CN112403521B - Polyacid catalyst, preparation method and application thereof in preparation of phenolic compounds - Google Patents
Polyacid catalyst, preparation method and application thereof in preparation of phenolic compounds Download PDFInfo
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- CN112403521B CN112403521B CN202011399724.XA CN202011399724A CN112403521B CN 112403521 B CN112403521 B CN 112403521B CN 202011399724 A CN202011399724 A CN 202011399724A CN 112403521 B CN112403521 B CN 112403521B
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Abstract
The invention relates to the technical field of catalyst preparation and application, in particular to a polyacid catalyst and a preparation method thereofAnd in the preparation of phenolic compounds. Adding silicon carbide serving as a carrier into an ethanol solution, then adding phosphomolybdic acid, carrying out reflux stirring reaction, removing redundant ethanol in vacuum, drying the obtained solid material, grinding into fine powder, and calcining the fine powder to obtain the polyacid catalyst. Mixing lignin, polyacid catalyst, ethanol and water solution and H 2 O 2 Adding the mixture into a high-pressure reaction kettle, and setting the reaction temperature and the reaction time to hydrolyze biomass to obtain phenolic compounds. After the reaction is finished, extracting, decompressing and distilling to obtain the product. Heterogeneous catalytic system plus H 2 O 2 The active free radical with medium and high concentration can more effectively promote the cleavage of beta-O-4 bond, better meet the requirements of selective cleavage of beta-O-4 bond and side chain oxidation in lignin depolymerization process, and depolymerize lignin into monophenol compound under mild condition.
Description
Technical Field
The invention relates to the technical field of catalyst preparation and application, in particular to a polyacid catalyst, a preparation method and application in preparation of phenolic compounds. Also comprises the polyacid catalyst and H 2 O 2 The novel high-efficiency oxidation system is formed, and biomass is hydrolyzed to obtain phenolic compounds under the high-efficiency oxidation system.
Background
Lignin is formed by carrying out random coupling or addition reaction on three alcohol monomers of coumaryl alcohol, coniferyl alcohol and sinapyl alcohol, and has three phenylpropane units of p-hydroxybenzoyl type, guaiacyl type and syringyl type. Lignin may be the only viable renewable resource for the production of aromatics due to its unique structure. The method can relieve the production pressure of phenolic compounds which are only refined by petroleum at present, but has great difficulty in degrading and industrially utilizing lignin due to the stability of the structure, and most of lignin is not reasonably used, so that huge waste of resources is caused.
The main lignin depolymerization technologies include biological depolymerization lignin, oxidative depolymerization, base-catalyzed depolymerization, acid-catalyzed depolymerization, hydrotreated depolymerization, and the like. Alkaline solution and alkaline catalyst are effective methods for alkali catalysis of lignin, lignin is dissolved in alkaline solution, alkali or alkaline earth metal ions polarize ether bonds in lignin structure, and bond rupture mainly occurs under the reaction conditionbeta-O-4 linkage and 4-O-5 linkage (diaryl ether linkage), while arylalkyl ether linkage is the weakest linkage in lignin. Common basic solvents are NaOH, KOH and Ca (OH) 2 An alkaline solvent of equal strength. Researchers added KOH solution to supercritical alcohol and found that the addition of strong base solution promoted lignin depolymerization, resulting in excellent conversion. Because the strong alkali solvent has strong corrosion effect on the reactor, and can not be recycled, the environment is polluted, and the economical efficiency is poor. The obtaining of bio-based phenolic compounds from lignin is an important measure for the efficient application of lignin. Among the various processes for value-added conversion of lignin, acid-catalyzed depolymerization is relatively more advantageous.
In recent years, research on novel catalysts has been reported to be endless, and the novel catalysts mainly comprise organic complexes of transition metals, supported nano noble metals, ionic liquids, mesoporous silicates, organic catalysts, polyoxometallates and the like. Polyoxometalates (POMs) are composed of a large number of polynuclear oxo-bridged transition metal compounds, with rich topology and multifunctional chemical and physical properties. Most commonly octahedra are connected to each other by corner and side sharing. However, due to their inherent drawbacks, their use is limited, such as low specific surface area, low stability under catalytic conditions, and their high solubility in aqueous solutions. Therefore, there is increasing research into polyoxometallates immobilized on various porous solid supports to improve their catalytic ability. Silicon carbide, chemical formula SiC, commonly known as silicon carbide, the name diamond is diamond, and is a ceramic compound formed by bonding silicon and carbon. Silicon carbide exists in nature in the form of a rare mineral, morganite. The natural oxidation resistance exhibited by silicon carbide, and the discovery of cubic beta-silicon carbide with a larger surface area, has enabled one to use it as a heterogeneous catalyst support.
Oxidative depolymerization typically uses oxidizing agents, such as molecular oxygen and H 2 O 2 . We need to study oxidative depolymerization of lignin under mild operating conditions, the principle of bond depolymerization during depolymerization being different from one oxidant to another due to the special function of the oxidant on bond cleavage. H 2 O 2 Is greenColored oxidants, and are converted to water as a byproduct during the reaction.
Many researchers also confirm H 2 O 2 Is reported to be H by Ouyang et al 2 O 2 As an oxidant to depolymerize wheat alkali lignin. By means of CuO/Fe 2 (SO 4 ) 3 As a catalyst, naOH was used to treat lignin in various solvents (methanol, 1, 4-dioxane, tetrahydrofuran, ethanol and co-solvents thereof), and it was observed that the water-methanol solvent mixture was effective in depolymerizing lignin, and that the degree of depolymerization of wheat alkali lignin was as high as 90.2% in the 16ml methanol and 4ml water solvent mixture. The highest yields (17.8%) of the monophenolic products of vanillin, vanillic acid, acetogenins, syringaldehyde and acetoxylins were observed under conditions of 10ml methanol and 10ml water, with Avnish Kumar et al at 120 ℃/30min under conditions of 1ml H 2 O 2 In the presence of (2), the maximum liquefaction amount of lignin is 80.0wt%.
From the green chemistry perspective, H 2 O 2 And O 2 Is the most ideal clean and economical oxidant, although the oxidation degradation of lignin and the compounds thereof adopts O at present 2 As the oxidizing agent, H is used 2 O 2 The depolymerization of lignin can be performed under milder conditions as an oxidizing agent, and the selectivity of the target product can be improved. This is because of H 2 O 2 Facilitating the transfer of functional groups under the system, activation of C-H bonds, cleavage of C-C and c=c. And we have adopted heterogeneous catalyst, solved and compared with single heteropolyacid catalyst supported structure usually has bigger specific surface area, better dispersibility and stability, the recovery of the catalyst of being convenient for is utilized.
Disclosure of Invention
Aiming at the technical problems, the invention provides a technical scheme for converting lignin into phenolic compounds by catalytic oxidation of a polyacid/hydrogen peroxide system, which is more efficient, more environment-friendly and environment-friendly.
The technical scheme comprises the following steps:
the polyacid catalyst is characterized by being a polyacid compound with a Keggin structure; the general formula of the polyacid compound with the Keggin structure is as follows:
xH 4 PMo 12 O 40 SiC, x is H 4 PMo 12 O 40 The mass ratio of x to SiC is 0.1-0.4.
The preparation method of the polyacid catalyst comprises the following steps:
adding silicon carbide as a carrier to an ethanol solution, and then adding phosphomolybdic acid (H 4 PMo 12 O 40 ) Removing redundant ethanol in vacuum after reflux stirring reaction, drying the obtained solid material, grinding into fine powder, and calcining the fine powder to obtain H 4 PMo 12 O 40 SiC composite, i.e. polyacid catalyst.
The ratio of the ethanol solution to silicon carbide was 4ml to 1g.
The H is 4 PMo 12 O 40 The amount of added is such that H 4 PMo 12 O 40 In the SiC composite material, H 4 PMo 12 O 40 The loading rate is 10-40wt%.
The reflux temperature is room temperature: the stirring time was 12h.
The temperature conditions for removing excess ethanol in vacuo were 78 ℃.
The drying temperature is 120 ℃ and the drying time is 24 hours.
The calcination temperature is 200-500 ℃ and the calcination time is 4 hours.
The polyacid/H for preparing the phenolic compound in an efficient and environment-friendly way 2 O 2 The method for preparing the phenolic compound by catalyzing the hydrolysis of biomass comprises the following steps: mixing lignin, polyacid catalyst, ethanol and water solution and H 2 O 2 Adding the mixture into a high-pressure reaction kettle, setting the reaction temperature to be between 90 and 160 ℃ and the reaction time to be between 0.5 and 5 hours, and hydrolyzing biomass to obtain phenolic compounds. After the reaction is finished, the product is extracted by methylene dichloride, and the organic solvent is distilled under reduced pressure at 45 ℃ to obtain the product.
The lignin, polyacid catalyst and H 2 O 2 The ratio of (2) is 0.25-0.4 g:0.25-0.4 g, 0.5 ml-2 ml; in the mixed solution of ethanol and water, the mass ratio of the ethanol to the water is 1:1-1:10.
The beneficial effects are that:
heterogeneous catalytic system plus H 2 O 2 The active free radical with medium and high concentration can more effectively promote the cleavage of beta-O-4 bond, better meet the requirements of selective cleavage of beta-O-4 bond and side chain oxidation in lignin depolymerization process, and depolymerize lignin into monophenol compound under mild condition.
Drawings
FIG. 1 is a gas quality test chart of the product after the reaction.
Detailed Description
Example 1
1.25g of silicon carbide as a carrier was added to 5ml of ethanol solution, followed by 0.25g of phosphomolybdic acid (H) 4 PMo 12 O 40 ) Reflux stirring at room temperature for 12H, vacuum removing excessive ethanol at 78deg.C, oven drying the obtained solid material at 120deg.C for 24H, grinding into fine powder, calcining the fine powder at 200deg.C for 4H to obtain H 4 PMo 12 O 40 SiC composite material, i.e. polyacid catalyst, H 4 PMo 12 O 40 In the SiC composite material, H 4 PMo 12 O 40 The loading was 20wt%.
The method for preparing the phenolic compound by catalyzing the hydrolysis of biomass comprises the following steps: a mixed solution of 0.25g lignin, 1.5g polyacid catalyst, 10ml ethanol and water and 0.5ml H 2 O 2 Adding the mixture into a high-pressure reaction kettle, setting the reaction temperature to 130 ℃, and reacting for 2 hours to hydrolyze biomass to obtain phenolic compounds. After the reaction is finished, the product is extracted by methylene dichloride, and the organic solvent is distilled under reduced pressure at 45 ℃ to obtain the product.
In the mixed solution of ethanol and water, the mass ratio of the ethanol to the water is 1:1.
The bio-oil yield was 56% and the lignin conversion was 65%.
Example 2
To 2ml of ethanol solution was added 0.5g of silicon carbide as a carrier, followed by 0.25g of phosphomolybdic acid (H) 4 PMo 12 O 40 )，Reflux stirring at room temperature for reaction for 12H, vacuum removing excessive ethanol at 78deg.C, oven drying at 120deg.C for 24H, grinding into fine powder, calcining at 400deg.C for 4H to obtain H 4 PMo 12 O 40 SiC composite material, i.e. polyacid catalyst, H 4 PMo 12 O 40 In the SiC composite material, H 4 PMo 12 O 40 The loading was 40wt%.
The polyacid/hydrogen peroxide system for preparing the phenolic compound in an efficient and environment-friendly way provided by the invention is used for catalyzing biomass hydrolysis to prepare the phenolic compound, and the method is as follows: a mixed solution of 0.4g lignin, 0.4g polyacid catalyst, 10ml ethanol and water and 1ml H 2 O 2 Adding the mixture into a high-pressure reaction kettle, setting the reaction temperature to 160 ℃, and reacting for 5 hours to hydrolyze biomass to obtain phenolic compounds. After the reaction is finished, the product is extracted by methylene dichloride, and the organic solvent is distilled under reduced pressure at 45 ℃ to obtain the product.
The mass ratio of the ethanol to the water is 3:7.
The bio-oil yield was 50% and the lignin conversion was 73%.
FIG. 1 shows the gas quality detection diagram of the product after the reaction, and the peaks of the phenolic compounds such as 6.879-6.925min phenol, 10.710-10.790min catechol, 13.310-13.365min vanillin and the like can be clearly seen by comparison of a spectrum library.
Claims (6)
1. The application of the polyacid catalyst is characterized in that the polyacid catalyst is a polyacid compound with a Keggin structure; the general formula of the polyacid compound with the Keggin structure is as follows: xH (x H) 3 PMO 12 O 40 SiC, x is H 3 PMO 12 O 40 The mass ratio of the silicon carbide to the SiC is 0.1 to 0.4; the method is characterized in that the biomass is catalyzed to hydrolyze to prepare phenolic compounds; mixing lignin, polyacid catalyst, ethanol and water solution and H 2 O 2 Adding the mixture into a high-pressure reaction kettle, setting the reaction temperature to be 90-160 ℃ and the reaction time to be 0.5-5 h, hydrolyzing biomass to obtain phenolic compounds, extracting the products with dichloromethane after the reaction is finished, and distilling the organic solvent at 45 ℃ under reduced pressure to obtain the product.
2. Use of a polyacid catalyst according to claim 1, wherein the lignin, the polyacid catalyst and H 2 O 2 The ratio of the (C) is 0.25-0.4 g, 0.25-0.4 g and 0.5 mL-2 mL; in the mixed solution of ethanol and water, the mass ratio of the ethanol to the water is 1:1-1:10.
3. Use of a polyacid catalyst according to claim 1, characterized in that the polyacid catalyst is prepared by the following method: adding silicon carbide as a carrier into an ethanol solution, and then adding phosphomolybdic acid H 3 PMO 12 O 40 Removing redundant ethanol in vacuum after reflux stirring reaction, drying the obtained solid material, grinding into fine powder, and calcining the fine powder to obtain H 3 PMO 12 O 40 SiC composite, i.e. polyacid catalyst.
4. Use of a polyacid catalyst according to claim 3, wherein the ratio of ethanol solution to silicon carbide is 4ml to 1 g; the H is 3 PMO 12 O 40 The amount of added is such that H 3 PMO 12 O 40 In the SiC composite material, H 3 PMO 12 O 40 The loading rate is 10-40wt%.
5. Use of a polyacid catalyst according to claim 3, wherein the reflux temperature is room temperature and the stirring time is 12 hours; the temperature conditions for removing excess ethanol in vacuo were 78 ℃.
6. Use of a polyacid catalyst according to claim 3, wherein the drying temperature is 120 ℃ and the drying time is 24 hours; the calcination temperature is 200-500 ℃ and the calcination time is 4 hours.
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| CN103846099A (en) * | 2014-02-20 | 2014-06-11 | 宁波高新区夏远科技有限公司 | Supported polyoxometallate and preparation method thereof |
| CN107827732A (en) * | 2017-10-26 | 2018-03-23 | 吉林农业科技学院 | Biomass oxidative degradation prepares the method for organic acid and obtained organic acid |
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| US3395178A (en) * | 1965-03-08 | 1968-07-30 | Standard Oil Co | Process for producing unsaturated carboxylic acids with phosphomolybdic acid on silicon carbide as catalyst |
| CN1390643A (en) * | 2002-06-17 | 2003-01-15 | 中国科学院大连化学物理研究所 | Application method of heteropoly acid type catalyst |
| CN102476980B (en) * | 2010-11-30 | 2014-06-04 | 中国科学院大连化学物理研究所 | Application of tungsten-based catalyst in lignin catalytic hydrogenation for producing aromatic compound |
| BR112017009030B1 (en) * | 2014-10-30 | 2021-01-12 | Organofuel Sweden Ab | METHODS FOR CONVERTING A CO OR C = O CONNECTION TO A C-H CONNECTION |
| CN109833892A (en) * | 2017-11-29 | 2019-06-04 | 昌吉学院 | A kind of novel processing step of solid-carrying heteropolyacid catalyst and its application of aromatic compound is prepared in catalysis oxidation lignin |
| CN108689819B (en) * | 2018-05-24 | 2021-03-30 | 中国石油大学(华东) | Novel method for degrading wood chips through catalytic oxidation of polyoxometallate |
| CN109382104B (en) * | 2018-10-16 | 2020-06-26 | 中国科学技术大学 | Method and catalyst for preparing ethanol from lignocellulose biomass in one step |
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| CN103846099A (en) * | 2014-02-20 | 2014-06-11 | 宁波高新区夏远科技有限公司 | Supported polyoxometallate and preparation method thereof |
| CN107827732A (en) * | 2017-10-26 | 2018-03-23 | 吉林农业科技学院 | Biomass oxidative degradation prepares the method for organic acid and obtained organic acid |
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