CN112812080A - Method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural - Google Patents
Method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural Download PDFInfo
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- CN112812080A CN112812080A CN202110045689.XA CN202110045689A CN112812080A CN 112812080 A CN112812080 A CN 112812080A CN 202110045689 A CN202110045689 A CN 202110045689A CN 112812080 A CN112812080 A CN 112812080A
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- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
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- 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
- B01J23/755—Nickel
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
Abstract
A method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural comprises the steps of adding 5-hydroxymethylfurfural, a nickel-cobalt bimetallic catalyst and tetrahydrofuran into a high-pressure reaction kettle, introducing hydrogen, and carrying out heating reaction to obtain the 2, 5-furandimethanol. The method for preparing the 2, 5-furandimethanol by using the nickel-cobalt bimetallic catalyst has the advantages of mild reaction conditions, simple operation and high product selectivity; the nickel-cobalt bimetallic catalyst has the advantages of cheap and easily-obtained raw materials, simple preparation process, low production cost, easy recovery and separation, and good catalytic activity and stability.
Description
Technical Field
The invention relates to a method for preparing 2, 5-furandimethanol, in particular to a method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural.
Background
With the increasingly shrinking of fossil resources, biomass has received wide attention as a rich, environmentally friendly, renewable, sustainable resource. The 5-hydroxymethylfurfural prepared from carbohydrate which is most widely available in biomass has good reaction activity due to the fact that the molecule contains hydroxyl, carbonyl, furan rings and other functional groups, a series of high-quality derivatives which can replace fossil-based products can be prepared through the 5-hydroxymethylfurfural, and the 5-hydroxymethylfurfural is an important bridge for connecting biomass raw materials and energy chemical engineering in the biomass refining process. The 2, 5-furandimethanol obtained by selective hydrogenation of 5-hydroxymethylfurfural serves as diol with high added value, can serve as an artificial receptor in the research of molecular recognition, and has important application in the preparation research of fine chemical synthesis, novel functionalized polyether, polyurethane and polyheterocyclic compounds of medicines.
CN110698440A discloses a method for preparing 2, 5-furandimethanol from solvent-free 5-hydroxymethylfurfural, wherein the used catalyst comprises noble metal catalysts such as Ru/C, Pd/C or Pt/C, the reaction temperature is 80-140 ℃, the reaction time is 1-3 h, the hydrogen pressure is 3-6 Mpa, and the yield of the obtained 2, 5-furandimethanol is 14.9-93.7%. The method has the advantages of high catalyst cost, high hydrogen pressure requirement, high technical requirement on production equipment and great potential safety hazard.
CN110204519A discloses a method for preparing 2, 5-furandimethanol by transfer hydrogenation of 5-hydroxymethylfurfural, wherein a solid acid catalyst MnO @ C-N is prepared by taking sucrose and urea as raw materials, the catalysis conditions are 150-200 ℃ and 1-30 hours, and the yield of the obtained 2, 5-furandimethanol is 45-93%. The method has higher reaction temperature and high production energy consumption, and limits the practical production and subsequent application of the 2, 5-furandimethanol to a great extent.
CN111574483A discloses a preparation method of 2, 5-furandimethanol, which takes nano platinum encapsulated by a Y molecular sieve as a catalyst, and 5-hydroxymethylfurfural is efficiently converted into 2, 5-furandimethanol by selective transfer hydrogenation reaction, wherein the highest yield can reach 97.0%. However, the noble metal catalyst used in the method has high manufacturing cost and complicated preparation process.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, which has the advantages of mild reaction conditions, simple operation, high product selectivity and low production cost.
The technical scheme adopted for solving the technical problem is that the method for preparing the 2, 5-furandimethanol from the 5-hydroxymethylfurfural comprises the steps of adding the 5-hydroxymethylfurfural, a nickel-cobalt bimetallic catalyst and tetrahydrofuran into a high-pressure reaction kettle, introducing hydrogen, and carrying out heating reaction to obtain the 2, 5-furandimethanol.
Further, the reaction temperature is 80-160 ℃, and preferably 100-120 ℃; the reaction time is 0.5-6 h, preferably 2-4 h.
Further, the pressure of the hydrogen is 0.1 to 1.0MPa, preferably 0.5 to 0.75 MPa.
Further, the amount of the 5-hydroxymethylfurfural is 0.7-2.8% of the mass of tetrahydrofuran, and preferably 1.0-2.0%.
Further, the dosage of the nickel-cobalt bimetallic catalyst is 10-50% of the mass of the 5-hydroxymethylfurfural, and preferably 30-40%.
Further, the nickel-cobalt bimetallic catalyst is prepared by the following method:
(1) adding nickel salt and cobalt salt into a mortar for mixing, grinding uniformly, then adding citric acid, and continuously grinding until the mixture is viscous to obtain viscous liquid; drying the viscous liquid to be fluffy, and then crushing the viscous liquid into powder to obtain a nickel-cobalt bimetallic catalyst precursor;
(2) and (2) roasting the nickel-cobalt bimetallic catalyst precursor obtained in the step (1) in a nitrogen atmosphere to obtain the nickel-cobalt bimetallic catalyst.
Further, in the step (1) of the preparation method of the nickel-cobalt bimetallic catalyst, the nickel salt is one or more of nickel nitrate, nickel chloride and nickel acetylacetonate; the cobalt salt is one or more of cobalt nitrate, cobalt chloride and cobalt acetylacetonate.
Further, in the step (1) of the preparation method of the nickel-cobalt bimetallic catalyst, the molar ratio of the nickel salt to the cobalt salt is 0.5-3.0: 1, preferably 1.0-2.0: 1; the molar ratio of the nickel salt to the citric acid is 0.5-2.0: 1, preferably 1.0-1.5: 1.
Further, in the step (1) of the preparation method of the nickel-cobalt bimetallic catalyst, the grinding time is 20-40 min; the drying temperature is 100-120 ℃; the drying time is 16-24 h.
Further, in the step (2) of the preparation method of the nickel-cobalt bimetallic catalyst, the roasting temperature is 300-400 ℃, and preferably 350 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses nickel-cobalt bimetallic catalyst, takes hydrogen as hydrogen donor, efficiently catalyzes selective hydrogenation of 5-hydroxymethylfurfural into 2, 5-furandimethanol, has mild reaction condition, simple operation and high product selectivity, can realize efficient conversion of biomass resources, and provides practical support for comprehensive utilization and industrialization of the biomass resources.
(2) The nickel-cobalt bimetallic catalyst has the advantages of cheap and easily-obtained raw materials, simple preparation process, low production cost, convenience for realizing large-scale production, easiness in recovery and separation, and excellent catalytic activity and stability.
Drawings
FIG. 1 is a mass spectrum of 2, 5-furandimethanol obtained in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments, wherein only some, but not all embodiments of the invention are described, and the embodiments should not be construed as limiting the scope of the claims of the present application. All other changes and modifications which can be made by one skilled in the art based on the embodiments of the present invention without inventive faculty are within the scope of the claims of the present application.
The chemicals used in the examples, unless otherwise specified, were obtained from conventional commercial sources.
Example 1
This example is a process for the preparation of 2, 5-furandimethanol from 5-hydroxymethylfurfural: 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst0.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 1h, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
The mass spectrum of 2, 5-furandimethanol obtained in this example is shown in FIG. 1.
Ni-Co bimetallic catalyst Ni used in this example0.5Co, made by the following method:
(1) adding 0.712g of nickel nitrate hexahydrate and 1.422g of cobalt nitrate hexahydrate into a mortar for mixing, uniformly grinding, then adding 1.255g of citric acid, and continuously grinding until the mixture is viscous to obtain viscous liquid; drying the viscous liquid for 24 hours at 120 ℃ to be fluffy, and then crushing the fluffy viscous liquid into powder to obtain a nickel-cobalt bimetallic catalyst precursor;
(2) roasting the nickel-cobalt bimetallic catalyst precursor obtained in the step (1) for 4 hours at 350 ℃ in a nitrogen atmosphere to obtain the nickel-cobalt bimetallic catalyst Ni0.5Co。
The test method comprises the following steps: the reaction solution was centrifuged to remove the nickel-cobalt bimetallic catalyst, and the conversion, selectivity and yield of 2, 5-furandimethanol in this example were quantitatively determined by GC (shimadzu), and the results are shown in table 1.
The following examples 2, 5-furandimethanol test methods were the same as the 2, 5-furandimethanol test method of this example. The test results are also shown in Table 1.
Example 2
This example is a process for the preparation of 2, 5-furandimethanol from 5-hydroxymethylfurfural: 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst1.0Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 1h, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Ni-Co bimetallic catalyst Ni used in this example1.0Co, made by the following method:
(1) adding 1.402g of nickel nitrate hexahydrate and 1.412g of cobalt nitrate hexahydrate into a mortar for mixing, uniformly grinding, then adding 2.512g of citric acid, and continuously grinding until the mixture is viscous to obtain viscous liquid; drying the viscous liquid for 24 hours at 120 ℃ to be fluffy, and then crushing the fluffy viscous liquid into powder to obtain a nickel-cobalt bimetallic catalyst precursor;
(2) roasting the nickel-cobalt bimetallic catalyst precursor obtained in the step (1) for 4 hours at 350 ℃ in a nitrogen atmosphere to obtain the nickel-cobalt bimetallic catalyst Ni1.0Co。
Example 3
This example is a process for the preparation of 2, 5-furandimethanol from 5-hydroxymethylfurfural: 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 1h, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Ni-Co bimetallic catalyst Ni used in this example1.5Co, made by the following method:
(1) adding 2.120g of nickel nitrate hexahydrate and 1.410g of cobalt nitrate hexahydrate into a mortar for mixing, uniformly grinding, then adding 2.505g of citric acid, and continuously grinding until the mixture is viscous to obtain viscous liquid; drying the viscous liquid for 24 hours at 120 ℃ to be fluffy, and then crushing the fluffy viscous liquid into powder to obtain a nickel-cobalt bimetallic catalyst precursor;
(2) roasting the nickel-cobalt bimetallic catalyst precursor obtained in the step (1) for 4 hours at 350 ℃ in a nitrogen atmosphere to obtain the nickel-cobalt bimetallic catalyst Ni1.5Co。
Ni-Co bimetallic catalyst for use in examples 7-21 below1.5Preparation method of Co and Ni-Co bimetallic catalyst Ni of the embodiment1.5The preparation method of Co is the same.
Example 4
This example is a process for the preparation of 2, 5-furandimethanol from 5-hydroxymethylfurfural: mixing 0.126g of 5-hydroxymethylfurfural and 0.0378g of nickel-cobalt-goldBelongs to catalyst Ni2.0Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 1h, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Ni-Co bimetallic catalyst Ni used in this example2.0Co, made by the following method:
(1) adding 2.817g of nickel nitrate hexahydrate and 1.411g of cobalt nitrate hexahydrate into a mortar for mixing, uniformly grinding, then adding 2.502g of citric acid, and continuously grinding until the mixture is viscous to obtain viscous liquid; drying the viscous liquid for 24 hours at 120 ℃ to be fluffy, and then crushing the fluffy viscous liquid into powder to obtain a nickel-cobalt bimetallic catalyst precursor;
(2) roasting the nickel-cobalt bimetallic catalyst precursor obtained in the step (1) for 4 hours at 350 ℃ in a nitrogen atmosphere to obtain the nickel-cobalt bimetallic catalyst Ni2.0Co。
Example 5
This example is a process for the preparation of 2, 5-furandimethanol from 5-hydroxymethylfurfural: 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst2.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 1h, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Ni-Co bimetallic catalyst Ni used in this example2.5Co, made by the following method:
(1) 1.751g of nickel nitrate hexahydrate and 0.711g of cobalt nitrate hexahydrate are added into a mortar to be mixed and uniformly ground, then 2.511g of citric acid is added, and grinding is continued until the mixture is viscous to obtain viscous liquid; drying the viscous liquid for 24 hours at 120 ℃ to be fluffy, and then crushing the fluffy viscous liquid into powder to obtain a nickel-cobalt bimetallic catalyst precursor;
(2) roasting the nickel-cobalt bimetallic catalyst precursor obtained in the step (1) for 4 hours at 350 ℃ in a nitrogen atmosphere to obtain the nickel-cobalt bimetallic catalyst Ni2.5Co。
Example 6
EXAMPLE 5-hydroxymethylfurfural production of 2, 5-FuranMethod for dimethanol: 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst3.0Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 1h, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Ni-Co bimetallic catalyst Ni used in this example3.0Co, made by the following method:
(1) adding 2.108g of nickel nitrate hexahydrate and 0.709g of cobalt nitrate hexahydrate into a mortar for mixing, uniformly grinding, then adding 2.524g of citric acid, and continuously grinding until the mixture is viscous to obtain viscous liquid; drying the viscous liquid for 24 hours at 120 ℃ to be fluffy, and then crushing the fluffy viscous liquid into powder to obtain a nickel-cobalt bimetallic catalyst precursor;
(2) roasting the nickel-cobalt bimetallic catalyst precursor obtained in the step (1) for 4 hours at 350 ℃ in a nitrogen atmosphere to obtain the nickel-cobalt bimetallic catalyst Ni3.0Co。
Example 7
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 0.5h, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 8
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 2 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 9
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran 50Introducing 0.50Mpa H into a mL stainless steel closed reactor2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 10
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0126g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 80 ℃ at a stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 11
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0126g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 12
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0126g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 120 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 13
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0126g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 140 ℃ at a stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 14
This example is a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural,0.126g of 5-hydroxymethylfurfural and 0.0126g of nickel-cobalt bimetallic catalyst Ni1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 160 ℃ at a stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 15
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0189g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 16
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, mixing 0.126g of 5-hydroxymethylfurfural with 0.0252g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 17
This example, a method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0315g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 18
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, mixing 0.126g of 5-hydroxymethylfurfural with 0.0441g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.50Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 19
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.10Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 20
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.25Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
Example 21
This example, a process for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, comprises mixing 0.126g of 5-hydroxymethylfurfural and 0.0378g of Ni-Co bimetallic catalyst1.5Co and 10mL tetrahydrofuran are added into a 50mL stainless steel closed reactor, and 0.75Mpa H is introduced2Heating to 100 ℃ at the stirring speed of 500rpm and keeping for 4 hours, and cooling to room temperature after the reaction is finished to obtain the 2, 5-furandimethanol.
TABLE 1 results of examining the reaction conditions and parameters of 2, 5-furandimethanol obtained in examples 1 to 21 of the present invention
Claims (10)
1. A method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural is characterized by adding 5-hydroxymethylfurfural, a nickel-cobalt bimetallic catalyst and tetrahydrofuran into a high-pressure reaction kettle, introducing hydrogen, and carrying out heating reaction to obtain the 2, 5-furandimethanol.
2. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to claim 1, characterized in that the temperature of the reaction is 80 to 160 ℃, preferably 100 to 120 ℃; the reaction time is 0.5-6 h, preferably 2-4 h.
3. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to claim 1 or 2, characterized in that the pressure of the hydrogen is 0.1 to 1.0Mpa, preferably 0.5 to 0.75 Mpa.
4. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to any one of claims 1 to 3, wherein the 5-hydroxymethylfurfural is used in an amount of 0.7 to 2.8%, preferably 1.0 to 2.0%, based on the mass of tetrahydrofuran.
5. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to any one of claims 1 to 4, characterized in that the amount of the nickel-cobalt bimetallic catalyst is 10 to 50%, preferably 30 to 40%, based on the mass of 5-hydroxymethylfurfural.
6. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to any one of claims 1 to 5, wherein the nickel-cobalt bimetallic catalyst is prepared by the following method:
(1) adding nickel salt and cobalt salt into a mortar for mixing, grinding uniformly, then adding citric acid, and continuously grinding until the mixture is viscous to obtain viscous liquid; drying the viscous liquid to be fluffy, and then crushing the viscous liquid into powder to obtain a nickel-cobalt bimetallic catalyst precursor;
(2) and (2) roasting the nickel-cobalt bimetallic catalyst precursor obtained in the step (1) in a nitrogen atmosphere to obtain the nickel-cobalt bimetallic catalyst.
7. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to claim 6, wherein in the step (1) of the method for preparing the nickel-cobalt bimetallic catalyst, the nickel salt is one or more of nickel nitrate, nickel chloride and nickel acetylacetonate; the cobalt salt is one or more of cobalt nitrate, cobalt chloride and cobalt acetylacetonate.
8. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to claim 6 or 7, characterized in that in the step (1) of the method for preparing the nickel-cobalt bimetallic catalyst, the molar ratio of the nickel salt to the cobalt salt is 0.5-3.0: 1, preferably 1.0-2.0: 1; the molar ratio of the nickel salt to the citric acid is 0.5-2.0: 1, preferably 1.0-1.5: 1.
9. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to any one of claims 6 to 8, characterized in that in the step (1) of the method for preparing a nickel-cobalt bimetallic catalyst, the grinding time is 20 to 40 min; the drying temperature is 100-120 ℃; the drying time is 16-24 h.
10. The method for preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural according to any one of claims 6 to 9, wherein in the step (2) of the method for preparing a nickel-cobalt bimetallic catalyst, the calcination temperature is 300 to 400 ℃, preferably 350 ℃.
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| CN114029081A (en) * | 2021-11-29 | 2022-02-11 | 湖南师范大学 | Bimetallic copper-cobalt-nitrogen-carbon material catalyst and preparation method and application thereof |
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| CN114029081A (en) * | 2021-11-29 | 2022-02-11 | 湖南师范大学 | Bimetallic copper-cobalt-nitrogen-carbon material catalyst and preparation method and application thereof |
| CN114029081B (en) * | 2021-11-29 | 2023-02-28 | 湖南师范大学 | Bimetallic copper-cobalt-nitrogen-carbon material catalyst and preparation method and application thereof |
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