CN114456132A - Surfactant-promoted synthesis method of 5-hydroxymethylfurfural - Google Patents
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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 55
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 239000005715 Fructose Substances 0.000 claims abstract description 53
- 229930091371 Fructose Natural products 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 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims abstract description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims abstract description 4
- VUFOSBDICLTFMS-UHFFFAOYSA-M ethyl-hexadecyl-dimethylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)CC VUFOSBDICLTFMS-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 abstract description 21
- 239000006227 byproduct Substances 0.000 abstract description 12
- 239000002663 humin Substances 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 11
- 230000018044 dehydration Effects 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 150000007524 organic acids Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000005882 aldol condensation reaction Methods 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 229940040102 levulinic acid Drugs 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940115457 cetyldimethylethylammonium bromide Drugs 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- -1 small-molecule organic acids Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
Abstract
A synthesis method of 5-hydroxymethyl furfural promoted by a surfactant. Fructose is used as a raw material, 1, 4-dioxane and water are used as a mixed solvent, dodecyl trimethyl ammonium bromide, hexadecyl dimethyl ethyl ammonium bromide, octadecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium chloride are used as a surfactant, sulfuric acid is used as a catalyst, and 5-hydroxymethyl furfural is synthesized in a closed reactor with air removed. The method utilizes the surfactant to create a solvent microenvironment which is beneficial to fructose dehydration and timely removal of HMF, reduces the generation of byproducts such as micromolecular organic acid, humin and the like, and has high utilization rate of raw material carbon; the method is suitable for dehydration reaction of high-concentration fructose, and the synthesis efficiency of HMF is high; the HMF has high yield, few byproducts, easy separation and purification, low synthesis energy consumption and good industrial application prospect.
Description
Technical Field
The invention relates to a synthesis method of 5-hydroxymethyl furfural promoted by a surfactant.
Background
5-Hydroxymethylfurfural (HMF) is an important biomass-based platform chemical, and can be used as a raw material to prepare various fine chemicals, liquid fuels, polymer monomers, furan resins and other important downstream products through oxidation, hydrogenation, hydro-dehydration, aldol condensation, amination and other reactions, so that the product is known as a Sleeping huge person (Sleeping giant) in the field of sustainable chemistry, and large-scale production is not realized so far. The synthetic research thereof is receiving extensive and continuous attention from both academic and industrial fields.
HMF is typically prepared from fructose via an acid-catalyzed dehydration reaction. However, under the action of acid catalysts, this reaction often involves a number of side reactions (fig. 1), such as: fructose can be subjected to degradation condensation reaction to generate by-products of formic acid/acetic acid/levulinic acid and humins; ② fructose can be made into by-product humin by dehydration condensation reaction; ③ fructose can generate by-product lactic acid through inverse aldol condensation reaction; fructose can be subjected to isomerization reaction to generate glucose, and the glucose can be further subjected to inverse aldol condensation reaction to generate a byproduct of acetic acid; the product HMF can be subjected to hydration decomposition reaction to generate by-products formic acid and levulinic acid, and the latter can be further subjected to condensation reaction to generate humins. Therefore, in the reaction for preparing HMF by dehydrating fructose, besides the target product HMF, various small-molecule organic acids and soluble/insoluble humins are also generated, so that the utilization rate of raw material carbon is low, the yield and selectivity of HMF are low, the product is difficult to separate and purify, the energy consumption for producing HMF is high, and the HMF is expensive. This problem is even more pronounced as the fructose concentration used in the reaction process increases, severely limiting the large-scale production of HMF. From the present point of view, the small-scale production of HMF (300 tons/year) is only achieved at AVA biochemical company, switzerland. How to improve the yield and selectivity of HMF by inhibiting the generation of byproducts such as small-molecular organic acid and humins becomes a bottleneck problem limiting the large-scale production of HMF.
The solvent is one of the main factors affecting the HMF yield and selectivity. For example, fructose has good solubility in water, however, when water is used as a solvent for fructose dehydration reaction, under the action of a Bronsted acid catalyst, fructose can simultaneously undergo side reactions such as isomerization, retro-aldol condensation, dehydration condensation, degradation condensation and the like, and the product HMF can undergo a hydration decomposition side reaction and participate in the production of humin, so that the yield and selectivity of HMF are low, and the production of humin is very serious. Dimethyl sulfoxide (DMSO) is a well-known solvent suitable for dehydration of fructose, and as a polar aprotic solvent, it can stabilize HMF and reduce the reactivity of HMF to some extent, however, fructose still undergoes a degradation condensation reaction in DMSO under the action of a bronsted acid catalyst to generate by-products such as formic acid, levulinic acid and soluble humin. Further, a mixed solvent composed of water and a water-soluble organic solvent is often used for dehydration reaction of fructose. For example, Bicker et al, Green Chemistry 5(2003)280, reported dehydration of fructose in a 9:1 volume ratio acetone-water mixed solvent, with sulfuric acid as the catalyst, 10.0g/L fructose at 180 ℃ under 20MPa for 1 minute, with fructose conversion near 100%, HMF yield 77%, but with the formation of levulinic acid and other by-products. Svenningsen et al reported in ACS Catalysis 8(2018)5591 studies that the effect of water content in solvent on fructose dehydration reaction was observed, using sulfuric acid as catalyst, dimethyl sulfoxide and water as mixed solvent, 25.0g/L fructose was reacted at 105 ℃ for 30 minutes, and when the water content in solvent was 30 mol%, fructose conversion and HMF yield were about 73% and 57%, respectively; when the water content of the solvent is 80 mol%, the conversion rate of fructose and the yield of HMF are respectively reduced to 18% and 10%, and the water content is increased, so that the dehydration reaction rate is reduced, and the dehydration condensation of the fructose is promoted to generate a dimer, and the further conversion of the dimer generates humins.
However, despite the higher yield of HMF in the above report, the actual synthesis efficiency of HMF is low due to the lower concentration of fructose as the starting material. The research result shows that when the concentration of the fructose is increased to be more than 100.0g/L, the side reaction accompanied with the dehydration reaction of the fructose is aggravated, and the yield and the selectivity of the HMF are obviously reduced. For example, Gomes et al examined the effect of fructose concentration on HMF yield in Brazilian Journal of Chemical Engineering 32(2015)119, reacted at 180 ℃ for 10 minutes in a mixed solvent of water and acetone in a volume ratio of 1/1 and phosphoric acid as a catalyst, and when the fructose concentration was 25.0g/L, the conversion of fructose was 100% and the yield of HMF was 66%; when the fructose concentration is increased to 125.0g/L, the conversion rate of the fructose is 98%, and the yield of HMF is reduced to 55%. Liu et al, Industrial & Engineering Chemistry Research 59(2020)17218, reported dehydration of fructose in a mixed solvent of 1, 4-dioxane and water (1, 4-dioxane to water volume ratio of 95:5) with a highly sulfonated polyaniline as catalyst and 45.0g/L fructose at 140 ℃ for 60 minutes with fructose conversion and HMF yield of about 100% and 83%, respectively; while when the fructose concentration was increased to 400.0g/L, the fructose conversion and HMF yield were reduced to about 91% and 50%, respectively.
The microenvironment of the solvent can influence the reaction path and product selectivity of fructose dehydration by influencing the configuration and conformation of fructose, the interaction sites between fructose and catalyst, the stability of reaction intermediates and products, and the like. Surfactants contain both hydrophilic and lipophilic groups and are commonly used in the chemical industry as catalysts, solubilizers, dispersants, and the like. The method is characterized in that a surfactant is added into a mixed solvent consisting of water and an organic solvent, a micro-reactor can be formed by utilizing micelles formed by the surfactant in the solvent, fructose generates a dehydration reaction in an aqueous solution of the micro-reactor, and the generated HMF can be transferred into the organic solvent outside the micro-reactor, so that the dehydration reaction of the fructose and the real-time separation of the HMF are realized simultaneously, and the yield and the selectivity of the HMF are expected to be improved.
Disclosure of Invention
The invention aims to provide a surfactant-promoted 5-hydroxymethylfurfural synthesis method, which overcomes the defects of low utilization rate of raw material carbon, low HMF synthesis efficiency, high synthesis energy consumption and the like in the prior art.
The invention is characterized in that: the method comprises the steps of taking fructose as a raw material, taking 1, 4-dioxane and water as a mixed solvent, taking dodecyl trimethyl ammonium bromide, hexadecyl dimethyl ethyl ammonium bromide, octadecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium chloride as a surfactant, and taking sulfuric acid as a catalyst, and synthesizing the 5-hydroxymethylfurfural in a closed reactor with air removed. Wherein the concentration of fructose is 20.0-600.0 g/L, the volume ratio of 1, 4-dioxane to water is 80: 20-100: 0, the concentration of a surfactant is 5.0-45.0 g/L, the concentration of sulfuric acid is 1.0-10.0 g/L, the reaction temperature is 120-150 ℃, and the reaction time is 1-30 minutes.
In the invention, the concentration of fructose is preferably 100.0-500.0 g/L, the volume ratio of 1, 4-dioxane to water is preferably 90: 10-100: 0, the concentration of a surfactant is preferably 15.0-35.0 g/L, the concentration of a catalyst is preferably 2.0-5.0 g/L, the reaction temperature is preferably 140-150 ℃, the reaction time is preferably 10-20 minutes, and the surfactant is preferably octadecyl trimethyl ammonium bromide.
The invention has the characteristics that: firstly, a surfactant is utilized to create a solvent microenvironment which is beneficial to fructose dehydration and timely removal of HMF, the generation of byproducts such as small molecular organic acid and humin is reduced, and the utilization rate of raw material carbon is high; the system is suitable for dehydration reaction of high-concentration fructose, and the synthesis efficiency of HMF is high; and thirdly, the yield of HMF is high, the byproducts are few, the separation and purification are easy, and the synthesis energy consumption is low.
Drawings
FIG. 1 shows the side reaction pathways involved in the dehydration of fructose to 5-hydroxymethylfurfural.
Detailed Description
Example 1:
a magnetic stirrer, 500.0mg of fructose, 0.95mL of 1, 4-dioxane, 0.05mL of water, 5.0mg of cetyltrimethylammonium bromide (CTAB) and 2.0mg of H were sequentially added to a pressure-resistant tube2SO4The catalyst was purged with nitrogen for 3 minutes to remove air from the thick walled glass pressure tube. And (3) raising the temperature of the oil bath pot to 140 ℃, placing the oil bath pot into a pressure-resistant pipe after the temperature is constant, and stirring and heating the oil bath pot for reaction for 15 minutes under a closed condition. After the reaction was stopped, the reaction system was naturally cooled to room temperature, and the solution was taken out for HPLC analysis. The yield of HMF was 63.3%.
Examples 2 to 15:
the reaction was carried out according to the method of example 1, using fructose as substrate at various concentrations, with or without CTAB (5.0g/L), the reaction conditions and results being shown in Table 1.
TABLE 1
Examples 16 to 18:
the reaction was carried out according to the method of example 1 using 1, 4-dioxane and water as a mixed solvent in various volume ratios, and the reaction conditions and results are shown in Table 2.
TABLE 2
| Example number | V1, 4-dioxane:VWater (W) | HMF yield (%) |
| 16 | 80:20 | 35.2 |
| 17 | 90:10 | 58.6 |
| 18 | 1:0 | 58.1 |
Examples 19 to 27:
the reaction was carried out according to the procedure of example 1, using CTAB as additive in various concentrations, and the reaction conditions and results are shown in Table 3.
TABLE 3
| Example number | CTAB concentration (g/L) | HMF yield (%) |
| 19 | 0.0 | 47.0 |
| 20 | 10.0 | 64.6 |
| 21 | 15.0 | 67.2 |
| 22 | 20.0 | 67.8 |
| 23 | 25.0 | 70.3 |
| 24 | 30.0 | 68.1 |
| 25 | 35.0 | 67.2 |
| 26 | 40.0 | 66.7 |
| 27 | 45.0 | 66.1 |
Examples 28 to 31:
the reaction was carried out according to the procedure of example 23 using different concentrations of the catalyst, and the reaction conditions and results are shown in Table 4.
TABLE 4
| Example number | Catalyst concentration (g/L) | HMF yield (%) |
| 28 | 1.0 | 60.4 |
| 29 | 5.0 | 68.0 |
| 30 | 7.5 | 64.8 |
| 31 | 10.0 | 61.1 |
Examples 32 to 34:
the reaction was carried out according to the procedure of example 23, using different reaction temperatures, and the reaction conditions and results are shown in Table 5.
TABLE 5
| Example number | Reaction temperature (. degree.C.) | HMF yield (%) |
| 32 | 120 | 39.1 |
| 33 | 130 | 59.7 |
| 34 | 150 | 69.3 |
Examples 35 to 41:
the reaction was carried out according to the procedure of example 23, using different reaction times, and the reaction conditions and results are shown in Table 6.
TABLE 6
Examples 42 to 45:
the reaction was carried out according to the procedure of example 23 using different surfactants, and the reaction conditions and results are shown in Table 7.
TABLE 7
| Example number | Surface active agent | Surfactant concentration (g/L) | HMF yield (%) |
| 42 | Dodecyl trimethyl ammonium bromide | 21.2 | 68.4 |
| 43 | Cetyl Dimethylethylammonium Bromide | 26.0 | 70.5 |
| 44 | Octadecyl trimethyl ammonium Bromide | 26.9 | 71.5 |
| 45 | Hexadecyl trimethyl ammonium chloride | 22.0 | 60.0 |
Claims (7)
1. A synthesis method of 5-hydroxymethylfurfural promoted by a surfactant is characterized in that fructose is used as a raw material, 1, 4-dioxane and water are used as a mixed solvent, dodecyl trimethyl ammonium bromide, hexadecyl dimethyl ethyl ammonium bromide, octadecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium chloride is used as the surfactant, sulfuric acid is used as a catalyst, 5-hydroxymethylfurfural is synthesized in a closed reactor with air removed, wherein the concentration of fructose is 20.0-600.0 g/L, the volume ratio of 1, 4-dioxane to water is 80: 20-100: 0, the concentration of a surfactant is 5.0-45.0 g/L, the concentration of sulfuric acid is 1.0-10.0 g/L, the reaction temperature is 120-150 ℃, the reaction time is 1-30 minutes, and the surfactant is preferably octadecyl trimethyl ammonium bromide.
2. The method according to claim 1, wherein the fructose concentration is 100.0 to 500.0 g/L.
3. The method according to claim 1, wherein the volume ratio of 1, 4-dioxane to water is 90:10 to 100: 0.
4. The method of claim 1, wherein the surfactant concentration is 15.0 to 35.0 g/L.
5. The method according to claim 1, wherein the concentration of sulfuric acid is 2.0 to 5.0 g/L.
6. The process according to claim 1, wherein the reaction temperature is 140 to 150 ℃.
7. The method according to claim 1, wherein the reaction time is 10 to 20 minutes.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863999A (en) * | 2018-07-03 | 2018-11-23 | 沈阳化工大学 | The method of hydroxymethylfurfural is prepared under a kind of temperate condition |
| CN111961017A (en) * | 2020-08-25 | 2020-11-20 | 浙江恒澜科技有限公司 | Method for preparing 5-hydroxymethylfurfural in two-phase solution system |
| CN112424179A (en) * | 2018-07-13 | 2021-02-26 | 诺瓦蒙特股份公司 | Method for producing and separating 5-hydroxymethylfurfural by using quaternary ammonium salt |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108863999A (en) * | 2018-07-03 | 2018-11-23 | 沈阳化工大学 | The method of hydroxymethylfurfural is prepared under a kind of temperate condition |
| CN112424179A (en) * | 2018-07-13 | 2021-02-26 | 诺瓦蒙特股份公司 | Method for producing and separating 5-hydroxymethylfurfural by using quaternary ammonium salt |
| CN111961017A (en) * | 2020-08-25 | 2020-11-20 | 浙江恒澜科技有限公司 | Method for preparing 5-hydroxymethylfurfural in two-phase solution system |
Non-Patent Citations (1)
| Title |
|---|
| 楼炯涛: "5-羟甲基糠醛氢解制备2, 5-二甲基呋喃中催化剂的设计与反应性能研究", 中国博士学位论文全文数据库, pages 37 - 45 * |
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