CN112341414A - Method for preparing 2, 5-furandicarboxylic acid by two-step hydrolysis and oxidation of 5-chloromethyl furfural - Google Patents
Method for preparing 2, 5-furandicarboxylic acid by two-step hydrolysis and oxidation of 5-chloromethyl furfural Download PDFInfo
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- KAZRCBVXUOCTIO-UHFFFAOYSA-N 5-(chloromethyl)furan-2-carbaldehyde Chemical compound ClCC1=CC=C(C=O)O1 KAZRCBVXUOCTIO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 44
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910001868 water Inorganic materials 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 claims description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910004878 Na2S2O4 Inorganic materials 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000003864 humus Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- -1 polyethylene furandicarboxylate Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002663 humin Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
Classifications
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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
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Abstract
The invention discloses a method for preparing 2, 5-furandicarboxylic acid by a two-step method of hydrolysis and oxidation of 5-chloromethyl furfural, which comprises the following steps: 1) mixing sodium hydrosulfite, alkali neutralizer and solvent, and placing the mixture in a container; heating to a specified temperature, and adding 5-chloromethyl furfural; maintaining the specified temperature, carrying out hydrolysis reaction under the condition of stirring, extracting the reaction liquid with an organic solvent after the reaction is finished, and then carrying out rotary evaporation and recovery on an extracting agent to obtain a crude product of the 5-hydroxymethylfurfural; 2) mixing the 5-hydroxymethylfurfural crude product, an alkali neutralizing agent and a solvent, then placing the mixture into a reaction vessel, adding a catalyst, reacting under a closed condition by taking air or oxygen as an oxygen source, adjusting the pH of a reaction solution after the reaction is finished to obtain 2, 5-furandicarboxylic acid precipitate, and filtering to obtain a 2, 5-furandicarboxylic acid product. The 5-hydroxymethylfurfural in the hydrolysate does not need to be refined and purified with high energy consumption, and the obtained 5-hydroxymethylfurfural crude product can be directly used for synthesizing 2, 5-furandicarboxylic acid by high-efficiency catalytic oxidation reaction.
Description
Technical Field
The invention relates to a method for preparing 2, 5-furandicarboxylic acid by a two-step method of hydrolysis and oxidation of 5-chloromethyl furfural.
Background
The continuous excavation of non-renewable resources such as petroleum and the rapidly increasing energy demand put a great pressure on the environment and economy. Biomass has received much attention in recent years as a renewable carbon resource that can replace petroleum-based chemicals. Among them, the biomass-based 2, 5-furandicarboxylic acid (FDCA) has a chemical structure and physical and chemical properties similar to those of petroleum-based terephthalic acid, and particularly, a polyester product thereof with ethylene glycol, polyethylene furandicarboxylate (PEF), shows better performance than polyethylene terephthalate (PET), so that FDCA and its polyester PEF are considered as the most ideal bio-based substitute products for terephthalic acid and PET.
Catalytic oxidation of biomass-based platform molecule 5-Hydroxymethylfurfural (HMF) is the most promising synthesis route for FDCA. However, the process for preparing HMF from cheap raw materials such as cellulose and glucose is complex, the HMF yield is low, and the separation and purification difficulty is high, so that the cost for preparing HMF from raw materials such as cellulose is high, which further hinders the large-scale production of FDCA from cellulose-based biomass. Recently, researchers have proposed that cheap and easily available raw materials such as cellulose can be efficiently converted to prepare 5-Chloromethylfurfural (CMF), and the chemical stability of CMF is much higher than that of HMF, so CMF is considered to be a novel biomass-based platform molecule (ChemSusChem 2(2009) 859-. Most catalytic conversion pathways for HMF can be directly applied to CMF, however due to the presence of chlorine atoms in CMF, the selectivity of catalytic oxidation of CMF to FDCA is very low.
CMF is easily hydrolyzed to give HMF, and thus CMF can synthesize FDCA by a two-step process of hydrolysis and oxidation. However, it should be noted that due to the unstable chemical properties of HMF, a considerable portion of HMF will undergo side reactions such as polycondensation during the hydrolysis of CMF to form brown-black humus. These humins are easily adsorbed to the catalyst surface during catalytic oxidation of HMF resulting in catalyst deactivation. The separation of HMF and byproducts such as humus can be realized by modes such as reduced pressure distillation, but the energy consumption for refining HMF is high, and the loss of thermally unstable HMF in the high-temperature distillation process is also high.
Disclosure of Invention
The invention mainly aims to provide a method for preparing 2, 5-furandicarboxylic acid by a two-step method of hydrolysis and oxidation of 5-chloromethyl furfural.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a method for preparing 2, 5-furandicarboxylic acid by a two-step hydrolysis and oxidation method of 5-chloromethyl furfural comprises the following steps:
1) mixing sodium hydrosulfite, an alkali neutralizing agent and a first solvent, and then placing the mixture into a container; heating to a specified temperature, adding 5-chloromethylfurfural, keeping the specified temperature, performing hydrolysis reaction under the stirring condition, extracting 5-chloromethylfurfural with an organic solvent after the reaction is finished, and performing rotary evaporation to recover an extracting agent to obtain a crude product of 5-hydroxymethylfurfural; the specified temperature is 60-100 ℃, the hydrolysis time is 2-80min, and the concentration of 5-chloromethyl furfural in the solvent is 10-20 wt%;
2) mixing the 5-hydroxymethylfurfural crude product, sodium bicarbonate and a second solvent, placing the mixture into a reaction container, and adding Ru/Al2O3The catalyst reacts under a closed condition by taking air or oxygen as an oxygen source, the pH of a reaction solution is adjusted after the reaction is finished to obtain 2, 5-furandicarboxylic acid precipitate, the 2, 5-furandicarboxylic acid is obtained after filtration, the reaction temperature is 120-140 ℃, the time is 2-5h, the pressure is 10-30bar, and the concentration of the crude product of 5-hydroxymethylfurfural in a solvent is 0.5-20 wt%.
Preferably, the mass ratio of the sodium hydrosulfite to the 5-chloromethyl furfural used in the step 1) is 0.02-0.06: 1.
Preferably, the alkali neutralizing agent in step 1) comprises at least one of calcium carbonate, barium carbonate, calcium oxide or calcium hydroxide.
Preferably, the molar ratio of the amount of the alkali neutralizing agent and the 5-hydroxymethylfurfural in the step 1) is 0.1-2: 1.
Preferably, the first solvent used in step 1) is water or a mixed solvent system composed of water and an organic solvent, the organic solvent is one of acetone or 1, 4-dioxane, and the mass ratio of the organic solvent to the water is as follows: 1: 5-5: 1.
Preferably, the extractant in the step 1) is one of 1, 2-dichloroethane or methyl isobutyl ketone.
Preferably, the second solvent used in step 2) is a mixed solvent system consisting of water and 1, 4-dioxane.
Preferably, the mass ratio of the water to the 1, 4-dioxane is 1: 8-12.
The invention develops a 5-chloromethyl furfural hydrolysis process for inhibiting the formation of humus by sodium hydrosulfite, the 5-hydroxymethyl furfural in the hydrolysate does not need to be refined and purified with high energy consumption, and a crude product of the 5-hydroxymethyl furfural can be obtained only by recovering an extracting agent, and the crude product can be directly used for synthesizing 2, 5-furandicarboxylic acid by high-efficiency catalytic oxidation reaction.
Drawings
The invention is further illustrated by the following figures and examples.
FIG. 1: photographs of 5-Chloromethylfurfural (CMF) hydrolysate and 5-Hydroxymethylfurfural (HMF) crude product. (a) Sodium dithionite Na2S2O4Time CMF hydrolysate (i.e., example 1); (b) adding Na2S2O4Time CMF hydrolysate (example 2); (c) no Na2S2O4Crude HMF (example 1); (d) adding Na2S2O4Crude HMF (example 2).
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Examples 95% HMF and RuCl3·3H2O was purchased from Shanghai Aladdin Biotechnology Ltd. 5 wt% Ru/Al2O3The preparation process of the catalyst comprises the following specific steps: 2g of gamma-Al2O3Stirring in water solution for 30min, and dripping RuCl3Aqueous solution (0.26g RuCl)3·3H2O+2g H2O), stirring for 16 hours and stirring for 16 hours,after rotary steaming and drying, the solution is at 10% H2Reducing for 3 hours at 300 ℃ in the atmosphere to obtain 5 wt% Ru/Al2O3A catalyst.
Example 1
Adding 0.35g of calcium carbonate and 10g of deionized water into a 50mL round-bottom flask, heating to 80 ℃, adding 1g of 5-chloromethyl furfural, vigorously stirring (500rpm) and keeping for 15min, finishing the reaction, rapidly cooling to room temperature in an ice-water bath, extracting the reaction liquid with 1, 2-dichloroethane for three times in an equal volume, evaporating the extractant at 40 ℃ by using a rotary evaporator and sampling. Qualitative and quantitative measurements were carried out using GC-MS (Shimadzu) and GC (Agilent), and the results are given in Table 1 under the reference number 1.
The CMF hydrolysate and HMF crude product are shown in FIGS. 1(a) and (c).
Example 2
Adding 0.04g of sodium hydrosulfite, 0.35g of calcium carbonate and 10g of deionized water into a 50mL round-bottom flask, heating to 80 ℃, adding 1g of 5-chloromethyl furfural, vigorously stirring (500rpm), keeping for 15min, finishing the reaction, rapidly cooling to room temperature in an ice-water bath, extracting the reaction liquid with 1, 2-dichloroethane for three times in an equal volume, evaporating the extractant at 40 ℃ by using a rotary evaporator, sampling, and carrying out qualitative and quantitative detection by using GC-MS (Shimadzu corporation) and GC (Agilent), wherein the detection result is serial number 2 in Table 1.
The CMF hydrolysate and HMF crude product are shown in FIGS. 1(b) and (d).
Examples 3 to 4
A50 mL round-bottom flask was charged with 0.04g of sodium dithionite, 0.35g of calcium carbonate and 10g of water/acetone (wherein the mass ratio of water to acetone is 1:4) or a mixed solvent of 10g of water/1, 4-dioxane (wherein the mass ratio of water to 1, 4-dioxane is 1:4), heated to 80 ℃ and then added with 1g of 5-chloromethylfurfural, vigorously stirred (500rpm) and kept for 30min, the reaction was rapidly cooled to room temperature in an ice-water bath, the reaction solution was extracted three times with an equal volume of 1, 2-dichloroethane, and then the extractant was evaporated and sampled at 40 ℃ by a rotary evaporator, and qualitative and quantitative measurements were carried out by GC-MS (Shimadzu) and GC (Agilent), and the results of the measurements are shown in Table 1 as numbers 3 to 4.
Examples 5 to 7
A50 mL round-bottom flask was charged with 0.04g of sodium dithionite, 10g of water/acetone (wherein the mass ratio of water to acetone was 1:4) and 0.68g of barium carbonate, 0.20g of calcium oxide or 0.26g of calcium hydroxide, heated to 80 ℃ and then charged with 1g of 5-chloromethylfurfural, vigorously stirred (500rpm) and kept for 30min, the reaction was rapidly cooled to room temperature in an ice-water bath, the reaction solution was extracted three times with an equal volume of 1, 2-dichloroethane, and then the extractant was evaporated and sampled at 40 ℃ by a rotary evaporator, and qualitative and quantitative determinations were carried out by GC-MS (Shimadzu) and GC (Agilent), and the results of the determinations are shown in Table 1 as numbers 5 to 7.
Examples 8 to 9
Adding 0.04g of sodium hydrosulfite, 0.35g of calcium carbonate and 10g of water/acetone (wherein the mass ratio of water to acetone is 1:4) into a 50mL round-bottom flask, heating to 60 ℃ or 100 ℃, adding 1g of 5-chloromethylfurfural, violently stirring (500rpm), keeping for 40min or 30min, ending the reaction, rapidly cooling to room temperature in an ice water bath, extracting the reaction liquid for three times by using 1, 2-dichloroethane as the same volume, evaporating and sampling the extracting agent by using a rotary evaporator at 40 ℃, and carrying out qualitative and quantitative detection by using GC-MS (Shimadzu) and GC (Agilent), wherein the detection result is listed as serial number 8-9 in Table 1.
Examples 10 to 19
A20 mL autoclave was charged with 0.3g of 95% 5-hydroxymethylfurfural or 5-hydroxymethylfurfural crude product (5-hydroxymethylfurfural crude product obtained in example 1 was designated as HMF-1, 5-hydroxymethylfurfural crude product obtained in example 2 was designated as HMF-2, and so on), 0.4g of sodium bicarbonate (twice the molar equivalent relative to 5-hydroxymethylfurfural), 2.7g of water/1, 4-dioxane (wherein the mass ratio of water to 1, 4-dioxane was 1:9), and 0.3g of 5 wt% Ru/Al2O3As a catalyst, the reaction vessel was sealed, charged with 40bar of oxygen, vigorously stirred (600rpm), heated to 140 ℃ for 3 hours, quenched to room temperature and sampled, and qualitatively and quantitatively determined by HPLC (Water 2695), the results of which are given in Table 2 under numbers 1 to 10.
TABLE 1 results of the measurement in each example of CMF hydrolysis reaction
Table 2 results of measurement in each example of HMF oxidation reaction
Claims (8)
1. A method for preparing 2, 5-furandicarboxylic acid by a two-step method of hydrolysis and oxidation of 5-chloromethyl furfural is characterized by comprising the following steps: the method comprises the following steps:
1) mixing sodium hydrosulfite, an alkali neutralizing agent and a first solvent, and then placing the mixture into a container; heating to a specified temperature, adding 5-chloromethylfurfural, keeping the specified temperature, performing hydrolysis reaction under the stirring condition, extracting 5-chloromethylfurfural with an organic solvent after the reaction is finished, and performing rotary evaporation to recover an extracting agent to obtain a crude product of 5-hydroxymethylfurfural; the specified temperature is 60-100 ℃, the hydrolysis time is 2-80min, and the concentration of 5-chloromethyl furfural in the solvent is 10-20 wt%;
2) mixing the 5-hydroxymethylfurfural crude product, sodium bicarbonate and a second solvent, placing the mixture into a reaction container, and adding Ru/Al2O3The catalyst reacts under a closed condition by taking air or oxygen as an oxygen source, the pH of a reaction solution is adjusted after the reaction is finished to obtain 2, 5-furandicarboxylic acid precipitate, the 2, 5-furandicarboxylic acid is obtained after filtration, the reaction temperature is 120-140 ℃, the time is 2-5h, the pressure is 10-30bar, and the concentration of the crude product of 5-hydroxymethylfurfural in a solvent is 0.5-20 wt%.
2. The method for preparing 2, 5-furandicarboxylic acid by the two-step hydrolysis and oxidation of 5-chloromethyl furfural according to claim 1, characterized in that: the mass ratio of the sodium hydrosulfite and the 5-chloromethyl furfural in the step 1) is 0.02-0.06: 1.
3. The method for preparing 2, 5-furandicarboxylic acid by the two-step hydrolysis and oxidation of 5-chloromethyl furfural according to claim 1, characterized in that: the alkali neutralizing agent used in the step 1) comprises at least one of calcium carbonate, barium carbonate, calcium oxide or calcium hydroxide.
4. The method for preparing 2, 5-furandicarboxylic acid by the two-step hydrolysis and oxidation of 5-chloromethyl furfural according to claim 3, characterized in that: the molar ratio of the amount of the alkali neutralizing agent to the 5-hydroxymethylfurfural is 0.1-2: 1.
5. The method for preparing 2, 5-furandicarboxylic acid by the two-step hydrolysis and oxidation of 5-chloromethyl furfural according to claim 1, characterized in that: the first solvent used in the step 1) is water or a mixed solvent system consisting of water and an organic solvent, the organic solvent is acetone or one of 1, 4-dioxane, and the mass ratio of the organic solvent to the water is as follows: 1: 5-5: 1.
6. The method for preparing 2, 5-furandicarboxylic acid by the two-step hydrolysis and oxidation of 5-chloromethyl furfural according to claim 1, characterized in that: the extracting agent in the step 1) is one of 1, 2-dichloroethane or methyl isobutyl ketone.
7. The method for preparing 2, 5-furandicarboxylic acid by the two-step hydrolysis and oxidation of 5-chloromethyl furfural according to claim 1, characterized in that: the second solvent used in the step 2) is a mixed solvent system consisting of water and 1, 4-dioxane.
8. The method for preparing 2, 5-furandicarboxylic acid by the two-step hydrolysis and oxidation of 5-chloromethylfurfural according to claim 5, wherein: the mass ratio of the water to the 1, 4-dioxane is 1: 8-12.
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| CN114105914A (en) * | 2021-11-04 | 2022-03-01 | 厦门大学 | Method for preparing 2, 5-furandimethanol by using 5-chloromethyl furfural |
Citations (5)
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| CN114105914A (en) * | 2021-11-04 | 2022-03-01 | 厦门大学 | Method for preparing 2, 5-furandimethanol by using 5-chloromethyl furfural |
| WO2023077822A1 (en) * | 2021-11-04 | 2023-05-11 | 厦门大学 | Method for preparing 2,5-bishydroxymethylfuran by using 5-chloromethylfurfural |
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