CN112979596A - Method for preparing dimethyl 2, 5-furandicarboxylate - Google Patents
Method for preparing dimethyl 2, 5-furandicarboxylate Download PDFInfo
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Abstract
The invention discloses a method for preparing 2, 5-furan dicarboxylic acid dimethyl ester, which comprises the following steps: in an oxidizing atmosphere, carrying out catalytic oxidation on 5-hydroxymethylfurfural in the presence of a non-noble metal catalyst to prepare dimethyl 2, 5-furandicarboxylate; the non-noble metal catalyst comprises a nitrogen-containing carrier and a non-noble metal active component loaded on the nitrogen-containing carrier. The method does not need to use an additional alkaline additive, has little pollution, avoids the use of a noble metal catalyst, reduces the preparation cost of the 2, 5-furandicarboxylic acid dimethyl ester, has simple process and is suitable for wide industrial application.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a method for preparing 2, 5-furan dicarboxylic acid dimethyl ester.
Background
Fossil resources are non-renewable primary energy, and the consumption of fossil resources is gradually increased every year, so that the exhaustion of fossil energy is inevitable for a long time. Biomass resources are widely stored on earth, and only a few of them are utilized, so that the conversion of biomass-derived substrates into value-added platform chemicals and fuels is one of the major concerns of current scientific research.
Therefore, it is necessary to provide a method for preparing dimethyl 2, 5-furandicarboxylate with simple process, low pollution and low cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing dimethyl 2, 5-furandicarboxylate, which has low cost and little pollution and can be widely applied to industrial application, under the condition of not adding an additional alkaline additive, 5-hydroxymethylfurfural is used for preparing the dimethyl 2, 5-furandicarboxylate under the catalytic oxidation action of a catalyst which has a nitrogen-containing carrier and loads non-noble metal active components, the nitrogen-containing carrier improves the adsorption firmness of a non-noble metal composition on the nitrogen-containing carrier, the catalytic activity is high, the overall preparation process is simple, the cost is low, and the pollution is little.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
providing a method for preparing dimethyl 2, 5-furandicarboxylate, wherein 5-hydroxymethylfurfural is catalytically oxidized in the presence of a non-noble metal catalyst in an oxidizing atmosphere to prepare dimethyl 2, 5-furandicarboxylate; the non-noble metal catalyst comprises a nitrogen-containing carrier, wherein the nitrogen-containing carrier supports non-noble metal active components.
Alternatively, the conditions of catalytic oxidation include:
the reaction temperature is 25-100 ℃;
the lower limit of the reaction temperature is independently selected from 25 ℃, 45 ℃, 75 ℃, 80 ℃ and 90 ℃;
the upper limit of the reaction temperature is independently selected from 35 deg.C, 55 deg.C, 85 deg.C, 95 deg.C, and 100 deg.C.
Optionally, the reaction time is 1-24 h;
the reaction time is independently selected from 1h, 2h, 4h, 6h, 8h, 10h, 12h, 16h, 18h, 20h and 24 h.
The reaction pressure is normal pressure to 1 MPa;
the lower limit of the reaction pressure is independently selected from 0.1MPa, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa and 0.9 MPa;
the upper limit of the reaction pressure is independently selected from 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa and 1 MPa.
The oxidizing atmosphere comprises air or oxygen.
Optionally, no alkaline additive is added during the catalytic oxidation.
Optionally, the nitrogen-containing carrier comprises at least one of urea, melamine, dicyanodiamine, ethylenediamine, carbon nitride, polypyrrole, polyaniline.
Optionally, the non-noble metal active component comprises a non-noble metal element.
The non-noble metal element includes at least one of manganese, iron, cobalt, copper, nickel, zinc, titanium, and vanadium.
Optionally, the loading amount of the non-noble metal active component in the non-noble metal catalyst is 5-25%;
wherein the loading of the non-noble metal active component is calculated by the loading of non-noble metal elements.
The content of the non-noble metal active elements can be independently selected from 5%, 10%, 15%, 20% and 25%.
Optionally, the preparation process of the non-noble metal catalyst at least comprises the following steps:
adding a nitrogen-containing carrier into a non-noble metal salt soaking solution for soaking to obtain a precursor;
and pyrolyzing the precursor under an inactive atmosphere to obtain the non-noble metal catalyst.
Optionally, the nitrogen-containing carrier is added into the non-noble metal salt impregnation solution for impregnation, and then the precursor is obtained through drying.
The drying temperature is 45-80 ℃.
The lower limit of the drying temperature is independently selected from 45 deg.C, 55 deg.C, 60 deg.C, 70 deg.C, and 75 deg.C;
the upper limit of the drying temperature is independently selected from 55 deg.C, 60 deg.C, 65 deg.C, 75 deg.C, and 80 deg.C.
Optionally, the non-noble metal salt impregnation liquid comprises an organic ligand and a non-noble metal salt;
when the nitrogen-containing carrier is added into the non-noble metal salt immersion liquid for immersion, the mass ratio of the nitrogen-containing carrier to the organic ligand to the non-noble metal salt is 10-20: 0.1-4: 0.1-2.
Optionally, the mass ratio of the nitrogen-containing support, the organic ligand, and the non-noble metal salt is 10:0.1:0.1, 10:4:0.1, 10:0.1:2, 20:0.1:0.1, 20:0.1:2, 20:4:0.1, 20:4:2, 10:1.5:2, 10:1.3:2, 5:2:2, 10:2.5:2, 10:2:2, 10:3.5: 2.
Alternatively, the inert atmosphere includes an inert gas atmosphere or a nitrogen atmosphere.
Specifically, the inert gas includes helium, argon.
Optionally, the pyrolysis temperature for pyrolyzing the precursor is 500-800 ℃.
The lower limit of the pyrolysis temperature is independently selected from 500 ℃, 550 ℃, 600 ℃, 650 ℃ and 750 ℃;
the upper limit of the pyrolysis temperature is independently selected from 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C, 800 deg.C.
Optionally, the organic ligand comprises at least one of pyridine, imidazole, 2-methylimidazole, 1, 10-phenanthroline, 2 '-bipyridine, 2' -bipyridine amine.
Optionally, the non-noble metal salt is selected from at least one of chloride, nitrate, sulfate, acetate, and acetylacetonate of a non-noble metal element.
Wherein the concentration of non-noble metal salt in the impregnation liquid is 1-70 g/L.
Optionally, the solvent in the impregnation fluid comprises ethanol, methanol or water.
Specifically, 5-hydroxymethylfurfural, a non-noble metal catalyst and methanol are reacted to obtain the dimethyl 2, 5-furandicarboxylate.
Optionally, the amount of methanol is 5-15 mL;
the lower limit of the dosage of the methanol is independently selected from 5mL, 7mL, 9mL, 11mL and 13 mL;
the upper limit of the dosage of the methanol is independently selected from 7mL, 9mL, 11mL, 13mL and 15 mL;
preferably, the amount of methanol used is 5 mL.
The invention has the beneficial effects that:
1. under the condition that no alkaline additive is added, the preparation of the 2, 5-dimethyl furan dicarboxylate is realized under relatively mild conditions under the action of a non-noble metal catalyst, the preparation cost is saved, the pollution of the alkaline additive to the environment is avoided, the method is conveniently and widely applied to industry, and the method is an effective method for preparing the 2, 5-dimethyl furan dicarboxylate.
2. The preparation method has the advantages that the dimethyl 2, 5-furandicarboxylate is prepared by one-step oxidation esterification of 5-hydroxymethylfurfural in the presence of a non-noble metal catalyst, so that the preparation process of the dimethyl 2, 5-furandicarboxylate is simplified.
3. The non-noble metal catalyst that this application used includes the nitrogenous carrier, and the nitrogenous carrier load non-noble metal active ingredient, and the existence of nitrogenous carrier has promoted the adsorption degree of non-noble metal complex above that, and the reunion of metal on the carrier has been avoided in organic ligand's addition, promotes the dispersion degree of metal on the nitrogenous carrier, conveniently promotes the activity of catalyst.
Drawings
FIG. 1 is a transmission electron micrograph of a catalyst obtained in exemplary example 10 of the present invention;
FIG. 2 shows sample C obtained in example 10 of the present invention10GC-MS spectrum (gas chromatography-mass spectrometry combined test spectrum).
Detailed Description
The present invention will be described in detail with reference to examples.
Unless otherwise specified, the raw materials in the examples were purchased commercially and used without treatment; the used instruments and equipment adopt the use parameters recommended by manufacturers.
In the examples, transmission electron microscopy of the Hitachi 7700 type was used for the morphological analysis of the catalysts prepared.
In the examples, an Empyrean-100X-ray powder diffractometer was used for X-ray diffraction analysis of the prepared catalysts.
In the examples, the prepared dimethyl 2, 5-furandicarboxylate was analyzed by an Agilent 7890 gas chromatography analyzer.
Example 1
1. Preparing a non-noble metal catalyst Mn-N/C:
(1) preparing non-noble metal salt impregnation liquid: adding pyridine and manganese acetate with the mass ratio of 3:2 into 30mL of methanol, and fully stirring for 1 h;
(2) adding nitrogen-containing carrier urea into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the nitrogen-containing carrier urea to the manganese acetate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) in N2And (3) pyrolyzing the non-noble metal-loaded complex precursor obtained in the step (3) under the atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst Mn-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of Mn-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) heating from 25 deg.C to 100 deg.C at a rate of 5 deg.C/min, and O at 0.2MPa2Reaction for 2h under an atmosphere to obtain a product containing dimethyl 2, 5-furandicarboxylate, which is marked as sample C1。
The samples were analyzed using a gas chromatograph.
Example 2
1. Preparing a non-noble metal catalyst Fe-N/C:
(1) preparing non-noble metal salt impregnation liquid: imidazole and ferric sulfate in a mass ratio of 3:4 are added into 40mL of methanol and are fully stirred for 1 h;
(2) adding melamine containing a nitrogen carrier into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the melamine containing the nitrogen carrier to the ferric sulfate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) and (3) pyrolyzing the non-noble metal-loaded complex precursor obtained in the step (3) in Ar atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst Fe-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of Fe-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) the temperature is increased from 25 ℃, the temperature is increased to 80 ℃ at the speed of 5.5 ℃/min, and the reaction is carried out for 4h under the air atmosphere of 0.4MPa, so that a product containing the 2, 5-furan dicarboxylic acid dimethyl ester is obtained, and the product is marked as a sample C2。
The samples were analyzed using a gas chromatograph.
Example 3
1. Preparing a non-noble metal catalyst Co-N/C:
(1) preparing non-noble metal salt impregnation liquid: adding 1, 10-phenanthroline and cobalt nitrate in a mass ratio of 1:1 into 50mL of methanol, and fully stirring for 1 h;
(2) adding dicyandiamide containing a nitrogen carrier into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the dicyandiamide containing the nitrogen carrier to the cobalt nitrate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) in N2And (3) pyrolyzing the non-noble metal-loaded complex precursor obtained in the step (3) under the atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst Co-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of Co-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) heating from 25 deg.C to 100 deg.C at a rate of 5 deg.C/min, and O at 0.6MPa2Reaction for 6h under an atmosphere to obtain a product containing dimethyl 2, 5-furandicarboxylate, which is marked as sample C3。
The samples were analyzed using a gas chromatograph.
Example 4
1. Preparing a non-noble metal catalyst Ni-N/C:
(1) preparing non-noble metal salt impregnation liquid: adding 2-methylimidazole and nickel nitrate in a mass ratio of 3:2 into 60mL of methanol, and fully stirring for 1 h;
(2) adding nitrogen-containing carrier ethylenediamine into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the nitrogen-containing carrier ethylenediamine to the nickel nitrate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) and (3) pyrolyzing the non-noble metal-loaded complex precursor obtained in the step (3) in Ar atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst Ni-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of Ni-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) the temperature is increased from 25 ℃, the temperature is increased to 80 ℃ at the speed of 5.5 ℃/min, and the reaction is carried out for 8 hours under the air atmosphere of 0.8MPa, so that a product containing the 2, 5-furan dicarboxylic acid dimethyl ester is obtained, and the product is marked as a sample C4。
The samples were analyzed using a gas chromatograph.
Example 5
1. Preparing a non-noble metal catalyst Cu-N/C:
(1) preparing non-noble metal salt impregnation liquid: adding 2,2' -bipyridine and copper acetate in a mass ratio of 2:3 into 30mL of methanol, and fully stirring for 1 h;
(2) adding nitrogen-containing carrier carbon nitride into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the nitrogen-containing carrier carbon nitride to the copper acetate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) in N2And (3) pyrolyzing the non-noble metal-loaded complex precursor obtained in the step (3) under the atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst Cu-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of Cu-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) heating from 25 deg.C to 100 deg.C at a rate of 5 deg.C/min, and heating to O at 1MPa2Reacting for 10 hours under the atmosphere to obtainTo a product containing dimethyl-2, 5-furandicarboxylate designated as sample C5。
The samples were analyzed using a gas chromatograph.
Example 6
1. Preparing a non-noble metal catalyst MnFe-N/C:
(1) preparing non-noble metal salt impregnation liquid: adding 2,2' -bipyridine amine, ferric sulfate and manganese acetate in a mass ratio of 3:3:1 into 40mL of methanol, and fully stirring for 1 h;
(2) adding a nitrogen-containing carrier polypyrrole into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the nitrogen-containing carrier polypyrrole to the total amount of ferric sulfate and manganese acetate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) and (3) pyrolyzing the non-noble metal-loaded complex precursor obtained in the step (3) in Ar atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst MnFe-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of MnFe-N/C catalyst, 0.063g of 5-hydroxymethyl furfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) the temperature is increased from 25 ℃, the temperature is increased to 80 ℃ at the speed of 5.5 ℃/min, and the reaction is carried out for 12h under the air atmosphere of 0.2MPa, so that a product containing the dimethyl 2, 5-furandicarboxylate is obtained, and the product is marked as a sample C6。
The samples were analyzed using a gas chromatograph.
Example 7
1. Preparation of non-noble metal catalyst CoNi-N/C:
(1) preparing non-noble metal salt impregnation liquid: adding pyridine, nickel nitrate and cobalt nitrate in a mass ratio of 3.5:1:1 into 50mL of methanol, and fully stirring for 1 h;
(2) adding nitrogen-containing carrier urea into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the nitrogen-containing carrier urea to the total amount of the nickel nitrate and the cobalt nitrate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) in N2And (3) pyrolyzing the non-noble metal-loaded complex precursor obtained in the step (3) under the atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature, so that the non-noble metal catalyst CoNi-N/C is obtained.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of CoNi-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) heating from 25 deg.C to 100 deg.C at a rate of 5 deg.C/min, and O at 0.4MPa2Reaction for 2h under an atmosphere to obtain a product containing dimethyl 2, 5-furandicarboxylate, which is marked as sample C7。
The samples were analyzed using a gas chromatograph.
Example 8
1. Preparing a non-noble metal catalyst CuMn-N/C:
(1) preparing non-noble metal salt impregnation liquid: imidazole, manganese acetate and copper acetate in a mass ratio of 3:1:2 are added into 60mL of methanol and fully stirred for 1 h;
(2) adding dicyandiamide containing a nitrogen carrier into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the dicyandiamide containing the nitrogen carrier to the total amount of manganese acetate and copper acetate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) and (3) pyrolyzing the non-noble metal supported complex precursor obtained in the step (3) in Ar atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst CuMn-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of CuMn-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) the temperature is increased from 25 ℃, the temperature is increased to 80 ℃ at the speed of 5.5 ℃/min, and the reaction is carried out for 4h under the air atmosphere of 0.6MPa, so that a product containing the 2, 5-furan dicarboxylic acid dimethyl ester is obtained, and the product is marked as a sample C8。
The samples were analyzed using a gas chromatograph.
Example 9
1. Preparing a non-noble metal catalyst FeNi-N/C:
(1) preparing non-noble metal salt impregnation liquid: adding 2-methylimidazole, nickel nitrate and ferric sulfate in a mass ratio of 3:1.5:1 into 30mL of methanol, and fully stirring for 1 h;
(2) adding nitrogen-containing carrier ethylenediamine into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the nitrogen-containing carrier ethylenediamine to the total amount of the nickel nitrate and the ferric sulfate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) in N2And (3) pyrolyzing the non-noble metal-loaded complex precursor obtained in the step (3) under the atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst FeNi-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of FeNi-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) heating from 25 deg.C to 100 deg.C at 5 deg.C/min, and O at 0.8MPa2Reacting for 6 hours under the atmosphere to obtain a catalyst containingThe product of dimethyl 2, 5-furandicarboxylate, designated sample C9。
The samples were analyzed using a gas chromatograph.
Example 10
1. Preparing a non-noble metal catalyst CoMnCuZn-N/C:
(1) preparing non-noble metal salt impregnation liquid: adding 1, 10-phenanthroline, zinc sulfate, copper acetate, manganese acetate and cobalt nitrate in a mass ratio of 3:0.5:1:0.5:1 into 40mL of methanol, and fully stirring for 1 h;
(2) adding a nitrogen-containing carrier melamine into the non-noble metal salt impregnation liquid prepared in the step (1), wherein the mass ratio of the nitrogen-containing carrier melamine to the total amount of zinc sulfate, copper acetate, manganese acetate and cobalt nitrate added in the step (1) is 10:2, and fully impregnating;
(3) drying the non-noble metal salt impregnation liquid impregnated with the nitrogen-containing carrier obtained in the step (2) at 60 ℃ to load a non-noble metal complex precursor;
(4) and (3) pyrolyzing the non-noble metal supported complex precursor obtained in the step (3) in Ar atmosphere, wherein the pyrolysis condition is that the temperature is increased to 800 ℃ at the speed of 10 ℃/min under the condition of 25 ℃, and the temperature is kept for 2h at the temperature to obtain the non-noble metal catalyst CoMnCuZn-N/C.
2.5-oxidative esterification of hydroxymethylfurfural:
(1) putting 0.06g of CoMnCuZn-N/C catalyst, 0.063g of 5-hydroxymethylfurfural and 5mL of methanol into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sealing the kettle;
(2) heating from 25 ℃, raising the temperature to 80 ℃ at the speed of 5.5 ℃/min, and reacting for 6h under the air atmosphere of 1MPa to obtain a product containing 2, 5-furan dicarboxylic acid dimethyl ester, and marking as a sample C10。
The samples were analyzed using a gas chromatograph.
Table 1 shows the results of the catalytic esterification of 5-hydroxymethylfurfural with the catalysts prepared in examples 1 to 10, wherein the conversion of 5-Hydroxymethylfurfural (HMF) and the selectivity of dimethyl 2, 5-Furandicarboxylate (FDMC) were both calculated on the basis of molar conservation, in particular:
HMF conversion ═ 1- (moles of residual HMF/moles of initial HMF) × 100%
FDMC yield (mol of FDMC/mol of initial HMF in the reaction solution) × 100%
TABLE 1
FIGS. 1-2 show a transmission electron micrograph and an X-ray diffraction pattern of the non-noble metal catalyst CoMnCuZn-N/C obtained in example 10, and a sample C obtained under the catalytic action of the CoMnCuZn-N/C10The following is a description of a partial characterization of the non-noble metal catalyst obtained in accordance with the present invention, using the GC-MS spectrum of example 10 as an example. From fig. 1, it can be seen that the non-noble metal elements can be uniformly distributed on the nitrogen-containing carrier; as can be seen from FIG. 2, the abundance of dimethyl 2, 5-furandicarboxylate is significant, which indicates that the yield of dimethyl 2, 5-furandicarboxylate is high, indicating that the yield of dimethyl 2, 5-furandicarboxylate obtained by catalytic oxidation of 5-hydroxymethylfurfural is high under the action of the prepared non-noble metal catalyst.
As can be seen from Table 1, the catalytic oxidation of 5-hydroxymethylfurfural in the presence of different non-noble metal catalysts can obtain dimethyl 2, 5-furandicarboxylate with higher yield, for example, in example 2, the yield of dimethyl 2, 5-furandicarboxylate under the catalytic action of Fe-N/C reaches 15%, in example 10, the yield of dimethyl 2, 5-furandicarboxylate under the catalytic action of CoMnCuZn-N/C reaches 87%, and so on; in conclusion, different types of catalysts are obtained by adjusting the types of non-noble metal elements to a certain extent, and under the existence of the obtained non-noble metal catalyst, the direct oxidation and esterification of 5-hydroxymethylfurfural into dimethyl 2, 5-furandicarboxylate (other products comprise methyl 5-hydroxymethyl-2-furanate, methyl 5-formyl-2-furanate 2, 5-diformylfuran and the like) is realized under relatively mild conditions, the preparation process is simple, the cost is low, no alkaline additive is required to be added, the environmental pollution is reduced, and the method can be widely applied to the industrial field.
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 dimethyl 2, 5-furandicarboxylate is characterized in that 5-hydroxymethylfurfural is catalytically oxidized in the presence of a non-noble metal catalyst in an oxidizing atmosphere to prepare dimethyl 2, 5-furandicarboxylate; the non-noble metal catalyst comprises a nitrogen-containing carrier and a non-noble metal active component loaded on the nitrogen-containing carrier.
2. The process for the preparation of dimethyl-2, 5-furandicarboxylate according to claim 1, wherein the catalytic oxidation conditions comprise:
the reaction temperature is 25-100 ℃; the reaction time is 1-24 h; the reaction pressure is normal pressure to 1 MPa;
the oxidizing atmosphere comprises air or oxygen.
3. The method of claim 1, wherein the catalytic oxidation is carried out without the addition of a basic additive.
4. The method of claim 1, wherein the nitrogen-containing carrier comprises at least one of urea, melamine, dicyanodiamine, ethylenediamine, carbon nitride, polypyrrole, polyaniline;
the non-noble metal active component comprises non-noble metal elements;
the non-noble metal element comprises at least one of manganese, iron, cobalt, copper, nickel, zinc, titanium and vanadium.
5. The method for preparing dimethyl 2, 5-furandicarboxylate according to claim 1, wherein the loading amount of the non-noble metal active component in the non-noble metal catalyst is 5 to 25%;
wherein the loading of the non-noble metal active component is calculated by the loading of non-noble metal elements.
6. The method for preparing dimethyl 2, 5-furandicarboxylate according to claim 1, wherein the preparation process of the non-noble metal catalyst at least comprises:
adding a nitrogen-containing carrier into a non-noble metal salt soaking solution for soaking to obtain a precursor;
and pyrolyzing the precursor under an inactive atmosphere to obtain the non-noble metal catalyst.
7. The method of claim 6, wherein the non-noble metal salt impregnation solution comprises an organic ligand and a non-noble metal salt;
after a nitrogen-containing carrier is added into a non-noble metal salt soaking solution for soaking, the mass ratio of the nitrogen-containing carrier to the organic ligand to the non-noble metal salt is 10-20: 0.1-4: 0.1-2.
8. The method of claim 6, wherein the pyrolyzing the precursor comprises:
the pyrolysis temperature is 500-800 ℃.
9. The method of claim 7, wherein the organic ligand comprises at least one of pyridine, imidazole, 2-methylimidazole, 1, 10-phenanthroline, 2 '-bipyridine, and 2,2' -bipyridine amine.
10. The method for preparing dimethyl-2, 5-furandicarboxylate according to claim 7, wherein the non-noble metal salt is at least one selected from chloride, nitrate, sulfate, acetate, acetylacetonate of non-noble metal element;
the concentration of non-noble metal salt in the non-noble metal impregnation liquid is 1-70 g/L.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN111253353A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural |
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| 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 |
| CN111253353A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furandicarboxylic acid dimethyl ester by catalyzing oxidation esterification of 5-hydroxymethylfurfural |
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| KANG-KANG SUN等: ""Synthesis of a ZIF-derived hollow yolk–shell Co@CN catalyst for the oxidative esterification of 5-hydroxymethylfurfural"", 《GREEN CHEMISTRY》 * |
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