CN107629027A - A kind of method that phosphorylation composite oxide catalytic biomass prepares 5 hydroxymethylfurfurals - Google Patents
A kind of method that phosphorylation composite oxide catalytic biomass prepares 5 hydroxymethylfurfurals Download PDFInfo
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Abstract
The present invention relates to a kind of method that phosphorylation composite oxide catalytic biomass prepares 5 hydroxymethylfurfurals, the described method comprises the following steps：1) biomass material is dissolved or dispersed in water, forms the aqueous solution or suspension；2) sodium chloride, catalysis and extractant is added to be reacted；3) after reaction terminates, cool separating catalyst, and product is obtained with separatory funnel liquid separation.The present invention uses phosphorylation composite oxide solid acid as catalyst, by adjusting the ratio between the addition of phosphoric acid and Ti/Si components, adjust the acidity of catalyst, optimization glucose and biomass dehydration prepare HMF catalytic performance, the separation problem of catalyst and product can be efficiently solved, it is easy to reuse, reduces production cost, reduce environmental pollution problem.Simultaneously compared with the preparation method of ion liquid system, the HMF yield of diphasic system preparation method of the invention remains basically stable.
Description
Technical field
The present invention relates to the field of chemical synthesis, in particular to a kind of preparation method of 5 hydroxymethyl furfural.
Background technology
5 hydroxymethyl furfural (HMF) is a kind of multiduty platform chemicals, contains an aldehyde radical and a hydroxyl in molecule
Methyl, can by aoxidizing, hydrogenating, being esterified, halogenation, polymerization, the chemical reaction such as hydrolysis be used to synthesize a series of important chemistry
Product and novel high polymer material, including resin, medicine, fuel, bulk chemical etc. have high value-added product.
At present, HMF many preparation methods also mainly stay in the laboratory research stage, and industrialization there is not reported success also
Cross.Wherein, when fructose is substrate, yield is higher.Relative to fructose, the source of glucose is more extensive, cheap, still
Yield is relatively relatively low, and the yield prepared by solid catalyst is lower, therefore prepares HMF with bigger by glucose and its polymer
Challenge.In preparation process, catalyst and reaction dissolvent are two very important restraining factors.When reaction dissolvent is water-soluble
During liquid, using inorganic acid as catalyst, HMF yield is relatively low, it is impossible to meets industrialized requirement, after the use of inorganic acid is brought
Continuous separation and the restriction key element that problem of environmental pollution is also that needs consider.So people are strive to find can be effective now
Degraded glucose and high yield HMF catalysts and solvents can be obtained.Wherein, Chinese patent CN200710158825.6 is disclosed
A kind of method for preparing HMF, this method with ionic liquid 1- methyl -3- alkyl imidazole bromines etc. for reaction dissolvent, with acidity from
Sub- liquid (imidazole bisulfate, 1- methyl -3- butyl imidazoles disulfate), inorganic acid (hydrochloric acid, nitric acid, phosphoric acid) and organic acid
(formic acid, acetic acid, citric acid) is catalyst, catalysis fructose production HMF.The shortcomings that this method：Viscosity of il is big, price is held high
Expensive, fructose is low in the nature amount of having, and price is higher, and a large amount of uses of the inorganic acid such as hydrochloric acid, sulfuric acid to equipment corrosion more
Seriously, it is not easy industrialized production.Zhao Haibo and its seminar (Science, 2007,316,1597) utilize ionic liquid as reaction
Solvent, using chromium dichloride as catalyst, effectively catalytic degradation glucose is converted into HMF, but this method also uses costliness
Ionic liquid as reaction dissolvent, while the chloride for also using the big crome metal of toxicity is catalyst.Later, Binder,
J.B and its partner (Science, 2009,131,1979) use organic solvent (acetone or dimethyl sulfoxide or dimethylacetamide
Amine) prepare HMF, but these organic solvents are miscible with water, the problems such as high energy consumption be present with solvent recovery in product separation.It is right
For catalyst, heavy dose of use such as inorganic acid (hydrochloric acid, sulfuric acid etc.) and metal chloride can cause serious corruption to equipment
Erosion, there is also reuse problem of catalyst etc..The preparation side of the metal oxide utilized in the B of Chinese patent CN 104250237
Method, it is to use direct dipping process for oxide, can so causes catalyst locally to produce strong acid center and tie during the course of the reaction
Jiao produces solid by-product obstruction catalyst duct；The substrate of reaction is fructose, and source is deficient, and price is high；The system of reaction is
The single_phase system of high boiling organic solvent, the separation relative difficulty of product.Therefore, efficient and good stability solid catalysis is found
Early realization industrialization of the reaction system of agent and the simple high catalytic efficiency of technique to 5 hydroxymethyl furfural is particularly important.
The content of the invention
In order to solve the shortcomings that above prior art and weak point, it is an object of the invention to provide one kind to utilize biology
The method that matter raw material dehydration prepares HMF, the technical solution adopted by the present invention are：It is adjustable multiple using sour amount, acid strength, acids type
It is catalyst to close phosphorylation composite oxides, in diphasic system, grape carbohydrates and their derivative is converted and prepares HMF.
According to the preparation method of the present invention, comprise the following steps：
1) at room temperature, biomass material is dissolved or dispersed in water, it is 2wt%- to form mass percent concentration
The 10wt% aqueous solution or suspension；
2) aqueous solution obtained in the step 1) based on 100 parts by weight, the sodium chloride of 5 to 60 parts by weight is added to reaction
In device, it is stirred at room temperature 30 minutes.Then relative to comprising 100 parts by weight glucose, add 0.01 to 50 parts by weight
Catalyst, add a certain amount of extractant, be warming up to 130-200 DEG C, react -12 hours 30 minutes；
3) after reaction terminates, room temperature is cooled to, is separated by filtration catalyst, after catalyst is washed three times with acetone, at 80 DEG C
Baking oven in dry overnight, storage is reused, and filtrate is with separatory funnel liquid separation, after standing about 30 minutes to 2 hours, point
From two-phase, take the two-phase liquid of separation a small amount of respectively, aqueous phase film and organic phase membrane filtration are used after dilution, utilizes high performance liquid chromatograph
Detect the yield of product.
Preferably, biomass material described in step 1) is selected from agriculture and forestry organic waste material enzymolysis liquid, agriculture and forestry organic waste material, phosphorus
Acid-treated microcrystalline cellulose or glucose, wherein the agriculture and forestry organic waste material enzymolysis liquid is selected from maize straw enzymolysis liquid, corn
Core enzymolysis liquid and/or poplar enzymolysis liquid, the agriculture and forestry organic waste material are selected from maize straw, corncob, xylose residue, strange hilllock energy
Source grass and/or Poplar Powder etc..
Preferably, biomass material described in step 1) is the microcrystalline cellulose or glucose that phosphoric acid treats.
Preferably, biomass material is dissolved or dispersed in water in step 1), forming mass percent concentration is
The 2wt%-10wt% aqueous solution or suspension, wherein when biomass material is agriculture and forestry organic waste material enzymolysis liquid, wherein to include
Glucose meter, when biomass material is agriculture and forestry organic waste material, with the Theoretical glucose content meter in biomass.
Preferably, the glucose and biomass are dissolved or dispersed in water by step 1), form mass percent concentration
For the 5wt%-20wt% aqueous solution or suspension.
Preferably, relative to the glucose of 100 parts by weight, the catalyst of 1 to 30 parts by weight of addition in step 2).
Preferably, the aqueous solution obtained in the step 1) based on 100 parts by weight in step 2), 5 to 40 parts by weight are added
Sodium chloride.
Preferably, the extractant added in step 2) is 2 with the aqueous solution volume ratio obtained in step 1):1 to
4:1。
Preferably, it is different to be selected from tetrahydrofuran, dimethyl-tetrahydrofuran, n-butanol, methyl for extractant described in step 2)
One or more in butyl ketone equal solvent, preferably tetrahydrofuran.
Preferably, reaction temperature is 140-190 DEG C in step 2), and the reaction time is 1-4 hours.
Preferably, catalyst described in step 2) is phosphorylation TiO2-SiO2Composite oxide catalysts.
Preferably, the catalyst is prepared as follows：At a temperature of 20-50 DEG C, using tetraethyl orthosilicate and butyl titanate before
Body is driven, using alcohol as solvent, 5-30wt% amounts is added and (is based on TiO2-SiO2Quality) phosphoric acid or phosphate, by solvent-solidifying
Glue legal system obtains composite holes phosphorylation composite oxides.After removing solvent, high-temperature roasting obtains this experiment to dried sample again
Catalyst.
Beneficial effect
The beneficial effect brought of preparation method of the present invention is：
(1) present invention uses phosphorylation composite oxides as catalyst, and the catalyst has suitable acid amount and acids type,
By adjusting the ratio between the addition of phosphoric acid and Ti/Si components, the acidity of catalyst is adjusted, optimizes glucose and biomass
Dehydration prepares HMF catalytic performance.
(2) solid acid catalyst that the present invention uses has composite pore structural, on the one hand can increase reactant and catalysis
Effective contact of agent active sites, improve the transformation efficiency of raw material；On the other hand product HMF desorption can be improved, reduces production
The side reactions such as further polymerization and hydrolysis occur on acid centre for thing, improve the selectivity and yield of product.Composite holes knot
Structure is also beneficial to expand the applicability of substrate.
(3) present invention uses solid acid catalyst, can efficiently solve the separation problem of catalyst and product, is easy to weight
It is multiple to utilize, production cost is reduced, reduce environmental pollution problem.
(4) compared with the preparation method of ion liquid system, the 5- methylol chaffs of diphasic system preparation method of the invention
The yield of aldehyde remains basically stable, but has the advantages that solvent is inexpensive, is easy to get, situ extracting separation；
(5) present invention produces bio-based platform chemicals HMF, this side by raw material of glucose and biomass cheap and easy to get
Method has that raw material is cheap and easy to get, products collection efficiency is high, accessory substance is few, environment-friendly, reaction condition is gentle, simple to operate, equipment is rotten
The advantages that corrosion is low, and catalyst and extractant can recycle and reuse, it can effectively overcome HMF systems in the prior art
The shortcomings such as standby cost height, high energy consumption, yield be low.With great industrial prospect and strategic importance.
Embodiment
Hereinafter, it will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims in the term that uses should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of appropriate definition term is to carry out the principle of best interpretations, according to implication corresponding with the technical elements of the present invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The scope of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
According to the present invention, phosphorylation composite oxide catalysts are the phosphorylation TiO prepared by neutral sol-gel process2-
SiO2Composite oxides, this catalyst are a kind of higher solid catalysts of heat endurance, the rack knot in composite oxides
Four-coordination unsaturation titanium in structure and the substantial amounts of oh group in surface so that catalyst have Lewis acids type and
Acids type, abundant suitable acid activity site is provided for the dehydration of glucose.Can be by adjusting phosphoric acid addition
With Ti/Si ratio and then adjust the acidity of catalyst, optimization gluconate dehydratase prepare HMF catalyst optimal acid strength and
Distribution.On the other hand, the catalyst has specific area, drastically increases substrate and is connect with the effective of acidity of catalyst center
Touch, improve the conversion ratio of substrate；The diffusion of product is enhanced simultaneously so that the reactivity of catalyst improves and substrate selection
Property is more extensive.
According to the present invention, the preparation method of above-mentioned catalyst is：At a certain temperature, with tetraethyl orthosilicate and butyl titanate
For presoma, using alcohol as solvent, a certain amount of phosphoric acid or phosphate are added, composite holes phosphorylation is obtained by sol-gel legal system
Composite oxides.After removing solvent, high-temperature roasting obtains the catalyst of the present invention to dried sample again.
Wherein phosphorylation carrier TiO2-SiO2Middle Ti/Si ratios are with phosphorylation degree to sour amount, acid strength, sour patterns affect
It is very big.Wherein Ti/Si molar ratio is preferably 6/1 to 1/8；If higher than 6/1,Sour ratio is relatively low, it is necessary to mend
Add more phosphoric acid amount, and the stability of catalyst can also substantially reduce；When less than 1/8, the Lewis acid in catalyst is too low,
Total acid content can also reduce, and be unfavorable for glucose isomerization and reacted to fructose so that reaction product HMF yield is relatively low.It is preferred that phosphoric acid
Addition is accounting for the 3wt%-30wt% of total amount, if addition is less than 3wt%, total acid content is relatively low, urging used in course of reaction
Agent amount is higher, increases production cost, and the low yield of reaction product, when addition is higher than 30wt%, is much not associated with
Phosphate is attached to catalyst surface, and course of reaction is easy to be lost in, and is covered in above hole, reduces specific surface area, also reduces L/B ratios
Example, so as to be unfavorable for the lifting of HMF yield.
According to the present invention, extractant can preferably dissolve HMF in selected diphasic system, be advantageous to depositing for HMF
Storage；Preferably, the extractant is in tetrahydrofuran, dimethyl-tetrahydrofuran, n-butanol, methyl iso-butyl ketone (MIBK) equal solvent
One or more, more preferably tetrahydrofuran.Selected tetrahydrofuran, dimethyl-tetrahydrofuran equal solvent are molten to glucose
Solution property is poor, is so advantageous to the separation of substrate and product, reduces the generation for the side reaction such as polymerizeing of substrate and product.The present invention
The diphasic system mixed using the extractant of one or more mixing with brine system, with expensive ionic liquid body phase
Than, these extractant wide material sources, be readily available, stability preferably, be easy to separate beneficial to reuse with product；For extensive work
Industry provides certain technical support.
Preferably, the glucose and biomass are dissolved or dispersed in water in step 1), it is dense forms mass percent
The aqueous solution or suspension for 5wt%-20wt% are spent, if being less than 5wt% so that whole course of reaction raw material availability is low；If
Higher than 20wt%, concentration is too high, influences the mass transfer of chemical reaction, and then influence the yield of target product.
Preferably, relative to the glucose of 100 parts by weight, the catalyst of 1 to 30 parts by weight of addition in step 2).If it is less than
1 part, the yield of reaction product is relatively low, if higher than 30 parts, the yield increase of reaction product is not notable, causes the waste of catalyst.
Preferably, the aqueous solution obtained in the step 1) based on 100 parts by weight in step 2), 5 to 40 parts by weight are added
Sodium chloride.If less than 5 parts, it is impossible to effectively play effect of saltouing；If higher than 40 parts, it is unfavorable for the mass transfer of reaction, can also increases corruption
The generation of black thing accessory substance, reduce the selectivity of target product.
Preferably, the extractant added in step 2) is 2 with the aqueous solution volume ratio obtained in step 1):1 to
4:1.If less than 2:1, the target product of extraction is very little；If higher than 4:1, target product extraction quantity increase unobvious, and can increase
The cost of extractant recovery.
Preferably, it is different to be selected from tetrahydrofuran, dimethyl-tetrahydrofuran, n-butanol, methyl for extractant described in step 2)
Butyl ketone equal solvent.
Preferably, reaction temperature is 140-190 DEG C in step 2), and the reaction time is 1-4 hours.If less than 1 hour, reaction
Temperature is less than 140 DEG C, and reactant does not convert completely, target product low yield；Reaction temperature is too high, and the reaction time is long, removes
Outside increase energy consumption, the selectivity of target product can be also reduced.
Following examples are enumerated only as the example of embodiment of the present invention, do not form any limit to the present invention
System, it will be appreciated by those skilled in the art that the modification in the range of without departing from the essence of the present invention and design each falls within the present invention
Protection domain.Unless stated otherwise, the reagent and instrument used in following examples is commercially available product.
Embodiment 1
Take 6.5g tetraethyl orthosilicates, 10.6g butyl titanates to be dissolved in respectively in 13g and 10g ethanol, then mix, mix
Liquid be solution 1, then go 0.71g ammonium dihydrogen phosphates to be dissolved in 18g water, stir, this solution is solution 2, then
Solution 2 is added dropwise in solution 1, after being flowed back 24 hours at 70 DEG C, solvent is rotated, 3 is calcined at 500 DEG C after drying
Hour, obtain the TiO of phosphorylation2-SiO2Catalyst (catalyst A).
Embodiment 2
(1) weigh 0.1g glucose to add in 1g water, make the abundant solution transfer of glucose at room temperature into reactor；
(2) the catalyst A prepared in 10mg embodiment 1 is added in reactor, then adds 0.2g sodium chloride,
It is stirred at room temperature 30 minutes；Then the tetrahydrofuran of 4 times of volumes is added thereto, reactor is sealed, in reaction temperature 170
DEG C, the reaction time is 60 minutes；
(3) question response terminates, and after cooling to room temperature, opens reactor, is separated by filtration catalyst, reaction solution separatory funnel
Liquid separation, water intaking phase and organic phase, dilute certain multiple, with corresponding aqueous phase film and organic phase membrane filtration, use efficient liquid phase respectively
Chromatograph carries out the measure of 5 hydroxymethyl furfural content.5 hydroxymethyl furfural yield is 53.5%.Catalyst is washed with acetone,
Dried at 80 DEG C overnight, storage recycles.
Embodiment 3
Except the quantitative change of the ammonium dihydrogen phosphate of addition is 1.42g, other preparation process are same as Example 1.Prepare
Catalyst is catalyst B.
Embodiment 4
In addition to dissolving is changed into n-butanol, other preparation process are same as Example 1.The catalyst of preparation is catalyst
C。
Embodiment 5
Except addition bonderite for phosphoric acid in addition to, other preparation process are same as Example 1.The catalyst of preparation is
Catalyst D.
Embodiment 6
In addition to sintering temperature is changed to 600 DEG C, other preparation process are identical with implementing 1.The catalyst of preparation is catalysis
Agent E.
Embodiment 7
The catalyst prepared using embodiment 3 to 6, is reacted according to the course of reaction of embodiment 2, the HMF's measured
Yield is listed in table one.
Embodiment 8
HMF is prepared using catalyst A, except catalyst amount is changed into 20wt%, reaction temperature is 170 DEG C, the reaction time
For 90min, solvent is outside tetrahydrofuran saline solution, is reacted according to the course of reaction of embodiment 2, HMF yield is
63.0%.
Embodiment 9
Using catalyst A, except reaction substrate is changed into the treated microcrystalline cellulose of phosphoric acid, reaction temperature is 180 DEG C, instead
It is outer for 2 hours between seasonable, reacted according to the course of reaction of embodiment 2, HMF yield is 53%.
Embodiment 10
Using catalyst A, except reaction substrate becomes corncob enzymolysis liquid, reaction temperature is 170 DEG C, the reaction time 90
Outside minute, reacted according to the course of reaction of embodiment 2, HMF yield is 65%.
Embodiment 11
Using catalyst A, except reaction substrate is changed into corncob, reaction temperature is 180 DEG C, and the reaction time is 3 hours outer,
Course of reaction according to embodiment 2 is reacted, and HMF yield is 45%.
Table one
Embodiment 12
In addition to without using extractant, other reaction conditions are with embodiment 2, as long as HMF yield 18.5% after reaction.
Embodiment 13
In addition to without using catalyst, other conditions are as embodiment 2, and HMF yield only has 2.0% after reaction.
Embodiment 14
It is used without the TiO of phosphorylation2-SiO2As catalyst, (it is prepared with embodiment 1, and simply no phosphorylation is anti-
Answer step), other reaction conditions are as implementation 2, and HMF yield only has 40% after reaction.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention.It is any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit according to the present invention
Any simple modification, equivalent change and modification made to above example, in the range of still falling within technical solution of the present invention.
In a word, the present invention has catalyst to selectivity of product and yield height, operating condition is gentle, reaction speed is fast, work
Outside the features such as skill is simple, environment-friendly, there are some outstanding features, it is adjustable such as to prepare acidity of catalyst；Course of reaction accessory substance
It is low；Product can be with quick separating；Organic solvent and catalyst, which recycle, reduces cost, to be starting point work from biomass sugar source
Industry metaplasia production prepares 5 hydroxymethyl furfural and provides new technology, is opened newly to prepare material, chemicals and energy fuel on a large scale
Approach.
Claims (10)
1. a kind of method that phosphorylation composite oxide catalytic biomass prepares 5 hydroxymethyl furfural, methods described includes following step
Suddenly：
1) at room temperature, biomass material is dissolved or dispersed in water, it is 2wt%-10wt%'s to form mass percent concentration
The aqueous solution or suspension；
2) aqueous solution obtained in the step 1) based on 100 parts by weight, the sodium chloride of 5 to 60 parts by weight is added to reactor
In, be stirred at room temperature 30 minutes, then relative to comprising 100 parts by weight glucose, add 0.01 to 50 parts by weight
Catalyst, a certain amount of extractant is added, be warming up to 130-200 DEG C, reacted -12 hours 30 minutes；
3) after reaction terminates, room temperature is cooled to, is separated by filtration catalyst, after catalyst is washed three times with acetone, in 80 DEG C of baking
Overnight, storage is reused for drying in case, and filtrate separates two with separatory funnel liquid separation, standing after about 30 minutes to 2 hours
Phase, take the two-phase liquid of separation a small amount of respectively, aqueous phase film and organic phase membrane filtration are used after dilution, is detected using high performance liquid chromatograph
The yield of product.
2. the method according to claim 1 for preparing 5 hydroxymethyl furfural, it is characterised in that biomass described in step 1)
Raw material is selected from the treated microcrystalline cellulose or glucose of agriculture and forestry organic waste material enzymolysis liquid, agriculture and forestry organic waste material, phosphoric acid, wherein
The agriculture and forestry organic waste material enzymolysis liquid is selected from maize straw enzymolysis liquid, corncob enzymolysis liquid and/or poplar enzymolysis liquid, and the agricultural are given up
Gurry biomass is selected from maize straw, corncob, xylose residue, strange hilllock energy grass and/or Poplar Powder etc..
3. the method according to claim 1 for preparing 5 hydroxymethyl furfural, it is characterised in that biomass described in step 1)
Raw material is the microcrystalline cellulose or glucose that phosphoric acid treats.
4. the method according to claim 1 for preparing 5 hydroxymethyl furfural, it is characterised in that in step 1) that biomass is former
Material is dissolved or dispersed in water, the aqueous solution or suspension that mass percent concentration is 2wt%-10wt% is formed, wherein working as life
When raw material of substance is agriculture and forestry organic waste material enzymolysis liquid, with the glucose meter wherein included, when biomass material is agriculture and forestry organic waste material,
With the Theoretical glucose content meter in biomass.
5. the method according to claim 1 for preparing 5 hydroxymethyl furfural, it is characterised in that step 1) is by the glucose
It is dissolved or dispersed in biomass in water, forms the aqueous solution or suspension that mass percent concentration is 5wt%-20wt%.
6. the method according to claim 1 for preparing 5 hydroxymethyl furfural, it is characterised in that relative to 100 in step 2)
The glucose of parts by weight, add the catalyst of 1 to 30 parts by weight；Obtained in step 1) based on 100 parts by weight in step 2)
The aqueous solution, add the sodium chloride of 5 to 40 parts by weight；, the extractant that adds in step 2) and the water obtained in step 1)
Liquor capacity ratio is 2:1 to 4:1.
7. the method according to claim 1 for preparing 5 hydroxymethyl furfural, it is characterised in that extraction is molten described in step 2)
One or more of the agent in tetrahydrofuran, dimethyl-tetrahydrofuran, n-butanol, methyl iso-butyl ketone (MIBK) equal solvent, it is preferably
Tetrahydrofuran.
8. the method according to claim 1 for preparing 5 hydroxymethyl furfural, it is characterised in that reaction temperature is in step 2)
140-190 DEG C, the reaction time is 1-4 hours.
9. the method according to claim 1 for preparing 5 hydroxymethyl furfural, it is characterised in that catalyst described in step 2)
For phosphorylation TiO2-SiO2Composite oxide catalysts.
10. the method according to claim 9 for preparing 5 hydroxymethyl furfural, it is characterised in that the catalyst is made as follows
It is standby：At a temperature of 20-50 DEG C, using tetraethyl orthosilicate and butyl titanate as presoma, using alcohol as solvent, 5-30wt% amounts are added
(it is based on TiO2-SiO2Quality) phosphoric acid or phosphate, composite holes phosphorylation composite oxides are obtained by sol-gel legal system.
After removing solvent, high-temperature roasting obtains the catalyst of this experiment to dried sample again.
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| CN111229264A (en) * | 2020-02-17 | 2020-06-05 | 浙江大学 | Method for preparing 5-hydroxymethylfurfural, catalyst thereof and preparation method of catalyst |
| CN114957173A (en) * | 2022-05-12 | 2022-08-30 | 浙江恒逸石化研究院有限公司 | Method for continuously converting and separating 5-hydroxymethylfurfural from high-concentration biomass sugar under catalysis of solid acid |
| CN114957173B (en) * | 2022-05-12 | 2024-04-05 | 浙江恒逸石化研究院有限公司 | Method for continuously converting and separating 5-hydroxymethylfurfural by catalyzing high-concentration biomass sugar through solid acid |
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