain mixed solution, freezing for 4-8 hr, drying to obtain black powder, and drying at 350 deg.C, 550 deg.C, H2Roasting for 2-3 hours under the protection of atmosphere to obtain the carbon-supported metal type heterogeneous catalyst.
Preferably, the metal salt is a cobalt salt dissolved in water. More preferably, the cobalt salt is cobalt nitrate.
Preferably, the mass ratio of the metal to the activated carbon is 0.05-0.30: 1.
Preferably, the homogeneous base catalyst is selected from the group consisting of NaOH, KOH and Na2CO3One kind of (1).
Preferably, the hydrogenolysis reaction has the reaction temperature of 240-260 ℃, the reaction time of 2-8h and the hydrogen pressure in the reaction system of 2.0 MPa.
Preferably, the aromatic hydrocarbon compounds include benzene compounds, guaiacol compounds, benzene alcohol compounds and phenol compounds.
Preferably, the organic solvent in the lignin obtained by organic solvent extraction is ethanol, ethylene glycol or 1, 4-butanediol. The lignin in the biomass is extracted using an organic solvent under heated conditions.
The invention has the beneficial effects that: the homogeneous alkali catalyst and the heterogeneous Co/C catalyst provided by the invention have the advantages of rich raw materials, low price, mild preparation conditions, simple preparation method, excellent catalytic activity and high hydrodeoxygenation efficiency, and lignin can be efficiently converted into aromatic hydrocarbon compounds under the action of the catalyst.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Unless otherwise specified, the devices and materials mentioned in the present invention are commercially available.
Example 1:
the preparation of the Co/C catalyst comprises the following steps: fully dissolving 2.62g of cobalt nitrate into 5mL of deionized water, slowly adding 3.00g of activated carbon under the stirring condition, continuously stirring for 12 hours, heating to 60 ℃ after stirring is finished, stirring for 12 hours to obtain a mixed solution, wherein the stirring speed is 400rpm, then putting the mixed solution into a refrigerator for freezing for 12 hours, putting the mixed solution into a freeze drying box for drying for 12 hours after freezing to obtain a black powder sample, and putting the black powder sample into a reduction furnace and placing the black powder sample into H2Roasting and reducing under the protection of atmosphere, wherein the reduction temperature is 500 ℃, the heating rate is 2 ℃/min, and roasting is carried out at the constant temperature of 500 ℃ for 3 hours to obtain the 15 wt% Co/C catalyst.
Weighing 0.1g of Co/C catalyst prepared above, 0.2g of NaOH, 0.5g of glycol lignin and 30.0mL of ethanol, putting the materials into a 100mL high-pressure reaction kettle, sealing the reaction kettle, and adding H into the reaction kettle2Replacing gas in the kettle for 5 times, charging H2Pressurizing to 2.0 MPa. Starting a stirring paddle (400rpm), heating the reaction kettle to 240 ℃ at a heating rate of 3 ℃/min, starting timing reaction, wherein the reaction time is 4h, and after the reaction is finished, carrying out GC-MS (gas chromatography-Mass Spectrometry) qualitative analysis and GC quantitative analysis tests on the obtained product to obtain the aromatic hydrocarbon product with the yield of 43.3%, wherein the aromatic hydrocarbon product comprises a benzene compound, a guaiacol compound, a benzene alcohol compound and a phenol compound.
Examples 2 to 17:
reference example 1, with the difference that the metal loading, reaction temperature, reaction pressure, reaction time and mass ratio of homogeneous to heterogeneous catalyst were different, wherein the mass of Co/C catalyst in example 15 was 0.3g, see table 1 in particular:
TABLE 1
As can be seen from Table 1, in example 17, when only the homogeneous base catalyst was added, the yield of the aromatic hydrocarbon product was 4.7%, in example 15, when only the Co/C catalyst was added, the yield of the aromatic hydrocarbon product was 1.3%, and in the case where the same amount of the catalyst was used, the yield of the aromatic hydrocarbon product was 43.3% when the Co/C catalyst and the homogeneous base catalyst were added and the catalysts were coupled to each other in example 1.
Examples 18 to 20:
reactions for the hydrogenolysis of various lignins to aromatic hydrocarbon products
Referring to example 1, except that the lignin was an ethanolic lignin, a 1, 4-butanediol lignin, or an industrial lignin, the reaction results are shown in table 2.
TABLE 2
| Examples | Reactants | Yield of aromatic hydrocarbons (%) |
| 18 | Ethanol lignin | 32.3 |
| 19 | 1, 4-butanediol Lignin | 35.4 |
| 20 | Industrial lignin | 24.0 |
While the method for hydrogenolysis of lignin by coupling a heterogeneous catalyst with a homogeneous catalyst provided by the present invention has been described in detail, the above examples are only for the purpose of helping to understand the technical solution of the present invention and the core idea thereof, it should be noted that, for those skilled in the art, it is possible to make several modifications and modifications to the present invention without departing from the principle of the present invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
Claims (8)
1. A method for hydrogenolysis of lignin by coupling a heterogeneous catalyst and a homogeneous catalyst is characterized by comprising the following steps: the method comprises the steps of taking lignin extracted by an organic solvent as a raw material, dissolving the lignin in an alcohol solvent, carrying out hydrogenolysis reaction on the lignin under the action of a homogeneous base catalyst and a heterogeneous catalyst to convert the lignin into an aromatic hydrocarbon compound, wherein the reaction temperature is 180-260 ℃, the reaction time is 0.5-15h, the hydrogen pressure in a reaction system is 1.0-4.0MPa, the solid-liquid ratio of the lignin to the alcohol solvent is 1:60, the mass ratio of the homogeneous base catalyst to the lignin is 2:5, and the mass ratio of the heterogeneous catalyst to the lignin is 1: 5.
2. The method for hydrogenolysis of lignin by coupling a heterogeneous catalyst and a homogeneous catalyst according to claim 1, wherein the heterogeneous catalyst is a carbon-supported metal type heterogeneous catalyst, and is prepared by the following preparation method: dissolving metal salt in deionized water, adding active carbon under stirring, stirring at room temperature for 10-16 hr, heating to 40-80 deg.CStirring for 12 hr to obtain mixed solution, freezing for 10-16 hr, drying to obtain black powder, and drying at 350-550 deg.C under H2Roasting for 2-3 hours under the protection of atmosphere to obtain the carbon-supported metal type heterogeneous catalyst.
3. The method for hydrogenolysis of lignin coupled with a heterogeneous catalyst and a homogeneous catalyst according to claim 2, wherein the metal salt is cobalt dissolved in water.
4. The method for hydrogenolysis of lignin by coupling a heterogeneous catalyst and a homogeneous catalyst according to claim 2, wherein the mass ratio of the metal to the activated carbon is 0.05-0.30: 1.
5. The method for hydrogenolysis of lignin coupled with a heterogeneous catalyst and a homogeneous catalyst according to claim 1, wherein the homogeneous base catalyst is selected from the group consisting of NaOH, KOH and Na2CO3One kind of (1).
6. The method for hydrogenolysis of lignin coupled with heterogeneous catalyst and homogeneous catalyst as claimed in claim 1, wherein the hydrogenolysis reaction is carried out at a temperature of 240 ℃ and 260 ℃ for 2-8h and under a hydrogen pressure of 2.0 MPa.
7. The method for hydrogenolysis of lignin coupled with a heterogeneous catalyst and a homogeneous catalyst according to claim 1, wherein: the aromatic hydrocarbon compounds comprise benzene compounds, guaiacol compounds, benzene alcohol compounds and phenol compounds.
8. The method for hydrogenolysis of lignin coupled with a heterogeneous catalyst and a homogeneous catalyst according to claim 1, wherein: the organic solvent in the lignin obtained by the organic solvent extraction is ethylene glycol or 1, 4-butanediol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113527065A (en) * | 2021-07-14 | 2021-10-22 | 中国科学院广州能源研究所 | Method for preparing aviation oil precursor by catalyzing and depolymerizing alkali lignin in ethanol-water solvent by using Pd/C catalyst and alkali catalyst |
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