CN111253353A - Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural - Google Patents

Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural Download PDF

Info

Publication number
CN111253353A
CN111253353A CN201811460246.1A CN201811460246A CN111253353A CN 111253353 A CN111253353 A CN 111253353A CN 201811460246 A CN201811460246 A CN 201811460246A CN 111253353 A CN111253353 A CN 111253353A
Authority
CN
China
Prior art keywords
transition metal
hydroxymethylfurfural
pyrolysis
catalyst
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811460246.1A
Other languages
Chinese (zh)
Inventor
徐杰
刘鑫
马红
高进
苗虹
张树静
罗杨
张美云
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201811460246.1A priority Critical patent/CN111253353A/en
Publication of CN111253353A publication Critical patent/CN111253353A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt

Abstract

The application discloses a method for preparing 2, 5-dimethyl furandicarboxylate by catalyzing 5-hydroxymethylfurfural through oxidative esterification, wherein 5-hydroxymethylfurfural is in contact with a transition metal catalyst for catalysis under the condition of an oxidizing atmosphere to obtain the 2, 5-dimethyl furandicarboxylate. The method can be used for efficiently and selectively catalyzing, oxidizing and esterifying the 5-hydroxymethylfurfural into the dimethyl 2, 5-furandicarboxylate without an alkali additive.

Description

Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural
Technical Field
The application relates to a method for preparing dimethyl 2, 5-furandicarboxylate by catalyzing 5-hydroxymethylfurfural through oxidative esterification, and belongs to the technical field of chemical material preparation.
Background
The 2, 5-furan dicarboxylic acid dimethyl ester is used as a chemical product of a biomass source and can be used for preparing the PEF of the bio-based polyester, and compared with the important PET of the petroleum-based polyester, the PEF polyester has similar monomer structure characteristics, biodegradability, high application potential and high food safety certification of European Union. Therefore, the development of a simple, efficient, green and environment-friendly synthetic route of 2, 5-furandicarboxylic acid dimethyl ester is of great significance. The 5-hydroxymethylfurfural can be obtained by hydrolyzing, isomerizing and dehydrating cellulose and hemicellulose from biomass, and is an important bio-based platform compound. A great deal of literature reports that cellulose, glucose and the like from biomass are taken as raw materials for dehydration to prepare 5-hydroxymethylfurfural (Xujie, Argent autumn, Huangyi war, Malanhong, Miao hong, Gaohong, Gaohao, a method for preparing 5-hydroxymethylfurfural by utilizing fructose conversion catalyzed by a solid catalyst, 201310272819.9), so that the development of a novel method for preparing 2, 5-dimethyl furandicarboxylate by catalytic oxidation esterification of 5-hydroxymethylfurfural in a non-petroleum route has feasibility and sustainable development significance.
Currently, the preparation of dimethyl 2, 5-furandicarboxylate by oxidative esterification of 5-hydroxymethylfurfural mainly adopts a heterogeneous noble metal active component catalytic system. For example, by using a TiO2 supported Au catalyst, and CH3ONa as a basic additive, the reaction is carried out at 0.4MPa O2 and 105 ℃ for 3 hours, the 5-hydroxymethylfurfural is completely converted, and the selectivity of the obtained 2, 5-furandicarboxylic acid dimethyl ester is 98% (Taarning E, Nielsen I S, Egeblad K, et al. ChemSusChem,2008,1, 75-78.). Casanova et al used a nano CeO 2-loaded Au catalyst to catalyze 5-hydroxymethylfurfural oxidative esterification reaction under the conditions of 1.0MPa O2 and 130 ℃ to obtain dimethyl 2, 5-furandicarboxylate (Casanova O, Iborra S, Corma A. J. Catal.,2009,265,109-116.) with a yield of 99%. In consideration of the high price and limited large-scale application of noble metals, the preparation of dimethyl 2, 5-furandicarboxylate by the oxidative esterification of 5-hydroxymethylfurfural with a non-noble metal active component heterogeneous catalyst attracts attention, however, the reported non-noble metal catalytic system has low efficiency and unsatisfactory yield, and needs alkaline additives such as NaOH or K2CO3 to promote the reaction, and the post-treatment process needs to be neutralized by acid. Therefore, developing a green and environment-friendly route, designing a high-efficiency non-noble metal-based catalyst, and preparing 2, 5-furandicarboxylic acid dimethyl ester by using the high-efficiency high-selectivity oxidation esterification of 5-hydroxymethylfurfural face certain challenges.
Disclosure of Invention
According to one aspect of the application, a method for preparing 2, 5-dimethyl furan dicarboxylate by catalyzing 5-hydroxymethylfurfural oxidation and esterification is provided, and the method can be used for efficiently and selectively catalyzing 5-hydroxymethylfurfural oxidation and esterification into the 2, 5-dimethyl furan dicarboxylate without alkali additives.
The method for preparing the dimethyl 2, 5-furandicarboxylate by catalyzing the oxidative esterification of 5-hydroxymethylfurfural is characterized in that the 5-hydroxymethylfurfural is in contact with a transition metal catalyst for catalysis under the condition of an oxidizing atmosphere to obtain the dimethyl 2, 5-furandicarboxylate.
Optionally, the transition metal catalyst comprises a support and a transition metal active component supported on the support;
the carrier is selected from at least one of aluminum oxide, ferroferric oxide, zirconium dioxide, magnesium oxide, cerium dioxide and carbon materials;
the transition metal active component comprises a compound containing a transition metal active element, wherein the transition metal active element is selected from at least one of manganese, iron, cobalt and copper.
Specifically, the carbon material includes activated carbon.
Optionally, the loading amount of the transition metal active component in the transition metal catalyst is 3-25%; wherein the mass of the transition metal active component is measured as the mass of the transition metal active element.
The upper limit of the loading of the transition metal active component in the transition metal catalyst is selected from 5.8%, 5.9%, 6.0%, 6.1%, 6.3%, 6.7%, 6.8%, 6.9%, 7.2%, 7.6%, 7.7%, 25%, and the lower limit of the loading of the transition metal active component in the transition metal catalyst is selected from 3%, 5.8%, 5.9%, 6.0%, 6.1%, 6.3%, 6.7%, 6.8%, 6.9%, 7.2%, 7.6%, 7.7%.
In the present application, the active component of the catalyst is prepared as a uniformly dispersed nanostructure to improve the catalytic performance of the catalyst.
The present application also provides a method for preparing a transition metal catalyst, comprising:
(a) soaking the carrier in a mixture containing transition metal salt and an organic ligand, and drying to obtain a solid A;
(b) and carrying out pyrolysis I on the solid A in an inactive atmosphere to obtain a solid B, namely the transition metal catalyst.
Specifically, in the step (a), adding an organic ligand into an ethanol solution of transition metal salt, stirring at room temperature, adding a carrier, continuously stirring for 5-8 hours at 50-70 ℃, removing the solvent by rotary evaporation, and drying in an oven to obtain the solid A.
In the step (B), the obtained solid A is heated to the pyrolysis temperature at the heating rate of 10-20 ℃/min in an inactive atmosphere, and the temperature is kept for 2-3 h, so that the solid B, namely the transition metal catalyst, is obtained.
Optionally, the transition metal salt comprises at least one of chloride, nitrate, sulfate, acetate and acetylacetonate containing transition metal elements;
the organic ligand comprises at least one of 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine and 2, 6-bis (2-phenylimidazole).
Optionally, the molar ratio of the transition metal salt to the organic ligand is 1: 3-5; wherein the transition metal salt is present in moles based on the transition metal salt itself; the moles of the organic ligand are measured as the organic ligand itself.
Optionally, further comprising step (c): and (3) carrying out acid treatment on the solid B obtained after the pyrolysis I, drying, doping a nitrogenous additive, and carrying out pyrolysis II in an inactive atmosphere to obtain a solid C, namely the transition metal catalyst.
Specifically, after pyrolysis I is finished, carrying out acid treatment on the obtained solid B at 70-90 ℃, washing with water, drying, doping a nitrogen-containing additive, heating to a pyrolysis temperature at a heating rate of 10-30 ℃/min in an inactive atmosphere, and carrying out heat preservation for 2-3 h to obtain solid C, namely the transition metal catalyst.
The acid in the acid treatment in step (c) comprises at least one of sulfuric acid, hydrochloric acid, nitric acid and acetic acid.
Optionally, the nitrogen-containing additive comprises urea, dicyanodiamine, triethylamine, ethylenediamine, polypyrrole, C3N4At least one of (1).
Optionally, the pyrolysis temperature of the pyrolysis I and the pyrolysis II is 300-900 ℃.
The upper limit of the pyrolysis temperature of the pyrolysis I is selected from 800 ℃ and 900 ℃, and the lower limit of the pyrolysis temperature of the pyrolysis I is selected from 300 ℃ and 800 ℃. The pyrolysis temperature of pyrolysis II is selected from the same range as that of pyrolysis I, and will not be described in detail herein.
In the application, the catalyst obtained after further pyrolysis has high activity of catalyzing the oxidative esterification of 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxylic acid dimethyl ester.
In the present application, the catalyst is prepared by an impregnation method and a pyrolysis method, so that the metal components form metals and metal oxides with a nano structure and uniform dispersion.
When the 5-hydroxymethylfurfural is catalyzed to be oxidized and esterified to prepare the dimethyl 2, 5-furandicarboxylate, optionally, the oxidizing atmosphere comprises at least one of oxygen and air.
The pressure of the oxidizing atmosphere is 0.1-1.0 MPa.
The temperature of the catalytic reaction is 40-120 ℃.
The upper limit of the temperature of the catalytic reaction is selected from 100 ℃ and 120 ℃, and the lower limit of the temperature of the catalytic reaction is selected from 40 ℃ and 100 ℃.
The time of catalytic reaction is 1-24 h.
The upper limit of the time for the catalytic reaction is selected from 8h, 10h, 12h and 24h, and the lower limit of the time for the catalytic reaction is selected from 1h, 8h, 10h and 12 h.
In the process of preparing dimethyl 2, 5-furandicarboxylate from 5-hydroxymethylfurfural, the molar ratio of the transition metal catalyst to the 5-hydroxymethylfurfural is 0.1-0.2: 1, preferably, 0.12: 1, wherein the number of moles of the transition metal catalyst is the number of moles of the transition metal element.
In the present application, the inert atmosphere includes at least one of nitrogen and argon.
The beneficial effects that this application can produce include:
1) according to the method for preparing the dimethyl 2, 5-furandicarboxylate by catalyzing the oxidative esterification of 5-hydroxymethylfurfural, the 5-hydroxymethylfurfural is efficiently and selectively catalyzed, oxidized and esterified into the dimethyl 2, 5-furandicarboxylate without an alkali additive.
2) The heterogeneous transition metal catalyst is used to realize the efficient catalytic oxidation esterification of 5-hydroxymethylfurfural into dimethyl 2, 5-furandicarboxylate under mild conditions.
3) The transition metal catalyst has the advantages of low cost and less dosage.
4) The catalyst prepared by the invention takes a carbon material as a carrier, can provide the stability of metal nanoparticles in the reaction process, and the introduction of heteroatom nitrogen plays a role in promoting the preparation of 2, 5-furandicarboxylic acid dimethyl ester by catalytic oxidation and esterification of 5-hydroxymethylfurfural.
5) The invention uses the prepared transition metal catalyst, can avoid adding alkali additives into the system and post-treatment processes of acidification, and is a green and environment-friendly synthetic route.
6) The catalyst prepared by the invention has good reusability; the catalyst and the preparation method of the 2, 5-furan dimethyl diformate have innovativeness and high popularization and application values.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the conversion of 5-hydroxymethylfurfural and the selectivity to dimethyl-2, 5-furandicarboxylate were calculated on the basis of carbon moles:
conversion of 5-hydroxymethylfurfural ═ [ (5-hydroxymethylfurfural carbon moles in the reactant) - (5-hydroxymethylfurfural carbon moles in the product) ]/(5-hydroxymethylfurfural carbon moles in the reactant) × (100%);
selectivity to dimethyl 2, 5-furandicarboxylate dimethyl carbon moles ÷ sum of carbon moles of different organics of the product x 100%.
Example 1
Preparation of Fe @ NC-1
(1) Adding 2,2 '-bipyridine amine ligand (the molar ratio of the iron acetate to the 2,2' -bipyridine amine is 1:4) into 50mL of ethanol solution of iron acetate with the concentration of 0.01mol/L, stirring for 1h at room temperature, adding 0.6g of carrier aluminum oxide-zirconium dioxide, continuing stirring for 5h at 60 ℃, removing the solvent by rotary evaporation, and drying in an oven at 80 ℃ for 12h to obtain solid A;
(2) the solid A obtained is placed in an inert atmosphere N2Heating at a heating rate of 20 ℃/min, and keeping the temperature at 900 ℃ for 2h to obtain the Fe @ NC-1 catalyst.
Example 2
Preparation of Mn @ NC-2
(1) Adding 2,2 '-bipyridyl ligand (the molar ratio of manganese acetate to 2,2' -bipyridyl is 1:4) into 50mL of ethanol solution of manganese acetate with the concentration of 0.01mol/L, stirring at room temperature for 0.5h, adding 0.6g of carrier zirconium dioxide, continuing stirring at 60 ℃ for 6h, removing the solvent by rotary evaporation, and drying in an oven at 80 ℃ for 12h to obtain solid A;
(2) heating the obtained solid A in an inert atmosphere Ar at the heating rate of 10 ℃/min, and keeping the temperature at 900 ℃ for 3h to obtain a solid B;
(3) and then treating the solid B with nitric acid at 80 ℃ for 12h, washing with water, drying at 100 ℃ for 24h to obtain a precursor of the catalyst, doping triethylamine (the mass ratio of the triethylamine to the precursor is 4: 1), heating at the heating rate of 10 ℃/min in an inert atmosphere Ar, and keeping at 800 ℃ for 2h to obtain the Mn @ NC-2 catalyst.
Example 3
Preparation of u @ NC-3 at C DEG C
(1) Adding 1, 10-phenanthroline ligand (the molar ratio of cobalt acetate to copper nitrate to 1, 10-phenanthroline is 0.5:0.5:4) into 60mL of an ethanol solution of a mixture of cobalt acetate and copper nitrate (the concentrations of Co and Cu are 0.005mol/L and 0.005mol/L respectively), stirring at room temperature for 1h, adding 0.6g of carrier magnesium oxide, continuously stirring at 60 ℃ for 8h, removing the solvent by rotary evaporation, and drying in an oven at 80 ℃ for 12h to obtain a solid A;
(2) heating the obtained solid A in an inert atmosphere Ar at the heating rate of 15 ℃/min, and keeping the temperature at 800 ℃ for 2h to obtain a solid B;
(3) then treating the solid B with acetic acid at 80 ℃ for 12h, washing with water, drying at 100 ℃ for 24h to obtain a precursor of the catalyst, and doping C3N4(C3N4The mass ratio of the precursor to the precursor is 4: 1) heating at the heating rate of 30 ℃/min in an inert atmosphere Ar, and keeping at 800 ℃ for 2h to obtain the CoCu @ NC-3 catalyst.
Example 4
Preparation of CoCu @ NC-4
The preparation of CoCu @ NC-4 is the same as in example 3, except that: the organic ligand is 2,2' -bipyridine, the carrier is 0.6g of ferroferric oxide, and the nitrogen-containing additive is dicyanodiamide (the mass ratio of dicyanodiamide to the precursor is 4: 1).
Example 5
Preparation of CoCu @ NC-5
The preparation of CoCu @ NC-5 is the same as in example 3, except that: the organic ligand is 2,2' -bipyridine amine, the carrier is 0.6g of cerium dioxide, and the doped nitrogen-containing additive is dicyanodiamide (the mass ratio of dicyanodiamide to the precursor is 4: 1).
Example 6
Preparation of CoCu @ NC-6
The preparation of CoCu @ NC-6 is the same as in example 3, except that: the organic ligand is 2,2' -bipyridine, the carrier is 0.6g of magnesium oxide, and the nitrogen-containing additive is ethylenediamine (the mass ratio of ethylenediamine to the precursor is 4: 1).
Example 7
Preparation of MnCo @ NC-7
The preparation method of MnCo @ NC-7 is the same as that of example 3, except that: the metal salt is manganese acetate and cobalt acetate, the organic ligand is 2,2' -bipyridine amine, the carrier is 0.6g of magnesium oxide, and the doped nitrogen-containing additive is triethylamine (the mass ratio of triethylamine to the precursor is 4: 1).
Example 8
Preparation of Co @ NC-8
The preparation of Co @ NC-8 is the same as in example 2, except that: the metal salt is cobalt acetate, the organic ligand is 1, 10-phenanthroline, the carrier is 0.6g of magnesium oxide, and the nitrogen-containing additive is doped into the carrier C3N4(C3N4The mass ratio of the precursor to the precursor is 4: 1).
Example 9
Preparation of Mn @ NC-9
The preparation of Mn @ NC-9 is the same as in example 2, except that: the organic ligand is 1, 10-phenanthroline, the carrier is 0.6g of magnesium oxide, and the nitrogen-containing additive is polypyrrole (the mass ratio of polypyrrole to the precursor is 4: 1).
Example 10
Preparation of MnCo @ NC-10
The preparation method of MnCo @ NC-10 is the same as that of example 3, except that: the metal salt is manganese acetate and cobalt acetate, the organic ligand is 4,4' -bipyridine, the carrier is 0.6g of zirconium dioxide, and the doped nitrogen-containing additive is urea (the mass ratio of urea to the precursor is 4: 1).
Example 11
Preparation of Mn @ NC-11
The preparation of Mn @ NC-11 is the same as in example 2, except that: the organic ligand is 2, 6-bis (2-phenylimidazole), the carrier is 0.6g of cerium dioxide, and the nitrogen-containing additive is triethylamine (the mass ratio of triethylamine to the precursor is 4: 1).
Example 12
Preparation of MnCo @ NC-12
The preparation method of MnCo @ NC-12 is the same as that of example 3, except that: the metal salt is manganese acetate and cobalt acetate, the organic ligand is 2,2' -bipyridine, the carrier is 0.6g of magnesium oxide, and the doped nitrogen-containing additive is urea (the mass ratio of urea to precursor is 4: 1).
Example 13
Adding Fe @ NC-1 (Fe7.2wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5 ml methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 14
Adding Mn @ NC-2(Mn 6.9 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 15
Adding CoCu @ NC-3 (Co2.9wt% Cu3.2wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5 ml methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside the stainless steel high-pressure reaction kettle, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 16
Adding CoCu @ NC-4 (Co3.7wt% Cu2.3wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside the stainless steel high-pressure reaction kettle, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 10 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 17
Adding CoCu @ NC-5 (Co3.1wt% Cu2.8wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside the stainless steel high-pressure reaction kettle, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 10 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 18
Adding CoCu @ NC-5 (Co3.1wt% Cu2.8 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside the stainless steel high-pressure reaction kettle, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 120 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 10 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 19
Adding CoCu @ NC-6 (Co3.4wt% Cu2.4wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside the stainless steel high-pressure reaction kettle, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 10 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 20
Adding MnCo @ NC-7 (Mn4.1wt% Co2.7wt%) catalyst, 0.5mmol of 5-hydroxymethyl furfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside the stainless steel high-pressure reaction kettle, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 21
Adding MnCo @ NC-7 (Mn4.1wt% Co2.7wt%) catalyst, 0.5mmol of 5-hydroxymethyl furfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside the stainless steel high-pressure reaction kettle, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 0.6MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 22
Adding Co @ NC-8 (Co7.6wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, wherein a polytetrafluoroethylene lining is attached to the inside of the stainless steel high-pressure reaction kettle, and the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 23
Adding Mn @ NC-9 (Mn7.6wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, wherein a polytetrafluoroethylene lining is attached to the inside of the stainless steel high-pressure reaction kettle, and the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.5MPa of oxygen, reacting for 8 hours, and keeping the pressure unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 24
Adding MnCo @ NC-10 (Mn3.8wt% Co2.9wt%) catalyst, 0.5mmol 5-hydroxymethyl furfural and 5 ml methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining in the stainless steel high-pressure reaction kettle, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.5MPa of oxygen, reacting for 8 hours, and keeping the pressure unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 25
Adding Mn @ NC-11 (Mn7.7wt%) catalyst, 0.5mmol of 5-hydroxymethyl furfural and 5 ml of methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.5MPa of oxygen, reacting for 8 hours, and keeping the pressure unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
Example 26
Adding MnCo @ NC-12 (Mn3.5wt% Co2.8wt%) catalyst, 0.5mmol 5-hydroxymethyl furfural and 5 ml methanol into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.12: 1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.5MPa of oxygen, reacting for 8 hours, and keeping the pressure unchanged in the reaction process. The reaction products were analyzed by GC and the results are shown in Table I.
TABLE-catalytic Oxidation esterification results of 5-hydroxymethylfurfural on different catalysts
Figure BDA0001888502770000111
Figure BDA0001888502770000112
Figure BDA0001888502770000121
HMF: 5-hydroxymethylfurfural, FDMC: 2, 5-Furan dicarboxylic acid dimethyl ester
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A method for preparing 2, 5-dimethyl furan dicarboxylate by catalyzing 5-hydroxymethylfurfural through oxidative esterification is characterized in that 5-hydroxymethylfurfural is in contact with a transition metal catalyst for catalysis under the condition of an oxidizing atmosphere to obtain the 2, 5-dimethyl furan dicarboxylate.
2. The method according to claim 1, wherein the transition metal catalyst comprises a carrier and a transition metal active component supported on the carrier;
the carrier is selected from at least one of aluminum oxide, ferroferric oxide, zirconium dioxide, magnesium oxide, cerium dioxide and carbon materials;
the transition metal active component comprises a compound containing a transition metal active element, wherein the transition metal active element is selected from at least one of manganese, iron, cobalt and copper.
3. The method according to claim 2, wherein the loading amount of the transition metal active component in the transition metal catalyst is 3-25%;
wherein the mass of the transition metal active component is measured as the mass of the transition metal active element.
4. The method according to claim 2, wherein the method for preparing the transition metal catalyst comprises:
(a) soaking the carrier in a mixture containing transition metal salt and an organic ligand, and drying to obtain a solid A;
(b) and carrying out pyrolysis I on the solid A in an inactive atmosphere to obtain a solid B, namely the transition metal catalyst.
5. The method of claim 4, further comprising step (c): and (3) carrying out acid treatment on the solid B obtained after the pyrolysis I, drying, doping a nitrogenous additive, and carrying out pyrolysis II in an inactive atmosphere to obtain a solid C, namely the transition metal catalyst.
6. The method of claim 4, wherein the transition metal salt comprises at least one of chloride, nitrate, sulfate, acetate, acetylacetonate containing a transition metal element;
the organic ligand comprises at least one of 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine and 2, 6-bis (2-phenylimidazole).
7. The method according to claim 4, wherein the molar ratio of the transition metal salt to the organic ligand is 1:3 to 5;
wherein the transition metal salt is present in moles based on the transition metal salt itself;
the moles of the organic ligand are measured as the organic ligand itself.
8. The method of claim 5, wherein the nitrogen-containing additive comprises urea, dicyanodiamine, triethylamine, ethylenediamine, polypyrrole, C3N4At least one of (1).
9. The method as claimed in claim 4 or 5, wherein the pyrolysis temperature of pyrolysis I and pyrolysis II is 300 to 900 ℃.
10. The method of claim 1, wherein the oxidizing atmosphere comprises at least one of oxygen, air;
the pressure of the oxidizing atmosphere is 0.1-1.0 MPa;
the temperature of the catalytic reaction is 40-120 ℃;
the time of catalytic reaction is 1-24 h.
CN201811460246.1A 2018-11-30 2018-11-30 Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural Pending CN111253353A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811460246.1A CN111253353A (en) 2018-11-30 2018-11-30 Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811460246.1A CN111253353A (en) 2018-11-30 2018-11-30 Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural

Publications (1)

Publication Number Publication Date
CN111253353A true CN111253353A (en) 2020-06-09

Family

ID=70944874

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811460246.1A Pending CN111253353A (en) 2018-11-30 2018-11-30 Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural

Country Status (1)

Country Link
CN (1) CN111253353A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979596A (en) * 2019-12-13 2021-06-18 中国科学院大连化学物理研究所 Method for preparing dimethyl 2, 5-furandicarboxylate
CN113198512A (en) * 2021-05-11 2021-08-03 莆田达凯新材料有限公司 Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate
CN114308036A (en) * 2021-12-06 2022-04-12 深圳信息职业技术学院 Method for oxidizing and repairing polluted soil by activated carbon-based monatomic iron catalyst
CN114507200A (en) * 2020-11-14 2022-05-17 中国科学院大连化学物理研究所 Method for preparing 2, 5-furan diformate by heterogeneous catalysis

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108084123A (en) * 2016-11-22 2018-05-29 中国科学院大连化学物理研究所 A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters
CN108148023A (en) * 2016-12-04 2018-06-12 中国科学院大连化学物理研究所 A kind of method for synthesizing methyl 2-furoate
CN108148024A (en) * 2016-12-04 2018-06-12 中国科学院大连化学物理研究所 A kind of method of furfural oxidative esterification methylfuroate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108084123A (en) * 2016-11-22 2018-05-29 中国科学院大连化学物理研究所 A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters
CN108148023A (en) * 2016-12-04 2018-06-12 中国科学院大连化学物理研究所 A kind of method for synthesizing methyl 2-furoate
CN108148024A (en) * 2016-12-04 2018-06-12 中国科学院大连化学物理研究所 A kind of method of furfural oxidative esterification methylfuroate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUXIA SUN等: "A High-Performance Base-Metal Approach for the Oxidative Esterification of 5-Hydroxymethylfurfural", 《CHEMCATCHEM》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979596A (en) * 2019-12-13 2021-06-18 中国科学院大连化学物理研究所 Method for preparing dimethyl 2, 5-furandicarboxylate
CN114507200A (en) * 2020-11-14 2022-05-17 中国科学院大连化学物理研究所 Method for preparing 2, 5-furan diformate by heterogeneous catalysis
CN113198512A (en) * 2021-05-11 2021-08-03 莆田达凯新材料有限公司 Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate
CN113198512B (en) * 2021-05-11 2022-06-24 莆田达凯新材料有限公司 Nitrogen-carbon-doped cobalt-based bimetallic catalyst, preparation method thereof and preparation method of dimethyl 2, 5-furandicarboxylate
CN114308036A (en) * 2021-12-06 2022-04-12 深圳信息职业技术学院 Method for oxidizing and repairing polluted soil by activated carbon-based monatomic iron catalyst

Similar Documents

Publication Publication Date Title
CN111253353A (en) Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural
CN108712931B (en) Catalyst for producing 2, 5-furandicarboxylic acid and method for producing 2, 5-furandicarboxylic acid using the same
CN110102350B (en) Catalyst for oxidative synthesis of 2, 5-furandicarboxylic acid and preparation method and application thereof
CN108084123A (en) A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters
CN111377890B (en) Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural
CN108148024B (en) Method for preparing methyl furoate by oxidizing and esterifying furfural
CN101695657B (en) Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin
CN110437190B (en) Method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural
CN109836315B (en) Catalytic preparation method of veratraldehyde
CN111408392A (en) Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof
CN108148023A (en) A kind of method for synthesizing methyl 2-furoate
CN114213368B (en) Method for preparing furan dicarboxylic acid by oxidizing 5-hydroxymethylfurfural with composite catalyst
CN112121845A (en) cobalt/N-doped nanosheet graphite phase carbon nitride composite material and preparation method and application thereof
CN111250126A (en) Catalyst, preparation method and application thereof
CN112661729B (en) Application of nitrate-assisted carbon catalytic system in preparation of 2, 5-furan dicarboxaldehyde by catalytic conversion of 5-hydroxymethylfurfural
CN113318735B (en) Application of composite oxide supported Pt catalyst in preparation of pentanediol from furfural
CN102336733A (en) Method of catalytic oxidation of cyclohexane
CN114621166A (en) Preparation method of 2, 5-furandicarboxylic acid
Machado et al. Catalysts and processes for gluconic and glucaric acids production: A comprehensive review of market and chemical routes
CN114105917B (en) Method for preparing 2,5-furandicarboxylic acid by efficiently catalyzing 5-hydroxymethylfurfural
CN111393397B (en) Preparation method of 2, 5-furandicarboxylic acid
CN110860297B (en) Preparation method of Cu-Ag/La @ HAP catalyst and application of catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propanediol
CN114618546A (en) Preparation method of transition metal catalyst and application of transition metal catalyst in preparation of aromatic aldehyde
CN111253230B (en) Method for preparing 3-hydroxymethylcyclopentanone by hydrogenating 5-hydroxymethylfurfural under catalysis of water phase
CN113698373B (en) Method for preparing 2, 5-furandicarboxylic acid by high-efficiency photocatalytic oxidation

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200609

RJ01 Rejection of invention patent application after publication