CN112851499A - Method for preparing maleic acid by catalyzing cellulose with bifunctional solid catalyst - Google Patents
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
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Abstract
The invention discloses a method for preparing maleic acid by catalyzing cellulose with a bifunctional solid catalyst, and belongs to the field of new energy and new materials. The invention makes full use of the heteropoly acid substituted salt composite catalyst and simultaneously has Lewis acidity,
The acid and strong oxidizing property can be respectively used as an acid catalyst and an oxidation catalyst to selectively catalyze the hydrolysis of cellulose, the dehydration of glucose and the oxidation of 5-hydroxymethylfurfural under hydrothermal conditions, so that the higher yield of maleic acid is obtained. The method has cellulose hydrolysis rate up to 73.1%, glucose conversion rate up to 93.5%, and 5-hydroxymethylThe yield of the furfural reaches 85 percent, and the final yield of the maleic acid reaches 44.2 percent. The process is simple and convenient to operate, low in cost and environment-friendly, and can provide a new catalytic process for producing high-added-value bio-based chemicals by converting cellulose-based biomass.
Description
Technical Field
The invention belongs to the field of new energy and new materials, and relates to a method for preparing bio-based chemicals by biomass conversion, in particular to a method for preparing maleic acid by hydrolysis, dehydration and oxidation reactions of cellulose.
Background
As fossil resources are reduced, the demand for renewable energy development is increasing. Due to its environmental friendliness and abundant resources, biomass is considered as an ideal substitute for traditional fossil resources. A huge amount of lignocellulose exists in nature and is decomposed into a series of C5-C6Sugars, and can be further converted into renewable platform compounds such as furfural, 5-Hydroxymethylfurfural (HMF), furanone, and maleic acid, among others. At present, starting from biomass, platform compounds can be obtained by two methods, namely sequential conversion and one-step method. The sequential conversion method has complex process and higher production cost; the one-step method such as gasification and pyrolysis is easier to industrialize, but has low utilization efficiency of raw materials, low product value and great pollution to the environment.
A series of previous studies on the preparation of 5-hydroxymethylfurfural by cellulose hydrolysis and glucose dehydration and furfural oxidative conversion (BioResource Technol 2011,102(17): 8017-. It has been shown that by reducing the crystallinity of cellulose, its solubility and subsequent yield to glucose by hydrolysis are improved; further isomerizing glucose to greatly improve the yield and selectivity of the 5-hydroxymethylfurfural.
However, the solvent in the hydrolysis reaction system of cellulose has H2O or product H2O, inhibits the further dehydration and transformation of the glucose which is a subsequent intermediate product, and leads to the difficulty in obtaining the ideal yield of the 5-hydroxymethylfurfural by a one-pot method. Furthermore, 5-hydroxymethylfurfural can be converted to a series of C's by different catalytic processes, such as selective hydrogenation, oxidation, hydrogenolysis and decarboxylation4And C5A molecule. Wherein the oxidation reaction can be converted into a plurality of chemical intermediates and final products, including furanone, furoic acid, fumaric acid, succinic acid, maleic acid and the like, according to the types of catalysts and reaction solvent systems. However, most of the reported catalysisAgent with Lewis alone
Due to acidity or oxidizability, the hydrolysis, glucose dehydration conversion and 5-hydroxymethylfurfural oxidation of cellulose are difficult to realize by using one catalyst, and the cellulose cannot be converted into high-value-added products such as maleic acid by a one-pot method.
Disclosure of Invention
Aiming at the defects of the existing preparation process, the invention provides a method for preparing maleic acid by catalyzing cellulose with a bifunctional solid catalyst, which takes cellulose as a starting material and obtains the final product maleic acid through the hydrolysis-dehydration-oxidation process catalyzed by heteropolyacid salt.
A method for preparing maleic acid by catalyzing cellulose with a bifunctional solid catalyst comprises the step of using the bifunctional solid catalyst heteropolyacid salt to perform reaction in a hydrophilic DES (eutectic solvent) solution system
Acidity, catalyzing hydrolysis of cellulose; the Lewis acidity of the cellulose hydrolysate contributes to the isomerization of glucose serving as a cellulose hydrolysate, so that the selective dehydration of the glucose is improved to prepare the 5-hydroxymethylfurfural; finally, dichloroethane is introduced into the reaction system to form a two-phase solvent system, so that the product inhibition is reduced, and the selectivity and the yield of maleic acid prepared by oxidizing 5-hydroxymethylfurfural with heteropolyacid salt are improved.
The invention provides a method for preparing maleic acid by catalyzing cellulose with a bifunctional solid catalyst, which comprises the following steps:
firstly, adding a hydrophilic DES solution into a reactor, preheating to 80-160 ℃, adding cellulose accounting for 5-15% of the weight of the DES solution, and dissolving; then adding a solid catalyst which accounts for 1-10% of the mass ratio of the DES solution, wherein the solid catalyst is a heteropolyacid salt composite material, and the molar ratio of metal ions to heteropolyacid is 0.25-2: 1; adding H accounting for 1-5% of the volume percentage of the DES solution at the preheating temperature2O, stirring and carrying out hydrolysis reaction for 1-10 hours to obtain a mixed solution A;
secondly, adding dichloroethane into the mixed solution A, wherein the volume ratio of the dichloroethane to the hydrophilic DES solution in the first step is 0.1-1: 1; uniformly mixing and preheating to 30-110 ℃, and adding 1-4 mL of H per 10g of DES solution2O2And continuing to react for 0.5-2.5 h, and separating and purifying the product after the reaction is finished to prepare the maleic acid.
Further, the hydrophilic DES solution is obtained by mixing choline chloride and oxalic acid according to the volume ratio of 1: 1-2.
The heteropoly acid salt composite material is synthesized by phosphotungstic heteropoly acid and transition metal salt through a hydrothermal method.
Further, the separation and purification in the second step are: and after the reaction is finished, separating the hydrophilic DES solution and the dichloroethane solution, and enriching the maleic acid product in the hydrophilic phase.
The invention has the advantages that the solid catalyst heteropoly acid salt simultaneously has Lewis acidity,
The acidity and strong oxidizing property can be used for hydrolysis reaction of cellulose and dehydration reaction of glucose, and can also be used for oxidation reaction of 5-hydroxymethylfurfural. So that the cellulose can be hydrolyzed, dehydrated and oxidized under the same catalytic system to obtain the final product maleic acid. This process usually requires more than two different types of catalysts and can be completed in two to three reaction steps. In addition, the bifunctional solid catalyst heteropolyacid salt has simple preparation process and is easy to recover and reuse.
Drawings
FIG. 1 shows the conversion of the product in a biphasic system.
FIG. 2 is an SEM spectrum of the bifunctional solid catalyst.
Fig. 3 is a graph of the results of the dual function solid catalyst DES measurements.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
Example one
Weighing phosphotungstic heteropoly acid and SnCl according to the molar ratio of 1:1:0.254And CsCl, and synthesizing the solid catalyst heteropolyacid salt in a water phase at 90 ℃, wherein an SEM spectrogram and a DES measurement result chart are respectively shown in a figure 2 and a figure 3.
Weighing 10g of hydrophilic DES, fully mixing in a reactor, heating to 140 ℃, adding and dissolving 0.5g of cellulose, adding 0.5g of solid catalyst, adding 0.3mL of water, performing hydrolysis reaction for 10h, sampling, and performing HPLC analysis, wherein the cellulose hydrolysis rate is 73.1%, and the yield of 5-hydroxymethylfurfural is 75%.
The reaction system was further charged with an equal volume of dichloroethane, heated to 50 ℃ and 3mL of H were added2O2And continuing to react for 2.0h, separating and purifying the product after the reaction is finished, wherein the yield of the maleic acid reaches 44.2 percent.
Example two
Firstly weighing 10g of hydrophilic DES, fully mixing in a reactor, heating to 160 ℃, then adding 1.5g of cellulose and dissolving, then adding 0.5g of solid catalyst, adding 0.5mL of water, carrying out hydrolysis reaction for 10h, sampling for HPLC analysis, wherein the cellulose hydrolysis rate is 62.4%, and the yield of 5-hydroxymethylfurfural is 59%.
The reaction was continued by adding an equal volume of dichloroethane, heating to 90 ℃ and adding 4mL of H2O2And continuing to react for 2.0h, separating and purifying the product after the reaction is finished, wherein the yield of the maleic acid reaches 37.4 percent.
EXAMPLE III
Firstly weighing 10g of hydrophilic DES, fully mixing in a reactor, heating to 100 ℃, then adding 0.5g of cellulose and dissolving, then adding 0.5g of solid catalyst, adding 0.1mL of water, carrying out hydrolysis reaction for 10h, sampling for HPLC analysis, wherein the cellulose hydrolysis rate is 45.6%, and the yield of 5-hydroxymethylfurfural is 39%.
The reaction was continued by adding an equal volume of dichloroethane, heating to 90 ℃ and adding 4mL of H2O2And continuing to react for 2.5h, separating and purifying the product after the reaction is finished, wherein the yield of the maleic acid reaches 27.4 percent.
Example four
Firstly weighing 10g of hydrophilic DES, fully mixing in a reactor, heating to 80 ℃, then adding 0.1g of cellulose and dissolving, then adding 0.05g of solid catalyst, adding 0.3mL of water, carrying out hydrolysis reaction for 10h, sampling and carrying out HPLC analysis, wherein the cellulose hydrolysis rate is 36.3%, and the yield of 5-hydroxymethylfurfural is 31%.
The reaction system was further charged with an equal volume of dichloroethane, heated to 30 ℃ and 1mL of H was added2O2And continuing to react for 2.5h, separating and purifying the product after the reaction is finished, wherein the yield of the maleic acid reaches 22.8 percent.
EXAMPLE five
Firstly weighing 10g of hydrophilic DES, fully mixing in a reactor, heating to 140 ℃, then adding 0.5g of cellulose and dissolving, then adding 0.15g of solid catalyst, adding 0.3mL of water, carrying out hydrolysis reaction for 1h, sampling for HPLC analysis, wherein the cellulose hydrolysis rate is 31.4%, and the yield of 5-hydroxymethylfurfural is 29.2%.
The reaction system was further charged with an equal volume of dichloroethane, heated to 30 ℃ and 1mL of H was added2O2And continuing to react for 0.5h, separating and purifying the product after the reaction is finished, wherein the yield of the maleic acid reaches 15.1%.
Claims (4)
1. A method for preparing maleic acid by catalyzing cellulose with a bifunctional solid catalyst is characterized by comprising the following steps:
firstly, adding a hydrophilic DES solution into a reactor, preheating to 80-160 ℃, adding cellulose accounting for 5-15% of the weight of the DES solution, and dissolving; then adding a solid catalyst which accounts for 1-10% of the mass ratio of the DES solution, wherein the solid catalyst is a heteropolyacid salt composite material, and the molar ratio of metal ions to heteropolyacid is 0.25-2: 1; adding H accounting for 1-5% of the volume percentage of the DES solution at the preheating temperature2O, stirring and carrying out hydrolysis reaction for 1-10 hours to obtain a mixed solution A;
secondly, adding dichloroethane into the mixed solution A, wherein the volume ratio of the dichloroethane to the hydrophilic DES solution in the first step is 0.1-1: 1; uniformly mixing and preheating to 30-110 ℃, and adding 1-4 mL of H per 10g of DES solution2O2Continuously reacting for 0.5-2.5 h, and after the reaction is finished, reactingAnd separating and purifying the product to obtain maleic acid.
2. The method for preparing maleic acid by catalyzing cellulose through the bifunctional solid catalyst according to claim 1, wherein the hydrophilic DES solution is prepared by mixing choline chloride and oxalic acid in a volume ratio of 1: 1-2.
3. The method for preparing maleic acid by catalyzing cellulose with the bifunctional solid catalyst as claimed in claim 1, wherein the heteropoly acid salt composite material is synthesized by a hydrothermal method from phosphotungstic heteropoly acid and transition metal salt.
4. The method for preparing maleic acid by catalyzing cellulose with the bifunctional solid catalyst as claimed in claim 1, wherein the separation and purification in the second step are as follows: and after the reaction is finished, separating the hydrophilic DES solution and the dichloroethane solution, and enriching the maleic acid product in the hydrophilic phase.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950091A (en) * | 2018-07-31 | 2018-12-07 | 河北科技大学 | A kind of eutectic solvent, preparation method and the application in glucose is prepared in hydrocellulose |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950091A (en) * | 2018-07-31 | 2018-12-07 | 河北科技大学 | A kind of eutectic solvent, preparation method and the application in glucose is prepared in hydrocellulose |
Non-Patent Citations (6)
| Title |
|---|
| FEI LIU, ET AL.,: ""Selectivity enhancement in the aqueous acid-catalyzed conversion of glucose to 5-hydroxymethylfurfural induced by choline chloride"", 《GREEN CHEM.,》 * |
| QIANG YU ET AL.,: ""A sustainable system for maleic acid synthesis from biomass-derived sugar"", 《J CHEM TECHNOL BIOTECHNOL》 * |
| XIAOQIAN GUO ET AL.,: ""Dehydration of D-xylose into furfural over bimetallic salts of heteropolyacid in DMSO/H2O mixture"", 《APPLIED CATALYSIS A, GENERAL》 * |
| YONG NI, ET AL.,: ""Deep eutectic solvent (DES) as both solvent and catalyst for oxidation of furfural to maleic acid and fumaric acid"", 《GREEN CHEM.》 * |
| 倪镛: ""在新型DES中氧化糠醛制备马来酸和富马酸"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
| 兰蕾: ""低共熔溶剂中多酸催化剂催化碳水化合物制备5-羟甲基糠醛的研究"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
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