CN108658904B - Method for preparing 5-ethoxymethylfurfural by using glucose - Google Patents
Method for preparing 5-ethoxymethylfurfural by using glucose Download PDFInfo
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- CCDRPZFMDMKZSZ-UHFFFAOYSA-N 5-(ethoxymethyl)furan-2-carbaldehyde Chemical compound CCOCC1=CC=C(C=O)O1 CCDRPZFMDMKZSZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 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 title claims abstract description 40
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- CMWINYFJZCARON-UHFFFAOYSA-N 6-chloro-2-(4-iodophenyl)imidazo[1,2-b]pyridazine Chemical compound C=1N2N=C(Cl)C=CC2=NC=1C1=CC=C(I)C=C1 CMWINYFJZCARON-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000002195 synergetic effect Effects 0.000 claims abstract description 16
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 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 8
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- SIWVGXQOXWGJCI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;2-ethenylbenzenesulfonic acid Chemical compound C=CC1=CC=CC=C1C=C.OS(=O)(=O)C1=CC=CC=C1C=C SIWVGXQOXWGJCI-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 2
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- 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
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- LBOVMDOAMWYGHK-UHFFFAOYSA-N ethanol;methylsulfinylmethane Chemical compound CCO.CS(C)=O LBOVMDOAMWYGHK-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
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- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0228—Sulfur-containing compounds with a metal-sulfur link, e.g. mercaptides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B01J35/19—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing 5-ethoxymethylfurfural by using glucose, which takes glucose as a reaction substrate, a cosolvent system consisting of absolute ethyl alcohol and dimethyl sulfoxide as a reaction medium, and a combination of aluminum trifluoromethanesulfonate and ion exchange resin Amberlyst 15 as a synergistic catalyst, so as to form a conversion reaction system, the 5-ethoxymethylfurfural is prepared by reaction at the temperature of 140-160 ℃, and the dimethyl sulfoxide is added as the cosolvent, so that the occurrence of side reactions can be effectively inhibited, the glucose can be converted into a target product, namely 5-ethoxymethylfurfural, with high selectivity, and the maximum yield of 48.8%; the preparation method is simple and effective, the catalyst is easy to recover and reuse, glucose with wide sources and low price is used as a reaction raw material, the economic benefit is high, and the method has good industrial application prospect.
Description
Technical Field
The invention relates to a method for preparing 5-ethoxymethylfurfural, in particular to a method for preparing 5-ethoxymethylfurfural by glucose in an ethanol-organic solvent cosolvent system by adopting a combination of Lewis acid and Bronsted acid as a synergistic catalyst, and belongs to the technical field of fine chemical preparation.
Background
With the gradual reduction of the reserves of non-renewable fossil fuels, environmental pollution and global warming become more and more serious, and the preparation of chemicals and fuels by using renewable biomass resources has important strategic significance. 5-ethoxymethylfurfural is considered as an important biomass-based platform compound, and can be used for producing various high-value chemical products and high-quality liquid fuels. In recent years, the preparation and application of the compound have attracted more and more extensive attention of researchers. 5-ethoxymethylfurfural has good oxidation stability and higher cetane number, the energy density of the 5-ethoxymethylfurfural reaches 8.7 kW. h/L, is close to the energy density of standard gasoline (8.8 kW. h/L) and is far higher than that of bioethanol (6.1 kW. h/L), and the characteristics determine that the 5-ethoxymethylfurfural can be used as an excellent potential alternative fuel or fuel additive and is expected to play an important role in alternative energy in the post-petroleum age. Meanwhile, the high oxidation stability of the fuel can reduce the emission of smoke dust, sulfur oxides and nitrogen oxides, and the fuel has good environmental benefit and is a clean novel biofuel. In addition, 5-ethoxymethylfurfural also has good chemical reaction activity, and can be used as a chemical intermediate to synthesize other industrially important products, such as cyclopentenone and the like.
As for the synthesis of 5-ethoxymethylfurfural, 5-hydroxymethylfurfural can be directly etherified with ethanol under the action of acid catalysis to produce 5-ethoxymethylfurfural, and the product yield can reach more than 90% (Fuel, 2014, 117: 68-73). However, the method is limited by the limitations of high cost of 5-hydroxymethylfurfural and the like, and the selective synthesis of 5-ethoxymethylfurfural by directly using abundant and cheap saccharides (such as fructose, glucose, sucrose and the like) as raw materials in one pot has obviously more competitive advantages and is also paid more attention and attention by researchers. At present, a great deal of research shows that fructose can be efficiently and directly converted into 5-ethoxymethylfurfural in an ethanol system through specific acid catalysis. In addition, inulin, a natural fructose polymer, can also be effectively and directly converted to synthesize the 5-ethoxymethylfurfural. At present, in the preparation process of 5-ethoxy methyl furfural, a series of problems of equipment corrosion, complex catalyst preparation process, high production cost, difficult recovery, more side reactions and the like exist.
Glucose is a richer and cheaper biomass raw material, and is one of the most significant raw materials for preparing biomass chemicals. Therefore, from the perspective of economic and practical feasibility, the method for preparing 5-ethoxymethylfurfural by directly utilizing glucose undoubtedly has better development prospect and advantages, and is an important way for developing 5-ethoxymethylfurfural products on a large scale. Compared with the method using fructose as a reaction raw material, the method has the advantages that the direct conversion of glucose into 5-ethoxymethylfurfural is more difficult, mainly because glucose is required to be capable of forming fructose, related effective research reports are few at present, and the product yield can only reach about 30%. Therefore, the development of an economical and efficient method for preparing 5-ethoxymethylfurfural by directly converting glucose is of great significance, and the technical reference is expected to be provided for the industrial practical application of the method.
Disclosure of Invention
The invention aims to provide a method for preparing 5-ethoxymethylfurfural by directly utilizing glucose, and a multifunctional synergistic catalytic system combining Lewis acid and Bronsted acid is constructed in a relatively high-temperature environment, so that the isomerization and subsequent reaction of glucose can be effectively carried out, and necessary early-stage conditions are provided for high-selectivity synthesis of 5-ethoxymethylfurfural. Then, a cosolvent system is formed by doping a specific aprotic polar organic matter and absolute ethyl alcohol, a solvent regulation and control system which can stably protect the product 5-ethoxymethylfurfural from degradation is formed, the direct reaction is selectively synthesized and even promoted, and therefore an effective regulation and control way and a method which can strengthen the direct conversion and selective synthesis of the 5-ethoxymethylfurfural by glucose are constructed.
The method specifically comprises the following steps:
taking glucose as a reaction substrate, adding Lewis acid and Bronsted acid as a synergistic catalyst into an absolute ethyl alcohol-organic solvent cosolvent system, and reacting while stirring, wherein the stirring speed is 700-900 r/min, the reaction temperature is 140-160 ℃, and the reaction time is 4-10 h; and after the reaction is finished, obtaining a target product 5-ethoxymethylfurfural, and recycling the used synergistic catalyst.
The molar concentration of the reaction substrate glucose is 0.05-0.2 mol/L.
The organic solvent is dimethyl sulfoxide, and the volume ratio of absolute ethyl alcohol to dimethyl sulfoxide is 7: 3-5: 5.
The Lewis acid is aluminum trifluoromethanesulfonate, and the dosage of the aluminum trifluoromethanesulfonate is 0.025-0.07 mol/L; the Bronsted acid is ion exchange resin Amberlyst 15, and the dosage of the Bronsted acid is 2-14 g/L.
The method for recycling the synergistic catalyst comprises the steps of cooling a reaction liquid to room temperature, filtering and separating to obtain the Bronsted acid and a liquid substance, and drying the Bronsted acid for reuse; distilling the liquid substance for many times to remove low boiling point substances (ethanol) in the system, extracting with hexane, collecting hexane extraction layer, and distilling to obtain 5-ethoxymethylfurfural crude extract; the mixed system of dimethyl sulfoxide and Lewis acid of the extracted lower layer liquid can be directly reused.
The invention has the beneficial effects that:
the method has the advantages that the simple Lewis acid catalyst aluminum trifluoromethanesulfonate with high catalytic activity and the Bronsted acid catalyst ion exchange resin Amberlyst 15 are used as the synergistic catalyst, the product 5-ethoxymethylfurfural can be stabilized at a relatively high temperature by adding the organic solvent dimethyl sulfoxide, side reactions are effectively inhibited, the yield of the target product 5-ethoxymethylfurfural is effectively improved, the waste acid after reaction is less, the treatment is easy, the environmental pollution is small, the catalyst is easy to recover, the production cost of the 5-ethoxymethylfurfural can be remarkably reduced, the economic benefit is improved, and the method has a good industrial application prospect.
Drawings
FIG. 1 is a schematic diagram of a process for recycling a synergistic catalyst.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to the examples.
Example 1: the method for preparing 5-ethoxymethylfurfural by using glucose specifically comprises the following steps:
adding glucose as a substrate, aluminum trifluoromethanesulfonate and Amberlyst 15 as a synergistic catalyst into a stainless steel high-pressure reaction kettle filled with 5mL of absolute ethanol and 5mL of dimethyl sulfoxide, reacting for 8.2h at 150 ℃ of oil bath through magnetic stirring at the rotating speed of 800r/min, immediately immersing the reaction kettle into cold water to cool after the reaction is finished, filtering the reaction mixture and collecting filtrate after the temperature of the reaction kettle is reduced to the normal temperature, and analyzing and calculating by a High Performance Liquid Chromatography (HPLC) to obtain a target product 5-ethoxymethylfurfural with the yield of 48.8%, wherein the addition amount of the glucose is 0.2mol/L, the amount of the aluminum trifluoromethanesulfonate is 0.052mol/L, and the amount of the Amberlyst 15 as an ion exchange resin is 5.56 g/L.
The method for recycling the synergistic catalyst system comprises the following steps: filtering the reaction mixture and collecting filtrate, wherein the filter residue is ion exchange resin Amberlyst 15, and drying for repeated use; distilling the filtrate for multiple times to remove low-boiling-point substance ethanol in the system, extracting with hexane, collecting hexane extraction layer, and distilling to obtain 5-ethoxymethylfurfural crude extract; the mixed system of the extracted subnatant dimethyl sulfoxide and the aluminum trifluoromethanesulfonate is directly reused, and the specific steps are shown in figure 1. The specific steps and reaction conditions of the repeated use experiment of the catalyst system in the reaction for synthesizing 5-ethoxymethylfurfural by converting glucose are the same as those in example 1, and the repeated use results are shown in table 1;
table 1: synergistic catalyst reuse effect
As can be seen from Table 1, after the catalytic system is recycled for three times, the conversion rate of glucose and the yield of 5-ethoxymethylfurfural are basically kept unchanged, which indicates that the catalytic system can be recycled and the catalytic activity of the catalytic system is not obviously reduced.
Example 2: the method for preparing 5-ethoxymethylfurfural by using glucose specifically comprises the following steps:
adding glucose as a substrate, aluminum trifluoromethanesulfonate and Amberlyst 15 as a synergistic catalyst into a stainless steel high-pressure reaction kettle filled with 7mL of absolute ethyl alcohol and 3mL of dimethyl sulfoxide, reacting for 5 hours at an oil bath temperature of 160 ℃ by magnetic stirring at a rotating speed of 700r/min, immediately immersing the reaction kettle into cold water to reduce the temperature after the reaction is finished, filtering the reaction mixture and collecting filtrate after the temperature of the reaction kettle is reduced to the normal temperature, and analyzing and calculating by a High Performance Liquid Chromatography (HPLC) to obtain a target product 5-ethoxymethyl furfural with a yield of 41.1%, wherein the addition amount of the glucose is 0.1mol/L, the use amount of the aluminum trifluoromethanesulfonate is 0.03mol/L, and the use amount of the Amberlyst 15 as an ion exchange resin is 10 g/L.
Example 3: the method for preparing 5-ethoxymethylfurfural by using glucose specifically comprises the following steps:
glucose is used as a substrate, aluminum trifluoromethanesulfonate and Amberlyst 15 ion exchange resin are used as a synergistic catalyst, the substrate is added into a stainless steel high-pressure reaction kettle containing 6mL of absolute ethyl alcohol and 4mL of dimethyl sulfoxide, the stainless steel high-pressure reaction kettle is magnetically stirred at the oil bath temperature of 140 ℃ and reacts for 10 hours at the rotating speed of 900r/min, after the reaction is finished, the reaction kettle is immediately immersed into cold water for cooling, the temperature of the reaction kettle is reduced to the normal temperature, a reaction mixture is filtered and filtrate is collected, and the yield of a target product 5-ethoxymethyl furfural is 38.5% through High Performance Liquid Chromatography (HPLC) analysis and calculation, wherein the adding amount of the glucose is 0.05 mol/L, the using amount of the aluminum trifluoromethanesulfonate is 0.07mol/L, and the using amount of the Amberlyst 15 ion exchange resin is 13 g/L.
Example 4: the method for preparing 5-ethoxymethylfurfural by using glucose specifically comprises the following steps:
glucose is used as a substrate, aluminum trifluoromethanesulfonate and Amberlyst 15 ion exchange resin are used as a synergistic catalyst, the substrate is added into a stainless steel high-pressure reaction kettle filled with 5mL of absolute ethyl alcohol and 5mL of dimethyl sulfoxide, the stainless steel high-pressure reaction kettle is magnetically stirred at the oil bath temperature of 140 ℃ and reacts for 9 hours at the rotating speed of 800r/min, after the reaction is finished, the reaction kettle is immediately immersed into cold water for cooling, the temperature of the reaction kettle is reduced to the normal temperature, a reaction mixture is filtered and filtrate is collected, and the yield of a target product 5-ethoxymethyl furfural is obtained by High Performance Liquid Chromatography (HPLC) analysis and calculation, wherein the adding amount of the glucose is 0.15mol/L, the using amount of the aluminum trifluoromethanesulfonate is 0.045mol/L, and the using amount of the Amberlyst 15 ion exchange resin is 5 g/L.
Example 5 comparative experiment
The specific steps of the method for preparing 5-ethoxymethylfurfural by directly utilizing glucose in this example are the same as those of example 1, except that the target product, 5-ethoxymethylfurfural, is obtained by analysis and calculation with a High Performance Liquid Chromatography (HPLC) using only ion exchange resin Amberlyst 15 as a catalyst, and the yield of 5-ethoxymethylfurfural is 0.92%.
Example 6: comparative experiment
The method for preparing 5-ethoxymethylfurfural by directly utilizing glucose in this example has the same specific steps as example 1, except that the target product, 5-ethoxymethylfurfural, is obtained by analysis and calculation with a High Performance Liquid Chromatography (HPLC) using only aluminum trifluoromethanesulfonate as a catalyst, with a yield of 20.63%.
Example 7: comparative experiment
The method for preparing 5-ethoxymethylfurfural by directly utilizing glucose in this example has the same specific steps as example 1, except that 10mL of anhydrous ethanol is used as a single solvent system, and the yield of the target product 5-ethoxymethylfurfural is obtained by High Performance Liquid Chromatography (HPLC) analysis and calculation.
The results of the above examples show that in an anhydrous ethanol-dimethyl sulfoxide mixed system, aluminum trifluoromethanesulfonate and Amberlyst 15, which are used as a synergistic catalyst, have a good catalytic effect on the preparation of 5-ethoxymethylfurfural by conversion of glucose in a one-pot process, and in addition, as can be seen by comparing with comparative experiment 7, the addition of dimethyl sulfoxide as a cosolvent can stabilize the product 5-ethoxymethylfurfural at a relatively high temperature, thereby effectively improving the yield of the target product 5-ethoxymethylfurfural.
Claims (2)
1. A method for preparing 5-ethoxymethylfurfural by using glucose is characterized by comprising the following steps: taking glucose as a reaction substrate, adding Lewis acid and Bronsted acid as a synergistic catalyst into an absolute ethyl alcohol-organic solvent cosolvent system, and reacting while stirring, wherein the stirring speed is 700-900 r/min, the reaction temperature is 140-160 ℃, and the reaction time is 4-10 h; after the reaction is finished, obtaining a target product 5-ethoxymethylfurfural;
the organic solvent is dimethyl sulfoxide, and the volume ratio of absolute ethyl alcohol to dimethyl sulfoxide is 7: 3-5: 5;
the Lewis acid is aluminum trifluoromethanesulfonate, and the dosage of the Lewis acid is 0.025-0.07 mol/L; the Bronsted acid is ion exchange resin Amberlyst 15, and the dosage of the Bronsted acid is 2-14 g/L.
2. The method for preparing 5-ethoxymethylfurfural using glucose according to claim 1, characterized in that: the addition amount of the reaction substrate glucose is 0.05-0.2 mol/L.
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| CN107501215A (en) * | 2017-09-18 | 2017-12-22 | 中国农业大学 | The method and apparatus that a kind of serialization prepares 5 hydroxymethylfurfurals and its derivative |
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