CN111995602A - Method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose - Google Patents
Method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose Download PDFInfo
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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 73
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000005715 Fructose Substances 0.000 title claims abstract description 45
- 229930091371 Fructose Natural products 0.000 title claims abstract description 45
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 10
- 239000011347 resin Substances 0.000 title claims abstract description 10
- 229920005989 resin Polymers 0.000 title claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 22
- 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 abstract description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 15
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 15
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 230000003113 alkalizing effect Effects 0.000 claims description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 9
- 238000006297 dehydration reaction Methods 0.000 abstract description 7
- 230000018044 dehydration Effects 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 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 9
- 239000008103 glucose Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011636 chromium(III) chloride Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 1
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- YPJJABHAGGFGAM-UHFFFAOYSA-M lithium;n,n-dimethylacetamide;chloride Chemical compound [Li+].[Cl-].CN(C)C(C)=O YPJJABHAGGFGAM-UHFFFAOYSA-M 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- 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 relates to the field of biomass energy conversion, and discloses a method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose, which comprises the following steps: 1) putting fructose and a solvent into a reactor, adding a sulfonic acid type ion exchange resin catalyst, heating for reaction, and cooling to obtain a reaction solution containing 5-hydroxymethylfurfural; 2) and adding sodium bisulfite into the reaction solution for reaction, cooling until solid salt is separated out, separating the solid salt, and performing alkalization treatment to obtain the 5-hydroxymethylfurfural. The invention uses the strongly acidic sulfonic acid type ion exchange resin as a catalyst in the reaction of preparing 5-hydroxymethylfurfural (5-HMF) by fructose dehydration, and then is matched with the combination of sodium bisulfite and alkalization treatment, so that the defects of more byproducts, low selectivity of 5-HMF, poor catalyst stability, difficulty in separation and purification and the like in the prior art can be overcome, the yield and the selectivity of 5-HMF are improved, the product separation is promoted, and the energy consumption is reduced.
Description
Technical Field
The invention relates to the field of biomass energy conversion, in particular to a method for synthesizing 5-hydroxymethylfurfural by utilizing fructose under the catalysis of acidic resin.
Background
5-hydroxymethylfurfural (5-HMF) is an important platform molecule for converting biomass into liquid fuels and chemicals, has very active chemical properties, and can be subjected to esterification, addition, reduction, halogenation, hydrolysis and the like to obtain a series of important chemical products. For example, 2, 5-diformylfuran obtained by oxidation can be used as a pharmaceutical intermediate, a polymer precursor and an antibacterial agent; the liquid fuel 2, 5-dimethylfuran with high octane number and high boiling point can be obtained by catalytic reduction; important chemicals such as levulinic acid and formic acid can be obtained through hydrolysis; can also be condensed with acetone and then further hydrogenated to obtain gasoline and diesel oil; the 2, 5-furandicarboxylic acid obtained by catalytic oxidation is considered to have the potential of replacing the polyester monomer terephthalic acid, and is listed as one of 12 bio-based platform compounds by the U.S. department of energy.
Through extensive literature research and experimental demonstration, it can be found that the carbohydrates for preparing 5-HMF mainly comprise three main types of cellulose, glucose and fructose:
(1) the synthesis of 5-HMF from cellulose is the goal in the industry and academia, however, the conventional aqueous phase or organic phase reaction system is difficult to react with high efficiency, and the adopted process has the problems of low yield, more byproducts, harsh reaction conditions and the like. For example, Li and the like improve the degradation rate of cellulose in ionic liquid by using a microwave heating mode, and CrCl3The yield of 5-HMF can reach 42% by heating with 400W of microwave, but the reaction condition is harsh and needs to use a large amount of expensive ionic liquid. Su subject group is CuCl2-CrCl2As catalyst, ionic liquid chloridizes 1-ethyl-3-methylimidazole [ EMIM]Cl is used as a solvent, and the conversion of cellulose into 5-HMF under mild conditions can be realizedBut only 35% yield. Binder et al reported DMA-LiCl/[ EMIM]Cl (DMA is dimethylacetamide) is used as a solvent, untreated cornstalks are used as raw materials, and the content of the raw materials is 10 percent CrCl3And 10 percent hydrochloric acid mixed acid for 2 hours at 140 ℃ under the catalysis of the catalyst, the yield of the 5-HMF can reach 48 percent, but a large amount of expensive solvent is still needed.
(2) The use of glucose as a substrate ensures the economy of the starting material and the availability of sufficient source, but the yield of 5-HMF obtained is generally low and the reaction is difficult. When Takagaki et al research on the preparation of 5-HMF by catalyzing glucose through combination of solid base and solid acid, the fact that glucose needs to be isomerized into fructose first and then dehydrated to obtain 5-HMF is found, the conversion rate of glucose is 60%, the yield of HMF is 46%, the reaction conditions are harsh, and the yield is low. SO for Yan et al4 2-/ZrO2And SO4 2-/ZrO2-Al2O35-HMF was prepared by catalytic conversion of glucose, and when the Zr/A1 molar ratio was 1, a solution of 7.6 wt% glucose in dimethyl sulfoxide (DMSO) was reacted at 130 ℃ for 4h to give only a 48% yield of 5-HMF.
(3) Fructose can be converted to 5-HMF easily and in high yield compared to biomass such as glucose, starch, cellulose and the like. In 2011, Wang and the like use a novel sulfonated carbon material to catalyze fructose to dehydrate to prepare 5-HMF, DMSO is used as a solvent in the reaction, the reaction is carried out at 130 ℃ for 1.5h, and the yield of the 5-HMF is as high as 91%. Bicker et al studied the catalytic process of dehydration of fructose to 5-HMF in subcritical or supercritical acetone-water mixed systems and found that in supercritical acetone-water (V/V ═ 9: 1) mixed systems, the 5-HMF selectivity was 77% and the fructose conversion was 99%. In conclusion, compared with other biomasses, the fructose can synthesize the 5-HMF more efficiently and has moderate price, so that the preparation of the 5-HMF by taking the fructose as the raw material is still the synthesis path with the most industrial prospect at present.
From the perspective of the catalyst, the soluble inorganic acid and inorganic salt catalyst has high dehydration activity for catalyzing carbohydrate, but the catalyst is not easy to separate from the product after the reaction, and the reaction process has the problems of large equipment corrosivity, serious environmental pollution and the like. In 2007, Zhao et al studied CrCl2In ionic liquids [ EMIM]Process for preparing 5-HMF by efficiently catalyzing glucose dehydration in Cl, 5The yield of HMF is about 70%, but the catalyst is difficult to separate from the product. In 2010, Thomas B and the like take fructose as a raw material and sulfuric acid as a catalyst, and react in a DMSO system for 15 hours at 150 ℃ to obtain 99% of yield of 5-HMF, but the sulfuric acid as the catalyst is high in equipment corrosion and is not environment-friendly. Compared with homogeneous catalysts, solid acids such as molecular sieves, heteropolyacids and the like have weaker catalytic effect, but the problem of catalyst recovery can be well solved. Li using D001-C resin as catalyst, [ BMIM]Cl is used as a solvent, the reaction for synthesizing 5-HMF by fructose dehydration is studied, and the yield of 5-HMF reaches 61%, so that the search for a proper recyclable heterogeneous catalyst is very important. From the perspective of solvents, the current solvent systems are mainly divided into two types, namely single-phase and two-phase, water is used as a reaction solvent, substrate conversion is easy to realize due to the relatively good solubility of saccharides in water, while 5-HMF is easy to decompose in pure water, and high selectivity of 5-HMF cannot be obtained by using water as a single-phase solvent. Therefore, researchers have tried to use a two-phase system, and ideally, the organic solvent should be selected from a solvent with a lower boiling point, so as to combine the advantages of the respective reactions under the conditions of the aqueous phase and the organic solvent, and to achieve efficient preparation of 5-HMF.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for synthesizing 5-hydroxymethylfurfural by catalyzing fructose with acidic resin, which uses sulfonic acid type ion exchange resin with strong acidity as a catalyst in the reaction of preparing 5-hydroxymethylfurfural (5-HMF) by dehydrating fructose, and then is matched with the combination of sodium bisulfite and alkalization treatment, so that the defects of more byproducts, low selectivity of 5-HMF, poor stability of the catalyst, difficulty in separation and purification and the like in the prior art can be overcome, the yield and the selectivity of 5-HMF are improved, the product separation is promoted, and the energy consumption is reduced.
The specific technical scheme of the invention is as follows: a method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose comprises the following steps:
1) putting fructose and a solvent into a reactor, adding sulfonic acid type ion exchange resin as a catalyst, heating for reaction, and cooling to obtain a reaction solution containing 5-hydroxymethylfurfural.
2) Adding sodium bisulfite into the reaction solution for reaction, cooling until solid salt is separated out, separating the solid salt, and then alkalizing the solid salt to convert the solid salt into 5-hydroxymethylfurfural again to obtain the 5-hydroxymethylfurfural.
The key points of the method of the invention are as follows:
(1) in the prior art, sulfonic acid type ion exchange resin is used as a catalyst for esterification reaction, but the sulfonic acid type ion exchange resin is not used as a catalyst for fructose dehydration reaction. The invention adopts the solid resin which is easy to separate after the reaction as the catalyst, and can avoid the problems of complex subsequent treatment, difficult product separation, serious equipment corrosion, large amount of industrial wastewater discharge and the like of the conventional acid catalyst. In addition, the catalyst shows good heat-resistant stability and high-efficiency catalytic activity (the molar reaction yield is up to 95%) in the reaction for preparing 5-HMF, and meanwhile, the reaction condition is mild, and the production cost can be saved.
(2) The invention skillfully adopts the combination of sodium bisulfite and alkalization treatment, firstly converts the reaction product into solid through salification, and then recovers the solid after separation, thereby further solving the problem that the reaction product is difficult to be separated subsequently.
Preferably, in step 1), the catalyst is used in an amount of 50 to 300wt% based on fructose.
Preferably, in step 1), the amount of the catalyst is 200wt% to 100 wt% of fructose.
Preferably, in step 1), the solvent is a mixed solvent of one or more of tetrahydrofuran, methyltetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and gamma-valerolactone and water.
Further preferably, in step 1), the solvent is a mixed solvent of water and at least one of tetrahydrofuran and dimethyl sulfoxide.
Preferably, in the step 1), the mass ratio of the fructose to the solvent is 1: 1-20.
Preferably, in the step 1), the reaction temperature is 110-140 ℃, and the reaction time is 10-40 min.
Preferably, in step 2), the sodium bisulfite is added until it is saturated in the reaction solution.
Preferably, in step 2), the alkalization treatment is adding sodium hydroxide.
The reaction conditions in the above steps have a significant influence on the reaction yield, and therefore, strict control is required.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses the strongly acidic sulfonic acid type ion exchange resin as a catalyst in the reaction of preparing 5-hydroxymethylfurfural (5-HMF) by fructose dehydration, and then is matched with the combination of sodium bisulfite and alkalization treatment, so that the defects of more byproducts, low selectivity of 5-HMF, poor catalyst stability, difficulty in separation and purification and the like in the prior art can be overcome, the yield and the selectivity of 5-HMF are improved, the product separation is promoted, and the energy consumption is reduced. The reaction yield of the invention can reach more than 95 percent, and the yield of the 5-HMF pure product after separation can reach more than 76 percent.
Drawings
FIG. 1 is a graph of the effect of different solvents and on the yield of 5-HMF for examples 2-6;
FIG. 2 is a graph showing the effect of solvent amounts on 5-HMF yield for examples 10-12;
FIG. 3 is a graph of the effect of reaction time on the yield of 5-HMF for examples 13-18.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose comprises the following steps:
1) putting fructose and a solvent into a reactor, adding sulfonic acid type ion exchange resin as a catalyst, heating at 110-140 ℃ for reaction for 10-40min, and cooling to obtain a reaction solution containing 5-hydroxymethylfurfural. Wherein the amount of the catalyst is 50-300wt%, preferably 100-200wt% of the fructose. The mass ratio of the fructose to the solvent is 1: 1-20. The solvent is a mixed solvent of one or more of tetrahydrofuran, methyltetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and gamma-valerolactone and water. Further preferably, the solvent is a mixed solvent of water and at least one of tetrahydrofuran and dimethyl sulfoxide. The reaction formula of step 1) is as follows:
2) adding sodium bisulfite into the reaction solution until the reaction solution is saturated, reacting, cooling until solid salt is separated out, separating the solid salt, and alkalizing the solid salt (sodium hydroxide) to convert the solid salt into 5-hydroxymethylfurfural again to obtain the 5-hydroxymethylfurfural. The reaction formula of step 2) is as follows:
the composition of the reaction solution and the purity of related products are analyzed by high performance liquid chromatography, an Agilent TC-C18 chromatographic column is adopted, the constant detection column temperature is 30 ℃, a mobile phase adopts 80/20 volume ratio methanol aqueous solution, and an ultraviolet detector collects signals at the position of 283nm in wavelength.
And (3) quantitatively analyzing the product by adopting an external standard method, preparing standard solutions with different concentrations corresponding to various product standard samples, and measuring the peak area of the liquid chromatogram. A standard curve is drawn as the relationship between concentration and peak area.
Example 1
Preparation of 5-HMF: a50 mL reaction vessel was charged with fructose (1g), distilled water (1g), and tetrahydrofuran (9g) sulfonic acid type ion exchange resin (0.5g), reacted at 130 ℃ under normal pressure for 30min, and cooled to room temperature, giving a liquid-phase detection yield of 65%. And adding sodium bisulfite into the reaction solution until the reaction solution is saturated and an addition reaction occurs, cooling to separate out solids, and releasing 5-hydroxymethylfurfural again through alkalization treatment (adding sodium hydroxide) to obtain pure 5-HMF. The final product yield was 52%.
Examples 2 to 6
Experimental procedures were carried out in the same manner as in example 1 (experimental conditions: fructose 1g, distilled water 1g, solvent 9g, sulfonic acid type ion exchange resin catalyst 0.5g, reaction temperature 130 ℃ C., reaction time 30min), except for the kind of solvent to be added. FIG. 1 shows different solvents and the effect on the yield of 5-HMF.
Examples 7 to 9
Experimental procedures were carried out in the same manner as in example 1 (experimental conditions: fructose 1g, distilled water 1g, DMSO 9g, sulfonic acid type ion exchange resin as a catalyst, reaction temperature 130 ℃ C., reaction time 30min), except that the amount of the catalyst to be added was changed. The following table shows the effect of catalyst amount on 5-HMF yield
| Examples | DMSO(g) | Amount of catalyst (g) | Reaction yield (%) | Final yield (%) |
| 3 | 9 | 0.5 | 85 | 68 |
| 7 | 9 | 1 | 95 | 76 |
| 8 | 9 | 2 | 92 | 74 |
| 9 | 9 | 3 | 91 | 73 |
Examples 10 to 12
Experimental procedure was carried out in the same manner as in example 1 (experimental conditions: fructose 1g, distilled water 1g, DMSO as a solvent, catalyst 1g, reaction temperature 130 ℃ C., reaction time 30 min). Except for the amount of DMSO solvent added. FIG. 2 is a graph showing the effect of solvent content on 5-HMF yield.
Examples 13 to 18
Experimental other procedures were the same as in example 1 (experimental conditions: fructose 1g, distilled water 1g, solvent DMSO 9g, catalyst 1g, reaction temperature 130 ℃ C.), except that the reaction time was changed, and FIG. 3 shows the influence of the reaction time on the yield of 5-HMF.
Example 19
Dropwise adding and feeding in a 500ml reaction kettle: tetrahydrofuran (250g) and 10g of sulfonic acid type ion exchange resin are added into a 500mL reaction kettle, 50g of aqueous solution of fructose and water in a ratio of 1:1 is prepared in advance, the aqueous solution of the fructose enters the 500mL reaction kettle system by a plunger pump, the feeding speed is 5g/min, the reaction is carried out for 40min at the temperature of 110 ℃ under normal pressure, the reaction is cooled to the room temperature, and the liquid phase detection yield is 55%. Adding a proper amount of sodium bisulfite into the reaction solution to carry out addition reaction, cooling to separate out solid, and then carrying out alkalization treatment to release 5-hydroxymethylfurfural again, wherein the final yield is 44%.
Example 20
Dropwise adding and feeding in a 500ml reaction kettle: tetrahydrofuran (250g) and 10g of sulfonic acid type ion exchange resin are added into a 500mL reaction kettle, 50g of aqueous solution of fructose and water in a ratio of 1:1 is prepared in advance, the aqueous solution of the fructose enters the 500mL reaction kettle system by a plunger pump, the feeding speed is 4g/min, the reaction is carried out for 40min at the temperature of 110 ℃ under normal pressure, the reaction is cooled to the room temperature, and the liquid phase detection yield is 65%. Adding a proper amount of sodium bisulfite into the reaction solution to carry out addition reaction, cooling to separate out solid, and then carrying out alkalization treatment to release 5-hydroxymethylfurfural again, wherein the final yield is 52%.
Example 21
Dropwise adding and feeding in a 500ml reaction kettle: tetrahydrofuran (250g) and 10g of sulfonic acid type ion exchange resin are added into a 500mL reaction kettle, 50g of aqueous solution of fructose and water in a ratio of 1:1 is prepared in advance, the aqueous solution of the fructose enters the 500mL reaction kettle system by a plunger pump, the feeding speed is 2g/min, the reaction is carried out for 40min at the temperature of 110 ℃ under normal pressure, the reaction is cooled to the room temperature, and the liquid phase detection yield is 40%. Adding a proper amount of sodium bisulfite into the reaction solution to carry out addition reaction, cooling to separate out solid, and then carrying out alkalization treatment to release 5-hydroxymethylfurfural again, wherein the final yield is 32%.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose is characterized by comprising the following steps:
1) putting fructose and a solvent into a reactor, adding sulfonic acid type ion exchange resin as a catalyst, heating for reaction, and cooling to obtain a reaction solution containing 5-hydroxymethylfurfural;
2) adding sodium bisulfite into the reaction solution for reaction, cooling until solid salt is separated out, separating the solid salt, and then alkalizing the solid salt to convert the solid salt into 5-hydroxymethylfurfural again to obtain the 5-hydroxymethylfurfural.
2. The method of claim 1, wherein in step 1), the catalyst is used in an amount of 50 to 300wt% of the fructose.
3. The method as claimed in claim 2, wherein the catalyst is used in an amount of 100-200wt% based on the fructose in step 1).
4. The method according to claim 1, wherein in step 1), the solvent is a mixed solvent of one or more of tetrahydrofuran, methyltetrahydrofuran, dimethylsulfoxide, N-dimethylformamide and γ -valerolactone with water.
5. The method according to claim 4, wherein in step 1), the solvent is a mixed solvent of water and at least one of tetrahydrofuran and dimethylsulfoxide.
6. The method according to claim 1, wherein in the step 1), the mass ratio of the fructose to the solvent is 1: 1-20.
7. The method as claimed in claim 1, wherein the reaction temperature in step 1) is 110-140 ℃ and the reaction time is 10-40 min.
8. The method according to claim 1, wherein the sodium hydrogen sulfite is added in step 2) until it is saturated in the reaction solution.
9. The method as claimed in claim 1 or 8, wherein in step 2), the alkalization treatment is addition of sodium hydroxide.
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| CN113234043A (en) * | 2021-04-26 | 2021-08-10 | 浙江大学衢州研究院 | Preparation and separation method for preparing 5-hydroxymethylfurfural by fructose dehydration |
| CN113861139A (en) * | 2021-11-04 | 2021-12-31 | 浙江糖能科技有限公司 | Method for preparing 5-hydroxymethylfurfural |
| CN115785033A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Preparation method of 5-hydroxymethylfurfural |
| CN115894193A (en) * | 2021-09-30 | 2023-04-04 | 中国石油化工股份有限公司 | Method for decomposing hydroperoxide acid |
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