CN112898355A - Method for preventing lignin degradation intermediate product from polycondensation - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07G1/00—Lignin; Lignin derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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Abstract
The invention discloses a method for preventing lignin degradation intermediate product from polycondensation, and relates to the technical field of biomass catalytic conversion. Mixing and heating a biomass raw material, a lignin protective agent, a lignin extraction solvent and an inorganic acid aqueous solution, filtering, performing rotary evaporation, centrifuging and drying to obtain lignin; then mixing lignin with the amphiphilic heteropoly acid catalyst, the reaction solvent and the oxidant, degrading, filtering, extracting and rotary evaporating to obtain a lignin degradation product. The lignin degradation monomer prepared by the invention is a highly functionalized aromatic compound, and has high additional value; and the yield of the degradation monomer reaches 10-14%, which is far superior to the yield of 2-5% of the conventional lignin oxidative degradation monomer.
Description
Technical Field
The invention relates to the technical field of biomass catalytic conversion, in particular to a method for preventing lignin degradation intermediate products from polycondensation.
Background
Lignin is one of the most abundant natural polymers in nature, can replace the problem of resource exhaustion caused by petroleum-based raw materials as a renewable resource, and draws more and more attention in related fields such as materials, chemistry, biology and the like. Lignin has a high carbon content and high aromaticity, and despite its great potential as a feedstock for the fuel and chemical industries, lignin remains the least available of the lignocellulosic biopolymers. Lignin is the only natural resource in the nature which can directly prepare aromatic chemicals, and can obtain a plurality of small molecular compounds through degradation reaction under certain conditions, and through further conversion of the small molecular compounds, high value-added products which can replace petroleum-based chemicals can be produced, thus having important significance for adjustment of energy structure and sustainable development of economic society. In chemical composition, the content of lignin accounts for about 15-30% of the dry weight of the biomass, and the complex three-dimensional network structure is mainly formed by three phenylpropane units of coumaryl alcohol (H), coniferyl alcohol (G) and sinapyl alcohol (S) through C-C bonds and C-O bonds in a nonlinear and disordered manner. Due to the three-dimensional aromatic ring structure and the complex connection mode between the phenylpropane units, the lignin is more difficult to convert into low molecular weight chemicals. On one hand, after industrial waste lignin generated by the traditional pulping and papermaking is treated by the process flows of high temperature, strong acid, strong alkali and the like, lignin fragments can be condensed to form a stable C-C bond structure which is difficult to degrade, so that the degradation difficulty is increased; secondly, the polycondensation phenomenon between degradation intermediate products generated in the catalysis process can greatly reduce the yield of lignin target products and hinder the application of lignin to high-value chemical conversion.
There are various degradation methods for lignin, wherein the pyrolysis and hydrogenation reduction depolymerization methods tend to destroy the connecting bonds between lignin structural units and remove groups on benzene rings when destroying lignin macromolecules, and although the yield of the obtained lignin monomers is high, the degradation requires more severe reaction conditions (high temperature, high pressure and longer reaction time), the selectivity of degradation products is poor, and the added value is low. On the contrary, oxidative depolymerization of lignin is an important and promising method for depolymerization of lignin, the reaction conditions are relatively mild, the linkage bond energy of lignin can be significantly reduced, highly functionalized aromatic compounds and the like are generated, functional groups of depolymerization products tend to be increased, such as carboxyl groups, aldehyde groups and the like are formed, and the depolymerization products can be directly used as platform chemicals or converted into fine chemicals, so that the high-value utilization of lignin is facilitated.
CN107417498B (2017.12.01) discloses a method for catalytic depolymerization of lignin, which adopts a solid acid catalyst to degrade lignin, but the adopted degradation temperature is high (200-300 ℃), lignin degradation intermediate products are easily condensed at the temperature to form refractory oligomers with stable structures, and the yield of lignin monomers is low.
CN105237371B (2017.03.22) discloses a method for preparing vanillin by catalytic oxidative degradation of lignin, which adopts a plurality of heteropolyacids to degrade lignin under an oxidation condition to obtain an aromatic hydrocarbon compound taking vanillin as a main product, but the lignin is common industrial lignin, the structure of the lignin is different from that of the original plant lignin, and the catalytic system enables lignin degradation intermediate products to be easily condensed and the yield of target products is low.
Disclosure of Invention
The invention aims to provide a method for preventing polycondensation of lignin degradation intermediate products, which aims to solve the problems in the prior art, so that lignin degradation monomers are highly functionalized aromatic compounds, and the yield of the lignin degradation monomers is improved.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for preventing lignin degradation intermediate product from polycondensation, which comprises the following steps:
the method comprises the following steps: mixing and heating a biomass raw material, a lignin protective agent, a lignin extraction solvent and an inorganic acid aqueous solution, filtering, evaporating, centrifuging and drying to obtain lignin;
step two: mixing lignin with an amphiphilic heteropoly acid catalyst, a reaction solvent and an oxidant, degrading, filtering, extracting and evaporating to obtain a lignin degradation product;
the biomass raw material is one or a mixture of several of broad-leaved wood, coniferous wood and herbaceous plants;
the lignin protective agent is one or a mixture of more of formaldehyde, acetaldehyde and propionaldehyde;
the reaction solvent is methanol or ethanol and water in a mass ratio of (3-4): 1 and mixing.
Further, the biomass raw material in the first step also comprises a step of crushing or ball milling treatment before mixing; the broadleaf wood is birch, poplar, ash tree or oak; the needle-leaved wood is spruce, larch, cedar or yellow fir; the herbaceous plant is corn straw, rice straw, wheat straw or bamboo.
Further, in the step one, the lignin extraction solvent is one or a mixture of more of 1, 4-dioxane, tetrahydrofuran, dichloromethane, ethanol, acetone and ethyl acetate.
Further, in the step one, the inorganic acid aqueous solution is one or a mixture of more of sulfuric acid, hydrochloric acid and nitric acid aqueous solutions; the concentration of the inorganic acid aqueous solution is 0.15-0.25 mol/L.
Further, the heating temperature in the first step is 70-90 ℃, and the time is 1-3 hours.
Further, in the step one, the biomass raw material, the lignin protective agent, the lignin extraction solvent and the inorganic acid aqueous solution are mixed according to a mass ratio of 1: (0.7-1.1): (9-9.5): (0.4-0.6) mixing.
Further, in the second step, the amphiphilic heteropoly acid catalyst is a cationic surfactant substituted Keggin type heteropoly acid, the cationic surfactant is one or a mixture of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the Keggin type heteropoly acid is H3PW12O40、H3PMo12O40、H5PMo10V2O40Any one or a mixture of several of them.
Further, the degradation in the second step is carried out in a high-pressure reaction kettle; the oxidant is oxygen; the dosage of the oxidant is aerated to ensure that the pressure in the high-pressure reaction kettle is 1 MPa.
Further, the temperature of degradation in the second step is 120-160 ℃, and the time is 0.5-3 h.
Further, in the second step, the mass ratio of the lignin to the amphiphilic heteropolyacid catalyst to the reaction solvent is 1: 1: (32-34).
The invention discloses the following technical effects:
(1) the lignin protective agent protects the C alpha (benzyl) position active site in the primary structure of lignin, and avoids the polycondensation reaction of lignin fragments in the process of extracting lignin under acidic conditions;
(2) the amphiphilic heteropoly acid provided by the invention can protect intermediate products in the lignin degradation process, and the polycondensation reaction of the intermediate products is avoided;
(3) the reaction system adopted by the invention is mild, and the solvent system is a mixed system of micromolecular alcohols and water, so that the polycondensation of lignin intermediate products in the reaction process can be effectively reduced;
(4) the lignin degradation monomer obtained by the invention is a highly functionalized aromatic compound, can be directly used as a platform chemical or converted into a fine chemical, has high additional value, and is more beneficial to high-value utilization of lignin;
(5) the method for preventing the polycondensation of the lignin degradation intermediate product can enable the yield of the degradation monomer to reach 10-14%, is far superior to the yield of 2-5% of the conventional lignin oxidative degradation monomer, has mild reaction conditions, can recycle the catalyst, and accords with the green chemical development concept.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic view of the method of the present invention for preventing polycondensation of lignin-degrading intermediates;
FIG. 2 is a GC-MS spectrum of a lignin degradation product of example 7 of the present invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
FIG. 1 is a schematic view of the method of the present invention for preventing polycondensation of lignin-degrading intermediates;
FIG. 2 is a GC-MS spectrum of a lignin degradation product of example 7 of the present invention.
Example 1:
preparing formaldehyde pretreatment lignin: adding 10g of birch wood powder, 90mL of 1, 4-dioxane, 4.2mL of 0.15mol/L hydrochloric acid and 9.5mL of formaldehyde into a three-neck flask, reacting for 3h at 80 ℃, and after the reaction is finished, filtering, rotary steaming and centrifuging to obtain formaldehyde pretreated lignin.
Example 2:
preparing acetaldehyde pretreatment lignin: adding 10g of spruce wood powder, 90mL of dichloromethane, 4.2mL of 0.2mol/L sulfuric acid and 9.5mL of acetaldehyde into a three-neck flask, reacting at 70 ℃ for 1h, and after the reaction is finished, filtering, rotary steaming and centrifuging to obtain acetaldehyde pretreated lignin.
Example 3:
preparing propionaldehyde pretreatment lignin: adding 10g of corn straw powder, 90mL of isometric mixed solution of tetrahydrofuran and ethanol, 4.2mL of isometric mixed solution of 0.25mol/L hydrochloric acid and nitric acid and 9.5mL of propionaldehyde into a three-neck flask, reacting for 2 hours at 90 ℃, and filtering, rotary steaming and centrifuging after the reaction is finished to obtain the propionaldehyde pretreated lignin.
Example 4
Preparation of amphiphilic heteropolyacid Catalyst (CTA)1H4PMo10V2O40: 1.37g of metered cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) is dissolved in 100mL of deionized water and gradually added dropwise to Keggin type heteropoly acid H under magnetic stirring5PMo10V2O40Adding 6.55g of the solution into 100mL of deionized water, mixing and stirring for 30min, filtering, precipitating, washing with deionized water, washing with ethanol, and washing with water at 60 deg.CEvaporating to dryness in bath, calcining in a tube furnace at 100 deg.C for 3h to obtain amphiphilic heteropolyacid Catalyst (CTA)1H4PMo10V2O40。
Example 5
Preparation of amphiphilic heteropolyacid catalysts (TTA)1H2PMo12O40: 1.48g of metered cationic surfactant octadecyl trimethyl ammonium bromide (TTAB) is dissolved in 100mL of deionized water, and the solution is gradually dripped into Keggin type heteropoly acid H under magnetic stirring3PMo12O40Adding 6.86g of the solution into 100mL of deionized water, mixing and stirring for 30min, filtering, precipitating, washing with deionized water, washing with ethanol, evaporating to dryness in a water bath at 60 ℃, calcining in a tubular furnace at 100 ℃ for 3h to obtain the amphiphilic heteropolyacid catalyst (TTA)1H2PMo12O40。
Example 6
Preparation of amphiphilic heteropolyacid catalyst (DTA)1H2PW12O40: 1.16g of metered cationic surfactant Dodecyl Trimethyl Ammonium Bromide (DTAB) is dissolved in 100mL of deionized water, and is gradually dripped into Keggin type heteropoly acid H under magnetic stirring3PW12O40Adding 10.83g of the solution into 100mL of deionized water, mixing and stirring for 30min, filtering, precipitating, washing with deionized water, washing with ethanol, evaporating to dryness in a water bath at 60 ℃, calcining in a tubular furnace at 100 ℃ for 3h to obtain the amphiphilic heteropolyacid catalyst (DTA)1H2PW12O40。
Example 7:
0.25g of the above formaldehyde-pretreated lignin, 0.25g of amphiphilic polyacid Catalyst (CTA)1H4PMo10V2O408mL of methanol and 2mL of water are put in a high-pressure reaction kettle, oxygen is filled to 1.0MPa, the reaction is carried out for 0.5h at the temperature of 150 ℃, and after the reaction is finished and the temperature is reduced to the room temperature, the lignin degradation product is obtained by filtration, extraction and rotary evaporation.
The yield of lignin degradation products is calculated as follows:
as a result: the GC-MS spectrum of the lignin degradation product is shown in figure 2; as can be seen from fig. 2, the yield of lignin degradation products is: 4.4% of vanillin, 3.8% of methyl vanillic acid, 2.6% of syringaldehyde and 1.4% of other aromatic compounds; the total yield of degradation products reaches 12.2 percent; the molecular weight of the product was approximately 660 g/mol.
Example 8:
the difference from example 7 is that lignin is pretreated with acetaldehyde, the reaction temperature is 120 ℃, and the reaction time is 3 h.
As a result: the yield of lignin oil product and lignin monomer and the molecular weight of the product are shown in Table 1.
Example 9:
the difference from example 7 is that the lignin is pretreated by propionaldehyde, the reaction temperature is 140 ℃, and the reaction time is 1 h.
As a result: the yield of lignin oil product and lignin monomer and the molecular weight of the product are shown in Table 1.
Example 10:
the difference from example 7 is that a amphiphilic heteropolyacid catalyst is used (TTA)1H2PMo12O40The reaction temperature is 120 ℃, and the reaction time is 2 h.
As a result: the yield of lignin oil product and lignin monomer and the molecular weight of the product are shown in Table 1.
Example 11:
the difference from example 7 is that the amphiphilic heteropolyacid catalyst used is (DTA)1H2PW12O40The reaction temperature was 140 ℃.
As a result: the yield of lignin oil product and lignin monomer and the molecular weight of the product are shown in Table 1.
Example 12:
the difference from example 7 is that the amphiphilic heteropolyacid catalyst used is (DTA)1H2PW12O40The reaction temperature was 160 ℃.
As a result: the yield of lignin oil product and lignin monomer and the molecular weight of the product are shown in Table 1.
Comparative example 1:
the difference from example 7 is that no protective agent is added to the lignin during the extraction stage (i.e. no formaldehyde is added on the basis of example 1).
As a result: the yield of lignin oil product and lignin monomer and the molecular weight of the product are shown in Table 1.
Comparative example 2:
the difference from example 7 is that the catalyst used is a non-amphiphilic heteropolyacid catalyst H which does not contain micellar nanoclusters5PMo10V2O40。
As a result: the yield of lignin oil product and lignin monomer and the molecular weight of the product are shown in Table 1.
Comparative example 3:
the difference from the example 7 is that no protective agent is added in the lignin extraction stage (i.e. no formaldehyde is added on the basis of the example 1), and the catalyst adopted is the non-amphiphilic heteropolyacid catalyst H without micelle structure5PMo10V2O40。
As a result: the yield of lignin oil product and lignin monomer and the molecular weight of the product are shown in Table 1.
TABLE 1
From examples 7 to 12, it can be seen that the lignin protective agent is added in the lignin pretreatment stage, and the amphiphilic heteropolyacid catalyst is adopted in the catalytic degradation stage, so that the monomer yield in the lignin degradation product can be effectively increased to 10 to 14%. By adopting a single degradation strategy, such as adopting the pretreatment without adding the lignin protective agent in the comparative example 1 and adopting the non-amphiphilic heteropolyacid catalyst in the comparative example 2, the monomer yield in the lignin monomer product is only about 6 percent, and the molecular weight of the product is higher. The method completely does not contain lignin degradation intermediate product polycondensation, namely no lignin protective agent is added in the lignin extraction stage and a non-amphiphilic heteropoly acid catalyst is adopted, as in comparative example 3, the yield of the lignin monomer product is lower and is only 3.4%, and the molecular weight of the product is high.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A method for preventing polycondensation of lignin-degrading intermediates, comprising the steps of:
the method comprises the following steps: mixing and heating a biomass raw material, a lignin protective agent, a lignin extraction solvent and an inorganic acid aqueous solution, filtering, evaporating, centrifuging and drying to obtain lignin;
step two: mixing lignin with an amphiphilic heteropoly acid catalyst, a reaction solvent and an oxidant, degrading, filtering, extracting and evaporating to obtain a lignin degradation product;
the biomass raw material is one or a mixture of several of broad-leaved wood, coniferous wood and herbaceous plants;
the lignin protective agent is one or a mixture of more of formaldehyde, acetaldehyde and propionaldehyde;
the reaction solvent is methanol or ethanol and water in a mass ratio of (3-4): 1 and mixing.
2. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein the biomass raw material in the first step further comprises a step of pulverizing or ball milling before mixing; the broadleaf wood is birch, poplar, ash tree or oak; the needle-leaved wood is spruce, larch, cedar or yellow fir; the herbaceous plant is corn straw, rice straw, wheat straw or bamboo.
3. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein the lignin extraction solvent in step one is one or more of 1, 4-dioxane, tetrahydrofuran, dichloromethane, ethanol, acetone, and ethyl acetate.
4. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein in step one, the aqueous solution of inorganic acid is one or a mixture of sulfuric acid, hydrochloric acid and nitric acid; the concentration of the inorganic acid aqueous solution is 0.15-0.25 mol/L.
5. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein the heating temperature in step one is 70-90 ℃ for 1-3 h.
6. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein in step one, the biomass raw material, the lignin protecting agent, the lignin extraction solvent, and the aqueous solution of inorganic acid are mixed in a mass ratio of 1: (0.7-1.1): (9-9.5): (0.4-0.6) mixing.
7. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein in step two, the amphiphilic heteropolyacid catalyst is a cationic surfactant substituted Keggin heteropolyacid, the cationic surfactant is one or a mixture of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the Keggin heteropolyacid is H3PW12O40、H3PMo12O40、H5PMo10V2O40Any one or a mixture of several of them.
8. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein said degradation of step two is performed in a high pressure autoclave; the oxidant is oxygen; the dosage of the oxidant is aerated to ensure that the pressure in the high-pressure reaction kettle is 1 MPa.
9. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein the temperature of degradation in step two is 120-160 ℃ for 0.5-3 h.
10. The method for preventing polycondensation of lignin degradation intermediate products according to claim 1, wherein the mass ratio of the lignin to the amphiphilic heteropolyacid catalyst and the reaction solvent in the second step is 1: 1: (32-34).
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| CN115669993A (en) * | 2022-10-26 | 2023-02-03 | 河南农业大学 | Method for improving near-critical water extraction tobacco leaf biomass by using inorganic catalyst |
| CN116196950A (en) * | 2023-02-16 | 2023-06-02 | 北华大学 | Synthesis method of bimetal doped heteropolyacid catalyst and application of bimetal doped heteropolyacid catalyst in lignin conversion |
| CN116196950B (en) * | 2023-02-16 | 2024-05-24 | 北华大学 | Synthesis method of bimetal doped heteropolyacid catalyst and application of bimetal doped heteropolyacid catalyst in lignin conversion |
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| CN116196950A (en) * | 2023-02-16 | 2023-06-02 | 北华大学 | Synthesis method of bimetal doped heteropolyacid catalyst and application of bimetal doped heteropolyacid catalyst in lignin conversion |
| CN116196950B (en) * | 2023-02-16 | 2024-05-24 | 北华大学 | Synthesis method of bimetal doped heteropolyacid catalyst and application of bimetal doped heteropolyacid catalyst in lignin conversion |
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