CN117658958A - Method for preparing 5-hydroxymethylfurfural based on adsorption catalytic system - Google Patents
Method for preparing 5-hydroxymethylfurfural based on adsorption catalytic system Download PDFInfo
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- CN117658958A CN117658958A CN202211047083.0A CN202211047083A CN117658958A CN 117658958 A CN117658958 A CN 117658958A CN 202211047083 A CN202211047083 A CN 202211047083A CN 117658958 A CN117658958 A CN 117658958A
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 104
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 229930091371 Fructose Natural products 0.000 claims abstract description 53
- 239000005715 Fructose Substances 0.000 claims abstract description 53
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 52
- 239000003463 adsorbent Substances 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- 238000004821 distillation Methods 0.000 claims description 45
- 238000000605 extraction Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 18
- 239000002808 molecular sieve Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 14
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 14
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000002608 ionic liquid Substances 0.000 claims description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012621 metal-organic framework Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000002210 silicon-based material Substances 0.000 claims description 7
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 2
- 239000013177 MIL-101 Substances 0.000 claims description 2
- 239000013132 MOF-5 Substances 0.000 claims description 2
- 239000013118 MOF-74-type framework Substances 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 5
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- 238000002360 preparation method Methods 0.000 description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- 229910021641 deionized water Inorganic materials 0.000 description 3
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- BJHIKXHVCXFQLS-UYFOZJQFSA-N fructose group Chemical group OCC(=O)[C@@H](O)[C@H](O)[C@H](O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
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Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application discloses a method for preparing 5-hydroxymethylfurfural based on an adsorption catalytic system, which comprises the following steps: reacting a solution containing fructose, a catalyst and an adsorbent to obtain 5-hydroxymethylfurfural; the catalyst comprises an acid B dissolved in a solvent; the adsorbent comprises a porous material. The method can effectively improve the conversion rate and selectivity of fructose, reduce the acidity of a reaction system, is environment-friendly, reduces the cost of raw materials and equipment maintenance, and is beneficial to efficiently producing 5-hydroxymethylfurfural.
Description
Technical Field
The application relates to a method for preparing 5-hydroxymethylfurfural based on an adsorption catalytic system, and belongs to the field of 5-hydroxymethylfurfural preparation.
Background
The renewable raw material source can relieve the increasingly intense crisis of fossil energy, and provides a broad prospect for the sustainable development of industry. Among them, biomass-based chemicals are receiving extensive attention as alternatives to, and even superior to, petrochemical in functionality. Biomass is a variety of organisms produced by photosynthesis, and fundamentally, biomass energy is solar energy, an inexhaustible green energy source. The efficient utilization of biomass has important significance for reducing carbon and emission, researches on the special structural characteristics based on bio-based compounds provide innovative source power for developing novel energy products, and is expected to replace petroleum-based products in a certain application range.
The 5-hydroxymethylfurfural (5-HMF) is an important biomass-based platform compound and is derived from two abundant hexose molecules, namely fructose and glucose, and the special furan ring structure enables the hexose molecules to be capable of deriving thousands of furan compounds through further oxidation, hydrogenation, etherification, esterification and other reactions, so that the 5-hydroxymethylfurfural (5-HMF) is widely applied to the fields of functional polyesters, bio-based lubricating oils, feeds/food additives, surfactants, medical intermediates, engineering/degradable plastics, water-based coatings and the like, and has wide market space.
At present, the traditional 5-hydroxymethylfurfural is prepared by inorganic acid catalysis under the condition of a solvent, the conversion rate of fructose or glucose is lower under the condition of low acid quantity, and the further reaction of the 5-hydroxymethylfurfural is easy to generate humins under the condition of high acid quantity. The humins are humic substances which are inactive and difficult to decompose in nature, and the generation of the humins means the loss of 5-hydroxymethylfurfural products, and simultaneously, the corrosion and blockage of reaction equipment are accompanied, so that the further extraction of 5-hydroxymethylfurfural from reaction liquid is hindered, and the production cost and the maintenance cost are greatly increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an efficient solution. The application provides a method for preparing 5-hydroxymethylfurfural based on an adsorption catalytic system, which can efficiently catalyze the conversion of fructose into 5-hydroxymethylfurfural. Compared with the traditional homogeneous acid catalytic system, the porous material is introduced to serve as the adsorbent, and the adsorbent does not have catalytic performance, so that the catalytic capability of the system is improved by adsorbing the B acid on the surface of the adsorbent. The fructose is efficiently converted on the surface of the adsorbent to obtain high fructose conversion rate and 5-hydroxymethylfurfural selectivity, and meanwhile, due to weak interaction between the adsorbent and the 5-hydroxymethylfurfural, side reaction of the 5-hydroxymethylfurfural can be avoided, and no humins are generated after the reaction. The method is environment-friendly, low in economic cost, beneficial to industrial production and amplification, low in equipment maintenance cost and capable of efficiently producing the high-purity 5-hydroxymethylfurfural.
Aiming at the characteristics of low fructose conversion rate and easiness in generation of humins of an acid catalytic system, the application provides a scheme for effectively improving the reaction efficiency by introducing an adsorbent. The invention adopts the following technical scheme:
a method for preparing 5-hydroxymethylfurfural based on an adsorption catalytic system, the preparation method comprising the steps of:
reacting a solution containing fructose, a catalyst and an adsorbent to obtain 5-hydroxymethylfurfural; the solvent is at least one selected from water, ethanol and ionic liquid;
the catalyst is selected from at least one of B acid dissolved in a solvent;
the adsorbent is a porous material without catalytic performance for catalyzing the reaction;
the mass ratio of the catalyst to the fructose is 0.01-1:0.1-10;
the mass ratio of the adsorbent to the fructose is 0.01-1:0.1-10.
Optionally, the solvent of the solution is at least one selected from water, ethanol and ionic liquid.
Optionally, the solvent is an ionic liquid.
Optionally, the ionic liquid is selected from [ Bmim ]][BF 4 ]、[Emim]Cl、[Emim]Br、[Emim][CF 3 SO 4 ]At least one of them.
Optionally, the acid catalyst B is at least one selected from phosphoric acid, hydrochloric acid, sulfuric acid, boric acid, methane sulfonic acid and sulfonic ionic liquid.
Optionally, the mass ratio of fructose to solvent is 0.1-10:1-20.
Optionally, the mass ratio of the fructose to the solvent is 1:1-5.
Optionally, the mass ratio of the catalyst to the fructose is 0.01-0.1:1.
Optionally, the mass ratio of the adsorbent to the fructose is 0.1-1:1.
Optionally, the adsorbent is selected from at least one of molecular sieves, metal organic framework materials, ion exchange resins, carbon materials, silicon materials, oxide materials, and other porous materials.
Optionally, the porosity of the porous material is more than 60%, the pore size distribution comprises micropores, mesopores and macropores, and the BET specific surface area is between 100 and 5000m 2 /g。
Optionally, the molecular sieve is selected from at least one of MCM-41, X molecular sieve, Y molecular sieve, beta molecular sieve.
Optionally, the metal organic framework material is selected from at least one of MOF-5, MOF-74, MIL-101, MIL-125.
Optionally, the ion exchange resin is selected from sodium ion exchange resins.
Optionally, the carbon material is at least one selected from activated carbon, graphene, nanocarbon sol and carbon nanotubes.
Optionally, the silicon material is at least one selected from white carbon black, silica gel and nano silicon material.
Optionally, the oxide material is selected from alumina.
Alternatively, the temperature of the reaction is 20-140 ℃, and the time of the reaction is 1-12 hours.
Optionally, after the reaction is finished, the method further comprises a purification step: and (3) adding an extractant into the reaction solution for extraction to obtain an extract, and carrying out reduced pressure distillation on the extract to obtain the 5-hydroxymethylfurfural.
Optionally, the extractant comprises at least one of methyl isobutyl ketone, ethyl acetate, and dimethyl carbonate.
Optionally, the number of extractions is 3-5.
Optionally, the conditions of the reduced pressure distillation include: the vacuum degree is 0.01-5 KPa, the temperature is 30-70 ℃ and the time is 0.5-3 hours.
Optionally, the yield of 5-hydroxymethylfurfural is greater than 80%.
Optionally, the yield of the 5-hydroxymethylfurfural is 80% -95%.
As one embodiment, the application discloses a method for preparing 5-hydroxymethylfurfural, which comprises the steps of mixing fructose solution with a catalyst and an adsorbent in proportion, reacting by adopting a batch kettle reactor to generate 5-hydroxymethylfurfural, extracting 5-hydroxymethylfurfural by using an extractant after the reaction, and separating the 5-hydroxymethylfurfural and recycling the extractant by adopting a reduced pressure distillation method. The adsorbent added in the method can effectively improve the conversion rate and selectivity of reactants, and simultaneously, the problems of product yield reduction and great increase of equipment maintenance cost caused by the formation of humins by side reaction of 5-hydroxymethylfurfural are avoided. The system for synthesizing the 5-hydroxymethylfurfural has the advantages of larger economic benefit, lower system cost, environmental friendliness, simple operation and easy repetition, and can efficiently produce the high-purity 5-hydroxymethylfurfural.
The method comprises the following steps:
(1) Under the adsorption catalysis of a catalyst and an adsorbent, a batch kettle reactor is adopted to obtain 5-hydroxymethylfurfural through dehydration reaction by taking fructose solution as a raw material;
(2) Extracting 5-hydroxymethylfurfural by using an extractant after the reaction, and recovering and separating an extraction solvent from a product by adopting a reduced pressure distillation method.
Optionally, the solvent is selected from at least one of water, ethanol and ionic liquid;
optionally, the catalyst is selected from at least one of B acids dissolved in a solvent;
optionally, the adsorbent is selected from at least one of molecular sieves, metal organic framework materials, ion exchange resins, carbon materials, silicon materials, oxide materials, and other porous materials.
Optionally, the mass ratio of fructose to solvent is 0.1-10:1-20.
Optionally, the mass ratio of the catalyst to the fructose is 0.01-1:0.1-10;
optionally, the mass ratio of the adsorbent to the fructose is 0.01-1:0.1-10.
Alternatively, the conditions of the reaction are: the reaction temperature is 20-140 ℃ and the reaction time is 1-12 hours.
Alternatively, the upper temperature limit of the reaction is selected from 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, or 140 ℃; the lower limit is selected from 20 ℃,30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or 130 ℃.
Optionally, the reduced pressure distillation conditions of the extraction are: the vacuum degree is 0.01-5 KPa, the temperature is 30-70 ℃ and the time is 0.5-3 hours.
Optionally, the detection of the yield of the 5-hydroxymethylfurfural adopts a high performance liquid chromatography, and deionized water is added for mixing and volume fixing.
Optionally, the extracting agent is one of methyl isobutyl ketone, ethyl acetate or dimethyl carbonate, and the extracting process is to add the solution obtained after the reaction into the extracting agent for extraction operation. After shaking and standing, separating out an organic extractant phase, wherein the extractant contains 5-hydroxymethylfurfural, adding the extractant again into the rest solution after separating the extractant, extracting, and repeating the operation for a plurality of times.
The mass ratio of the extractant to the solution after the reaction is 1-5:1;
optionally, the number of times of repeating the operation of the extraction is 3 to 5.
Optionally, the method comprises:
a) Mixing the fructose solution with a catalyst and an adsorbent, and reacting in a stirring state, wherein the reaction temperature is 20-140 ℃ and the reaction time is 1-12 hours;
b) And c) extracting the solution obtained after the reaction in the step a) for multiple times by using an extracting agent, performing reduced pressure distillation operation after the extraction, controlling the vacuum degree of a system to be 0.01-5 KPa, and obtaining the product 5-hydroxymethylfurfural, wherein the reaction temperature is 30-70 ℃ and the reduced pressure distillation operation time is 0.5-3 hours.
The invention provides a preparation method of 5-hydroxymethylfurfural. Compared with the traditional method, the adsorbent is introduced in the preparation process, so that the occurrence of side reaction can be effectively controlled, the generation of humins is avoided, the conversion rate and selectivity of the reaction are improved, and the raw material and equipment maintenance cost is greatly reduced.
The preparation route of the preparation method is that the fructose solution is mixed with the catalyst and the adsorbent, the 5-hydroxymethylfurfural is obtained through dehydration reaction, the adsorbent is introduced to effectively improve the conversion rate and selectivity of the reaction, the side reaction of the 5-hydroxymethylfurfural is inhibited, no humins are generated after the reaction, and meanwhile, no pollution waste water and waste liquid are discharged after the reaction. After the reaction, methyl isobutyl ketone, dimethyl carbonate or ethyl acetate is used as an extractant to extract 5-hydroxymethylfurfural, and a reduced pressure distillation method is adopted to realize recovery and separation of an extraction solvent and a product, but the traditional preparation process of 5-hydroxymethylfurfural is generally difficult to balance the reaction conversion rate caused by acid quantity and the influence of generating humins, and the reaction efficiency is not high enough.
The preparation method of 5-hydroxymethylfurfural takes fructose solution as a raw material, and obtains the 5-hydroxymethylfurfural through dehydration reaction under the action of a catalyst and an adsorbent.
The solvent is at least one selected from water, ethanol and ionic liquid;
optionally, the mass ratio of the fructose to the water is fructose: water=1:0.8 to 10;
optionally, the upper mass ratio of fructose to water is selected from 1:0.8, 1:0.9, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1:9; the lower limit is selected from 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, or 1:0.9.
The catalyst is selected from at least one of B acid dissolved in a solvent;
optionally, the catalyst is added in an amount of 0.1wt% to 5wt% of the fructose added.
Optionally, the upper limit of the mass percentage content of the added amount of the catalyst is 0.2wt%, 0.5wt%, 0.8wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt% or 5.0wt% of the added amount of the fructose; the lower limit is selected from 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt% or 4.5wt%.
The adsorbent is a porous material without catalytic performance for catalyzing the reaction;
the adsorbent is selected from at least one of porous materials such as molecular sieves, metal organic framework materials, ion exchange resins, carbon materials, silicon materials, oxide materials and the like.
Optionally, the adding amount of the adsorbent is 0.1-5 wt% of the adding amount of the fructose.
Optionally, the upper limit of the mass percentage content of the added amount of the adsorbent is 0.2wt%, 0.5wt%, 0.8wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt% or 5.0wt% of the added amount of the fructose; the lower limit is selected from 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt% or 4.5wt%.
Alternatively, the conditions of the reaction are: the reaction temperature is 20-140 ℃ and the reaction time is 1-12 hours.
Optionally, the reaction to produce 5-hydroxymethylfurfural is performed under stirring.
Alternatively, the upper temperature limit of the reaction is selected from 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, or 140 ℃; the lower limit is selected from 20 ℃,30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or 130 ℃.
Alternatively, the upper time limit of the reaction is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours; the lower limit is selected from 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or 11 hours.
Optionally, taking a certain amount of reacted solution after the reaction is finished, adding deionized water, mixing to constant volume, and detecting the yield of the 5-hydroxymethylfurfural.
Alternatively, the detection method used is high performance liquid chromatography: obtaining a liquid chromatography peak area by configuring the content of 5-hydroxymethylfurfural in a standard solution, and obtaining a standard curve by taking the peak area as an abscissa and the concentration of 5-hydroxymethylfurfural as an ordinate; further, the concentration of 5-hydroxymethylfurfural in the reacted solid can be calculated, and the yield of 5-hydroxymethylfurfural is calculated through the concentration.
Alternatively, the solution obtained after the reaction is added to methyl isobutyl ketone, ethyl acetate or dimethyl carbonate for extraction operation. After shaking, standing, separating out an organic extractant phase, wherein the extractant contains 5-hydroxymethylfurfural, adding the extractant again into the rest solution after separating the extractant, extracting, and repeating the operation for a plurality of times.
Optionally, the mass ratio of the methyl isobutyl ketone, ethyl acetate or dimethyl carbonate serving as an extractant to the solution is 1-5:1.
Optionally, the upper mass ratio of extractant to anti-solids is selected from 5:1, 4:1, 3:1 or 2:1; the lower limit is selected from 1:1, 2:1, 3:1 or 4:1.
Optionally, the number of times of repeated operation of the extraction is 3-5 times.
Optionally, the upper limit of the number of extraction operations is selected from 5 or 4; the lower limit is selected from 3 or 4 times.
Optionally, the solvent methyl isobutyl ketone, ethyl acetate or dimethyl carbonate used for extraction is recovered by a reduced pressure distillation method from the extract of methyl isobutyl ketone, ethyl acetate or dimethyl carbonate in the extract phase, and the product 5-hydroxymethylfurfural is obtained at the same time.
Optionally, the conditions of the reduced pressure distillation include: and under the condition of vacuum degree of 0.01-5 KPa, the temperature is 30-70 ℃, and the pressure is reduced for 0.5-3 hours.
Optionally, in the reduced pressure distillation process, the upper limit of the vacuum degree of the system is selected from 0.02KPa, 0.05KPa, 0.1KPa, 0.5KPa, 1KPa, 2KPa, 3KPa, 4KPa, 4.5KPa or 5KPa; the lower limit is selected from 0.01KPa, 0.02KPa, 0.05KPa, 0.1KPa, 0.5KPa, 1KPa, 2KPa, 3KPa, 4KPa, or 4.5KPa.
Optionally, the upper temperature limit is selected from 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, or 70 ℃; the lower limit is selected from 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or 65 ℃.
Alternatively, in the reduced pressure distillation process, the upper time limit of the reduced pressure distillation operation is selected from 0.6 hours, 0.8 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours; the lower limit is selected from 2.5 hours, 2 hours, 1.5 hours, 1 hour, 0.8 hours, 0.6 hours or 0.5 hours.
Optionally, the method comprises:
a) Mixing the fructose solution with the catalyst and the adsorbent, and reacting in a stirring state, wherein the reaction temperature is 20-140 ℃ and the reaction time is 1-12 hours;
b) And c), extracting the solution obtained after the reaction in the step a) with methyl isobutyl ketone, ethyl acetate or dimethyl carbonate for a plurality of times, and carrying out reduced pressure distillation on the extract. Controlling the vacuum degree of the system at 0.01-5 KPa, the reaction temperature at 30-70 ℃, and the reduced pressure distillation operation time at 0.5-3 hours, thus obtaining the product 5-hydroxymethylfurfural.
As a specific embodiment, the method comprises:
1) The fructose and the catalyst are uniformly mixed in a batch kettle reactor, and the reaction is carried out in a stirring state, wherein the reaction temperature is 20-140 ℃ and the reaction time is 1-12 hours.
2) And (3) taking a small amount of the solution obtained after the reaction in the step (1) to fix the volume, and then carrying out liquid chromatography analysis to determine the yield of the 5-hydroxymethylfurfural, wherein the yield of the 5-hydroxymethylfurfural is more than 80%. Adding methyl isobutyl ketone, ethyl acetate or dimethyl carbonate into the reacted solution for multiple extraction operations, wherein the extraction times are 3-5 times, carrying out reduced pressure distillation on the extract to obtain the product 5-hydroxymethylfurfural, connecting a water pump or an oil pump to the device for reduced pressure distillation, controlling the vacuum degree of the system to be 0.01-5 KPa, and the reduced pressure distillation temperature to be 30-70 ℃ and the reduced pressure distillation operation time to be 0.5-3 hours.
The beneficial effects that this application can produce include:
1) The application provides a preparation method of 5-hydroxymethylfurfural. Compared with the traditional method, the preparation process of the invention realizes the efficient conversion of fructose under the condition of low acid content by introducing the adsorbent, can effectively control the further reaction of 5-hydroxymethylfurfural, avoids the generation of humins, improves the selectivity of the reaction and greatly reduces the cost.
2) The system for synthesizing the 5-hydroxymethylfurfural, which is used in the method, has larger economic benefit, lower system cost, reduced acid consumption in the reaction, simple operation, easy repetition and environmental protection, and can efficiently produce the high-purity 5-hydroxymethylfurfural.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of the product synthesized in example 1 of the present application;
FIG. 2 is a hydrogen nuclear magnetic spectrum of a 5-hydroxymethylfurfural standard;
FIG. 3 is a carbon nuclear magnetic spectrum of the product synthesized in example 1 of the present application;
FIG. 4 is a carbon nuclear magnetic spectrum of a 5-hydroxymethylfurfural standard.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analytical method in the examples of the present application is as follows:
the reaction solid was dissolved in deuterated reagent by performing carbon and hydrogen nuclear magnetic resonance spectroscopy using a liquid nuclear magnetic resonance apparatus manufactured by bruck, model number AVANCE II 400M.
In the examples of the present application, the yield of 5-hydroxymethylfurfural was calculated by:
obtaining a liquid chromatography peak area by configuring the content of 5-hydroxymethylfurfural in a standard solution, and obtaining a standard curve by taking the peak area as an abscissa and the concentration of 5-hydroxymethylfurfural as an ordinate; further, the concentration of 5-hydroxymethylfurfural in the solution after the reaction can be calculated, and the yield of 5-hydroxymethylfurfural is calculated through the concentration.
According to one embodiment of the present application, the method for preparing 5-hydroxymethylfurfural comprises the steps of:
a) The fructose solution, the catalyst and the adsorbent are uniformly mixed in a batch kettle reactor, and the mixture is reacted in a stirring state, wherein the reaction temperature is 20-140 ℃, and the reaction time is 1-12 hours.
b) And c) taking a small amount of the solution obtained after the reaction in the step a), and carrying out liquid chromatography analysis to calculate the yield of the 5-hydroxymethylfurfural, wherein the yield of the 5-hydroxymethylfurfural is more than 80%. Adding methyl isobutyl ketone, ethyl acetate or dimethyl carbonate into the reacted product for multiple extraction operations, wherein the extraction times are 3-5 times, obtaining the product 5-hydroxymethylfurfural by adopting reduced pressure distillation operation of extract liquid, connecting a water pump or an oil pump to the device for reduced pressure distillation, controlling the vacuum degree of the system to be 0.01-5 KPa, controlling the reduced pressure distillation temperature to be 30-70 ℃, and controlling the reduced pressure distillation operation time to be 0.5-3 hours.
The solvent in the step a) is at least one selected from water, ethanol and ionic liquid, and the mass ratio of the fructose to the solvent is 1:0.8-20;
the catalyst in the step a) comprises at least one of B acid such as phosphoric acid, hydrochloric acid, sulfuric acid, boric acid, methane sulfonic acid and sulfonic ionic liquid, wherein the mass ratio of fructose to the catalyst is that: catalyst=1:0.01 to 50;
the adsorbent in the step a) is a porous material without catalytic performance for catalyzing the reaction;
the adsorbent in the step a) is at least one of porous materials such as molecular sieves, metal organic framework materials, ion exchange resins, carbon materials, silicon materials, oxide materials and the like, and the mass ratio of the adsorbent to the fructose is 1:0.01-10;
the reaction conditions in step a) are: the reaction temperature is 20-140 ℃ and the reaction time is 1-12 hours;
and b) taking a certain amount of reacted solution after the reaction in the step b), adding deionized water, mixing to a certain volume, and detecting the yield of the 5-hydroxymethylfurfural.
And b) adding methyl isobutyl ketone, ethyl acetate or dimethyl carbonate into the solution obtained after the reaction in the step b) for extraction operation. After shaking, standing, layering the solution, separating out an extract containing 5-hydroxymethylfurfural, adding an extractant again into the rest lower solution, extracting, and repeating the operation for a plurality of times.
The volume ratio of the extractant to the reaction liquid in the step b) is 1-5:1.
The number of repeated operation processes of the extraction in the step b) is 3 to 5.
And b) recovering the extractant for extraction by a reduced pressure distillation method of the upper layer extract liquid in the step b), and simultaneously obtaining the product 5-hydroxymethylfurfural.
The conditions for the reduced pressure distillation in step b) include: and under the condition of vacuum degree of 0.01-5 KPa, the temperature is 30-70 ℃, and the pressure is reduced for 0.5-3 hours.
Example 1
5g of fructose, 5g of water, 5g of boric acid and 1g of NaY molecular sieve are added into a batch kettle reactor, the temperature is raised to 100 ℃, the reaction time is 6 hours, and the color of a reaction system is gradually increased. After the reaction, a small amount of solution is taken for high performance liquid chromatography analysis, and the result shows that the yield of the 5-hydroxymethylfurfural is 86%. And adding dimethyl carbonate (the mass ratio of the dimethyl carbonate to the solution is 3:1) into the solution after the reaction to perform multiple extraction operations, wherein the extraction times are 3 times, obtaining an extract after the extraction is completed, connecting the device with a water pump to perform reduced pressure distillation, controlling the vacuum degree of the system at 1KPa, and performing reduced pressure distillation at 40 ℃ for 2 hours, wherein the purity of the obtained 5-hydroxymethylfurfural is 96%.
Example 2
10g of fructose, 20g of water, 1g of sulfuric acid and 1g of ZSM-5 molecular sieve are added into a batch kettle reactor, the temperature is raised to 140 ℃ under the stirring state, the reaction time is 8 hours, and the color of a reaction system is gradually deepened. After the reaction, a small amount of solution was analyzed by high performance liquid chromatography, and the result showed that the yield of 5-hydroxymethylfurfural was 91%. Ethyl acetate (the mass ratio of ethyl acetate to reaction solid is 2:1) is added into the reaction solution for multiple extraction operations, the extraction times are 4 times, an extraction liquid is obtained after the extraction is completed, the device is connected with a water pump for reduced pressure distillation, the vacuum degree of the system is controlled at 0.5KPa, the reduced pressure distillation temperature is 35 ℃, the reduced pressure distillation operation time is 2 hours, and the purity of the obtained 5-hydroxymethylfurfural is 95%.
Example 3
8g of fructose, 16g of absolute ethyl alcohol, 1g of hydrochloric acid and 1g of metal organic framework material MIL-125 are added into a batch kettle reactor, the temperature is raised to 120 ℃ under the stirring state, the reaction time is 5 hours, and the color of a reaction system is gradually deepened. And after the reaction is finished, a small amount of the mixture is taken for high performance liquid chromatography analysis, the result shows that the yield of the 5-hydroxymethylfurfural is 87 percent, methyl isobutyl ketone (the mass ratio of the methyl isobutyl ketone to the reaction solution is 3:1) is added into the reaction solution for multiple extraction operations, the extraction times are 5 times, an extraction liquid is obtained after the extraction is finished, the device is connected with a water pump for reduced pressure distillation, the vacuum degree of the system is controlled at 3KPa, the reduced pressure distillation temperature is 70 ℃, the reduced pressure distillation operation time is 3 hours, and the purity of the obtained 5-hydroxymethylfurfural is 96 percent.
Examples 4 to 13
The specific ingredients, materials and reaction conditions are shown in Table 1, and the other operations in the synthesis process are the same as in example 1.
Table 1 raw material compositions, proportions and reduced pressure distillation conditions of examples 4 to 13
EXAMPLE 14 liquid Nuclear magnetic resonance analysis
Liquid nuclear magnetic resonance analysis was performed on the 5-hydroxymethylfurfural prepared in examples 1 to 13, and typical examples are shown in fig. 1 and 3, and fig. 2 and 4 are standard spectra of 5-hydroxymethylfurfural. Fig. 1 corresponds to the hydrogen nuclear magnetic resonance spectrum of 5-hydroxymethylfurfural prepared in example 1, and it can be seen from a comparison of fig. 1 and fig. 2 that the 5-hydroxymethylfurfural prepared in example 1 has a typical standard hydrogen nuclear magnetic spectrum of 5-hydroxymethylfurfural.
FIG. 3 corresponds to the carbon nuclear magnetic resonance spectrum of 5-hydroxymethylfurfural prepared in example 1. As can be seen from a comparison of FIGS. 3 and 4, the carbon nuclear magnetic spectrum of 5-hydroxymethylfurfural prepared in example 1 has typical standard 5-hydroxymethylfurfural.
The test results for 5-hydroxymethylfurfural in other examples were similar to those described above, and standard 5-hydroxymethylfurfural was obtained by the present invention.
Comparative example 1
10g of fructose, 10g of water and 1g of boric acid are added into a batch kettle reactor, the temperature is raised to 140 ℃ under the stirring state, the reaction time is 8 hours, and a large amount of solid humins appear in the reaction system. After the reaction, a small amount of the obtained product was analyzed by high performance liquid chromatography, and the result showed that the yield of 5-hydroxymethylfurfural was 30%. Adding ethyl acetate (the mass ratio of the ethyl acetate to the reaction solid is 2:1) into the reaction solid for multiple extraction operations, wherein the extraction times are 3 times, obtaining an extract after the extraction is completed, connecting the device with a water pump for reduced pressure distillation, controlling the vacuum degree of the system at 0.5KPa, and obtaining less 5-hydroxymethylfurfural after the reduced pressure distillation at 35 ℃ and the reduced pressure distillation operation time of 2 hours. By contrast, 10g of fructose, 10g of water, 1g of boric acid and 1g of nay molecular sieve were added to a batch kettle reactor, and the same procedure was followed to obtain a yield of 5-hydroxymethylfurfural of 85% and a purity of 97%.
Comparative example 2
10g of fructose, 10g of ethanol and 2g of phosphoric acid are added into a batch kettle reactor, the temperature is raised to 120 ℃ under the stirring state, the reaction time is 6 hours, and a large amount of solid humins appear in the reaction system. After the reaction, a small amount of the obtained product was analyzed by high performance liquid chromatography, and the result showed that the yield of 5-hydroxymethylfurfural was 20%. Adding ethyl acetate (the mass ratio of the ethyl acetate to the reaction solid is 2:1) into the reaction solid for multiple extraction operations, wherein the extraction times are 3 times, obtaining an extract after the extraction is completed, connecting the device with a water pump for reduced pressure distillation, controlling the vacuum degree of the system at 0.5KPa, and obtaining less 5-hydroxymethylfurfural after the reduced pressure distillation at 35 ℃ and the reduced pressure distillation operation time of 2 hours. By contrast, 10g of fructose, 10g of ethanol, 2g of phosphoric acid and 1g of alumina were added to a batch kettle reactor, and the same procedure was followed to obtain 78% yield of 5-hydroxymethylfurfural with 96% purity.
Comparative example 3
8g of fructose, 20g of water and 1g of methane sulfonic acid are added into a batch kettle reactor, the temperature is raised to 100 ℃ under the stirring state, the reaction time is 8 hours, and the color of a reaction system is unchanged. After the reaction, a small amount of the obtained product was analyzed by high performance liquid chromatography, and the result showed that the yield of 5-hydroxymethylfurfural was 50%. Ethyl acetate (the mass ratio of the ethyl acetate to the reaction solid is 2:1) is added into the reaction solid to carry out multiple extraction operations, the extraction times are 3 times, an extraction liquid is obtained after the extraction is completed, the device is connected with a water pump to carry out reduced pressure distillation, the vacuum degree of the system is controlled at 0.5KPa, the reduced pressure distillation temperature is 35 ℃, and the reduced pressure distillation operation time is 2 hours, so that a small amount of 5-hydroxymethylfurfural is obtained. By contrast, 8g of fructose, 20g of water, 1g of methanesulfonic acid and 1g of NaX molecular sieve were charged into a batch-type reactor, and the same procedure was carried out to obtain 89% yield of 5-hydroxymethylfurfural and 98% purity.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. A method for preparing 5-hydroxymethylfurfural based on an adsorption catalytic system, which is characterized by comprising the following steps:
reacting a solution containing fructose, a catalyst and an adsorbent to obtain 5-hydroxymethylfurfural;
the catalyst comprises an acid B dissolved in a solvent;
the adsorbent comprises a porous material;
the mass ratio of the catalyst to the fructose is 0.01-1:0.1-10;
the mass ratio of the adsorbent to the fructose is 0.01-1:0.1-10.
2. The method according to claim 1, wherein the solvent of the solution is selected from at least one of water, ethanol, ionic liquid;
preferably, the solvent is an ionic liquid;
preferably, the ionic liquid is selected from [ Bmim ]][BF 4 ]、[Emim]Cl、[Emim]Br、[Emim][CF 3 SO 4 ]At least one of them.
3. The method according to claim 1, wherein the mass ratio of fructose to solvent in the solution is 0.1-10:1-20;
preferably, the mass ratio of the fructose to the solvent is 1:1-5;
preferably, the mass ratio of the catalyst to the fructose is 0.01-0.1:1;
preferably, the mass ratio of the adsorbent to the fructose is 0.1-1:1.
4. The method of claim 1, wherein the B acid is selected from at least one of phosphoric acid, hydrochloric acid, sulfuric acid, boric acid, methane sulfonic acid, sulfonic acid-based ionic liquids.
5. The method of claim 1, wherein the porous material is selected from at least one of molecular sieves, metal organic framework materials, ion exchange resins, carbon materials, silicon materials, oxide materials;
preferably, the porosity of the porous material is more than 60%, the pore size distribution comprises micropores, mesopores and macropores, and the BET specific surface area is between 100 and 5000m 2 /g。
6. The method of claim 5, wherein the molecular sieve is selected from at least one of MCM-41, X molecular sieve, Y molecular sieve, beta molecular sieve;
preferably, the metal organic framework material is selected from at least one of MOF-5, MOF-74, MIL-101, MIL-125;
preferably, the ion exchange resin is a sodium ion exchange resin;
preferably, the carbon material is at least one selected from activated carbon, graphene, nanocarbon sol and carbon nanotubes;
preferably, the silicon material is at least one selected from white carbon black, silica gel and nano silicon material;
preferably, the oxide material is selected from alumina.
7. The method of claim 1, wherein the reaction conditions comprise: the reaction temperature is 20-140 ℃ and the reaction time is 1-12 hours.
8. The method according to claim 1, characterized in that after the end of the reaction, a purification is also carried out, said purification comprising the steps of: and (3) adding an extractant into the solution for extraction to obtain an extract, and carrying out reduced pressure distillation on the extract to obtain the 5-hydroxymethylfurfural.
9. The method of claim 8, wherein the extractant comprises at least one of methyl isobutyl ketone, ethyl acetate, and dimethyl carbonate;
preferably, the number of times of extraction is 3 to 5;
preferably, the conditions of the reduced pressure distillation include: the vacuum degree is 0.01-5 KPa, the temperature is 30-70 ℃ and the time is 0.5-3 hours.
10. The process according to any one of claims 1 to 9, characterized in that the yield of 5-hydroxymethylfurfural is greater than 80%.
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