CN112479823A - Method for preparing 4-alkylphenol by auto-reforming hydrogenolysis of lignin or lignin oil - Google Patents
Method for preparing 4-alkylphenol by auto-reforming hydrogenolysis of lignin or lignin oil Download PDFInfo
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Abstract
The invention relates to a method for preparing 4-alkylphenol by lignin or lignin oil through a one-pot method without an external hydrogen source. The method takes lignin or lignin oil as a raw material, and hydrogen is produced by self-reforming and hydrogenolysis under the action of a metal catalyst loaded by a nickel-aluminum composite material to obtain the 4-alkylphenol. The birch organic lignin and the lignin oil are used as raw materials, and the yield of the 4-alkylphenol is respectively as high as 17 wt% and 25 wt%. The lignin is obtained by using biomass containing lignin as a raw material and performing acidolysis or biological enzymolysis depolymerization. The lignin oil is obtained by a method of depolymerizing biomass containing lignin as a raw material by hydrogenolysis. The raw materials have wide sources and low cost. Meanwhile, the process does not need an additional hydrogen source, has single product, less by-products, easy separation and green solvent. In addition, the phenolic product is an important chemical product, is suitable for the polyester industry and has wide application prospect.
Description
Technical Field
The invention provides a method for preparing 4-alkylphenol by auto-reforming hydrogenolysis of lignin. Takes lignin as a raw material, and realizes depolymerization and hydrogenolysis by self-reforming hydrogen production of the lignin (or lignin oil) under the action of a platinum-based supported catalytic material to obtain a monophenol product mainly containing 4-ethylphenol. Belongs to the research field of utilizing lignin to catalyze, convert and synthesize chemicals.
Background
The problems of energy shortage and environmental pollution in the world are increasingly prominent, and the development and use of renewable resources to replace the traditional fossil energy are not slow. Biomass is a renewable energy source with a wide source and low price, and new technologies for preparing fuels and fine chemicals using it as a raw material are receiving wide attention all over the world. Lignin, an important component of woody biomass, is a major byproduct in the ethanol production industry and the pulp and paper industry from lignocellulosic biomass by hydrolytic fermentation. The full utilization of lignin is very challenging due to its stability due to the highly random polymeric structure. Currently, most of lignin as industrial residue adopts a direct combustion strategy, so that the lignin becomes an environmental pollutant, thereby bringing great pressure to the environment. Therefore, the development of safe, green and efficient lignin conversion means has important significance.
Lignin is an aromatic high molecular polymer with a three-dimensional structure, and comprises a large number of phenyl propanol structural units (including p-hydroxyphenyl propanol, guaiacyl propanol, syringyl propanol, etc.). Generally, the conversion and utilization of lignin are mainly divided into two steps, firstly, depolymerization is carried out, and then, the depolymerized monomers are converted and upgraded to produce chemicals or liquid fuels with high added value. In recent years, research on the preparation of phenol compounds from lignin as a raw material has been receiving much attention in the industry. As an important organic chemical raw material, the phenol compound can be used for preparing bulk chemicals such as phenolic resin, caprolactam, bisphenol A and the like and medical intermediates, and has important application in the industries such as synthetic rubber, medicine, fuel, coating, oil refining and the like. Therefore, the catalytic conversion of the renewable energy lignin into the phenol compound (4-alkylphenol) has important significance. Chinese patent (CN 109942378A) adopts Au/Nb2O5The lignin oil is selectively hydrodeoxygenated to prepare 4-alkylphenol and benzenediol. Chinese patent (CN 108101751A) adopts a two-step method of oxidation and hydrogenation reduction to realize the high-efficiency conversion of lignin into phenolic chemicals. Chinese patent (CN 109503330A) adopts Co and Fe bimetallic catalyst to selectively hydrogenate and demethoxylate lignin oil to prepare alkylphenol products. However, the phenol compounds produced by the above method are still many, and if the traditional separation method is adopted, the phenol compounds are difficult to separatePurifying one or more products, or further upgrading. In addition, the processes of the invention all need to consume a large amount of hydrogen or oxygen, and the production cost is higher.
The invention starts from the fact that lignin is rich in hydroxyl and methoxyl, and realizes the process of preparing the 4-alkylphenol with high added value from the lignin directly by utilizing the capabilities of dehydrogenation, hydrogenolysis and methanol aqueous phase reforming of the catalyst to prepare hydrogen. The method fully utilizes hydrogen sources (namely aliphatic hydroxyl and methoxyl) of lignin, obtains the single product 4-alkylphenol by self-reforming hydrogen supply and hydrogenolysis under the condition of no external hydrogen source, and has high selectivity, low energy consumption and little pollution. The lignin raw material of the invention has wide source, relatively mild reaction condition and wide application prospect.
Disclosure of Invention
The invention aims to provide a method for preparing 4-alkylphenol by hydrogenolytic self-reforming of lignin or lignin oil without an additional hydrogen source, which mainly comprises the following processes. The method takes lignin as a raw material, and selectively obtains a 4-alkylphenol product under the action of a supported platinum-based metal catalyst, wherein the total yield of the 4-alkylphenol is up to 17 wt%. If lignin oil rich in syringyl, guaiacyl and p-hydroxyphenylpropanol is used as a raw material, the total yield of the 4-alkylphenol is up to 25 wt%. The method avoids the problem of large hydrogen consumption in the hydrogenolysis process of lignin, and simultaneously reserves oxygen-containing functional groups in the product, thereby not only improving the added value of the product, but also reducing the hydrogen consumption and the danger in the production process; and the catalyst has good stability, low production cost and obvious technical and cost advantages.
The invention relates to a catalyst and a method for preparing 4-alkylphenol by self-reforming lignin, which are characterized in that:
the method takes lignin as a raw material, takes the raw material as a hydrogen source under the action of a catalyst, and uses self-reforming hydrogen production for depolymerization and quality improvement to obtain a product mainly comprising 4-ethylphenol. The catalyst is a composite catalyst and comprises a component A and a component B: the component A is one or more of supported platinum, palladium and ruthenium, is optimized to be platinum and is used as an active center for hydrogen production by hydrogenation or reforming, and the mass fraction of the metal elements of the component A in the total amount of the catalyst is more than 0 and less than 10 percent, preferably 0.5 to 5 percent; and the component B (II) is one or more of aluminum oxide, silicon dioxide, niobium pentoxide, a cobalt-aluminum composite material, an iron-aluminum composite material and a nickel-aluminum composite material, and preferably is a nickel-aluminum composite material.
The lignin is obtained by using biomass containing lignin as a raw material and performing acidolysis or biological enzymolysis depolymerization.
The catalyst can be prepared by adopting a one-step or two-step method; in the one-step method, a coprecipitation method is used for preparing the catalyst; in the two-step method, a carrier is prepared firstly, and then metal is loaded, wherein the metal is loaded by adopting an isometric impregnation method, an excess impregnation method and a deposition precipitation method, and preferably the isometric impregnation method.
The lignin oil is obtained by taking wood residue containing lignin as a raw material through a reduction depolymerization method, and the main chemical composition of the lignin oil is a mixture of monomer aromatic compounds mainly comprising syringyl, guaiacyl and p-hydroxyphenylpropanol.
The filling protective gas is mainly inert gas, comprises one or more of nitrogen, argon and helium, and is preferably nitrogen.
Preferably, the specific reaction steps for preparing the 4-alkylphenol by the self-reforming of the lignin in the invention are as follows:
the weight ratio of the lignin to the catalyst is 1: 0.2-2, and preferably, the weight ratio of the lignin to the catalyst is 1: 1-2; the weight ratio of the lignin oil to the catalyst is 1: 0.01-1, and preferably the weight ratio of the lignin oil to the catalyst is 1: 0.01-0.5; the reaction temperature is 200-350 ℃, and preferably, the reaction temperature is 250-300 ℃; the reaction time is 2-35 hours, preferably 12-30 hours; the pressure of the filling protective gas is 1 MPa-10 MPa, and preferably, the pressure of the filling nitrogen is 1 MPa-2.5 MPa.
The reaction medium comprises one or more of water and an organic solvent, and the preferred reaction medium is water. The reaction is a batch reaction process, and is preferably a batch reaction kettle.
The invention has the following advantages:
1. according to the method for preparing the 4-alkylphenol by self-reforming the lignin or the lignin oil, hydrogen in the lignin or the lignin oil is directly used as a hydrogen source, no additional hydrogen source is consumed, the cost is low, and the danger is small;
2. the product of the invention keeps phenolic hydroxyl functional groups in lignin, and compared with the traditional lignin catalytic conversion process, the added value of the product is improved, and the quality yield of the product is also improved;
3. the solid catalyst used in the invention can be separated from the product, can be recycled for many times, has stable working condition and saves cost.
The technical solutions of the present invention are described below by way of specific examples, but the scope of the present invention is not limited thereto.
Detailed description of the preferred embodiments
The method for preparing the 4-alkylphenol by using the lignin as the raw material comprises the following steps: under the action of a metal catalyst loaded by a nickel-aluminum composite material, lignin is subjected to self-reforming depolymerization and quality improvement to obtain a mixture of 4-alkylphenols.
The preparation of the nickel-aluminum composite material adopts an ammonia coprecipitation method, which specifically comprises the following steps: 40mmol nickel nitrate hexahydrate and 80mmol aluminum nitrate nonahydrate were dissolved in 200mL deionized water and stirred well, the aqueous ammonia solution was added dropwise to pH =9, stirring was continued for 2h, followed by aging at room temperature for 10 h. And (4) performing suction filtration and washing until the pH of the washing liquor is =7, and placing the filter cake in an oven at 100 ℃ for drying overnight. Finally, the catalyst precursor was placed in a muffle furnace at 450oRoasting for 4 hours under C to obtain a nickel-aluminum composite oxide material; at 800oRoasting for 6 hours under C to obtain the nickel aluminate spinel carrier, wherein the heating rate is 5oAnd C/min. Marking the finally obtained nickel-aluminum composite oxide material carrier as Ni-Al-O; the carrier of the nickel-aluminum spinel material is marked as NiAl2O4。
Composite oxide materials with different metals are prepared according to the coprecipitation method, except that ferric nitrate and cobalt nitrate are used as precursors to replace nickel nitrate. The finally obtained composite oxides are respectively marked as Fe-Al-O, Co-Al-O.
Niobium pentoxide is prepared by a hydrothermal synthesis method, specifically, 19.2g of niobium oxalate aqueous solution with niobium ion concentration of 5mmol/L and 0.711g of ammonium oxalate are dissolved in 50mL of deionized water and fully stirred and dissolved, the solution is transferred to a 100mL polytetrafluoroethylene crystallization kettle inner container and placed in a 180 mL polytetrafluoroethylene crystallization kettle inner containeroAnd C, crystallizing for 24 hours. The obtained white solid is filtered, washed and then placed in 80oAnd C, fully drying in an oven. The silicon dioxide adopts a commercial mesoporous silicon dioxide carrier; the alumina carrier adopts commercial pseudo-boehmite as a precursor, 500oAnd C, roasting for 12 hours.
The loading of the metal platinum adopts an incipient wetness impregnation method, which specifically comprises the following steps: the chloroplatinic acid solution is used as a steeping liquor, is fully mixed and stirred with the carrier, and is dried for 12 hours in an oven at 80 ℃; then roasting for 4 hours at 450 ℃ in nitrogen atmosphere, wherein the heating rate is 5oAnd C/min. Before each reaction, the catalyst needs to be reduced for 4 hours in a hydrogen atmosphere at 350 ℃ and the heating rate is 5oAnd C/min. According to the method, different carrier materials are replaced, so that different supported platinum-based catalysts can be prepared, the platinum loading amounts are all 2 wt%, and the finally obtained catalyst is marked as 2% Pt/gamma-Al2O3、2%Pt/Nb2O5、2%Pt/SiO2、2%Pt/Ni-Al-O、2%Pt/Fe-Al-O、2%Pt/Co-Al-O、2%Pt/NiAl2O4。
Ni-Al-O catalyst loaded with different noble metals is prepared according to the incipient wetness impregnation method, except that aqueous solution of palladium nitrate and ruthenium trichloride is used as impregnation liquid. The final catalysts were labeled 2% Pd/Ni-Al-O, 2% Ru/Ni-Al-O.
In the second step, the batch reactor was operated as follows: 0.1g of lignin, 0.2g of catalyst and deionized water are added into a 50mL batch reactor, and the temperature is 250 ℃ under the pressure of 1-2 MPaoC~300oAnd C, reacting for 10-30 hours. Qualitative analysis and quantitative analysis of the reaction product by gas chromatography-mass spectrometry (GC-MS Agilent 7890A-5975C) and gas chromatography (GC Agilent 7890A), wherein HP-5 is used for the chromatographic columns, and the temperature programming conditions of the chromatographic columns are as follows: 50oMaintaining for 10min afterAt 10oThe temperature rise rate of C/min is increased to 250oC, and at 250oC for 5 min.
Wherein, the calculation formula of the yield is as follows: mass yield (%) of 4-alkylphenol mixture (= mass of 4-alkylphenol mixture in product/mass of lignin added before reaction) × 100%.
Mass yield (%) of other products (= mass of product other than 4-alkylphenol mixture in product/mass of lignin before reaction) × 100%.
The analytical results are shown in Table 1.
Table 1 comparison of catalytic depolymerization of different lignin feedstocks to alkylphenol monomers.
As shown in the above table, when the raw material is birch lignin, the reaction conditions are 280oC, 20 hours, 2MPa N2, 15mL H2When O is present, NiAl is used2O4With spinel supported Pt based catalysts, the mass yield of 4-alkylphenol is highest, 17.3 wt%, the yield of other hydrocarbons is only 3.5 wt%. In contrast to comparative examples 1 to 4, in the case where an additional hydrogen source was added, the yield of 4-alkylphenol was greatly reduced, and side reactions were also caused to generate hydrocarbons such as cycloalkanes, aromatics and the like.
The method for preparing the 4-alkylphenol by using the lignin oil as the raw material comprises the following steps: firstly, extracting lignin oil from lignocellulose residues, and then carrying out self-reforming hydrodeoxygenation on the lignin oil under the action of a metal catalyst loaded by a nickel-aluminum composite material to obtain a mixture of 4-alkylphenols.
In the first step, the lignin oil is extracted by a reduction depolymerization method in the literature, and is obtained at a certain temperature by taking wood residue containing lignin as a raw material, taking methanol, ethanol, isopropanol, butanol and the like as reaction media, preferably methanol, and taking a commercial hydrogenation catalyst 5% Pd/C as a catalyst. The obtained lignin oil mainly comprises aromatic compound monomers of syringyl, guaiacyl and p-hydroxy-phenyl propanol.
The extraction steps of the lignin oil are as follows: in a 1000mL mechanically stirred tank reactor, 10g of wood residue powder (40 mesh), 300mL of anhydrous methanol at 205 deg.C were addedoC~235oAnd C, reacting for 8 hours under the condition that the hydrogen partial pressure is 2-3 MPa. Filtering and separating filter residues of the filtrate, and removing the solvent in the filtrate by rotary evaporation. The resulting concentrate was washed with 20mL of deionized water and then CH was used2Cl2The lignin oil product was extracted in three steps. And finally, collecting the organic phase part extracted for three times, and performing rotary evaporation to remove the solvent to obtain dark brown liquid, namely the lignin oil.
And step two, the batch type reaction kettle comprises the following steps: 0.1g of lignin oil, 0.05g of catalyst and 15mL of deionized water are added into a 50mL batch reactor under the pressure of 1-2 MPa and the temperature of 250oC~400oAnd C, reacting for 10-20 hours. Performing qualitative analysis and quantitative analysis on the reaction product by gas chromatography-mass spectrometry (GC-MS Agilent 7890A-5975C) and gas chromatography (GC Agilent 7890A), wherein an HP-5 chromatographic column is adopted, and the temperature programming conditions of the chromatographic column are as follows: 50oMaintaining for 10min at 10%oThe temperature rise rate of C/min is increased to 250oC, and at 250oC for 5 min. The analytical results are shown in Table 2.
Wherein, the calculation formula of the yield is as follows: mass yield (%) of 4-alkylphenol mixture (= mass of 4-alkylphenol mixture in product/mass of lignin oil before reaction) × 100%.
Mass yield (%) of other products = (mass of products other than 4-alkylphenol mixture in product/mass of lignin oil before reaction) × 100%.
The analytical results are shown in Table 2.
Table 2 comparison of the properties of lignin oil auto-reforming to produce a mixture of 4-alkylphenols.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
While the present invention has been described in conjunction with specific embodiments thereof, many alternatives, modifications, and variations of these embodiments will be apparent to those of ordinary skill in the art in light of the foregoing description.
The embodiments of the invention are intended to embrace all such alternatives, modifications and variances that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A catalyst and a method for preparing 4-alkylphenol by auto-reforming hydrogendonating hydrogenolysis of lignin or lignin oil are characterized by comprising the following processes: the method comprises the following steps of (1) reforming lignin or lignin oil serving as a raw material under the action of a catalyst to produce hydrogen, and meanwhile, carrying out hydrogenolysis to obtain a 4-alkylphenol product; the lignin is used as a raw material, and the total yield of the 4-alkylphenol can reach 17 wt%; the total yield of the 4-alkylphenol can reach 25 wt% by taking the lignin oil as a raw material.
2. The method according to claim 1, wherein the lignin is a high polymer obtained by acidolysis or bioenzymolysis using a biomass containing a lignin component as a raw material; the lignin oil is obtained by taking biomass containing lignin as a raw material and carrying out hydrogenolysis depolymerization, and the main chemical composition of the lignin oil is a mixture of aromatic compounds mainly comprising syringyl, guaiacyl and p-hydroxy-phenyl propanol.
3. The process as claimed in claim 1, wherein the catalyst used is a bifunctional catalyst comprising a component A and a component B: the component A is one or more of ruthenium, platinum and palladium, preferably platinum, and is used as an active center for reforming and hydrogenolysis, and the mass fraction of the metal elements of the component A in the total amount of the catalyst is more than 0 and less than 5 percent, preferably 2 percent; and the component B (II) is one or more of silicon dioxide, niobium pentoxide, aluminum oxide, an iron-aluminum composite material, a cobalt-aluminum composite material and a nickel-aluminum composite material, and preferably is a nickel-aluminum composite material.
4. According to claim 3, the catalyst can be prepared in a single-stage or two-stage process; in the one-step method, a coprecipitation method is used for preparing the catalyst; in the two-step method, a carrier is prepared firstly, and then metal is loaded, wherein the metal is loaded by adopting an isometric impregnation method, an excess impregnation method and a deposition precipitation method, and preferably the isometric impregnation method.
5. A process according to claim 1 for obtaining a 4-alkylphenol product from reforming hydrogenolysis, characterized in that:
the weight ratio of the lignin to the catalyst is 1: 0.2-3, preferably, the weight ratio of the lignin to the catalyst is 1: 1-2;
the weight ratio of the lignin oil to the catalyst is 1: 0.01-1, and preferably the weight ratio of the lignin oil to the catalyst is 1: 0.01-0.5;
and, the reaction temperature is 200-350 ℃, preferably, the reaction temperature is 250-300 ℃;
and, the reaction time is 2-35 hours, preferably, the reaction time is 12-30 hours;
and the pressure of the filled inert gas is 1 MPa-10 MPa, and preferably the pressure of the filled nitrogen is 1 MPa-2.5 MPa.
6. The method according to claim 5, wherein the reaction medium comprises one or more of water and an organic solvent, and the preferred reaction medium is water.
7. The process according to claim 5, wherein the reaction is a batch reaction process, preferably the reactor is a batch autoclave.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115041190A (en) * | 2022-05-13 | 2022-09-13 | 安徽工业大学 | Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 Preparation of catalyst and its use |
| WO2024124661A1 (en) * | 2022-12-13 | 2024-06-20 | 华东理工大学 | Method for preparing cellulose and lignin oil from exogenous-hydrogen-free depolymerized lignocellulose |
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- 2020-11-04 CN CN202011214520.4A patent/CN112479823A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115041190A (en) * | 2022-05-13 | 2022-09-13 | 安徽工业大学 | Hydrotalcite topology transition high-dispersion Ni-Ru/Al 2 O 3 Preparation of catalyst and its use |
| WO2024124661A1 (en) * | 2022-12-13 | 2024-06-20 | 华东理工大学 | Method for preparing cellulose and lignin oil from exogenous-hydrogen-free depolymerized lignocellulose |
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