CN113372307B - Preparation method of 2, 5-furandimethanol - Google Patents

Preparation method of 2, 5-furandimethanol Download PDF

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CN113372307B
CN113372307B CN202011619660.XA CN202011619660A CN113372307B CN 113372307 B CN113372307 B CN 113372307B CN 202011619660 A CN202011619660 A CN 202011619660A CN 113372307 B CN113372307 B CN 113372307B
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furandimethanol
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何凤林
胡云函
陈晨
王磊
张宇
金海涛
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Zhejiang Tangneng Technology Co ltd
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    • 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
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    • C07D307/44—Furfuryl alcohol
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    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]

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Abstract

The invention discloses a preparation method of 2, 5-furandimethanol, which adopts a catalyst containing heteroatom-doped aluminum phosphate molecular sieves to prepare the 2, 5-furandimethanol from raw materials containing biomass and a hydrogen source; the heteroatom is selected from transition metal elements; the transition metal element is at least one selected from Cu, Ni, Fe and Co. The method has the advantages of simple process, low energy consumption and suitability for industrial production.

Description

Preparation method of 2, 5-furandimethanol
Technical Field
The invention relates to a preparation method of 2, 5-furandimethanol, belonging to the field of chemistry and chemical engineering.
Background
2, 5-furandimethanol (BHMF) as an important biomass platform derivative can be applied to adhesives, plasticizers, surfactants, drug intermediates and the like, can also be used as monomer synthetic resin materials, fiber materials, foam materials and the like (CN107442177A), and has wide application value.
Currently, 5-Hydroxymethylfurfural (HMF) is adopted as a catalyst through noble metals (Pt, Pd, Ru, etc.) or non-noble metals (Co, Ni, Cu, etc.), and hydrogen is directly hydrogenated or is subjected to catalytic transfer hydrogenation to prepare 2, 5-furandimethanol. However, 5-hydroxymethylfurfural as a biomass platform compound is active and unstable in nature, tends to be polymerized or oxidized after being stored for a long time, is difficult to avoid and leave more impurities in the preparation process, is expensive in market price, and becomes a bottleneck restricting the synthesis research and the industrial development of downstream derivatives thereof.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing 2, 5-furandimethanol by catalyzing biomass in a one-step method, which has the advantages of simple process and low energy consumption and is suitable for industrial production.
According to one aspect of the application, a one-step method for preparing 2, 5-furandimethanol is provided, wherein 2, 5-furandimethanol is prepared from raw materials containing biomass and a hydrogen source by using a catalyst containing a heteroatom-doped aluminum phosphate molecular sieve; according to another aspect of the present application, a method for preparing a heteroatom-doped aluminum phosphate molecular sieve catalyst having both Lewis acidic and reducing properties is provided.
According to one aspect of the application, a preparation method of 2, 5-furandimethanol is provided, wherein 2, 5-furandimethanol is prepared from raw materials containing biomass and a hydrogen source by using a catalyst containing a heteroatom-doped aluminum phosphate molecular sieve;
the heteroatom is selected from transition metal elements;
the transition metal element is at least one selected from Cu, Ni, Fe and Co.
The hydrogen source is at least one selected from formic acid, isopropanol, ethanol, methanol and hydrogen.
Preferably, the hydrogen source is selected from hydrogen gas.
Optionally, the biomass comprises a carbohydrate; the saccharide compound is at least one selected from fructose, sucrose and glucose, preferably fructose.
Optionally, the mass of the heteroatom-doped aluminum phosphate molecular sieve is 4-60 wt% of the mass of the saccharide compound.
Alternatively, the heteroatom-doped aluminum phosphate molecular sieves have an upper limit independently selected from 60%, 50%, 40%, 30%, 20%, 10%, and a lower limit independently selected from 50%, 40%, 30%, 20%, 10%, 4% of the mass of the saccharide compound.
Optionally, the aluminum phosphate molecular sieves are selected from AlPO4-5 molecular sieves, AlPO4-11 molecular sieves, AlPO4-41 molecular sieves, AlPO4-42 molecular sieves.
Optionally, the mass content of the heteroatom in the heteroatom-doped aluminum phosphate molecular sieve is 0.1-20 wt%.
Alternatively, the upper limit of the mass content of the heteroatom in the heteroatom-doped aluminum phosphate molecular sieve is independently selected from 20%, 10%, 5%, 1%, and the lower limit is independently selected from 10%, 5%, 1%, 0.1%.
Optionally, the heteroatom-doped aluminum phosphate molecular sieve is prepared by an ionothermal method in the presence of an imidazole-halogenated ionic liquid.
Optionally, the method comprises at least:
(a) adding biomass and a catalyst containing a heteroatom-doped aluminum phosphate molecular sieve into an imidazole halide solvent, and reacting I to obtain an intermediate product;
(b) and adding a hydrogen source into the intermediate product, and reacting II to obtain the 2, 5-furandimethanol.
Optionally, the method comprises at least:
(1) adding an imidazole halide solvent, biomass and a catalyst containing a heteroatom-doped aluminum phosphate molecular sieve into a high-pressure reaction kettle, and stirring for reaction at a certain temperature to obtain an intermediate product;
(2) adding a hydrogen source into the intermediate product, and reacting at a certain temperature and pressure to obtain the 2, 5-furandimethanol.
The catalyst has Lewis acidity and reducibility, and has the functions of dehydrating carbohydrate and reducing aldehyde group.
Optionally, the conditions of reaction I are: the reaction temperature is 60-150 ℃; the reaction time is 10 min-2 h.
Alternatively, the upper temperature limit of reaction I is independently selected from 150 ℃, 130 ℃, 100 ℃, 80 ℃, and the lower temperature limit is independently selected from 130 ℃, 100 ℃, 80 ℃, 60 ℃.
Alternatively, the upper time limit of reaction I is independently selected from 2h, 1.5h, 1.0h, 0.5h, and the lower time limit is independently selected from 1.5h, 1.0h, 0.5h, 10 min.
Alternatively, the conditions of reaction II are: the reaction temperature is 80-150 ℃; the reaction time is 0.5-20 h.
Alternatively, the upper temperature limit of reaction II is independently selected from 150 ℃, 130 ℃, 100 ℃, and the lower temperature limit is independently selected from 130 ℃, 100 ℃, 80 ℃.
Alternatively, the upper time limit of the reaction II is independently selected from 20h, 10h, 5h, 1h, and the lower time limit is independently selected from 10h, 5h, 1h, 0.5 h.
Alternatively, the hydrogen source is preferably hydrogen; the pressure of the reaction II is 1-5 Mpa;
optionally, the halogenated imidazole solvent is at least one selected from 1-butyl-3-methylimidazole bromide salt, 1-ethyl-3-methylimidazole bromide salt, 1-butyl-3-methylimidazole chloride salt and 1-ethyl-3-methylimidazole chloride salt.
Optionally, the step (b) comprises at least: adding a hydrogen source and a solvent into the intermediate product, and reacting II to obtain the 2, 5-furandimethanol;
the solvent is at least one selected from water, halogenated imidazole solvent, tetrahydrofuran, formic acid, isopropanol, ethanol and methanol;
the hydrogen source is selected from at least one of hydrogen, formic acid, isopropanol, ethanol and methanol, and hydrogen is preferred.
Alternatively, the reactions I and II are carried out in an autoclave.
As a specific embodiment, the heteroatom-doped aluminum phosphate molecular sieve is prepared by a method comprising the following steps:
a) preparing a raw material mixture containing imidazole halide ionic liquid, a phosphorus source, an aluminum source, organic amine, a heteroatom source and fluoride;
b) and (b) crystallizing the raw material mixture obtained in the step a) at 180-280 ℃ for 5-300 minutes, and filtering, washing, drying and roasting to obtain the heteroatom-doped aluminum phosphate molecular sieve.
Preferably, the crystallized product in the step b) is dried at 100 ℃ for 8-12 h, and then is roasted at 400-600 ℃ for 2-12 h, so as to obtain the heteroatom-doped aluminum phosphate molecular sieve.
As a specific embodiment, the heteroatom-doped aluminum phosphate molecular sieve is prepared by a method comprising the following steps:
1) crystallizing a mixture containing halogenated imidazole ionic liquid, a phosphorus source, organic amine, an aluminum source and hydrofluoric acid at 180-280 ℃ for 5-300 min, and then filtering, washing, drying and roasting to obtain an aluminum phosphate molecular sieve;
2) and mixing the aluminum phosphate molecular sieve with a solution containing a heteroatom source, soaking and roasting to obtain the heteroatom-doped aluminum phosphate molecular sieve.
Optionally, the imidazole halide ionic liquid is selected from at least one of 1-butyl-3-methylimidazole bromide salt, 1-ethyl-3-methylimidazole bromide salt, 1-butyl-3-methylimidazole chloride salt and 1-ethyl-3-methylimidazole chloride salt.
Optionally, the raw material mixture contains the imidazole halide ionic liquid, the phosphorus source, the aluminum source, the organic amine and the fluoride in a molar ratio of: 8-16: 1-4: 1: 0.5-5: 0.05-1.
Preferably, the phosphorus source is selected from at least one of phosphoric acid, phosphate, phosphorus pentoxide. Further preferably, the phosphorus source is selected from phosphoric acid.
Preferably, the aluminum source is selected from at least one of aluminum oxide, aluminum isopropoxide, aluminum nitrate, aluminum hydroxide, aluminum chloride, aluminum sulfate, and sodium metaaluminate. Further preferably, the aluminium source is selected from aluminium isopropoxide.
Preferably, the heteroatom source is selected from at least one of nitrate, sulfate, acetate, and halide salts of transition metal elements.
Preferably, the heteroatom source is selected from at least one of copper acetate, nickel acetate, iron acetate, cobalt nitrate, copper nitrate, nickel nitrate, iron nitrate.
Preferably, the organic amine is selected from at least one of n-dipropylamine, iso-dipropylamine, diethylamine, triethylamine and tetraethylammonium hydroxide. Further preferably, the organic amine is tetraethylammonium hydroxide.
Optionally, the method comprises at least: mixing an imidazole halide solvent, biomass, a catalyst containing a heteroatom-doped aluminum phosphate molecular sieve and a hydrogen source, and reacting III to obtain the 2, 5-furandimethanol.
Optionally, the conditions of reaction III are: the reaction temperature is 80-150 ℃; the reaction time is 0.5-20 h.
The beneficial effects of the invention include but are not limited to:
1) the application provides a method for preparing 2, 5-furandimethanol (BHMF) by catalyzing carbohydrate compounds with one-step method, which avoids the separation and purification processes of 5-Hydroxymethylfurfural (HMF) in an intermediate link, and the renewable carbohydrate compounds have wide sources and low price, accord with technical and economic production modes, and have good application prospects.
2) The heteroatom-doped aluminum phosphate molecular sieve provided by the application has Lewis acidity and reducibility, and the preparation method has the characteristics of simplicity and suitability for industrial production.
Drawings
FIG. 1 is an XRD pattern of catalyst # 1;
FIG. 2 is an XRD pattern of catalyst # 2;
figure 3 is an XRD pattern of catalyst # 3.
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.
In the embodiment, 2, 5-furandimethanol reactants and products prepared by using a heteroatom-doped aluminum phosphate molecular sieve catalytic carbohydrate compound through a one-step method are analyzed by a high performance liquid chromatograph model 1260 of Agilent company, and the quantification is performed by adopting an external standard method.
The conversion and yield in the reaction of preparing 2, 5-furandimethanol from saccharides by using the heteroatom-doped aluminum phosphate molecular sieve in a one-step method are calculated as follows (the conversion of saccharides and the yield of 2, 5-furandimethanol are calculated based on the molar number of the saccharides):
Figure BDA0002875819830000051
Figure BDA0002875819830000052
example 1
Adding 40g of ionic liquid 1-butyl-3-methyl imidazole bromide [ BMIM ] Br into a three-neck flask, heating and stirring at 400rmp/min in an oil bath at 80 ℃, sequentially adding 7.056g of phosphoric acid, 6.8g of tetraethylammonium hydroxide, 4.902g of aluminum isopropoxide, 0.453g of copper acetate and 0.4g of hydrofluoric acid at intervals of half an hour, pouring the solution into a crucible after stirring, and moving the crucible to a muffle furnace at 180 ℃ for crystallization for 5 hours. After the reaction is finished, the obtained product is poured into deionized water for washing, filtering and drying at 100 ℃ for 10 hours. Then, the product is roasted in a muffle furnace, roasted at 600 ℃ for 2h, cooled and taken out to obtain a copper-doped aluminum phosphate molecular sieve, which is marked as # 1 (the aluminum phosphate molecular sieve prepared in the embodiment is an AlPO4-5 molecular sieve, and the mass content of copper in # 1 is 0.66 wt.%), and XRD characterization is performed on sample # 1, and the result is shown in fig. 1.
Example 2
Adding 40g of ionic liquid 1-butyl-3-methyl imidazole bromide [ BMIM ] Br into a three-neck flask, heating and stirring at 400rmp/min in an oil bath at 80 ℃, sequentially adding 7.056g of phosphoric acid, 6.8g of tetraethylammonium hydroxide, 4.902g of aluminum isopropoxide, 0.54g of nickel acetate and 0.4g of hydrofluoric acid at intervals of half an hour, pouring the solution into a crucible after stirring, and moving the crucible to a muffle furnace at 280 ℃ for sublimation for 15 min. After the reaction is finished, the obtained product is poured into deionized water for washing, filtering and drying at 100 ℃ for 10 hours. And then, roasting the product in a muffle furnace for 12 hours at 400 ℃, cooling and taking out the product to obtain the nickel-doped aluminum phosphate molecular sieve, marking the nickel-doped aluminum phosphate molecular sieve as No. 2 (the mass content of nickel in the No. 2 is 0.4 wt.%), and performing XRD (X-ray diffraction) characterization on the sample No. 2, wherein the result is shown in figure 2.
Example 3
Adding 40g of ionic liquid 1-butyl-3-methyl imidazole bromide [ BMIM ] Br into a three-neck flask, heating and stirring at 400rmp/min in an oil bath at 80 ℃, sequentially adding 7.056g of phosphoric acid, 6.8g of tetraethylammonium hydroxide, 4.902g of aluminum isopropoxide, 0.58g of ferric nitrate and 0.4g of hydrofluoric acid at intervals of half an hour, pouring the solution into a crucible after stirring, and moving the crucible to a muffle furnace at 220 ℃ for sublimation for 2 hours. After the reaction is finished, the obtained product is poured into deionized water for washing, filtering and drying at 100 ℃ for 10 hours. And then, roasting the product in a muffle furnace for 8 hours at 500 ℃, cooling and taking out the product to obtain the iron-doped aluminum phosphate molecular sieve, marking the molecular sieve as 3# (the mass content of iron in the molecular sieve 3# is 0.51 wt.%), and performing XRD characterization on the sample 3#, wherein the result is shown in figure 3.
Example 4
Adding 40g of ionic liquid 1-butyl-3-methyl imidazole bromide [ BMIM ] Br into a three-neck flask, heating and stirring at 400rmp/min in an oil bath at 80 ℃, sequentially adding 7.056g of phosphoric acid, 6.8g of tetraethylammonium hydroxide, 4.902g of aluminum isopropoxide and 0.4g of hydrofluoric acid at intervals of half an hour, pouring the solution into a crucible after stirring, and moving the crucible to a muffle furnace at 280 ℃ for crystallization for 1 h. After the reaction is finished, the obtained product is poured into deionized water for washing, filtering and drying at 100 ℃ for 10 hours. And then, roasting the product in a muffle furnace at 550 ℃ for 6 hours, cooling and taking out to obtain the aluminum phosphate molecular sieve, which is marked as 0 #.
Then, 0# catalyst was immersed in an aqueous solution of cobalt nitrate at a constant concentration, dried at 100 ℃ and then subjected to H2Roasting in an atmosphere tube furnace at 500 ℃ for 2h, cooling and taking out to prepare the 18 wt.% cobalt-loaded aluminum phosphate molecular sieve, which is marked as No. 4.
Example 5
Soaking catalyst 0# in nickel acetate water solution of certain concentration, drying at 100 deg.C, and adding into H2Roasting in an atmosphere tube furnace at 500 ℃ for 2h, cooling and taking out to prepare 11 wt.% of nickel-loaded aluminum phosphate molecular sieve, which is marked as No. 5.
Example 6
Soaking 0# catalyst in aqueous solution of ferric acetate with certain concentration, drying at 100 deg.C, and adding into H2Roasting in an atmosphere tube furnace at 500 ℃ for 2h, cooling and taking out to prepare the 5 wt.% iron-loaded aluminum phosphate molecular sieve, which is marked as 6 #.
Example 7
Adding 20g of 1-butyl-3-methylimidazolium bromide into a high-pressure reaction kettle, adding 5g of fructose and 0.5g of sample No. 1 catalyst, mixing, reacting the mixed solution at 100 ℃ for 1h, naturally cooling, adding 15g of water, replacing three times with hydrogen, keeping the hydrogen pressure at 2.5MPa, and reacting at 100 ℃ for 8 h. And (3) taking liquid before and after the reaction, testing and analyzing the liquid by using a high performance liquid chromatograph, and calculating the fructose conversion rate of 92% and the yield of 49% of the 2, 5-furandimethanol.
Example 8
Adding 20g of 1-butyl-3-methylimidazolium bromide into a high-pressure reaction kettle, adding 5g of fructose and 2.5g of sample No. 2 catalyst, mixing, reacting the mixed solution at 150 ℃ for 15min, naturally cooling, adding 15g of ethanol, replacing three times with hydrogen, keeping the hydrogen pressure at 5MPa, and reacting at 150 ℃ for 1 h. And (3) taking liquid before and after the reaction, testing and analyzing by using a high performance liquid chromatograph, and calculating the fructose conversion rate to be 98% and the yield of the 2, 5-furandimethanol to be 32%.
Example 9
Adding 20g of 1-butyl-3-methylimidazolium bromide into a high-pressure reaction kettle, adding 5g of fructose and 0.25g of sample No. 3 catalyst, mixing, reacting the mixed solution at 80 ℃ for 2h, naturally cooling, adding 15g of tetrahydrofuran, replacing three times with hydrogen, keeping the hydrogen pressure at 2MPa, and reacting at 90 ℃ for 20 h. And (3) taking liquid before and after the reaction, testing and analyzing the liquid by using a high performance liquid chromatograph, and calculating the fructose conversion rate of 87% and the yield of the 2, 5-furandimethanol of 30%.
Example 10
Adding 20g of 1-butyl-3-methylimidazolium bromide into a high-pressure reaction kettle, adding 5g of fructose and 1.25g of sample No. 4 catalyst, mixing, reacting the mixed solution at 110 ℃ for 1h, naturally cooling, adding 15g of methanol, replacing three times with hydrogen, keeping the hydrogen pressure at 3MPa, and reacting at 140 ℃ for 4 h. And (3) taking liquid before and after the reaction, testing and analyzing the liquid by using a high performance liquid chromatograph, and calculating the fructose conversion rate of 97 percent and the yield of the 2, 5-furandimethanol of 39 percent.
Example 11
Adding 1 g of butyl-3-methylimidazolium bromide salt into a high-pressure reaction kettle, adding 5g of fructose and 0.5g of sample No. 5 catalyst, and mixing. After three times of replacement with hydrogen, the reaction was carried out for 5 hours while maintaining the hydrogen pressure at 3MPa and the temperature at 120 ℃. And (3) taking liquid before and after the reaction, testing and analyzing by using a high performance liquid chromatograph, and calculating the fructose conversion rate of 95% and the yield of the 2, 5-furandimethanol of 40%.
Example 12
Adding 1 g of butyl-3-methylimidazolium bromide salt into a high-pressure reaction kettle, adding 5g of fructose and 0.5g of sample No. 6 catalyst, and mixing. After three times of replacement with hydrogen, the reaction was carried out for 5 hours while maintaining the hydrogen pressure at 4MPa and the temperature at 120 ℃. And (3) taking liquid before and after the reaction, testing and analyzing by using a high performance liquid chromatograph, and calculating the fructose conversion rate of 96% and the yield of the 2, 5-furandimethanol of 35%.
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 (9)

1. A process for the preparation of 2, 5-furandimethanol, which comprises at least:
(a) adding a carbohydrate and a catalyst containing a heteroatom-doped aluminum phosphate molecular sieve into an imidazole halide solvent, and reacting I to obtain an intermediate product;
(b) adding a hydrogen source into the intermediate product, and reacting II to obtain the 2, 5-furandimethanol;
the heteroatoms in the catalyst are selected from transition metals; the transition metal element is at least one selected from Cu, Ni, Fe and Co;
the mass content of the heteroatom in the heteroatom-doped aluminum phosphate molecular sieve is 0.1-20 wt%;
the mass of the heteroatom-doped aluminum phosphate molecular sieve is 4-60 wt% of that of the saccharide compound;
the hydrogen source is at least one of formic acid, isopropanol, ethanol, methanol and hydrogen;
the aluminum phosphate molecular sieve is selected from AlPO4-5 molecular sieves, AlPO4-11 molecular sieves, AlPO4-41 molecular sieves, AlPO4-42 molecular sieves.
2. The method according to claim 1, wherein the sugar compound is at least one selected from the group consisting of fructose, sucrose and glucose.
3. The method of claim 1, wherein the heteroatom-doped aluminum phosphate molecular sieve is prepared by an ionothermal method in the presence of an imidazole-halogenated ionic liquid.
4. The process according to claim 1, characterized in that the conditions of reaction I are: the reaction temperature is 60-150 ℃; the reaction time is 10 min-2 h.
5. The process according to claim 1, wherein the conditions of reaction II are: the reaction temperature is 80-150 ℃; the reaction time is 0.5-20 h.
6. The method of claim 1, wherein the hydrogen source is hydrogen gas; and the pressure of the reaction II is 1-5 Mpa.
7. The method according to claim 1, wherein the halogenated imidazole solvent is at least one selected from the group consisting of 1-butyl-3-methylimidazole bromide salt, 1-ethyl-3-methylimidazole bromide salt, 1-butyl-3-methylimidazole chloride salt and 1-ethyl-3-methylimidazole chloride salt.
8. The method according to claim 1, wherein the step (b) comprises at least: adding a hydrogen source and a solvent into the intermediate product, and reacting II to obtain the 2, 5-furandimethanol;
the solvent is at least one selected from water, halogenated imidazole solvent, tetrahydrofuran, formic acid, isopropanol, ethanol and methanol;
the hydrogen source is at least one selected from hydrogen, formic acid, isopropanol, ethanol and methanol.
9. The process of claim 1, wherein the reactions I and II are carried out in an autoclave.
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