CN113004232A - Method for preparing FDCA (fully drawn yarn) by carbohydrate in two steps in one pot - Google Patents

Method for preparing FDCA (fully drawn yarn) by carbohydrate in two steps in one pot Download PDF

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CN113004232A
CN113004232A CN202110284662.6A CN202110284662A CN113004232A CN 113004232 A CN113004232 A CN 113004232A CN 202110284662 A CN202110284662 A CN 202110284662A CN 113004232 A CN113004232 A CN 113004232A
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fructose
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李振环
李潇然
苏坤梅
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Tianjin Polytechnic University
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    • 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
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Abstract

The invention discloses a method for preparing FDCA by saccharide compounds in two steps in one pot. The method starts from saccharides, takes solid acid as a dehydration catalyst, takes a polar aprotic organic solvent as a serial two-step solvent, takes a commercial tap water disinfectant as an oxidant in an oxidation catalyst-free system, and oxidizes HMF in situ to prepare FDCA under mild oxidation conditions and a wider pH range, wherein the yield of FDCA reaches more than 90 percent, and the problem that the final yield of FDCA is generally low in the method for preparing FDCA by a one-pot method starting from saccharides at the present stage is solved. The invention discovers the oxidation activity of the cheap commercial tap water disinfectant in the field of producing FDCA as the oxidant for the first time, and does not need any catalyst catalysis including noble metal catalyst, thus leading the production cost of FDCA to be lower.

Description

Method for preparing FDCA (fully drawn yarn) by carbohydrate in two steps in one pot
Technical Field
The invention belongs to the field of preparation of bio-based polymer monomers, and particularly relates to a method for preparing FDCA (fully drawn yarn) by using carbohydrate compounds in two steps in one pot.
Background
With the increasing depletion of fossil resources, people are beginning to vigorously develop bio-based alternatives to petroleum products, and it is expected to reduce the consumption of non-renewable resources and alleviate environmental pollution. Biomass carbohydrates can be converted to a wide variety of basic biobased compounds through various oxidative pathways, such as 2, 5-furandicarboxylic acid (FDCA), 5-Hydroxymethylfurfural (HMF), levulinic acid, and the like. The compounds have excellent reaction characteristics, can be used as precursors of many high-value-added bio-based chemicals or materials, and have important significance for relieving the crisis of fossil resource shortage.
FDCA, an oxidized derivative of HMF, which is drawing attention because of its chemical structure similar to terephthalic acid (PTA), is considered to be one of the most promising bio-based monomers for the production of sustainable polymeric materials. PTA is a monomer derived from petroleum resources and is used primarily to produce some important polymers or plasticizers, such as polyethylene terephthalate (PET). PET is widely used as fiber, film and plastic, and is widely applied to various fields of clothing, engineering, food packaging and the like. However, the use of PET not only causes great consumption of petroleum resources and causes energy crisis, but also cannot be naturally degraded and causes white pollution. Polyethylene glycol furandicarboxylate (PEF) synthesized by using FDCA as a raw material is a bio-based substitute of PET, is easy to degrade, is environment-friendly and renewable, and has more remarkable advantages in the aspects of mechanical strength, mechanical strength and the like. However, the ability to apply PEF on a large scale is primarily limited by the cost of FDCA production. Therefore, the development of a production process for inexpensively preparing FDCA is the focus of research at this stage.
The direct conversion of carbohydrates (e.g. fructose, glucose and cellulose) to FDCA by the "one-pot" process is a focus of recent research and also a successful search for the direct conversion of biomass resources to functional small molecules. Starting from carbohydrate compounds, the synthesis of FDCA via the HMF route specifically comprises two steps: (1) catalyzing the dehydration of the carbohydrate compound by the acid catalyst to generate HMF; (2) HMF is oxidized to FDCA. The one-pot method is to directly oxidize HMF stock solution obtained by dehydrating carbohydrate in situ without separation and refining to obtain the target product FDCA, and the whole reaction can be completed in one pot. The one-pot method can greatly reduce the energy consumption, simplify the production process and reduce the production cost of the FDCA.
The one-pot method can be further classified into a "one-pot one-step method" and a "one-pot two-step method" according to whether the solid acid catalyst needs to be separated between the dehydration step and the oxidation step. However, whether the "one-pot one-step method" or the "one-pot two-step method", the current research results still face a plurality of technical problems, such as: mostly, only low FDCA yield can be obtainedThe rate and the overall conversion time are longer, the oxidation temperature is still higher, and expensive noble metal catalysts are mostly needed for the oxidation step.
Figure BDA0002979937930000011
Et al (Topics in Catalysis,2000,13(3): 237-. However, due to the diffusion rate of the PTFE membrane, the HMF formed in the aqueous phase cannot diffuse into the MIBK phase in a timely manner, resulting in the majority of the HMF produced being hydrolyzed to the by-product levulinic acid without being oxidized, with a final FDCA yield of only 25%, with a total consumption of about 168 h.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing FDCA by carbohydrate compounds in two steps in one pot.
The technical scheme for solving the technical problems is to provide a method for preparing FDCA by carbohydrate compounds in two steps in one pot, which is characterized by comprising the following steps:
step 1, dissolving a saccharide compound in a polar aprotic organic solvent to obtain a solution A after the saccharide compound is completely dissolved; the mass fraction of the carbohydrate in the solution A is 2-25 percent;
step 2, under the protection of inert gas, heating and dehydrating the solution A under the catalytic action of a solid acid catalyst, and filtering the solid acid catalyst after the reaction is finished to obtain a solution B; the mass of the solid acid catalyst is 5-80% of that of the saccharide compound;
and 3, adding a polar aprotic organic solvent into the solution B until the concentration of HMF in the solution B is 0.04-0.3 mol/L, adding an alkali additive to adjust the pH of the solution to 3-12, adding an aqueous solution of a tap water disinfectant as an oxidant after the system reaches an oxidation temperature, and carrying out sealed and light-proof oxidation reaction to obtain the FDCA.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to a series preparation process for converting carbohydrate into FDCA by a one-pot two-step method. The method is characterized in that the method starts from saccharides, takes solid acid as a dehydration catalyst, takes a polar aprotic organic solvent as a serial two-step solvent, takes a commercial tap water disinfectant as an oxidant in an oxidation catalyst-free system, and oxidizes HMF in situ to prepare FDCA under mild oxidation conditions and a wider pH range, wherein the yield of FDCA reaches over 90 percent, and the problem that the final yield of FDCA is generally low in the method for preparing FDCA by a one-pot method starting from saccharides at the present stage is solved.
(2) The invention discovers the oxidation activity of the cheap commercial tap water disinfectant in the field of producing FDCA as the oxidant for the first time, and does not need any catalyst catalysis including noble metal catalyst, thus leading the production cost of FDCA to be lower.
(3) The invention can control the temperature of the oxidation step to be 0-100 ℃ and the oxidation time to be 5 min-10 h, greatly reduces the energy consumption required by the oxidation step, has low requirements on reaction equipment, and provides possibility for realizing industrial production of FDCA.
(4) The method adopts cheap carbohydrate as a raw material, converts fructose by a one-pot two-step method without a separation and purification step of an intermediate product HMF, saves separation cost and time, reduces raw material loss caused by the separation process, makes the preparation process of FDCA simpler and more economic, and greatly reduces the cost of the raw material.
(5) Compared with the traditional method which can only obtain the salt solution of the FDCA, the method can directly obtain the stable solution of the FDCA, avoid strong acid pollution possibly caused by the subsequent precipitation of the FDCA, and ensure that the preparation process of the FDCA is more environment-friendly.
Drawings
FIG. 1 is a reaction scheme for preparing FDCA from saccharide compounds according to the present invention;
FIG. 2 is an HPLC chromatogram of solution B obtained in step 2 of example 1 of the present invention;
FIG. 3 is an HPLC chromatogram of the product obtained in step 3 of example 1 of the present invention.
Detailed Description
Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The invention provides a method for preparing FDCA (fully drawn yarn) by carbohydrate in two steps in one pot (short method), which is characterized by comprising the following steps:
step 1, dissolving a saccharide compound in a polar aprotic organic solvent, and stirring at normal temperature until the saccharide compound is completely dissolved to obtain a solution A; the mass fraction of the carbohydrate in the solution A is 2-25 percent (preferably 2-18 percent), the range can ensure that the HMF has higher yield, and humus generated by dehydration can not influence the oxidation step of the HMF, and is preferably 5-18 percent);
preferably, in step 1, the saccharide compound is at least one of fructose, glucose, sucrose, starch, cellulose or inulin, preferably fructose;
preferably, in step 1, the polar aprotic organic solvent is at least one of DMSO, acetone, butanone, an ionic liquid, NMP, N-dimethylacetamide, or N, N-dimethylformamide, preferably DMSO;
step 2, under the protection of inert gas, heating and dehydrating the solution A under the catalytic action of a solid acid catalyst, continuously stirring in the reaction process, filtering the solid acid catalyst after the reaction is finished, obtaining a solution B, and cooling to room temperature;
preferably, in step 2, the solid acid catalyst is used to catalyze the dehydration of the carbohydrate compound by a mass of 5% to 80% (preferably 20% to 50%) of the mass of the carbohydrate compound.
Preferably, in step 2, the solid acid catalyst is natural clay substance, inorganic acid wetting substance, cation exchange resin, transition metal oxide, composite transition metal oxide loaded with sulfate ions, metal salt, composite heteropoly acid or heteropoly acid salt-metal organic framework material or titanic acid nanotube/graphene (H) with main components of silicon oxide and aluminum oxide2Ti3O7NT/RGO) composite material, preferably Amberlyst-15, which has the best catalytic effect, high yield of 5-HMF and by-product generationLess;
the natural clay substance with the main components of silicon oxide and aluminum oxide is kaolin, bentonite, montmorillonite or natural zeolite;
the inorganic acid infiltration substance refers to HCI and H2SO4、H3PO4Inorganic acids such as heteropoly acid, etc. on corresponding carriers (such as alumina, silica, zirconia, titania and their composite oxides or molecular sieves);
the cation exchange resin is Amberlyst-15 or DOWEX50WX 8-100;
the transition metal oxide TiO2、ZrO2、WO3Or MoO3；
The composite transition metal oxide is WO3-ZrO2Or MoO3-ZrO2；
The compound transition metal oxide loaded with sulfate ions is SO4 2-@WOx-ZrO2Or SO4 2-@MoOx-ZrO2；
The metal salt is NiSO4、AlPO4、AlCl3Or CrCl3；
The composite heteropoly acid or heteropoly acid salt-metal organic framework material refers to phosphotungstic acid, copper phosphotungstate or cesium phosphotungstate loaded by a Cu-BTC metal organic framework material;
the inert gas is nitrogen or argon.
Preferably, in the step 2, the heating dehydration reaction temperature is 50-180 ℃ (preferably 100-150 ℃), and the heating dehydration reaction time is 1-600 min (preferably 5-60 min); the heating mode is oil bath heating, microwave radiation, infrared heating or high-frequency electromagnetic heating; preferably, the heating mode is microwave radiation, infrared heating or high-frequency electromagnetic heating, the HMF yield is high, and the heating power is 200W-1200W (preferably 350-800W). Preferably, a microwave radiation mode is adopted, the heating power is 350-550W, the reaction temperature is 100-140 ℃, the reaction time is 5-45 min, and when the reaction is carried out within the condition range, the yield of HMF is high, and humus is less.
And 3, adding a polar aprotic organic solvent into the solution B until the concentration of HMF in the solution B is 0.04-0.3 mol/L, adding an alkali additive to adjust the pH value of the solution to 3-12 (preferably 5-10), adding an aqueous solution of a tap water disinfectant as an oxidant after the system reaches an oxidation temperature, and carrying out sealed and light-proof oxidation reaction to obtain the FDCA.
The water solution of the tap water disinfectant is prepared by dissolving the tap water disinfectant in deionized water and stirring in a dark place until the tap water disinfectant is completely dissolved; the tap water disinfectant is at least one of commercial chlorine dioxide, dichloroisocyanuric acid and sodium salt thereof, trichloroisocyanuric acid and sodium salt thereof or hypochloric acid and sodium salt thereof, the effective chlorine content is more than 6%, and chlorine dioxide is preferred;
preferably, in step 3, the alkali additive is KOH, NaOH or Na2CO3、K2CO3、NaHCO3Or KHCO3At least one of;
preferably, in the step 3, the oxidation temperature is 0-100 ℃ (preferably 25-70 ℃); the oxidation time is 5 min-10 h (preferably 30 min-3 h).
Preferably, in step 3, the polar aprotic organic solvent is added to adjust the concentration of HMF, and the base additive is added to adjust the pH of the solution.
Example 1
1. Adding 2g of fructose and 38g of DMSO into a 100mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose, namely a solution A;
2. adding 0.8g of Amberlyst-15 catalyst into the solution obtained in the step 1, keeping the nitrogen atmosphere, adopting 480W microwave radiation power, heating to 130 ℃, preserving the heat for 9min to obtain a DMSO solution of HMF, namely a solution B, filtering Amberlyst-15, and cooling to room temperature for later use;
3. putting 7.5g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 8 percent into 30g of water to be completely dissolved to obtain chlorine dioxide solution; and 3.5g of stock solution prepared in the step 2 is taken, 10g of DMSO is added, then NaOH solid is added to adjust the pH value of the system to be 10, the mixed solution is heated in a water bath to 50 ℃ and is continuously stirred, 20mL of chlorine dioxide solution is added into the mixed solution, and the mixed solution is sealed and protected from light to react for 1.5 hours, so that the target product FDCA can be obtained.
The fructose conversion rate and HMF and FDCA obtained in the reaction process are qualitatively and quantitatively determined by high performance liquid chromatography, the fructose conversion rate is more than 98%, the HMF yield is 93.7%, the FDCA yield is 92.47%, and the total conversion time is about 2 h.
Example 2
1. Adding 3.3g of fructose and 38g of DMSO into a 100mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. adding 1.32g of Amberlyst-15 catalyst into the solution obtained in the step 1, keeping the nitrogen atmosphere, adopting 560W microwave radiation power, heating to 130 ℃, preserving the heat for 12min to obtain a DMSO solution of HMF, filtering the Amberlyst-15, and cooling to room temperature for later use;
3. putting 7.5g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 8 percent into 30g of water to be completely dissolved to obtain chlorine dioxide solution; and (3) adding 10.6g of DMSO into 2.95g of stock solution prepared in the step 2, adding NaOH solid to adjust the pH value of the system to 10, heating the mixed solution in a water bath to 50 ℃, continuously stirring, adding 20mL of chlorine dioxide solution into the mixed solution, and carrying out sealed light-proof reaction for 1.5h to obtain the target product FDCA.
The fructose conversion rate and HMF and FDCA obtained in the reaction process are qualitatively and quantitatively determined by a high performance liquid chromatography, the fructose conversion rate is more than 90 percent, the HMF yield is 62 percent, the FDCA yield is 90.4 percent, and the total conversion time is about 2 hours.
Example 3
1. Adding 1g of fructose and 19g of DMSO (dimethyl sulfoxide) into a 50mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. adding 0.4g of Amberlyst-15 catalyst into the solution obtained in the step 1, keeping the nitrogen atmosphere, adopting 720W microwave radiation power, heating to 140 ℃, preserving the heat for 9min to obtain a DMSO solution of HMF, filtering the Amberlyst-15, and cooling to room temperature for later use;
3. putting 7.5g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 8 percent into 30g of water to be completely dissolved to obtain chlorine dioxide solution; taking 3g of stock solution prepared in the step 2, adding 10.5g of DMSO and then adding NaHCO3Solid adjusting system pH 8And (10) heating the mixed solution to 45 ℃ in a water bath, continuously stirring, adding 19mL of chlorine dioxide solution into the mixed solution, and carrying out sealed and light-proof reaction for 1.8h to obtain the target product FDCA.
The conversion rate of fructose and the obtained HMF and FDCA in the reaction process are qualitatively and quantitatively determined by high performance liquid chromatography, the conversion rate of fructose is more than 98 percent, the yield of HMF is 96 percent, the yield of FDCA is 92.78 percent, and the total conversion time is about 2.5 hours.
Example 4
1. Adding 1.5g of fructose and 36g of DMSO into a 100mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. adding 0.45g of Amberlyst-15 catalyst into the solution obtained in the step 1, keeping the nitrogen atmosphere, adopting 480W microwave radiation power, heating to 120 ℃, preserving the heat for 20min to obtain a DMSO solution of HMF, filtering the Amberlyst-15, and cooling to room temperature for later use;
3. putting 7.5g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 8 percent into 30g of water to be completely dissolved to obtain chlorine dioxide solution; taking 3.7g of stock solution prepared in the step 2, adding 9.8g of DMSO and then adding Na2CO3And (3) heating the mixed solution to 45 ℃ in a water bath, continuously stirring, adding 19mL of chlorine dioxide solution into the mixed solution, and reacting for 1.3h in a sealed and light-proof manner to obtain the target product FDCA.
The conversion rate of fructose and the obtained HMF and FDCA in the reaction process are qualitatively and quantitatively determined by high performance liquid chromatography, the conversion rate of fructose is more than 98 percent, the yield of HMF is 95.27 percent, the yield of FDCA is 92.16 percent, and the total conversion time is about 2 hours.
Example 5
1. Adding 1.5g of fructose and 36g of DMSO into a 100mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. adding 0.45g of Amberlyst-15 catalyst into the solution obtained in the step 1, keeping the nitrogen atmosphere, adopting 480W microwave radiation power, heating to 120 ℃, preserving the heat for 20min to obtain a DMSO solution of HMF, filtering the Amberlyst-15, and cooling to room temperature for later use;
3. 6g of a quotient having an available chlorine content of 10%Putting the chlorine dioxide effervescent tablets into 25g of water to be completely dissolved to obtain chlorine dioxide solution; taking 3.7g of stock solution prepared in the step 2, adding 9.8g of DMSO and then adding Na2CO3And (3) heating the mixed solution to 45 ℃ in a water bath, continuously stirring, adding 17mL of chlorine dioxide solution into the mixed solution, and carrying out sealed light-proof reaction for 1.5h to obtain the target product FDCA.
The conversion rate of fructose and the obtained HMF and FDCA in the reaction process are qualitatively and quantitatively determined by high performance liquid chromatography, the conversion rate of fructose is more than 98 percent, the yield of HMF is 95.27 percent, the yield of FDCA is 92.3 percent, and the total conversion time is about 2.5 hours.
Example 6
1. Adding 1g of fructose and 10mL of DMSO (dimethyl sulfoxide) into a 25mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. adding 50mg of titanic acid nanotube/graphene composite material (H) into the solution obtained in the step 12Ti3O7NT/RGO) catalyst, maintaining nitrogen atmosphere, adopting 560W microwave radiation power, heating to 150 deg.C, maintaining for 11min to obtain DMSO solution of HMF, filtering out H2Ti3O7Cooling to room temperature for later use after NT/RGO;
3. putting 6g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 10% into 25g of water to be completely dissolved to obtain chlorine dioxide solution; and 3g of stock solution prepared in the step 2 is taken, 10.5g of DMSO is added, then NaOH solid is added to adjust the pH value of the system to be 10, the mixed solution is heated in a water bath to 40 ℃, the mixture is continuously stirred, 20mL of chlorine dioxide solution is added into the mixed solution, and the mixture is sealed and protected from light to react for 1h, so that the target product FDCA is obtained.
The HMF and the FDCA obtained in the reaction process are qualitatively and quantitatively determined by high performance liquid chromatography, the yield of the HMF is 51.3 percent, the yield of the FDCA is 92.9 percent, and the total conversion time is about 1.5 h.
Said H2Ti3O7The preparation method of the NT/RGO catalyst comprises the following steps:
(1) 2g TiO was added to 120mL of 10mol/L NaOH solution2(P25), sonicating for 1.5 h;
(2) according to the proportion of Graphite Oxide (GO) in TiO2Weighing GO with the mass fraction of 5%, dissolving in a proper amount of deionized water, and alternately performing ultrasonic treatment and stirring to obtain a uniformly dispersed GO solution; then slowly dripping the GO solution into the solution obtained in the step (1) under the stirring condition, and continuously stirring for 4 hours to obtain uniform and stable alkaline suspension;
(3) transferring the alkaline suspension obtained in the step (2) into a reaction kettle with a 100mL polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 24h, and naturally cooling to room temperature; centrifuging to obtain precipitate, washing with deionized water to pH 6-7, soaking the product in 0.1mol/L excessive HCl solution, stirring for 12 hr, washing the precipitate with deionized water to pH 6-7, and drying at 80 deg.C for 12 hr to obtain titanate nanotube/graphene (H)2Ti3O7NT/RGO) composite material.
Example 7
1. Adding 1g of fructose and 19g of DMSO (dimethyl sulfoxide) into a 100mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. adding 0.35g of Amberlyst-15 catalyst into the solution obtained in the step 1, keeping the nitrogen atmosphere, adopting 640W microwave radiation power, heating to 140 ℃, preserving the heat for 6min to obtain a DMSO solution of HMF, filtering out Amberlyst-15, and cooling to room temperature for later use;
3. putting 5g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 12% into 20g of water to be completely dissolved to obtain chlorine dioxide solution; and 3.03g of stock solution prepared in the step 2 is taken, 10.5g of DMSO is added, then NaOH solid is added to adjust the pH value of the system to be 10, the mixed solution is heated in a water bath to 50 ℃ and is continuously stirred, 18mL of chlorine dioxide solution is added into the mixed solution, and the mixture is sealed and protected from light for reaction for 50min, so that the target product FDCA can be obtained.
The fructose conversion rate and HMF and FDCA obtained in the reaction process are qualitatively and quantitatively determined by a high performance liquid chromatography, the fructose conversion rate is more than 98 percent, the HMF yield is 95.06 percent, the FDCA yield is 92.75 percent, and the total conversion time is about 1.5 h.
Example 8
1. Adding 2g of fructose and 38g of DMSO into a 100mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. in step (b)0.3g of SO was added to the solution obtained in step 14 2-@WOX-ZrO2Keeping the catalyst in a nitrogen atmosphere, adopting 350W microwave radiation power, heating to 150 ℃, preserving heat for 6min to obtain a DMSO solution of HMF, filtering SO4 2-@WOX-ZrO2Then cooling to room temperature for later use;
3. putting 7.5g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 8 percent into 30g of water to be completely dissolved to obtain chlorine dioxide solution; and 3.5g of stock solution prepared in the step 2 is taken, 10g of DMSO is added, then NaOH solid is added to adjust the pH value of the system to be 10, the mixed solution is heated in a water bath to 50 ℃ and is continuously stirred, 20mL of chlorine dioxide solution is added into the mixed solution, and the mixed solution is sealed and protected from light to react for 1.5 hours, so that the target product FDCA can be obtained.
The fructose conversion rate and HMF and FDCA obtained in the reaction process are qualitatively and quantitatively determined by high performance liquid chromatography, the fructose conversion rate is more than 95 percent, the HMF yield is 83.8 percent, the FDCA yield is 92.05 percent, and the total conversion time is about 2 hours.
The SO4 2-@WOX-ZrO2The preparation method of the catalyst comprises the following steps:
(1) weighing 2.5g of hexadecyl trimethyl ammonium bromide, dissolving the hexadecyl trimethyl ammonium bromide in 20mL of n-butanol, stirring the solution at 40 ℃ for 10min to obtain a transparent solution, adding 0.02mol of zirconium isopropoxide, and continuously stirring the solution for 10min to uniformly mix the solution to obtain a mixed solution;
(2) dissolving 0.002mol of transition metal source (W) in 10mL of deionized water, then adding the solution into the mixed solution obtained in the step (1), vigorously stirring the solution for 24 hours at normal temperature, transferring the solution into a polytetrafluoroethylene reaction kettle, crystallizing the solution for 24 hours at 80 ℃, filtering, washing and drying the solution;
(3) soaking the solid obtained in step (2) in 1mol/L sulfuric acid water solution for 30min, filtering, washing to neutrality, drying, calcining at 550 deg.C for 4h at a temperature rise rate of 2 deg.C/min to obtain SO (n (W): n (Zr): 1: 10)4 2-@WOX-ZrO2A catalyst.
Example 9
1. Placing 0.56g of fructose, 3.5g of acetone and 3.5g of DMSO in a 25mL small beaker, continuously stirring at normal temperature until the fructose is completely dissolved, and transferring the obtained solution into a 10mL thick-wall Pyrex glass tube;
2. adding 0.4g of DOWEX50WX8-100 catalyst into the solution obtained in the step (1), keeping the nitrogen atmosphere, adopting 700W microwave radiation power, heating to 150 ℃, and preserving heat for 20min to obtain a DMSO solution of HMF; after the reaction is finished, filtering out the DOWEX50WX8-100 catalyst, and cooling to room temperature for later use;
3. putting 5g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 12% into 20g of water to be completely dissolved to obtain chlorine dioxide solution; and (3) adding 10g of DMSO into 1g of stock solution prepared in the step (2), adding NaOH solid to adjust the pH value of the system to be 10, heating the mixed solution in a water bath to 50 ℃, continuously stirring, adding 18mL of chlorine dioxide solution into the mixed solution, and carrying out sealed and light-proof reaction for 50min to obtain the target product FDCA.
The fructose conversion rate and HMF and FDCA obtained in the reaction process are qualitatively and quantitatively determined by a high performance liquid chromatography, the fructose conversion rate is more than 98 percent, the HMF yield is 82 percent, the FDCA yield is 90 percent, and the total conversion time is about 1.5 h.
Example 10
1. Adding 1g of fructose and 10mL of DMSO (dimethyl sulfoxide) into a 25mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. 0.1g of WO was added to the solution obtained in step 13-ZrO2Catalyst, keeping nitrogen atmosphere, heating to 130 ℃ in oil bath, condensing and refluxing for reaction for 3h to obtain DMSO solution of HMF, and filtering WO3-ZrO2Then cooling to room temperature for later use;
3. putting 6g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 10% into 25g of water to be completely dissolved to obtain chlorine dioxide solution; and (3) adding 10.5g of DMSO into 1g of stock solution prepared in the step 2, then adding NaOH solid to adjust the pH value of the system to be 10, heating the mixed solution in a water bath to 40 ℃, continuously stirring, adding 20mL of chlorine dioxide solution into the mixed solution, and carrying out sealed and light-proof reaction for 1h to obtain the target product FDCA.
The HMF and the FDCA obtained in the reaction process are qualitatively and quantitatively carried out by high performance liquid chromatography, the yield of the HMF is 80.26 percent, the yield of the FDCA is 90.82 percent, and the total conversion time is about 5 hours.
The W isO3-ZrO2The preparation method of the catalyst comprises the following steps: 16 wt% of zirconium oxychloride (ZrOCI) was prepared in a molar ratio of W to Zr of 1:102·8H2O) water solution and 11 wt% ammonium tungstate water solution, dropwise adding the ammonium tungstate water solution into the zirconium oxychloride water solution under the stirring condition, and continuously stirring for 0.5h to uniformly mix the two; then dropwise adding concentrated ammonia water under strong stirring until the pH value of the mixed solution is 9-10; the generated precipitate is vigorously stirred for 2h, kept stand and aged for 24h at room temperature, and then refluxed for 24h at 100 ℃; then filtering, washing, drying, grinding and roasting the obtained solid at 750 ℃ for 4 hours to obtain WO3-ZrO2A catalyst.
Example 11
1. Adding 1g of fructose and 10mL of DMSO (dimethyl sulfoxide) into a 25mL three-neck flask, and continuously stirring at normal temperature until the fructose is completely dissolved to obtain a DMSO solution of the fructose;
2. 0.3g of zirconia supported phosphotungstic acid catalyst (TPA/ZrO) was added to the solution obtained in step 12) Catalyst, TPA/ZrO2The loading amount of phosphotungstic acid (TPA) in the catalyst is 20 percent; keeping nitrogen atmosphere, heating to 120 deg.C in oil bath for 1.5h to obtain DMSO solution of HMF, filtering to remove TPA/ZrO2Then cooling to room temperature for later use;
3. putting 6g of commercial chlorine dioxide effervescent tablets with the effective chlorine content of 10% into 25g of water to be completely dissolved to obtain chlorine dioxide solution; and (3) adding 10.5g of DMSO into 1g of stock solution prepared in the step 2, then adding NaOH solid to adjust the pH value of the system to be 10, heating the mixed solution in a water bath to 40 ℃, continuously stirring, adding 20mL of chlorine dioxide solution into the mixed solution, and carrying out sealed and light-proof reaction for 1h to obtain the target product FDCA.
The HMF and the FDCA obtained in the reaction process are qualitatively and quantitatively determined by high performance liquid chromatography, the yield of the HMF is 73 percent, the yield of the FDCA is 90 percent, and the total conversion time is about 3 hours.
The high performance liquid chromatograph is adopted for measuring the yield and the conversion rate, and the model is Waters e 2695-2489.
Nothing in this specification is said to apply to the prior art.

Claims (10)

1. A one-pot two-step method for preparing FDCA from saccharide compounds is characterized by comprising the following steps:
step 1, dissolving a saccharide compound in a polar aprotic organic solvent to obtain a solution A after the saccharide compound is completely dissolved; the mass fraction of the carbohydrate in the solution A is 2-25 percent;
step 2, under the protection of inert gas, heating and dehydrating the solution A under the catalytic action of a solid acid catalyst, and filtering the solid acid catalyst after the reaction is finished to obtain a solution B; the mass of the solid acid catalyst is 5-80% of that of the saccharide compound;
and 3, adding a polar aprotic organic solvent into the solution B until the concentration of HMF in the solution B is 0.04-0.3 mol/L, adding an alkali additive to adjust the pH of the solution to 3-12, adding an aqueous solution of a tap water disinfectant as an oxidant after the system reaches an oxidation temperature, and carrying out sealed and light-proof oxidation reaction to obtain the FDCA.
2. The one-pot two-step preparation method of FDCA using saccharide compounds according to claim 1, wherein in step 1, the saccharide compound is at least one of fructose, glucose, sucrose, starch, cellulose or inulin; the polar aprotic organic solvent is at least one of DMSO, acetone, butanone, ionic liquid, NMP, N-dimethylacetamide or N, N-dimethylformamide.
3. The one-pot two-step process for preparing FDCA from a saccharide compound according to claim 1 or 2, wherein in step 1, the saccharide compound is fructose; the polar aprotic organic solvent is DMSO.
4. The one-pot two-step process for preparing FDCA from glucide according to claim 1, wherein the mass of the solid acid catalyst in the step 2 is 20 to 50% of the mass of the glucide.
5. The one-pot two-step FDCA preparation method of saccharide compounds according to claim 1, wherein in step 2, the solid acid catalyst is a natural clay-like material, an inorganic acid-wetting-like material, a cation exchange resin, a transition metal oxide, a composite transition metal oxide, a sulfate ion-loaded composite transition metal oxide, a metal salt, a composite heteropoly acid or heteropoly acid salt-metal organic framework material, or a titanate nanotube/graphene composite material, the main components of which are silicon oxide and aluminum oxide;
the natural clay substance with the main components of silicon oxide and aluminum oxide is kaolin, bentonite, montmorillonite or natural zeolite;
the inorganic acid infiltration substance is formed by loading inorganic acid on alumina, silicon oxide, zirconium oxide, titanium oxide or a molecular sieve carrier;
the cation exchange resin is Amberlyst-15 or DOWEX50WX 8-100;
the transition metal oxide TiO2、ZrO2、WO3Or MoO3；
The composite transition metal oxide is WO3-ZrO2Or MoO3-ZrO2；
The compound transition metal oxide loaded with sulfate ions is SO4 2-@WOx-ZrO2Or SO4 2-@MoOx-ZrO2；
The metal salt is NiSO4、AlPO4、AlCl3Or CrCl3；
The composite heteropoly acid or heteropoly acid salt-metal organic framework material refers to phosphotungstic acid, copper phosphotungstate or cesium phosphotungstate loaded by a Cu-BTC metal organic framework material.
6. The one-pot two-step process for preparing FDCA from saccharide compounds according to claim 1 or 5, wherein the solid acid catalyst in step 2 is Amberlyst-15.
7. The one-pot two-step method for preparing FDCA from saccharides according to claim 1, wherein in step 2, the temperature of the heating dehydration reaction is 50 to 180 ℃, and the time of the heating dehydration reaction is 5 to 60 min; the heating mode is microwave radiation, infrared heating or high-frequency electromagnetic heating, and the heating power is 200W-1200W.
8. The method as claimed in claim 1, wherein in step 3, the tap water disinfectant is at least one of chlorine dioxide, dichloroisocyanuric acid and sodium salt thereof, trichloroisocyanuric acid and sodium salt thereof, or hypochlorous acid and sodium salt thereof, and the effective chlorine content is more than 6%; the oxidation temperature is 0-100 ℃; the oxidation time is 5 min-10 h.
9. The method as claimed in claim 1, wherein in step 3, the tap water disinfectant is chlorine dioxide; the oxidation temperature is 25-70 ℃; the oxidation time is 30 min-3 h.
10. The method of claim 1, wherein in step 3, the alkali additive is KOH, NaOH or Na2CO3、K2CO3、NaHCO3Or KHCO3At least one of (1).
CN202110284662.6A 2021-03-17 2021-03-17 Method for preparing FDCA (fully drawn yarn) by carbohydrate in two steps in one pot Pending CN113004232A (en)

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