CN114588910B - Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization - Google Patents

Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization Download PDF

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CN114588910B
CN114588910B CN202210249077.7A CN202210249077A CN114588910B CN 114588910 B CN114588910 B CN 114588910B CN 202210249077 A CN202210249077 A CN 202210249077A CN 114588910 B CN114588910 B CN 114588910B
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lignin
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崔勍焱
颜超
王廷海
袁珮
张宏伟
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Fuzhou University
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Abstract

The invention discloses a preparation method and application of a Ni-Zn supported catalyst for lignin depolymerization, wherein a precursor of an active carbon supported Ni-Zn catalyst is prepared by an impregnation method, then baked in a nitrogen atmosphere, and metal is reduced by a carbon reduction method to obtain an active carbon supported Ni-Zn catalyst material. The catalyst is applied to the hydrogenolysis of a poaceae lignin suspension bed to produce high added value chemicals, has higher hydrogenolysis reaction activity and liquid product yield, and when the catalyst/lignin=20%, the total monomer yield can reach 18.25 wt%; when the catalyst/lignin=40%, the selectivity of the ester compound and the 4-hydroxy-3, 5-dimethoxy phenylacetaldehyde can reach about 36.43 percent and 16.75 percent respectively. Provides a new way for expanding the industrialization of woody biomass chemicals.

Description

Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization
Technical Field
The invention belongs to the technical field of energy chemical industry, and particularly relates to preparation of a Ni-Zn supported catalyst and application of the Ni-Zn supported catalyst in production of fine chemicals by adding hydrogen to lignin in a suspension bed for polymerization.
Background
In recent years, under the heavy background of carbon neutralization and the dual standards of international regulations for reducing carbon emissions, biomass as renewable organic carbon has attracted widespread attention in the hopes of being able to replace, in part, increasingly depleted fossil fuels in the future. Lignin is the only renewable organic carbon source containing aromatic compounds in nature and has great potential for conversion to liquid fuels and high value-added chemicals. The challenge in the preparation of high value-added chemicals from lignin is to develop a catalyst that is efficient, highly stable and highly selective.
Among the various reported lignin chemical decomposition strategies, the use of supported noble metal catalysts to catalyze lignin hydrogenolysis is one of the most popular methods. The noble metals used for lignin degradation are Pd, pt and Ru loaded on various carriers. Dou et al uses Pd-PdO/TiO in water as solvent at 180deg.C 2 The lignin is used as a catalyst, so that the monomer yield of the lignin can reach 40 wt percent (Applied Catalysis B: environmental, 2022, 301: 120767). Although noble metals have high catalytic activity and mild reaction conditions, the scarcity of noble metals and excessive hydrogenation of depolymerized products result in inability to put into production.
The catalyst supports which are relatively widely used at present are all oxide supports, in particular Al 2 O 3 . But for lignin degradation reactions, first, due to gamma-Al 2 O 3 Is liable to generate carbon deposition on the surface thereof, resulting in reduced catalytic activity, and secondly, water is a byproduct of HDO, gamma-Al under hydrothermal conditions 2 O 3 Is metastable and is converted into beta-Al 2 O 3 Is unfavorable for the effective degradation of lignin. Carbon carriers are increasingly studied because of the advantages of developed pores, large specific surface area, small density, good heat resistance, acid and alkali resistance and the like. Patent CN 111659400A discloses a bimetallic catalyst composed of Ni and Cu, and uses rGO as a carrier to prepare a highly dispersed hydrogenation catalyst using Ni-Cu as an active component. It is reported that the organic solvent poplar lignin is depolymerized by using NiCu/C as a catalyst, ethanol and isopropanol are used as mixed solvents, and the phenolic monomer can be obtained by 63.4 wt percent [ ACS Sustainable Chemistry ]& Engineering, 2020, 8(43): 16217-16228.】。
In view of the above, it is necessary to develop a suspension bed hydrogenation catalyst having high activity, good selectivity, low cost and good stability in the production of high value-added chemicals. The key point is how to select the material with high hydrogenation activity and low price as the active component, and prepare the catalyst with high dispersibility, high stability and high selectivity. In order to achieve the effect, the invention promotes the depolymerization degree of lignin by adjusting the proper synergistic effect between the acid site and the metal site of the catalyst, and invents a Ni-Zn supported catalyst material for depolymerizing lignin by hydrogenation to prepare ester-type high-added-value chemicals.
Disclosure of Invention
The invention aims to apply Ni-Zn supported catalyst material to the aspect of producing high added value chemicals by the suspension bed hydrogenation depolymerization of lignin. Active sites are highly dispersed by taking active carbon with high specific surface area as a carrier and carrying out ultrasonic treatment, and the proportion of a nickel source and a zinc source is adjusted, so that a series of active carbon supported Ni-Zn bimetallic catalysts are prepared and used for catalytic hydrogenolysis of corn straw lignin serving as an organic solvent in a methanol solvent. In the catalytic hydrogenolysis process, under the synergistic effect between the metal active site and the acid site, the liquid product yield is higher, and the total monomer yield and the target product selectivity are also higher. The prepared activated carbon supported Ni-Zn bimetallic catalyst material has good application prospect in the production of high-added-value chemicals by the hydrogenation depolymerization of lignin suspension bed.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of Ni-Zn supported catalyst material is characterized in that a Ni-Zn supported catalyst for producing fine chemicals by depolymerizing lignin suspended bed is prepared by taking a nickel source and a zinc source as raw materials, dipping, dispersing the raw materials on the surface of active carbon by ultrasonic, roasting at high temperature in nitrogen atmosphere and reducing carbon.
In the invention, the molar ratio of the nickel source to the zinc source is 10: 1-5: 4, preferably 2.2:1.
In the invention, the nickel source is a soluble nickel salt of nickel, such as nickel nitrate, nickel acetate, nickel sulfate, and the like.
In the invention, the zinc source is a soluble zinc salt of zinc, such as zinc nitrate, zinc acetate, zinc sulfate and the like.
In the invention, the impregnation is a conventional impregnation process, such as constant volume impregnation and over-volume impregnation reaction at normal temperature.
In the invention, the carbon is reduced and activated for 3-6 hours in a nitrogen atmosphere at 350-600 ℃.
In the invention, the activated carbon is one or more of wood activated carbon, shell activated carbon, coconut activated carbon and coal activated carbon.
In the invention, the activated carbon is mesoporous activated carbon, and the specific surface area of the activated carbon can reach 1632 m 2 /g。
In the invention, the ultrasonic frequency is 30-60 KHz, and the ultrasonic temperature is 45-55 ℃.
The invention relates to a preparation method of a Ni-Zn supported catalyst for lignin depolymerization, which specifically comprises the following steps:
(1) Mixing a metal nickel source and a zinc source according to a certain molar ratio, adding a certain amount of deionized water, and performing ultrasonic treatment until the metal nickel source and the zinc source are completely dissolved to form a mixed solution;
(2) Dropwise adding the mixed solution into a certain amount of active carbon carrier, performing ultrasonic treatment, standing and drying to obtain a compound;
(3) And heating the composite to 300-600 ℃ at a heating rate of 3-6 ℃/min, and carrying out reduction and activation for 3-6 hours in a nitrogen atmosphere to obtain the Ni-Zn supported catalyst for lignin depolymerization.
In the step (1), the concentration of the zinc source in deionized water is preferably 0.4-1.2 mol/L; the ultrasonic temperature is 20-40 ℃ and the ultrasonic time is 2-8 min;
in the step (1), the deionized water is 3-5 mL;
in the step (2), the dripping time is 15-30 min, the ultrasonic temperature is kept unchanged at 40-55 ℃, and the ultrasonic time is 10-14 min;
in the step (2), the standing time is kept between 6 and 8 h; the drying temperature was kept at 80 ℃ for 2 h.
In the step (3), the temperature of the compound is raised to 300-550 ℃ at the temperature rising rate of 4-5 ℃/min, and the compound is reduced and activated for 3-5 hours in the atmosphere of nitrogen, so that the Ni-Zn supported catalyst for lignin depolymerization is obtained.
The application of a Ni-Zn supported catalyst for lignin depolymerization: mixing lignin, ni-Zn supported catalyst and reaction solvent, adding the mixture into a reaction kettle, sealing, introducing nitrogen to replace air in the device, heating to a reaction temperature, cooling, decompressing, opening the kettle after the reaction is finished, filtering out solids in the mixture, obtaining a liquid product, and weighing the weight of the liquid product by extraction rotary evaporation to calculate the yield of the liquid product. And then, adding 20 mg internal standard substances, and carrying out qualitative and quantitative analysis by a GC-MS instrument to obtain the monomer yield and selectivity.
In the invention, the lignin comprises organic dissolution corn stalk lignin, organic dissolution bagasse lignin and organic dissolution miscanthus lignans.
In the invention, the reaction solvent is selected from one of methanol, ethanol, isopropanol, 1, 4-dioxane and formic acid, or the solvents mixed in any proportion, and the liquid product is a phenolic compound, an ester compound or an oligomer compound.
In the invention, the mass ratio of the catalyst to the lignin is (1:1) - (1:8), and the mass ratio of the lignin to the reaction solvent is (1:50) - (1:100).
The specific operation conditions in the application process are as follows: introducing nitrogen at room temperature of 20-30 ℃ under the pressure of 0-6 MPa, heating to a target reaction temperature (220-300 ℃) for 30-100 min, stirring at the stirring speed of 400-800 rpm/min in the reaction process, stirring for 1-6h, naturally cooling to room temperature after the reaction is finished, and reducing the pressure to normal pressure.
The liquid product yield, monomer yield and monomer selectivity were all calculated according to the following formulas:
Figure DEST_PATH_IMAGE001
Y residues from the treatment of plant diseases Represents the residue rate after the reaction; y is Y Liquid product Representing the yield of liquid product; m is m Liquid product Representing the mass of the liquid product; m is m Lignin Represents the mass of lignin; y is Y Monomer(s) Represents the yield of the monomer; m is m Internal standard Represents the mass of the internal standard; delta Monomer(s) Represents the influencing factor of the monomer; s is S Area of monomer peak Representing the relative peak area of the monomers detected in the GC-MS; s is S Peak area of internal standard Representing the relative peak area of the internal standard detected in GC-MS. L (L) Monomer(s) Representing the selectivity of the monomer.
According to the method, ni and Zn are simultaneously loaded on the carrier by using an impregnation method, and the rapid dispersion of the mixed solution on the surface of the carrier and better entering into the pore canal can be promoted by using ultrasonic waves; the reduction of the metal is carried out by utilizing the self-reduction capability of the active carbon at high temperature, so that the reduction temperature of the simple substance Ni can be reduced, and the interaction between the metal and the carrier is facilitated; meanwhile, the existence of Zn not only can provide Lewis acid sites, but also can promote the high dispersion of Ni components and improve Ni in the catalyst 0 The content of (2) improves the catalytic activity; meanwhile, the active carbon with the advantages of large specific surface area, porous structure and the like is used as a carrier, so that the dispersibility of active metal and active catalytic sites are further improved, and the catalytic efficiency is further improved.
The invention also provides the Ni-Zn supported catalyst for lignin depolymerization, which is prepared by the method and is applied to lignin depolymerization, when the mass of the catalyst/the mass of lignin is=20% (corresponding to example 1), the liquid product yield after lignin hydrogenolysis can reach 73.1 wt%, the total monomer yield can reach 18.25 wt%, and when the mass of the catalyst/the mass of lignin is=40% (corresponding to example 5), the selectivity of the ester (compounds f and h) and aldehyde (compound g) monomer compounds is 36.43 wt% and 16.75 wt%, respectively.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention uses soluble nickel salt (such as nitric acidNickel) and zinc salts (such as zinc nitrate) as precursor materials, the preparation process is simple, safe, easy to control and low in manufacturing cost, and the Ni-Zn supported catalyst prepared by the method has the following advantages: (1) The ultrasonic effect can rapidly promote the dispersity of the metal on the carrier and enter the pore canal as much as possible, thereby being beneficial to the re-reaction of the small molecular compound; (2) Compared with H 2 The reduction of atmosphere and carbon reduction not only can reduce the reduction temperature of metal, but also can promote the interaction between the metal and the carrier and prevent the loss of the metal; (3) The metal nickel and zinc are uniformly dispersed on the active carbon carrier to form NiZn alloy, and the nickel and the metal and the Ni are used for preparing the nickel-zinc alloy 0 The synergistic effect between the metal site and the Lewis acid site improves the catalytic activity of the catalyst; (4) The liquid product of lignin has high yield, and ester compounds and 4-hydroxy-3, 5-dimethoxy phenylacetaldehyde in the product are used as main products, so that the selectivity is high. (5) The new way is developed for the utilization of lignin, so that the dependence on fossil resources such as petroleum and the like can be reduced, the added value of chemicals can be considered, and the economy is improved.
Drawings
FIG. 1 is a GC-MS spectrum of the liquid product of examples 1, 5.
FIG. 2 is XRD patterns of the Ni-Zn supported catalysts of examples 1 to 3 and the Ni supported catalyst of comparative example 1.
FIG. 3 is N of the Ni-Zn supported catalysts of examples 1 to 3 and the Ni supported catalyst of comparative example 1 2 Adsorption and desorption isotherm plot.
FIG. 4 is a Py-IR diagram of the Ni-Zn supported catalyst of example 1 and the Ni supported catalyst of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are all available from commercial sources.
Example 1
First, 0.99g nickel nitrate and 0.46g zinc nitrate (molar ratio of nickel to zinc is 2.2:1) were added to 3.8In mL deionized water, ultrasonic treatment is carried out for 4 min at the temperature of 30 ℃, the mixture is fully mixed to form a mixed solution, the solution is dropwise added to 2.0 g active carbon, ultrasonic treatment is carried out for 10 min at the temperature of 45 ℃, then standing is carried out for 7 h at the temperature of 30 ℃, and drying is carried out for 2 h at the temperature of 80 ℃ to obtain the black solid compound. Then transferring the catalyst into a tube furnace, and heating to 450 ℃ at a heating rate of 4 ℃/min under the nitrogen atmosphere of 80 mL/min to perform reduction activation for 4 h, thereby obtaining the Ni-Zn supported catalyst, wherein the mass percent of Ni is 10 wt%, and the mass percent of Zn is 5 wt%. The mass ratio of Zn/Ni was 50%, and the catalyst was designated as NiZn/AC-50. BET specific surface area of the catalyst is 1080 m 2 g -1 Average pore volume of 0.911 cm 3 g -1 The average pore size was 4.73 and nm.
Loading 0.5 g of organic-soluble corn stalk lignin and 0.1 g of Ni-Zn supported catalyst material into a hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline with nitrogen, and then filling 2 MPa of high-purity hydrogen into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, and the product after the hydrogenation and depolymerization is filtered and extracted and the physical properties of the liquid phase product are analyzed.
Example 2
Firstly, 0.99g nickel nitrate and 0.68 g zinc nitrate (molar ratio of nickel to zinc is 1.5:1) are added into 3.8 mL deionized water, ultrasonic treatment is carried out for 4 min at the temperature of 30 ℃, mixed solution is formed by fully mixing, the solution is dropwise added onto 2.0 g active carbon, ultrasonic treatment is carried out for 10 min at the temperature of 45 ℃, standing is carried out for 7 h at the temperature of 30 ℃, and drying is carried out for 2 h at the temperature of 80 ℃, so that a black solid compound is obtained. Then transferring the catalyst into a tube furnace, and heating to 450 ℃ at a heating rate of 4 ℃/min under the nitrogen atmosphere of 80 mL/min to perform reduction activation for 4 h, thereby obtaining the Ni-Zn supported catalyst, wherein the mass percent of Ni is 10 wt%, and the mass percent of Zn is 7.5 wt%. The mass ratio of Zn/Ni was 75%, and the catalyst was designated as NiZn/AC-75. BET specific surface area of catalyst 931 m 2 g -1 Average pore volume of 0.81 cm 3 g -1 The average pore size was 5.17. 5.17 nm.
Loading 0.5 g of organic-soluble corn stalk lignin and 0.1 g of Ni-Zn supported catalyst material into a hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline with nitrogen, and then filling 2 MPa of high-purity hydrogen into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, and the product after the hydrogenation and depolymerization is filtered and extracted and the physical properties of the liquid phase product are analyzed.
Example 3
Firstly, 0.99g nickel nitrate and 0.23 g zinc nitrate (the molar ratio of nickel to zinc is 4.5:1) are added into 3.8 mL deionized water, ultrasonic treatment is carried out for 4 min at the temperature of 30 ℃, the mixture is fully mixed to form a mixed solution, the solution is dropwise added onto 2g active carbon, ultrasonic treatment is carried out for 10 min at the temperature of 45 ℃, standing is carried out for 7 h at the temperature of 30 ℃, and 2 h is dried at the temperature of 80 ℃, so that a black solid compound is obtained. Then transferring the catalyst into a tube furnace, and heating to 450 ℃ at a heating rate of 4 ℃/min under the nitrogen atmosphere of 80 mL/min to perform reduction activation for 4 h, thereby obtaining the Ni-Zn supported catalyst, wherein the mass percent of Ni is 10 wt%, and the mass percent of Zn is 2.5 wt%. Theoretically, the mass ratio of Zn/Ni was 25%, and the catalyst was designated as NiZn/AC-25. BET specific surface area of the catalyst was 1122m 2 g -1 Average pore volume of 0.96 cm 3 g -1 The average pore size was 5.1. 5.1 nm.
Loading 0.5 g organic soluble corn stalk lignin and 0.1 g Ni-Zn supported catalyst material into a hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline with nitrogen, and then filling 2 MPa high-purity hydrogen into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, and the product after the hydrogenation and depolymerization is filtered and extracted and the physical properties of the liquid phase product are analyzed.
Figure 2 is an XRD spectrum of the catalyst. As can be seen from the graph, the synthesized series of catalysts have characteristic diffraction peaks of simple substance Ni at 2θ=44.3°,51.7 ° and 76.6 ° which are consistent with the Ni standard card (pdf#65-2865), and correspond to the (111), (200) and (220) crystal faces respectively. Diffraction characteristic peaks for oxidized NiO were not found in the spectra, probably because the low concentration of NiO was not detected or was in an amorphous state. As the Zn content increases, there is no characteristic diffraction peak with respect to Zn element at Zn/ni=25% and Zn/ni=50%, which may indicate that Zn element is highly dispersed in the structure of Ni or characteristic diffraction peaks of its oxide are observed due to a lower Zn content, and as the Zn content continues to increase, characteristic diffraction peaks of ZnO (31.8 °, 34.4 °, 36.3 °, 47.5 °, 56.6 °, 62.9 °, 68.0 ° and 69.1 °) appear in the NiZn/AC-75 catalyst, indicating that Zn species are aggregated. And with the addition of Zn, the characteristic diffraction peak of Ni starts to slightly shift to the left, indicating that the formation of the NiZn alloy is possible.
Example 4 (the reaction temperature during lignin depolymerization is different compared to example 1)
0.5 g organic soluble corn stalk lignin and 0.1 g of NiZn/AC-50 catalyst material in the example 1 are filled into a hastelloy reactor of a simulated suspension bed reactor, the reactor and air in a pipeline are purged by nitrogen, and then 2 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature is 220 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, and the product after the hydrogenation and depolymerization is filtered and extracted and the physical properties of the liquid phase product are analyzed.
Example 5 (compared to example 1, the amount of catalyst used in the depolymerization of lignin is different)
0.5 g organic soluble corn stalk lignin and 0.2g of NiZn/AC-50 catalyst material in the example 1 are filled into a hastelloy reactor of a simulated suspension bed reactor, the reactor and air in a pipeline are purged by nitrogen, and then 2 MPa high-purity hydrogen is filled into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, and the product after the hydrogenation and depolymerization is filtered and extracted and the physical properties of the liquid phase product are analyzed.
Example 6 (catalyst preparation compared to example 5, reduction activation temperature is different)
First, 0.99g nickel nitrate and 0.46g zinc nitrate (molar ratio of nickel to zinc of 2.2:1) were added to 3.8 mL deionized water, and the mixture was super heated at 30 ℃And (3) sound for 4 min, fully mixing to form a mixed solution, dropwise adding the solution onto 2g active carbon, performing ultrasonic treatment at 45 ℃ for 10 min, standing at 30 ℃ for 7 h, and drying at 80 ℃ for 2 h to obtain a black solid compound. Then transferring the catalyst into a tube furnace, and heating to 525 ℃ at a heating rate of 4 ℃/min under the nitrogen atmosphere of 80 mL/min for reduction and activation of 4 h to obtain the Ni-Zn supported catalyst. Wherein, the mass percent of Ni is 10 wt percent, and the mass percent of Zn is 5 wt percent. The mass ratio of Zn/Ni was 50%, and the catalyst was designated as NiZn/AC-50-525. BET specific surface area of 1126m for the catalyst 2 g -1 Average pore volume of 0.94 cm 3 g -1 The average pore size was 4.7. 4.7 nm.
Loading 0.5 g of organic-soluble corn stalk lignin and 0.2g of Ni-Zn supported catalyst material into a hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline with nitrogen, and then filling 2 MPa of high-purity hydrogen into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, and the product after the hydrogenation and depolymerization is filtered and extracted and the physical properties of the liquid phase product are analyzed.
Comparative example 1
Firstly, 0.99g nickel nitrate is added into 3.8 mL deionized water, ultrasonic treatment is carried out for 4 min at the temperature of 30 ℃, the solution is fully mixed to form a solution, the solution is dropwise added into 2g active carbon serving as a carrier, ultrasonic treatment is carried out for 10 min at the temperature of 45 ℃, then standing is carried out for 7 h at the temperature of 30 ℃, and drying is carried out for 2 h at the temperature of 80 ℃, so that a black solid compound is obtained. Then transferring into a tube furnace, and under the nitrogen atmosphere of 80 mL/min, heating to 525 ℃ at the heating rate of 4 ℃/min for reduction and activation of 4 h to obtain the Ni supported catalyst, wherein the Ni mass percent is 10 wt%, and the BET specific surface area of the catalyst is 1165m 2 g -1 Average pore volume of 0.96 cm 3 g -1 The average pore size was 4.66 and nm.
Loading 0.5 g organic soluble corn stalk lignin and 0.1 g Ni supported catalyst material into a hastelloy reactor of a simulated suspension bed reactor, purging the reactor and air in a pipeline with nitrogen, and then filling 2 MPa high-purity hydrogen into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature is 220 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm/min, and the product after the hydrogenation and depolymerization is filtered and extracted and the physical properties of the liquid phase product are analyzed.
The yields of the reaction products obtained in the above examples and comparative examples are shown in Table 1.
Table 1 comparison of yields of examples and comparative phenolic monomers
Figure 17956DEST_PATH_IMAGE002
The yields of the objective products obtained in the above examples and comparative examples are shown in table 2.
TABLE 2 yields and selectivity comparisons of example and comparative examples target monomers
Figure DEST_PATH_IMAGE003
Figure DEST_PATH_IMAGE005
From the reaction data (examples 1-3), as the Zn loading was increased, the liquid yield was decreased and the residue rate was increased on the basis of the fixed Ni loading, indicating that the acidic sites provided by ZnO promoted the refolding of the product intermediate; while the monomer ratio tends to increase and decrease with increasing Zn loading, the molar ratio of nickel to zinc is 2.2:1, this is best achieved, probably because the hydrogenolysis reaction during lignin depolymerization is in competition with the repolymerization, the molar ratio of nickel to zinc being 2.2:1 is preceded by hydrogenolysis reaction, and along with the increase of Lewis acid sites provided by ZnO, the depolymerization depth of lignin is promoted, and meanwhile, side reaction-the progress of the repolymerization reaction is also promoted; the molar ratio of nickel to zinc is 2.2:1, the Ni metal site and the Lewis acid site provided by ZnO reach proper synergistic effect, and the monomer yield obtained under the condition is maximum and the maximum benefit is achieved; the molar ratio of nickel to zinc is 2.2: after 1, there may be a dominant site for the repolymerization reaction, resulting in a decrease in monomer yield and an increase in residue rate.
From the reaction data (examples 1 and 4), the reaction temperature has a great influence on depolymerization of lignin, and the reason why the monomer yield in the depolymerization reaction at 220℃is low compared to the supercritical reaction system at 260℃may be that the depolymerization reaction is not sufficiently progressed. Under subcritical conditions, the energy conditions required for breaking the C-O or C-C bond linkage in the lignin macromolecular structure monomer are not reached, and the macromolecular structure is not broken off in the form of small molecular monomers, so that the phenomenon that the yield of monomers is low due to depolymerization of lignin is caused. In contrast, 260 ℃ is a suitable reaction temperature.
From the reaction data (examples 1, 5), as the catalyst amount increases, the residue rate increases, the yield of liquid product and the total monomer yield decreases, but the monomer yields of 4-ethylphenol, 4-ethylcycloguaiacol decrease, and the monomer yields of methyl p-hydroxyphenylpropionate, methyl dihydroferulate increase, which may be the monomer intermediates of hydroxycinnamic acid and ferulic acid produced by depolymerization of gramineous lignin, have two main reaction pathways: esterification with methanol is carried out, one is decarbonylation free radical reaction, and the two paths have competition. The catalyst amount is increased, so that the substrate can be fully contacted with the active site of the catalyst, and the reduction degradation degree of lignin is deepened. At the same time, the degree of reductive depolymerization is deepened, the side reaction, namely the heavy polymerization reaction, is obviously aggravated, the liquid yield is reduced, and the residue rate is increased. Example 1 works best in terms of total monomer yield; whereas example 5 works best in terms of the choice of target monomer.
From the reaction data (examples 5 and 6), the yield and the residue rate of the liquid product did not change much with the increase in the reduction-activation temperature of the catalyst, but the total monomer yield and the target monomer yield increased, which is probably that the increase in the reduction temperature promoted the metal-active Ni 0 The increase in content promotes the depolymerization process of lignin. But is provided withIs a decrease in selectivity for esters and aldehydes, which indicates Ni 0 The increase in the content of (c) tends to promote the progress of other reactions, decreasing the selectivity of esters and aldehydes.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (1)

1. The application of the Ni-Zn supported catalyst in the hydrogenation and depolymerization of lignin suspension bed is characterized in that: filling 0.5 g organic solvent corn stalk lignin and 0.2g Ni-Zn supported catalyst material into a hastelloy reactor of a simulated suspension bed reactor, purging air in the reactor and a pipeline with nitrogen, and filling 2 MPa high-purity hydrogen into the suspension bed reactor for hydrogenation reaction under the following reaction conditions: the temperature is 260 ℃, the hydrogen pressure is 2 MPa, the stirring speed is 700 rpm, and the product after the hydrogenation and depolymerization is filtered and extracted and the physical properties of the liquid phase product are analyzed;
the preparation method of the Ni-Zn supported catalyst comprises the following steps:
first, the molar ratio of nickel to zinc is 2.2:1, adding 0.99g nickel nitrate and 0.46g zinc nitrate into 3.8 mL deionized water, carrying out ultrasonic treatment at 30 ℃ for 4 min, fully mixing to form a mixed solution, dropwise adding the solution onto 2.0 g active carbon, carrying out ultrasonic treatment at 45 ℃ for 10 min, standing at 30 ℃ for 7 h, drying at 80 ℃ for 2 h to obtain a black solid compound, transferring the black solid compound into a tubular furnace, and carrying out reduction and activation at a heating rate of 4 ℃/min to 450 ℃ for 4 h under a nitrogen atmosphere of 80 mL/min to obtain the Ni-Zn supported catalyst, wherein the Ni mass percentage is 10 wt%, the Zn mass percentage is 5 wt%, and the specific surface area of the catalyst is 1080 m 2 g -1 Average pore volume of 0.911 cm 3 g -1 The average pore size was 4.73 and nm.
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