CN113788865B - Method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material - Google Patents

Method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material Download PDF

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CN113788865B
CN113788865B CN202110730130.0A CN202110730130A CN113788865B CN 113788865 B CN113788865 B CN 113788865B CN 202110730130 A CN202110730130 A CN 202110730130A CN 113788865 B CN113788865 B CN 113788865B
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ionic liquid
glucose
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fructose
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龙金星
李宣
张嘉恒
陈正件
秦弦
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Zhuhai Institute Of Advanced Technology Chinese Academy Of Sciences Co ltd
South China University of Technology SCUT
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Abstract

The invention discloses a method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by an organic metal framework material; under the condition that air is compressed to 0.5-1MPa in an inert gas displacement reactor, taking a supported ionic liquid with an organic metal framework material as a carrier as a catalyst, glucose as a reaction substrate and water as a reaction solvent; reacting at 70-150deg.C for 5-120min; the ionic liquid is alkyl imidazole amino acid salt ionic liquid, and the organic metal framework material is UiO-66. The ionic liquid catalyst supported by the organic metal framework material combines the advantages of the organic metal framework material and the ionic liquid, has the properties of high catalytic activity, easy recovery and the like, particularly has the advantages of repeated use for more than 30 times, does not obviously reduce the activity, and successfully overcomes the technical bottleneck that a homogeneous ionic liquid system is difficult to recover.

Description

Method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material
Technical Field
The invention relates to a preparation method of fructose, in particular to a method for preparing fructose by catalyzing glucose isomerization through an alkyl imidazole type amino acid ionic liquid supported by an organic metal framework material and having high catalytic activity and excellent recycling performance, and belongs to the technical field of biomass efficient recycling and energy utilization.
Background
With the consumption of traditional fossil fuels and the increasing greenhouse effect caused by the use of fossil fuels, it is important to find a renewable energy source to change the energy structure. Biomass, which is a renewable resource, has attracted the interest of researchers, can be used as a raw material for preparing numerous chemicals and fuels, reduces the use of traditional fossil fuels, and searches for a reasonable solution for promoting economic growth and protecting ecological environment. The use of biodegradable sugars for the preparation of platform compounds of significant industrial value is a challenging and significant topic, for example, 5-HMF has been identified as the primary raw material for the production of furan polyesters, polyester amides and polyurethanes similar to petroleum polymers. How to form and perfect an effective production flow and process for preparing 5-hydroxymethylfurfural (5-HMF) is a problem to be solved.
Glucose is used as the six-carbon sugar with the most abundant content in the nature, and has wide application in food and pharmacy. It can also be used as a raw material for synthetic fuels, polymers and important platform compounds. Glucose is also a monomer of polysaccharide such as cellulose, starch, glycogen, etc., and can be used to obtain glucose by hydrolysis. Fructose is another important saccharide, and has a smaller reserve than glucose in nature, but has a wider range of applications than glucose and has chemical properties that glucose does not possess. The reaction rate of preparing the platform compounds such as 5-HMF, levulinic acid and the like by utilizing fructose for dehydration is much higher than that of utilizing glucose as a substrate, so that the glucose isomerase fructose has great application prospect in industry.
Fructose has many functional effects in the food and beverage industries, such as sweeteners, flavor additives, humectants, color enhancers, freezing point depression and stable osmotic pressure, so fructose has wide application in the food industry. The high fructose corn syrup has extremely rich fructose content, and the preparation of fructose by glucose isomerization has become the largest immobilized enzyme catalytic process in the world.
At present, the preparation of fructose by glucose isomerization in an aqueous phase by using immobilized glucose isomerase has realized large-scale industrial application. The industrial fructose production comprises the following steps: 1. hydrolyzing starch under the action of saccharifying enzyme to prepare glucose; 2. glucose is subjected to the action of isomerase (GI, EC 5.3.15) to obtain fructose-glucose syrup; 3. separating fructose from fructose and glucose syrup by chromatography. Glucose isomerase is used as a catalyst, after the reaction reaches the reaction balance, the mass fraction of glucose in the system is about 50%, the mass fraction of fructose is about 42%, and the rest 8% are other saccharides. The optimum pH of the isomerase is usually weak alkaline, and is between 7.0 and 9.0, and the activity of the isomerase is low under the condition of slightly acidity, so that a buffer solution needs to be added into a reaction system, and meanwhile, the preferable reaction temperature of the isomerase is 70-80 ℃, and the catalytic activity of the isomerase is drastically reduced due to the fact that the reaction temperature is too high or too low, so that the enzyme catalysis has some limitations.
Chinese patent application 202010363309.2 discloses a method for preparing fructose by catalyzing glucose isomerization by guanidino ionic liquid. The method takes guanidinium ionic liquid as a catalyst and water as a reaction medium, and under the conditions that the initial reaction concentration of glucose is 0.05-4 mol/L, the mole fraction of the guanidinium ionic liquid catalyst to glucose is 0.5-40%, the nitrogen pressure is 0.5-1.2 MPa, the reaction temperature is 60-120 ℃ and the reaction time is 2-60 min, the selective isomerization of glucose to prepare fructose is realized, the cation of the guanidinium ionic liquid is guanidine or tetramethyl guanidine, and the anion is formate, acetate, lactate, proline, histidine, lysine or arginine. The catalyst system of the method has the characteristics of no toxicity, biodegradability, environmental protection, high catalytic activity and high fructose selectivity, and the method has the advantages of mild reaction conditions, short reaction time and good recycling performance.
The above guanidinium ionic liquid catalyst has the problems that the activity of the catalyst is reduced after multiple uses, and the catalyst is recovered and separated after multiple uses, so that the catalyst is greatly lost mechanically. For the guanidino ionic liquid catalyst, the catalyst is a homogeneous catalyst, the common separation and recovery means are evaporation concentration and extraction by adopting an organic solvent diethyl ether and the like, and in the extraction process, the ionic liquid has a dissolution balance in a water phase and an organic phase, so that the ionic liquid still remains in the water phase partially, the complete recovery of the ionic liquid is difficult to realize, and the loss and the waste of the catalyst are caused.
The invention adopts the supported ionic liquid for preparing the fructose by catalyzing glucose isomerization, the supported ionic liquid is a heterogeneous catalyst, and is easier to separate and recycle, and the catalytic activity is not obviously reduced after repeated recycling, so that the problem that the separation and recycling are difficult after repeated use of the guanidino ionic liquid can be effectively solved. The supported ionic liquid catalyst prepared by the method is a heterogeneous catalyst, after the catalyst is used, the catalyst can be effectively recovered by adopting common filtering and centrifuging means, the recovery efficiency can reach more than 95 percent, and the recovery efficiency is far higher than that of a homogeneous guanidyl ionic liquid catalyst, so that the problems of difficult separation and great loss of the homogeneous guanidyl ionic liquid can be overcome. The recovery efficiency is calculated by dividing the mass of catalyst recovered by the initial charge of catalyst.
Disclosure of Invention
The invention aims to provide a method for preparing fructose by catalyzing glucose isomerization through an ionic liquid loaded by an organic metal framework material with high activity and excellent recycling performance.
The homogeneous ionic liquid catalyst is used for catalyzing glucose to isomerise to prepare fructose, and has the advantages of high catalytic efficiency, high catalyst utilization rate and the like, but the homogeneous catalyst is difficult to separate from a reaction system, and industrial utilization is difficult to realize. The invention constructs a method for preparing fructose by catalyzing glucose isomerization by using ionic liquid loaded by an organic metal framework material by taking alkyl imidazole amino acid ionic liquid as an active component, and the catalyst related by the method has the advantages of simplicity and convenience in synthesis, excellent stability, easiness in recycling, repeated use and the like, so that the method successfully solves the technical problem that a homogeneous ionic liquid system catalyst is difficult to recycle.
The aim of the invention is achieved by the following technical scheme:
the method for preparing fructose by catalyzing glucose isomerization by using ionic liquid loaded by an organometallic framework material comprises the following steps: under the condition that air is compressed to 0.5-1MPa in an inert gas displacement reactor, taking a supported ionic liquid with an organic metal framework material as a carrier as a catalyst, glucose as a reaction substrate and water as a reaction solvent; reacting at 70-150deg.C for 5-120min; the ionic liquid is alkyl imidazole amino acid salt ionic liquid, and the organic metal framework material is UiO-66.
In the invention, the ionic liquid cation is alkyl imidazole cation, and the anion is amino acid anion.
For further achieving the object of the present invention, preferably, the alkyl imidazole amino acid salt is one or more of alkyl imidazole proline salt, alkyl imidazole arginine salt, alkyl imidazole tryptophan salt, alkyl imidazole lysine salt, alkyl imidazole serine salt, alkyl imidazole isoleucine salt, alkyl imidazole glutamine salt, alkyl imidazole methionine salt, alkyl imidazole aspartic acid salt and alkyl imidazole threonine salt.
Preferably, the alkyl imidazole proline salt ionic liquid is one or more of the following structural formulas:
The alkyl imidazole arginine salt ionic liquid is one or more of the following structural formulas:
preferably, the alkyl imidazole tryptophan salt ionic liquid is one or more of the following structural formulas:
the alkyl imidazole lysine salt ionic liquid is one or more of the following structural formulas:
preferably, the alkyl imidazole serine salt ionic liquid is one or more of the following structural formulas:
the alkyl imidazole glutamine salt ionic liquid is one or more of the following structural formulas:
the alkyl imidazole methionine salt ionic liquid is one or more of the following structural formulas:
preferably, the alkyl imidazole aspartate ionic liquid is one or more of the following structural formulas:
the alkyl imidazole threonine salt ionic liquid is one or more of the following structural formulas:
preferably, the glucose aqueous solution is a mixture of a reaction substrate and a solvent, and the concentration of glucose in the mixture is 4.5-180g/L; the dosage of the supported ionic liquid catalyst taking the organic metal framework material as the carrier is 0.01-0.3g/10mL glucose aqueous solution.
Preferably, the ionic liquid catalyst supported by the organometallic framework material is prepared by the following method: the method is characterized in that bromotetrabenzoquinone is used as an organic ligand, alkyl imidazole is used as a modifier, one of copper chloride, copper bromide and copper iodide and potassium hydroxide are used as a catalyst, and dimethyl sulfoxide is used as a reaction solvent, so that the modification of the organic ligand is realized;
Crystallizing the modified organic ligand and zirconium chloride serving as reaction substrates at 120 ℃ for 12-48 hours, removing supernatant, and washing solids to obtain a catalyst precursor;
and (3) carrying out ion exchange on the catalyst precursor and sodium salt of the amino acid, washing, and drying in vacuum to finally obtain the ionic liquid catalyst loaded by the organic metal framework material.
Preferably, the alkyl carbon chain length of the alkyl imidazole amino acid salt ionic liquid is C1-C6.
Preferably, the inert gas is N 2 And Ar; after the reaction is finished, the supported ionic liquid is used as a catalyst again after being filtered and washed.
The catalyst is tested in the following way, an ionic liquid catalyst loaded by an appropriate amount of organic metal framework material is weighed and put into a reaction kettle, an appropriate amount of reaction substrate and reaction solvent are added, and an appropriate amount of inert gas is filled for reaction at an appropriate reaction temperature. And then cooling, separating and recovering the catalyst by adopting filtration, collecting the reaction liquid, fixing the volume, analyzing by adopting high performance liquid chromatography, washing the recovered catalyst with deionized water for three times, placing the catalyst in a vacuum drying oven for drying, weighing the mass of the catalyst after the reaction, and completing one catalytic cycle. Based on the method, after the ionic liquid catalyst loaded by the organic metal framework material is recycled for 30 times, the catalytic activity is not obviously reduced.
Compared with the existing technology for preparing fructose by glucose isomerization, the invention has the following advantages:
1) The supported ionic liquid catalyst constructed by the invention is used for catalyzing glucose to isomerise to prepare fructose, and the catalyst can be effectively separated and recovered through filtration after use. The catalyst after each use can be used for the next cycle after being filtered and simply treated by washing, drying and the like. Experimental study shows that after the supported ionic liquid catalyst is recycled for 30 times, the glucose conversion rate is still kept at about 20%, the fructose yield is kept at about 15%, and the catalytic result does not obviously fluctuate each time, so that the catalyst has excellent stability, the ionic liquid catalyst supported by the organic metal framework material can be recycled for multiple times, and the catalytic activity is not obviously reduced.
2) The invention designs and constructs a novel glucose isomerism catalyst system with excellent recycling performance by using an organic metal framework material UiO-66 as a carrier and using an alkyl imidazolyl ionic liquid as an active component. The catalyst has the treatment capacity of glucose up to 1mol/L and good selectivity to fructose.
3) The catalyst has the characteristics of high ionic liquid thermal stability, lower vapor pressure, low melting point, low volatility and the like; the UiO-66 uniform porous structure enables the ionic liquid to be uniformly distributed and dispersed, and electrostatic fields and the like exist between the carrier and the ionic liquid, so that stable composite materials can be formed. The catalyst can be recycled and reused by adopting simple filtration.
4) The method for preparing fructose by glucose isomerization by taking the ionic liquid loaded by the organic metal framework material as the core is beneficial to realizing the industrial catalytic isomerization of glucose.
Drawings
FIG. 1 is a standard curve of glucose.
FIG. 2 is a standard curve of fructose.
Fig. 3 is a standard curve for mannose.
FIG. 4 is a liquid chromatogram of glucose and fructose obtained in example 1.
FIG. 5 is a graph showing the glucose conversion, fructose yield and fructose selectivity for multiple cycles of the catalyst of example 1.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following examples, but embodiments of the present invention are not limited thereto.
Example 1
Preparation of the catalyst: the synthesis of the supported 1-methyl-3-methylimidazole proline ionic liquid with UIO-66 as a carrier is divided into three steps.
First, the ligand is modified: weighing 50mmol of 2-bromotetrabenzoquinone, 75mmol of N-methylimidazole, 5mmol of copper chloride, 100mmol of potassium hydroxide and 40ml of dimethyl sulfoxide (DMSO), magnetically stirring at 130 ℃ for 36 hours, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the supernatant liquid, removing the ethyl acetate by rotary evaporation, and drying for later use;
Secondly, hydrothermal crystallization: weighing 5g of zirconium chloride in a pressure-resistant bottle, adding 200ml of N, N-Dimethylformamide (DMF), ultrasonically dissolving 40ml of acetic acid, adding the modified ligand, uniformly mixing, placing in a 120 ℃ oven for hydrothermal crystallization for 24 hours, centrifuging to remove supernatant, washing with deionized water and ethanol for three times respectively, and vacuum drying at 60 ℃ for 24 hours;
finally, ion exchange: dissolving 2g of the dried product and 6g of sodium prolinate in 20ml of ethanol, stirring at room temperature for 24 hours, centrifuging, removing clear liquid, repeating the steps for three times, and drying at 60 ℃ in vacuum for 24 hours.
0.18g glucose, 0.05g supported 1-methyl-3-methylimidazole proline ionic liquid with UiO-66 as a carrier and 10mL deionized water were added sequentially to a 25mL reactor with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the kettle is replaced for 5 times and then pressurized to 1.0MPa,then the reaction kettle is put into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product.
The glucose isomerisation product was measured using an Agilini 1260 II type high performance liquid chromatograph, the detector being an Agilini 1311 differential refractive detector, the column being an Agilini Hi-Plix-H ion exclusion/ligand exchange column (7.7mm×300mm,8 μm). Mobile phase: ultrapure water, flow rate: sample injection amount of 0.6 mL/min: 20 μl, column temperature: 65 ℃, detector temperature: 50 ℃. The qualitative analysis of the product is judged by using retention time, and the quantitative analysis is performed by using a standard curve method.
Glucose conversion, fructose yield and fructose selectivity were calculated as follows
Aqueous solutions of glucose, fructose and mannose were prepared at concentration gradients of 0.0001mol/L, 0.001mol/L, 0.005mol/L, 0.01mol/L, 0.05mol/L and 0.1mol/L, respectively. And (3) feeding the standard solution into liquid chromatography according to the sequence of low concentration to high concentration, recording peak areas corresponding to different concentrations, and performing linear fitting by taking the concentration as an abscissa and the peak area as an ordinate, wherein the fitting result is shown in figures 1-3. R of standard curves for glucose, fructose and mannose 2 Is more than or equal to 0.99993, and the linear interval is 0.0001-0.1mol/L. The standard curve has larger linear interval and extremely small curve error, so the standard curve canAs standard curve for the external standard method. The concentration of glucose, fructose and mannose after the reaction can be quantitatively analyzed through a standard curve, so that the reaction condition is analyzed and evaluated.
Filtering a reaction solution catalyzed by using a supported ionic liquid as a catalyst, collecting the reaction solution, fixing the volume of the reaction solution, adding the reaction solution into a high performance liquid chromatograph, analyzing the high performance liquid chromatograph, obtaining peak areas of different saccharides as shown in a figure 4, calculating the concentration of various saccharides after the reaction through a standard curve, further calculating the amounts of substances of glucose and fructose after the reaction, and calculating the glucose conversion rate and the fructose yield through formulas 1-1, 1-2 and 1-3. The glucose conversion was tested to 33.2% and the fructose yield was 18.5%. And collecting the filtered catalyst, washing with deionized water, drying to obtain the used catalyst, and repeating the steps to test the recycling performance of the catalyst, wherein the experimental test result is shown in figure 5. The catalyst is excellent in recycling performance and good in stability, as is evident from fig. 5. Compared with the Chinese patent application 202010363309.2, the invention adopts the UiO-66 as the carrier, loads the ionic liquid onto the UiO-66 to prepare the supported ionic liquid catalyst, and the supported ionic liquid catalyst prepared by the invention is a heterogeneous catalyst, so that the problems of large loss, difficult separation and recovery and the like of the homogeneous catalyst after multiple uses can be overcome.
The damage of the supported ionic liquid catalyst prepared by the invention to reaction equipment is far smaller than that of the traditional acid-base catalyst, and the catalyst can be effectively separated and recycled through filtration, so that the catalyst can be used for multiple times.
The supported ionic liquid catalyst is constructed by taking the supported ionic liquid in the example as a catalyst, taking the organic metal framework material UiO-66 as a carrier and taking the alkyl imidazole amino acid ionic liquid active component as a catalyst for catalyzing glucose isomerization to prepare fructose. Compared with a homogeneous catalyst, the supported ionic liquid catalyst can effectively solve the problem that the homogeneous catalyst is difficult to separate and recycle, and meanwhile, the service life of the catalyst is far longer than that of the homogeneous catalyst. Compared with the conventional solid acid-base catalyst, the supported ionic liquid catalyst has higher stability, and meanwhile, the catalyst does not contain heavy metal ions, so that the pollution to the reacted reaction liquid is avoided, and the subsequent treatment procedures can be effectively reduced. Compared with enzyme catalysis, the supported ionic liquid catalyst has the advantages of larger operable temperature range, low requirement on the pH value of reaction liquid, excellent cycle performance, good stability and no irreversible deactivation of enzyme. The preparation path of preparing fructose by glucose isomerization can be effectively widened by preparing the supported ionic liquid catalyst.
Example 2
Catalyst preparation
Modifying the ligand: weighing 50mmol of 2-bromotetrabenzoquinone, 75mmol of N-ethylimidazole, 5mmol of copper chloride, 100mmol of potassium hydroxide and 40ml of dimethyl sulfoxide (DMSO), magnetically stirring at 130 ℃ for 36 hours, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the upper liquid, removing the ethyl acetate by rotary evaporation, and drying for later use; hydrothermal crystallization and ion exchange were the same as in example 1.
0.18g of glucose, 0.05g of supported 1-methyl-3-ethylimidazole proline ionic liquid comprising a carrier and. 10mL of deionized water was added sequentially to a 25mL reactor with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 28.7% and the fructose yield was 15.5%. The test method and test conditions were the same as in example 1.
Example 3
Catalyst preparation
Modifying the ligand: weighing 50mmol of 2-bromotetrabenzoquinone, 75mmol of N-propylimidazole, 5mmol of copper chloride, 100mmol of potassium hydroxide and 40ml of dimethyl sulfoxide (DMSO), magnetically stirring at 130 ℃ for 36 hours, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the upper liquid, removing the ethyl acetate by rotary evaporation, and drying for later use; hydrothermal crystallization and ion exchange were the same as in example 1.
0.18g glucose, 0.05g supported 1-methyl-3-propylimidazol-proline ionic liquid including carrier and 10mL deionized water were added sequentially to a 25mL reactor with polytetrafluoroethylene liner and magnetons. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 30.1% and the fructose yield was 17.2%. The test method and test conditions were the same as in example 1.
Example 4
Catalyst preparation
Modifying the ligand: weighing 50mmol of 2-bromotetrabenzoquinone, 75mmol of N-butylimidazole, 5mmol of copper chloride, 100mmol of potassium hydroxide and 40ml of dimethyl sulfoxide (DMSO), magnetically stirring at 130 ℃ for 36 hours, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the upper liquid, removing the ethyl acetate by rotary evaporation, and drying for later use; hydrothermal crystallization and ion exchange were the same as in example 1.
0.18g of glucose, 0.05g of supported 1-methyl-3-butylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were added sequentially to a 25mL reactor with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Mixing the materials in a kettleTransferring the substance (containing unreacted glucose, fructose as an isomerisation product, mannose as an epimerisation product and the like) into a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerisation product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 27.1% and the fructose yield was 16.4%. The test method and test conditions were the same as in example 1.
Example 5
Catalyst preparation
Modifying the ligand: weighing 50mmol of 2-bromotetrabenzoquinone, 75mmol of N-pentylimidazole, 5mmol of copper chloride, 100mmol of potassium hydroxide and 40ml of dimethyl sulfoxide (DMSO), magnetically stirring at 130 ℃ for 36 hours, cooling, adjusting pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, removing ethyl acetate by rotary evaporation of the upper liquid, and drying for later use; hydrothermal crystallization and ion exchange were the same as in example 1.
0.18g of glucose, 0.05g of supported 1-methyl-3-pentylimidazolium proline ionic liquid including a carrier, and 10mL of deionized water were sequentially added to a 25mL reaction vessel with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 26.5% and the fructose yield was 15.8%. The test method and test conditions were the same as in example 1.
Example 6
Catalyst preparation
Modifying the ligand: 50mmol of 2-bromotetrabenzoquinone, 75mmol of N-hexylimidazole, 5mmol of copper chloride, 100mmol of potassium hydroxide and 40ml of dimethyl sulfoxide (DMSO) are weighed, magnetically stirred at 130 ℃ for 36 hours, cooled, extracted by adopting ethyl acetate after the pH is regulated to 2-3 by concentrated sulfuric acid, and the upper liquid is taken for later use after the ethyl acetate is removed by rotary evaporation; hydrothermal crystallization and ion exchange were the same as in example 1.
0.18g glucose, 0.05g supported 1-methyl-3-hexylimidazole proline ionic liquid including a carrier, and 10mL deionized water were added sequentially to a 25mL reactor with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 26.3% and the fructose yield was 11.1%. The test method and test conditions were the same as in example 1.
Example 7
Catalyst preparation
Ligand modification and hydrothermal crystallization were the same as in example 1. Ion exchange: dissolving 2g of the dried product and 6g of tryptophan sodium in 20ml of ethanol, stirring for 24 hours at room temperature, centrifuging, removing clear liquid, repeating the steps for three times, and drying in vacuum at 60 ℃ for 24 hours.
0.18g of glucose, 0.05g of supported 1-methyl-3-ethylimidazole tryptophan ionic liquid comprising a carrier and 10mL of deionized water were added sequentially to a 25mL reaction vessel with a polytetrafluoroethylene liner and a magneton. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography shows that under this condition, grape isThe sugar conversion was 36.3% and the fructose yield was 15.1%. The test method and test conditions were the same as in example 1.
Example 8
Catalyst preparation
Ligand modification and hydrothermal crystallization were the same as in example 1. Ion exchange: dissolving 2g of the dried product and 6g of sodium arginine in 20ml of ethanol, stirring at room temperature for 24 hours, centrifuging, removing clear liquid, repeating the steps for three times, and drying at 60 ℃ in vacuum for 24 hours.
0.18g of glucose, 0.05g of supported 1-methyl-3-ethylimidazole arginine ionic liquid comprising a carrier and 10mL of deionized water were added sequentially to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 33.1% and the fructose yield was 14.3%. The test method and test conditions were the same as in example 1.
Example 9
Catalyst preparation
Ligand modification and hydrothermal crystallization were the same as in example 1. Ion exchange: dissolving 2g of the dried product and 6g of threonine sodium in 20ml of ethanol, stirring at room temperature for 24 hours, centrifuging, removing clear liquid, repeating the steps for three times, and drying at 60 ℃ in vacuum for 24 hours.
0.18g of glucose, 0.05g of supported 1-methyl-3-ethylimidazole threonine ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magneton. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction is finished, the reaction kettle is placed in cold water for rapid coolingTo room temperature. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 23.1% and the fructose yield was 10.2%. The test method and test conditions were the same as in example 1.
Example 10
Catalyst preparation
Ligand modification and hydrothermal crystallization were the same as in example 1. Ion exchange: dissolving 2g of the dried product and 6g of sodium glutamine in 20ml of ethanol, stirring for 24 hours at room temperature, centrifuging, removing clear liquid, repeating the steps for three times, and drying in vacuum at 60 ℃ for 24 hours.
0.18g of glucose, 0.05g of supported 1-methyl-3-ethylimidazole glutamine ionic liquid comprising a carrier and 10mL of deionized water were added sequentially to a 25mL reactor with polytetrafluoroethylene lining and a magneton. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 43.5% and the fructose yield was 16.4%. The test method and test conditions were the same as in example 1.
The synthesis of supported 1-methyl-3-methylimidazole proline ionic liquid with UiO-66 as carrier in the following examples is described in example 1.
Example 11
0.18g glucose, 0.01g supported 1-methyl-3-methylimidazole proline ionic liquid using UiO-66 as a carrier and 10mL deionized water were added sequentially to a 25mL reactor with a polytetrafluoroethylene liner and a magnet.By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 18.7% and the fructose yield was 13.5%. The test method and test conditions were the same as in example 1.
Example 12
0.18g of glucose, 0.08g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 40.1% and the fructose yield was 17.2%. The test method and test conditions were the same as in example 1.
Example 13
0.18g of glucose, 0.1g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magneton. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Mixing the mixture (containing unreacted glucose, fructose as isomerised product and mannose as epimesed product) Sugar, etc.), transferring to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, purifying and separating out the isomerised product fructose, and obtaining the target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 46.3% and the fructose yield was 15.1%. The test method and test conditions were the same as in example 1.
Example 14
0.18g of glucose, 0.3g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magneton. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 70.2% and the fructose yield was 13.5%. The test method and test conditions were the same as in example 1.
Example 15
0.045g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 76.2% and the fructose yield was 11.5%. Test method and test conditions and implementationExample 1 is the same.
Example 16
0.09g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 56.1% and the fructose yield was 16.3%. The test method and test conditions were the same as in example 1.
Example 17
0.36g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 31.2% and the fructose yield was 15.4%. The test method and test conditions were the same as in example 1.
Example 18
0.54g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 28.6% and the fructose yield was 15.2%. The test method and test conditions were the same as in example 1.
Example 19
0.72g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 26.4% and the fructose yield was 15.1%. The test method and test conditions were the same as in example 1.
Example 20
1.8g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magneton. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as isomerisation product, mannose as epimerisation product, etc.) in the kettle And (3) diluting the fructose to a 100mL volumetric flask with ultrapure water until the fructose is used up, and purifying and separating the fructose to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 19.4% and the fructose yield was 14.8%. The test method and test conditions were the same as in example 1.
Example 21
0.18g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid after 5 uses including carriers and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 19.4% and the fructose yield was 14.7%. The test method and test conditions were the same as in example 1.
Example 22
0.18g of glucose, 0.05g of the supported 1-methyl-3-methylimidazole proline ionic liquid after 10 times of use of the carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 21.5% and the fructose yield was 14.7%. Test methodThe test conditions were the same as in example 1.
Example 23
0.18g of glucose, 0.05g of 15-time used supported 1-methyl-3-methylimidazole proline ionic liquid containing a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 20.1% and the fructose yield was 14.4%. The test method and test conditions were the same as in example 1.
Example 24
0.18g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid after 20 times of use of the carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 20.2% and the fructose yield was 14.6%. The test method and test conditions were the same as in example 1.
Example 25
0.18g glucose, 0.05g supported 1-methyl-3-methylimidazole proline ionic liquid after 25 uses including carrier and 10mL deionized water were sequentially addedAdded to a 25mL reactor with polytetrafluoroethylene lining and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 20.9% and the fructose yield was 14.2%. The test method and test conditions were the same as in example 1.
Example 26
0.18g of glucose, 0.05g of supported 1-methyl-3-methylimidazole proline ionic liquid after 30 uses including carriers and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and a magnet. By N 2 Air in the reaction kettle is replaced for 5 times and then pressurized to 1.0MPa, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30min. After the reaction, the reaction vessel was cooled to room temperature rapidly in cold water. Transferring the mixture (containing unreacted glucose, fructose as an isomerization product, mannose as an epimerization product and the like) in the kettle to a 100mL volumetric flask, diluting with ultrapure water to a scale mark for later use, and purifying and separating the fructose as the isomerization product to obtain a target product. Analysis by high performance liquid chromatography showed that under this condition, the glucose conversion was 20.8% and the fructose yield was 14.9%. The test method and test conditions were the same as in example 1.
The used supported 1-methyl-3-methylimidazole proline ionic liquid is recovered through filtration, and then is washed with water and dried to be used as a catalyst for the next time. The repeated use performance of the supported 1-methyl-3-methylimidazole proline ionic liquid is shown in a figure 3, the activity is not obviously reduced after the catalyst is recycled for 30 seconds, and the fructose yield is kept at about 15%, so that the repeated use performance of the supported 1-methyl-3-methylimidazole proline ionic liquid is very excellent.
The foregoing examples are illustrative of the present invention and are not intended to be limiting, and other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the invention are intended to be equivalent in scope.

Claims (3)

1. The method for preparing fructose by catalyzing glucose isomerization by using ionic liquid loaded by an organic metal framework material is characterized in that under the condition that air is in an inert gas replacement reactor and the pressure is 0.5-1 MPa, the supported ionic liquid taking the organic metal framework material as a carrier is used as a catalyst, glucose is used as a reaction substrate, and water is used as a reaction solvent; reacting at 70-150deg.C for 5-120 min, and purifying to obtain the final product;
the ionic liquid catalyst supported by the organic metal framework material is prepared by the following method:
the method is characterized in that bromotetrabenzoquinone is used as an organic ligand, alkyl imidazole is used as a modifier, one of copper chloride, copper bromide and copper iodide and potassium hydroxide are used as a catalyst, and dimethyl sulfoxide is used as a reaction solvent, so that the modification of the organic ligand is realized;
crystallizing the modified organic ligand and zirconium chloride serving as reaction substrates at 120 ℃ for 12-48 hours, removing supernatant, and washing solids to obtain a catalyst precursor;
ion exchange is carried out on the catalyst precursor and sodium salt of amino acid, then washing and vacuum drying are carried out, and finally the ionic liquid catalyst loaded by the organic metal framework material is obtained;
the alkyl imidazole is N-methyl imidazole, N-ethyl imidazole, N-propyl imidazole, N-butyl imidazole, N-amyl imidazole or N-hexyl imidazole;
The sodium salt of the amino acid is sodium proline, sodium tryptophan, sodium arginine, sodium threonine or sodium glutamine acid.
2. The method for preparing fructose by catalyzing glucose isomerization with ionic liquid supported by organic metal framework material according to claim 1, wherein the glucose aqueous solution is a mixture of a reaction substrate and a solvent, and the concentration of glucose in the mixture is 4.5-180 g/L; the dosage of the supported ionic liquid catalyst taking the organic metal framework material as the carrier is 0.01-0.3 g/10 mL glucose aqueous solution.
3. The method for preparing fructose by catalyzing glucose isomerization with ionic liquid supported by organic metal framework material as set forth in claim 1, wherein the inert gas is N 2 And Ar; after the reaction is finished, the supported ionic liquid is used as a catalyst again after being filtered and washed.
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