CN111229264A - Method for preparing 5-hydroxymethylfurfural, catalyst thereof and preparation method of catalyst - Google Patents
Method for preparing 5-hydroxymethylfurfural, catalyst thereof and preparation method of catalyst Download PDFInfo
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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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
- B01J27/14—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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to the field of chemical synthesis, and discloses a method for preparing 5-hydroxymethylfurfural, a catalyst and a catalyst preparation method, wherein the catalyst is a phosphorylated composite metal oxide, and the doping amount of phosphorus is 5-30% of the total molar number of metal elements in the catalyst; the composite metal oxide is a composite of titanium oxide and zirconium oxide; the molar ratio of titanium to zirconium in the catalyst is 1: 9-9: 1. The catalyst is prepared by dissolving titanium salt and zirconium salt, adding phosphoric acid, and stirring to obtain gel and roasting. Under the condition of 150-200 ℃, the catalyst is used for catalyzing carbohydrate in a two-phase solvent to generate 5-hydroxymethylfurfural, and high raw material conversion rate and HMF yield can be obtained under the catalysis effect of the catalyst. The catalyst has the advantages of simple preparation process, high dispersion degree of active component elements, strong hydrothermal stability, no obvious reduction of catalytic performance after repeated recycling, and excellent economy and environmental protection.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for preparing 5-hydroxymethylfurfural, a catalyst thereof and a preparation method of the catalyst.
Background
The biomass resource in China is abundant, but the biomass resource can not be effectively utilized for a long time, and the biomass resource causes serious environmental pollution. If biomass with abundant resources in China can be efficiently converted to prepare chemicals and biological liquid fuels with high added values, the method is beneficial to solving the problems of energy shortage and environment in China. 5-Hydroxymethylfurfural (HMF) is a high value-added platform compound that can be prepared from biomass sources and can be further converted into a series of chemicals and biofuels. Therefore, the research and development of the technology for preparing HMF by accelerating the efficient conversion of biomass resources can promote the optimization of energy structure in China, relieve the pressure of ecological environment and meet the great national requirements.
The preparation process of HMF mainly comprises two steps, namely firstly hydrolyzing cellulose and hemicellulose in biomass to generate monosaccharide, and then dehydrating and converting the monosaccharide to generate the HMF. Due to the complex structure of biomass, the six-carbon glucose with the highest content in the biomass and the important intermediate fructose in the glucose conversion process are widely applied to exploring HMF generation rules and developing novel reaction systems. Although the basic research of the current HMF preparation has obtained many promising achievements, the problems of difficult catalyst recycling, poor economy of the reaction process, environmental pollution of waste liquid and waste residue and the like still exist, and the development of a novel green catalytic reaction system is urgently needed to improve the recycling performance of the catalyst, thereby accelerating the promotion of the industrialization of the HMF preparation technology.
The solvents currently used in the research of preparing HMF by six-carbon sugar conversion mainly include a single-phase system and a two-phase system. Water is the most common solvent in single phase systems, but due to its strong polarity, HMF is produced in low yields in water and readily reacts with water to form other byproducts. Therefore, organic solvent-water co-dissolving systems are often used to suppress the occurrence of side reactions. A better solution is to use a biphasic system, where the aqueous phase is the reaction phase and the organic phase is the extraction phase. The HMF is rapidly extracted to the organic phase after being generated, and the hydration side reaction of the HMF is inhibited.
The choice of catalyst is also one of the most important influencing factors in HMF production technology, which is mainly divided into homogeneous catalysts and heterogeneous catalysts. Early researchers often used homogeneous catalysts, inorganic acids (e.g., sulfuric acid, hydrochloric acid, phosphoric acid) to catalyze the conversion of sugars to produce HMF, and could obtain HMF yields of greater than 70% from fructose. However, the inorganic acid is easy to cause equipment corrosion, and the catalyst and the product are difficult to separate, so that the recycling is not facilitated. Heterogeneous solid acid catalysts have the advantages of low corrosivity, strong thermal stability, easy separation and the like, and thus have become a hot point of research in recent years. Common heterogeneous catalysts include protonated zeolites, transition metal oxides, carbon based catalysts, and the like. Metal phosphates are well known for their excellent acid strength and are suitable for use in a variety of acid catalyzed reactions, including the dehydration of carbohydrates to produce HMF.
The zirconium phosphate catalyst is not easy to hydrolyze under hydrothermal conditions, has strong stability, but has poor catalytic effect. The titanium phosphate catalyst has excellent catalytic performance, can catalyze glucose conversion to obtain the HMF yield of more than 80%, but has poor recycling performance. Therefore, if the hydrothermal stability of zirconium phosphate can be combined with the high catalytic activity of titanium phosphate, it is possible to obtain a solid acid with more excellent catalytic performance.
Patent publication No. CN106699703A discloses a method for preparing 5-hydroxymethylfurfural by catalyzing biomass sugar with zirconium phosphate-loaded titanium dioxide. According to the method, biomass sugar is used as a raw material, zirconium phosphate loaded titanium dioxide is used as a catalyst, tetrahydrofuran and water are used as reaction solvents, and the biomass sugar is converted in a high-pressure reaction kettle to obtain HMF. The preparation method of the catalyst is an impregnation method, namely, zirconium phosphate is loaded on a titanium dioxide carrier. The method has the problems that active elements (Ti, Zr and P) are not uniformly dispersed, and surface components are easy to agglomerate and run off after multiple reactions, and are not beneficial to catalytic reaction.
Disclosure of Invention
The invention aims to solve the problems of low raw material conversion rate, poor catalytic performance of the catalyst, easy inactivation and poor cycle stability in the HMF preparation process. The catalyst for preparing HMF provided by the invention can promote the dehydration and conversion of carbohydrates to generate HMF under mild conditions, remarkably inhibit the occurrence of side reactions induced by strong Lewis acidity of the catalyst, is not easy to inactivate, has good recycling performance, has the conversion rate of raw materials of more than 80 percent, and has high yield of the obtained HMF.
In order to achieve the purpose, the invention adopts the technical scheme that:
a catalyst for preparing 5-hydroxymethylfurfural is a phosphorylated composite metal oxide, wherein the doping amount of phosphorus is 5-30% of the total mole number of metal elements in the catalyst; the composite metal oxide is a composite of titanium oxide and zirconium oxide; the molar ratio of titanium to zirconium in the catalyst is 1: 9-9: 1.
The titanium element in the catalyst is increased within a certain range, so that the carbohydrate conversion rate and the acidity of the catalyst can be improved, but the stability of the catalyst is reduced, side reactions are easy to occur in the catalytic process, so that byproducts are deposited on the surface of the catalyst, the catalyst is easy to deactivate, the recycling performance of the catalyst is reduced, and the economical efficiency of the technological process is influenced. The content of zirconium element in the catalyst is increased within a certain range, so that the hydrothermal stability of the catalyst can be improved, but ZrO2The oxygen vacancy of (a) increases the proportion of Lewis acid centers, promotes the occurrence of side reactions of carbohydrate polycondensation in the early stage of the reaction, and reduces the yield of HMF.
Therefore, the mol ratio relationship of the titanium and the zirconium in the catalyst plays a key role in the activity, the stability and the recycling performance of the catalyst.
Preferably, the molar ratio of the titanium element to the zirconium element in the catalyst is 3: 7-7: 3. The ratio of the two metal elements is in the range, the HMF selectivity is high, the carbohydrate conversion rate is high, and the process economy is high.
The catalyst is a phosphated composite metal oxide,the composite metal oxide of titanium oxide and zirconium oxide is phosphorylated by introducing P-OH group into the composite metal oxide to strengthen the catalyst
The acidity is favorable for promoting the hydrolysis and dehydration reaction of carbohydrate, and the catalyst can be improved
Acid to Lewis acid site ratio, thereby increasing HMF yield. In addition, the introduction of phosphorus improves the anti-sintering performance of the catalyst precursor in the roasting process, so that the pore volume and the specific surface area of the catalyst are improved, and the catalytic activity of the catalyst is further improved. However, too high a phosphorus content will cause clogging of catalyst channels, impairing the catalytic performance of the catalyst. Preferably, the phosphorus element is 10-20% of the total mole number of the metal elements in the catalyst.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
(1) dissolving titanium salt and zirconium salt in a solvent, adding phosphoric acid after uniformly stirring, standing and drying to obtain gel;
(2) and (2) roasting the gel prepared in the step (1) to obtain the catalyst.
In the preparation method, as for reaction raw materials, zirconium salt and titanium salt are both soluble salts, and the titanium salt is any one of isopropyl titanate, tetrabutyl titanate and titanium tetrachloride; the zirconium salt is any one of zirconium oxychloride, zirconium acetate, zirconium n-butoxide, zirconium n-propoxide and zirconium chloride.
Preferably, the titanium salt is isopropyl titanate or tetrabutyl titanate, the zirconium salt is n-butyl zirconium or n-propyl zirconium, and the obtained alkoxide metal salt after the two are mixed has stable chemical performance, is not easy to react with water, and the prepared catalyst has high purity and better catalytic activity.
The solvent is water or alcohol; preferably, the solvent is an alcohol to avoid loss of the metal salt by hydrolysis. The alcohol comprises any one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol.
In the preparation method, regarding the reaction conditions, the standing time in the step (1) is 12-36 h, the drying temperature is 100-120 ℃, the drying time is 10-20 h, and in order to ensure the sufficient and uniform reaction between the two metal salts and the phosphoric acid, the standing time is not too short, and the preferred standing time is 20-30 h.
In the step (2), the roasting temperature is 400-700 ℃, and the time is 4-8 h. When the roasting temperature is too low, volatile organic compounds cannot be completely removed, the crystal form conversion is slow, and the obtained catalyst has low mechanical strength. When the roasting temperature is too high, the catalyst is easy to agglomerate, and the catalytic activity is reduced. When the calcination time is too short, the desired calcination effect cannot be obtained, and when the calcination time is too long, the catalyst agglomeration will be caused.
In conclusion, the condition factors of the roasting process have great relation to the catalytic effect of the catalyst, preferably, the roasting temperature is 500-600 ℃, the roasting time is 5-6 h, and experiments prove that the catalyst has the best catalytic efficiency and is not easy to inactivate when being roasted under the condition.
The invention also provides a method for preparing HMF, which is characterized in that the catalyst is adopted to catalyze carbohydrate to generate 5-hydroxymethylfurfural at the temperature of 150-200 ℃ in a two-phase solvent consisting of water and a hydrophobic organic phase. The catalytic reaction time is 0.5-3 h, and the specific reaction time can be adjusted according to reaction raw materials.
The catalyst provided by the invention can be used for dehydrating carbohydrate to generate HMF under mild conditions, the conversion rate of the raw material is high, the catalytic effect of the catalyst is good, and the catalyst is not easy to inactivate.
The carbohydrate is a raw material commonly used for preparing HMF, namely various components from biomass raw materials, including monosaccharide, disaccharide or polysaccharide, such as fructose, glucose, galactose, sucrose, maltose, inulin and the like.
The hydrophobic organic phase is used as an extraction phase, preferably methyl isobutyl ketone, butanone, tetrahydrofuran, cyclopentyl methyl ether, toluene, xylene, 1-butanol or cyclohexanol; the organic phase can extract the HMF product generated in the reaction process in time, and water and side reactions are prevented from occurring.
Preferably, the hydrophobic organic phase is one of methyl isobutyl ketone, butanone, tetrahydrofuran and cyclopentyl methyl ether. The organic phase has low cost, low toxicity and less environmental pollution, and is not easy to react with the substances in the solution, so the organic phase is more suitable to be used as a hydrophobic organic phase.
In the two-phase solvent, the volume ratio of water to the hydrophobic organic phase is 1: 1-1: 19. Preferably, the volume ratio of the water to the hydrophobic organic phase is 1: 4-1: 10. When the volume ratio is too low, the product HMF cannot be sufficiently protected, and side reactions are exacerbated. When the volume ratio is too high, the reactants cannot be sufficiently dissolved in water, resulting in a decrease in the reaction rate.
The mass ratio of the catalyst to the carbohydrate is 1: 1-1: 20; the initial concentration of the carbohydrate in the reaction solution is 0.02-0.2 g/mL.
Preferably, the mass ratio of the catalyst to the carbohydrate is 1: 5-1: 10; the initial concentration of carbohydrate in the solution is 0.02-0.1 g/mL. Within the above range, the yield of HMF is high and the process is most economical. If the concentration of carbohydrate is too low or the amount of catalyst used is too high, the process economics are poor; if the concentration of the carbohydrate is too high or the amount of the catalyst is too low, the dehydration conversion of the carbohydrate is poor.
The existing catalyst has the defect of easy inactivation, but the catalyst of the invention is not easy to inactivate in the reaction process, and the catalyst can be recycled after the reaction is finished, and the recycling method comprises the following steps: and after the reaction is finished, filtering to obtain a solid, washing with an organic solvent, and drying to obtain the recovered catalyst. The recovered catalyst is reused, the catalytic efficiency of the catalyst is still good, the conversion rate of the raw materials is high, and the catalyst has excellent repeatability and high economy.
In the recovery process of the catalyst, the organic solvent is preferably ethanol, n-hexane or acetone, and is preferably dried for 2-10 hours at 100-120 ℃ after being washed.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst disclosed by the invention is excellent in catalytic activity, can realize dehydration of carbohydrates to generate HMF under a mild condition, and is high in raw material conversion rate and high in yield of the obtained HMF.
(2) The preparation method of the catalyst is simple, the high catalytic activity of titanium dioxide and the high hydrothermal stability of zirconium dioxide are innovatively combined, the catalyst is not easy to inactivate, the catalytic efficiency is high, and the catalytic activity is still good after repeated cyclic utilization.
(3) The method for preparing HMF provided by the invention adopts a two-phase solvent system consisting of water and a hydrophobic organic phase, so that the yield of HMF is improved to the maximum extent, the organic phase can be kept stable in the reaction process and can be repeatedly used, and the catalyst and the product can be automatically separated after the reaction.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
In the following specific embodiment, fructose, glucose, sucrose, inulin, 5-hydroxymethylfurfural, isopropyl titanate and zirconium n-butoxide are purchased from Aladdin reagent. Isopropyl alcohol, phosphoric acid and methyl ethyl ketone were purchased from the national pharmaceutical group chemical agents limited.
In the application example, an UltiMate 3000 high performance liquid chromatograph (Thermo Scientific, usa) is used for quantitative analysis, wherein the calculation formulas of the reactant conversion rate and the HMF yield are respectively as follows:
reactant conversion ═ (moles of reactant consumed/moles of reactant before reaction) × 100 mol%; wherein the mole number of the inulin is calculated by the mole number of monosaccharide units.
HMF yield ═ 100 mol% (moles HMF produced/moles monosaccharide in the reaction before reaction).
Example 1
Preparation of the catalyst:
(1) 0.05mol (14.211g) of isopropyl titanate and 0.05mol (19.184g) of zirconium n-butoxide are dissolved in 4mol (240g) of isopropanol. The resulting solution was stirred well, then 0.02mol (1.96g) of phosphoric acid was added, followed by stirring for 3 hours. Then the solution is kept stand for 24h at room temperature and then is dried in an oven at 110 ℃ for 12h to obtain gel.
(2) And roasting the obtained gel at 600 ℃ for 6h to obtain the catalyst. The molar ratio of titanium and zirconium elements in the catalyst is 1:1, and the doping amount of phosphorus is 20% of the total mole number of metal elements.
Examples 2 to 5
The same preparation process as in example 1 was carried out except that the amounts of isopropyl titanate in step (1) were 0.01mol, 0.03mol, 0.07mol and 0.09mol, respectively, and the amounts of n-butyl alcohol and zirconium were 0.09mol, 0.07mol, 0.03mol and 0.01mol, respectively, to obtain catalysts in which the molar ratios of titanium and zirconium elements were 1:9, 3:7, 7:3 and 9:1, respectively.
Examples 6 to 8
The same production method as in example 1 was used except that the amounts of phosphoric acid in step (1) were 0.005mol, 0.01mol, and 0.03mol, respectively. The doping amount of the phosphorus in the obtained catalyst is 5 percent, 10 percent and 30 percent of the total mole number of the metal elements.
Examples 9 to 11
The same preparation method as in example 1 was used except that the calcination temperatures in step (2) were 400 deg.C, 500 deg.C, and 700 deg.C, respectively.
Application example 1
Adding 1.2g of fructose, 0.3g of the catalyst prepared in the example 1-11, 10mL of deionized water and 40mL of tetrahydrofuran into a 100mL batch reactor, reacting for 1h at 170 ℃, and catalyzing the dehydration of the fructose to generate HMF. After cooling, the solution was filtered through a 0.22 μm organic filter, and the filtrate was diluted 10 times and then subjected to product quantitative analysis by High Performance Liquid Chromatography (HPLC), and the conversion of the reactant and the yield of HMF were calculated. The performance of the catalysts of examples 1-11 in catalyzing fructose dehydration to prepare HMF is shown in Table 1.
The results show that the catalyst prepared by the invention has excellent catalytic activity for preparing HMF by fructose dehydration, can realize efficient conversion of fructose to HMF under mild conditions, has high raw material conversion rate (all over 84.2 percent), and can obtain HMF with high yield (all over 59.4 percent and up to 75.7 percent).
By comparing examples 1-5, it can be seen that too high a ratio of zirconium or titanium elements in the catalyst results in a decrease in the final HMF yield, whereas the HMF yield is highest at a molar ratio of titanium to zirconium of 1: 1.
The results of examples 6 to 8 show that when the molar ratio of the titanium element to the zirconium element in the catalyst is 1:1, the doping amount of phosphorus is not good enough, the doping amount of phosphorus in the experiment is 10% of the total molar amount of the metals, and the yield of HMF is the highest.
As can be seen from comparative examples 9 to 11, the calcination temperature of the catalyst in the preparation process also has a great influence on the activity of the catalyst, and when the calcination temperature is low (such as 400 ℃ in example 9), the yield of the obtained catalyst for preparing HMF by catalysis is at least 59.4%, and when the calcination temperature is 500 ℃, the yield of HMF is high, and is 72.3%.
TABLE 1 Performance of HMF preparation by fructose dehydration catalyzed by catalysts of examples 1-11
Application examples 2 to 8
The catalyst of example 1 was tested by the same reaction process as in application example 1, the kinds of reactants of the reaction, the kinds of hydrophobic organic phase, the volume ratio of the aqueous phase to the hydrophobic organic phase and the reaction time were changed, and the reaction product was quantitatively analyzed. The catalyst of example 1 was tested for its performance in catalyzing the dehydration conversion of various carbohydrates to HMF under various reaction conditions, and the results of the modified reaction conditions and the tested performance are shown in table 2.
The results show that the catalyst prepared by the invention has excellent catalytic activity, can realize the high-efficiency conversion from carbohydrates to HMF under mild conditions, and has high raw material conversion rate and high yield of the obtained HMF aiming at the preparation of HMF by dehydration conversion of different carbohydrates.
By observing application examples 1-4, increasing the volume of the hydrophobic organic phase in the reaction system is beneficial to improving the conversion rate of the reactant and the yield of the HMF, but too high volume of the hydrophobic organic phase can also cause the reduction of the conversion rate of the reactant and the yield of the HMF.
From application example 1 and application examples 6 to 8, the production of HMF by dehydration and conversion of fructose is easier, but the catalytic activity of the catalyst of the invention applied to the production of HMF by dehydration and conversion of glucose, sucrose and inulin is also good, the conversion rate of reactants is above 72.2%, and the yield of HMF is above 43.1%.
Table 2 properties of the catalyst of example 1 for the preparation of HMF at different reaction conditions
Application examples 9 to 11
In order to prove that the catalyst of the invention has good stability, is not easy to inactivate and can be reused, the reaction product is filtered to obtain a solid by adopting the reaction process which is the same as the reaction process in the application example 1, the solid is washed by ethanol and dried for 2 hours at the temperature of 110 ℃ to obtain a recovered catalyst, the recovered catalyst is used for catalyzing fructose to prepare HMF according to the reaction process which is the same as the application example 1, the steps are repeated for many times, and the catalyst is subjected to a recycling performance test, and the result is shown in Table 3.
As can be seen from Table 3, the catalytic efficiency of the recycled catalyst is hardly reduced, and the yield of HMF is still kept above 73.3%, so that the catalyst is not easy to deactivate, and has good recycling catalytic effect, good economical efficiency and good industrial application prospect.
TABLE 3 Cyclic Performance testing of the catalyst of example 1
Claims (10)
1. The catalyst for preparing 5-hydroxymethylfurfural is characterized by being a phosphorylated composite metal oxide, wherein the doping amount of phosphorus is 5-30% of the total mole number of metal elements in the catalyst; the composite metal oxide is a composite of titanium oxide and zirconium oxide; the molar ratio of titanium to zirconium in the catalyst is 1: 9-9: 1.
2. The catalyst for preparing 5-hydroxymethylfurfural according to claim 1, wherein the molar ratio of titanium to zirconium in the catalyst is 3:7 to 7: 3.
3. The method for producing a catalyst for 5-hydroxymethylfurfural according to claim 1 or 2, characterized by comprising the steps of:
(1) dissolving titanium salt and zirconium salt in a solvent, adding phosphoric acid after uniformly stirring, standing and drying to obtain gel;
(2) and (2) roasting the gel prepared in the step (1) to obtain the catalyst.
4. The method for preparing a catalyst for 5-hydroxymethylfurfural according to claim 3, wherein the titanium salt is any one of isopropyl titanate, tetrabutyl titanate, and titanium tetrachloride;
the zirconium salt is any one of zirconium oxychloride, zirconium acetate, zirconium n-butoxide, zirconium n-propoxide and zirconium chloride.
5. The method for preparing a catalyst for 5-hydroxymethylfurfural according to claim 3, wherein the solvent is water or an alcohol; the alcohol comprises any one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol.
6. The preparation method of the catalyst for preparing 5-hydroxymethylfurfural according to claim 3, wherein the standing time in the step (1) is 12 to 36 hours, the drying temperature is 100 to 120 ℃, and the drying time is 10 to 20 hours; in the step (2), the roasting temperature is 400-700 ℃, and the time is 4-8 h.
7. A method for preparing 5-hydroxymethylfurfural, characterized by catalyzing carbohydrate to generate 5-hydroxymethylfurfural at 150-200 ℃ by using the catalyst of claim 1 or 2 in a two-phase solvent consisting of water and a hydrophobic organic phase.
8. The method of claim 7, wherein the hydrophobic organic phase is methyl isobutyl ketone, methyl ethyl ketone, tetrahydrofuran, cyclopentyl methyl ether, toluene, xylene, 1-butanol or cyclohexanol; in the two-phase solvent, the volume ratio of water to the hydrophobic organic phase is 1: 1-1: 19.
9. The method for preparing 5-hydroxymethylfurfural according to claim 7, wherein the mass ratio of the catalyst to the carbohydrate is 1:1 to 1: 20; the initial concentration of the carbohydrate in the reaction solution is 0.02-0.2 g/mL.
10. The method for preparing 5-hydroxymethylfurfural according to claim 7, wherein the catalyst is recycled after the reaction is finished, and the recycling method comprises the following steps: and after the reaction is finished, filtering to obtain a solid, washing the solid with an organic solvent, and drying to obtain the recovered catalyst.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300101A (en) * | 2020-10-16 | 2021-02-02 | 中国科学技术大学 | Method for preparing bis- (5-formylfurfuryl) ether from 5-hydroxymethylfurfural |
| CN114315768A (en) * | 2021-12-08 | 2022-04-12 | 南京工业大学 | Method for one-step synthesis of 5-hydroxymethylfurfural and derivatives thereof by catalyzing fructose through microwave-microreactor |
| CN114558596A (en) * | 2022-03-21 | 2022-05-31 | 上海太洋科技有限公司 | Preparation method of metal-doped titanium pyrophosphate composite material, product and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300101A (en) * | 2020-10-16 | 2021-02-02 | 中国科学技术大学 | Method for preparing bis- (5-formylfurfuryl) ether from 5-hydroxymethylfurfural |
| CN112300101B (en) * | 2020-10-16 | 2022-12-30 | 中国科学技术大学 | Method for preparing bis- (5-formyl furfuryl) ether from 5-hydroxymethyl furfural |
| CN114315768A (en) * | 2021-12-08 | 2022-04-12 | 南京工业大学 | Method for one-step synthesis of 5-hydroxymethylfurfural and derivatives thereof by catalyzing fructose through microwave-microreactor |
| CN114315768B (en) * | 2021-12-08 | 2023-06-16 | 南京工业大学 | Method for one-step synthesis of 5-hydroxymethylfurfural and derivatives thereof by using microwave-microreactor to catalyze fructose |
| CN114558596A (en) * | 2022-03-21 | 2022-05-31 | 上海太洋科技有限公司 | Preparation method of metal-doped titanium pyrophosphate composite material, product and application thereof |
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