CN112375052A - Method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction - Google Patents

Method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction Download PDF

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CN112375052A
CN112375052A CN202011123788.7A CN202011123788A CN112375052A CN 112375052 A CN112375052 A CN 112375052A CN 202011123788 A CN202011123788 A CN 202011123788A CN 112375052 A CN112375052 A CN 112375052A
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glucose
diformylfuran
catalyst
graphene oxide
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雷俊禧
蔡珠华
王志成
李翔
李凯欣
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Guangzhou Weigang Environmental Protection Technology Co ltd
Guangdong University of Technology
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Guangdong University of Technology
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Abstract

The invention discloses a method for preparing 2, 5-diformylfuran through glucose three-step cascade reactionStep-by-step cascade reaction: 1) isomerizing glucose to prepare fructose; 2) dehydrating fructose to generate 5-hydroxymethylfurfural (5-HMF)3) and oxidizing 5-HMF to synthesize the DFF. Step 1) selecting TiO containing anatase phase and rutile phase2The catalyst, the step 2) to the step 3) adopts a graphene oxide catalyst, so that the direct and efficient conversion of the biomass (glucose) into the platform product (2, 5-diformylfuran) with high added value is realized.

Description

Method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction
Technical Field
The invention relates to the technical field of preparation of 2, 5-diformylfuran, in particular to a method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction.
Background
The isomerization of glucose to fructose is one of the most important biomass conversion reactions. Cellulose is a biomass resource abundant in nature, and a constituent monomer of the cellulose is glucose. Fructose is widely used as a key sugar intermediate in the biorefinery process to synthesize high molecular substances such as 5-hydroxymethylfurfural (5-HMF), 2, 5-Diformylfuran (DFF), 25-furandicarboxylic acid (FDCA), levulinic acid, lactic acid, and the like ]. Currently, the industrial production of fructose is mainly realized by enzymatic isomerization of glucose, however, the enzymatic system itself faces some unavoidable problems, such as short service life, unrecoverable catalytic material and harsh reaction conditions [6 ]. Therefore, the development of a heterogeneous catalyst which is easy to separate and can be reused is urgently needed, and the heterogeneous catalyst is applied to the process of preparing fructose by high-efficiency and high-selectivity isomerization of glucose.
Many conventional basic heterogeneous catalysts are currently available for glucose isomerization, such as alkali-modified zeolites, Mg-Al mixed oxides, metal silicates, and the like. Although the product selectivity of the process is good, the conversion rate of glucose can reach 40%, when the initial concentration of glucose reaches 30%, the fructose selectivity of the traditional catalytic process is greatly reduced due to side reactions including base-triggered trans-aldol reaction, and the efficiency of enzymatic isomerization conversion is still far higher than that of the traditional catalytic process.
In recent years, Lewis acid is used as a high-efficiency catalyst and is also applied to the glucose isomerization conversion process. Homogeneous Lewis catalysts (e.g. AlCl)3,BF3And transition metal halides) are unstable in the aqueous phase and the catalytic activity is unstable, affecting the yield of fructose obtained by glucose isomerization.
The catalytic conversion of fructose to 2, 5-Diformylfuran (DFF) is one of the most attractive research directions at present because the product has high added value, great potential in organic synthesis and pharmaceutical industry, and low-cost and easily available raw materials. DFF is typically synthesized from fructose by a two-step conversion process involving the catalytic dehydration of fructose acids to 5-HMF and the catalytic oxidation of 5-HMF with a metal-based catalyst to DFF. If the two-step process is integrated into one-step operation, the process is more economical and environment-friendly, and the development of the bifunctional/multifunctional catalyst can realize the integration of the domino/cascade reaction of the process into one-step operation. However, the bifunctional catalysts developed and used at present have extremely low catalytic efficiency.
At present, no industrial application of preparing 2, 5-diformylfuran by directly converting glucose exists.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing 2, 5-diformylfuran by glucose three-step cascade reaction, and the technical route comprises the three-step cascade reaction: the method comprises the steps of preparing fructose through glucose isomerization, dehydrating the fructose to generate 5-hydroxymethylfurfural (5-HMF), and oxidizing the 5-HMF to synthesize 2, 5-diformylfuran, so that the biomass (glucose) is directly and efficiently converted into a platform product (2, 5-diformylfuran) with a high added value.
The purpose of the invention is realized by adopting the following technical scheme:
a process for the preparation of 2, 5-diformylfuran by a three-step cascade of glucose reactions comprising the steps of:
1) adjusting the pH value to 3-5 in a glucose solution, adding a multi-phase Lewis acid catalyst, and reacting at 120-180 ℃ to obtain a fructose solution; wherein the multi-phase Lewis acid catalyst is TiO containing anatase phase and rutile phase2A catalyst; TiO containing both anatase phase and rutile phase2The catalyst is more traditional single-phase TiO2Has better structural performance. Due to the presence of large amounts of TiO6Octahedron and TiO4Tetrahedral sites, and presence of anatase TiO2To rutile TiO2The interfacial electron transfer can show stronger Lewis acidity and catalytic activity, and improve the selectivity of generating fructose;
2) adding a graphene oxide catalyst into the fructose solution obtained in the step 1), and reacting at 120-200 ℃ to obtain 2, 5-diformylfuran; specifically, under the action of a graphene oxide catalyst, a fructose solution is dehydrated to generate 5-hydroxymethylfurfural (5-HMF), and then the 5-hydroxymethylfurfural (5-HMF) is subjected to hydrogenation reaction to prepare 2, 5-Diformylfuran (DFF).
The graphene oxide catalyst is prepared by sulfonating graphene oxide sheets and loading noble metal, so that the graphene oxide catalyst has double catalytic active centers (acid active center and noble metal active center) and can provide proper acidity and high-efficiency redox sites, and the catalyst has high catalytic activity in the process of preparing 2, 5-diformylfuran by fructose one-pot catalytic conversion.
Further, the mass ratio of the multi-phase lewis acid catalyst to the glucose in the step 1) is 0.05 to 0.1: 1.
further, in step 1), a sulfuric acid solution is added to adjust the pH.
Further, in the step 1), the precursor of the multi-phase Lewis acid catalyst is TiOSO4，Ti[OCH(CH3)2]4And TiBr4One or more of them.
Still further, the precursor of the multi-phase Lewis acid catalyst is reacted in a glucose solution to prepare the multi-phase Lewis acid catalyst.
Further, in the step 2), the mass ratio of the graphene oxide catalyst to the fructose solution is 0.01-0.1: 1.
further, in the step 2), the graphene oxide catalyst is prepared by sulfonating graphene oxide sheets and then loading noble metals on the sulfonated graphene oxide sheets by adding a reducing agent. Specifically, the first step in preparing the graphene oxide catalyst is to sulfonate graphene oxide sheets in an organic acid, and the second step is to fix noble metal nanoparticles in situ on the sulfonated graphene oxide sheets.
Further, in the step 2), the sulfonating agent used for sulfonating the graphene oxide catalyst is one or more of chlorosulfonic acid, fuming sulfuric acid and alkyl sultone.
Further, in the step 2), the noble metal is one or more of ruthenium, rhodium, platinum and palladium; the reducing agent is NaBH4One or more of KBH, hydrazine hydrate and polyamine.
Further, in the step 1), adding a multi-phase Lewis acid catalyst after the glucose is deionized and dissolved; the multi-phase Lewis acid catalysts used in the present invention are shown to have water resistance and are more stable in aqueous solution than conventional multi-phase Lewis acid catalysts.
In the step 2), adding an organic solvent after adding a graphene oxide catalyst into the fructose solution; the organic solvent is one or more of toluene, dimethyl sulfoxide, isopropanol and methyl isobutyl ketone. 5-HMF is unstable in a single solvent phase (usually the aqueous phase) and changes in the concentration gradient over the acid active center result in the oligomerization of 5-HMF to produce humus by-products. Therefore, in order to stabilize the furan intermediate (5-HMF) and to improve the yield of the furan Derivative (DFF), a biphasic solution system was introduced (deionized water as the aqueous phase and one or more of toluene, dimethyl sulfoxide, isopropanol and methyl isobutyl ketone as the organic phase).
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes glucose as raw material, firstly passes through TiO containing anatase phase and rutile phase2The catalyst isomerizes glucose to prepare fructose, graphene oxide which is sulfonated and loaded with noble metals is added into a fructose solution, the fructose is firstly dehydrated to generate 5-hydroxymethylfurfural, then the 5-hydroxymethylfurfural is subjected to hydrogenation reaction to prepare 2, 5-Diformylfuran (DFF), and the reactions are all performed in the same reactor, so that the direct and efficient conversion of biomass (glucose) into a high-added-value platform product (2, 5-diformylfuran) is realized.
(2) Since 5-HMF is unstable in the aqueous phase, the present invention employs a two-phase solution system of an organic phase and an aqueous phase in order to stabilize the furan intermediate (5-HMF) and improve the yield of the furan Derivative (DFF).
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The invention discloses TiO containing anatase phase and rutile phase2The catalyst and the graphene oxide catalyst are applied to a three-step cascade reaction for preparing the DFF from the glucose to realize direct catalytic conversion of the glucose to prepare the DFF, and the technical route is as follows:
Figure BDA0002732912550000051
TiO comprising anatase phase and rutile phase according to the invention2The catalyst and the graphene oxide catalyst are suitable for various reactors, such as a moving bed reactor, a tubular reactor, a stirred tank reactor and the like.
TiO comprising anatase phase and rutile phase according to the invention2The catalyst and the graphene oxide catalyst can be recycled by simple centrifugal separation.
TiO containing anatase phase and rutile phase used in preparation of fructose by isomerization of glucose in the invention2The preparation method of the catalyst comprises the following steps:
1) adding a titanium precursor solution into a glucose (not less than 99 percent, Sigma-Aldrich) solution with the concentration of 7 percent to obtain a mixed solution; wherein the titanium precursor is TiOSO4(ii) a The concentration range of the titanium precursor is 10-12 mg/mL;
2) stirring and heating the solution obtained in the step 1) at 160 ℃ and 600rpm for 1h, cooling, filtering to obtain a solid product, washing the solid product with deionized water, and performing vacuum drying at 70 ℃ for 8 h;
3) then calcining at 550 deg.C for 100min to remove organic impurities, and then calciningGrinding the solid to obtain TiO containing anatase phase and rutile phase2A catalyst.
The preparation method of the graphene oxide catalyst selected in the steps of generating 5-HMF by catalytic dehydration of the pectic acid and generating DFF by hydrogenation of the 5-HMF comprises the following steps:
1) graphene oxide (Cobat Corporation) was added to a chloroform solution of 1mol/L chlorosulfonic acid (98%, Sigma-Aldrich), and the mixed solution was heated at 60 ℃ and in N2Stirring and refluxing vigorously for 24h, cooling the suspension obtained by refluxing to room temperature, repeatedly centrifuging and washing in an ice bath by using deionized water and ethanol, and freeze-drying for 24h to obtain monofunctional graphene oxide;
2) adding monofunctional graphene oxide into ethylene glycol, carrying out ultrasonic oscillation for 1-3 h, adding 14mg/mL ruthenium (III) chloride hydrate (ruthenium content 40.00 wt%, Sigma-Aldrich) for standing for 3h, adding NaOH solution to adjust pH to 13, heating the solution to 130 ℃, and reacting with NaBH with a concentration of 20mg/mL4The ethylene glycol solution is slowly mixed; wherein, NaBH4The mass ratio of the ethylene glycol solution to the ruthenium trichloride solution is 3 percent;
3) refluxing the solution obtained in the step 2) at 130 ℃ for 1h, cooling to room temperature, dropwise adding 2L of deionized water into the solution, adjusting the pH value to the pH value in the step 1) by using 0.1mol/L HCl solution, filtering, washing with water, and drying in vacuum at 70 ℃ for 12h to obtain the graphene oxide catalyst.
Example 1
A process for the preparation of 2, 5-diformylfuran by a three-step cascade of glucose reactions comprising the steps of:
1) 0.5g of glucose was added to 10mL of deionized water, and after stirring and dissolving the resulting glucose solution, 0.0209mol/L of sulfuric acid solution was added to adjust the pH to 4, followed by addition of 10mg of TiO containing anatase phase and rutile phase2The catalyst reacts for 2 hours at 160 ℃ to obtain a fructose solution;
in this example, TiO comprising anatase phase and rutile phase2Anatase TiO in catalyst2In a proportion of 60%, rutile TiO2The proportion of (B) is 40%.
2) Directly adding 10mL of methyl isobutyl ketone into the fructose solution reacted in the step 1), then adding 10mg of graphene oxide catalyst, and reacting for 2h at 140 ℃ to obtain 2, 5-diformylfuran.
Example 2
A process for the preparation of 2, 5-diformylfuran by a three-step cascade of glucose reactions comprising the steps of:
1) 0.5g of glucose was added to 10mL of deionized water, and after stirring and dissolving the resulting glucose solution, 0.0209mol/L of sulfuric acid solution was added to adjust the pH to 3, followed by addition of 10mg of TiO containing anatase phase and rutile phase2The catalyst reacts for 1 hour at 180 ℃ to obtain a fructose solution;
in this example, TiO comprising anatase phase and rutile phase2Anatase TiO in catalyst2In a proportion of 50%, rutile TiO2The proportion of (B) is 50%.
2) Directly adding 10mL of toluene into the fructose solution reacted in the step 1), then adding 10mg of graphene oxide catalyst, and reacting for 3h at 120 ℃ to obtain 2, 5-diformylfuran.
Example 3
A process for the preparation of 2, 5-diformylfuran by a three-step cascade of glucose reactions comprising the steps of:
1) 0.5g of glucose was added to 10mL of deionized water, and after stirring and dissolving the resulting glucose solution, 0.0209mol/L of sulfuric acid solution was added to adjust the pH to 5, followed by addition of 10mg of TiO containing anatase phase and rutile phase2The catalyst reacts for 3 hours at the temperature of 120 ℃ to obtain a fructose solution;
in this example, TiO comprising anatase phase and rutile phase2Anatase TiO in catalyst2In a proportion of 80%, rutile TiO2The proportion of (B) is 20%.
2) Directly adding 10mL of isopropanol into the fructose solution reacted in the step 1), then adding 10mg of graphene oxide catalyst, and reacting at 200 ℃ for 1h to obtain 2, 5-diformylfuran.
Comparative example 1
Step 1) of comparative example 1 selects 10mgNb2O5Replacement of TiO comprising anatase and rutile phases2Catalyst, and in the step 2), 10mg of ZSM-5 is selected to replace the graphene oxide catalyst. The other steps and components were the same as in example 1.
Comparative example 2
Step 1) of comparative example 2 selects 10mgNb2O5Replacement of TiO comprising anatase and rutile phases2Catalyst, 10mg of SBA is selected to replace the graphene oxide catalyst in the step 2). The other steps and components were the same as in example 1.
Comparative example 3
Step 1) of comparative example 3 used 10mg TiO2-V2O5Replacement of TiO comprising anatase and rutile phases2Catalyst, 10mg of graphene is selected to replace the graphene oxide catalyst in the step 2). The other steps and components were the same as in example 1.
Comparative example 4
10mg TiO was used for both step 1) and step 2) of comparative example 42Ionic liquid, the other steps and components are the same as in example 1.
Comparative example 5
Comparative example 5 step 1) 10mg TiO was used2-V2O5Replacement of TiO comprising anatase and rutile phases2The catalyst, other steps and components were the same as in example 1.
Comparative example 6
10mg of graphene was selected to replace the graphene oxide catalyst in step 2) of comparative example 6. The other steps and components were the same as in example 1.
Performance testing
The 2, 5-diformylfuran prepared in examples 1-3 and comparative examples 1-6 was analyzed, the furyl products in the organic and aqueous phases were analyzed by HPLC (Agilent 1100Series) equipped with a 282nm UV detector, a C18 reverse phase column, using acetonitrile: acetic acid (3:7v/v) as mobile phase. The sugars and sugar intermediates in the organic and aqueous phases were collected using a Refractive Index Detector (RID) and a Bio-Rad Aminex HPX-87H pre-packed column (300 mm. times.7.8 mm) with 5mmol/L sulfuric acid as the mobile phase. The product was quantified using an external standard method and an autosampler (Agilent G1329A) was used to improve the reproducibility of the detection. Fructose conversion, furan derivative yield and by-products were calculated as carbon-based on product concentration in the two phases (as can be derived from HPLC measurements). Then, the yield of 2, 5-diformylfuran and the conversion rate of glucose are calculated, wherein the conversion rate of glucose refers to the conversion rate of directly converting glucose into 2, 5-diformylfuran, and the data are shown in the following table:
TABLE 1 Effect of different catalysts on the catalytic conversion of glucose to 2, 5-diformylfuran
Catalyst and process for preparing same Yield (%) Glucose conversion (%)
Example 1 38.1 50.2
Example 2 37.6 49.1
Example 3 37.2 49.4
Comparative example 1 11.5 23.1
Comparative example 2 22.9 33.2
Comparative example 3 19.3 48.6
Comparative example 4 40.4 52.1
Comparative example 5 32.1 44.8
Comparative example 6 33.3 46.5
As can be seen from the data in Table 1, in comparative examples 1 to 6, except for comparative example 4, the glucose conversion and the yield of 2, 5-diformylfuran were lower than in examples 1 to 3. For comparative example 4, TiO was used due to homogeneity and multifunctionality of the ionic liquid itself2In the case of the ionic liquid, the glucose conversion rate and the yield of the 2, 5-diformylfuran are slightly higher than those of examples 1 to 3, but the ionic liquid is expensive and is not suitable for large-scale industrial production. The TiO2 catalyst containing anatase phase and rutile phase used in the step 1) in the embodiments 1-3 has interface electrons transferred from anatase phase to rutile phase and double-layer coupling between the two phases, so that the charge separation efficiency is improved, and the catalyst shows excellent activity in the process of preparing fructose by glucose aqueous phase catalytic conversion. The graphene oxide catalyst used in step 2) of examples 1 to 3 includes a sulfonic acid group and Ru nanoparticles, and exhibits high efficiency similar to that of a homogeneous catalyst due to high efficiency of the acid group and good dispersibility of the metal active center on the surface of the graphene oxide sheetThe method can realize the maximum contact of reactant molecules and catalytic activity centers.
The invention realizes the process of preparing the 2, 5-diformylfuran by the catalytic conversion of the glucose in the aqueous solution for the first time, the catalyst has obvious effect, and has feasibility and great potential in the aspect of preparing the 2, 5-diformylfuran by the catalytic conversion of low-cost biomass (glucose).
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (10)

1. A process for the preparation of 2, 5-diformylfuran by a three-step cascade of glucose reactions, comprising the steps of:
1) adjusting the pH value to 3-5 in a glucose solution, adding a multi-phase Lewis acid catalyst, and reacting at 120-180 ℃ to obtain a fructose solution; wherein the multi-phase Lewis acid catalyst is TiO containing anatase phase and rutile phase2A catalyst;
2) adding a graphene oxide catalyst into the fructose solution obtained in the step 1), and reacting at 120-200 ℃ to obtain 2, 5-diformylfuran; the graphene oxide catalyst is prepared by sulfonating graphene oxide sheets and loading noble metal.
2. The method for preparing 2, 5-diformylfuran by glucose three-step cascade reaction according to claim 1, wherein in step 1), the mass ratio of the multi-phase lewis acid catalyst to the glucose is 0.05 to 0.1: 1.
3. the method for preparing 2, 5-diformylfuran by glucose three-step cascade reaction according to claim 1, wherein in step 1), a sulfuric acid solution is added to adjust the pH.
4. The method for preparing 2, 5-diformylfuran by glucose three-step cascade reaction according to claim 1, wherein the precursor of the multi-phase lewis acid catalyst in step 1) is TiOSO4，Ti[OCH(CH3)2]4And TiBr4One or more of them.
5. The method of claim 4, wherein the precursor of the multi-phase Lewis acid catalyst is reacted in a glucose solution to produce a multi-phase Lewis acid catalyst.
6. The method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction according to claim 1, wherein in the step 2), the mass ratio of the graphene oxide catalyst to the fructose solution is 0.01-0.1: 1.
7. the method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction according to claim 1, wherein, in the step 2), the graphene oxide catalyst is prepared by sulfonating graphene oxide sheets and then loading noble metal on the sulfonated graphene oxide sheets by adding a reducing agent.
8. The method for preparing 2, 5-diformylfuran through glucose three-step cascade reaction according to claim 1 or 7, wherein in the step 2), the sulfonating agent used for sulfonating the graphene oxide catalyst is one or more of chlorosulfonic acid, oleum and alkyl sultone.
9. The method for preparing 2, 5-diformylfuran by glucose three-step cascade reaction according to claim 7, wherein in step 2), the noble metal is one or more of ruthenium, rhodium, platinum and palladium; the reducing agent is NaBH4KBH, hydrazine hydrate and polyaminesOne or more of (a).
10. The method for preparing 2, 5-diformylfuran by glucose three-step cascade reaction according to claim 1, wherein in step 1), after the glucose is added with deionized water and dissolved, a multi-phase lewis acid catalyst is added; in the step 2), adding an organic solvent after adding a graphene oxide catalyst into the fructose solution; the organic solvent is one or more of toluene, dimethyl sulfoxide, isopropanol and methyl isobutyl ketone.
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