CN105777674A - Method for preparing furfural, hydroxymethylfurfural and levulinic acid by means of microchannel reaction device - Google Patents
Method for preparing furfural, hydroxymethylfurfural and levulinic acid by means of microchannel reaction device Download PDFInfo
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- CN105777674A CN105777674A CN201610231738.8A CN201610231738A CN105777674A CN 105777674 A CN105777674 A CN 105777674A CN 201610231738 A CN201610231738 A CN 201610231738A CN 105777674 A CN105777674 A CN 105777674A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Abstract
The invention discloses a method for preparing furfural, hydroxymethylfurfural and levulinic acid by means of a microchannel reaction device.The method is characterized by comprising the following steps that 1, lignocellulose is utilized for preparing a soluble oligosaccharide solution; 2, oligosaccharide in the soluble oligosaccharide solution is catalyzed by HCl to be converted into furfural or hydroxymethylfurfural or levulinic acid in the microchannel reaction device, wherein during the catalysis process, the molar ratio of soluble oligosaccharide to HCl is 1:(1-3), the temperature of the catalytic reaction ranges from 140 DEG C to 210 DEG C, the flow velocity of the catalytic reaction ranges from 1 ml/min to 6 ml/min, and the retention time of the catalytic reaction ranges from 2 min to 10 min; 3, after the reaction is completed, the reaction fluid is cooled, and furfural, hydroxymethylfurfural and levulinic acid in the reaction fluid are extracted.By means of the method, the conversion rate of pentose is 90%-97%, the highest yield of furfural reaches 92%, the conversion rate of hexose is 83%-92%, the highest yield of 5-HMF is 85%, and the height yield of levulinic acid is 87%.
Description
Technical field
The invention belongs to technical field of biochemical industry, be specifically related to a kind of lignocellulose and combine microchannel reaction unit height
The new technique that value utilizes
Background technology
For tackling increasingly serious energy crisis, countries in the world pay much attention to the exploitation of biomass resource in recent years.
Lignocellulose is renewable biomass resource the abundantest on the earth, compared with other biomass resource such as starch, oils and fats, and wood
Matter cellulose has the unique advantage do not striven grain with people, do not strive ground with grain.From lignocellulosic sources preparation biomass energy
Source and bio-based chemicals, progressively set up biorefinery economic model, can alleviate the dependence to petroleum industry and reduce right
The pollution of environment.In the conversion process of lignocellulose, conversion technology based on sugar platform is gentle due to reaction condition,
Advantages of environment protection gains great popularity.But, crack composition complicated in lignocellulose the most efficiently and be still that wooden fibre
A difficult problem for dimension element biorefinery development.
Due to the complicated structure of wood fibre, the hemicellulose in cell wall is formed by covalent bond with lignin
Network structure, cellulose is inlayed wherein.And, cellulose itself has the supramolecular structure of highly crystalline makes it have height water
Insoluble, each component in such lignocellulose utilizes the most extremely difficult.Therefore, natural lignocellulose is carried out pre-place
Reason, changes the structure of wood fibre, and appropriateness destroys the join domain between cellulose, hemicellulose, lignin, reduces cellulose
Degree of crystallinity, increase raw material sponginess, just can improve the utilization ratio of lignocellulose.
At present, the preprocess method of lignocellulose is roughly divided into four kinds: Physical, chemical method, physical-chemical process and life
Thing method.Physical mainly improves fibre by means such as mechanical activation comminution grinding, microwave radiation, steam explosions (CN 1952162A)
Dimension element enzyme enzymolysis efficiency, is disadvantageous in that too high energy consumption, big to equipment investment.Chemical method utilize chemical reagent (acid, alkali,
Organic solvent) hydrolyzed hemicellulose or lignin (CN 101235605A), while changing lignocellulose chemical composition also
The change of its physical characteristic can be caused, such as degree of crystallinity, internal surface area etc..Chemical method is owing to process operation is simple, effect is obvious
In the commercial production that advantage has been applied, but acid-alkali treatment is relatively strong to the corrosivity of equipment, and energy consumption is the most of a relatively high, therefore exists
Actual application also encounters a lot of problem.Biological rule mainly uses white rot fungi or lignin-degrading enzymes (CN 1884569)
Deng the lignin in lignocellulose degradation raw material, thus improve the enzymolysis efficiency of cellulase.But the enzymolysis cycle is longer, high
The enzyme of effect needs to develop application.Physical is combined with chemical method and takes by physical-chemical process (M.Ballesteros)
Obtain some good effects, but be not widely applied and commercial production.At present, most preprocess methods are difficult to simultaneously
The full constituent realizing lignocellulose separates and efficient enzymolysis.And traditional pretreatment thinking also tends to be confined to acquisition and can convert
For the cellulose of ethanol, the process to hemicellulose, lignin does not gives fully to pay attention to.Therefore, in order to reduce production cost, energy
Preprocessing process should while realizing cellulose efficiently saccharifying by its three big Component seperation, purification and then each inverting
For useful products, just it is particularly important.What Roberto Rinaldi etc. invented is changed into soluble oligomeric by lignocellulose
Sugar and obtain lignin and achieve well progress.
Because microchannel reaction unit has that intermolecular diffusion length is short, the specific surface area of microchannel is big, heat transfer and mass transfer
The advantages such as speed is fast, it is possible to achieve reaction rate faster.Simultaneously in its course of reaction due to whole process be flowing, so
Decrease the humus that agglomerates into of compound the most to a great extent, reduce products collection efficiency.Therefore microchannel reaction unit exists
In biomass chemical industry, it is extremely important.
Summary of the invention
The technical problem to be solved in the present invention is to provide one and utilizes microchannel reaction unit to prepare furfural, methylol bran
Aldehyde, the method for levulic acid, improve lignocellulose and prepare the efficiency of the compounds such as furfural, Hydroxymethylfurfural, levulic acid.
Technical scheme: a kind of method utilizing microchannel reaction unit to prepare furfural, Hydroxymethylfurfural, levulic acid, its
It is characterised by, comprises the steps:
(1) lignocellulose is utilized to prepare soluble oligomeric sugar juice；
(2) in the reaction unit of microchannel, the oligosaccharide in HCl catalysis soluble oligomeric sugar juice is utilized to be converted into bran
Aldehyde, Hydroxymethylfurfural or levulic acid, during catalysis, soluble oligosaccharide is 1:1～3 with the mol ratio of HCl, the temperature of catalytic reaction
Degree is 140～210 DEG C, and catalytic reaction flow velocity is 1～6ml/min, and catalytic reaction retention time is 2～10min；
(3) reactant liquor, the furfural in extractive reaction liquid, Hydroxymethylfurfural, levulic acid are cooled down after reaction terminates.
2, according to claim 1 microchannel reaction unit is utilized to prepare furfural, Hydroxymethylfurfural, levulic acid
Method, it is characterised in that in step (1), is prepared as follows soluble oligomeric sugar juice:
(1a) corn straw, corn cob, straw, bagasse or wood dust are broken to the wooden fibre that particle diameter is 100 mesh～1 centimetre
Dimension crude granule；
(2a) acid mixes with organic solvent, obtains cracking mixed liquor, puts into 50g/L lignocellulosic particles cracking mixed liquor
In, keeping acid is 10～20mmol/g with the ratio of lignocellulose, stirs 1～3h；
(3a) decompression distillation under the conditions of 40～60 DEG C, removes the organic solvent in cracking mixed liquor, obtains impregnating wooden
Cellulose；
(4a) impregnating wooden cellulose grain to be placed in ball mill, room-temperature ball-milling, ball milling temperature is less than 45 DEG C, and Ball-milling Time is
2h, rotational speed of ball-mill is 500rpm/min, obtains soluble oligosaccharide and lignin mixture.
(5a) by soluble in water for the mixture that obtains in step 4a, remove insoluble matter, obtain soluble oligomeric sugar juice, no
Molten thing is lignin.
In step (2a), described acid is the mixture of one or more in sulphuric acid, hydrochloric acid, phosphoric acid, acetic acid, propanoic acid,
Described acid is preferably sulphuric acid.
In step (2a), described organic solvent is one or more in ether, acetone, MIBK, n-butyl alcohol, isobutanol
Mixture, described organic solvent is preferably ether.
In step (2a), described acid is 10～20mmol/g with the ratio of lignocellulose, preferably 15mmol/g.
In step (2), described microchannel reaction unit includes: the first raw material storage tank, the second raw material storage tank, micro structure are mixed
Clutch, micro-structured reactor, extraction and stripping apparatus, the first raw material storage tank and the second raw material storage tank are respectively by constant flow pump and micro-knot
Structure blender is connected, and microstucture mixer, micro-structured reactor, extraction and stripping apparatus are sequentially communicated, and described micro structure is reacted
Temperature control modules on device.
The method utilizing microchannel reaction device reaction is as follows: soluble oligomeric sugar juice is placed in the first raw material storage tank
In, HCl solution is placed in the second raw material storage tank, and soluble oligomeric sugar juice and HCl solution mix in microstucture mixer, mixed
Compound flows in micro-structured reactor and reacts, and reaction temperature is 140～210 DEG C, and flow velocity is 1～6ml/min, and retention time is 2
～10min.
Beneficial effect:
Compared with prior art, the main advantage of the present invention:
It is short that the present invention processes the time, and energy consumption is low, low to the extent of corrosion of equipment, and solid lignocellulosic is converted into liquid
Oligosaccharide makes lignocellulose utilization ratio be greatly improved.
Can hydrolyze efficiently in conjunction with microchannel reaction unit again can be by controlled bar while oligosaccharide obtains monosaccharide
Part, directly carries out dehydration to monosaccharide and obtains a series of platform chemicals.The conversion ratio of this kind of method pentose is 90～95%,
Furfural productivity is up to 92%；The conversion ratio of hexose is 83～90%, and the productivity of 5-HMF is the highest by 85%, the product of levulic acid
Rate is up to 87%.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of lignocellulose pretreatment and microchannel reaction unit.
Fig. 2 is the ESI-Mass figure of soluble oligosaccharide after pretreatment.
Fig. 3 be by cellulose treatment soluble oligosaccharide after liquid phase figure.
Fig. 4 is furfural for reaction afterproduct, Hydroxymethylfurfural, the chromatogram of levulic acid.
Fig. 5 is to react the chromatogram that afterproduct is furfural and levulic acid.
Fig. 6 is the mass spectrum of furfural.
Fig. 7 is the mass spectrum of levulic acid.
Fig. 8 is the mass spectrum of Hydroxymethylfurfural.
Detailed description of the invention
According to following embodiment, the present invention be may be better understood.But, as it will be easily appreciated by one skilled in the art that reality
Execute the content described by example and be merely to illustrate the present invention, and should be also without limitation on basis described in detail in claims
Invention.
The instrument used in the present invention and model:
Agitator: the mechanical agitator of big dragon, model is OS20-S.
Ball mill: model is FritschGMBH, Idar-Oberstein.
Heretofore described microchannel reaction unit includes: the first raw material storage tank, the second raw material storage tank, micro structure mix
Device, micro-structured reactor, extraction and stripping apparatus, the first raw material storage tank and the second raw material storage tank are respectively by constant flow pump and micro structure
Blender is connected, and microstucture mixer, micro-structured reactor, extraction and stripping apparatus are sequentially communicated, described micro-structured reactor
Upper temperature control modules.
Described microstucture mixer is slit plate mixer LH25 (Hastelloy C), purchased from Ehrfeld
Mikrotechnik BTS GmbH, model is 0109-4-0004-F；
Described micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed
Meander reactor HC, preferably sandwich reactor HC, purchased from Ehrfeld Mikrotechnik BTS
GmbH, model is 0211-2-0314-F or 0222-2-2004-F.
Described tubulose temperature control modules, purchased from Ehrfeld Mikrotechnik BTS GmbH, model is 0501-
2-1004-F。
Embodiment 1:
The concentrated sulphuric acid of 9.2mmol is dissolved in 100ml ether, takes 10.0g corn straw (60 mesh) and be distributed to ether sulphuric acid
In solution, after 300 turns of stirring 1h, decompression distills ether.The corn straw of acid dip is put into ball milling in ball mill
(500rpm/min).Notice that temperature does not exceeds 45 DEG C of batch (-type) ball millings.Then milled corn straw powder is taken out and weigh
To solubility lignocellulose.Take 1g solubility lignocellulose to be distributed in 10ml water, shake 5min, filter out the most tolerant i.e.
Obtain soluble oligosaccharide and lignin.The productivity of soluble oligosaccharide is more than 95%.
The productivity of soluble oligosaccharide is calculated as follows:
m0: the quality before the dissolving of solubility lignocellulose；
Quality after residual residue is dried after the dissolving of m: solubility lignocellulose；
F: ratio shared by cellulose hemicellulose in lignocellulose.
Embodiment 2:
Being dissolved in 100ml ether by the acetic acid of 9.2mmol, taking 10.0g corn straw (60 mesh), to be distributed to ether acetic acid molten
In liquid, after 300 turns of stirring 1h, decompression distills ether.The corn straw of acid dip is put into ball milling (500rpm/ in ball mill
min).Notice that temperature does not exceeds 45 DEG C of batch (-type) ball millings.Then take out to weigh by milled corn straw powder and obtain solubility
Lignocellulose.Take 1g solubility lignocellulose to be distributed in 10ml water, shake 5min, filter out the most tolerant i.e. obtain solvable
Property oligosaccharide and lignin.The productivity of soluble oligosaccharide is more than 85%.
Embodiment 3～5:
Use the condition identical with embodiment 1, except that, embodiment 3 replaces ether with acetone；Embodiment 4 with
MIBK replaces ether；Embodiment 5 replaces ether with n-butyl alcohol；Productivity is shown in Table 1.
Table 1 embodiment 3～5 testing result
| Embodiment is numbered | Soluble oligomeric sugar yield |
| 3 | 92% |
| 4 | 87% |
| 5 | 80% |
Embodiment 6:
By soluble sugar solution (the 1,2-dichloroethane solution of 50%) and hydrochloric acid solution 1:1 velocity ratio 1:1 in molar ratio
(overall flow rate is 2ml/min) by constant flow pump be injected separately into microstucture mixer be sufficiently mixed laggard enter micro-structured reactor,
Micro-structured reactor stops at 140 DEG C 15min react.Extract and separate is entered after the hot solution of microreactor cools down
Device.Entering solution AUTOMATIC ZONING after extraction equipment, upper strata is the 1 of furfural and Hydroxymethylfurfural, 2-dichloroethane solution, lower floor
For aqueous solution, upper solution is detected by GC-MS, and pentose conversion ratio is 88%, and furfural productivity is 84%, the conversion of hexose
Rate is 79%, and 5-HMF productivity is 73%, and levulic acid productivity is 2%.Lower aqueous solution passes through Liquid Detection, and remaining sugar can
With cycling and reutilization.
Embodiment 7～13:
Use the condition identical with embodiment 6, except that, reaction temperature is changed into 150 DEG C by embodiment 7；Embodiment 8
Temperature is changed into 160 DEG C；Temperature is changed into 170 DEG C by embodiment 9；Embodiment 10 velocity ratio changes 1:2 (overall flow rate is 3ml/min) into
Retention time is 10min；It is 7.5min that embodiment 11 velocity ratio changes 1:3 (overall flow rate is 4ml/min) retention time into；Embodiment
12 replace 1,2-dichloroethane solution with n-butyl alcohol；Embodiment 13 replaces 1,2-dichloroethane solution with ethyl acetate.Result is shown in
Table 2.
Table 2 embodiment 7～13 testing result
Embodiment 14:
By soluble sugar solution (the 1,2-dichloroethane solution of 50%) and hydrochloric acid solution 1:1 velocity ratio 1:1 in molar ratio
(overall flow rate 2ml/min) by constant flow pump be injected separately into microstucture mixer be sufficiently mixed laggard enter micro-structured reactor, micro-
Structural response device stops at 190 DEG C 15min react.Extract and separate dress is entered after the hot solution of microreactor cools down
Put.Entering solution AUTOMATIC ZONING after extraction equipment, upper strata is the 1 of furfural and levulic acid, 2-dichloroethane solution, and lower floor is water
Solution, upper solution is detected by GC-MS, and pentose conversion ratio is 95%, and furfural productivity is 93%, and the conversion ratio of hexose is
92%, 5-HMF productivity is 4%, and levulic acid productivity is 87%.Lower aqueous solution passes through Liquid Detection, and remaining sugar can follow
Ring recycles.
Embodiment 15～21:
Use the condition identical with embodiment 14, except that, reaction temperature is changed into 180 DEG C by embodiment 15；Implement
Temperature is changed into 200 DEG C by example 16；Temperature is changed into 210 DEG C by embodiment 17；Embodiment 18 velocity ratio changes 1:2 into, and (overall flow rate is
3ml/min) retention time is 10min；Embodiment 19 velocity ratio changes 1:3 (overall flow rate is 4ml/min) retention time into
7.5min；Embodiment 20 replaces 1,2-dichloroethane solution with n-butyl alcohol；Embodiment 21 replaces 1,2-bis-chloroethene with ethyl acetate
Alkane solution.The results are shown in Table 3.
Table 3
Claims (6)
1. one kind utilizes the method that microchannel reaction unit prepares furfural, Hydroxymethylfurfural, levulic acid, it is characterised in that bag
Include following steps:
(1) lignocellulose is utilized to prepare soluble oligomeric sugar juice；
(2) in the reaction unit of microchannel, the oligosaccharide in HCl catalysis soluble oligomeric sugar juice is utilized to be converted into furfural, hydroxyl
Methyl furfural or levulic acid, during catalysis, soluble oligosaccharide is 1:1～3 with the mol ratio of HCl, and the temperature of catalytic reaction is
140～210 DEG C, catalytic reaction flow velocity is 1～6ml/min, and catalytic reaction retention time is 2～10min；
(3) reactant liquor, the furfural in extractive reaction liquid, Hydroxymethylfurfural, levulic acid are cooled down after reaction terminates.
The side utilizing microchannel reaction unit to prepare furfural, Hydroxymethylfurfural, levulic acid the most according to claim 1
Method, it is characterised in that in step (1), is prepared as follows soluble oligomeric sugar juice:
(1a) corn straw, corn cob, straw, bagasse or wood dust are broken to particle diameter is 100 mesh～the lignocellulose of 1 centimetre
Granule；
(2a) acid mixes with organic solvent, obtains cracking mixed liquor, puts into 50g/L lignocellulosic particles in cracking mixed liquor
In, keeping acid is 10～20mmol/g with the ratio of lignocellulose, stirs 1～3h；
(3a) decompression distillation under the conditions of 40～60 DEG C, removes the organic solvent in cracking mixed liquor, obtains impregnating wood fibre
Element；
(4a) impregnating wooden cellulose grain to be placed in ball mill, room-temperature ball-milling, ball milling temperature is less than 45 DEG C, and Ball-milling Time is 2h,
Rotational speed of ball-mill is 500rpm/min, obtains soluble oligosaccharide and lignin mixture.
(5a) by soluble in water for the mixture that obtains in step 4a, remove insoluble matter, obtain soluble oligomeric sugar juice, insoluble matter
For lignin.
The side utilizing microchannel reaction unit to prepare furfural, Hydroxymethylfurfural, levulic acid the most according to claim 2
Method, it is characterised in that in step (2a), described acid is the mixed of one or more in sulphuric acid, hydrochloric acid, phosphoric acid, acetic acid, propanoic acid
Compound.
The side utilizing microchannel reaction unit to prepare furfural, Hydroxymethylfurfural, levulic acid the most according to claim 2
Method, it is characterised in that in step (2a), described organic solvent is the one in ether, acetone, MIBK, n-butyl alcohol, isobutanol
Or several mixture.
The side utilizing microchannel reaction unit to prepare furfural, Hydroxymethylfurfural, levulic acid the most according to claim 1
Method, it is characterised in that in step (2), described microchannel reaction unit includes: the first raw material storage tank, the second raw material storage tank, micro-
Structural mixer, micro-structured reactor, extraction and stripping apparatus, the first raw material storage tank and the second raw material storage tank pass through constant flow pump respectively
Being connected with microstucture mixer, microstucture mixer, micro-structured reactor, extraction and stripping apparatus are sequentially communicated, described micro-knot
Temperature control modules on structure reactor.
The side utilizing microchannel reaction unit to prepare furfural, Hydroxymethylfurfural, levulic acid the most according to claim 5
Method, it is characterised in that soluble oligomeric sugar juice is placed in the first raw material storage tank, HCl solution is placed in the second raw material storage tank,
Soluble oligomeric sugar juice and HCl solution mix in microstucture mixer, and mixture flows in micro-structured reactor and reacts, instead
Answering temperature is 140～210 DEG C, and flow velocity is 1～6ml/min, and retention time is 2～10min.
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| CN106977473A (en) * | 2017-04-14 | 2017-07-25 | 四川金象赛瑞化工股份有限公司 | A kind of method that utilization continuous stream micro passage reaction prepares hemicellulose in furfural |
| CN106977473B (en) * | 2017-04-14 | 2019-06-21 | 四川金象赛瑞化工股份有限公司 | A method of hemicellulose being prepared into furfural using continuous flow micro passage reaction |
| CN107163007A (en) * | 2017-06-02 | 2017-09-15 | 四川金象赛瑞化工股份有限公司 | A kind of method that continuous stream micro passage reaction hemicellulose two-step method prepares furfural |
| CN107163007B (en) * | 2017-06-02 | 2019-08-16 | 四川金象赛瑞化工股份有限公司 | A kind of method that continuous flow micro passage reaction hemicellulose two-step method prepares furfural |
| CN107267688A (en) * | 2017-07-03 | 2017-10-20 | 南京工业大学 | A kind of method that utilization mill grinding prepares xylo-oligosaccharide or xylose |
| CN107267688B (en) * | 2017-07-03 | 2018-06-29 | 南京工业大学 | A kind of method that xylo-oligosaccharide or xylose are prepared using mill grinding |
| CN113956219A (en) * | 2021-11-01 | 2022-01-21 | 上海昶法新材料有限公司 | Process flow for producing furfural from papermaking wastewater |
| CN114315767A (en) * | 2021-11-29 | 2022-04-12 | 青岛三力本诺新材料股份有限公司 | Preparation method and preparation device of 5-hydroxymethylfurfural |
| CN114315767B (en) * | 2021-11-29 | 2023-07-28 | 青岛三力本诺新材料股份有限公司 | Preparation method and preparation device of 5-hydroxymethylfurfural |
| CN115536619A (en) * | 2022-09-30 | 2022-12-30 | 中建安装集团有限公司 | Method for continuously synthesizing 5-hydroxymethylfurfural by using microchannel reactor |
| CN115536619B (en) * | 2022-09-30 | 2023-11-03 | 中建安装集团有限公司 | Method for continuously synthesizing 5-hydroxymethylfurfural by utilizing microchannel reactor |
| WO2024065968A1 (en) * | 2022-09-30 | 2024-04-04 | 中建安装集团有限公司 | Method for continuously synthesizing 5-hydroxymethylfurfural by using microchannel reactor |
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