阅读说明：本技术 一种基于液相重整体系解聚木质素制备4-乙基苯酚的方法 (Method for preparing 4-ethylphenol by depolymerizing lignin based on liquid phase reforming system ) 是由 李雪辉 李昊天 梁晋榕 龙金星 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种基于液相重整体系解聚木质素制备4-乙基苯酚的方法；该方法以木质素作为原料,在溶剂中,加入Ru/C催化剂,经惰性气体置换并充压至0.1～2MPa后,控制温度于220～280℃,搅拌下反应1～8h,将木质素催化降解为单酚类化学品；单酚类化学品主要为对羟苯基类衍生物的4-乙基苯酚。本发明工艺简单,反应条件温和,无外加氢源下可实现木质素氢解,单酚收率为20.9％,4-乙基苯酚收率为93.1mg/g,选择性高达44.5％,所得小分子物质可用于制备医药中间体或食品添加剂等高附加值化学品。(The invention discloses a method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system; the method comprises the steps of taking lignin as a raw material, adding a Ru/C catalyst into a solvent, replacing the mixture by inert gas, pressurizing the mixture to 0.1-2MPa, controlling the temperature to be 220-280 ℃, reacting the mixture for 1-8 hours under stirring, and catalytically degrading the lignin into monophenol chemicals; the monophenol chemicals are mainly 4-ethylphenol which is a p-hydroxyphenyl derivative. The method has the advantages of simple process, mild reaction conditions, no additional hydrogen source, realization of lignin hydrogenolysis, monophenol yield of 20.9%, 4-ethylphenol yield of 93.1mg/g, and selectivity of 44.5%, and the obtained micromolecule substance can be used for preparing high-value-added chemicals such as medical intermediates or food additives.)

1. A method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system is characterized by comprising the following steps: taking lignin as a raw material, adding a Ru/C catalyst into a liquid phase reforming solvent, controlling the temperature to be 220-280 ℃, reacting for 1-8 hours under stirring under the condition of inert gas pressure of 0.1-2Mpa, and catalytically degrading the raw material into a monophenol product taking 4-ethylphenol as a main product; the Ru/C catalyst comprises a catalyst carrier, namely activated carbon and an active component Ru: the liquid phase reforming solvent consists of ultrapure water and alcohols: the alcohol is C1-C3 fatty alcohol.

2. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 1, wherein: the active component contains Ru accounting for 1-5% of the total mass of the catalyst.

3. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 1, wherein: the volume ratio of the alcohols to the ultrapure water is 4:1-1: 1.

4. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 1, wherein: the mass ratio of the Ru/C catalyst to the lignin is 0.1-0.5: 1.

5. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 1, wherein: the mass ratio of the liquid phase reforming solvent to the lignin is 300: 1-2.

6. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 1, wherein: the liquid phase reforming solvent is obtained by uniformly mixing ultrapure water and alcohols; the inert gas is nitrogen, argon or helium.

7. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 1, wherein: the lignin is agriculture and forestry herbaceous lignin.

8. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 7, wherein: the agroforestry herbal lignin is derived from bagasse, bamboo, miscanthus, corncobs, wheat straw, corn straw or rice straw.

9. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 8, wherein: the agriculture and forestry herbaceous lignin is extracted by the following method: adding 30 parts of deionized water, 100-150 parts of ethanol, 1.5-2.0 parts of sulfuric acid and 10-15 parts of agriculture and forestry herb powder into a reaction kettle by mass fraction, reacting at 110-130 ℃ for 2-6h, filtering and separating, adding deionized water into a liquid phase, filtering and separating, wherein the obtained solid phase is lignin.

10. The method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system according to claim 1, wherein: the rotating speed of the stirring is 300-800 r/min.

Technical Field

The invention relates to 4-ethylphenol, in particular to a method for preparing 4-ethylphenol by utilizing liquid phase reforming Ru/C catalyst to prepare hydrogen and depolymerize lignin, and belongs to the field of high-value utilization of renewable biomass.

Background

Currently, the consumption of fossil energy and the emission of greenhouse gases are increasing, and the development of renewable energy becomes a research hotspot, and many researchers focus on the utilization of renewable energy. In the renewable energy field, biomass resources have entered the field of scientists as the only renewable resource containing fixed carbon. Biomass resources consist of cellulose, hemicellulose and lignin resources. As a renewable aromatic polymer with wide sources in nature, lignin can be degraded into a phenol monomer, and the lignin has a plurality of applications in the fields of biological fuels, food additives and medicines. Therefore, efficient and directional conversion of lignin into high value-added chemicals has attracted extensive attention of researchers.

Currently, lignin can be depolymerized by pyrolysis, hydrogenolysis, oxidation, and the like to yield over 100 phenolic products. Researchers have made great efforts in optimizing the lignin depolymerization process, but still have the characteristics of complicated reaction flow, harsh reaction conditions, low product selectivity and yield, and difficult separation. The difficulty is that a catalyst and a catalytic system are scientifically constructed, high-selectivity depolymerization of lignin under mild conditions is realized, and chemicals with high added values are obtained. Therefore, the method for preparing monophenol by high-selectivity catalytic depolymerization of lignin is developed, and has great significance for realizing high-valued utilization of biomass and breaking through the development bottleneck of fossil energy.

4-ethylphenol is mainly used as phenolic resin, rubber anti-aging agent, plastic anti-aging agent and surfactant at present; GB 2760-1996 states food flavors which are approved for use. In addition, it can also be used for preparing essence such as whisky, rum, smoked pork, ham, coffee, etc. Meanwhile, 4-ethylphenol can be used as an organic synthesis intermediate and a chemical reagent, is an important pesticide intermediate, and can be used for producing a series of high-grade, low-toxicity and low-residue pesticides. The conventional preparation method of 4-ethylphenol is characterized in that phenol and ethanol are used as raw materials, anhydrous aluminum oxide is used as a catalyst, and the reaction is carried out at 350-430 ℃ and 4.0-4.5 MPa to prepare the 4-ethylphenol. The defects of the method are that the raw materials are expensive, the production cost is high, the reaction conditions are severe, and the like.

Chinese patent 201710466874X discloses a method for preparing 4-ethylphenol by selective hydrogenolysis of lignin. Adding lignin, a nickel catalyst and a reaction solvent into a reaction kettle, sealing, filling hydrogen, controlling the pressure in the reaction kettle to be 0-4Mpa, and reacting at the temperature of 210-290 ℃ for 1-5 h; after the reaction, filtering the reaction liquid to obtain a liquid product containing 4-ethylphenol and a recovered catalyst; the nickel catalyst consists of a carrier and nickel metal loaded on the carrier; the catalyst can promote the generation of 4-ethylphenol in the hydrogenolysis process of lignin. The method obtains the 4-ethylphenol by loading nickel metal hydrogenolysis lignin on a carrier, the highest yield is lower than 70mg/g, and meanwhile, the reaction atmosphere of the method is hydrogen, and the hydrogen is known to be expensive, dangerous, flammable and explosive in reaction operation. Therefore, a method for efficiently hydrogenating and polymerizing lignin to obtain 4-ethylphenol under the condition of no hydrogen is urgently needed, and the yield and the selectivity of the target product obtained by the method are high.

Chinese patent 2014105583251 discloses a method for preparing 4-ethylphenol by catalytic pyrolysis of biomass with palladium catalyst. According to the method, biomass is used as a raw material, the biomass and a palladium catalyst are mechanically mixed and then are subjected to fast pyrolysis at 250-380 ℃ under an anaerobic condition, and pyrolysis gas is condensed to obtain a liquid product rich in 4-ethylphenol. The liquid product can be simply separated and purified to obtain the 4-ethylphenol. In addition, the method takes biomass with low price and wide sources as raw materials, and can obviously reduce the production cost of the 4-ethylphenol. The method prepares the 4-ethylphenol by catalytic pyrolysis of biomass by using the palladium catalyst, the yield is lower than 20mg/g, meanwhile, the pyrolysis gas contains hydrogen and inert gas, the reaction atmosphere is expensive and dangerous to operate, and the temperature range (250 ℃ and 380 ℃) is higher. Therefore, a method for preparing 4-ethylphenol by hydro-polymerizing lignin without an external hydrogen source is urgently needed, the yield and the selectivity of the target product are high, the conditions of the method are mild, and the operation is safe.

The Chinese patent application 2017101275166 relates to a method for preparing 4-ethylphenol by catalytic pyrolysis of bagasse by activated carbon. The invention takes bagasse as raw material and active carbon as catalyst, wherein the active carbon is prepared from biomass by a steam activation method; mechanically mixing bagasse and the activated carbon, performing catalytic pyrolysis at 240-410 ℃ in a hydrogen atmosphere, and condensing pyrolysis gas to obtain a liquid product rich in 4-ethylphenol; the yield of 4-ethylphenol and its purity in the liquid product are both high. In addition, the method takes bagasse with wide sources as raw material and active carbon with low price as catalyst, and can obviously reduce the production cost of 4-ethylphenol. According to the method, 4-ethylphenol is prepared by catalytically pyrolyzing bagasse by using activated carbon, the highest yield is lower than 50mg/g, meanwhile, the pyrolysis gas temperature is 240-410 ℃, the temperature condition is harsh, the hydrogen concentration is 2-14 vol%, and the operation of the reaction atmosphere is dangerous and expensive. Therefore, a method for preparing 4-ethylphenol by hydro-polymerizing lignin without an external hydrogen source is urgently needed, the yield and the selectivity of the target product are high, the conditions of the method are mild, and the operation is safe.

The chinese invention patent 2020101021570 relates to a method for preparing ethylbenzene from lignocellulose, which comprises the following steps: mixing a lignin raw material, a first catalyst and a first solvent, carrying out a first reaction to degrade lignin to obtain a lignin monomer, and separating and purifying to obtain a first product; mixing the obtained first product with a second catalyst and a second solvent, and carrying out a second reaction to obtain a second product; and mixing the obtained second product with isopropanol, a third catalyst and a third solvent to carry out a third reaction to obtain ethylbenzene. In the first step, the yield of the lignin monomer can reach 43-58 wt%, in the second step, the yield of the 4-ethylphenol compound can reach 66-86 wt%, and in the third step, the selectivity of the ethylbenzene can reach 77 wt%. The reaction condition of the used catalytic system is mild, the product yield is high, and the expanded production is easy. The method degrades lignocellulose into ethylbenzene by three steps, wherein 6 4-ethylphenol compounds with the total weight of 66-86 wt% are generated in the second step, so that the selectivity is poor and the reaction steps are complex. Therefore, a method for preparing 4-ethylphenol by hydro-polymerizing lignin without an external hydrogen source is urgently needed, the yield and the selectivity of the target product are high, the conditions of the method are mild, and the operation is safe.

Disclosure of Invention

The invention aims to provide a method for selectively degrading lignin into high-added-value phenol micromolecule chemicals by a liquid phase reforming system, which realizes no additional hydrogen source in the reaction process under the combined action of a liquid phase reforming catalyst and a solvent, improves the product yield of 4-ethylphenol, and has the selectivity of 4-ethylphenol as high as 44.5 percent and the yield of monophenol as high as 20.9 percent. Compared with a non-liquid phase reforming system, the selectivity of 4-ethylphenol is improved by 10.1-19.8%, and the yield of monophenol is improved by 27.2-50.5%.

The liquid phase reforming hydrogen production refers to that polyhydric alcohol and water generate reforming reaction to generate hydrogen under the condition of a catalyst. Compared with the hydrogen production by steam reforming, the hydrogen production by liquid phase reforming has the advantages of low reaction temperature, low energy consumption, high hydrogen purity, low price, easy obtaining and the like, so that the hydrogen production by liquid phase reforming has practical application potential and wide research value in low-temperature preparation and high-efficiency storage and transportation of hydrogen. The method utilizes a liquid phase reforming system to produce hydrogen, and prepares the 4-ethylphenol by carrying out hydrogenolysis on the lignin at the catalyst condition in one step with high selectivity, without adding an additional hydrogen source, and is safe and environment-friendly.

The purpose of the invention is realized by the following technical scheme:

a method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system comprises the following steps: taking lignin as a raw material, adding a Ru/C catalyst into a liquid phase reforming solvent, controlling the temperature to be 220-280 ℃, reacting for 1-8 hours under stirring under the condition of inert gas pressure of 0.1-2Mpa, and catalytically degrading the raw material into a monophenol product taking 4-ethylphenol as a main product; the Ru/C catalyst comprises a catalyst carrier, namely activated carbon and an active component Ru: the liquid phase reforming solvent consists of ultrapure water and alcohols: the alcohol is C1-C3 fatty alcohol.

In order to further achieve the aim of the invention, preferably, the active component contains Ru accounting for 1-5% of the mass of the whole catalyst.

Preferably, the volume ratio of the alcohol to the ultrapure water is 4:1-1: 1.

Preferably, the mass ratio of the Ru/C catalyst to the lignin is 0.1-0.5: 1.

Preferably, the mass ratio of the liquid phase reforming solvent to the lignin is 300: 1-2.

Preferably, the liquid phase reforming solvent is obtained by uniformly mixing ultrapure water and alcohols; the inert gas is nitrogen, argon or helium.

Preferably, the lignin is agroforestry herbaceous lignin.

Preferably, the agroforestry herbal lignin is derived from bagasse, bamboo, miscanthus, corncobs, wheat straw, corn stover, or rice straw.

Preferably, the agroforestry herbaceous lignin is extracted by the following method: adding 30 parts of deionized water, 100-150 parts of ethanol, 1.5-2.0 parts of sulfuric acid and 10-15 parts of agriculture and forestry herb powder into a reaction kettle by mass fraction, reacting at 110-130 ℃ for 2-6h, filtering and separating, adding deionized water into a liquid phase, filtering and separating, wherein the obtained solid phase is lignin.

Preferably, the rotation speed of the stirring is 300-800 r/min.

Compared with the prior art, the invention has the following advantages and effects:

1) the liquid phase reforming hydrogen production system adopted by the invention has the characteristics of simple operation, safe process, mild conditions, economy, environmental protection and the like, can produce hydrogen with high efficiency without adding a hydrogen source, and achieves the aim of depolymerizing lignin;

2) the yield of monophenol biomass chemicals obtained by hydrogenolysis of lignin is up to 209.2mg/g, and the yield of 4-ethylphenol is 93.1 mg/g; compared with a non-liquid phase reforming system, the yield of monophenols is improved by 50.5%, the yield of 4-ethylphenol is improved by 19.8%, and compared with the existing lignin hydrogenation depolymerization route and method, the yield and selectivity have obvious advantages;

3) compared with the existing conditions that the hydrogen pressure is generally higher than 5MPa and the depolymerization temperature is higher than 300 ℃ in the lignin depolymerization process, the method controls the reaction pressure to be in the range of 0.1-2MPa and the reaction temperature to be within 280 ℃, and has lower requirements on equipment;

4) the invention has simple process condition and can realize batch reaction or continuous reaction.

Drawings

FIG. 1 is a graph showing the hydrogen production of Ru/C at various times.

FIG. 2 is a graph showing the peak time of the product detected by the mass spectrometry in example 1.

FIG. 3 is a mass spectrum of a 4-ethylphenol standard sample.

Detailed Description

For a better understanding of the present invention, the present invention is further illustrated below with reference to the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto.

The method for measuring the hydrogen content based on the RK real gas state equation comprises the following steps:

wherein a and b are respectively:

p: gas pressure in pascals (pa)

V: gas molar volume in units of cubic meters per mole (m)³/mol)

T: temperature, unit Kelvin (K)

R: gas constant, value 8.314J/(mol. K)

a: correction constants for correcting intermolecular attraction

b: correction constant for correcting volume

The RK real gas equation is applicable to the conditions: the accuracy of nonpolar gases such as hydrocarbon, nitrogen, hydrogen and the like is good, the applicable temperature and pressure ranges are wide, and the nonpolar gases are not applicable to polar gases generally.

When Ar is selected as an internal standard gas, the critical temperature and the critical pressure are as follows:

Tc＝250.71K，Pc＝4.9Mpa

tc: the critical temperature, the maximum temperature at which a substance changes from a gaseous state to a liquid state, is called the critical temperature. Each substance has a specific temperature above which the gaseous substance does not liquefy, no matter how the pressure is increased, which is the critical temperature.

Pc: the critical pressure, the minimum pressure required to liquefy the gas at the critical temperature. I.e. the saturated vapour pressure of the liquid at the critical temperature.

And (4) calculating the hydrogen production of the liquid phase reforming system by combining the RK real gas state equation and the gas chromatography.

Comparative example 1

A method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system does not add a catalyst and comprises the following operation steps:

weighing 0.1g of bagasse lignin, adding 30ml of liquid phase reforming solvent (ultrapure water: methanol: 1:4, volume ratio) into a 50ml reaction kettle, completely sealing, introducing argon to ensure that the pressure is 1Mpa, then evacuating, repeating for three times to achieve the purpose of replacing air, finally introducing argon to maintain the pressure at 1Mpa, reacting for 4 hours at 250 ℃, and stirring at 700 r/min. Cooling to room temperature after the reaction, collecting gas product with air bag, filtering reaction solution, adding internal standard solution (internal standard is dimethyl phthalate, 0.2g dimethyl phthalate is added into 9.8g methanol and mixed uniformly to obtain 2 wt% internal standard solution, weighing about 0.2g each time, the same below) into the filtered reaction solution, taking 5ml solution and removing water with anhydrous magnesium sulfate, adopting gas chromatography-mass spectrometry (FBX-WAX MS-0.25mm-0.25 μm-30 μm-Crossbond. heating program: maintaining 50 deg.C for 1min, and heating at 10 deg.C. min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

Volatile components in the sample can be obtained through gas chromatography-mass spectrometry analysis. In the case of known quality of the internal standard dimethyl phthalate, the product content is determined on the basis of the internal standard method: the yield of monophenol chemicals is 63.1mg/g and the conversion rate of lignin is 60.3 percent. Due to no addition of the catalyst, the hydrogen production is ignored, the reaction is not sufficiently carried out, the product is mainly pyrolyzed unsaturated product 4-vinylphenol, the yield is 37.4mg/g, and the yield of 4-ethylphenol is only 9.5 mg/g.

Comparative example 2

A method for preparing 4-ethylphenol by catalyzing selective depolymerization of lignin by using a single solvent methanol as a reaction medium is added with a catalyst.

Weighing 0.1g of bagasse lignin and 0.05g of 5 wt% (0.05g of catalyst only contains 5% of Ru) Ru/C catalyst, adding 30ml of methanol into a 50ml high-pressure reaction kettle, completely sealing, filling argon to ensure that the air pressure is 1Mpa, then emptying, repeating for three times to achieve the purpose of replacing air, finally filling argon to maintain the pressure to be 1Mpa, reacting for 4 hours at 250 ℃, and stirring at the speed of 700 r/min. Cooling to room temperature after the reaction, collecting gas product with air bag, filtering reaction solution, adding internal standard solution (internal standard is dimethyl phthalate, 0.2g dimethyl phthalate is added into 9.8g methanol and mixed uniformly to obtain 2 wt% internal standard solution, weighing about 0.2g each time, the same below) into the filtered reaction solution, taking 5ml solution and removing water with anhydrous magnesium sulfate, adopting gas chromatography-mass spectrometry (FBX-WAX MS-0.25mm-0.25 μm-30 μm-Crossbond. heating program: maintaining 50 deg.C for 1min, and heating at 10 deg.C. min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

The qualitative analysis of the product obtained by GC-MS was carried out, while the quality of the product was obtained by internal standard integration (see Table 1).

TABLE 1 Classification and Mass fraction of volatile products from GC-MS measurements

Corresponding lignin conversion (C)_L) Yield of volatile product (Y)_VP) Yield of 4-ethylphenol (4-EP) (Y)_4-EP) And selectivity (S) thereof_4-EP) Calculated according to the formulas (1-1) to (1-4). Wherein, W_FAnd W_RRepresents the weight of the original lignin and the regenerated lignin; w_VPAnd W_4-EPThe weight of total volatile products and 4-ethylphenol, respectively.

The volatile components in the sample are obtained by gas chromatography-mass spectrometry analysis. The product content can be determined based on an internal standard method: the yield of monophenolic chemicals was 129.1mg/g, with a yield of 46.1mg/g 4-ethylphenol and a selectivity of 35.7% by calculation. As only pure methanol is used as a solvent, the hydrogen yield of the system is only 0.418mmol, which is not enough for completely hydrogenolyzing lignin, and shows that the alcoholysis lignin is incomplete, the yield of monophenol and the selectivity of 4-ethylphenol are low, and the products are mainly 4-ethylphenol and propenyl guaiacol.

Example 1

A method for preparing 4-ethylphenol by depolymerizing lignin based on a liquid phase reforming system comprises the following operation steps:

(1) hydrogen production test of Ru/C catalyst in liquid phase reforming solvent: adding 24mL of methanol, 6mL of ultrapure water and 0.05g of Ru/C catalyst into a 50mL high-pressure reaction kettle, stirring at 250 ℃ and 1Mpa Ar atmosphere at the rotating speed of 700r/min for 1, 2, 3, 4, 5, 6, 7 and 8 hours, and collecting gas by using a gas bag after the reaction is cooled to room temperature. Injecting the gas into an Agilent 7820A gas chromatograph, performing gas separation in a chromatographic column CP-Molsieve 5A, and detecting the peak area of argon and hydrogen by a TCD detector. The absolute molar quantity of argon in the kettle at room temperature can be obtained by applying a RK real gas state equation, and the absolute molar quantity of hydrogen can be obtained by calculating by using an internal standard method. The molar quantity of the generated hydrogen within different reaction time (1-8 h) is sequentially measured, and is shown in figure 1. From fig. 1, it can be observed that the Ru/C catalyst can catalyze methanol and ultrapure water to generate hydrogen, and the hydrogen amount of the reaction system increases with time, which indicates that the liquid phase reforming system does generate hydrogen, and the capability of the system for hydrogenolysis of lignin is verified in the next step.

(2) Catalytic depolymerization of lignin: weighing 0.1g of bagasse lignin (the bagasse lignin is extracted by the following method, by mass fraction, adding 30 parts of deionized water, 100 parts of ethanol, 2.0 parts of sulfuric acid and 10 parts of dry bagasse into a reaction kettle, reacting at 120 ℃ for 4 hours, filtering and separating, adding deionized water into a liquid phase, filtering and separating, wherein the obtained solid phase is the bagasse lignin, 0.05g of 5 wt% (0.05g of catalyst which only contains 5 wt% of Ru) Ru/C catalyst, uniformly mixing 24ml of methanol and 6ml of ultrapure water, adding into a 50ml high-pressure reaction kettle, completely sealing, filling argon to ensure that the air pressure is 1Mpa, then emptying, repeating for three times, and achieving the purpose of replacing air. And finally, filling argon to maintain the pressure at 1Mpa, and reacting at 250 ℃ for 4h at the stirring speed of 700 r/min. And (3) cooling to room temperature after the reaction is finished, collecting a gas product by using an air bag, and analyzing the residual amount of the hydrogen in an Agilent 7820A gas chromatography. Filtering the reaction solution, adding an internal standard solution (the internal standard substance is dimethyl phthalate, 0.2g of dimethyl phthalate is added into 9.8g of methanol and mixed uniformly to obtain 2 wt% of internal standard solution, about 0.2g is weighed when the internal standard solution is used each time, the same is used below) into the filtered reaction solution, taking 5ml of the solution, removing water by using anhydrous magnesium sulfate, adopting gas chromatography-mass spectrometry (FBX-WAX MS-0.25mm-0.25 mu m-30m-Cross bond. heating program: maintaining the temperature at 50 ℃ for 1min, and maintaining the temperature at 10 ℃ for min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

GC-MS-FID spectra of the product can be obtained by GC-MS (gas chromatography-mass spectrometry) analysis (figure 2), volatile components in the sample can be obtained by GC-MS analysis, and the content of the product is calculated based on the known mass of the dimethyl phthalate serving as an internal standard: in the embodiment, the hydrogen yield is 3.25mmol, the residual hydrogen content in the reaction is 0.66mmol, the calculated hydrogen consumption is 2.59mmol, the lignin conversion rate is 91.3%, the yield of monophenol chemicals is up to 209.21mg/g, the product is mainly p-hydroxyphenyl (H) derivatives, the yield of 4-ethylphenol is 93.1mg/g, and the selectivity is up to 44.5%. Other products detected by the GC-MS are guaiacyl (G) unit ethyl guaiacol 14.7mg/G, propyl guaiacol 26.8mg/G, propenyl guaiacol 17.8mg/G and syringyl (S) unit 4-allyl-2, 6-dimethoxyphenol 20.2 mg/G.

FIG. 3 shows the mass spectrum of a 4-ethylphenol standard sample obtained by injecting the 4-ethylphenol standard sample into a GC, and the comparison shows that the main product is 4-ethylphenol.

The hydrogen production effect of the liquid phase reforming solvent introduced in example 1 is significantly enhanced relative to the depolymerization systems of comparative examples 1 and 2. Compared with comparative example 1 and comparative example 2, the yield of monophenol chemical is increased by 69.8% and 38.2%, and the selectivity of 4-ethylphenol is increased by 29.5% and 8.79%, respectively. Compared with pyrolysis and alcoholysis, the method combines lignin depolymerization and liquid-phase reforming hydrogen production, and the Ru/C catalyst not only participates in the solvent liquid-phase reforming hydrogen production, but also catalyzes the lignin depolymerization in the reaction process, so that the coupling effect of the solvent hydrogen production and the lignin depolymerization of the catalyst is reflected, and the yield of monophenol chemicals and the selectivity of target products are improved.

Example 2

Catalytic depolymerization of lignin: weighing 0.1g of bagasse lignin (the bagasse lignin is extracted by the following method, by mass fraction, adding 30 parts of deionized water, 150 parts of ethanol, 1.5 parts of sulfuric acid and 15 parts of agriculture and forestry herb powder into a reaction kettle, reacting at 110 ℃ for 6 hours, filtering and separating, adding deionized water into a liquid phase, filtering and separating, wherein the obtained solid phase is the bagasse lignin), 0.05g of 5 wt% (0.05g of catalyst contains 5% of Ru) Ru/C catalyst and the proportion of a liquid phase reforming solvent: 20ml of methanol and 10ml of ultrapure water were measured to obtain a liquid-phase reforming solvent prepared in a volume ratio of 1:1, and the two were mixed uniformly. Adding the proportioned liquid phase reforming solvent into 50ml of high pressureAnd (3) completely sealing the reaction kettle, filling argon to ensure that the pressure is 1Mpa, then evacuating, repeating for three times to achieve the purpose of replacing air, finally filling argon to maintain the pressure to be 1Mpa, reacting for 4 hours at 250 ℃, and stirring at the speed of 700 r/min. And (3) cooling to room temperature after the reaction is finished, collecting a gas product by using an air bag, and analyzing the residual amount of the hydrogen in an Agilent 7820A gas chromatography. Filtering the reaction solution, adding an internal standard solution (the internal standard substance is dimethyl phthalate, 0.2g of dimethyl phthalate is added into 9.8g of methanol and mixed uniformly to obtain 2 wt% of internal standard solution, about 0.2g is weighed when the internal standard solution is used each time, the same is used below) into the filtered reaction solution, taking 5ml of the solution and removing water by anhydrous magnesium sulfate, adopting gas chromatography-mass spectrometry (FBX-WAX MS-0.25mm-0.25 μm-30m-Cross bond. heating program: maintaining the temperature at 50 ℃ for 1min, and maintaining the temperature at 10 ℃ for min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

Volatile components in the sample are obtained through gas chromatography-mass spectrometry analysis, and the content of the product is calculated based on the known mass of the internal standard dimethyl phthalate: in this example, theoretical hydrogen amount is 4.03mmol, and hydrogen amount remained in the reaction is 1.20mmol, and the calculated hydrogen consumption is 2.83mmol, the conversion rate of lignin is 81.1%, the yield of monophenol chemicals is 164.2mg/g, the yield of 4-ethylphenol is 79.8mg/g, and the selectivity is 48.6%. Due to the reduced methanol ratio, the solubility for lignin is insufficient, resulting in reduced yield and selectivity.

Example 3

Catalytic depolymerization of lignin: weighing 0.1g of bagasse lignin (the bagasse lignin is extracted by the following method, by mass fraction, adding 30 parts of deionized water, 120 parts of ethanol, 1.8 parts of sulfuric acid and 12 parts of agriculture and forestry herb powder into a reaction kettle, reacting for 3 hours at 130 ℃, filtering and separating, adding deionized water into a liquid phase, filtering and separating, wherein the obtained solid phase is the bagasse lignin), 0.03g of 5 wt% (0.05g of catalyst only contains 5% of Ru) Ru/C catalyst, uniformly mixing 24ml of methanol and 6ml of ultrapure water, adding the mixture into a 50ml high-pressure reaction kettle, completely sealing, filling argon to ensure that the air pressure is 1Mpa, emptying, repeating for three times to achieve the purpose of replacing air, filling argon to maintain the pressure to be 1Mpa, and reacting at 250 ℃ for three times4h, the stirring speed is 700 r/min. And (3) cooling to room temperature after the reaction is finished, collecting a gas product by using an air bag, and analyzing the residual amount of the hydrogen in an Agilent 7820A gas chromatography. Filtering the reaction solution, adding an internal standard solution (the internal standard substance is dimethyl phthalate, 0.2g of dimethyl phthalate is added into 9.8g of methanol and mixed uniformly to obtain 2 wt% of internal standard solution, about 0.2g is weighed when the internal standard solution is used each time, the same is used below) into the filtered reaction solution, taking 5ml of the solution, removing water by using anhydrous magnesium sulfate, adopting gas chromatography-mass spectrometry (FBX-WAX MS-0.25mm-0.25 mu m-30m-Cross bond. heating program: maintaining the temperature at 50 ℃ for 1min, and maintaining the temperature at 10 ℃ for min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

Volatile components in the sample are obtained through gas chromatography-mass spectrometry analysis, and the content of the product is calculated based on the known mass of the internal standard dimethyl phthalate: in this example, theoretical hydrogen amount is 2.42mmol, and residual hydrogen amount in the reaction is 0.51mmol, and the hydrogen consumption is calculated to be 1.91mmol, the conversion rate of lignin is 75.1%, the yield of monophenol chemicals is 159.3mg/g, wherein the yield of 4-ethylphenol is 71.4mg/g, and the selectivity is 44.8%. Due to the reduction of the using amount of the catalyst, the hydrogen production of the system and the lignin hydrogenation process are influenced, so that the yield and the selectivity are reduced.

Example 4

Catalytic depolymerization of lignin: weighing 0.1g of corn straw lignin (the corn straw lignin is extracted by the following method that 30 parts of deionized water, 110 parts of ethanol, 1.6 parts of sulfuric acid and 15 parts of agriculture and forestry herb powder are added into a reaction kettle by mass fraction, the mixture is reacted for 4 hours at 110 ℃ and then filtered and separated, the liquid phase is added with the deionized water and then filtered and separated, the obtained solid phase is the corn straw lignin, 0.05g of 5 wt% (0.05g of catalyst only contains 5% of Ru) Ru/C catalyst, 24ml of methanol and 6ml of ultrapure water are uniformly mixed and then added into a 50ml high-pressure reaction kettle, the sealing is complete, argon is filled to ensure that the air pressure is 1Mpa, then the evacuation and the repetition are carried out for three times to achieve the purpose of replacing the air, finally, the argon is filled to maintain the pressure to be 1Mpa, the reaction is carried out for 4 hours at 270 ℃, and. After the reaction is finished and the temperature is reduced to room temperature, gas products are collected by using an air bag, and hydrogen is analyzed by Agilent 7820A gas chromatographyThe residual amount of gas. Filtering the reaction solution, adding an internal standard solution (the internal standard substance is dimethyl phthalate, 0.2g of dimethyl phthalate is added into 9.8g of methanol and mixed uniformly to obtain 2 wt% of internal standard solution, about 0.2g is weighed when the internal standard solution is used each time, the same is used below) into the filtered reaction solution, taking 5ml of the solution, removing water by using anhydrous magnesium sulfate, adopting gas chromatography-mass spectrometry (FBX-WAX MS-0.25mm-0.25 mu m-30m-Cross bond. heating program: maintaining the temperature at 50 ℃ for 1min, and maintaining the temperature at 10 ℃ for min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

Volatile components in the sample are obtained through gas chromatography-mass spectrometry analysis, and the content of the product is calculated based on the known mass of the internal standard dimethyl phthalate: in this example, theoretical hydrogen amount is 2.49mmol, reaction residual hydrogen amount is 0.97mmol, hydrogen consumption is calculated to be 1.52mmol, conversion rate of lignin is 85.3%, yield of monophenol chemicals is 181.5mg/g, yield of 4-ethylphenol is 72.3mg/g, selectivity is 39.8%, and yield and selectivity of main products are reduced because high temperature causes lignin to be re-polymerized to generate coke substances.

Example 5

Catalytic depolymerization of lignin: weighing 0.1g of straw lignin (the straw lignin is extracted by the following method, by mass fraction, adding 30 parts of deionized water, 120 parts of ethanol, 2 parts of sulfuric acid and 18 parts of agriculture and forestry herb powder into a reaction kettle, reacting for 3 hours at 120 ℃, filtering and separating, adding deionized water into a liquid phase, filtering and separating, wherein the obtained solid phase is the straw lignin), 0.05g of 5 wt% (0.05g of catalyst only contains 5% of Ru) Ru/C catalyst, uniformly mixing 24ml of methanol and 6ml of ultrapure water, adding into a 50ml high-pressure reaction kettle, completely sealing, filling argon to ensure that the air pressure is 1Mpa, then evacuating, repeating for three times to achieve the purpose of replacing air, finally filling the argon to maintain the pressure to be 2Mpa, reacting for 4 hours at 250 ℃, and stirring speed to be 700 r/min. And (3) cooling to room temperature after the reaction is finished, collecting a gas product by using an air bag, and analyzing the residual amount of the hydrogen in an Agilent 7820A gas chromatography. Filtering the reaction solution, adding an internal standard solution (the internal standard substance is preferably dimethyl phthalate, adding 0.2g of dimethyl phthalate into 9.8g of methanol, and uniformly mixing to obtain 2 wt% of internal standardAbout 0.2g of the solution, which is the same as below, was weighed in each use) was added to the filtered reaction solution, and 5ml of the solution was taken and dehydrated with anhydrous magnesium sulfate, and gas chromatography (FBX-WAX MS-0.25mm-0.25 μm-30 m-Crossbond) was used. Temperature rising procedure: maintaining at 50 deg.C for 1min, and maintaining at 10 deg.C/min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

Volatile components in the sample are obtained through gas chromatography-mass spectrometry analysis, and the content of the product is calculated based on the known mass of the internal standard dimethyl phthalate: in this example, theoretical hydrogen amount is 3.93mmol, the residual hydrogen amount in the reaction is 1.35mmol, the calculated hydrogen consumption is 2.91mmol, the conversion rate of lignin is 83.6%, the yield of monophenol chemicals is 163.6mg/g, the yield of 4-ethylphenol is 72.2mg/g, the selectivity is 44.1%, and the decrease of the yield and selectivity of the main product is due to the increase of the pressure, which induces the depolymerization of lignin micromolecule to generate depolymerization.

Examples 6,

Catalytic depolymerization of lignin: weighing 0.1g of wheat straw lignin (the wheat straw lignin is extracted by the following method, by mass fraction, adding 30 parts of deionized water, 120 parts of ethanol, 2 parts of sulfuric acid and 18 parts of agriculture and forestry herb powder into a reaction kettle, reacting for 3 hours at 120 ℃, filtering and separating, adding deionized water into a liquid phase, filtering and separating, wherein the obtained solid phase is the wheat straw lignin), 0.05g of 5 wt% (0.05g of catalyst only contains 5% of Ru) Ru/C catalyst, uniformly mixing 24ml of methanol and 6ml of ultrapure water, adding into a 50ml high-pressure reaction kettle, completely sealing, filling argon to ensure that the air pressure is 1Mpa, then emptying, repeating for three times to achieve the purpose of replacing air, filling the argon to maintain the pressure to be 1Mpa, reacting for 8 hours at 250 ℃, and stirring speed to be 700 r/min. And (3) cooling to room temperature after the reaction is finished, collecting a gas product by using an air bag, and analyzing the residual amount of the hydrogen in an Agilent 7820A gas chromatography. Filtering the reaction solution, adding an internal standard solution (the internal standard substance is dimethyl phthalate, 0.2g of dimethyl phthalate is added into 9.8g of methanol and mixed uniformly to obtain 2 wt% of internal standard solution, and 0.2g of internal standard solution is weighed when the internal standard solution is used each time, the same is used below) into the filtered reaction solution, taking 5ml of the solution, removing water by using anhydrous magnesium sulfate, and adopting gas chromatography-mass spectrometry (FBX-WAX)MS-0.25mm-0.25 μm-30 m-Crossbond. Temperature rising procedure: maintaining at 50 deg.C for 1min, and maintaining at 10 deg.C/min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

Volatile components in the sample are obtained through gas chromatography-mass spectrometry analysis, and the content of the product is calculated based on the known mass of the internal standard dimethyl phthalate: in this example, theoretical hydrogen amount is 5.84mmol, and hydrogen amount remained in the reaction is 1.01mmol, and the hydrogen consumption is calculated to be 4.83mmol, the conversion rate of lignin is 83.4%, the yield of monophenol chemicals is 172.7mg/g, wherein the yield of 4-ethylphenol is 70.5mg/g, and the selectivity is 40.8%.

Example 7

Catalytic depolymerization of lignin: weighing 0.1g of mango lignin (the mango lignin is extracted by the following method, by mass fraction, adding 30 parts of deionized water, 120 parts of ethanol, 1.8 parts of sulfuric acid and 20 parts of agriculture and forestry herb powder into a reaction kettle, reacting for 4 hours at 130 ℃, filtering and separating, adding deionized water into a liquid phase, filtering and separating, wherein the obtained solid phase is the mango lignin, 0.05g of 5 wt% (0.05g of catalyst only contains 5% of Ru) Ru/C catalyst, uniformly mixing 24ml of methanol and 6ml of ultrapure water, adding into a 50ml high-pressure reaction kettle, completely sealing, filling argon to ensure that the air pressure is 1Mpa, emptying, repeating for three times to achieve the purpose of replacing air, filling argon to maintain the pressure to be 1Mpa, reacting for 4 hours at 250 ℃, and stirring for 700 r/min. And (3) cooling to room temperature after the reaction is finished, collecting a gas product by using an air bag, and analyzing the residual amount of the hydrogen in an Agilent 7820A gas chromatography. Filtering the reaction solution, adding an internal standard solution (the internal standard substance is dimethyl phthalate, 0.2g of dimethyl phthalate is added into 9.8g of methanol and mixed uniformly to obtain 2 wt% of internal standard solution, about 0.2g is weighed when the internal standard solution is used each time, the same is used below) into the filtered reaction solution, taking 5ml of the solution, removing water by using anhydrous magnesium sulfate, adopting gas chromatography-mass spectrometry (FBX-WAX MS-0.25mm-0.25 mu m-30m-Cross bond. heating program: maintaining the temperature at 50 ℃ for 1min, and maintaining the temperature at 10 ℃ for min^-1The temperature rise rate of (1) was raised to 250 ℃ for 10min, the same applies hereinafter) and the amount of product was analyzed and calculated.

Volatile components in the sample are obtained through gas chromatography-mass spectrometry analysis, and the content of the product is calculated based on the known mass of the internal standard dimethyl phthalate: in this example, theoretical hydrogen amount is 4.37mmol, and hydrogen amount remained in the reaction is 1.51mmol, and the hydrogen consumption is calculated to be 2.86mmol, the conversion rate of lignin is 79.1%, the yield of monophenol chemicals is 162.1mg/g, wherein the yield of 4-ethylphenol is 71.3mg/g, and the selectivity is 43.9%.

Compared with Chinese patent 201710466874X, Chinese patent 2014105583251, Chinese patent application 2017101275166 and Chinese patent application 2020101021570, the method uses a liquid-phase reforming hydrogen production system to realize the selective catalytic depolymerization of bagasse, bamboo, miscanthus, corncobs, wheat straws, corn straws or straws and other forestry and agricultural waste lignin to prepare 4-ethylphenol, and the catalyst and the liquid-phase solvent are combined to produce hydrogen to solve the problem of reaction atmosphere, thereby achieving the purposes of safe reaction operation, low cost of the reaction system and easy realization. Meanwhile, the lignin is subjected to high-efficiency directional hydrogenolysis to achieve the conversion rate of the lignin of 50-90 percent, the yield of monophenol chemicals of 60-200mg/g, the yield of 4-ethylphenol of 40-100mg/g and the corresponding selectivity of 30-45 percent, so that the method is an effective method for efficiently preparing the 4-ethylphenol proved by the highest level in the prior patent technology and has an industrial application prospect. Meanwhile, the method has the advantages of green and renewable raw materials, no external hydrogen source, safe process, simple process flow, higher reaction efficiency and the like.

The embodiments of the present invention are not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.