A method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF
By synthesizing a composite catalytic system using metal salt compounds and catalyst additives, catalytic oxidation of 5-HMF is solved, and the efficient preparation of DFF and the recovery of catalysts are achieved.
Patent Information
- Application Number
- CN202411937335.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-26
- Publication Date
- 2025-04-04
AI Technical Summary
In the prior art, the oxidation reaction of 5-HMF requires a catalyst, but the catalyst is difficult to recycle and utilize, resulting in a high overall cost.
A composite catalytic system is synthesized by metal salt compounds and catalyst additives, and 5-HMF is catalytically oxidized by air or oxygen at a certain temperature and pressure to produce 2,5-furan diformaldehyde (DFF).
High yield and selectivity of DFF are achieved, with a DFF yield of up to 94.17%, a selectivity of up to 98.53%, a 5-HMF conversion rate of up to 95.57%, and the catalyst can be recycled by magnets.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of utilization and conversion of biological resources, and in particular to a method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF. Background Art
[0002] Carbohydrates are a form of biomass energy. Carbohydrates can be converted into 5-HMF (5-hydroxymethylfurfural), LA (levulinic acid), DFF (2,5-furandicarboxaldehyde), FDM (2,5-furan dimethanol), FDCA (2,5-furandicarboxylic acid) and FFCA (5-formyl-2-furancarboxylic acid), which can be further reacted to produce other intermediate chemicals used in pharmaceuticals, polyesters and organic metal precursors. 5-HMF can be oxidized to produce FDCA, FFCA and DFF, among which DFF is more stable and easier to separate and purify. This oxidation reaction requires a catalyst to reduce the reaction energy barrier and improve selectivity. Generally speaking, this type of oxidation reaction mainly involves uniformly dispersing the catalyst in the substrate solution to form a homogeneous catalytic system. However, the catalyst in the homogeneous catalytic system is difficult to recycle, resulting in a higher overall cost; on the premise of being recyclable, heterogeneous system products are easier to separate and purify the products.
[0003] Therefore, the present invention aims to provide a method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF, thereby providing a new path for the efficient utilization of 5-HMF. Summary of the invention
[0004] In view of the problems existing in the prior art, the purpose of the present invention is to provide a method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF, firstly using metal salt compounds and initiators and other substances to synthesize a composite catalytic system, and then catalytic oxidation reaction of 5-HMF is carried out by air or oxygen at a certain temperature and pressure to generate DFF.
[0005] To achieve the above object, the technical solution of the present invention is as follows:
[0006] A method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF comprises the following steps:
[0007] 1) Putting the metal salt compound and the auxiliary agent into a solvent for dispersion, introducing N2 after uniform dispersion, maintaining the mixture at a certain temperature for a period of time, filtering the mixture to separate the solid and the liquid after returning to room temperature, and washing and drying the solid to obtain a composite catalyst;
[0008] 2) 5-HMF and the composite catalyst prepared in step 1) are uniformly dispersed in a solvent, reacted in air or O2 atmosphere for a period of time, and after the reaction, the mixed solution is collected and completely spin-dried, and then pure water is added and stirred to obtain the desired product, and the remaining composite catalyst solid is recovered by a magnet.
[0009] Furthermore, the metal salt compound in step 1) is one or more of KCl, NaCl, KBr, NaBr, CuCl, CuCl2, RuCl3, KMnO4, Fe(NO3)2, Fe(NO3)3·9H2O, Ni(NO3)2·6H2O, Co(OAc)2·4H2O, Mn(OAc)2·4H2O, Cu(NO3)2·3H2O, Co(NO3)2·6H2O, and Zn(NO3)2·6H2O;
[0010] The auxiliary agent is one or more of Al2O3, SiO2, CeO2, TiO2, K2S2O8, Fe3O4, ZnO, activated carbon, 9-azabicyclo[3.3.1]nonane-N-oxyl free radical, 2,2,6,6-tetramethylpiperidinyl oxide, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl oxide, o-phenylenediamine-N-oxyl, N-hydroxysuccinimide, and N-hydroxyo-phenylenediamine.
[0011] Furthermore, in step 1), the solvent is one or more mixed solvents selected from water, acetone, methanol, ethanol, formic acid, acetic acid, acetonitrile, dimethyl sulfoxide, chloromethane, dichloromethane, chloroform, pyridine, 1,2-dichloroethane, N,N-dimethylformamide, 1-butanol, 1,4-dioxane, isopropanol and toluene.
[0012] Furthermore, in step 1), the volume ratio of the mass of the metal salt compound to the mass of the auxiliary agent and the solvent is 1:0.5-20:20-100, with the mass unit being g and the volume unit being mL.
[0013] Furthermore, in step 1), the reaction temperature is 20-150° C., and the reaction time is 0.5-3 h.
[0014] Furthermore, in step 2), the volume ratio of the mass of 5-HMF to the mass of the composite catalyst and the solvent is 1:0.5-10:20-100, respectively, with the mass unit being g and the volume unit being mL.
[0015] Furthermore, in step 2), the reaction temperature is 20-100° C., the reaction time is 1-36 h, and the pressure of the air or oxygen is 0.5-3.5 MPa.
[0016] Furthermore, in step 2), the solvent is one or more mixed solvents selected from water, acetone, methanol, ethanol, formic acid, acetic acid, acetonitrile, dimethyl sulfoxide, chloroform, dichloromethane, chloroform, pyridine, 1,2-dichloroethane, N,N-dimethylformamide, N,N-dimethylacetamide, 1,4-dioxane, isopropanol, ethyl acetate and toluene.
[0017] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0018] 1) The present invention prepares a composite catalytic system with a catalyst and an auxiliary agent, and catalytically oxidizes 5-HMF to generate DFF, and the DFF yield can reach up to 94.17%; the DFF selectivity can reach up to 98.53%, and the 5-HMF conversion rate can reach up to 95.57%;
[0019] 2) Compared with traditional chemical catalysis, the present invention uses a composite catalytic system to oxidize 5-HMF into an important intermediate chemical DFF using air or oxygen as an oxidant under alkaline conditions, effectively avoiding possible instrument corrosion and the generation of insoluble by-products;
[0020] 3) The catalytic oxidation efficiency of the present invention is high, and the catalytic effect decreases less after multiple cycles, providing a new reference method for preparing pharmaceutical and polyester intermediate DFF. DETAILED DESCRIPTION
[0021] The present invention will be further described below in conjunction with specific embodiments, but the scope of protection of the present invention is not limited to the described scope.
[0022] Example 1
[0023] This example provides an oxidation pathway for 5-HMF to generate DFF using Fe(NO3)3 / KCl as the catalytic center, and the process is as follows:
[0024] Step 1: Weigh 0.72g Fe(NO3)3·9H2O, 0.09g KCl, 1.40g Fe3O4, 0.30g 4-OH-TEMPO and 36mL ACN into a 50mL high temperature and high pressure reactor, stir at 50°C for at least 12h under 0.5MPa N2 atmosphere, return to room temperature, filter and separate the solid and liquid, wash the solid with ethanol three times and dry at 30°C for 5h to obtain a composite catalyst.
[0025] Step 2: 1.20 g 5-HMF and 2.50 g composite catalyst were added to 40 mL dichloromethane. After replacing the air with N2 three times, 1.5 MPa O2 was introduced and kept at 80°C for 18 h. After cooling to room temperature, the reaction liquid was rotary evaporated, and 50 mL pure water was added and stirred for 0.5 h. The solid in the rotary evaporator was recovered by a magnet and dried at 75°C for 16 h. The aqueous solution was collected and the mass was recorded, and then sampled and tested.
[0026] In the present application, the contents of 5-HMF and DFF were detected by Agilent 1260Ⅱ liquid chromatograph and quantified by external standard method. The calculation formulas of the conversion rate (C), selectivity (S) and DFF yield (Y) of 5-HMF are as follows (the detection and calculation methods of the following embodiments are the same as those of this embodiment):
[0027]
[0028] m0——initial mass of 5-HMF; m——mass of 5-HMF after catalytic oxidation, mg / L,
[0029] n DFF ——the amount of substance in DFF; n HMF ——Amount of 5-HMF substance, mol.
[0030] Calculation showed that the DFF yield (Y) was 86.25%, the 5-HMF conversion (C) was 89.94%, and the reaction selectivity was 95.90%.
[0031] Example 2
[0032] In step 1, the 4-OH-TEMPO of the catalyst promoter is replaced with TEMPO; other conditions are the same as those in Example 1.
[0033] Example 3
[0034] In step 1, no catalyst promoter is added; other conditions are the same as those in Example 1.
[0035] Example 4
[0036] In step 1, the metal compound Fe(NO3)3·9H2O is replaced by Cu(NO3)2·3H2O, and no catalyst promoter is added; other conditions are the same as in Example 1.
[0037] Example 5
[0038] In step 1, the metal compound KCl is replaced with Cu(NO3)2·3H2O, and the total mass of Cu(NO3)3·9H2O is 0.72 g, and the ratio is 1:1 (w / w); other conditions are the same as in Example 2.
[0039] Example 6
[0040] In step 2, the added mass of 5-HMF was increased from 1.20 g to 2.40 g, and other conditions were the same as those in Example 5.
[0041] Example 7
[0042] In step 2, the added mass of 5-HMF was increased from 1.20 g to 4.80 g, and other conditions were the same as those in Example 5.
[0043] Example 8
[0044] The metal compound KCl was replaced with KBr in equal amounts; other conditions were the same as in Example 1.
[0045] Example 9
[0046] In step 1, the catalyst promoter 4-OH-TEMPO was replaced with NHPI; in step 2, the reaction temperature was set to 8h, and the other conditions were the same as in Example 1.
[0047] Example 10
[0048] In step 1, the catalyst promoter 4-OH-TEMPO was replaced with NHSI; in step 2, the reaction temperature was set to 8h, and the other conditions were the same as in Example 1.
[0049] Embodiment 11
[0050] In step 1, the metal compounds KCl and Fe(NO3)3·9H2O are replaced with Co(NO3)2·6H2O and Cu(NO3)3·9H2O, with a total mass of 0.72 g and a ratio of 1:1 (w / w), and the catalyst promoter 4-OH-TEMPO is replaced with NHPI; the reaction temperature is set to 100°C, the reaction time is set to 5h, and other conditions and operations are the same as in Example 1.
[0051] Example 12
[0052] In step 1, the catalyst promoter NHPI is replaced by NHSI; other conditions and operations are the same as those in Example 11.
[0053] Embodiment 13
[0054] In step 1, the metal compounds KCl and Fe(NO3)3·9H2O were replaced with Co(NO3)2·6H2O and Cu(NO3)3·9H2O, with a total mass of 0.72 g and a ratio of 1:1 (w / w);
[0055] In step 2, the added mass of 5-HMF was increased from 1.20 g to 2.40 g, the reaction temperature was set to 100° C., the reaction time was set to 3 h, and other conditions and operations were the same as in Example 1.
[0056] Embodiment 14
[0057] In step 1, the metal compounds KCl and Fe(NO3)3·9H2O were replaced with Co(NO3)2·6H2O and Cu(NO3)3·9H2O, with a total mass of 0.72 g and a ratio of 1:1 (w / w);
[0058] In step 2, the added mass of 5-HMF was increased from 1.20 g to 2.40 g, the reaction temperature was set to 100° C., the reaction time was set to 3 h, and other conditions and operations were the same as in Example 1.
[0059] Embodiment 15
[0060] In step 1, the metal compounds KCl and Fe(NO3)3·9H2O were replaced with Mn(OAc)2·4H2O and Co(NO3)2·6H2O, with a total mass of 0.60 g and a ratio of 1:1 (w / w);
[0061] In step 2, the added mass of 5-HMF was increased from 1.20 g to 2.40 g, the reaction temperature was set to 100° C., the reaction time was set to 1.5 h, and other conditions and operations were the same as in Example 1.
[0062] Example 16
[0063] In step 1, the metal compounds KCl and Fe(NO3)3·9H2O were replaced by Mn(OAc)2·4H2O and Co(NO3)2·6H2O, with a total mass of 0.60 g and a ratio of 1:1 (w / w), and the catalyst promoter 4-OH-TEMPO was replaced by TEMPO;
[0064] In step 2, the added mass of 5-HMF was increased from 1.20 g to 2.40 g, the reaction temperature was set to 100 °C, the reaction time was set to 1.5 h, and the other conditions and operations were the same as in Example 1.
[0065] Embodiment 17
[0066] In step 1, the metal compounds KCl and Fe(NO3)3·9H2O were replaced with Mn(OAc)2·4H2O and Co(OAc)2·4H2O, with a total mass of 0.60 g and a ratio of 1:1 (w / w);
[0067] In step 2, the solvent was changed from DCM to HOAc; the reaction temperature was set to 100° C., the reaction time was set to 8 h, and other conditions and operations were the same as in Example 1.
[0068] Embodiment 18
[0069] In step 1, the metal compound KCl is replaced by Cu(NO3)2·3H2O and Fe(NO3)3·9H2O with a total mass of 0.72 g and a ratio of 1:1 (w / w);
[0070] In step 2, the solvent was changed from DCM to HOAc; the reaction temperature was set to 100° C., the reaction time was set to 8 h, and other conditions and operations were the same as in Example 1.
[0071] Embodiment 19
[0072] In step 2, the solvent was changed from HOAc to ACN, the reaction time was set to 12 h, and other conditions and operations were the same as in Example 17.
[0073] Embodiment 20
[0074] In step 2, the solvent was changed from HOAc to DCE, the reaction time was set to 10 h, and other conditions and operations were the same as in Example 17.
[0075] Embodiment 21
[0076] In step 2, the solvent was changed from HOAc to MeOH, the reaction time was set to 10 h, and other conditions and operations were the same as in Example 17.
[0077] Embodiment 22
[0078] In step 2, the solvent was changed from HOAc to pure water, the reaction time was set to 36 h, and other conditions and operations were the same as in Example 17.
[0079] Table 1: Analysis results of Examples 1-16
[0080]
[0081]
[0082]
[0083] Table 2: Analytical results of Examples 17-22
[0084]
[0085]
[0086] It can be seen from the above experimental results that the method of the present invention has a relatively high yield for oxidizing 5-HMF to DFF, and still maintains a high DFF yield and selectivity at a higher substrate concentration, with the DFF yield being as high as 94.17%; the DFF selectivity being as high as 98.53%, and the 5-HMF conversion rate being as high as 95.57%.
[0087] Embodiment 23
[0088] The recovered composite catalysts of Examples 5, 8 and 14 were washed with clean water for several times, dried at 75° C. for 8 h and then recovered. The conditional experiments of Examples 5, 8 and 14 were repeated in sequence, and each catalyst was subjected to at least 5 cycle experiments. Sampling tests were performed after each cycle experiment.
[0089] Table 4: Analysis results of Example 23
[0090]
[0091]
[0092] In summary, the present invention uses air or oxygen as an oxygen source, and a metal compound and a catalytic aid are combined to form a catalytic oxidation system to catalyze the oxidation of 5-HMF. The reaction process is relatively efficient, and the catalytic effect decreases less after multiple cycles, providing a new idea for high value-added chemical catalysis of biomass.
Claims
1. A method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF, characterized in that The steps include: 1) Put the metal salt compound and the auxiliary agent into the solvent for dispersion, introduce N2 after uniform dispersion, keep it at a certain temperature for a period of time, and filter it after returning to room temperature to separate the solid and liquid, wash and dry the solid to obtain the composite catalyst; 2) 5-HMF and the composite catalyst prepared in step 1) are uniformly dispersed in a solvent, reacted in air or O2 atmosphere for a period of time, and after the reaction, the mixed solution is collected and completely spin-dried, and then pure water is added and stirred to obtain the desired product, and the remaining composite catalyst solid is recovered by a magnet.
2. The method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF according to claim 1, characterized in that In step 1), the metal salt compound is one or more of KCl, NaCl, KBr, NaBr, CuCl, CuCl2, RuCl3, KMnO4, Fe(NO3)2, Fe(NO3)3·9H2O, Ni(NO3)2·6H2O, Co(OAc)2·4H2O, Mn(OAc)2·4H2O, Cu(NO3)2·3H2O, Co(NO3)2·6H2O, and Zn(NO3)2·6H2O; The auxiliary agent is one or more of Al2O3, SiO2, CeO2, TiO2, K2S2O8, Fe3O4, ZnO, activated carbon, 9-azabicyclo[3.3.1]nonane-N-oxyl free radical, 2,2,6,6-tetramethylpiperidinyl oxide, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl oxide, o-phenylenediamine-N-oxyl, N-hydroxysuccinimide, and N-hydroxyo-phenylenediamine.
3. The method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF according to claim 1, characterized in that In step 1), the solvent is one or a mixed solvent of water, acetone, methanol, ethanol, formic acid, acetic acid, acetonitrile, dimethyl sulfoxide, chloromethane, dichloromethane, chloroform, pyridine, 1, 2-dichloroethane, N, N-dimethylformamide, 1-butanol, 1, 4-dioxane, isopropanol and toluene.
4. The method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF according to claim 1, characterized in that Step 1) The volume ratio of the mass of the metal salt compound to the mass of the auxiliary agent and the solvent is 1:0.5-20:20-100, with the mass unit being g and the volume unit being mL.
5. The method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF according to claim 1, characterized in that In step 1), the reaction temperature is 20-150°C and the reaction time is 0.5-3h.
6. The method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF according to claim 1, characterized in that In step 2), the volume ratio of the mass of 5-HMF to the mass of the composite catalyst and the solvent is 1:0.5-10:20-100, respectively, with the mass unit being g and the volume unit being mL.
7. The method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF according to claim 1, characterized in that In step 2), the reaction temperature is 20-100° C., the reaction time is 1-36 hours, and the pressure of the air or oxygen is 0.5-3.5 MPa.
8. The method for preparing 2,5-furandicarboxaldehyde by catalytic oxidation of 5-HMF according to claim 1, characterized in that In step 2), the solvent is one or a mixed solvent of water, acetone, methanol, ethanol, formic acid, acetic acid, acetonitrile, dimethyl sulfoxide, chloroform, dichloromethane, chloroform, pyridine, 1, 2-dichloroethane, N, N-dimethylformamide, N, N-dimethylacetamide, 1, 4-dioxane, isopropanol, ethyl acetate and toluene.