CN113788865A - 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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CN113788865A
CN113788865A CN202110730130.0A CN202110730130A CN113788865A CN 113788865 A CN113788865 A CN 113788865A CN 202110730130 A CN202110730130 A CN 202110730130A CN 113788865 A CN113788865 A CN 113788865A
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ionic liquid
glucose
alkyl imidazole
framework material
fructose
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CN113788865B (en
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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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    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
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    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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Abstract

The invention discloses a method for preparing fructose by catalyzing glucose isomerization by using an ionic liquid loaded by an organic metal framework material; replacing air in a reactor with inert gas, pressurizing to 0.5-1MPa, using supported ionic liquid with organic metal framework material as a carrier as a catalyst, using glucose as a reaction substrate, and using water as a reaction solvent; reacting at 70-150 deg.C for 5-120 min; the ionic liquid is alkyl imidazole amino acid salt ionic liquid, and the organic metal framework material is UiO-66. The ionic liquid catalyst loaded by the organic metal framework material combines the advantages of the organic metal framework material and the ionic liquid, has the performances of high catalytic activity, easy recovery and the like, particularly the activity of the ionic liquid catalyst can be repeatedly used for more than 30 times without obvious reduction, 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 organic metal framework material loaded alkyl imidazole type amino acid ionic liquid with high catalytic activity and excellent cyclic use performance, and belongs to the technical field of efficient biomass recycling and energy utilization.
Background
With the consumption of traditional fossil fuels and the increasing greenhouse effect brought by the use of fossil fuels, it is important to seek a renewable energy source to change the energy structure. Biomass as a renewable resource arouses the interest of researchers, can be used as a raw material for preparing a plurality of chemicals and fuels, reduces the use of traditional fossil fuels, and seeks a reasonable solution for promoting economic growth and protecting the ecological environment. The use of biodegradable saccharides 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 main raw material for the production of furan polyesters, polyester amides and polyurethanes like 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 urgently.
Glucose is used as the most abundant six-carbon sugar in nature, and is widely applied to food and pharmacy. It can also be used as a feedstock for synthetic fuels, polymers and important platform compounds. Glucose is also a monomer of polysaccharides such as cellulose, starch, glycogen, etc., and can be hydrolyzed to obtain glucose. Fructose, another important saccharide, is a smaller reserve in nature than glucose, but is used more widely than glucose and has chemical properties that glucose does not have. 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 preparing the platform compounds such as 5-HMF, levulinic acid and the like by utilizing glucose as a substrate, so that glucose fructose isomerate has a great application prospect in industry.
Fructose possesses many functional effects in the food and beverage industry, such as sweeteners, flavor additives, humectants, colorants, and also for freezing point depression and osmotic pressure stabilization, and is therefore widely used in the food industry. The high fructose corn syrup has rich fructose content, and the production of the high fructose corn syrup by preparing fructose through glucose isomerization becomes the largest immobilized enzyme catalysis process in the world.
At present, the preparation of fructose by glucose isomerization in an aqueous phase by adopting immobilized glucose isomerase has already realized large-scale industrial application. The steps for industrially producing the fructose are as follows: 1. hydrolyzing starch under the action of saccharifying enzyme to prepare glucose; 2. glucose is processed by isomerase (GI, EC 5.3.15) to obtain fructose-glucose syrup; 3. the fructose syrup is separated by chromatography to obtain fructose. Glucose isomerase is used as a catalyst, after the reaction reaches the reaction equilibrium, the mass fraction of glucose in the system is about 50%, the mass fraction of fructose is about 42%, and the rest 8% is other saccharides. The optimum pH of the isomerase is usually weak alkaline, between 7.0 and 9.0, and the activity of the isomerase is very low under a slightly acidic condition, so that a buffer needs to be added into a reaction system, and meanwhile, the catalytic activity of the isomerase is sharply reduced due to the fact that the reaction temperature of the isomerase is high or low and is preferably 70-80 ℃, so that the enzyme catalysis has some limitations.
Chinese patent application 202010363309.2 discloses a method for preparing fructose by catalyzing glucose isomerization with guanidino ionic liquid. According to the method, guanidino ionic liquid is used as a catalyst, water is used as a reaction medium, the initial reaction concentration of glucose is 0.05-4 mol/L, the mole fraction of the guanidino ionic liquid catalyst to glucose is 0.5-40%, the nitrogen pressure is 0.5-1.2 MPa, the reaction temperature is 60-120 ℃, the selective isomerization preparation of the glucose to fructose is realized under the condition that the reaction time is 2-60 min, the cation of the guanidino ionic liquid is guanidine or tetramethylguanidine, and the anion of the guanidino ionic liquid is formate, acetate, lactate, proline, histidine, lysine or arginine. The catalytic 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 reutilization property of the catalyst.
The guanidinium ionic liquid catalyst has the problems that the activity of the catalyst is reduced after the catalyst is used for many times, and the catalyst is greatly lost due to large mechanical loss caused by recovery and separation of the catalyst after the catalyst is used for many times. For the guanidino ionic liquid catalyst, the guanidino ionic liquid catalyst is a homogeneous catalyst, a common separation and recovery means is evaporation concentration and extraction by adopting an organic solvent, namely diethyl ether and the like, in the extraction process, the ionic liquid has a dissolution balance between an aqueous phase and an organic phase, so that the ionic liquid still partially remains in the aqueous phase, the ionic liquid is difficult to completely recover, and the loss and waste of the catalyst are caused.
The supported ionic liquid is used for catalyzing glucose isomerization to prepare fructose, is a heterogeneous catalyst and is easy to separate and recycle, and the catalytic activity is not obviously reduced after repeated recycling, so that the problem that the guanidino ionic liquid is difficult to separate and recycle after repeated use can be effectively solved. The supported ionic liquid catalyst prepared by the invention is a heterogeneous catalyst, after the catalyst is used, the catalyst can be effectively recovered by means of common filtration, centrifugation and the like, the recovery efficiency can reach more than 95 percent and is far higher than that of a homogeneous guanidino ionic liquid catalyst, and therefore the problems of difficult separation and great loss of the homogeneous guanidino ionic liquid can be solved. The recovery efficiency is calculated by dividing the mass of catalyst after recovery by the initial charge of catalyst.
Disclosure of Invention
The invention aims to provide a method for preparing fructose by catalyzing glucose isomerization by using an ionic liquid loaded by an organic metal framework material with high activity and excellent recycling performance.
The homogeneous ionic liquid catalyst is adopted to catalyze glucose isomerization to prepare fructose, and the preparation method has the advantages of high catalytic efficiency, high utilization rate of the catalyst and the like, but the homogeneous catalyst is difficult to separate from a reaction system and realize industrial utilization. The invention constructs a method for preparing fructose by catalyzing glucose isomerization by using ionic liquid loaded by organic metal framework material as an active component, and the catalyst related by the method has the advantages of simple and convenient synthesis, excellent stability, easy recycling, repeated use and the like, so that the technical problem that the catalyst of a homogeneous ionic liquid system is difficult to recycle is successfully overcome.
The purpose of the invention is realized by the following technical scheme:
the method for preparing fructose by catalyzing glucose isomerization by using the ionic liquid loaded by the organic metal framework material comprises the following steps: replacing air in a reactor with inert gas, pressurizing to 0.5-1MPa, using supported ionic liquid with organic metal framework material as a carrier as a catalyst, using glucose as a reaction substrate, and using water as a reaction solvent; reacting at 70-150 deg.C for 5-120 min; the ionic liquid is alkyl imidazole amino acid salt ionic liquid, and the organic metal framework material is UiO-66.
In the invention, the cation of the ionic liquid is alkyl imidazole cation, and the anion is amino acid anion.
To further achieve the object of the present invention, preferably, the alkyl imidazole amino acid salt is one or more of alkyl imidazole prolinate, alkyl imidazole arginine, alkyl imidazole tryptophan, alkyl imidazole lysine, alkyl imidazole serine, alkyl imidazole isoleucine, alkyl imidazole glutamine, alkyl imidazole methionine, alkyl imidazole aspartate, and alkyl imidazole threonine.
Preferably, the alkyl imidazole proline salt ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000041
the alkyl imidazole arginine salt ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000042
preferably, the alkyl imidazole tryptophan salt ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000051
the alkyl imidazole lysine salt ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000052
preferably, the alkyl imidazole serine salt ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000053
Figure BDA0003138984630000061
the alkyl imidazole glutamine salt ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000062
the alkyl imidazole methionine salt ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000063
preferably, the alkyl imidazole aspartate ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000064
Figure BDA0003138984630000071
the alkyl imidazole threonine salt ionic liquid is one or more of the following structural formulas:
Figure BDA0003138984630000072
preferably, the glucose aqueous solution is a mixture of a reaction substrate and a solvent, and the concentration of glucose in the mixture is 4.5-180 g/L; the dosage of the supported ionic liquid catalyst taking the organic metal framework material as the carrier is 0.01-0.3g/10mL of glucose aqueous solution.
Preferably, the organometallic framework material supported ionic liquid catalyst is prepared by the following method: the method comprises the following steps of (1) modifying an organic ligand by taking bromotetrabenzoquinone as the organic ligand, taking alkyl imidazole as a modifier, taking potassium hydroxide and one of copper chloride, copper bromide and copper iodide as catalysts, and taking dimethyl sulfoxide as a reaction solvent;
taking the modified organic ligand and zirconium chloride as reaction substrates, crystallizing at 120 ℃ for 12-48h, removing supernatant, and washing solids to obtain a catalyst precursor;
and (3) carrying out ion exchange on the catalyst precursor and sodium salt of 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 N2And Ar; after the reaction is finished, the supported ionic liquid is used as the catalyst again after being filtered and washed.
The cyclic performance test of the catalyst comprises the following steps of weighing a proper amount of the ionic liquid catalyst loaded by the organic metal framework material in a reaction kettle, adding a proper amount of reaction substrates and reaction solvents, filling a proper amount of inert gas, and reacting at a proper reaction temperature. And then cooling, separating and recovering the catalyst by adopting filtration, collecting reaction liquid, fixing the volume, analyzing by adopting a high performance liquid chromatography, washing the recovered catalyst with deionized water for three times, placing the catalyst in a vacuum drying box for drying, and weighing the mass of the catalyst after reaction to finish one catalytic cycle. Based on the above, the catalytic activity of the ionic liquid catalyst loaded by the organic metal framework material is not obviously reduced after the ionic liquid catalyst is recycled for 30 times.
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 isomerization to prepare fructose, and the catalyst can be effectively separated and recovered through filtration after being used. The catalyst after each use can be used for the next circulation after being filtered and simply treated by washing, drying and the like. Experimental research 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 catalysis result is not obviously fluctuated each time, which also shows that the catalyst is excellent in 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 isomerization catalyst system with excellent recycling performance by using an organic metal framework material UiO-66 as a carrier and alkyl imidazolyl ionic liquid as an active component. The catalyst has a glucose treatment amount of 1mol/L and good selectivity to fructose.
3) The catalyst has the characteristics of high thermal stability of the ionic liquid, lower vapor pressure, low melting point, difficult volatilization and the like; the uniform porous structure of UiO-66 enables the ionic liquid to be uniformly distributed, and the electrostatic field and other effects exist between the carrier and the ionic liquid, thereby being beneficial to forming a stable composite material. The catalyst can be recycled and reused by simple filtration.
4) The method for preparing fructose by glucose isomorphism, which is formed by taking the ionic liquid loaded by the organic metal framework material as the core, is favorable for realizing industrial catalytic isomerization of glucose.
Drawings
FIG. 1 is a standard curve for glucose.
FIG. 2 is a standard curve for 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 of 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 is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparation of the catalyst: the synthesis of the supported 1-methyl-3-methylimidazoline 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 36h, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the upper layer liquid, rotatably evaporating to remove ethyl acetate, 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, respectively cleaning with deionized water and ethanol for three times, and vacuum-drying at 60 ℃ for 24 hours;
finally, ion exchange: dissolving 2g of the dried product and 6g of sodium proline in 20ml of ethanol, stirring at room temperature for 24h, centrifuging, removing clear liquid, repeating the steps for three times, and vacuum drying at 60 ℃ for 24 h.
0.18g of glucose, 0.05g of supported 1-methyl-3-methylimidazoline proline ionic liquid containing a carrier and UiO-66 as a carrier and 10mL of deionized water are sequentially added into a 25mL reaction kettle with a polytetrafluoroethylene lining and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is put into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture in the kettle (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) to a 100mL volumetric flask, diluting the mixture to a scale mark for later use by ultrapure water, and purifying and separating the isomerized product fructose to obtain the target product.
The glucose isomerization product was measured by an Agilent model 1260 II HPLC using an Agilent 1311 differential refractometer column and an Agilent Hi-Plex-H ion exclusion/ligand exchange column (7.7 mm. times.300 mm,8 μm). Mobile phase: ultrapure water, flow rate: 0.6mL/min, sample size: 20 μ L, column temperature: 65 ℃, detector temperature: at 50 ℃. The qualitative analysis of the product adopts retention time to judge, and the quantitative analysis adopts a standard curve method.
The conversion rate of glucose, the yield of fructose and the selectivity of fructose are calculated by the following formulas
Figure BDA0003138984630000101
Figure BDA0003138984630000102
Figure BDA0003138984630000103
Preparing aqueous solutions of glucose, fructose and mannose with 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) allowing the standard solution to enter a liquid chromatogram 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 a horizontal coordinate and the peak area as a vertical coordinate, wherein the fitting result is shown in the attached figures 1-3. R of standard curves for glucose, fructose and mannose2Not less than 0.99993, and the linear interval is 0.0001-0.1 mol/L. The standard curve has a large linear interval and a small curve error, so that the standard curve can be used as a standard curve of an external standard method. The concentrations of glucose, fructose and mannose after reaction can be quantitatively analyzed through a standard curve, so that the reaction condition is analyzed and evaluated.
Filtering reaction liquid catalyzed by taking supported ionic liquid as a catalyst, collecting the reaction liquid, performing constant volume on the reaction liquid, driving the reaction liquid into a high performance liquid chromatography, analyzing the reaction liquid by the high performance liquid chromatography, obtaining peak areas of different saccharides by a liquid chromatogram as shown in figure 4, calculating the concentration of each saccharide after reaction by a standard curve, further calculating the amount of glucose and fructose after reaction, and then calculating the glucose conversion rate and the fructose yield by formulas 1-1, 1-2 and 1-3. The glucose conversion rate was tested to be 33.2% and the fructose yield 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 test result of the experiment is shown in figure 5. It is obvious from fig. 5 that the catalyst has excellent recycling performance and good stability. Compared with the Chinese patent application 202010363309.2, the invention adopts UiO-66 as a carrier, and ionic liquid is loaded on the UiO-66 to prepare the supported ionic liquid catalyst, and the supported ionic liquid catalyst prepared by the invention is a heterogeneous catalyst, and can overcome the problems of large loss after multiple use, difficult separation and recovery and the like of the homogeneous catalyst.
The damage of the prepared supported ionic liquid catalyst to reaction equipment is far less than that of the traditional acid-base catalyst, the catalyst can be effectively separated and recovered through filtration, and the catalyst can be repeatedly utilized.
The supported ionic liquid in the example is used as a catalyst, an organic metal framework material UiO-66 is used as a carrier, and an alkyl imidazole amino acid ionic liquid active component is used for constructing the supported ionic liquid 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 does not contain heavy metal ions, so that the reaction liquid after reaction can not be polluted, and the subsequent treatment procedures can be effectively reduced. Compared with enzyme catalysis, the supported ionic liquid catalyst has the advantages that the operable temperature range of the catalyst is large, the requirement on the pH value of a reaction solution is not high, the cycle performance is excellent, the stability is good, and the problem of irreversible enzyme inactivation is solved. By preparing the supported ionic liquid catalyst, the preparation route for preparing fructose by glucose isomerization can be effectively widened.
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 layer liquid, performing rotary evaporation to remove the ethyl acetate, 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-ethylimidazoline proline ionic liquid including a carrier and. 10mL of deionized water was added sequentially to a 25mL autoclave with a Teflon liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 28.7 percent, and the yield of fructose is 15.5 percent. 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 36h, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the upper layer liquid, performing rotary evaporation to remove the ethyl acetate, 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-propylimidazolium proline ionic liquid including a carrier and 10mL deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2Replacing air in the kettle for 5 times, pressurizing to 1.0MPa, and then putting the reaction kettle into the kettleThe reaction was carried out in an oil bath preheated to 130 ℃ for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 30.1 percent, and the yield of fructose is 17.2 percent. 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 36h, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the upper layer liquid, performing rotary evaporation to remove the ethyl acetate, 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-butylimidazolium proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 27.1 percent, and the yield of fructose is 16.4 percent. 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 36h, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the upper layer liquid, rotary evaporating to remove ethyl acetate, 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-pentylimidazole proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 26.5 percent, and the yield of fructose is 15.8 percent. The test method and test conditions were the same as in example 1.
Example 6
Catalyst preparation
Modifying the ligand: weighing 50mmol of 2-bromotetrabenzoquinone, 75mmol of N-hexylimidazole, 5mmol of copper chloride, 100mmol of potassium hydroxide and 40ml of dimethyl sulfoxide (DMSO), magnetically stirring at 130 ℃ for 36h, cooling, adjusting the pH to 2-3 with concentrated sulfuric acid, extracting with ethyl acetate, taking the upper layer liquid, performing rotary evaporation to remove the ethyl acetate, 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-hexylimidazole proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Mixing the mixture (containingGlucose, isomerized fructose, epimerized mannose and the like) in the reaction is transferred to a 100mL volumetric flask, diluted to a scale mark by ultrapure water for later use, and the isomerized fructose is purified and separated to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 26.3 percent, and the yield of fructose is 11.1 percent. 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: and (3) dissolving 2g of the dried product and 6g of sodium tryptophan in 20ml of ethanol, stirring for 24h at room temperature, centrifuging, removing clear liquid, repeating the steps for three times, and performing vacuum drying at 60 ℃ for 24 h.
0.18g of glucose, 0.05g of supported 1-methyl-3-ethylimidazole tryptophan ionic liquid including a carrier and 10mL of deionized water were added in sequence to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 36.3 percent, and the yield of fructose is 15.1 percent. 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 for 24h at room temperature, centrifuging, removing clear liquid, repeating the steps for three times, and vacuum drying for 24h at 60 ℃.
0.18g of glucose, 0.05g of supported 1-methyl-3-ethylimidazole essence including a carrierThe amino acid ionic liquid and 10mL of deionized water were sequentially added to a 25mL reaction vessel with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 33.1 percent, and the yield of fructose is 14.3 percent. 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 sodium threonine in 20ml of ethanol, stirring for 24h at room temperature, centrifuging, removing clear liquid, repeating the steps for three times, and vacuum drying at 60 ℃ for 24 h.
0.18g of glucose, 0.05g of supported 1-methyl-3-ethylimidazole threonine ion liquid containing a carrier and 10mL of deionized water were added in sequence to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 23.1 percent, and the yield of fructose is 10.2 percent. 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 dried product and 6g of sodium glutamate in 20ml of ethanol, stirring for 24h at room temperature, centrifuging, removing clear liquid, repeating the steps for three times, and vacuum drying at 60 ℃ for 24 h.
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 in sequence to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 43.5 percent, and the yield of fructose is 16.4 percent. The test method and test conditions were the same as in example 1.
For the synthesis of supported 1-methyl-3-methylimidazoline proline ionic liquids supported on UiO-66 in the following examples, see example 1.
Example 11
0.18g of glucose, 0.01g of supported 1-methyl-3-methylimidazolyl proline ionic liquid using UiO-66 as a carrier and 10mL of deionized water are sequentially added into a 25mL reaction kettle with a polytetrafluoroethylene lining and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture in the kettle (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) to a 100mL volumetric flask, diluting the mixture to a scale line with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The high performance liquid chromatography is adopted for analysis, and the result shows that under the condition, the glucose conversion rate is 18.7 percentThe 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-methylimidazoline proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 40.1 percent, and the yield of fructose is 17.2 percent. 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-methylimidazoline proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 46.3 percent, and the yield of fructose is 15.1 percent. 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-methylimidazoline proline ionic liquid including a carrier and 10mL of deionized water were added in sequenceTo a 25mL autoclave with a Teflon liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 70.2 percent, and the yield of fructose is 13.5 percent. 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-methylimidazoline proline ionic liquid comprising a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 76.2 percent, and the yield of fructose is 11.5 percent. The test method and test conditions were the same as in example 1.
Example 16
0.09g of glucose, 0.05g of supported 1-methyl-3-methylimidazoline proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Mixing the mixture in the kettle(containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) is transferred to a 100mL volumetric flask, diluted to a scale mark by ultrapure water for standby, and the isomerized product fructose is purified and separated to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 56.1 percent, and the yield of fructose is 16.3 percent. 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-methylimidazoline proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 31.2 percent, and the yield of fructose is 15.4 percent. 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-methylimidazoline proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis is carried out by adopting high performance liquid chromatography, and the result shows that under the conditionThe conversion of glucose was 28.6% and the yield of fructose 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-methylimidazoline proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 26.4 percent, and the yield of fructose is 15.1 percent. 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-methylimidazoline proline ionic liquid including a carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) in the kettle to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 19.4 percent, and the yield of fructose is 14.8 percent. The test method and test conditions were the same as in example 1.
Example 21
0.18g of glucose, 0.05g of the used supported 1-methyl-3-methylimidazole including the carrier 5 timesThe azole proline ionic liquid and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is placed into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture in the kettle (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) to a 100mL volumetric flask, diluting the mixture to a scale mark with ultrapure water for later use, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography shows that under the condition, the conversion rate of glucose is 19.4 percent, and the yield of fructose is 14.7 percent. The test method and test conditions were the same as in example 1.
Example 22
0.18g of glucose, 0.05g of the loaded 1-methyl-3-methylimidazoline proline ionic liquid after 10 uses including the carrier and 10mL of deionized water were added in sequence to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is put into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture in the kettle (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) to a 100mL volumetric flask, diluting the mixture to a scale mark for later use by ultrapure water, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography showed that under these conditions, the glucose conversion was 21.5% and the fructose yield was 14.7%. The test method and test conditions were the same as in example 1.
Example 23
0.18g of glucose, 0.05g of the supported 1-methyl-3-methylimidazoline proline ionic liquid after 15 uses including the carrier and 10mL of deionized water were added in sequence to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2Pressurizing to 1.0MPa after replacing air in the kettle for 5 times, and then putting the reaction kettle into an oil bath kettle preheated to 130 ℃ for reactionAnd (3) 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture in the kettle (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) to a 100mL volumetric flask, diluting the mixture to a scale mark for later use by ultrapure water, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography showed that under the conditions, the conversion rate of glucose was 20.1% and the yield of fructose 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 the loaded 1-methyl-3-methylimidazoline proline ionic liquid after 20 uses including the carrier and 10mL of deionized water were added in sequence to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is put into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture in the kettle (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) to a 100mL volumetric flask, diluting the mixture to a scale mark for later use by ultrapure water, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography showed that under the conditions, the conversion rate of glucose was 20.2% and the yield of fructose was 14.6%. The test method and test conditions were the same as in example 1.
Example 25
0.18g of glucose, 0.05g of the loaded 1-methyl-3-methylimidazoline proline ionic liquid after 25 uses including the carrier and 10mL of deionized water were added in sequence to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is put into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. The kettle mixture (containing unreacted glucose, isomerized fructose and epimerized mannose etc.) was transferred to a 100mL volumetric flask and diluted to the mark with ultra pure waterAnd (4) standing by after-line, and purifying and separating an isomerization product fructose to obtain a target product. The analysis by high performance liquid chromatography showed that under the conditions, the conversion rate of glucose was 20.9% and the yield of fructose 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 the supported 1-methyl-3-methylimidazoline proline ionic liquid after 30 uses including the carrier and 10mL of deionized water were sequentially added to a 25mL reaction kettle with a polytetrafluoroethylene liner and magnetons. With N2The air in the displacement kettle is pressurized to 1.0MPa after 5 times, and then the reaction kettle is put into an oil bath kettle preheated to 130 ℃ for reaction for 30 min. After the reaction is finished, the reaction kettle is placed in cold water to be rapidly cooled to room temperature. Transferring the mixture in the kettle (containing unreacted glucose, isomerized product fructose, epimerized product mannose and the like) to a 100mL volumetric flask, diluting the mixture to a scale mark for later use by ultrapure water, and purifying and separating the isomerized product fructose to obtain the target product. The analysis by high performance liquid chromatography showed that under the conditions, the conversion rate of glucose was 20.8% and the yield of fructose was 14.9%. The test method and test conditions were the same as in example 1.
And (3) filtering and recovering the used supported 1-methyl-3-methylimidazoline proline ionic liquid, washing the ionic liquid with water, and drying the ionic liquid to be used as a catalyst for the next time. The reusability of the supported 1-methyl-3-methylimidazoline proline ionic liquid is shown in the attached figure 3, after the catalyst is recycled for 30 days, the activity is not obviously reduced, the fructose yield is kept at about 15%, and the reusability of the supported 1-methyl-3-methylimidazoline proline ionic liquid is very excellent.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The method for preparing fructose by catalyzing glucose isomerization by using the ionic liquid loaded by the organic metal framework material is characterized in that under the conditions of replacing air in a reactor by inert gas and pressurizing to 0.5-1MPa, 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 70-150 deg.C for 5-120min, and purifying to obtain product; the ionic liquid is alkyl imidazole amino acid salt ionic liquid, and the organic metal framework material is UiO-66.
2. The method for preparing fructose by glucose isomerization catalyzed by organometallic framework material-supported ionic liquid according to claim 1, wherein 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 aspartate salt and alkyl imidazole threonine salt.
3. The method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organometallic framework material according to claim 2, characterized in that the alkyl imidazole proline salt ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000011
the alkyl imidazole arginine salt ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000012
Figure FDA0003138984620000021
4. the method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organometallic framework material according to claim 2, characterized in that the alkyl imidazole tryptophan salt ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000022
the alkyl imidazole lysine salt ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000023
5. the method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organometallic framework material according to claim 2, characterized in that the alkyl imidazole serine salt ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000031
the alkyl imidazole glutamine salt ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000032
the alkyl imidazole methionine salt ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000033
6. the method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material as claimed in claim 2, wherein the alkyl imidazole aspartate ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000041
the alkyl imidazole threonine salt ionic liquid is one or more of the following structural formulas:
Figure FDA0003138984620000042
7. the method for preparing fructose by glucose isomerization catalyzed by ionic liquid loaded by organometallic framework material according to claim 1, wherein the aqueous glucose solution is a mixture of reaction substrate and 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 0.01-0.3g/10mL of glucose aqueous solution.
8. The method for preparing fructose by glucose isomerization catalysis through the organometallic framework material supported ionic liquid according to claim 1, characterized in that the organometallic framework material supported ionic liquid catalyst is prepared by the following method: the method comprises the following steps of (1) modifying an organic ligand by taking bromotetrabenzoquinone as the organic ligand, taking alkyl imidazole as a modifier, taking potassium hydroxide and one of copper chloride, copper bromide and copper iodide as catalysts, and taking dimethyl sulfoxide as a reaction solvent;
taking the modified organic ligand and zirconium chloride as reaction substrates, crystallizing at 120 ℃ for 12-48h, removing supernatant, and washing solids to obtain a catalyst precursor;
and (3) carrying out ion exchange on the catalyst precursor and sodium salt of amino acid, washing, and drying in vacuum to finally obtain the ionic liquid catalyst loaded by the organic metal framework material.
9. The method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material as claimed in claim 1, wherein the alkyl carbon chain length of the alkyl imidazole amino acid salt ionic liquid is C1-C6.
10. The method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material as claimed in claim 1, wherein the inert gas is N2And Ar; after the reaction is finished, the supported ionic liquid is used as the catalyst again after being filtered and washed.
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