CN113117688A - MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation - Google Patents
MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/004—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from plant material or from animal material
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to a preparation method of a molybdenum-nickel catalyst taking MOF as a precursor and application of the molybdenum-nickel catalyst in lignin degradation, belonging to the field of utilization of biomass energy. Dissolving molybdenum trioxide and metal salt solution in deionized water, dissolving organic ligand and alkali in deionized water, and mixing the metal salt and molybdenum trioxide dissolved in solventThen transferring the mixture to a microwave reactor for reaction, filtering the mixture, washing the mixture for a plurality of times, and drying the mixture overnight to obtain a precursor MoO3-Ni-MOF, precursor MoO obtained3And putting the-Ni-MOF into a tube furnace, and roasting to obtain the MOF precursor molybdenum-nickel catalyst. The MOF catalyst synthesized by the method overcomes the defects of long time, high temperature and the need of using a large amount of organic solvent in the traditional MOF synthesis method. The synthesized catalyst is used for lignin degradation, and solves the problems of high price, difficult recovery, harsh reaction conditions and the like of the lignin degradation catalyst. The catalyst has the advantages of low price, simple recovery, simple degradation process and mild reaction conditions, and is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of a molybdenum-nickel catalyst taking MOF as a precursor and application of the molybdenum-nickel catalyst in lignin degradation, belonging to the field of utilization of biomass materials.
Background
With the rapid development of industrialization and the continuous development of natural resources by human beings, the energy problem becomes one of the most concerned problems in the world at present, and in order to solve the problem of gradual energy exhaustion in the world at present, many researchers focus on the development and utilization of biomass resources, wherein lignin degradation is considered to have great potential in raw material supply related to the production of biofuels, and is considered as the next research hotspot. The global annual lignin yield reaches 1700 million tons. Lignin is the second most abundant renewable biomass resource in nature and is the only renewable aromatic biomass raw material in the world. At present, more than 95 percent of lignin waste is directly discharged along with waste water, buried or concentrated and burned, and the like, so that the environment is polluted, and simultaneously, huge waste of resources is caused. Therefore, if the lignin can be efficiently utilized by lignin degradation technology, the replacement of fossil resources by biological resources in the society can be accelerated.
At present, the lignin degradation method is to weaken and break chemical bonds in lignin, or generate some groups or active sites which are easy to react, so as to increase the reaction activity of lignin, thereby achieving the purpose of degradation and further generating low molecular weight substances. Currently, various lignin depolymerization processes have been developed, such as pyrolysis, hydrocracking, hydrogenolysis, hydrolysis and oxidation. Among them, catalytic hydrogenolysis of lignin is one of the most promising and efficient methods for converting lignin to aromatic compounds. The hydrogenolysis method has the characteristics of stable degradation product and high selectivity, and is widely applied. Although hydrogenolysis has many advantages in many lignin depolymerization processes, most of the existing processes provide a hydrogen source for the lignin hydrogenolysis by introducing high pressure hydrogen before the reaction, which is a safety hazard.
In addition to the hydrogen source, the use of catalysts is also considered to be a key technology in the hydrogenolysis of lignin. The catalyst can directionally break chemical bonds in the lignin structure to generate a target product, promote the conversion of the lignin and prevent the polycondensation reaction of lignin macromolecules and the generation of coke. The high-performance catalyst has the characteristics of high catalytic efficiency, good selectivity, good repeatability, easy recovery and the like, and is wide in source, economical and feasible. Various catalysts are currently used to degrade lignin, such as mesoporous molecular sieves, activated carbons, metals, zeolites, and the like. Among them, metal catalysts are favored for their good catalytic activity, selectivity and stability. The transition metal carbon-based material with high dispersibility and high loading capacity prepared by using the MOF material as a precursor is expected to become a high-performance lignin degradation catalyst, and the hydrogenation performance and the selectivity of degradation products of the catalyst can be improved by utilizing the synergistic effect of double metals, so that the key elbow of obtaining the lignin degradation catalyst by carbonizing the double-metal MOF material formed by compounding the proper metal and the proper ligand, wherein the double-metal carbon-based material does not cover the original active site and can improve the performance is obtained.
The traditional hydrothermal synthesis method for synthesizing the MOF material has the defects of low efficiency, long time consumption, high energy consumption and the like, and the patent CN 110828193A provides a preparation method of the Ni-MOF material, wherein the Ni-MOF material is obtained by reacting sodium acetate and terephthalic acid in dimethylformamide/absolute ethyl alcohol/water at 160 ℃ for 24 hours. Patent CN 111375385A provides a preparation method of a bimetallic organic framework adsorbent, and a ligand and a metal salt react in a mixed solution of N, N-dimethylformamide/absolute ethyl alcohol/deionized water at 100 ℃ for 24h to obtain a Co-Ni-MOF material. The traditional MOF material synthesis method has long reaction time and low synthesis efficiency, and can be synthesized only in an alcohol solvent, so that the preparation cost is further increased, and the method is not beneficial to environmental protection.
Patent CN 11059086A provides a method for the reductive hydrogenolysis of lignin, nano ZrO2Pt (Pt/ZrO) loading2) Is used as a main catalyst and Lewis acid is used as a cocatalyst, and the H is 1-5 MPa in an alcohol/water medium2And reducing and degrading lignin under pressure. However, this method requires the use of a noble metal Pt and is carried out in a high-pressure hydrogen atmosphere, and the catalyst is expensive and not safe enough. Patent CN 110128247 a provides a method for depolymerizing lignin by reacting in an alcohol solution under the synergistic effect of iron powder and palladium carbon. However, this method requires the use of noble metal palladium on carbon, which is expensive and difficult to recover. The patent number CN108558608A provides a method for catalyzing lignin by a zirconium phosphate loaded nickel-based material, wherein a catalyst is added into an alcohol solution at the pressure of 1-4 MPa H2The lignin is catalytically hydrogenolyzed under pressure, but the method needs to be carried out in a high-pressure hydrogen atmosphere and is not safe enough. The patent CN 109174132A provides a catalyst for preparing aromatic hydrocarbon by catalyzing reaction of lignin model compound and a preparation method thereof, the method synthesizes a sulfide catalyst which takes CoAl hydrotalcite-like oxide as a carrier and adopts hydration method to load molybdenum disulfide as an active component, and MoS2/Co9S8-Al2O3Expressed in that H is at a reaction temperature of 250 to 270 DEG C2And degrading the lignin model compound under the conditions of initial pressure of 2-3 Mpa and reaction time of 5-10 h. However, this process is relatively high in reaction temperature and requires the use of H at high pressure2The reaction is carried out in the atmosphere, which is not safe enough.
The existing MOF synthesis process has long reaction time and low efficiency, and needs a large amount of organic solvents; the lignin degradation process has long integral reaction time and harsh conditions, and needs to be carried out in a high-pressure gas atmosphere or use an expensive noble metal catalyst, and the further application of lignin degradation is limited, so that a cheap and easily-obtained high-performance catalyst needs to be developed, the high-efficiency depolymerization of lignin is realized under mild conditions, and the problems and the defects of the current degradation process are solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of an MOF precursor molybdenum-nickel catalyst and application thereof in lignin degradation, which solve the problems of high price, difficult recovery, harsh degradation reaction conditions and the like of the current lignin degradation catalyst.
In order to achieve the technical purpose, the invention adopts the technical scheme that:
preparation of a MOF precursor molybdenum nickel catalyst, comprising the steps of:
(1) dissolving molybdenum trioxide and metal salt in deionized water for later use after the molybdenum trioxide and the metal salt are completely dissolved, dissolving an organic ligand and alkali in the deionized water, mixing the solution with the metal salt and the molybdenum trioxide after the organic ligand and the alkali are completely dissolved, transferring the mixture into a reaction kettle, and placing the reaction kettle into a microwave reactor for microwave hydrothermal reaction;
(2) after reaction, filtering, washing with deionized water for several times, and drying in a vacuum drying oven overnight to obtain a precursor MoO3-Ni-MOF；
(3) The obtained precursor MoO3And (3) putting the-Ni-MOF into a tube furnace, and roasting to obtain the metal catalyst named as Mo-Ni @ C-X, wherein X represents the carbonization temperature.
In the preparation step of the catalyst, the mass fraction of each component is as follows according to the sum of the mass percentages of 100 percent: metal salt: 3.0-12.0%, molybdenum trioxide: 0.5-2.0%, organic ligand: 1.0% -5.0%, solvent: 85.0 to 95.0 percent.
Preferably, the metal salt is one of nickel nitrate, ferric chloride, cobalt nitrate and zinc nitrate; the organic ligand is one of dimethyl imidazole, terephthalic acid, 1,3, 5-benzenetricarboxylic acid, 2, 5-dihydroxyterephthalic acid or 1, 4-cyclohexanedicarboxylic acid.
Preferably, the microwave hydrothermal reaction in the step (1) is carried out for 0.5-6 h at 60-120 ℃.
Preferably, the base in step (1) is one of NaOH, KOH and LiOH.
Preferably, the drying temperature in the step (2) is 50-110 ℃, and the drying time is 12-24 h.
Preferably, the roasting temperature in the step (3) is 300-700 ℃, and the roasting time is 3-8 h.
Preferably, the baking atmosphere in the step (3) is a hydrogen atmosphere or a mixed gas atmosphere of hydrogen and an inert gas.
An application of a MOF precursor molybdenum-nickel catalyst in lignin degradation comprises the following steps: according to the mass ratio, after a lignin raw material, an MOF precursor molybdenum-nickel catalyst and an organic solvent are subjected to ultrasonic homogenization, performing hydrothermal reaction at the temperature of 130-300 ℃ for 1-6 h, cooling the reaction liquid to 40-65 ℃, and filtering to obtain a liquid product and a recovered catalyst.
In the step of degrading the lignin, the added mass fractions of the components are as follows according to the sum of the mass percentages of 100 percent: MOF precursor molybdenum nickel catalyst: 1.0% -10.0%, lignin: 5.0% -25.0%, organic solvent: 70.0 to 95.0 percent.
Preferably, the lignin comprises organic solvent lignin, enzymatic hydrolysis lignin, ground lignin, sulfate lignin, sulfonate lignin, alkali lignin or natural lignin which is prepared from one or more of bamboo, bagasse, straw, wheat straw, willow, mango stem, poplar, reed, eucalyptus, oak, birch, masson pine, eucommia, palm fiber and corncob by organic solvent extraction, enzymatic hydrolysis, a membrane method, a sulfite method, a resin method or an alkaline method, and the lignin model compound is a dimer lignin model compound.
Preferably, the organic solvent is one of methanol, ethanol, isopropanol and n-propanol.
Compared with the prior art, the invention has the following advantages:
(1) the metal carbon-based catalyst prepared by the MOF precursor has the advantages of simple synthesis process, high performance and low price. Compared with the traditional metal carbon-based catalyst taking activated carbon as a carrier, the catalyst has the advantages of high dispersibility, high load capacity and the like, the types of lignin degradation products are few, and the main products, namely 4-ethylphenol and 2-methoxy-4-ethylphenol, have high selectivity and obvious advantages; the degradation rate of the lignin model compound is as high as 99 percent, and the like.
(2) The conversion rate of the lignin obtained by the method is higher than 83.6%, the yield of monophenol biomass chemicals is more than 13.2%, and compared with the conditions that the conversion rate of the lignin is lower than 70% and the yield of monophenol products is lower than 10% in the conventional hydrogenolysis process, the conversion rate of the lignin and the yield of the monophenol chemicals are obviously improved.
(3) The invention has simple process conditions and can realize continuous reaction;
(4) compared with the condition that high-pressure hydrogen is generally needed in the existing lignin hydrogenolysis process, the process provided by the invention does not need an additional hydrogen source, has mild reaction conditions, can be carried out in a hydrothermal reaction kettle, does not need a high-pressure reaction kettle, and has low equipment requirements.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following embodiments are described in detail. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
Example 1: preparation of Ni @ C-1-500 catalyst
47.8g of nickel nitrate hexahydrate is weighed into 465.0g of deionized water and stirred to be fully dissolved; 11.7g of 1, 4-cyclohexanedicarboxylic acid were weighed into 465.0g of deionized water with 10.5g of NaOH and dissolved by stirring. Transferring the solution dissolved with the nickel nitrate hexahydrate and the solution dissolved with the organic ligand into a reaction kettle, and then placing the reaction kettle into a microwave reactor to perform microwave hydrothermal reaction for 4 hours at 110 ℃ to obtain a precursor Ni-MOF-1. The prepared Ni-MOF-1 is placed in a tube furnace, and 5 vol% H is introduced2Heating and roasting at 500 ℃ for 5h under the condition of/Ar, wherein the gas flow rate is 120ml/min, and obtaining the Ni @ C-1-500 catalyst.
Example 2: preparation of Ni @ C-1-600 catalyst
47.8g of nickel nitrate hexahydrate was weighed into 465.0g of deionized water and stirred to be sufficiently dissolvedSolving; 11.7g of 1, 4-cyclohexanedicarboxylic acid were weighed into 465.0g of deionized water with 10.5g of NaOH and dissolved by stirring. Transferring the solution dissolved with the nickel nitrate hexahydrate and the solution dissolved with the organic ligand into a reaction kettle, and then placing the reaction kettle into a microwave reactor to perform microwave hydrothermal reaction for 4 hours at 110 ℃ to obtain a precursor Ni-MOF-1. The prepared Ni-MOF-1 is placed in a tube furnace, and 5 vol% H is introduced2Heating and roasting at 600 ℃ for 5h under the Ar condition, wherein the gas flow rate is 120ml/min, and obtaining the Ni @ C-1-600 catalyst;
example 3: preparation of Ni @ C-1-700 catalyst
47.8g of nickel nitrate hexahydrate is weighed into 465.0g of deionized water and stirred to be fully dissolved; 11.7g of 1, 4-cyclohexanedicarboxylic acid were weighed into 465.0g of deionized water with 10.5g of NaOH and dissolved by stirring. Transferring the solution dissolved with the nickel nitrate hexahydrate and the solution dissolved with the organic ligand into a reaction kettle, and then placing the reaction kettle into a microwave reactor to perform microwave hydrothermal reaction for 4 hours at 110 ℃ to obtain a precursor Ni-MOF-1. The prepared Ni-MOF-1 is placed in a tube furnace, and 5 vol% H is introduced2Heating and roasting at 700 ℃ for 5h under the/Ar condition, wherein the gas flow rate is 120ml/min, and obtaining the Ni @ C-1-700 catalyst;
example 4: preparation of Ni @ C-2-600 catalyst
Weighing 72.8g of nickel nitrate hexahydrate in 440.1g of deionized water, and stirring to fully dissolve the nickel nitrate hexahydrate; 35.8g of 1,3, 5-benzenetricarboxylic acid and 11.2g of NaOH were weighed into 440.1g of deionized water, and stirred to be sufficiently dissolved. Transferring the solution dissolved with the nickel nitrate hexahydrate and the solution dissolved with the organic ligand into a reaction kettle, and then placing the reaction kettle into a microwave reactor to perform microwave hydrothermal reaction for 4 hours at 110 ℃ to obtain a precursor Ni-MOF-2. The prepared Ni-MOF-2 is placed in a tube furnace, and 5 vol% H is introduced2Heating and roasting at 600 ℃ for 5h under the Ar condition, wherein the gas flow rate is 120ml/min, and obtaining the Ni @ C-2-600 catalyst;
example 5: preparation of Ni @ C-3-600 catalyst
Weighing 85.1g of nickel nitrate hexahydrate in 443.1g of deionized water, and stirring to fully dissolve the nickel nitrate hexahydrate; 20.8g of 2, 5-dihydroxyterephthalic acid are weighed in with 7.9g of NaOH443.1g of deionized water, and stirred to be sufficiently dissolved. Transferring the solution dissolved with the nickel nitrate hexahydrate and the solution dissolved with the organic ligand into a reaction kettle, and then placing the reaction kettle into a microwave reactor to perform microwave hydrothermal reaction for 4 hours at 110 ℃ to obtain a precursor Ni-MOF-3. The prepared Ni-MOF-3 is placed in a tube furnace, and 5 vol% H is introduced2Heating and roasting at 600 ℃ for 5h under the Ar condition, wherein the gas flow rate is 120ml/min, and obtaining the Ni @ C-3-600 catalyst;
example 6: preparation of Mo-Ni @ C-500 catalyst
42.9g of nickel nitrate hexahydrate and 19.2g of molybdenum trioxide are weighed into 457.7g of deionized water and stirred to be fully dissolved; 12.5g of 1, 4-cyclohexanedicarboxylic acid were weighed into 457.7g of deionized water with 10.0g of NaOH and dissolved by stirring. Transferring the solution dissolved with nickel nitrate hexahydrate and molybdenum trioxide and the solution dissolved with organic ligand into a reaction kettle, placing the reaction kettle into a microwave reactor to carry out microwave hydrothermal reaction for 4 hours at 110 ℃ to obtain a precursor MoO3-Ni-MOF. The obtained MoO3-Ni-MOF placed in a tube furnace with 5 vol% H2Heating and roasting at 500 ℃ for 5h under the condition of/Ar, wherein the gas flow rate is 120ml/min, and obtaining the Mo-Ni @ C-500 catalyst;
example 7: preparation of Mo-Ni @ C-600 catalyst
42.9g of nickel nitrate hexahydrate and 19.2g of molybdenum trioxide are weighed into 457.7g of deionized water and stirred to be fully dissolved; 12.5g of 1, 4-cyclohexanedicarboxylic acid were weighed into 457.7g of deionized water with 10.0g of NaOH and dissolved by stirring. Transferring the solution dissolved with nickel nitrate hexahydrate and molybdenum trioxide and the solution dissolved with organic ligand into a reaction kettle, placing the reaction kettle into a microwave reactor to carry out microwave hydrothermal reaction for 4 hours at 110 ℃ to obtain a precursor MoO3-Ni-MOF. The obtained MoO3-Ni-MOF placed in a tube furnace with 5 vol% H2Heating and roasting at 600 ℃ for 5h under the/Ar condition, wherein the gas flow rate is 120ml/min, and obtaining the Mo-Ni @ C-500 catalyst;
example 8: preparation of Mo-Ni @ C-700 catalyst
42.9g of nickel nitrate hexahydrate and 19.2g of molybdenum trioxide were weighed into 457.7g of deionized waterStirring in water to dissolve; 12.5g of 1, 4-cyclohexanedicarboxylic acid were weighed into 457.7g of deionized water with 10.0g of NaOH and dissolved by stirring. Transferring the solution dissolved with nickel nitrate hexahydrate and molybdenum trioxide and the solution dissolved with organic ligand into a reaction kettle, placing the reaction kettle into a microwave reactor to perform microwave hydrothermal reaction for 4 hours at 110 ℃ to obtain a precursor MoO3-Ni-MOF. The obtained MoO3-Ni-MOF placed in a tube furnace with 5 vol% H2Heating and roasting at 700 ℃ for 5h under the/Ar condition, wherein the gas flow rate is 120ml/min, and obtaining the Mo-Ni @ C-500 catalyst;
example 9:
the reaction was evaluated by using benzyl phenyl ether as a substrate, which is a model compound containing α -O-4 in the structure of lignin. Adding 30.3g of the catalyst obtained in the embodiment 1-8, 75.9g of benzyl phenyl ether and 893.8g of isopropanol into a hydrothermal reaction kettle, stirring to uniformly mix the components, heating to 160 ℃ for reaction for 5 hours, finally collecting a product, and feeding the obtained product into HPLC for analysis. Yield calculation formula: (molar amount of product formed by the reaction/initial molar amount of benzyl phenyl ether). times.100%, degradation rate was calculated by the formula: (molar amount of benzyl phenyl ether consumed by the reaction/initial molar amount of benzyl phenyl ether). times.100%. The results are shown in table 1:
TABLE 1 degradation results of benzyl phenyl ether by different catalysts
| Catalyst and process for preparing same | Rate of degradation | Phenol yield |
| Example 1 | 79.5％ | 12.3％ |
| Example 2 | 92.1％ | 10.6％ |
| Example 3 | 85.4％ | 8.7％ |
| Example 4 | 73.6％ | 40.6％ |
| Example 5 | 79.8％ | 43.1％ |
| Example 6 | 76.7％ | 66.3％ |
| Example 7 | 93.0％ | 90.7％ |
| Example 8 | 89.7％ | 79.9％ |
As can be seen from the results of the degradation of benzylphenyl ether by the different catalysts in Table 1, examples 1 to 3 show that the Ni @ C-1 catalyst obtained by calcination at different temperatures has the highest degradation effect at the calcination temperature of 600 ℃, because the calcination temperature is too low, the MOF decomposition is incomplete, and only part of Ni is in the form of Ni @ C-1 catalyst2+Is reduced. Excessive temperatures can accelerate catalyst agglomerationThereby affecting the activity, and therefore 600 ℃ is a suitable calcination temperature. From the degradation results of examples 1,4 and 5, it can be seen that the catalyst obtained in example 1 has the highest degradation rate. As can be seen from the degradation results of examples 1,6,7 and 8, the addition of molybdenum can effectively improve the yield of phenol without affecting the degradation rate.
Example 10:
the reaction was evaluated using phenoxyethylbenzene, a model compound containing beta-O-4 in the structure representing lignin, as a substrate. Adding 30.3g of the catalyst obtained in the embodiment 1-8, 75.9g of phenoxyethylbenzene and 893.8g of isopropanol into a hydrothermal reaction kettle, stirring to uniformly mix the phenoxyethylbenzene and the isopropanol, heating to 160 ℃ to react for 5 hours, finally collecting a product, and feeding the obtained product into HPLC for analysis. Yield calculation formula: (molar amount of product formed by reaction/initial molar amount of phenoxyethylbenzene). times.100%, the degradation rate is calculated by the formula: (molar amount of phenoxyethylbenzene consumed by the reaction/initial molar amount of phenoxyethylbenzene). times.100%. The results are shown in table 2:
TABLE 2 degradation results of phenylethane by different catalysts
| Catalyst and process for preparing same | Rate of degradation | Phenol yield |
| Example 1 | 81.1％ | 11.3％ |
| Example 2 | 92.4％ | 13.8％ |
| Example 3 | 87.5％ | 8.9％ |
| Example 4 | 75.5％ | 32.8％ |
| Example 5 | 78.2％ | 41.0％ |
| Example 6 | 89.9％ | 84.2％ |
| Example 7 | 95.2％ | 93.6％ |
| Example 8 | 91.3％ | 83.6％ |
Table 2 shows the degradation results of phenylethane by different catalysts, and the catalyst activity is consistent with that of the α -O-4 bond model compound, and it can be seen that the synthesized MOF precursor molybdenum nickel catalyst also has high catalytic activity for the β -O-4 bond model compound.
Example 11:
the reaction was evaluated by using benzyl phenyl ether as a substrate, which is a model compound containing α -O-4 in the structure of lignin. Adding 30.3g of the catalyst obtained in example 7, 75.9g of benzyl phenyl ether and 893.8g of isopropanol into a hydrothermal reaction kettle, stirring to uniformly mix the components, heating to 160-190 ℃ for reaction for 5 hours, finally collecting a product, and feeding the obtained product into HPLC for analysis. Yield calculation formula: (molar amount of product formed by the reaction/initial molar amount of benzyl phenyl ether). times.100%, degradation rate was calculated by the formula: (molar amount of benzyl phenyl ether consumed by the reaction/initial molar amount of benzyl phenyl ether). times.100%. The results are shown in Table 3:
TABLE 3 degradation results of benzyl phenyl ether at different reaction temperatures
| Reaction temperature | Rate of degradation | Phenol yield |
| 160℃ | 93.0％ | 90.7％ |
| 170℃ | 97.2％ | 71.4％ |
| 180℃ | 97.8％ | 57.6％ |
| 190℃ | 100％ | 36.6％ |
Table 3 shows the results of the degradation of benzyl phenyl ether at different reaction temperatures, and it can be seen that the degradation effect tends to increase with increasing temperature, but the phenol yield decreases.
Example 12:
reaction evaluation was performed using corncob lignin as a substrate. Adding 28.2g of the catalyst obtained in the examples 2,6,7 and 8, 141.1g of corncob lignin and 830.7g of isopropanol into a hydrothermal reaction kettle, stirring to uniformly mix the corncob lignin and the isopropanol, heating to 260 ℃ for reaction for 5 hours, filtering the mixed solution after the reaction is finished, and filtering filter residues to obtain undegraded lignin and the catalyst. After 3ml of the filtrate was rotary evaporated, 15ml of ethyl acetate was added to dissolve it. Then the internal standard (acetophenone) was added to the ethyl acetate solution and 1.5ml was taken for analysis and calculation of the amount of product by GC-MS. The results are shown in Table 4:
TABLE 4 degradation results of lignin from corncobs by different catalysts
| Catalyst and process for preparing same | Rate of degradation | Yield of phenolic monomer |
| Example 2 | 81.8％ | 13.2％ |
| Example 6 | 79.1％ | 13.9％ |
| Example 7 | 83.6％ | 15.5％ |
| Example 8 | 77.1％ | 14.1％ |
Table 4 shows the degradation results of different catalysts on corncob lignin, and it can be seen that the synthesized MOF precursor catalyst also has a higher degradation effect on actual lignin, the degradation rate on corncob lignin is higher than 77.1%, and the yield of phenolic monomers is higher than 13.2%. The catalyst obtained in example 7 showed the highest catalytic activity in terms of degradation rate and yield of phenolic monomers. This corresponds to the degradation effect of the model compound.
Example 13:
and (3) carrying out reaction evaluation by using green bamboo lignin as a substrate. Adding 28.2g of the catalyst obtained in the example 7, 141.1g of green bamboo lignin and 830.7g of isopropanol into a hydrothermal reaction kettle, stirring to uniformly mix the materials, heating to 260 ℃ for reaction for 5 hours, filtering the mixed solution after the reaction is finished, wherein filter residues are undegraded lignin and the catalyst. After 3ml of the filtrate was rotary evaporated, 15ml of ethyl acetate was added to dissolve it. Then the internal standard (acetophenone) was added to the ethyl acetate solution and 1.5ml was taken for analysis and calculation of the amount of product by GC-MS. The results are shown in Table 5:
TABLE 5 degradation results of Mo-Ni @ C-600 on green bamboo lignin
| Catalyst and process for preparing same | Rate of degradation | Yield of phenolic monomer |
| Mo-Ni@C-600 | 82.7％ | 14.9％ |
Example 14:
reaction evaluation was performed using corncob lignin as a substrate. Adding 28.2g of the catalyst obtained in the example 7, 141.1g of corncob lignin and 830.7g of isopropanol into a hydrothermal reaction kettle, stirring to uniformly mix, heating to 250-300 ℃ for reaction for 5 hours, filtering the mixed solution after the reaction is finished, wherein filter residues are undegraded lignin and the catalyst. After 3ml of the filtrate was rotary evaporated, 15ml of ethyl acetate was added to dissolve it. Then the internal standard (acetophenone) was added to the ethyl acetate solution and 1.5ml was taken for analysis and calculation of the amount of product by GC-MS. The results are shown in Table 6:
TABLE 6 degradation results of lignin from corncobs at different reaction temperatures
| Reaction temperature | Rate of degradation | Yield of phenolic monomer |
| 250℃ | 79.8％ | 13.3％ |
| 260℃ | 83.6％ | 15.5％ |
| 270℃ | 84.7％ | 15.9％ |
| 280℃ | 85.1％ | 16.6％ |
| 290℃ | 85.3％ | 17.2％ |
| 300℃ | 82.8％ | 15.1％ |
The above examples are merely illustrative for clearly illustrating the present invention and do not limit the embodiments. All such modifications, whether made by or performed within the spirit and scope of the invention, are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of MOF precursor molybdenum-nickel catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving molybdenum trioxide and metal salt in deionized water for later use after the molybdenum trioxide and the metal salt are completely dissolved, dissolving an organic ligand and alkali in the deionized water, mixing the solution with the metal salt and the molybdenum trioxide after the organic ligand and the alkali are completely dissolved, transferring the mixture into a reaction kettle, and placing the reaction kettle into a microwave reactor for microwave hydrothermal reaction;
(2) after reaction, filtering, washing with deionized water for several times, and drying in a vacuum drying oven overnight to obtain a precursor MoO3-Ni-MOF；
(3) The obtained precursor MoO3And (3) putting the-Ni-MOF into a tube furnace, and roasting to obtain the metal catalyst named as Mo-Ni @ C-X, wherein X represents the carbonization temperature.
2. The method for preparing the MOF precursor molybdenum-nickel catalyst according to claim 1, wherein the MOF precursor molybdenum-nickel catalyst is prepared by the following steps: in the preparation step of the catalyst, the mass fraction of each component is as follows according to the sum of the mass percentages of 100 percent: metal salt: 3.0-12.0%, molybdenum trioxide: 0.5-5.0%, organic ligand: 1.0% -5.0%, alkali: 0.5% -3.0%, solvent: 85.0% -95.0%.
3. The method for preparing the MOF precursor molybdenum-nickel catalyst according to claim 1, wherein the MOF precursor molybdenum-nickel catalyst is prepared by the following steps: the metal salt is one of nickel nitrate, ferric chloride, cobalt nitrate and zinc nitrate; the organic ligand is one of dimethyl imidazole, terephthalic acid, 1,3, 5-benzenetricarboxylic acid, 2, 5-dihydroxyterephthalic acid and 1, 4-cyclohexanedicarboxylic acid.
4. The method for preparing the MOF precursor molybdenum-nickel catalyst according to claim 1, wherein the MOF precursor molybdenum-nickel catalyst is prepared by the following steps: the alkali is one of NaOH, KOH and LiOH.
5. The method for preparing the MOF precursor molybdenum-nickel catalyst according to claim 1, wherein the MOF precursor molybdenum-nickel catalyst is prepared by the following steps: the microwave hydrothermal reaction in the step (1) is specifically a reaction at 60-120 ℃ for 0.5-5.0 h.
6. The method for preparing the MOF precursor molybdenum-nickel catalyst according to claim 1, wherein the MOF precursor molybdenum-nickel catalyst is prepared by the following steps: and (3) drying at the temperature of 50-110 ℃ for 12-24 h.
7. The method for preparing the MOF precursor molybdenum-nickel catalyst according to claim 1, wherein the MOF precursor molybdenum-nickel catalyst is prepared by the following steps: the roasting temperature in the step (3) is 300-700 ℃, and the roasting time is 3-8 h; the roasting atmosphere is hydrogen atmosphere or mixed gas atmosphere of hydrogen and inert gas.
8. Use of a MOF precursor molybdenum nickel catalyst prepared according to any one of claims 1 to 7 in lignin degradation, wherein: the method comprises the following steps: according to the mass ratio, after a lignin raw material, an MOF precursor molybdenum-nickel catalyst and an organic solvent are subjected to ultrasonic homogenization, performing hydrothermal reaction at the temperature of 130-300 ℃ for 1-6 h, cooling the reaction liquid to 40-65 ℃, and filtering to obtain a liquid product and a recovered catalyst.
9. Use according to claim 8, characterized in that: in the step of degrading the lignin, the added mass fractions of the components are as follows according to the sum of the mass percentages of 100 percent: MOF precursor molybdenum nickel catalyst: 1.0% -10.0%, lignin: 5.0% -25.0%, organic solvent: 70.0% -95.0%.
10. Use according to claim 8, characterized in that: the organic solvent is one of methanol, ethanol, isopropanol and n-propanol.
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