CN110078689B - Preparation method of 5-hydroxymethylfurfural - Google Patents

Preparation method of 5-hydroxymethylfurfural Download PDF

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CN110078689B
CN110078689B CN201810072364.9A CN201810072364A CN110078689B CN 110078689 B CN110078689 B CN 110078689B CN 201810072364 A CN201810072364 A CN 201810072364A CN 110078689 B CN110078689 B CN 110078689B
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cellulose
hmf
hydroxymethylfurfural
solid oxide
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CN110078689A (en
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王泽�
李松庚
宋文立
林伟刚
房孝维
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Institute of Process Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J27/055—Sulfates with alkali metals, copper, gold or silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

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Abstract

The invention provides a preparation method of 5-hydroxymethylfurfural. The preparation method comprises the following steps: in a closed environment, performing catalytic conversion on cellulose in a two-liquid-phase system to prepare 5-hydroxymethylfurfural; wherein the dual liquid phase system further comprises a solid oxide and hydrogen ions and non-hydrogen cations dissolved in the aqueous phase. According to the preparation method provided by the invention, a synergistic catalyst combining water-soluble hydrogen ions, non-hydrogen cations and solid oxides is adopted, selective catalysis is carried out according to different reaction steps of preparing 5-hydroxymethylfurfural by converting cellulose, and the conversion rate of cellulose and the yield of 5-hydroxymethylfurfural are improved.

Description

Preparation method of 5-hydroxymethylfurfural
Technical Field
The invention belongs to the field of chemical synthesis, and relates to a preparation method of 5-hydroxymethylfurfural.
Background
The reduction of fossil fuel reserves and the adverse environmental impact of overuse have forced mankind to develop new renewable energy sources. Biomass is an important renewable energy source and the only renewable resource that can be converted to chemicals and liquid fuels. 5-Hydroxymethylfurfural (HMF) obtained by biomass conversion is a very important bio-based platform chemical, is a high-value chemical and medical intermediate, can be widely used for preparing chemicals such as 2, 5-dimethylfuran, 2, 5-furandicarboxylic acid, levulinic acid and the like, and can be used for preparing high molecular polymers, liquid fuels and the like. In recent years, the production of HMF by using glucose, sucrose or fructose has attracted much attention, but the price of glucose, sucrose or fructose is relatively high, and if HMF can be prepared directly from cellulose, the cost of raw materials can be significantly reduced, and the separation process using glucose, sucrose or fructose as products can be avoided, thereby facilitating the simplification of the process, the reduction of equipment investment and the improvement of profit. In a word, the cellulose has the advantages of wide source, low price and the like, and the direct preparation of the HMF from the cellulose has better industrial application prospect.
In the conversion process of preparing HMF from cellulose, it is generally considered that cellulose is firstly hydrolyzed to obtain glucose, glucose is further isomerized to obtain fructose, and fructose is further dehydrated to obtain HMF as a target product, but HMF is very highly chemically active and is easily converted again to obtain other products, such as levulinic acid and the like, due to hydration reaction. The main challenge of preparing HMF by directly converting cellulose is that the structure of cellulose is stable, HMF is poor in stability and easy to generate side reaction, and the optimal catalytic reaction conditions of each step of reaction are different, so that the HMF yield is difficult to improve. Therefore, in the technology for preparing HMF by using cellulose as a raw material, the utilization of a combined catalyst, the construction of a reasonable reaction system and the condition optimization are important contents.
The comparison documents (CN102675264A, CN102491962A and CN106311345A) disclose the technology of preparing HMF by converting cellulose with ionic liquid as solvent, and the yield of HMF can reach 40-68% under the optimal condition. The ionic liquid as a reaction medium can effectively promote the hydrolysis of cellulose, so the ionic liquid is widely applied to the HMF preparation technology taking the cellulose as a raw material, but the ionic liquid has complex preparation process, high price and difficult separation and recovery.
When water is used as a solvent, the hydrolysis conversion of cellulose is usually carried out under the catalytic action of strong acid, and an organic solvent is added at the same time, so that the generated HMF is extracted into an organic phase in time, the secondary reaction probability of the HMF in a water phase is reduced, certain metal cations (such as aluminum salt, zinc salt, copper salt and the like) in a system also have a promoting effect on the yield improvement of the HMF, but the emission problem of part of heavy metal salts which are difficult to recover also threatens the environmental protection. CN106166499A and CN102617524A show that in the preparation process of HMF by using cellulose as a raw material, the yield of the HMF is 40-53% in a two-phase two-solvent system of water and an organic solvent. CN106467507A discloses a preparation method of 5-hydroxymethylfurfural, which takes solid acid as a catalyst, and carbohydrates react in a double-liquid-phase system consisting of metal salt, water and tetrahydrofuran to prepare HMF, wherein the yield of a target product is 62.5%. At present, there is a need to develop a new preparation method to further improve the yield of HMF.
Disclosure of Invention
The invention aims to provide a preparation method of 5-hydroxymethylfurfural.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a preparation method of 5-hydroxymethylfurfural, which comprises the following steps: and under a closed environment, performing catalytic conversion on cellulose in a two-liquid-phase system to prepare the 5-hydroxymethylfurfural.
Wherein the dual liquid phase system further comprises a solid oxide and hydrogen ions and non-hydrogen cations dissolved in the aqueous phase.
In the present invention, the solid oxide refers to a solid oxide existing in a solid form in both the oil phase and the water phase, that is, the solid oxide is not dissolved in both the oil phase and the water phase.
In the process of preparing 5-Hydroxymethylfurfural (HMF) from cellulose, the cellulose is subjected to hydrolysis reaction to obtain glucose, the glucose is subjected to isomerization reaction to obtain fructose, and the fructose is dehydrated to obtain the target product HMF.
In the present invention, the main roles of hydrogen ions dissolved in water are: (1) promoting hydrolysis of cellulose to obtain glucose, (2) after the glucose is converted into fructose, promoting dehydration of the fructose to obtain HMF; while the main role of the non-hydrogen cations dissolved in water is: (1) the method can promote the isomerization of glucose into fructose, (2) the water phase is separated from the oil phase, and a better HMF in-situ extraction process is provided; the solid oxide has the functions of: (1) when cellulose is hydrolyzed into glucose, the isomerization of the glucose into fructose is promoted by catalysis, and (2) the mass transfer rate of HMF from a water phase to an organic phase is improved by the rapid movement of solid oxide between the two phases, so that the conversion rate of the HMF in the water phase is reduced, and the yield of the HMF is improved.
The two-liquid phase system of the present invention is a reaction system having two reaction media (solvents), which includes reactants, additives, etc. dispersed or dissolved therein in addition to the two reaction media (solvents).
The solid oxide provided by the invention and the synergistic catalyst consisting of the hydrogen ions and the non-hydrogen cations dissolved in water have the synergistic effect, so that the conversion rate of cellulose can be effectively improved, the HMF conversion is reduced, and the aim of improving the HMF yield is fulfilled.
As one of the preferred technical solutions, in the two-liquid phase system, the hydrogen ion and the non-hydrogen cation are both provided by acid salt.
Preferably, the acid salt includes any one of ammonium bisulfate, sodium bisulfate, potassium bisulfate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate or a combination of at least two thereof.
In the present invention, an acid salt is understood to be a salt in which the acid group contains a hydrogen ion, and the cation generated upon ionization thereof has a hydrogen ion in addition to the metal ion (or ammonium group); when the acid salt of the present invention is dissolved in water, the solution is an acidic aqueous solution; acid salts of strong or medium acids are preferred in the present invention.
Preferably, the preparation method of the 5-hydroxymethylfurfural comprises the following steps: and adding acid salt into the double-liquid-phase system for dissolving, then adding solid oxide and cellulose, sealing the system, heating for catalytic conversion reaction, and preparing the 5-hydroxymethylfurfural.
In the second preferred embodiment, in the two-liquid phase system, the hydrogen ions are provided by an inorganic acid, and the non-hydrogen cations are provided by an inorganic salt.
Preferably, the inorganic salt is provided by including any one of ammonium sulfate, sodium sulfate, potassium sulfate, ammonium phosphate, sodium phosphate, potassium phosphate, ammonium chloride, sodium chloride and potassium chloride, or a combination of at least two thereof.
Preferably, the preparation method of the 5-hydroxymethylfurfural comprises the following steps: adding inorganic acid and inorganic salt into a two-liquid-phase system for dissolving, then adding solid oxide and cellulose, sealing the system, heating for catalytic conversion reaction, and preparing to obtain the 5-hydroxymethylfurfural.
In the present invention, the water-soluble hydrogen ions and the non-hydrogen cations can be obtained by two methods, one is to directly provide an acid salt, and after dissolving in water, simultaneously obtain the water-soluble hydrogen ions and the non-hydrogen cations; alternatively, inorganic acids and inorganic salts are added, which, when dissolved in water, yield water-soluble hydrogen ions and non-hydrogen cations. Other methods not disclosed for obtaining water soluble hydrogen ions and non-hydrogen cations may be used in the present invention.
In the present invention, the molar ratio of the hydrogen ion addition amount to the carbon atoms in the cellulose in the two-liquid phase system is 1 (4-20), for example, 1:4, 1:5, 1:10, 1:12, 1:15, 1:17, 1:20, etc.
Preferably, the molar ratio of the non-hydrogen cations to carbon atoms in the cellulose in the two-liquid system is 1 (4-20), such as 1:4, 1:5, 1:10, 1:12, 1:15, 1:17, 1:20, etc.
Cellulose is a macromolecular substance polymerized from a large number of structural monomers, which can be thought of as being formed by dehydration of glucose, the structural formula of which can be thought of as C6H10O5Thus, the formula for the calculation of the number of moles of carbon atoms in cellulose is:
Figure BDA0001558526980000051
wherein m isCellulose, process for producing the same, and process for producing the sameIs the mass of cellulose, 162 is a cellulose structural monomer (C)6H10O5) 6 represents the mole number of carbon atoms in 1mol of cellulose structural monomer, and the polymerization degree is the polymerization degree of a structural unit in the cellulose macromolecule.
In the present invention, the water-insoluble solid oxide includes titanium dioxide and/or zirconium dioxide.
Preferably, in the two-liquid phase system, the addition amount of the solid oxide and the molar ratio of carbon atoms in the cellulose are 1 (3-15), such as 1:3, 1:5, 1:7, 1:10, 1:11, 1:13, 1:15, and the like.
In the invention, when the addition amount of the solid oxide is too large or too small, the yield of the HMF is influenced, and when the addition amount of the solid oxide is too small, on one hand, the catalytic action for isomerizing the glucose into the fructose is weakened, on the other hand, the rate of the HMF organic phase entering the organic phase is influenced, and further, the secondary reaction of the HMF is possibly increased, so that the yield of the HMF is influenced; on the other hand, if the amount of the solid oxide added is too large, the amount of HMF adsorbed by the solid oxide may increase, and the amount of HMF dissolved in the organic phase may decrease, thereby affecting the HMF yield.
Preferably, the solvent of the two-liquid phase system is a mixed solvent of water and an organic solvent.
Preferably, the organic solvent comprises a monocyclic heteroatomic compound organic solvent.
Preferably, the monocyclic heteroatom compound organic solvent includes any one of furan, 2-methylfuran, 2, 5-dimethylfuran, tetrahydrofuran, 2-methyltetrahydrofuran, pyran, tetrahydropyran and 2-methyltetrahydropyran or a combination of at least two thereof.
Preferably, the mass ratio of the added amount of the organic solvent to water in the solvent of the two-liquid phase system is (5-15: 1), for example, 5:1, 6:1, 9:1, 10:1, 11:1, 13:1, 14:1, 15:1, and the like.
The invention adopts a double-liquid-phase system consisting of the monocyclic heteroatom compound organic solvent and water, on one hand, the aqueous-phase system provides a suitable conversion environment for hydrolysis of cellulose and isomerization of glucose into fructose and dehydration of fructose, which is beneficial to the production of HMF, on the other hand, the monocyclic heteroatom compound organic solvent has high extraction capacity for HMF, can reduce the probability of secondary reaction of HMF in the aqueous phase, and is further beneficial to improving the yield of HMF.
In the present invention, the reaction temperature of the catalytic conversion is 130-250 ℃ (e.g., 130 ℃, 150 ℃, 170 ℃, 190 ℃, 200 ℃, 210 ℃, 230 ℃, 250 ℃, etc.), preferably 150-210 ℃.
Preferably, the reaction time of the catalytic conversion is 10 to 300min (e.g., 10min, 20min, 30min, 60min, 90min, 100min, 130min, 150min, etc.), and more preferably 30 to 120 min.
In the invention, the closed environment is provided by a hastelloy reaction kettle.
The solid oxide used in the invention is insoluble in water and can be recycled after reaction; the preparation method provided by the invention has the advantages of simple process, mild reaction conditions and low preparation cost, does not need to add heavy metal salt, is an environment-friendly technical scheme and has good industrial prospect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method provided by the invention, a synergistic catalyst consisting of the solid oxide, the water-soluble hydrogen ions and the non-hydrogen cations is adopted, selective catalysis is carried out on different reaction processes of cellulose hydrolysis (cellulose hydrolysis, glucose isomerization into fructose and fructose dehydration), and the conversion rate of preparing the HMF from the cellulose is improved;
(2) the double-liquid-phase system provided by the invention provides a reaction phase (water phase) for preparing HMF from cellulose on one hand and an extraction phase (organic phase) for preparing HMF on the other hand, which is beneficial to reducing secondary reaction of HMF and improving the yield of HMF;
(3) the solid oxide in the synergistic catalyst provided by the invention is beneficial to transferring HMF from a water phase to an organic phase, so that in-situ extraction is realized, the probability of secondary reaction of HMF is reduced, the reaction is promoted to be carried out rightwards, and the yield of HMF is further improved, and the yield of HMF obtained by the preparation method provided by the invention can reach more than 60%;
(4) according to the preparation method provided by the invention, the solid oxide can be recycled, the cost is reduced, and a heavy metal salt solution is not required to be added, so that the risk of environmental pollution is reduced; the preparation method provided by the invention is simple and feasible.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
Weighing 0.2g of cellulose, 0.11g of sodium bisulfate, 0.39g of zirconium dioxide, 4g of water and 40g of tetrahydrofuran, and placing the mixture in a 100ml Hastelloy reaction kettle; heating the reaction kettle to 190 ℃ and keeping the temperature for 60min, and taking out the solution after the reaction is finished to obtain a HMF mixed solution; the remaining solid was zirconium dioxide, washed with deionized water to pH 7.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was 86% as compared with the known amount of added cellulose.
Example 2
Weighing 0.2g of cellulose, 0.11g of ammonium bisulfate, 0.20g of titanium dioxide, 4g of water, 20g of tetrahydrofuran and 20g of tetrahydropyran, and placing the mixture in a 100ml hastelloy reaction kettle; and (3) heating the reaction kettle to 190 ℃ and keeping the temperature for 90min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 71% by comparison with the known amount of added cellulose.
Example 3
Weighing 0.2g of cellulose, 0.11g of sodium sulfate, 0.37g of zirconium dioxide, 4g of sulfuric acid solution with the mass fraction of 5.8% and 40g of tetrahydrofuran, and placing the materials in a 100ml Hastelloy reaction kettle; and (3) heating the reaction kettle to 170 ℃ and keeping the temperature for 60min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 70% by comparison with the known amount of added cellulose.
Example 4
Weighing 0.2g of cellulose, 0.14g of monopotassium phosphate, 0.2g of zirconium dioxide, 4g of water and 24g of 2-methyltetrahydrofuran, and placing the mixture in a 100ml Hastelloy reaction kettle; and (3) heating the reaction kettle to 220 ℃ and keeping the temperature for 240min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 68% by comparison with the known amount of added cellulose.
Example 5
Weighing 0.2g of cellulose, 0.11g of sodium bisulfate, 0.12g of titanium dioxide, 0.13g of zirconium dioxide, 8g of water and 40g of 2-methyltetrahydrofuran, and placing the mixture in a 100ml Hastelloy reaction kettle; and (3) heating the reaction kettle to 190 ℃ and keeping the temperature for 60min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 73% by comparison with the known amount of added cellulose.
Example 6
Weighing 0.4g of cellulose, 0.15g of potassium bisulfate, 0.56g of titanium dioxide, 2g of water, 10g of tetrahydropyran and 20g of 2-methylfuran, and placing the materials in a 100ml hastelloy reaction kettle; and (3) heating the reaction kettle to 200 ℃ and keeping the temperature for 150min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 69% by comparison with the known amount of added cellulose. .
Example 7
Weighing 1g of cellulose, 0.7g of sodium chloride, 0.25g of titanium dioxide, 6g of hydrochloric acid solution with the mass fraction of 4%, 20g of 2-methyltetrahydrofuran and 10g of 2-methyltetrahydropyran, and placing the mixture in a 100ml hastelloy reaction kettle; and (3) heating the reaction kettle to 160 ℃ and keeping the temperature for 120min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 66% by comparison with the known amount of added cellulose.
Example 8
Weighing 0.2g of cellulose, 0.11g of sodium bisulfate, 0.12g of titanium dioxide, 0.37g of zirconium dioxide, 4g of water, 30g of 2-methyltetrahydrofuran and 10g of pyran, and placing the mixture in a 100m l hastelloy reaction kettle; and (3) heating the reaction kettle to 140 ℃ and keeping the temperature for 300min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 77% by comparison with the known amount of added cellulose.
Example 9
Weighing 0.2g of cellulose, 0.12g of ammonium bisulfate, 0.2g of zirconium dioxide, 4g of water, 20g of tetrahydrofuran and 20g of 2, 5-dimethylfuran, and placing the mixture in a 100ml Hastelloy reaction kettle; and (3) heating the reaction kettle to 160 ℃ and keeping the temperature for 180min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 70% by comparison with the known amount of added cellulose.
Example 10
Weighing 0.2g of cellulose, 0.11g of sodium bisulfate, 0.37g of zirconium dioxide, 4g of water and 40g of tetrahydrofuran, and placing the mixture in a 100ml Hastelloy reaction kettle; and (3) heating the reaction kettle to 130 ℃ and keeping the temperature for 280min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 84% by comparison with the known amount of added cellulose.
Example 11
Weighing 0.2g of cellulose, 0.11g of calcium chloride, 0.37g of zirconium dioxide, 8g of phosphoric acid solution with the mass fraction of 12% and 40g of tetrahydrofuran, and placing the mixture in a 100ml hastelloy reaction kettle; and (3) heating the reaction kettle to 250 ℃ and keeping the temperature for 10min, and removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 64% by comparison with the known amount of added cellulose.
Example 12
Weighing 0.2g of cellulose, 0.11g of calcium chloride, 0.37g of SBA-15, 8g of sulfuric acid solution with the mass fraction of 4% and 40g of tetrahydrofuran, and placing the mixture in a 100ml Hastelloy reaction kettle; and (3) heating the reaction kettle to 210 ℃ and keeping the temperature for 30min, and then removing the product to prepare the HMF mixed solution.
The HMF mixed solution was weighed and quantitatively analyzed for the composition of the components of the liquid product using a gas chromatography-mass spectrometer, and the yield of HMF was found to be 60% by comparison with the known amount of added cellulose.
Example 13
(1) Weighing 0.2g of cellulose, 0.11g of sodium bisulfate, 0.37g of zirconium dioxide recovered in example 1, 4g of water and 40g of tetrahydrofuran, placing the mixture in a 100ml Hastelloy reaction kettle, and heating the reaction kettle to 190 ℃ and keeping the temperature for 60 min;
(2) after the reaction is finished, taking out the solution as a HMF mixed solution, filtering, washing and drying the solution to obtain a solid which is the recycled zirconium dioxide, and washing the solid with deionized water until the pH value is 7;
(3) replacing the zirconium dioxide in the step (1) with the zirconium dioxide recovered in the step (2), and repeating the steps (1) to (2) to obtain a HMF mixed solution;
(4) repeating the steps (1) to (3)4 times, collecting the HMF mixed solution obtained in the last time, weighing, and quantitatively analyzing the component composition of the liquid product by using a gas chromatography-mass spectrometer, wherein the yield of the HMF is 84% compared with the known addition of the cellulose.
Example 14
The only difference from example 1 is that this example added 1.17g of zirconium dioxide (the molar ratio of the addition of solid oxide to carbon atoms in the cellulose was 1: 1); the yield of HMF obtained was 64%.
Example 15
The only difference from example 1 is that 0.059g of zirconium dioxide (the molar ratio of the addition of solid oxide to carbon atoms in the cellulose is 1:20) is added in this example; the yield of HMF obtained was 71%.
Comparative example 1
The only difference from example 1 is that in this comparative example no zirconium dioxide was added.
The yield of HMF was measured to be 45%.
From examples 1 to 15, it can be seen that the preparation method for 5-hydroxymethylfurfural provided by the invention is simple and easy to implement, and the yield of 5-hydroxymethylfurfural prepared by the preparation method provided by the invention is over 60%; as can be seen from the comparison between examples 1-10 and examples 11-12, when the hydrogen ions and non-hydrogen cations dissolved in the aqueous phase are from the inorganic acid and inorganic salt or acid salt related in the preferences of the present invention, the synergistic catalyst provided by the present invention has more excellent catalytic effect, and the yield of the prepared 5-hydroxymethylfurfural is above 66%; from example 13, it can be seen that the solid oxide added in the present invention can be recycled after being recycled, and after 5 times of recycling, the yield of HMF is not changed much compared with the first time, and the yield is not significantly reduced due to recycling of the solid oxide; as can be seen from the comparison between example 1 and examples 14 to 15, the yield of HMF is high when the molar ratio of the addition amount of the solid oxide to the carbon atoms in the cellulose is in the range of 1 (3-15). As can be seen from the comparison between example 1 and comparative example 1, the yield of HMF decreases in the synergistic catalyst provided by the present invention when no solid oxide is added, and presumably, the decrease in the HMF yield is caused by the decrease in the degree of reaction of isomerization of glucose to fructose and the occurrence of secondary reaction of a part of HMF in the aqueous phase.
The applicant states that the present invention is illustrated by the above examples to the preparation method of 5-hydroxymethylfurfural, but the present invention is not limited to the above examples, i.e., it is not meant to be construed as being limited thereto. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (9)

1. A preparation method of 5-hydroxymethylfurfural is characterized by comprising the following steps: in a closed environment, in a two-liquid phase system, performing catalytic conversion on cellulose at the reaction temperature of 130-250 ℃ to obtain the cellulose;
wherein the dual liquid phase system further comprises a solid oxide and hydrogen ions and non-hydrogen cations dissolved in the aqueous phase;
in the double-liquid-phase system, the molar ratio of the addition amount of the solid oxide to carbon atoms in the cellulose is 1 (3-15), the molar ratio of the addition amount of the hydrogen ions to the carbon atoms in the cellulose is 1 (4-20), and the molar ratio of the addition amount of the non-hydrogen cations to the carbon atoms in the cellulose is 1 (4-20);
in the solvent of the double-liquid-phase system, the solvent is a mixed solvent of water and an organic solvent, and the mass ratio of the addition amount of the organic solvent to the water is (5-15): 1;
the solid oxide is titanium dioxide and/or zirconium dioxide;
both the hydrogen ion and the non-hydrogen cation are provided by an acid salt.
2. The production method according to claim 1, wherein the acid salt comprises any one of ammonium bisulfate, sodium bisulfate, potassium bisulfate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, and potassium dihydrogen phosphate, or a combination of at least two thereof.
3. The method according to claim 1, wherein the method for preparing 5-hydroxymethylfurfural comprises: and adding acid salt into the double-liquid-phase system for dissolving, then adding solid oxide and cellulose, sealing the system, heating for catalytic conversion reaction, and preparing the 5-hydroxymethylfurfural.
4. The method of claim 1, wherein the organic solvent comprises a monocyclic heteroatomic compound organic solvent.
5. The method according to claim 4, wherein the monocyclic hetero atom compound organic solvent comprises any one of furan, 2-methylfuran, 2, 5-dimethylfuran, tetrahydrofuran, 2-methyltetrahydrofuran, pyran, tetrahydropyran and 2-methyltetrahydropyran or a combination of at least two thereof.
6. The method as claimed in claim 1, wherein the reaction temperature of the catalytic conversion is 150-210 ℃.
7. The production method according to claim 1, wherein the reaction time of the catalytic conversion is 10 to 300 min.
8. The production method according to claim 1, wherein the reaction time of the catalytic conversion is 30 to 120 min.
9. The method of claim 3, wherein the closed environment is provided by a hastelloy reaction vessel.
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