CN114736175B - Method for preparing 5-hydroxymethylfurfural by catalyzing glucose in aqueous phase - Google Patents
Method for preparing 5-hydroxymethylfurfural by catalyzing glucose in aqueous phase Download PDFInfo
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Abstract
The invention belongs to the technical field of glucose dehydration, and relates to a method for preparing 5-hydroxymethylfurfural by catalyzing glucose in a water phase, which comprises the following steps: fully dispersing a bifunctional solid acid catalyst in a glucose aqueous solution, reacting the bifunctional solid acid catalyst with glucose for 30-600 minutes at 130-170 ℃ according to the mass ratio of 1:10-1:50, centrifugally separating the bifunctional solid acid catalyst, and concentrating and refining to obtain 5-hydroxymethylfurfural; the bifunctional solid acid catalyst is any one or more ion doped niobium-based phosphate solid acid catalysts with mesoporous and macroporous structures in Ca, sr, ba, al, cd, ce, fe, la, mn, ni, sn, Y, zn, has the characteristics of catalyzing glucose to be converted into 5-hydroxymethylfurfural by taking pure water as a reaction solvent and having high reaction activity, and realizes the efficient water phase conversion of cellulose-derived glucose.
Description
Technical Field
The invention belongs to the technical field of preparation of 5-hydroxymethylfurfural, and particularly relates to a method for preparing 5-hydroxymethylfurfural by catalyzing glucose in a water phase.
Background
At present, the efficient utilization of carbohydrate biomass resources such as cellulose/hemicellulose is mainly realized by a platform compound path, namely, the cellulose hemicellulose/cellulose is hydrolyzed into micromolecular aldehyde type monosaccharides, and then the aldehyde type monosaccharides are dehydrated to generate furfural type compounds after ketosaccharification (such as glucose isomerization to fructose and xylose isomerization to xylulose). Particularly, if the efficient preparation of a platform compound such as 5-Hydroxymethylfurfural (HMF) in an aqueous phase can be realized, the practical economy of the utilization base of cellulosic biomass will be greatly affected. At present, the preparation method of HMF adopts fructose as a raw material in many ways, and has achieved a relatively high production efficiency. However, since fructose is expensive, many studies have focused on the production of HMF using glucose. In the method for preparing HMF from glucose, a homogeneous catalyst such as a metal salt or a mineral acid, and a water-organic solvent biphasic system are often used. Although higher HMF yields can be obtained by using such methods, practical applications are limited due to a number of problems such as catalyst recovery, wastewater treatment, environmental pollution, and organic solvent toxicity. On the other hand, many studies have focused on developing a bifunctional solid catalyst having a Lewis acidic site catalyzing glucose isomerization to fructose and a Bronsted acidic site catalyzing dehydration reaction. The catalyst can continuously catalyze glucose to be isomerized into fructose by a one-pot method and then carry out fructose dehydration reaction. At present, a water-organic solvent system is still commonly used for the application of the catalyst, and the problem of using an organic solvent is not solved effectively. Therefore, development of a bifunctional catalyst in pure water phase has been receiving more attention and research. Because of a series of problems of complex reaction paths of saccharides in a water phase, strong competition of side reaction dynamics and the like, the efficiency of the catalyst reported so far is still very low, and when glucose is used as a raw material to prepare 5-hydroxymethylfurfural in the water phase, the product yield is usually less than 20 percent or the catalyst cannot be effectively recycled. Therefore, development of a high-efficiency bifunctional solid catalyst capable of catalyzing aldehyde monosaccharides such as glucose to be converted into furfural-type platform compounds such as 5-hydroxymethylfurfural in an aqueous phase is needed.
Disclosure of Invention
The purpose of the invention is that: provides a method for preparing 5-hydroxymethylfurfural by catalyzing glucose in a water phase, so as to overcome the technical defects in the prior art. The method of the invention is as follows: the metal ion doped non-equilibrium phosphate difunctional solid acid is prepared by using metal niobium as a main element through a solution synthesis method. The synthesized catalyst has Lewis acidic catalytic sites and Bronsted acidic catalytic sites, can continuously catalyze the dehydration reaction of glucose to fructose and fructose to 5-hydroxymethylfurfural in a water phase, and realizes the efficient catalysis of biomass-based aldose to 5-hydroxymethylfurfural and other platform compounds by a one-pot method; the catalyst has macropores beneficial to the diffusion of reactants and mesoporous structures providing high-density catalytic sites, has small diffusion limit in the reaction process, has high apparent reaction speed, and is beneficial to the improvement of reaction selectivity. Thus, the difunctional solid acid catalyst for preparing the 5-hydroxymethylfurfural by efficiently catalyzing the glucose to be converted is prepared by a simple process, and a product with high 5-hydroxymethylfurfural content is obtained under a mild condition.
In order to achieve the aim of the invention, the adopted specific technical scheme is as follows:
the method for preparing 5-hydroxymethylfurfural by catalyzing glucose in an aqueous phase comprises the following steps: fully dispersing a bifunctional solid acid catalyst in a glucose aqueous solution, reacting the bifunctional solid acid catalyst with glucose for 30-600 minutes at 130-170 ℃ according to the mass ratio of 1:10-1:50, centrifugally separating the bifunctional solid acid catalyst, and concentrating and refining to obtain 5-hydroxymethylfurfural;
wherein the bifunctional solid acid catalyst is obtained by the following method: digesting ammonium niobium oxalate until the solution is colorless, clear and transparent (generally 8-16 hours) at 70-90 ℃ by using 30-35% hydrogen peroxide solution and alpha-hydroxy acid as a niobium ion complexing agent, cooling to room temperature, adding lactic acid, polyethylene glycol, polyacrylamide and other metal ion precursors, stirring and fully dissolving to a complete solution state, adding concentrated hydrochloric acid and/or glycerol, adding concentrated phosphoric acid to react with metal ion ligands and gelling to obtain a niobium-metal phosphate cogel material, and finally fully roasting and activating the niobium-metal phosphate cogel material at 500-900 ℃ in air or oxygen-containing atmosphere to obtain the difunctional solid acid catalyst; the doped metal ion precursor can be one or more of Ca, sr, ba, al, cd, ce, fe, la, mn, ni, sn, Y, zn chloride, nitrate or carbonate, and the prepared catalyst has better effect when doped with Cd, sn and Zn chloride, nitrate or carbonate.
Further, the alpha-hydroxy acid may be lactic acid, citric acid, acetic acid, tartaric acid, maleic acid or a mixture of the above organic acids, with citric acid and lactic acid being most effective.
The metal ion doped non-equilibrium state high-activity niobium-based phosphate is prepared by a solution synthesis method, a difunctional solid acid with Lewis acidic catalytic sites and Bronsted acidic catalytic sites is constructed, and the biomass-based aldose isomerization and dehydration are continuously catalyzed to prepare the platform compound 5-hydroxymethylfurfural. Thus, the 5-hydroxymethylfurfural is efficiently prepared in the water phase by a one-pot method under mild conditions by a simple process.
The invention further provides a preparation method of the high-efficiency bifunctional solid acid catalyst for preparing 5-hydroxymethylfurfural by catalyzing glucose in a water phase, which comprises the following steps: preparing an atomically dispersed niobium-organic acid coordination compound in a solution phase, doping other metal ion precursors, uniformly contacting the atomically dispersed niobium-organic acid coordination compound with other metal ions by using an organic coordination agent or reducing pH value, adding a polymer with a regular pore structure, and finally adding concentrated phosphoric acid to enable the two metal ions and phosphoric acid to generate a cogel material, wherein the cogel material is dried, roasted and activated to obtain the difunctional solid acid. Wherein, concentrated hydrochloric acid and other organic complexing agents can be added according to the gelation reaction control conditions. The synthesized bifunctional phosphate solid acid catalyst has a through type macroporous structure and mesoporous with high specific surface area in a framework; the niobium and the doped metal ions are mixed uniformly, and the catalyst has Lewis acid sites and Bronsted acid sites, so that the isomerization of aldose to ketose and the dehydration reaction of ketose can be efficiently and continuously catalyzed.
In order to ensure that the prepared difunctional phosphate solid acid generates mesoporous with uniform through macropores and pore size distribution, the invention further defines high polymers of polyacrylamide and polyethylene glycol according to specific reaction conditions, wherein the polyethylene glycol dosage is 12-25 g/mol of ammonium niobium oxalate, and the polyacrylamide dosage is 85-350 g/mol of ammonium niobium oxalate.
Compared with the prior art, the invention has the following beneficial effects:
1. the bifunctional solid acid catalyst provided by the invention has the performance of generating the platform compound 5-hydroxymethylfurfural by continuous reaction of biomass-based aldose through one-pot aqueous phase catalysis under mild conditions, and realizes green and efficient catalysis of aqueous phase conversion of saccharide biomass.
2. The Bronsted acid of the bifunctional solid acid catalyst not only can catalyze the dehydration of ketose, but also can catalyze the hydrolysis of glycosidic bonds, so that reactants can be expanded to disaccharides or polysaccharides containing glycosidic bonds, namely, the series catalytic hydrolysis-isomerization-dehydration reaction can be realized.
3. The bifunctional solid acid catalyst is a solid phase catalytic system, has small corrosiveness to equipment, and is separated by filtration or centrifugal separation after the reaction is finished. The production process is more operable, and the cost for converting cellulosic biomass into the platform compound can be reduced.
Drawings
FIG. 1 is a bifunctional niobium-based phosphate solid acid prepared in example 1 of the present invention.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The method for preparing 5-hydroxymethylfurfural from glucose in water phase comprises the steps of controlling a bifunctional solid acid catalyst to be fully dispersed in glucose water solution, enabling the bifunctional solid acid catalyst to react with glucose for 30-600 minutes at 130-170 ℃ according to a mass ratio of 1:10-1:50, centrifugally separating the bifunctional solid acid catalyst, and concentrating and refining to obtain 5-hydroxymethylfurfural; the difunctional solid acid catalyst is any one or more ion doped niobium-based phosphate solid acid catalysts with mesoporous and macroporous structures in Ca, sr, ba, al, cd, ce, fe, la, mn, ni, sn, Y, zn, and the surface phosphate radical is in a pyrophosphoric acid structure. The method can realize high-efficiency conversion of the 5-hydroxymethylfurfural, and has obvious technical advantages compared with the prior art. Meanwhile, the catalyst provided by the invention can also catalyze galactose, xylose and arabinose to dehydrate to obtain 5-hydroxymethylfurfural.
The invention is further described in detail below in connection with examples and comparative examples:
comparative example 1 preparation of 5-hydroxymethylfurfural from glucose catalyzed by niobium oxide phosphate
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out at 80 ℃ until transparency, cooling is carried out to room temperature, 50ml of hydrochloric acid with the mass concentration of 10.0mol/L and 100g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%) and 20g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) are added, after stirring until complete dissolution, 140ml of phosphoric acid with the mass concentration of 83% is added, standing is carried out until gelation, the obtained material is exchanged with methanol solvent, unreacted components in the material are removed, methanol is exchanged with n-hexane solvent, vacuum drying is carried out, and white solid niobium oxide phosphate which is expressed as NbPO is obtained after roasting at 600 ℃ for 8 hours in air atmosphere.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid NbPO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 13% after high performance liquid chromatography analysis.
Comparative example 2 preparation of 5-hydroxymethylfurfural from glucose catalyzed by solid acid niobium pentoxide
1g of glucose was dissolved in 100ml of deionized water, 0.1g of commercially available solid acid niobium pentoxide was added, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 10.6% after high performance liquid chromatography analysis.
Example 1 preparation of 5-hydroxymethylfurfural from Cd ion doped niobium-based bifunctional phosphate solid acid catalyzed glucose
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at 85 ℃ until the solution is clear and transparent, cooling is carried out to room temperature, 50ml of lactic acid with the mass concentration of 98%, 80ml of hydrochloric acid with the mass concentration of 10M are sequentially added, 175g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 12.4 g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of cadmium nitrate tetrahydrate are stirred until complete dissolution, 105ml of phosphoric acid with the mass concentration of 85% are added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with normal hexane solvent and dried in vacuum, and finally the material is roasted for 8 hours at 500-800 ℃ in air atmosphere, thus obtaining the cadmium-doped niobium-based bifunctional solid acid catalyst which is expressed as 0.2Cd-Nb-PO.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Cd-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 29% after high performance liquid chromatography analysis.
Example 2 preparation of 5-hydroxymethylfurfural from glucose catalyzed by Sn-doped niobium-based bifunctional phosphate solid acid
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at 85 ℃ until the solution is clear and transparent, the solution is cooled to room temperature, 100ml of lactic acid with the mass concentration of 98%, 83g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 15.3 g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of tin tetrachloride pentahydrate are sequentially added, after stirring until the solution is completely dissolved, 105ml of phosphoric acid with the mass concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with normal hexane solvent and vacuum-dried, and finally the tin-doped niobium-based bifunctional solid acid catalyst which is expressed as 0.2Sn-Nb-PO is obtained after roasting for 8 hours at 500-800 ℃ in air atmosphere.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Sn-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 25% after high performance liquid chromatography analysis.
Example 3 Zn ion doped niobium-based bifunctional phosphate solid acid catalyzed glucose preparation of 5-hydroxymethylfurfural
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at 85 ℃ until the solution is clear and transparent, cooling is carried out to room temperature, 100ml of hydrochloric acid with the mass concentration of 10M, 102g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 16g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of zinc chloride are sequentially added, stirring is carried out until the solution is completely dissolved, 105ml of phosphoric acid with the mass concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with normal hexane solvent and vacuum drying is carried out, and finally zinc-doped niobium-based bifunctional solid acid catalyst which is expressed as 0.2Zn-Nb-PO is obtained after roasting for 8 hours at 500-800 ℃.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Zn-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 27% after high performance liquid chromatography analysis.
Example 4 Ca ion doped niobium based bifunctional phosphate solid acid catalyzed glucose preparation of 5-hydroxymethylfurfural
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at 85 ℃ until the solution is clear and transparent, cooling is carried out to room temperature, 100ml of hydrochloric acid with the mass concentration of 5M, 125g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 15.4g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of calcium chloride dihydrate are sequentially added, stirring is carried out until the solution is completely dissolved, 140ml of phosphoric acid with the mass concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with n-hexane solvent and vacuum drying is carried out, and finally, the calcium doped niobium-based bifunctional solid acid catalyst which is obtained by roasting for 8 hours at 500-800 ℃ in air atmosphere is expressed as 0.2Ca-Nb-PO.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Ca-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 20.6% after high performance liquid chromatography analysis.
EXAMPLE 5 preparation of 5-hydroxymethylfurfural from Sr-ion doped niobium-based bifunctional phosphate solid acid catalyzed glucose
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at the temperature of 85 ℃ until the solution is clear and transparent, cooling is carried out to room temperature, 100ml of hydrochloric acid with the mass concentration of 5M, 131g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 14g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of strontium chloride hexahydrate are sequentially added, after stirring until the solution is completely dissolved, 140ml of phosphoric acid with the mass concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with n-hexane solvent and dried in vacuum, and finally, the strontium-doped niobium-based bifunctional solid acid catalyst which is obtained after roasting for 8 hours at the temperature of 500-800 ℃ in the air atmosphere is expressed as 0.2Sr-Nb-PO.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Sr-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 19.6% after high performance liquid chromatography analysis.
EXAMPLE 6 preparation of 5-hydroxymethylfurfural from glucose catalyzed by Ba-ion doped niobium-based bifunctional phosphate solid acid
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of 35% hydrogen peroxide solution, digested for 14 hours at 85 ℃ until the solution is clear and transparent, cooled to room temperature, 50ml of 5M hydrochloric acid, 50ml of 10M hydrochloric acid, 200ml of deionized water, 100ml of glycerin, 250g of polyacrylamide solution (weight average molecular weight is 1 ten thousand, mass concentration is 50%), 21g of polyethylene glycol (weight average molecular weight is 3.5 ten thousand) and 0.2mol of barium chloride dihydrate are sequentially added, stirred until the solution is completely dissolved, 105ml of 85% phosphoric acid is added, standing and gelation are carried out, unreacted components in the obtained material are removed, methanol is exchanged by using a methanol solvent, vacuum drying is carried out, and finally the barium-doped niobium-based bifunctional solid acid catalyst which is expressed as 0.2Ba-Nb-PO is obtained after roasting for 8 hours at 500-800 ℃ in air atmosphere.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Ba-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 20.0% after high performance liquid chromatography analysis.
EXAMPLE 7 preparation of 5-hydroxymethylfurfural from glucose catalyzed by Al ion doped niobium-based bifunctional phosphate solid acid
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, digested for 14 hours at the temperature of 85 ℃ until the solution is clear and transparent, cooled to room temperature, 63g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 14g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of aluminum nitrate nonahydrate are sequentially added, stirred until the solution is completely dissolved, 105ml of phosphoric acid with the concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with n-hexane solvent and dried in vacuum, and finally the aluminum-doped niobium-based bifunctional solid acid catalyst which is expressed as 0.2Al-Nb-PO is obtained after roasting for 8 hours at the temperature of 500-800 ℃.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Al-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 16.5% after high performance liquid chromatography analysis.
Example 8 preparation of 5-hydroxymethylfurfural from Ce-doped niobium-based bifunctional phosphate solid acid catalyzed glucose
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at 85 ℃ until the solution is clear and transparent, cooling is carried out to room temperature, 150ml of hydrochloric acid with the mass concentration of 10M, 180ml of glycerin, 160g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 16g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of cerium trichloride heptahydrate are sequentially added, stirring is carried out until the solution is completely dissolved, 105ml of phosphoric acid with the mass concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with normal hexane solvent and vacuum drying is carried out, and finally, the cerium doped niobium-based bifunctional solid acid catalyst which is expressed as 0.2Ce-Nb-PO is obtained after roasting for 8 hours at 500-800 ℃ in air atmosphere.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Ce-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 23.1% after high performance liquid chromatography analysis.
Example 9 preparation of 5-hydroxymethylfurfural from La-ion doped niobium-based bifunctional phosphate solid acid catalyzed glucose
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at 85 ℃ until the solution is clear and transparent, cooling is carried out to room temperature, 150ml of hydrochloric acid with the mass concentration of 10M, 200ml of glycerin, 167g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 16g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of lanthanum trichloride heptahydrate are sequentially added, stirring is carried out until the solution is completely dissolved, 105ml of phosphoric acid with the mass concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with normal hexane solvent and vacuum drying is carried out, and finally, the lanthanum-doped niobium-based bifunctional solid acid catalyst which is obtained by roasting for 8 hours at 500-800 ℃ in air atmosphere is expressed as 0.2La-Nb-PO.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Ce-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 18.7% after high performance liquid chromatography analysis.
Example 10 preparation of 5-hydroxymethylfurfural from V-ion doped niobium-based bifunctional phosphate solid acid catalyzed glucose
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at 85 ℃ until the solution is clear and transparent, the solution is cooled to room temperature, 50ml of lactic acid with the mass concentration of 98%, 120g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 18.5g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of ammonium vanadate are sequentially added, after stirring until the solution is completely dissolved, 105ml of phosphoric acid with the mass concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with n-hexane solvent and dried in vacuum, and finally the vanadium-doped niobium-based bifunctional solid acid catalyst which is expressed as 0.2V-Nb-PO is obtained after roasting for 8 hours at 500-800 ℃.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2V-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 21.0% after high performance liquid chromatography analysis.
Example 11 preparation of 5-hydroxymethylfurfural from Y-doped niobium-based bifunctional phosphate solid acid catalyzed glucose
1.0mol of ammonium niobium oxalate and 1mol of citric acid are mixed and dispersed in 235ml of hydrogen peroxide solution with the mass concentration of 35%, after digestion is carried out for 14 hours at 85 ℃ until the solution is clear and transparent, cooling is carried out to room temperature, 90ml of hydrochloric acid with the mass concentration of 5M, 300ml of glycerin, 350g of polyacrylamide solution (with the weight average molecular weight of 1 ten thousand and the mass concentration of 50%), 20g of polyethylene glycol (with the weight average molecular weight of 3.5 ten thousand) and 0.2mol of yttrium trichloride hexahydrate are sequentially added, stirring is carried out until the solution is completely dissolved, 105ml of phosphoric acid with the mass concentration of 85% is added, standing and gelation are carried out, the obtained material is exchanged with methanol solvent and unreacted components in the material are removed, methanol is exchanged with normal hexane solvent and vacuum drying is carried out, and finally yttrium-doped niobium-based bifunctional solid acid catalyst which is expressed as 0.2Y-Nb-PO is obtained after roasting for 8 hours at 500-800 ℃ in air atmosphere.
1g of glucose was dissolved in 100ml of deionized water, 0.1g of solid acid 0.2Y-Nb-PO was added thereto, and the reaction was stirred at 140℃for 5 hours, followed by cooling to room temperature. The reaction solution is centrifugally separated at 10000r/min to remove the solid catalyst, and the yield of the 5-hydroxymethylfurfural is 22.1% after high performance liquid chromatography analysis.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (5)
1. A method for preparing 5-hydroxymethylfurfural by catalyzing glucose in an aqueous phase is characterized by comprising the following steps of: the method comprises the following steps: the difunctional solid acid catalyst is controlled to be fully dispersed in glucose aqueous solution, the weight ratio of the difunctional solid acid catalyst to glucose is 1:10-1:50, the difunctional solid acid catalyst is reacted for 30-600 minutes at 130-170 ℃, the difunctional solid acid catalyst is centrifugally separated, and then 5 ‒ hydroxymethylfurfural is obtained through concentration and refining; the difunctional solid acid catalyst is any one or more ion doped niobium-based phosphate solid acid catalysts with mesoporous and macroporous structures in Ca, sr, ba, al, cd, ce, la, sn, Y, zn, and the surface phosphate radical is in a pyrophosphoric acid structure;
wherein the bifunctional solid acid catalyst is obtained by the following method: 30-35% hydrogen peroxide solution is used at 70-90℃,αThe hydroxyl acid is taken as a niobium ion complexing agent, ammonium niobium oxalate is digested until the solution is colorless, clear and transparent, cooled to room temperature, lactic acid, polyethylene glycol, polyacrylamide and a metal ion precursor are added, stirred and fully dissolved, concentrated hydrochloric acid and/or glycerol are added, concentrated phosphoric acid is added to react with a metal ion ligand and gel, a niobium-metal phosphate cogel material is obtained, and finally, the mixture is fully baked and activated in air or oxygen-containing atmosphere at 500-900 ℃ to obtain the difunctional solid acid catalyst; the metal ion precursor is any one or more of chloride, nitrate or carbonate of Ca, sr, ba, al, cd, ce, la, sn, Y, zn.
2. The method for preparing 5-hydroxymethylfurfural by catalyzing glucose in an aqueous phase according to claim 1, wherein the method comprises the following steps: in the reaction for obtaining 5 ‒ hydroxymethyl furfural, the mass ratio of the bifunctional solid acid catalyst to glucose is 1:10, the reaction temperature is 140 ℃, and the reaction time is 300 minutes.
3. The method for preparing 5-hydroxymethylfurfural by catalyzing glucose in an aqueous phase according to claim 1, wherein the method comprises the following steps: the mole ratio of phosphorus element to niobium element in the bifunctional solid acid catalyst is controlled at 1: 1-3: 1.
4. the method for preparing 5-hydroxymethylfurfural by catalyzing glucose in an aqueous phase according to claim 1, wherein the method comprises the following steps:αthe hydroxy acid is any one or more of lactic acid, citric acid, acetic acid, tartaric acid and maleic acid.
5. The method for preparing 5-hydroxymethylfurfural by catalyzing glucose in an aqueous phase according to claim 1, wherein the method comprises the following steps: the dosage of polyethylene glycol is 12-25 g/mol of ammonium niobium oxalate, and the dosage of polyacrylamide is 85-350 g/mol of ammonium niobium oxalate.
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| WO2010101024A1 (en) * | 2009-03-06 | 2010-09-10 | 国立大学法人北陸先端科学技術大学院大学 | Method for preparing 5-hydroxymethylfurfural |
| CN102962085A (en) * | 2011-09-01 | 2013-03-13 | 华东理工大学 | Preparation method of niobium phosphate solid acid catalyst and application in sugar dehydration |
| CN106669655A (en) * | 2016-11-01 | 2017-05-17 | 华东理工大学 | Preparation method of solid acid catalyst for preparing 5-hydroxymethylfurfural from biomass |
| CN110302816A (en) * | 2019-06-20 | 2019-10-08 | 广西科技大学鹿山学院 | ZnO@SiO2The synthetic method of loaded mesoporous phosphate niobium catalyst and its preparing the application in 5 hydroxymethyl furfural |
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| CN102962085A (en) * | 2011-09-01 | 2013-03-13 | 华东理工大学 | Preparation method of niobium phosphate solid acid catalyst and application in sugar dehydration |
| CN106669655A (en) * | 2016-11-01 | 2017-05-17 | 华东理工大学 | Preparation method of solid acid catalyst for preparing 5-hydroxymethylfurfural from biomass |
| CN110302816A (en) * | 2019-06-20 | 2019-10-08 | 广西科技大学鹿山学院 | ZnO@SiO2The synthetic method of loaded mesoporous phosphate niobium catalyst and its preparing the application in 5 hydroxymethyl furfural |
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