CN113908856A - Method for preparing sulfur-doped bimetallic catalyst by using MOF as carrier and application - Google Patents
Method for preparing sulfur-doped bimetallic catalyst by using MOF as carrier and application Download PDFInfo
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Abstract
The invention discloses a method for preparing a sulfur-doped bimetallic catalyst by using MOF as a carrier and application of the sulfur-doped bimetallic catalyst in hydrogenolysis of alcohol-water phase reforming coupling lignin. The catalyst prepared by the invention has excellent performance, shows good applicability in the applications of alcohol-water phase reforming and degradation of lignin and derivatives thereof, has mild degradation conditions, safe and simple process, no need of additional introduction of hydrogen and initial reaction pressure, can be used for batch-type and continuous production, and the obtained phenol monomer can be used as a high-value-added chemical, a biomass fuel precursor or a chemical raw material and has good application prospect.
Description
Technical Field
The invention relates to a preparation technology and application of an alcohol aqueous phase reforming and lignin hydrogenolysis catalyst, in particular to a method for preparing a sulfur-doped bimetallic catalyst by using MOF as a carrier and application of the sulfur-doped bimetallic catalyst in alcohol aqueous phase reforming coupled lignin hydrogenolysis, and belongs to the field of application of biomass energy.
Background
Under the great conditions of petrochemical energy exhaustion, serious environmental crisis and aggravated climate warming, the biomass is a good medicine for saving global sustainable development. The biomass energy is the only carbon-containing chemical energy in renewable energy sources and can replace fossil fuels. Lignin is the second most abundant renewable biomass resource in nature and is the only renewable aromatic biomass raw material in the world. As a natural polymer compound with a content second to that of cellulose, high-value utilization of lignin has a very positive significance in the aspects of new energy development, chemical raw material replacement, environmental protection and the like, but natural lignin has the problems of complex structure, generally between tens of thousands and hundreds of thousands of molecular weight, low reaction activity, poor compatibility with other materials, deep color and the like, is difficult to fully utilize for a long time, and causes great energy waste. 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.
After depolymerization, lignin can be converted into chemical intermediates such as high value-added phenolic compounds, and depolymerization reaction of lignin can generate active groups or reaction sites to increase chemical reaction activity. The depolymerization techniques of lignin include physical degradation, microbial degradation, and chemical degradation. Among them, the chemical degradation method is attracting attention because of its high selectivity to aromatic compounds and good depolymerization effect. Catalytic Hydrodeoxygenation (HDO) of lignin refers to a hydrodeoxygenation reaction that occurs under the action of a catalyst, which is an effective method for converting lignin into high value-added aromatic hydrocarbons or hydrocarbon fuels, and is the most widely used method in chemical degradation methods.
The HDO reaction of lignin has strong dependence on a catalyst, the activity of the catalyst determines the activity of the HDO reaction, and a connecting bond (such as aryl ether bond) of the lignin can be broken under the action of the catalyst and can stably generate a reaction product through a reduction path. Common catalysts are noble metal or supported transition metal catalysts and their composites. The high-performance catalyst should have the characteristics of high catalytic efficiency, good selectivity, good repeatability, easy recovery and the like (the types and application conditions of the partial lignin degradation catalyst are shown in table 1 at present).
TABLE 1 partial Lignin degradation catalyst types and applications
The existing lignin degradation catalysts mostly load active metals on a specific carrier by an impregnation method, and the catalysts synthesized by the method often have the defects of low load capacity, easy deactivation and agglomeration. In addition, the existing 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 expensive noble metal catalysts, so that the further application of lignin degradation is limited, and the industrial application is difficult to realize. Based on the above, the invention provides a high-performance bimetallic catalyst prepared by using an MOF derivative material as a carrier, wherein the catalyst can catalyze the aqueous phase reforming of alcohol to generate hydrogen in the degradation process, so that the hydrogen can be used as a hydrogen source for the subsequent lignin hydrogenolysis reaction, and can be continuously used as a catalyst for the lignin hydrogenolysis to catalyze the hydrodeoxygenation of lignin.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing a sulfur-doped bimetallic catalyst by using MOF as a carrier and application of the sulfur-doped bimetallic catalyst in alcohol aqueous phase reforming coupled lignin hydrogenolysis. The catalyst prepared by the invention has the advantages of low price, easy recovery, mild reaction conditions and environment-friendly degradation process, is suitable for industrial production, and solves the problems of high price, poor performance, harsh degradation reaction conditions and the like of the current lignin degradation catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a sulfur-doped bimetallic catalyst by using MOF as a carrier, which comprises the following steps:
1) dissolving nickel nitrate in part of the organic solution to obtain a nickel nitrate solution; in addition, after completely dissolving the organic ligand in the residual organic solution, mixing the organic ligand with the nickel nitrate solution, transferring the mixture into a hydrothermal reaction kettle, placing the reaction kettle into an oven for hydrothermal reaction, and drying to obtain a precursor Ni-MOF;
2) roasting the obtained precursor Ni-MOF to obtain Ni @ C serving as a metal catalyst carrier;
3) fully soaking the obtained Ni @ C in a mixed aqueous solution of sulfide and metal salt;
4) adding reducing agent sodium borohydride into the solution obtained in the step 3), stirring, reducing and drying to obtain the sulfur-doped bimetallic catalyst.
The dosage of the raw materials is as follows according to the sum of the mass percent of 100 percent: 2.0-7.0% of nickel nitrate, 0.6-5.0% of organic ligand, 50.0-65.0% of organic solvent, 1.0-10.0% of sodium borohydride, 0-7.0% of sulfide, 0.2-3.0% of metal salt and 20-45% of deionized water.
Wherein the organic ligand is one or more of dimethyl imidazole, terephthalic acid, 1,3, 5-benzene tricarboxylic acid, 2, 5-dihydroxy terephthalic acid and 1, 4-cyclohexane dicarboxylic acid;
the organic solvent is one or more of methanol, ethanol, N-dimethylformamide and N, N-dimethylacetamide;
the sulfide is one or more of mercaptan, thioether, thiophene, hydrogen sulfide, ammonium bisulfide, dimethyl sulfide, diethyl sulfide, diphenyl sulfide, sodium sulfide, potassium bisulfide, sulfur dioxide or carbonyl sulfide.
The metal salt is one or more of copper nitrate, ferric chloride, cobalt nitrate, zinc nitrate and ruthenium chloride;
the temperature of the hydrothermal reaction in the step (1) is 100-200 ℃, and the time is 12-36 h.
And (3) roasting in inert gas, hydrogen or a mixed atmosphere of the inert gas and the hydrogen at the temperature of 300-700 ℃ for 3-8 h.
The dipping time in the step (3) is 6-36 h;
the reduction time in the step (4) is 30min-2 h; the drying temperature is 50-110 ℃, and the drying time is 12-24 h.
The sulfur-doped bimetallic catalyst prepared by the method can be applied to hydrogenolysis of alcohol-water phase reforming coupling lignin, and the application method comprises the steps of taking a lignin model compound or lignin as a raw material, carrying out ultrasonic mixing with the sulfur-doped bimetallic catalyst, deionized water and alcohol, carrying out hydrothermal reaction for 1-6 h at a certain temperature, cooling reaction liquid to 40-65 ℃ after the reaction, and filtering to obtain a liquid product and a recovered catalyst.
The additive amount of each component is as follows according to the sum of the mass percent of 100 percent: 5.0-25.0% of lignin model compound or lignin, 1.0-10.0% of sulfur-doped bimetallic catalyst, 30.0-95.0% of alcohol and 0-60.0% of deionized water.
When the lignin model compound is used as a raw material, the hydrothermal reaction temperature is 80-160 ℃; when lignin is used as a raw material, the hydrothermal reaction temperature is 200-270 ℃.
The lignin comprises one or more of natural lignin or organic solvent lignin, enzymatic hydrolysis lignin, ground lignin, sulfate lignin, sulfonate lignin and alkali lignin which is prepared from any 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 alkali method; the lignin model compound is a dimer lignin model compound.
The alcohol is one or more of methanol, ethanol, isopropanol and n-propanol.
In the process, Ni-MOF is used as a self-sacrifice template to prepare a derivative Ni @ C, the derivative Ni @ C is used as a carrier by utilizing the characteristic that the derivative Ni @ C has high pore volume and pore diameter, and sulfide and metal ions are well dispersed and reduced after being adsorbed to form the sulfur-doped bimetallic catalyst. Wherein the synergistic effect between the nickel and the supported metal and the doped sulfur can further improve the performance of the catalyst. In an alcohol-water phase reforming reaction system, the catalyst can promote the alcohol solvent-water phase reforming to produce hydrogen and provide a hydrogen source for subsequent reaction, and can also be used as a lignin hydrogenolysis catalyst to break connecting bonds among lignin units. Compared with the traditional lignin degradation process, the whole process does not need additional hydrogen, and the cost of the alcohol-water reaction system is lower than that of the alcohol system, so that the method is more favorable for subsequent industrial application.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, a two-step method is adopted, Ni @ C obtained by taking a Ni-MOF material as a self-sacrifice template is taken as a carrier, and a sulfur-doped bimetallic carbon-based catalyst is obtained by reduction after metal and sulfide are impregnated in the catalyst, so that the catalyst not only retains the advantage of high nickel loading of a Ni-MOF precursor, but also well disperses doped sulfur and a second metal on the surface of the catalyst by utilizing the advantages of high specific surface area and high porosity of an MOF derivative material, and the HDO activity of the catalyst is greatly improved by utilizing the synergistic effect between sulfur and a metal center.
(2) The catalyst has the advantages of simple preparation process, mild reaction conditions, easy recovery, good repeatability and capability of realizing continuous reaction.
(3) Compared with the condition that high-pressure hydrogen is generally needed in the existing lignin hydrogenolysis process, the catalyst is used for catalyzing the alcohol aqueous phase reforming reaction to provide a hydrogen source to realize the hydrogenolysis of the lignin, the process is safe and simple, the reaction condition is mild, the process can be carried out in a hydrothermal reaction kettle, a high-pressure reaction kettle is not needed, and the requirement on equipment is low.
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 S-Cu/Ni @ C-1 catalyst
Weighing 25.2 g of nickel nitrate hexahydrate in 281.4g N, N-dimethylformamide, and stirring to fully dissolve the nickel nitrate; 10.3g of terephthalic acid was weighed into 281.4g N, N-dimethylformamide and dissolved by stirring. Mixing the solution dissolved with nickel nitrate hexahydrate and the solution dissolved with terephthalic acid, transferring the mixture into a hydrothermal reaction kettle, placing the reaction kettle into an oven, reacting at 150 ℃ for 24 hours, filtering, and vacuum drying at 80 ℃ for 12 hours to obtain the Ni-MOF. And (3) placing the prepared Ni-MOF into a tube furnace, roasting for 5 hours at 700 ℃ by taking argon as protective gas (the gas flow rate is 100 ml/min), and thus obtaining Ni @ C. Putting the obtained Ni @ C in 343.3 g of deionized water dissolved with 4.0g of mercaptan and 4.2g of copper nitrate, soaking for 20 hours, adding 50.2g of sodium borohydride, stirring and reducing for 1.5 hours, and drying at 90 ℃ for 18 hours to obtain the S-Cu/Ni @ C-1 catalyst.
Example 2: preparation of S-Fe/Ni @ C catalyst
Weighing 25.2 g of nickel nitrate hexahydrate in 281.4g N, N-dimethylformamide, and stirring to fully dissolve the nickel nitrate; 10.3g of terephthalic acid was weighed into 281.4g N, N-dimethylformamide and dissolved by stirring. Mixing the solution dissolved with nickel nitrate hexahydrate and the solution dissolved with terephthalic acid, transferring the mixture into a hydrothermal reaction kettle, placing the reaction kettle into an oven, reacting at 150 ℃ for 24 hours, filtering, and vacuum drying at 80 ℃ for 12 hours to obtain the Ni-MOF. And (3) placing the prepared Ni-MOF into a tube furnace, roasting for 5 hours at 700 ℃ by taking argon as protective gas (the gas flow rate is 100 ml/min), and thus obtaining Ni @ C. And putting the obtained Ni @ C in 343.3 g of deionized water dissolved with 4.0g of mercaptan and 4.2g of ferric chloride, soaking for 20 hours, adding 50.2g of sodium borohydride, stirring and reducing for 1.5 hours, and drying for 18 hours at 90 ℃ to obtain the S-Fu/Ni @ C catalyst.
Example 3: preparation of S-Co/Ni @ C catalyst
Weighing 25.2 g of nickel nitrate hexahydrate in 281.4g N, N-dimethylformamide, and stirring to fully dissolve the nickel nitrate; 10.3g of terephthalic acid was weighed into 281.4g N, N-dimethylformamide and dissolved by stirring. Mixing the solution dissolved with nickel nitrate hexahydrate and the solution dissolved with terephthalic acid, transferring the mixture into a hydrothermal reaction kettle, placing the reaction kettle into an oven, reacting at 150 ℃ for 24 hours, filtering, and vacuum drying at 80 ℃ for 12 hours to obtain the Ni-MOF. And (3) placing the prepared Ni-MOF into a tube furnace, roasting for 5 hours at 700 ℃ by taking argon as protective gas (the gas flow rate is 100 ml/min), and thus obtaining Ni @ C. And putting the obtained Ni @ C in 343.3 g of deionized water dissolved with 4.0g of mercaptan and 4.2g of cobalt nitrate, soaking for 20 hours, adding 50.2g of sodium borohydride, stirring and reducing for 1.5 hours, and drying for 18 hours at 90 ℃ to obtain the S-Co/Ni @ C catalyst.
Example 4: preparation of S-Cu/Ni @ C-2 catalyst
Weighing 25.2 g of nickel nitrate hexahydrate in 281.4g N, N-dimethylformamide, and stirring to fully dissolve the nickel nitrate; 10.3g of terephthalic acid was weighed into 281.4g N, N-dimethylformamide and dissolved by stirring. Mixing the solution dissolved with nickel nitrate hexahydrate and the solution dissolved with terephthalic acid, transferring the mixture into a hydrothermal reaction kettle, placing the reaction kettle into an oven, reacting at 150 ℃ for 24 hours, filtering, and vacuum drying at 80 ℃ for 12 hours to obtain the Ni-MOF. And (3) placing the prepared Ni-MOF into a tube furnace, roasting for 5 hours at 700 ℃ by taking argon as protective gas (the gas flow rate is 100 ml/min), and thus obtaining Ni @ C. And (2) putting the obtained Ni @ C in 341.3 g of deionized water in which 4.0g of mercaptan and 3.2g of copper nitrate are dissolved, soaking for 20 hours, adding 50.2g of sodium borohydride, stirring and reducing for 1.5 hours, and drying for 18 hours at 90 ℃ to obtain the S-Cu/Ni @ C-2 catalyst.
Example 5: preparation of S-Cu/Ni @ C-3 catalyst
Weighing 25.2 g of nickel nitrate hexahydrate in 281.4g N, N-dimethylformamide, and stirring to fully dissolve the nickel nitrate; 10.3g of terephthalic acid was weighed into 281.4g N, N-dimethylformamide and dissolved by stirring. Mixing the solution dissolved with nickel nitrate hexahydrate and the solution dissolved with terephthalic acid, transferring the mixture into a hydrothermal reaction kettle, placing the reaction kettle into an oven, reacting at 150 ℃ for 24 hours, filtering, and vacuum drying at 80 ℃ for 12 hours to obtain the Ni-MOF. And (3) placing the prepared Ni-MOF into a tube furnace, roasting for 5 hours at 700 ℃ by taking argon as protective gas (the gas flow rate is 100 ml/min), and thus obtaining Ni @ C. And (3) putting the obtained Ni @ C into 345.4 g of deionized water dissolved with 4.0g of mercaptan and 2.1g of copper nitrate, soaking for 20 hours, adding 50.2g of sodium borohydride, stirring and reducing for 1.5 hours, and drying for 18 hours at 90 ℃ to obtain the S-Cu/Ni @ C-3 catalyst.
Comparative example 1: preparation of S-Cu-Ni @ C catalyst
Weighing 25.2 g of nickel nitrate hexahydrate in 292.0g N-N dimethylformamide, and stirring to fully dissolve the nickel nitrate; 10.3g of terephthalic acid was weighed into 292.0g N-N dimethylformamide and dissolved by stirring. Transferring the solution dissolved with the nickel nitrate hexahydrate and the solution dissolved with the organic ligand to a hydrothermal reaction kettle, then placing the reaction kettle in a drying oven, reacting for 24 hours at 150 ℃, filtering, and vacuum drying for 12 hours at 80 ℃ to obtain the carrier Ni-MOF. And (3) putting the prepared Ni-MOF into 373.0 g of deionized water dissolved with 4.0g of mercaptan and 4.2g of copper nitrate, soaking for 20 hours, and drying to obtain a precursor S-Cu-Ni-MOF. And (3) putting the precursor S-Cu-Ni-MOF into a tube furnace, roasting for 5 hours at 700 ℃ by taking argon as protective gas, wherein the gas flow rate is 100ml/min, and thus obtaining the S-Cu-Ni @ C catalyst.
Comparative example 2: preparation of S-Ni @ C catalyst
26.8g of nickel nitrate hexahydrate is weighed into 310.5g N, N-dimethylformamide and stirred to be fully dissolved; 9.6g of terephthalic acid was weighed into 310.5g N, N-dimethylformamide and dissolved by stirring. Mixing the solution dissolved with nickel nitrate hexahydrate and the solution dissolved with terephthalic acid, transferring the mixture into a hydrothermal reaction kettle, placing the reaction kettle into an oven, reacting at 150 ℃ for 24 hours, filtering, and vacuum drying at 80 ℃ for 12 hours to obtain the Ni-MOF. And (3) placing the prepared Ni-MOF into a tube furnace, roasting for 5 hours at 700 ℃ by taking argon as protective gas (the gas flow rate is 100 ml/min), and thus obtaining Ni @ C. And (3) soaking the obtained Ni @ C in 307.8 g of deionized water dissolved with 4.0g of mercaptan for 20 hours, adding 30.8g of sodium borohydride, stirring and reducing for 1.5 hours, and drying at 90 ℃ for 18 hours to obtain S-Ni @ C.
Comparative example 3: preparation of Cu/Ni @ C catalyst
26.8g of nickel nitrate hexahydrate is weighed into 310.5g N, N-dimethylformamide and stirred to be fully dissolved; 9.6g of terephthalic acid was weighed into 310.5g N, N-dimethylformamide and dissolved by stirring. Mixing the solution dissolved with nickel nitrate hexahydrate and the solution dissolved with terephthalic acid, transferring the mixture into a hydrothermal reaction kettle, placing the reaction kettle into an oven, reacting at 150 ℃ for 24 hours, filtering, and vacuum drying at 80 ℃ for 12 hours to obtain the Ni-MOF. And (3) placing the prepared Ni-MOF into a tube furnace, roasting for 5 hours at 700 ℃ by taking argon as protective gas (the gas flow rate is 100 ml/min), and thus obtaining Ni @ C. And (3) soaking the obtained Ni @ C in 307.8 g of deionized water dissolved with 4.0g of copper nitrate for 20 hours, adding 30.8g of sodium borohydride, stirring and reducing for 1.5 hours, and drying at 90 ℃ for 18 hours to obtain Cu/Ni @ C.
Application example 1:
the reaction was evaluated by using benzyl phenyl ether as a substrate, which contained a model compound representing the type of the α -O-4 bond in the lignin structure. The steps are that 30.3g of the catalyst obtained in the example or the comparative example, 75.9g of benzyl phenyl ether, 357.7g of methanol and 536.1g of deionized water are added into a hydrothermal reaction kettle, stirred to be mixed uniformly, heated to 140 ℃ to react for 5 hours, collected and sent into HPLC to be analyzed. The calculation formula is as follows:
yield (%) = molar amount of product formed by reaction/initial molar amount of benzyl phenyl ether × 100%;
degradation rate (%) = mole amount of benzyl phenyl ether consumed for reaction/initial mole amount of benzyl phenyl ether × 100%.
The results are shown in Table 2.
TABLE 2 degradation results of benzyl phenyl ether by different catalysts
Application example 2:
the reaction was evaluated by using benzyl phenyl ether as a substrate, which contained a model compound representing the type of the α -O-4 bond in the lignin structure. Adding 30.3g of the catalyst obtained in the example or the comparative example, 75.9g of benzyl phenyl ether, 396.3g of isopropanol and 497.5g of deionized water into a hydrothermal reaction kettle, stirring to uniformly mix the components, heating to 140 ℃ for reaction for 5 hours, collecting a product, and feeding the obtained product into HPLC for analysis. The calculation formula is as follows:
yield (%) = molar amount of product formed by reaction/initial molar amount of benzyl phenyl ether × 100%;
degradation rate (%) = mole amount of benzyl phenyl ether consumed for reaction/initial mole amount of benzyl phenyl ether × 100%.
The results are shown in Table 3.
TABLE 3 degradation results of benzyl phenyl ether by different catalysts
Application example 3:
the reaction was evaluated by using benzyl phenyl ether as a substrate, which contained a model compound representing the type of the α -O-4 bond in the lignin structure. Adding 30.3g of the catalyst obtained in the example or the comparative example, 75.9g of benzyl phenyl ether, 421.7g of ethanol and 472.1g of deionized water into a hydrothermal reaction kettle, stirring to uniformly mix the components, heating to 140 ℃ for reaction for 5 hours, collecting a product, and feeding the obtained product into HPLC for analysis. The calculation formula is as follows:
yield (%) = molar amount of product formed by reaction/initial molar amount of benzyl phenyl ether × 100%;
degradation rate (%) = mole amount of benzyl phenyl ether consumed for reaction/initial mole amount of benzyl phenyl ether × 100%.
The results are shown in Table 4.
TABLE 4 degradation results of benzyl phenyl ether by different catalysts
Comparing the degradation results of the catalysts in different alcohol solvents in the tables 2, 3 and 4, it can be seen that compared with S-Cu-Ni @ C, S-Ni @ C and Cu-Ni @ C catalysts, the sulfur-doped bimetallic catalyst obtained by taking Ni @ C obtained by calcining Ni-MOF as a carrier can further improve the degradation activity on the basis of keeping the original Ni activity. The experiment effect of using isopropanol and water as solvents is best, the Cu-loaded S-Cu/Ni @ C obtains a degradation rate of more than 94.5% and a phenol yield of more than 92.3% in the solvent system, and the result shows that S and Cu can form a good synergistic effect with Ni in the catalyst, so that the hydrogen production of an alcohol-water phase reforming reaction is promoted, and the catalytic activity is improved.
Application example 4:
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 5, 75.9g of benzyl phenyl ether, 396.3g of isopropanol and 497.5g of deionized water into a hydrothermal reaction kettle, stirring to uniformly mix the components, heating to 100-150 ℃ for reaction for 5 hours, collecting a product, and feeding the obtained product into HPLC for analysis. The calculation formula is as follows:
yield (%) = molar amount of product formed by reaction/initial molar amount of benzyl phenyl ether × 100%;
degradation rate (%) = mole amount of benzyl phenyl ether consumed for reaction/initial mole amount of benzyl phenyl ether × 100%.
The results are shown in Table 5.
TABLE 5 degradation results of benzyl phenyl ether at different reaction temperatures
As can be seen from Table 3, the catalyst has an obvious degradation effect on benzyl phenyl ether at 100 ℃, and the degradation rate reaches 87.6 percent, so that the catalyst synthesized by the method can realize hydrodeoxygenation on lignin model compounds under mild conditions.
Application example 5:
the reaction evaluation was carried out using phenoxyethylbenzene, a model compound containing the beta-O-4 and 4-O-5 bonds representing the lignin structure, and diphenyl ether as substrates. Adding 30.3g of the catalyst obtained in example 5, 75.9g of the model compound, 396.3g of isopropanol and 497.5g of deionized water into a hydrothermal reaction kettle, stirring to uniformly mix the components, heating to 160 ℃ for reaction for 5 hours, collecting a product, and feeding the obtained product into HPLC for analysis. The calculation formula is as follows:
yield (%) = molar amount of reaction-produced product/initial molar amount of model compound × 100%;
degradation rate (%) = molar amount of model compound consumed for reaction/initial molar amount of model compound × 100%.
The results are shown in Table 6:
TABLE 6 degradation results of catalysts on different bond type model compounds
Application example 6:
and (3) performing reaction evaluation by using corncob enzymatic hydrolysis lignin as a substrate. The method comprises the steps of respectively adding 31.2g of the catalyst obtained in examples 1,4 and 5 or comparative example 1, 161.1g of corncob lignin, 328.7g of isopropanol and 479.0g of deionized water into a hydrothermal reaction kettle, stirring to uniformly mix the components, heating to 240 ℃ for reaction for 4 hours, filtering the mixed solution after the reaction is finished, and obtaining the filter residue which is the undegraded lignin and the catalyst. After 3ml of the obtained filtrate was subjected to rotary evaporation, 15ml of ethyl acetate was added to dissolve the filtrate, and then an internal standard substance (acetophenone) was added, and 1.5ml of the solution was analyzed by GC-MS and the amount of the product was calculated. The results are shown in Table 7.
TABLE 7 degradation results of lignin from enzymatic hydrolysis of corncobs by different catalysts
As can be seen from table 7, the obtained sulfur-doped bimetallic catalyst also has a good application effect in real lignin, the degradation rate of the sulfur-doped bimetallic catalyst on corncob lignin is higher than 79.1%, and the yield of phenolic monomers is higher than 11.6%, wherein the catalyst obtained in example 5 shows the highest catalytic activity in terms of the degradation rate and the yield of phenolic monomers, which corresponds to the degradation effect of a model compound.
Application example 7:
different lignins were used as substrates for reaction evaluation. Adding 31.2g of the catalyst obtained in the example 5, 161.1g of lignin, 328.7g of isopropanol and 479.0g of deionized water into a hydrothermal reaction kettle, stirring to uniformly mix the materials, heating to 240 ℃ for reaction for 4 hours, filtering the mixed solution after the reaction is finished, wherein filter residues are undegraded lignin and the catalyst. After 3ml of the obtained filtrate was subjected to rotary evaporation, 15ml of ethyl acetate was added to dissolve the filtrate, and then an internal standard substance (acetophenone) was added, and 1.5ml of the solution was analyzed by GC-MS and the amount of the product was calculated. The results are shown in Table 8.
TABLE 8 degradation results of Cu/Ni @ C-3 on different lignins
Application example 8:
and (3) performing reaction evaluation by using corncob enzymatic hydrolysis lignin as a substrate. Adding 31.2g of the catalyst obtained in the example 5, 161.1g of corncob lignin, 328.7g of isopropanol and 479.0g of deionized water into a hydrothermal reaction kettle, stirring to uniformly mix the components, heating to 220-270 ℃ for reaction for 4 hours, filtering the mixed solution after the reaction is finished, wherein filter residues are the undegraded lignin and the catalyst. After 3ml of the obtained filtrate was subjected to rotary evaporation, 15ml of ethyl acetate was added to dissolve the filtrate, and then an internal standard substance (acetophenone) was added, and 1.5ml of the solution was analyzed by GC-MS and the amount of the product was calculated. The results are shown in Table 9:
TABLE 9 degradation results of lignin from enzymatic hydrolysis of corncobs by different reaction temperatures
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 method for preparing a sulfur-doped bimetallic catalyst by using MOF as a carrier is characterized by comprising the following steps: the method comprises the following steps:
1) dissolving nickel nitrate in part of the organic solution to obtain a nickel nitrate solution; in addition, after completely dissolving the organic ligand in the residual organic solution, mixing the organic ligand with a nickel nitrate solution for hydrothermal reaction, and drying to obtain a precursor Ni-MOF;
2) roasting the obtained precursor Ni-MOF to obtain Ni @ C serving as a metal catalyst carrier;
3) fully soaking the obtained Ni @ C in a mixed aqueous solution of sulfide and metal salt;
4) adding sodium borohydride into the solution obtained in the step 3), stirring, reducing and drying to obtain the sulfur-doped bimetallic catalyst.
2. The method for preparing the sulfur-doped bimetallic catalyst by using the MOF as the carrier according to claim 1, characterized in that: the dosage of the raw materials is as follows according to the sum of the mass percent of 100 percent: 2.0-7.0% of nickel nitrate, 0.6-5.0% of organic ligand, 50.0-65.0% of organic solvent, 1.0-10.0% of sodium borohydride, 0-7.0% of sulfide, 0.2-3.0% of metal salt and 20-45% of deionized water.
3. The process for the preparation of sulfur-doped bimetallic catalysts using MOFs as supports according to claim 1 or 2, characterized in that: the organic ligand is one or more of dimethyl imidazole, terephthalic acid, 1,3, 5-benzene tricarboxylic acid, 2, 5-dihydroxy terephthalic acid and 1, 4-cyclohexane dicarboxylic acid;
the organic solvent is one or more of methanol, ethanol, N-dimethylformamide and N, N-dimethylacetamide;
the sulfide is one or more of mercaptan, thioether, thiophene, hydrogen sulfide, ammonium bisulfide, dimethyl sulfide, diethyl sulfide, diphenyl sulfide, sodium sulfide, potassium bisulfide, sulfur dioxide or carbonyl sulfide.
4. The metal salt is one or more of copper nitrate, ferric chloride, cobalt nitrate, zinc nitrate and ruthenium chloride;
the method for preparing the sulfur-doped bimetallic catalyst by using the MOF as the carrier according to claim 1, characterized in that: the temperature of the hydrothermal reaction in the step (1) is 100-200 ℃, and the time is 12-36 h.
5. The method for preparing the sulfur-doped bimetallic catalyst by using the MOF as the carrier according to claim 1, characterized in that: and (3) roasting in inert gas, hydrogen or a mixed atmosphere of the inert gas and the hydrogen at the temperature of 300-700 ℃ for 3-8 h.
6. The method for preparing the sulfur-doped bimetallic catalyst by using the MOF as the carrier according to claim 1, characterized in that: and 3) soaking for 6-36 h.
7. The method for preparing the sulfur-doped bimetallic catalyst by using the MOF as the carrier according to claim 1, characterized in that: the reduction time in the step 4) is 30min-2 h; the drying temperature is 50-110 ℃, and the drying time is 12-24 h.
8. Use of a sulfur-doped bimetallic catalyst prepared by the process of any one of claims 1 to 7 in alcohol aqueous phase reforming coupled lignin hydrogenolysis, characterized in that: the application method comprises the steps of taking a lignin model compound or lignin as a raw material, carrying out ultrasonic mixing on the lignin model compound or the lignin with a sulfur-doped bimetallic catalyst, deionized water and alcohol, carrying out hydrothermal reaction for 1-6 hours at a certain temperature, cooling reaction liquid to 40-65 ℃ after the reaction, and filtering to obtain a liquid product and a recovered catalyst.
9. Use according to claim 8, characterized in that: the additive amount of each component is as follows according to the sum of the mass percent of 100 percent: 5.0-25.0% of lignin model compound or lignin, 1.0-10.0% of sulfur-doped bimetallic catalyst, 30.0-95.0% of alcohol and 0-60.0% of deionized water;
the lignin comprises one or more of natural lignin or organic solvent lignin, enzymatic hydrolysis lignin, ground lignin, sulfate lignin, sulfonate lignin and alkali lignin which is prepared from any 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 alkali method; the lignin model compound is a dimer lignin model compound;
the alcohol is one or more of methanol, ethanol, isopropanol and n-propanol.
10. Use according to claim 8, characterized in that: when the lignin model compound is used as a raw material, the hydrothermal reaction temperature is 80-160 ℃; when lignin is used as a raw material, the hydrothermal reaction temperature is 200-270 ℃.
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