CN107442177A - The method that 5 hydroxymethylfurfural selective hydrogenations synthesize 2,5 furyl dimethyl carbinols - Google Patents

The method that 5 hydroxymethylfurfural selective hydrogenations synthesize 2,5 furyl dimethyl carbinols Download PDF

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CN107442177A
CN107442177A CN201710640261.3A CN201710640261A CN107442177A CN 107442177 A CN107442177 A CN 107442177A CN 201710640261 A CN201710640261 A CN 201710640261A CN 107442177 A CN107442177 A CN 107442177A
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acid
magnetic metal
catalyst
coordination polymer
reaction
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CN107442177B (en
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胡磊
李婷
徐宁
徐玲
胡佩佩
许家兴
周守勇
褚效中
戴本林
朱安峰
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Huaiyin Normal University
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    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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    • 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
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    • C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/58—One oxygen atom, e.g. butenolide
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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
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    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • B01J2531/57—Niobium

Abstract

The invention discloses a kind of 5 hydroxymethylfurfural selective hydrogenations synthesis 2, the method of 5 furyl dimethyl carbinols, this method is using magnetic metal organic coordination polymer as difunction catalyst, using low-carbon alcohols cheap and easy to get as hydrogen donor in situ, under mild operating conditionses by selectively transfer hydrogenation reaction by 5 hydroxymethylfurfural Efficient Conversions be 2,5 furyl dimethyl carbinols, its highest yield is up to 98.6%.The magnetic metal organic coordination polymer that the present invention uses not only has higher Acid-Base strengths, more soda acid site, larger specific surface area and suitable pore size, and manufacturing process is simple, it is easily isolated and recycled, shows splendid catalytic activity and catalytic stability.In addition, the present invention uses low-carbon alcohols not only to avoid the use of molecule hydrogen, increase the security of course of reaction as hydrogen donor in situ, and reaction dissolvent can be used as, reduce the introducing of allogenic material, can further reduce production cost.

Description

The method that 5 hydroxymethyl furfural selective hydrogenation synthesizes 2,5- furyl dimethyl carbinols
Technical field
The invention belongs to biomass energy chemical field, and in particular to a kind of 5 hydroxymethyl furfural selective hydrogenation synthesis 2, The method of 5- furyl dimethyl carbinols.
Background technology
In recent years, the biological-based chemicals for reproducible biomass resource being converted into high added value have become current society The important channel depended on unduly to non-renewable fossil resource can be reduced（Chemical Reviews, 2014, 114: 1827- 1870; Chemical Reviews, 2017, 117: 6834-6880）.In various biological-based chemicals, 5- methylol chaffs Aldehyde is considered as to be currently based on one of ten large platform compounds of biomass resource because it can prepare a series of high-quality and The derivative of fossil base product can be substituted（Renewable and Sustainable Energy Reviews, 2017, 74: 230-257）.Wherein, the 2,5-FDM obtained by 5 hydroxymethyl furfural selective hydrogenation is especially noticeable, it Both softening agent, wetting agent, binding agent, plasticizer, surfactant and medicine intermediate etc. can be used as to be used, can also As polymeric materials such as monomer synthetic resin material, fibrous material, foamed material and crown ether materials（ACS Catalysis, 2015, 5: 722-733）, there is boundless application prospect.
It is well known that contain an aldehyde radical, an alcoholic extract hydroxyl group and a furan nucleus in 5 hydroxymethyl furfural molecule simultaneously, this So that its chemical property is very active, product when hydrogenation reaction occurs is complex, therefore, how to ensure the preferential of aldehyde radical Hydrogenation, while the excessive hydrogenation of alcoholic extract hydroxyl group and furan nucleus is avoided as far as possible, it is 5 hydroxymethyl furfural selective hydrogenation synthesis 2,5- furans Muttering needs to solve the problems, such as first during dimethanol, and develops suitable catalystic converter system and then risen for solving this problem Vital effect.For now, carried noble metal（Such as Pt/C, Ru/C, Ru/SiO2, Ru/Al2O3, Ir/ TiO2, Ir/ReOx, Au/Al2O3 and Au/FeOx etc.）It is 5 hydroxymethyl furfural selective hydrogenation synthesis 2,5- furans respectively with hydrogen Dimethanol of muttering the most frequently used catalyst and hydrogen donor（RSC Advances, 2013, 3: 1033-1036; ChemCatChem, 2013, 5: 2822-2826; Catalysis Today, 2014, 234: 59-65; Chemical Communications, 2013, 49: 7034-7036; Green Chemistry, 2014, 16: 4734-4739; Energy & Environmental Science, 2015, 8: 230-240）.However, it is necessary to it is emphasized that by bearing 5 hydroxymethyl furfural selective hydrogenation is being converted into 2,5- furans two by the catalystic converter system of load type noble metal and hydrogen composition During methanol, there is it is a series of inevitable the shortcomings that, for example, the cost of manufacture of loaded noble metal catalyst is higher And preparation process is relatively complicated；The usage amount of carried noble metal is larger and repeat performance is not good enough；Hydrogen has high dispersive , larger potential safety hazard be present in property and inflammability；Solubility of the hydrogen in various solvents is not high, and atom utilization is relatively low.For Overcome the shortcomings of above-mentioned catalystic converter system, disproportionated reaction system（Green Chemistry, 2013, 15: 2849- 2853）, electrochemical reaction system（Environmental Science & Technology, 2015, 49: 13667- 13675）With photochemical reaction system（RSC Advances, 2016, 6: 101968-101973）Deng also gradually being answered recently For being catalyzed 5 hydroxymethyl furfural selective hydrogenation synthesis 2,5- furyl dimethyl carbinols.Although these new catalystic converter systems can To be carried out under conditions of non-precious metal catalyst and without external source hydrogen, but their catalytic efficiency include substrate conversion efficiency and Efficiency of pcr product is often relatively low, and which greatly limits the actual production of 2,5-FDM and subsequent applications.
The content of the invention
The problem of existing for prior art, it is an object of the invention to provide a kind of 5 hydroxymethyl furfural selective hydrogenation A kind of method for synthesizing 2,5-FDM, it is desirable to provide gentle efficient and economic security 5 hydroxymethyl furfural selectively adds The method that hydrogen synthesizes 2,5-FDM, present invention also offers a kind of new magnetic metal organic coordination polymer in addition For difunction catalyst, additionally provide and utilize above-mentioned catalyst for 5 methyl furfural, furfural, levulic acid and acetyl Application in the various carbonyls selective hydrogenation conversions such as propionic ester.
Present invention one side, there is provided：
A kind of magnetic metal organic coordination polymer catalyst, it is using magnetic ferroferric oxide as carrier, in its area load There is an organic multicomponent acid part and crosslinking agent is polymerize obtained high molecular polymer, be complexed and urge on organic multicomponent acid part Change active metal.
Described catalytically-active metals are selected from zinc, aluminium, tin, zirconium, hafnium or niobium；More preferably zirconium or hafnium.
Described organic multicomponent acid part is selected from phytic acid, cyanuric acid, citrazinic acid, ethylenediamine tetra-acetic acid, diethylenetriamine five Acetic acid, ATMP, in phenylene di 2 ethylhexyl phosphonic acid, ethylene diamine tetra methylene phosphonic acid or diethylene triamine pentamethylene phosphonic One kind；More preferably phytic acid, cyanuric acid or ATMP.
Described crosslinking agent is preferably polynary amine；More preferably triethylamine.
Second aspect of the present invention, there is provided：
A kind of preparation method of magnetic metal organic coordination polymer catalyst, comprises the following steps：
1st step, nano ferriferrous oxide is added to being mixed with the organic solution of metal chloride, be stirred by ultrasonic scattered equal It is even；
2nd step, then organic solvent and crosslinking agent dissolved with organic multicomponent acid part are added dropwise respectively, it is stirred reaction；
3rd step, separation of solid and liquid is carried out to solids using magnet, after being washed, dried to solids, grinding, produced.
In the 1st described step, concentration of the metal chloride in organic solution is 30~120mmol/L, metal chloride Mol ratio with iron is 1~3:1.
Described metal chloride is zinc dichloride, alchlor, butter of tin, zirconium chloride, hafnium tetrachloride or pentachloro- Change one kind in niobium, preferably zirconium chloride or hafnium tetrachloride.
In the 1st described step, the mol ratio of described metal ion and organic multicomponent acid part is 3:4~6:1, metal from The mol ratio of son and triethylamine is 1:10~1:4.
In the 2nd described step, the organic solvent rate of addition dissolved with organic multicomponent acid part is 2~8mL/min, dissolved with friendship The rate of addition for joining the organic solvent of agent is 0.5~1.5mL/min.
In the 2nd described step, the process for being stirred reaction is 2~12h of stirring under room temperature condition, is warming up to 60~90 DEG C Still aging 2~12h.
In the 3rd described step, described washing step refers to wash precipitation repeatedly with ethanol and ether successively until detection Exist less than chlorion；Drying steps refer to be dried in vacuo 8~16h under the conditions of 75~85 DEG C.
Third aspect of the present invention, there is provided：
Above-mentioned magnetic metal organic coordination polymer synthesizes 2,5- furans as catalyst in 5 hydroxymethyl furfural selective hydrogenation The application muttered in dimethanol.
In described application, magnetic metal organic coordination polymer, which serves, improves product yield, selectivity aspect, catalysis The effect of agent access times.
The 4th aspect of the present invention, there is provided：
A kind of method of 5 hydroxymethyl furfural selective hydrogenation synthesis 2,5-FDM, comprises the following steps：
Low-carbon alcohols, 5 hydroxymethyl furfural and magnetic metal organic coordination polymer are added among reactor, with nitrogen displacement it Afterwards, reacted, 2,5-FDM is obtained after reaction.
Described low-carbon alcohols are one kind in isopropanol, sec-butyl alcohol, sec-amyl alcohol or cyclopentanol.
Described 5 hydroxymethyl furfural dosage is 1~3wt% of low-carbon alcohols dosage, and described magnetic metal organic coordination gathers Compound dosage is 20~60wt% of 5 hydroxymethyl furfural dosage.
Mixing speed is 300~500rpm in reactor, and described reaction temperature is 120~150 DEG C, during described reaction Between be 2~10h.
The fifth aspect of the invention, there is provided：
Active metal is used to improve 5 hydroxymethyl furfural choosing as the activated centre of magnetic metal organic coordination polymer catalyst Application in selecting property hydrogenation synthesis 2,5- furyl dimethyl carbinols reaction yield, reaction selectivity, catalyst access times.
Described active metal is selected from zinc, aluminium, tin, zirconium, hafnium or niobium；More preferably zirconium or hafnium.
The 6th aspect of the present invention, there is provided：
Magnetic metal organic coordination polymer is as catalyst in 5 methyl furfural selective hydrogenation synthesizes 5- methyl furfuryl alcohols Using.
Above-mentioned magnetic metal organic coordination polymer answering in furfural selective hydrogenation synthesizes furfuryl alcohol as catalyst With.
Above-mentioned magnetic metal organic coordination polymer synthesizes valerolactone as catalyst in levulic acid selective hydrogenation In application.
Above-mentioned magnetic metal organic coordination polymer synthesizes penta as catalyst in ethyl levulinate selective hydrogenation Application in lactone.
Beneficial effect
It is creative on the basis of synthesizing 2,5-FDM reaction mechanism in research 5 hydroxymethyl furfural selective hydrogenation The magnetic metal organic coordination polymer catalyst with the effect of soda acid double-function catalyzing is prepared on ground, not only has higher acid Base strength, more soda acid site, larger specific surface area and suitable pore size, and manufacturing process is simple, are easy to point From recovery, splendid catalytic activity and catalytic stability have been shown；In addition, using low-carbon alcohols as hydrogen donor in situ, not only The use of molecule hydrogen can be avoided, increases the security of course of reaction, and reaction dissolvent can be used as, reduces allogenic material Introducing, can further reduce production cost.What is more important, method provided by the invention can also be used to be catalyzed 5- first The various carbonyls such as base furfural, furfural, levulic acid and levulinate are selectively converted to its corresponding product, have Very strong substrate universality, possesses good application value and industrial prospect.
Embodiment
The preparation of the magnetic metal organic coordination polymer of embodiment 1
By nano ferriferrous oxide according to metal chloride/iron mol ratio be 2:1, which is added to 400mL, contains 30mmol metal chlorinations In the dimethyl formamide solution of thing, 30min is stirred in the case where ultrasound is assisted；According to rate of addition it is 5mL/ into above-mentioned mixed liquor The dimethyl formamide solution and 240mmol that 400mL contains 10mmol organic multicomponents acid is slowly added dropwise in min and 1mL/min respectively Triethylamine；Continue to stir 4h at ambient temperature, be warming up to after 70 DEG C still aging 4h again；Solid is precipitated by magnet and carried out Separation, and precipitation is washed repeatedly until can't detect chlorion presence with ethanol and ether；Solid after washing is deposited in 80 12h is dried in vacuo at DEG C, and is ground to about 120 mesh, you can obtains magnetic metal organic coordination polymer catalyst.
Material quantity, reactant species when being prepared using different metal chlorides and organic multicomponent acid as raw material It is as shown in the table：
The characterize data of catalyst is as shown in the table：
Embodiment 2
5 hydroxymethyl furfural selective hydrogenation synthesis 2,5- is carried out using above-mentioned magnetic metal organic coordination polymer catalyst Furyl dimethyl carbinol.Synthetic method is：
20g isopropanols, 0.4g 5 hydroxymethyl furfurals and the polymerization of 0.16g magnetic metals organic coordination are added in 50mL reactors Thing catalyst, air 6 times in kettle are continuously replaced after sealing with nitrogen；Low whipping speed is that 130 DEG C are warming up under 400 rpm, choosing Selecting property hydrogenation reaction 8h can obtain 2,5- furyl dimethyl carbinols.
In order to investigate the reusability of catalyst, after completion of the reaction, additional magnet separates MZPCP from reaction solution Out, then washed and carry out selective hydrogenation next time by above-mentioned reaction condition after drying.
Contrasted as with catalyst provided by the invention and hydrogenation synthesis method, employ synthesis of the prior art Reaction and catalyst are as control：
Reference examples 1：Synthesis step in patent CN106008414A in embodiment 1~3.
As can be seen from the above table, building-up process provided by the invention has higher efficiency of pcr product and reaction selectivity, Particularly zirconium and hafnium show more preferable catalytic effect as active metal, and catalyst still can be protected after being used for multiple times Higher reactivity is held, better than the magnetic zirconium hydroxide catalyst used in reference examples.
The catalyst of embodiment 3~8 converts in other other carbonyls selective hydrogenations
Low-carbon alcohols, carbonyl containing compound and magnetic metal organic coordination polymer catalyst, sealing are added in 50mL reactors Air 6 times in kettle are continuously replaced with nitrogen afterwards；Low whipping speed is to be heated up under 400 rpm, and selective hydrogenation is i.e. available Corresponding product.
Wherein, the reaction substrate of use, catalyst, reaction condition are summarized as follows：
As can be seen from the above table, catalyst provided by the invention be also applied for other carbonyls selective hydrogenation it is anti- Should, there is preferable reaction yield.

Claims (10)

  1. A kind of 1. magnetic metal organic coordination polymer catalyst, it is characterised in that it be using magnetic ferroferric oxide as carrier, There is an organic multicomponent acid part in its area load and crosslinking agent is polymerize obtained high molecular polymer, match somebody with somebody in organic multicomponent acid Complexing has catalytically-active metals on body.
  2. 2. magnetic metal organic coordination polymer catalyst according to claim 1, it is characterised in that described catalysis is lived Property metal is selected from zinc, aluminium, tin, zirconium, hafnium or niobium；More preferably zirconium or hafnium；Described organic multicomponent acid part be selected from phytic acid, Cyanuric acid, citrazinic acid, ethylenediamine tetra-acetic acid, diethylene triamine pentacetic acid (DTPA), ATMP, to phenylene di 2 ethylhexyl phosphonic acid, One kind in ethylene diamine tetra methylene phosphonic acid or diethylene triamine pentamethylene phosphonic；More preferably phytic acid, cyanuric acid or amino trimethylene Methylphosphonic acid；Described crosslinking agent is preferably polynary amine；More preferably triethylamine.
  3. 3. the magnetic metal organic coordination polymer method for preparing catalyst described in claim 1, it is characterised in that including as follows Step：
    1st step, nano ferriferrous oxide is added to being mixed with the organic solution of metal chloride, be stirred by ultrasonic scattered equal It is even；
    2nd step, then organic solvent and crosslinking agent dissolved with organic multicomponent acid part are added dropwise respectively, it is stirred reaction；
    3rd step, separation of solid and liquid is carried out to solids using magnet, after being washed, dried to solids, grinding, produced.
  4. 4. magnetic metal organic coordination polymer method for preparing catalyst according to claim 3, it is characterised in that described The 1st step in, concentration of the metal chloride in organic solution is 30~120mmol/L, metal chloride and iron mol ratio For 1~3:1；Described metal chloride is zinc dichloride, alchlor, butter of tin, zirconium chloride, hafnium tetrachloride or pentachloro- Change one kind in niobium, preferably zirconium chloride or hafnium tetrachloride；In the 1st described step, described metal ion and organic multicomponent The mol ratio of sour part is 3:4~6:1, the mol ratio of metal ion and triethylamine is 1:10~1:4；It is molten in the 2nd described step The organic solvent rate of addition for having organic multicomponent acid part is 2~8mL/min, and the rate of addition of crosslinking agent is 0.5~1.5mL/ min；In the 2nd described step, the process for being stirred reaction is 2~12h of stirring under room temperature condition, is warming up to 60~90 DEG C of standings It is aged 2~12h；In the 3rd described step, described washing step refers to wash precipitation repeatedly with ethanol and ether successively until inspection Chlorion presence is not detected；Drying steps refer to be dried in vacuo 8~16h under the conditions of 75~85 DEG C.
  5. 5. the magnetic metal organic coordination polymer described in claim 1 is as catalyst in 5 hydroxymethyl furfural selective hydrogenation Synthesize the application in 2,5- furyl dimethyl carbinols.
  6. 6. application according to claim 5, it is characterised in that magnetic metal organic coordination polymer serves raising product Effect in terms of yield, selectivity, catalyst access times.
  7. A kind of 7. method of 5 hydroxymethyl furfural selective hydrogenation synthesis 2,5-FDM, it is characterised in that including as follows Step：The magnetic metal organic coordination polymerization described in low-carbon alcohols, 5 hydroxymethyl furfural and claim 1 is added among reactor Thing, after nitrogen displacement, reacted, 2,5-FDM is obtained after reaction.
  8. 8. the method for 5 hydroxymethyl furfural selective hydrogenation synthesis 2,5-FDM according to claim 7, it is special Sign is that described low-carbon alcohols are one kind in isopropanol, sec-butyl alcohol, sec-amyl alcohol or cyclopentanol；Described 5 hydroxymethyl furfural Dosage is 1~3wt% of low-carbon alcohols dosage, and described magnetic metal organic coordination polymer dosage is 5 hydroxymethyl furfural dosage 20~60wt%；Mixing speed is 300~500rpm in reactor, and described reaction temperature is 120~150 DEG C, and described is anti- It is 2~10h between seasonable.
  9. 9. active metal is used to improve 5 hydroxymethyl furfural as the activated centre of magnetic metal organic coordination polymer catalyst Application in selective hydrogenation synthesis 2,5- furyl dimethyl carbinols reaction yield, reaction selectivity, catalyst access times；Described Active metal is selected from zinc, aluminium, tin, zirconium, hafnium or niobium；More preferably zirconium or hafnium.
  10. 10. the magnetic metal organic coordination polymer described in claim 1 is as catalyst in 5 methyl furfural selective hydrogenation Synthesize 5- methyl furfuryl alcohol, furfural selective hydrogenation synthesis furfuryl alcohol, levulic acid selective hydrogenation synthesis valerolactone or levulinic Application in acetoacetic ester selective hydrogenation synthesis valerolactone.
CN201710640261.3A 2017-07-31 2017-07-31 Method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural Active CN107442177B (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109675638A (en) * 2019-01-28 2019-04-26 淮阴师范学院 A kind of composite catalyzing material, preparation method and dehydrogenation hydrogenation reaction mediates the application prepared in 2,5- dimethyl furan in situ
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CN110437182A (en) * 2019-07-16 2019-11-12 南昌大学 A method of BMFM is synthesized from 5-MFA green high-efficient
CN110882677A (en) * 2019-12-25 2020-03-17 鲁东大学 Adsorbing material based on phosphonic acid and preparation method thereof
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CN109772457A (en) * 2019-01-28 2019-05-21 淮阴师范学院 A kind of composite catalyzing material, preparation method and its application in double hydroxyls/bis- methylfurans class compound controllable preparation
CN109675638A (en) * 2019-01-28 2019-04-26 淮阴师范学院 A kind of composite catalyzing material, preparation method and dehydrogenation hydrogenation reaction mediates the application prepared in 2,5- dimethyl furan in situ
CN109772457B (en) * 2019-01-28 2021-09-03 淮阴师范学院 Composite catalytic material, preparation method and application thereof in controllable preparation of dihydroxyl/dimethyl furan compounds
CN109675638B (en) * 2019-01-28 2021-08-13 淮阴师范学院 Composite catalytic material, preparation method and application in-situ dehydrogenation hydrogenation reaction mediated preparation of 2, 5-dimethylfuran
CN109908957A (en) * 2019-03-18 2019-06-21 江南大学 A kind of corrdination type phosphotungstic acid Zr catalyst and its application in catalytic hydrogenation furfural
CN110437182B (en) * 2019-07-16 2021-07-20 南昌大学 Method for synthesizing bis (5-methylfuran-2-yl) methane BMFM from 5-methylfurfuryl alcohol 5-MFA
CN110437182A (en) * 2019-07-16 2019-11-12 南昌大学 A method of BMFM is synthesized from 5-MFA green high-efficient
CN110882677A (en) * 2019-12-25 2020-03-17 鲁东大学 Adsorbing material based on phosphonic acid and preparation method thereof
CN111574483A (en) * 2020-05-19 2020-08-25 中山大学 Preparation method of 2, 5-furandimethanol
CN111574483B (en) * 2020-05-19 2023-05-16 中山大学 Preparation method of 2, 5-furandimethanol
CN111961015A (en) * 2020-07-17 2020-11-20 昆明理工大学 Method for preparing 2, 5-furandimethanol by catalyzing 5-hydroxymethylfurfural
CN112979588A (en) * 2021-02-26 2021-06-18 厦门大学 Preparation of 2, 5-furandimethanol by transfer hydrogenation
CN112979588B (en) * 2021-02-26 2022-03-29 厦门大学 Preparation of 2, 5-furandimethanol by transfer hydrogenation
WO2022178955A1 (en) * 2021-02-26 2022-09-01 厦门大学 Preparation of 2,5-furan dimethanol by transfer hydrogenation
CN113527703A (en) * 2021-07-16 2021-10-22 淮阴师范学院 Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2, 5-furandimethanol
CN115779896A (en) * 2022-11-23 2023-03-14 河南省生物基材料产业研究院有限公司 Catalyst for preparing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural and preparation method thereof

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