CN108101751B - Method for preparing phenolic compound by degrading lignin through two-step method - Google Patents

Method for preparing phenolic compound by degrading lignin through two-step method Download PDF

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CN108101751B
CN108101751B CN201611042747.9A CN201611042747A CN108101751B CN 108101751 B CN108101751 B CN 108101751B CN 201611042747 A CN201611042747 A CN 201611042747A CN 108101751 B CN108101751 B CN 108101751B
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王峰
张超锋
李宏基
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Dalian Institute of Chemical Physics of CAS
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    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract

The invention relates to a method for preparing a phenolic compound by degrading lignin by a two-step method. The first step involves selective oxidative pretreatment of lignin. Adding degreased wood powder into organic solvent, and adding NaNO2The method comprises the steps of forming a nonmetal catalyst by DDQ and NHPI, sealing a reactor, filling oxygen of 0.3-2.0 MPa, reacting for 1-12 hours at the temperature of 60-120 ℃, centrifuging to obtain a solid after the reaction is finished, cleaning with absolute ethyl alcohol to remove residual organic catalyst, and then drying in vacuum at the temperature of 60 ℃ to obtain a solid product, namely wood powder containing preoxidized lignin. And the second step is a selective hydrogenation process, namely dispersing the wood powder containing the pre-oxidized lignin obtained in the previous step into an alcohol solvent, then adding the prepared nickel-molybdenum sulfide catalyst, sealing the reactor, filling 1.0-5.0 MPa of hydrogen, and reacting for 2-24 hours at the temperature of 160-250 ℃. The lignin in the wood flour is efficiently converted to phenolic chemicals.

Description

Method for preparing phenolic compound by degrading lignin through two-step method
Technical Field
The invention belongs to the technical field of energy, and particularly relates to a method for preparing a phenolic compound by degrading lignin by a two-step method.
Background
Energy and chemicals are important power and guarantee for the development of the current society. Fossil energy such as petroleum, natural gas, coal and the like is processed and refined by chemical industry, and a large amount of fuel and chemicals are provided for human society. However, with the continuous consumption and the rapid decline of reserves of various fossil energy sources, the long-term stable supply of the fossil energy sources is seriously challenged, and the search for novel renewable energy sources for preparing fuels and chemicals becomes a necessary trend of social development. Among a plurality of candidate green energy sources, renewable biomass energy sources and sources are wide, and reserves in the nature are abundant and are concerned by people.
The chemical structure of lignin is a complex compound consisting of phenylpropane structural units, and the lignin has three basic structures, namely a guaiacyl structure, a syringyl structure and a p-hydroxyphenyl structure. Lignin contains a large number of functionalized aromatic ring structures, and is a potential energy product with important application value, but the structure of the lignin is a complex three-dimensional high molecular weight polymer, and the chemical bond connecting the structural units is a C-O-C ether bond, a C-C bond and the like with strong chemical stability, so that the development of the energy is faced with important challenges. Despite the great challenges, much progress has been made in lignin conversion.
Bergman et al in RuH2(CO)(PPh3)3As a catalyst, its use in the hydrocracking process of C-O-C bonds in phenoxy-1-phenylethanol and its derivatives was investigated (j.am.chem.soc.,2010,132,15554.). Klankermayer et al reported a Ru catalyzed CγMethod for cleavage of C-C by dehydrogenation-retro-aldol condensation strategy (angelw. chem. int. ed.2015,54,5859.). Toste et al reported a strategy for V-catalyzed dehydrogenation-dearyloxy-auto-redox cleavage of C-O-C bonds (Angew. chem. int. Ed.2010,49,3791.). Goldman et al reported a strategy for cleaving the C-O-C bond by Ir-catalyzed dehydrogenation of a dearyloxy group (Angew. chem. int. Ed.2014,53,10160.). While these homogeneous catalysts are very good at converting lignin model compounds, homogeneous catalysts face the following challenges: (1) contradiction between high system selectivity and lignin complex structure; (2) the lignin contains sulfur components to poison central metals; (3) ligand stability, competitive coordination of the product phenol alcohol. This makes the homogeneous catalytic process trueThe application in the aspect of lignin conversion is less.
In addition, Stahl et al reported an oxidation-BV oxidation-hydrolysis strategy (J.am. chem. Soc.2013,135,6415.) and an oxidation-formic acid hydrolysis strategy (Nature 2014,515,249.) to degrade lignin. Westwood et al reported an oxidation-reduction strategy to degrade lignin (angelw. chem. int. ed.2015,54, 258.). Barta et al reported a series of acid hydrolysis-etherification, acid hydrolysis-hydrogenation, acid hydrolysis-decarbonylation strategies to efficiently degrade lignin (j.am. chem. soc.2015,137, 7456.). Although these two-step processes achieve conversion of lignin. However, they have structural sensitivity, and can only be effective on about 50% of the beta-O-4 linkage structures in the lignin structure, and still have a lot of lignin linkage structures which are not converted.
Because a plurality of lignin linked structures can be converted, the heterogeneous hydrogenation system has important application in the aspect of lignin conversion. In this regard, Koyama et al have studied many Fe-based Mo-based hydrogenation catalysts for the hydrogenation of compounds containing different types of ether linkages (Bioresource. Technol.,1993,44(3): 209-215.). Songqi et al investigated the hydrocracking performance of C-O-C bonds in phenyl phenetole, a lignin model compound on Ni-based catalysts (Chinese J Catal 2013,34(4), 651-. Many heterogeneous noble metal catalysts are available in the published documents, but the application of the materials is greatly limited because the catalysts have high activity, are easy to hydrogenate aromatic rings, are easy to sinter in the using process, and are easy to oxidize and lose activity due to air sensitivity. Among the non-noble metal catalysts, there are also many conventional molybdenum-based catalysts used in catalytic hydrogenation of lignin, but the activity is generally not high enough and needs to be performed under higher reaction conditions. Therefore, in combination with the corresponding pretreatment strategy, the development of a non-noble metal catalyst which is stable to air and has higher activity is a significant work for the high-quality conversion of lignin.
The invention provides a method for preparing phenolic compounds by degrading lignin by a two-step method, wherein an organic bionic homogeneous catalysis system which is developed firstly carries out preoxidation on lignin, then a nickel-molybdenum sulfide catalyst which is low in price, easy to prepare, high in efficiency and stable in air is used for catalyzing hydrogen to crack lignin under a mild condition, and lignin in wood flour is efficiently converted into phenolic compounds and other chemicals with aromatic structures by the two-step method.
Disclosure of Invention
The invention relates to a method for preparing a phenolic compound by degrading lignin by a two-step method. The first step involves selective oxidative pretreatment of lignin. Adding degreased wood powder into organic solvent, and adding NaNO2The method comprises the steps of forming a nonmetal catalyst by DDQ and NHPI, sealing a reactor, filling oxygen of 0.3-2.0 MPa, reacting for 1-12 hours at the temperature of 60-120 ℃, centrifuging to obtain a solid after the reaction is finished, cleaning with absolute ethyl alcohol to remove residual organic catalyst, and then drying in vacuum at the temperature of 60 ℃ to obtain a solid product, namely wood powder containing preoxidized lignin. And the second step is a selective hydrogenation process, namely dispersing the wood powder containing the pre-oxidized lignin obtained in the previous step into an alcohol solvent, then adding the prepared nickel-molybdenum sulfide catalyst, sealing the reactor, filling 1.0-5.0 MPa of hydrogen, and reacting for 2-24 hours at the temperature of 160-250 ℃. The lignin in the wood flour is efficiently converted to phenolic chemicals.
Degreasing the lignin first facilitates subsequent pre-oxidation and hydrogenation of the lignin. The specific process is to use a Soxhlet extractor, add wood powder, use benzene or toluene as an extracting solution, and continuously carry out degreasing treatment for about 24 hours. For the first oxidation process, the wood flour containing lignin may be one or more of birch, peach, poplar, pine, and bamboo. The oxidation substrate can also be pure lignin, and can be one or more of ground lignin, alkali lignin, ionic liquid separation lignin, enzymatic hydrolysis lignin, cuprammonium lignin, hydrochloric acid lignin, sulfuric acid lignin, organic soluble Acell lignin, 1, 4-dioxane lignin and wood powder. According to the subsequent conversion comparison, it is found that the non-organic soluble lignin, wood flour, is more favorable for the catalyst removal after the first step is completed, which is favorable for further hydroconversion.
For the first oxidation process, the organic solvent used may be one or more of acetonitrile, 1, 4-dioxane, methanol, tetrahydrofuran, and the effect of acetonitrile, 1, 4-dioxane was found to be preferable. The mass ratio of the substrate wood powder to the solvent is controlled to be 20-100 mg/mL-1. The pressure of the oxygen is 0.3-2.0 MPa, and the reaction is carried out for 1-12 h at the temperature of 60-100 ℃. The catalyst used is NaNO2DDQ (2, 3-dichloro-5, 6-dicyan-p-benzoquinone), NHPI (N-hydroxyphthalimide). Wherein, NaNO2The dosage of the substrate wood flour is 4-10 w%, the dosage of DDQ is 2-6 w%, and the dosage of NHPI is 2-6 w%. Taking a beta-O-4 lignin model compound as an example, the catalytic oxidation cycle process constructed is as follows:
Figure BDA0001160718690000041
and (3) preparing a hydrogenation catalyst, namely respectively dispersing equimolar amounts of ammonium tetrathiomolybdate and nickel chloride into two parts of aqueous solution, quickly mixing, reacting for 4-48 h at 80-100 ℃ under the protection of Ar atmosphere, cleaning the obtained precipitate, and drying in vacuum at 80 ℃. And (3) treating for 4-10 hours at 350-500 ℃ in Ar gas to obtain the catalyst, namely the nickel-molybdenum sulfide catalyst.
In the second step of selective hydrogenation, the solvent can be one or more of methanol, ethanol, isopropanol, butanol, glycol and glycerol, and subsequent control tests show that the effect of the single alcohol is better. The mass ratio of the substrate pre-oxidized wood powder to the solvent is controlled to be 20-100 mg/mL-1. The using amount of the nickel-molybdenum sulfide catalyst is 20-100 w% of the mass of the substrate oxidized wood powder. The pressure of the hydrogen gas is 1.0-5.0 MPa, and the reaction is carried out for 4-12 h at the temperature of 180-250 ℃. The lignin in the pre-oxidized wood flour is efficiently converted to phenolic chemicals.
Challenges exist for hydrocracking lignin ether oxygen bonds: (1) selectivity of chemical bonds; (2) the native lignin contains sulfur, poisoning the catalyst. TargetingSelectivity of chemical bond: from a substrate perspective, we can pass through Cα-OH to CαO makes the ether oxygen bond easier to convert. In addition, the angle of the catalyst and the adjustment of the arrangement of the hydrogenation center can promote selective hydrogenation, not only can perform hydroconversion on beta-O-4, but also has better effect on other ether oxygen bonds such as alpha-O-4, 4-O-5 and common ethers. The selective breakage of the lignin ether oxygen bond can be efficiently realized by selecting an oxidation-hydrogenation strategy. The invention provides a method for preparing phenolic compounds by degrading lignin by a two-step method, wherein an organic bionic homogeneous catalysis system which is developed firstly carries out preoxidation on lignin, then a nickel-molybdenum sulfide catalyst which is low in price, easy to prepare, high in efficiency and stable in air is used for catalyzing hydrogen to crack lignin under a mild condition, and lignin in wood flour is efficiently converted into phenolic compounds and other chemicals with aromatic structures by the two-step method.
Drawings
FIG. 1 shows the GC-MS spectrum (5.2min peak as internal standard) of NiMoS (450-6h) at 200 deg.C for hydrogenation pre-oxidation of birch wood powder.
Detailed Description
In order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
1. Preparation of the catalyst
Example 1: synthesis of nickel molybdenum sulfide catalyst
The nickel molybdenum sulfide catalyst is prepared by roasting solid precipitate formed by ammonium tetrathiomolybdate and nickel chloride. Ammonium tetrathiomolybdate and nickel chloride were dissolved in deionized water at a molar ratio of 1:1, respectively. Then, the aqueous solution of nickel chloride is quickly added into the aqueous solution of ammonium tetrathiomolybdate, Ar protection is added, and the mixture is stirred for 10 hours at the temperature of 100 ℃. Filtering to obtain solid, and washing with deionized water and absolute ethyl alcohol. After vacuum drying, the sample is treated in Ar gas at 350-450 ℃ for 4-8 h. The resulting sample was numbered NiMoS (y-z h) where y represents the temperature of treatment and z represents the time of treatment.
Example 2: comparative catalyst
Comparative catalysisAgent NiS, MoO2，MoO3，MoS2All purchased from a drug supplier.
2. Pre-oxidation treatment of wood flour and lignin
In the degreasing treatment process before the wood flour is subjected to pre-oxidation treatment, a Soxhlet extractor is used, and toluene is used as an extraction reagent to extract lipid substances in the wood flour.
Example 1: pre-oxidation of organosoluble Acell lignin
100mg of organosoluble Acell lignin was dispersed in 5mL of acetonitrile as catalyst NaNO2Adding 10 w% of the substrate, the DDQ being 6 w% of the substrate, the NHPI being 6 w% of the substrate, and sealing the reactor. Charging oxygen under 1.0MPa, and reacting at 90 deg.C for 6 h. After the reaction was complete, twice the amount of DDQ formic acid was added, the DDQ was removed by reaction at 60 ℃ for 4h, followed by removal of the acetonitrile solvent using rotary evaporation to give pre-oxidized Acell lignin.
Example 2: pre-oxidation of (organo-insoluble) enzymatically decomposed lignin
Dispersing 100mg of enzymatic hydrolysis lignin in 5mL of acetonitrile as a catalyst NaNO2Adding 10 w% of the substrate, the DDQ being 6 w% of the substrate, the NHPI being 6 w% of the substrate, and sealing the reactor. Charging oxygen under 1.0MPa, and reacting at 90 deg.C for 6 h. After completion of the reaction, centrifugation was carried out, the solid was washed with acetonitrile/ethanol, and the solid was dried under vacuum at 60 ℃. The obtained sample is pre-oxidized enzymatic lignin.
Example 3: pre-oxidation of (organic insoluble) virgin birch wood flour
Dispersing 100mg of crude birch wood powder (lignin content is 19 w%) in 5mL of acetonitrile, and using catalyst NaNO2Adding 10 w% of the substrate, the DDQ being 6 w% of the substrate, the NHPI being 6 w% of the substrate, and sealing the reactor. Charging oxygen under 1.0MPa, and reacting at 90 deg.C for 6 h. After completion of the reaction, centrifugation was carried out, the solid was washed with acetonitrile/ethanol, and the solid was dried under vacuum at 60 ℃. The resulting sample was pre-oxidized birch wood flour.
3. Conversion of wood flour and lignin
Example 1:
5mL of methanol, 100mg of organic soluble Acell lignin and 50mg of catalyst NiMoS (450-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled in the reaction kettle under 1MPa, and the reaction kettle is sealed. Reacted at 200 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 0.2mg after conversion using an internal standard.
Example 2:
5mL of methanol, 100mg of pre-oxidized organic soluble Acell lignin and 50mg of catalyst NiMoS (450-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled into the reaction kettle under 1MPa, and the reaction kettle is sealed. Reacted at 200 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 3.2mg after conversion using an internal standard.
Example 3:
5mL of methanol, 100mg of pre-oxidized enzymatic hydrolysis lignin and 50mg of catalyst NiMoS (450-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled in the reaction kettle under 2MPa, and the reaction kettle is sealed. Reacted at 200 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 3.2mg after conversion using an internal standard.
Example 4:
5mL of methanol, 100mg of pre-oxidized enzymatic hydrolysis lignin and 50mg of catalyst NiMoS (450-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled in the reaction kettle under 2MPa, and the reaction kettle is sealed. Reacted at 200 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 10.3mg after conversion using an internal standard.
Example 5:
adding 5mL methanol, 100mg primary birch wood powder and 50mg catalyst NiMoS (450-6h) into a 25mL reaction kettle with magnetic stirring, filling hydrogen gas into the reaction kettle under 2MPa, and sealing. Reacted at 210 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 1.3mg after conversion using an internal standard.
Example 6:
5mL of methanol, 100mg of birch preoxidation wood powder and 50mg of catalyst NiMoS (450-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled in the reaction kettle under 2MPa, and the reaction kettle is sealed. Reacted at 210 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 6.3mg after conversion using an internal standard.
Example 7:
5mL of methanol, 100mg of birch pre-oxidized wood powder and a catalyst MoS are added into a 25mL reaction kettle with magnetic stirring250mg of hydrogen was charged under 2MPa, and the mixture was sealed. Reacted at 220 ℃ for 6h, centrifuged and the resulting sample was qualitatively and quantitatively analyzed by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 0.3mg after conversion using an internal standard.
Example 8:
5mL of methanol, 100mg of birch pre-oxidized wood powder and a catalyst MoS are added into a 25mL reaction kettle with magnetic stirring250mg of hydrogen was charged under 2MPa, and the mixture was sealed. Reacted at 220 ℃ for 6h, centrifuged and the resulting sample was qualitatively and quantitatively analyzed by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 0.2mg after conversion using an internal standard.
Example 9:
5mL of methanol, 100mg of birch preoxidation wood powder and 50mg of catalyst NiS are filled with 2MPa of hydrogen and sealed in a 25mL reaction kettle with magnetic stirring. Reacted at 220 ℃ for 6h, centrifuged and the resulting sample was qualitatively and quantitatively analyzed by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 0.1mg after conversion using an internal standard.
Example 10:
adding 5mL of methanol, 100mg of birch preoxidation wood powder and a catalyst MoO into a 25mL reaction kettle with magnetic stirring350mg of hydrogen was charged under 2MPa, and the mixture was sealed. Reacted at 220 ℃ for 6h, centrifuged and the resulting sample was qualitatively and quantitatively analyzed by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 0.1mg after conversion using an internal standard.
Example 11:
adding 5mL of methanol, 100mg of birch preoxidation wood powder and a catalyst MoO into a 25mL reaction kettle with magnetic stirring250mg of hydrogen was charged under 2MPa, and the mixture was sealed. Reacting at 220 ℃ for 6h, and centrifuging to obtainThe resulting samples were analyzed qualitatively and quantitatively using GC-MS and GC. The amount of the phenolic compound produced by the conversion was 0.2mg after conversion using an internal standard.
Example 12:
5mL of methanol, 100mg of birch preoxidation wood powder and 50mg of catalyst NiMoS (450-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled in the reaction kettle under 1MPa, and the reaction kettle is sealed. Reacted at 210 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The phenolic compound produced by the conversion was 7mg after conversion using an internal standard.
Example 13:
5mL of ethanol, 100mg of birch preoxidation wood powder and 50mg of catalyst NiMoS (430-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled in the reaction kettle under 1MPa, and the reaction kettle is sealed. Reacted at 210 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 5.2mg after conversion using an internal standard.
Example 14:
5mL of isopropanol, 100mg of birch preoxidation wood powder and 50mg of catalyst NiMoS (450-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled in the reaction kettle under 1MPa, and the reaction kettle is sealed. Reacted at 210 ℃ for 6h, centrifuged and the resulting samples were analyzed qualitatively and quantitatively by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 6.1mg after conversion using an internal standard.
Example 15:
adding 5mL of ethylene glycol, 100mg of birch preoxidation wood powder and 50mg of catalyst NiMoS (450-6h) into a 25mL reaction kettle with magnetic stirring, filling hydrogen into the reaction kettle under 1MPa, and sealing the reaction kettle. Reacted at 220 ℃ for 6h, centrifuged and the resulting sample was qualitatively and quantitatively analyzed by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 2.3mg after conversion using an internal standard.
Example 16:
5mL of glycerol, 100mg of birch pre-oxidized wood powder and 50mg of catalyst NiMoS (450-6h) are added into a 25mL reaction kettle with magnetic stirring, hydrogen is filled in the reaction kettle under 2MPa, and the reaction kettle is sealed. Reacted at 220 ℃ for 6h, centrifuged and the resulting sample was qualitatively and quantitatively analyzed by GC-MS and GC. The phenolic compound produced by the conversion was 2.0mg after conversion using an internal standard.
Example 17:
adding 5mL of ethylene glycol, 100mg of birch preoxidation wood powder and 50mg of catalyst NiMoS (450-6h) into a 25mL reaction kettle with magnetic stirring, filling hydrogen into the reaction kettle under 1MPa, and sealing the reaction kettle. Reacted at 220 ℃ for 6h, centrifuged and the resulting sample was qualitatively and quantitatively analyzed by GC-MS and GC. The amount of the phenolic compound produced by the conversion was 2.3mg after conversion using an internal standard.

Claims (7)

1. A method for preparing phenolic compounds by degrading lignin by a two-step method is characterized by comprising the following steps:
the first step is selective oxidation pretreatment of wood flour containing lignin: adding degreased wood powder into organic solvent, and adding NaNO2DDQ and NHPI, sealing the reactor, charging 0.3-2.0 MPa oxygen at 60-120%oC, reacting for 1-12 hours, centrifuging to obtain a solid after the reaction is finished, cleaning with absolute ethyl alcohol to remove residual organic catalyst, and then 60-70%oC, vacuum drying is carried out under the condition, and the obtained solid product is wood powder containing preoxidized lignin;
the second step is a selective hydrogenation process, the wood flour containing the pre-oxidized lignin obtained in the previous step is dispersed in an alcohol solvent, then the prepared nickel-molybdenum sulfide catalyst is added, a reactor is sealed, 1.0-5.0 MPa hydrogen is filled, and the pressure is 160-250 MPaoReacting for 2-24 hours under the condition of C; the lignin in the wood flour is converted to phenolic chemicals;
the preparation method of the nickel molybdenum sulfide catalyst comprises the following steps: respectively dispersing equimolar amounts of ammonium tetrathiomolybdate and nickel chloride in two parts of aqueous solution, mixing, and under the protection of Ar atmosphere, 80-100%oC, reacting for 4-48 h, washing the obtained precipitate, and 80oC, vacuum drying; in Ar gas, 350-500oTreating for 4-10 hours under the condition of C to obtain a catalyst, namely a nickel-molybdenum sulfide catalyst;
for the first oxidation step, the wood flour is one or more than two of the following: birch, mahogany, poplar, pine, bamboo, pure lignin, ground lignin, alkali lignin, ionic liquid separated lignin, enzymatic lignin, cuprammonium lignin, hydrochloric lignin, sulfuric lignin, organosoluble Acell lignin or 1, 4-dioxane lignin.
2. The method of claim 1, wherein: for the first oxidation step, NaNO is used as the catalyst2DDQ (2, 3-dichloro-5, 6-dicyan-p-benzoquinone), NHPI (N-hydroxyphthalimide);
Figure DEST_PATH_IMAGE001
wherein, NaNO2The dosage of the substrate wood flour is 4-10 w%, the dosage of DDQ is 2-6 w%, and the dosage of NHPI is 2-6 w%.
3. The method of claim 1, wherein: for the first oxidation process, the used organic solvent is one or more of acetonitrile, 1, 4-dioxane, methanol and tetrahydrofuran; the mass ratio of the substrate wood powder to the solvent is controlled to be 20-100 mg/mL -1(ii) a The pressure of the oxygen is 0.3-2.0 MPa, and is 60-120oAnd C, reacting for 1-12 h.
4. A method according to claim 3, characterized by: the pressure of the oxygen gas is 0.3-1.0 MPa, 80-100oAnd C, reacting for 6-12 h.
5. The method of claim 1, wherein: the second step is in the selective hydrogenation process, the solvent can be one or more of methanol, ethanol, isopropanol, butanol, glycol and glycerol, and the mass ratio of the substrate preoxidized wood flour to the solvent is controlled to be 20-100 mg/mL -1(ii) a The using amount of the nickel-molybdenum sulfide catalyst is 20-100 w% of the mass of the substrate oxidized wood powder.
6. The method of claim 1, wherein: the second step is that in the selective hydrogenation process, the pressure of hydrogen filling is 1.0-5.0 MPa, and the reaction is carried out for 1-12 h under the condition of 160-250 ℃; the lignin in the pre-oxidized wood flour is efficiently converted to phenolic chemicals.
7. The method of claim 6, wherein: and the second step is that in the selective hydrogenation process, the pressure of hydrogen is 1.0-2.5 MPa, the reaction is carried out for 6-10 h at the temperature of 160-220 ℃, and the lignin in the pre-oxidized wood flour is efficiently converted into phenolic chemicals.
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