CN107629027B - Method for preparing 5-hydroxymethylfurfural by catalyzing biomass with phosphorylated composite oxide - Google Patents
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Abstract
The invention relates to a method for preparing 5-hydroxymethylfurfural by catalyzing biomass with phosphorylated composite oxide, which comprises the following steps: 1) dissolving or dispersing a biomass raw material in water to form an aqueous solution or suspension; 2) adding sodium chloride, a catalyzing and extracting solvent for reaction; 3) after the reaction is finished, the temperature is reduced to separate the catalyst, and a separating funnel is used for separating liquid to obtain a product. The method adopts the phosphorylation composite oxide solid acid as the catalyst, adjusts the acidity of the catalyst by adjusting the adding amount of the phosphoric acid and the proportion of the Ti/Si components, optimizes the catalytic performance of the glucose and biomass dehydration for preparing the HMF, can effectively solve the separation problem of the catalyst and the product, is convenient for recycling, reduces the production cost and reduces the environmental pollution problem. Meanwhile, compared with the preparation method of the ionic liquid system, the yield of the HMF prepared by the preparation method of the two-phase system is basically equal.
Description
Technical Field
The invention relates to the field of chemical synthesis, and particularly relates to a preparation method of 5-hydroxymethylfurfural.
Background
5-Hydroxymethylfurfural (HMF) is a multipurpose platform compound, contains an aldehyde group and a hydroxymethyl group in a molecule, and can be applied to synthesizing a series of important chemicals and novel high polymer materials through chemical reactions such as oxidation, hydrogenation, esterification, halogenation, polymerization, hydrolysis and the like, wherein the products comprise resins, medicines, fuels, bulk chemicals and the like with high added values.
At present, various preparation methods of HMF mainly stay in a laboratory research stage, and industrialization is not reported successfully. Wherein, when the fructose is used as a substrate, the yield is higher. Compared with fructose, glucose is more widely available and cheap, but the yield is relatively low, and the yield prepared by a solid catalyst is lower, so that the preparation of HMF from glucose and polymers thereof has more challenges. The catalyst and reaction solvent are two very important constraints in the preparation process. When the reaction solvent is an aqueous solution, the inorganic acid is used as a catalyst, the yield of HMF is low, the requirement of industrialization cannot be met, and the subsequent separation and environmental pollution problems caused by the use of the inorganic acid are also constraint factors to be considered. Efforts are now being made to find catalysts and solvents that can effectively degrade glucose and yield high yields of HMF. The Chinese patent CN200710158825.6 discloses a method for preparing HMF, which takes ionic liquid 1-methyl-3-alkyl imidazole bromide and the like as reaction solvents, takes acidic ionic liquid (imidazole hydrogen sulfate, 1-methyl-3-butyl imidazole hydrogen sulfate), inorganic acid (hydrochloric acid, nitric acid and phosphoric acid) and organic acid (formic acid, acetic acid and citric acid) as catalysts, and catalyzes fructose to produce HMF. The disadvantages of this method are: the ionic liquid has large viscosity and high price, the fructose is low in natural storage amount and high in price, and the hydrochloric acid, the sulfuric acid and other inorganic acids are seriously corroded on equipment when being used in large quantities, so that the industrial production is difficult. The Zhao Hai and the task group (Science,2007,316,1597) utilize ionic liquid as a reaction solvent and chromium dichloride as a catalyst to effectively catalyze and degrade glucose to be converted into HMF, but the method also uses expensive ionic liquid as a reaction solvent and also uses metal chromium chloride with high toxicity as a catalyst. Later, Binder, J.B and co-workers (Science,2009,131,1979) used organic solvents (acetone or dimethyl sulfoxide or dimethylacetamide) to prepare HMF, but these organic solvents were miscible with water and had high energy consumption problems in product separation and solvent recovery. For the catalyst, the use of inorganic acid (hydrochloric acid, sulfuric acid, etc.) and metal chloride in large amounts causes serious corrosion to equipment, and the catalyst also has the problem of recycling. The preparation method of the metal oxide utilized in the Chinese patent CN 104250237B adopts a direct impregnation method for the oxide, which causes that a strong acid center is locally generated by the catalyst and is coked in the reaction process to generate a solid byproduct to block the pore channel of the catalyst; the substrate of the reaction is fructose, so that the source is deficient and the price is high; the reaction system is a single-phase system of high-boiling organic solvent, and the separation of products is relatively difficult. Therefore, the search for a high-efficiency and good-stability solid catalyst and a reaction system with a simple process and high catalytic efficiency are very important for the early realization of industrialization of 5-hydroxymethylfurfural.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for preparing HMF by dehydrating biomass raw materials, which adopts the following technical scheme: the acid amount, the acid strength and the acid type adjustable composite phosphorylation composite oxide are used as a catalyst, and glucose and derivatives thereof are converted to prepare HMF in a two-phase system.
The preparation method comprises the following steps:
1) dissolving or dispersing the biomass raw material in water at room temperature to form an aqueous solution or suspension with the mass percent concentration of 2-10 wt%;
2) 5 to 60 parts by weight of sodium chloride based on 100 parts by weight of the aqueous solution obtained in step 1) was added to the reactor and stirred at room temperature for 30 minutes. Then adding 0.01 to 50 parts by weight of catalyst and a certain amount of extraction solvent relative to 100 parts by weight of glucose contained, heating to 130-200 ℃, and reacting for 30 minutes to 12 hours;
3) after the reaction is finished, cooling to room temperature, filtering and separating the catalyst, washing the catalyst with acetone for three times, drying in an oven at 80 ℃ overnight, storing and reusing, separating the filtrate by using a separating funnel, standing for about 30 minutes to 2 hours, separating two phases, respectively taking a small amount of separated two-phase liquid, diluting, filtering by using an aqueous phase membrane and an organic phase membrane, and detecting the yield of the product by using a high performance liquid chromatograph.
Preferably, the biomass raw material in the step 1) is selected from agricultural and forestry waste enzymatic hydrolysate, agricultural and forestry waste biomass, phosphoric acid-treated microcrystalline cellulose or glucose, wherein the agricultural and forestry waste enzymatic hydrolysate is selected from corn stalk enzymatic hydrolysate, corncob enzymatic hydrolysate and/or poplar enzymatic hydrolysate, and the agricultural and forestry waste biomass is selected from corn stalk, corncob, xylose residue, qigang energy grass and/or poplar powder and the like.
Preferably, the biomass raw material in step 1) is microcrystalline cellulose or glucose treated with phosphoric acid.
Preferably, the biomass raw material is dissolved or dispersed in water in the step 1) to form an aqueous solution or suspension with the mass percentage concentration of 2 wt% -10 wt%, wherein when the biomass raw material is the agricultural and forestry waste enzymolysis liquid, the theoretical glucose content in the biomass is calculated by the glucose contained in the agricultural and forestry waste enzymolysis liquid.
Preferably, step 1) dissolves or disperses the glucose and biomass in water to form an aqueous solution or suspension having a concentration of 5 wt% to 20 wt% by mass.
Preferably, 1 to 30 parts by weight of the catalyst is added with respect to 100 parts by weight of glucose in the step 2).
Preferably, 5 to 40 parts by weight of sodium chloride is added in step 2) based on 100 parts by weight of the aqueous solution obtained in step 1).
Preferably, the volume ratio of the extraction solvent added in step 2) to the aqueous solution obtained in step 1) is from 2:1 to 4: 1.
Preferably, the extraction solvent in step 2) is selected from one or more of tetrahydrofuran, dimethyl tetrahydrofuran, n-butanol, methyl isobutyl ketone and the like, and tetrahydrofuran is preferred.
Preferably, the reaction temperature in step 2) is 140 ℃ and 190 ℃, and the reaction time is 1-4 hours.
Preferably, the catalyst in step 2) is phosphated TiO2-SiO2A composite oxide catalyst.
Preferably, the catalyst is prepared as follows: adding 5-30 wt% (based on TiO) of ethyl orthosilicate and butyl titanate as precursors and alcohol as solvent at 20-50 deg.C2-SiO2Mass of (d) phosphoric acid or a phosphate, and a composite porous phosphorylated composite oxide is produced by a solvent-gel method. After the solvent is removed, the dried sample is roasted at high temperature to obtain the catalyst of the experiment.
Advantageous effects
The preparation method of the invention has the following beneficial effects:
(1) the invention adopts the phosphorylation composite oxide as the catalyst, the catalyst has proper acid amount and acid type, the acidity of the catalyst is adjusted by adjusting the adding amount of phosphoric acid and the proportion of Ti/Si components, and the catalytic performance of preparing HMF by dehydrating glucose and biomass is optimized.
(2) The solid acid catalyst adopted by the invention has a composite pore structure, so that on one hand, the effective contact of reactants and the active site of the catalyst can be increased, and the conversion efficiency of raw materials is improved; on the other hand, the desorption of the product HMF can be improved, side reactions such as further polymerization and hydrolysis of the product on an acid center are reduced, and the selectivity and the yield of the product are improved. The composite pore structure is also beneficial to expanding the applicability of the substrate.
(3) The invention adopts the solid acid catalyst, can effectively solve the separation problem of the catalyst and the product, is convenient for recycling, reduces the production cost and reduces the environmental pollution.
(4) Compared with the preparation method of the ionic liquid system, the preparation method of the two-phase system has the advantages that the yield of the 5-hydroxymethylfurfural is basically equal, but the solvent is low in price and easy to obtain, and the in-situ extraction separation is realized;
(5) the method for producing the bio-based platform compound HMF by using the cheap and easily obtained glucose and biomass as the raw materials has the advantages of cheap and easily obtained raw materials, high product yield, few byproducts, environmental friendliness, mild reaction conditions, simplicity in operation, low equipment corrosivity, capability of recycling the catalyst and the extraction solvent and the like, and can effectively overcome the defects of high HMF preparation cost, high energy consumption, low yield and the like in the prior art. Has great industrial prospect and strategic significance.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
According to the invention, the phosphorylated complex oxide catalyst is a phosphorylated TiO prepared by a neutral sol-gel process2-SiO2The composite oxide is a solid catalyst with high thermal stability, and the four-coordination unsaturated titanium in the grid structure of the composite oxide and a large number of hydroxyl groups on the surface of the composite oxide ensure that the catalyst has Lewis acid type and
acid type, which provides abundant and suitable acid active sites for the dehydration reaction of glucose. The acidity of the catalyst can be adjusted by adjusting the adding amount of phosphoric acid and the ratio of Ti to Si, and the optimal acid strength and distribution of the catalyst for preparing HMF by glucose dehydration can be optimized. On the other hand, the catalyst has a high specific area, so that the effective contact of a substrate and an acid center of the catalyst is greatly improved, and the conversion rate of the substrate is improved; meanwhile, the diffusion of products is enhanced, so that the reaction activity of the catalyst is improved, and the substrate selectivity is wider.
According to the invention, the preparation method of the catalyst comprises the following steps: at a certain temperature, taking ethyl orthosilicate and butyl titanate as precursors, taking alcohol as a solvent, adding a certain amount of phosphoric acid or phosphate, and preparing the composite porous phosphorylation composite oxide by a solvent-gel method. After the solvent is removed, the dried sample is roasted at high temperature to obtain the catalyst of the invention.
Wherein the support is phosphorylated, TiO2-SiO2Medium Ti/Si ratioExamples the degree of phosphorylation greatly affects the amount of acid, the acid strength, and the type of acid. Wherein the molar ratio of Ti/Si is preferably from 6/1 to 1/8; if higher than 6/1, then
The acid proportion is low, more phosphoric acid needs to be supplemented, and the stability of the catalyst is greatly reduced; when the content of the Lewis acid is lower than 1/8, the total acid content in the catalyst is also reduced, the isomerization of glucose to fructose is not facilitated, and the yield of the reaction product HMF is low. The preferred phosphoric acid is added in an amount of 3 wt% to 30 wt% based on the total amount, if the added amount is less than 3 wt%, the total acid amount is low, the amount of the catalyst used in the reaction process is high, the production cost is increased, and the yield of the reaction product is low, and when the added amount is more than 30 wt%, much unbound phosphate is attached to the surface of the catalyst, the reaction process is easy to run off, covers over the pores, reduces the specific surface area, and also reduces the L/B ratio, thereby being not favorable for improving the yield of HMF.
According to the invention, the selected extraction solvent in the two-phase system can better dissolve the HMF, thereby being beneficial to the storage of the HMF; preferably, the extraction solvent is selected from one or more of tetrahydrofuran, dimethyltetrahydrofuran, n-butanol, methyl isobutyl ketone and the like, and tetrahydrofuran is more preferred. The solvent such as tetrahydrofuran, dimethyl tetrahydrofuran and the like has poor solubility to glucose, so that the separation of the substrate and the product is facilitated, and the occurrence of side reactions such as polymerization of the substrate and the product is reduced. The invention adopts a biphase system formed by mixing one or more mixed extraction solvents with a saline water system, and compared with expensive ionic liquid, the extraction solvents have wide sources, are easy to obtain, have better stability, and are easy to separate from products to be beneficial to recycling; provides certain technical support for large-scale industrialization.
Preferably, the glucose and the biomass are dissolved or dispersed in water in the step 1) to form an aqueous solution or suspension with the mass percentage concentration of 5 wt% -20 wt%, and if the mass percentage concentration is lower than 5 wt%, the raw material utilization rate in the whole reaction process is low; above 20 wt%, too high a concentration affects the mass transfer of the chemical reaction and thus the yield of the target product.
Preferably, 1 to 30 parts by weight of the catalyst is added with respect to 100 parts by weight of glucose in the step 2). If the amount is less than 1 part, the yield of the reaction product is low, and if the amount is more than 30 parts, the yield of the reaction product is not increased significantly, resulting in waste of the catalyst.
Preferably, 5 to 40 parts by weight of sodium chloride is added in step 2) based on 100 parts by weight of the aqueous solution obtained in step 1). If the amount is less than 5 parts, the salting-out effect cannot be effectively exerted; if the amount is more than 40 parts, mass transfer is not beneficial to the reaction, the generation of humin byproducts is increased, and the selectivity of the target product is reduced.
Preferably, the volume ratio of the extraction solvent added in step 2) to the aqueous solution obtained in step 1) is from 2:1 to 4: 1. If the ratio is lower than 2:1, the extracted target product is too little; above 4:1, the amount of the desired product extracted is not significantly increased and the cost of the extraction solvent recovery is increased.
Preferably, the extraction solvent in step 2) is selected from tetrahydrofuran, dimethyltetrahydrofuran, n-butanol, methyl isobutyl ketone and the like.
Preferably, the reaction temperature in step 2) is 140 ℃ and 190 ℃, and the reaction time is 1-4 hours. If the reaction time is less than 1 hour, the reaction temperature is less than 140 ℃, reactants are not completely converted, and the yield of the target product is low; the reaction temperature is too high, the reaction time is too long, and the selectivity of the target product is reduced besides increasing energy consumption.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
Dissolving 6.5g of ethyl orthosilicate and 10.6g of butyl titanate in 13g of ethanol and 10g of ethanol respectively, mixing, taking the mixed liquid as a solution 1, then dissolving 0.71g of ammonium dihydrogen phosphate in 18g of water, stirring uniformly to obtain a solution 2, then dropwise adding the solution 2 into the solution 1, and carrying out stirring at 70 DEG CRefluxing for 24 hr, rotary evaporating to remove solvent, drying, and calcining at 500 deg.C for 3 hr to obtain phosphorylated TiO2-SiO2Catalyst (catalyst a).
Example 2
(1) Weighing 0.1g of glucose, adding the glucose into 1g of water, and fully dissolving the glucose at room temperature and transferring the glucose into a reactor;
(2) 10mg of catalyst A prepared in example 1 was added to a reactor, followed by addition of 0.2g of sodium chloride and stirring at room temperature for 30 minutes; then adding tetrahydrofuran with 4 times volume into the reaction kettle, sealing the reactor, and reacting for 60 minutes at the reaction temperature of 170 ℃;
(3) and after the reaction is finished and the temperature is reduced to the room temperature, opening the reactor, filtering and separating the catalyst, separating the reaction liquid by using a separating funnel, respectively taking a water phase and an organic phase, diluting by a certain multiple, filtering by using a corresponding water phase membrane and an organic phase membrane, and measuring the content of the 5-hydroxymethylfurfural by using a high performance liquid chromatograph. The yield of 5-hydroxymethylfurfural was 53.5%. The catalyst was washed with acetone, dried overnight at 80 ℃ and stored for recycle.
Example 3
The preparation process was the same as in example 1 except that the amount of ammonium dihydrogen phosphate added was changed to 1.42 g. The catalyst prepared was catalyst B.
Example 4
The preparation procedure was the same as in example 1 except that the dissolution was changed to n-butanol. The catalyst prepared was catalyst C.
Example 5
The procedure was the same as in example 1, except that phosphoric acid was used as the phosphating agent. The catalyst prepared was catalyst D.
Example 6
The preparation process was the same as in example 1 except that the firing temperature was changed to 600 ℃. The catalyst prepared was catalyst E.
Example 7
Using the catalysts prepared in examples 3 to 6, the reaction was carried out according to the reaction procedure of example 2, and the yields of HMF measured are shown in Table one.
Example 8
HMF was prepared using the catalyst a, and the reaction was carried out in the same manner as in example 2 except that the amount of the catalyst was changed to 20 wt%, the reaction temperature was 170 ℃, the reaction time was 90min, and the solvent was an aqueous tetrahydrofuran salt solution, whereby the yield of HMF was 63.0%.
Example 9
The reaction was carried out in the same manner as in example 2 using catalyst A except that the reaction substrate was changed to phosphoric acid-treated microcrystalline cellulose at a reaction temperature of 180 ℃ for 2 hours, and the yield of HMF was 53%.
Example 10
The reaction was carried out in the same manner as in example 2 using catalyst A except that the reaction substrate was changed to corncob enzymatic hydrolysate at a reaction temperature of 170 ℃ for 90 minutes, and the yield of HMF was 65%.
Example 11
The reaction was carried out in the same manner as in example 2 using catalyst A except that the reaction substrate was changed to corncobs, the reaction temperature was 180 ℃ and the reaction time was 3 hours, and the yield of HMF was 45%.
Watch 1
Example 12
The reaction conditions were the same as in example 2 except that no extraction solvent was used, and the yield of HMF after the reaction was 18.5%.
Example 13
The HMF yield after reaction was only 2.0% as in example 2, except that no catalyst was used.
Example 14
Using TiO not phosphorylated2-SiO2As a catalyst (prepared as in example 1, except for the reaction step without phosphorylation), the yield of HMF after the reaction was only 40% under the same other reaction conditions as in example 2.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof, since the present invention is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications can be made in the above embodiments without departing from the scope of the invention, and it is intended to cover all such modifications, equivalents and modifications as fall within the true spirit of the invention.
In a word, the method has the characteristics of high selectivity and yield of the catalyst to products, mild operation conditions, high reaction speed, simple process, environmental friendliness and the like, and has some outstanding characteristics, such as adjustable acidity of the prepared catalyst; the by-product in the reaction process is low; the product can be quickly separated; the recycling of the organic solvent and the catalyst reduces the cost, provides a new technology for preparing the 5-hydroxymethylfurfural from the biomass sugar source as a starting point in industrial production, and opens up a new way for preparing materials, chemicals and energy fuels on a large scale.
Claims (8)
1. A method for preparing 5-hydroxymethylfurfural from phosphorylated complex oxide catalytic biomass, comprising the steps of:
1) dissolving or dispersing the biomass raw material in water at room temperature to form an aqueous solution or suspension with the mass percent concentration of 2-10 wt%;
2) adding 5 to 60 parts by weight of sodium chloride based on 100 parts by weight of the aqueous solution obtained in the step 1) into a reactor, stirring at room temperature for 30 minutes, then adding 0.01 to 50 parts by weight of a catalyst relative to 100 parts by weight of glucose contained therein, adding a certain amount of an extraction solvent selected from one or more of tetrahydrofuran, dimethyltetrahydrofuran and n-butanol, heating to 130-200 ℃, and reacting for 30 minutes to 12 hours, wherein the extraction solvent is one or more of phosphorylated TiO2-SiO2A composite oxide catalyst;
3) after the reaction is finished, cooling to room temperature, filtering and separating the catalyst, washing the catalyst with acetone for three times, drying in an oven at 80 ℃ overnight, storing and reusing, separating the filtrate by a separating funnel, standing for about 30 minutes to 2 hours, separating two phases, respectively taking a small amount of separated two-phase liquid, diluting, filtering by an aqueous phase membrane and an organic phase membrane, detecting the yield of the product by using a high performance liquid chromatograph,
wherein the catalyst in step 2) is prepared as follows: adding TiO-based precursor of ethyl orthosilicate and butyl titanate at 20-50 deg.C, alcohol as solvent2-SiO25-30 wt% of phosphoric acid or phosphate, preparing a composite hole phosphorylation composite oxide by a solvent-gel method, removing the solvent, and roasting the dried sample at high temperature to obtain the catalyst;
the molar ratio of Ti/Si in the prepared catalyst is 6/1-1/8, and the phosphoric acid is added in an amount accounting for 3-30 wt% of the total amount.
2. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein the biomass raw material in the step 1) is selected from agricultural and forestry waste enzymatic hydrolysate, agricultural and forestry waste biomass, phosphoric acid-treated microcrystalline cellulose or glucose, wherein the agricultural and forestry waste enzymatic hydrolysate is selected from corn stalk enzymatic hydrolysate, corn cob enzymatic hydrolysate and/or poplar enzymatic hydrolysate, and the agricultural and forestry waste biomass is selected from corn stalk, corn cob, wood sugar residue, Qigang energy grass and/or poplar powder.
3. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein the biomass raw material in the step 1) is phosphoric acid-treated microcrystalline cellulose or glucose.
4. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein in the step 1), when the biomass raw material is an agricultural and forestry waste enzymatic hydrolysate, the theoretical glucose content in the biomass is calculated based on glucose contained therein when the biomass raw material is agricultural and forestry waste.
5. The method for preparing 5-hydroxymethylfurfural according to claim 1, characterized in that the glucose and the biomass are dissolved or dispersed in water in step 1) to form an aqueous solution or suspension with a concentration of 5 to 20% by weight.
6. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein 1 to 30 parts by weight of a catalyst is added with respect to 100 parts by weight of glucose in step 2); adding 5 to 40 parts by weight of sodium chloride based on 100 parts by weight of the aqueous solution obtained in step 1) in step 2); the volume ratio of the extraction solvent added in the step 2) to the aqueous solution obtained in the step 1) is 2:1 to 4: 1.
7. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein the extraction solvent in step 2) is tetrahydrofuran.
8. The method for preparing 5-hydroxymethylfurfural according to claim 1, wherein the reaction temperature in the step 2) is 140 ℃ and 190 ℃ and the reaction time is 1 to 4 hours.
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