CN114618548A - Cobalt-based catalyst, preparation method thereof and application of cobalt-based catalyst in catalytic oxidative cracking of lignin - Google Patents
Cobalt-based catalyst, preparation method thereof and application of cobalt-based catalyst in catalytic oxidative cracking of lignin Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 32
- 239000010941 cobalt Substances 0.000 title claims abstract description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229920005610 lignin Polymers 0.000 title claims abstract description 31
- 238000005336 cracking Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 methyl benzoate aromatic compounds Chemical class 0.000 claims abstract description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940095102 methyl benzoate Drugs 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001491 aromatic compounds Chemical class 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229940067107 phenylethyl alcohol Drugs 0.000 claims description 5
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 4
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 238000003776 cleavage reaction Methods 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- GSBICRJXEDSPTE-UHFFFAOYSA-N 2-phenoxy-1-phenylethanol Chemical compound C=1C=CC=CC=1C(O)COC1=CC=CC=C1 GSBICRJXEDSPTE-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 101000713585 Homo sapiens Tubulin beta-4A chain Proteins 0.000 description 1
- 102100036788 Tubulin beta-4A chain Human genes 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
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Classifications
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a preparation method of a cobalt-based catalyst and a method for catalytic oxidation cracking of lignin by using the cobalt-based catalyst. The catalyst takes activated carbon as a substrate, and the catalyst containing cobalt and nitrogen active sites is obtained by the way of co-impregnation loading and calcination of cobalt salt and nitrogen-containing components. The catalyst can be efficiently used for the oxidative cracking of lignin, and compared with the existing catalyst, the catalyst is cheap and easy to obtain, has long service life, and has the advantages of high selectivity of phenol and methyl benzoate aromatic compounds in the obtained product, high efficiency and environmental protection.
Description
Technical Field
The application relates to preparation of a cobalt-based catalyst and a method for catalytic oxidation cracking of lignin by using the cobalt-based catalyst, and belongs to the technical field of chemistry and chemical engineering.
Background
Lignocellulose is an important renewable biomass energy source and widely exists in tree, grass and crop wastes. The main components of lignocellulose are cellulose, hemicellulose and lignin. Wherein the lignin content is about 15-30 wt%, which is the most complex component of lignocellulose and has more energy storage. Therefore, the aromatic compound prepared by catalytic conversion of lignin can realize high-value utilization of lignin. Aromatic compounds are important chemical raw materials, are widely applied to industries such as medicines, polyesters, plastics, cosmetics and the like, and are derived from the petrochemical industry in the traditional synthetic route. Considering that lignin has a unique aromatic structure, the effective conversion of lignin into aromatic compounds for the production of high value-added chemicals is of great significance.
Lignin is a complex hypercrosslinked three-dimensional macromolecular polymer, and is mainly formed by connecting phenyl propane basic structural units through C-C bonds and C-O bonds in complex connection modes of beta-O-4, beta-5, beta-beta, beta-1, alpha-O-4 and the like, and the connection modes lead to the difficulty in breaking the bonds. It is a necessary direction to develop a high-efficiency catalytic system for catalytically cracking lignin. The current research means for lignin depolymerization include solvolysis, pyrolysis, reduction, oxidation, etc., where catalytic oxidation is an important depolymerization strategy and the depolymerization products are a class of compounds with increased oxygen-containing functional groups.
Disclosure of Invention
In order to realize high-selectivity cracking of lignin under mild conditions by using a cheap and easily-obtained catalyst to obtain phenol and methyl benzoate aromatic compounds, the invention provides a cobalt-based catalyst, a preparation method thereof and application thereof in catalytic oxidative cracking of lignin. The catalyst utilizes carbon material as a matrix and simultaneously contains nitrogen atoms for doping modification. The interaction between nitrogen atoms and cobalt active sites is utilized to improve the stability of cobalt and reduce the loss of metal.
According to one aspect of the present invention, there is provided a cobalt-based catalyst characterized in that the catalyst comprises a nitrogen-containing component and a cobalt-containing component supported on activated carbon.
According to a further aspect of the invention, a process for the preparation of said cobalt-based catalyst is provided, characterized in that it comprises at least the following steps:
the catalyst is prepared by calcining a mixture containing cobalt salt, a nitrogen-containing component and activated carbon.
Preferably, the cobalt salt comprises at least one of cobalt chloride, cobalt acetate, cobalt nitrate, cobalt oxalate, cobalt acetylacetonate.
Preferably, the nitrogen-containing component comprises at least one of 1, 10-phenanthroline, benzimidazole, indole, lutidine, 4-bipyridine, and 2, 2-bipyridine.
Preferably, the calcination is carried out in a nitrogen atmosphere, the calcination temperature is 400-900 ℃, and the calcination time is not less than 1 hour. Further preferably, the calcining temperature is 600-900 ℃, and the calcining time is 2-4 hours.
Preferably, the molar ratio of cobalt salt to nitrogen-containing component in the mixture is 1: 1-1: 5. optionally, the mass ratio of cobalt salt to nitrogen-containing component in the mixture is 73.5:180.2 to 178.1: 118.1.
As a specific embodiment, the cobalt-based catalyst may be prepared by the following steps: adding 0.5-1 mmol of cobalt salt and 0.5-2.5 mmol of nitrogen-containing organic matters into an ethanol solvent, stirring at room temperature for 0.5-2 hours, adding activated carbon into the whole solution, refluxing for 4-8 hours, cooling the liquid to room temperature, carrying out vacuum evaporation to remove the solvent, and drying the obtained solid at 60 ℃ overnight. And grinding the obtained solid into powder, calcining the powder in a tube furnace in a nitrogen atmosphere at the temperature of 400-900 ℃, and cooling the powder to room temperature to obtain the catalyst.
According to yet another aspect of the present invention, there is provided a method for catalytic oxidative cracking of lignin, characterized in that said method comprises at least the following steps: in an oxygen atmosphere, carrying out contact reaction on a raw material containing a lignin substrate and a cobalt-based catalyst to obtain an aromatic compound product;
the cobalt-based catalyst is selected from at least one of the cobalt-based catalysts described above, and cobalt-based catalysts prepared according to any of the methods described above.
The lignin substrate comprises 2-phenoxy-1-phenylethyl alcohol and methoxy-substituted 2-phenoxy-1-phenylethyl alcohol, and the cracking product comprises at least one of phenol and methyl benzoate.
The reaction conditions are as follows: the reaction temperature is 60-140 ℃; the reaction time is 4-24 h; the reaction pressure is 0.5-3 MPa.
Preferably, the reaction conditions are: the reaction temperature is 100-140 ℃; the reaction time is 12-24 h.
The raw material also contains a solvent, and the solvent comprises at least one of methanol, ethanol, acetonitrile and cyclohexane.
Preferably, the reaction is carried out in an autoclave.
The benefits that can be produced by the present invention include, but are not limited to:
the invention provides a preparation method of a cobalt-based catalyst and a method for catalytic oxidation cracking of lignin by using the cobalt-based catalyst, wherein the catalyst uses non-noble metals, is cheap and easy to obtain, has high efficiency and high selectivity, can be repeatedly used and has good performance.
Detailed Description
The process provided by the present invention is described in detail below with reference to examples, but the present invention is not limited thereto in any way.
The conversion rate of 2-phenoxy-1-phenylacetol is equal to 1- (2-phenoxy-1-acetophenone residual mole)/(2-phenoxy-1-acetophenone addition mole) 100%;
phenol selectivity (phenol yield)/(2-phenoxy-1-phenylethyl alcohol conversion) 100%.
Methyl benzoate selectivity (methyl benzoate yield)/(2-phenoxy-1-phenylethanol conversion) 100%.
EXAMPLE 1 preparation of catalyst 1#
73.5mg of cobalt oxalate and 180.2mg of 1, 10-phenanthroline were added to 50mL of an ethanol solvent, stirred at room temperature for 0.5 hour, 746.3mg of activated carbon was added to the whole solution under reflux for 4 hours, the liquid was cooled to room temperature, the solvent was removed by evaporation under vacuum, and the resulting solid was dried at 60 ℃ overnight. And grinding the obtained solid into powder, calcining the powder in a tubular furnace for 4 hours at the temperature of 600 ℃ in a nitrogen atmosphere, and cooling the powder to room temperature to obtain the catalyst.
Example 2 preparation of catalyst # 2
178.1mg of cobalt acetylacetonate and 118.1mg of benzimidazole were added to 50mL of an ethanol solvent, and stirred at room temperature for 2 hours, 703.8mg of activated carbon was added to the whole solution and refluxed for 6 hours, the liquid was cooled to room temperature, the solvent was removed by evaporation under vacuum, and the resulting solid was dried at 60 ℃ overnight. And grinding the obtained solid into powder, calcining the powder for 2 hours at 800 ℃ in a tube furnace in a nitrogen atmosphere, and cooling the powder to room temperature to obtain the catalyst.
Example 3 preparation of catalyst # 3
146.9mg of cobalt oxalate and 180.2mg of 1, 10-phenanthroline are added to 50mL of ethanol solvent, the mixture is stirred at room temperature for 2 hours, 672.9mg of activated carbon is added to the whole solution and refluxed for 6 hours, the liquid is cooled to room temperature, the solvent is removed by vacuum evaporation, and the obtained solid is dried at 60 ℃ overnight. And grinding the obtained solid into powder, calcining the powder for 2 hours at 800 ℃ in a tube furnace in a nitrogen atmosphere, and cooling the powder to room temperature to obtain the catalyst.
Example 4 preparation of catalyst # 4
178.1mg of cobalt acetylacetonate and 156.2mg of 2, 2-bipyridine were added to 50mL of an ethanol solvent, and stirred at room temperature for 1 hour, 665.7mg of activated carbon was added to the whole solution and refluxed for 4 hours, the liquid was cooled to room temperature, the solvent was removed by evaporation under vacuum, and the resulting solid was dried at 60 ℃ overnight. And grinding the obtained solid into powder, calcining the powder for 2 hours at 800 ℃ in a tube furnace in a nitrogen atmosphere, and cooling the powder to room temperature to obtain the catalyst.
Example 5 preparation of catalyst # 5
To 50mL of ethanol solvent were added 177.0mg of cobalt acetate and 118.1mg of benzimidazole, the mixture was stirred at room temperature for 2 hours, 704.9mg of activated carbon was added to the whole solution under reflux for 6 hours, the liquid was cooled to room temperature, the solvent was removed by evaporation under vacuum, and the resulting solid was dried at 60 ℃ overnight. And grinding the obtained solid into powder, calcining the powder in a tubular furnace for 1 hour at 900 ℃ under the nitrogen atmosphere, and cooling the powder to room temperature to obtain the catalyst.
Example 6: catalyst reactivity test
856mg of 2-phenoxy-1-phenethyl alcohol lignin model molecules and 200mg of catalyst 1 and 20mL of methanol are added into a 60mL high-pressure reaction kettle to be used as solvents, the reaction conditions are that the temperature is 100 ℃, the oxygen pressure is 1.0MPa, the reaction is carried out for 12 hours, after the reaction is finished, the conversion rate of a substrate and the selectivity of each aromatic compound are analyzed by GC, the conversion rate is 85%, and the total selectivity of the cracking of phenol and methyl benzoate is 96%.
Example 7: catalyst reactivity test
856mg of 2-phenoxy-1-phenethyl alcohol lignin model molecules and 200mg of catalyst 1 and 20mL of methanol are added into a 60mL high-pressure reaction kettle to be used as solvents, the reaction conditions are 120 ℃, the oxygen pressure is 1.0MPa, the reaction is carried out for 18h, after the reaction is finished, the substrate conversion rate and the selectivity of each aromatic compound are analyzed by GC, the conversion rate is 88%, and the cracking selectivity of the aromatic compound is 95%.
Example 8: catalyst reactivity test
856mg of 2-phenoxy-1-phenethyl alcohol lignin model molecules, 200mg of catalyst 2 and 20mL of methanol are added into a 60mL high-pressure reaction kettle to be used as solvents, the reaction conditions are 140 ℃, the oxygen pressure is 1.0MPa, the reaction is carried out for 20 hours, after the reaction is finished, the substrate conversion rate and the selectivity of each aromatic compound are analyzed by GC, the conversion rate is 93%, and the cracking selectivity of the aromatic compound is 90%.
Example 9: catalyst reactivity test
856mg of 2-phenoxy-1-phenethyl alcohol lignin model molecules, 200mg of catalyst 3 and 20mL of methanol as solvents are added into a 60mL high-pressure reaction kettle, the reaction conditions are 140 ℃, the oxygen pressure is 1.0MPa, the reaction is carried out for 24h, after the reaction is finished, the substrate conversion rate and the selectivity of each aromatic compound are analyzed by GC, the conversion rate is 95%, and the cracking selectivity of the aromatic compound is 92%.
Example 10: catalyst reactivity test
856mg of 2-phenoxy-1-phenethyl alcohol lignin model molecules, 200mg of catalyst 4 and 20mL of methanol are added into a 60mL high-pressure reaction kettle to serve as a solvent, the reaction conditions are that the temperature is 120 ℃, the oxygen pressure is 1.0MPa, the reaction is carried out for 12 hours, after the reaction is finished, the substrate conversion rate and the selectivity of each aromatic compound are analyzed by GC, the conversion rate is 81%, and the cracking selectivity of the aromatic compounds is 94%.
The catalyst performance tests are summarized in table 1 below, which lists different catalysts, temperature-run reactions, substrate conversions, and product cleavage selectivities.
Table 1 catalyst performance test reaction conditions and reaction results
Catalyst and process for preparing same | Temperature (. degree.C.) | Conversion (%) | Total selectivity (%) for cleavage of phenol and methyl benzoate |
Catalyst 1# | 100 | 85 | 96 |
Catalyst 1# | 120 | 88 | 95 |
Catalyst 1# | 140 | 96 | 92 |
Catalyst No. 2 | 120 | 82 | 96 |
Catalyst No. 2 | 140 | 93 | 90 |
Catalyst 3# | 120 | 91 | 95 |
Catalyst 3# | 140 | 95 | 92 |
Catalyst 4# | 120 | 81 | 94 |
Catalyst 5# | 140 | 85 | 96 |
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A cobalt-based catalyst, characterized in that the catalyst comprises a nitrogen-containing component and a cobalt-containing component supported on activated carbon.
2. A method for preparing a cobalt-based catalyst according to claim 1, characterized in that the method comprises at least the steps of:
the catalyst is prepared by calcining a mixture containing cobalt salt, a nitrogen-containing component and activated carbon.
3. The method of preparing a cobalt-based catalyst according to claim 2, wherein the cobalt salt comprises at least one of cobalt chloride, cobalt acetate, cobalt nitrate, cobalt oxalate, cobalt acetylacetonate;
the nitrogen-containing component comprises at least one of 1, 10-phenanthroline, benzimidazole, indole, lutidine, 4-bipyridine and 2, 2-bipyridine.
4. The method for preparing a cobalt-based catalyst according to claim 2, wherein the calcination is performed in a nitrogen atmosphere, the calcination temperature is 400 to 900 ℃, and the calcination time is not less than 1 hour;
preferably, the calcining temperature is 600-900 ℃, and the calcining time is 2-4 hours.
5. The method of preparing a cobalt-based catalyst according to claim 2, wherein a molar ratio of the cobalt salt to the nitrogen-containing component in the mixture is 1: 1-1: 5.
6. a method for catalytic oxidative cracking of lignin, characterized in that the method comprises at least the following steps: in an oxygen atmosphere, carrying out contact reaction on a raw material containing a lignin substrate and a cobalt-based catalyst to obtain an aromatic compound product;
the cobalt-based catalyst is selected from at least one of the cobalt-based catalyst of claim 1, and a cobalt-based catalyst prepared by the method of any one of claims 2 to 5.
7. The method of claim 6, wherein the lignin substrate comprises 2-phenoxy-1-phenylethyl alcohol and methoxy-substituted 2-phenoxy-1-phenylethyl alcohol, and the cleavage product comprises at least one of phenol and methyl benzoate.
8. The method for catalytic oxidative cracking of lignin according to claim 6, wherein the reaction conditions are: the reaction temperature is 60-140 ℃; the reaction time is 4-24 h; the reaction pressure is 0.5-3 Mpa;
preferably, the reaction conditions are: the reaction temperature is 100-140 ℃; the reaction time is 12-24 h.
9. The method for catalytic oxidative cracking of lignin according to claim 6, wherein the feedstock further comprises a solvent, wherein the solvent comprises at least one of methanol, ethanol, acetonitrile, cyclohexane.
10. The method for catalytic oxidative cracking of lignin according to claim 6, wherein the reaction is carried out in a high pressure autoclave.
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Citations (5)
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CN107952462A (en) * | 2017-12-07 | 2018-04-24 | 江西师范大学 | A kind of method and application for being pyrolyzed eutectic solvent and preparing loaded nano Co catalysts |
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