CN113527703B - Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2,5-furandimethanol - Google Patents
Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2,5-furandimethanol Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Abstract
The invention discloses a preparation method of a metal carbon-based coordination polymer, which takes natural lignin or glucose-based hydrothermal organic carbon with abundant content in nature to replace expensive organic phenolic acid, carboxylic acid and phosphonic acid as a ligand, synthesizes a metal carbon-based coordination polymer catalyst only containing Lewis acid sites and Lewis basic sites through a solvothermal self-assembly process, and the prepared catalyst not only has higher acid-base strength and acid-base content, but also has simple and controllable preparation process, cost advantage and catalytic activity. In addition, the metal carbon-based coordination polymer catalyst prepared by the method can also use cheap and easily-obtained low-carbon alcohol as an in-situ hydrogen donor and a reaction solvent at the same time, 5-hydroxymethylfurfural is directionally converted into 2,5-furandimethanol by transfer hydrogenation reaction under mild operation conditions, no external hydrogen donor and other reaction solvents are required to be additionally added in the whole reaction process, the composition of a reaction system is safe and simple, and the separation of a target product is facilitated.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of a metal carbon-based coordination polymer and application of the metal carbon-based coordination polymer in 2,5-furandimethanol directional synthesis.
Background
The biomass is an extremely important renewable resource and has the characteristics of being green, low-carbon, clean, renewable and the like. The realization of the comprehensive utilization of biomass resources is an important measure for deeply implementing the sustainable development strategy in China, and has important significance for optimizing energy structure, improving environmental quality, developing circular economy and promoting green transformation of society. In recent years, 5-hydroxymethylfurfural obtained by dehydration conversion of biomass is considered to be a very important platform compound, and the U.S. department of energy also ranks it as one of ten large platform compounds based on biomass resources because a series of high-value-added chemicals can be prepared from it. Among them, 2,5-furandimethanol obtained by selective hydrogenation of 5-hydroxymethylfurfural is attracting attention, and it can be used as a softener, a wetting agent, a binder, a plasticizer, a surfactant, a medical intermediate, etc., and also as a polymer material (ACS Catalysis,2015, 5.
The 5-hydroxymethylfurfural molecule simultaneously contains an aldehyde group, an alcoholic hydroxyl group and a furan ring, so that the chemical property of the 5-hydroxymethylfurfural is very active, and the product is complex when hydrogenation reaction occurs, therefore, how to ensure the preferential hydrogenation of the aldehyde group and avoid the excessive hydrogenation of the alcoholic hydroxyl group and the furan ring as much as possible is the first and key problem to be solved in the process of synthesizing 2,5-furandimethanol by selective hydrogenation of the 5-hydroxymethylfurfural, and the development of a proper catalytic reaction system is very important for solving the problem. At present, a catalytic reaction system consisting of a supported noble metal and hydrogen is the most common and classical catalytic reaction system for synthesizing 2,5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural, but the catalytic reaction system also has a series of inevitable defects, such as rare noble metal, high catalyst manufacturing cost and great preparation technical difficulty; hydrogen is flammable, potential safety hazards are high, solubility in various solvents is low, and atom utilization rate is low. In order to overcome the disadvantages of the above catalytic reaction system, disproportionation reaction systems (Green Chemistry,2013,15, 2849-2853), electrochemical reaction systems (Environmental Science & Technology,2015,49, 13667-13675), and photochemical reaction systems (RSC Advances,2016,6 101968-101973) and the like are gradually applied to the process of selective hydrogenation synthesis of 2,5-furandimethanol by 5-hydroxymethylfurfural. Although these new catalytic reaction systems can be carried out under the conditions of non-noble metal catalyst and no exogenous hydrogen, their catalytic efficiency including substrate conversion rate and product yield is often low, which also limits the large-scale production and practical application of 2,5-furandimethanol to a great extent.
Disclosure of Invention
The invention provides a preparation method of a metal carbon-based coordination polymer, and also provides an application of the catalyst prepared by the method in directionally converting 5-hydroxymethylfurfural into 2,5-furandimethanol without adding exogenous hydrogen.
A metal-carbon based coordination polymer, wherein the coordination polymer takes lignin and/or glucose-based hydrothermal organic carbon as an organic ligand and takes magnesium, cerium, tin, zirconium, hafnium or titanium as a metal center.
The preparation method of the coordination polymer comprises the following steps:
and 2, washing and drying the reaction precipitate to obtain the coordination polymer.
The metal ions are selected from metal ions containing magnesium, cerium, tin, zirconium, hafnium or titanium.
Preferably, the inorganic salt is selected from chloride salt and nitrate salt.
Preferably, the lignin is one of enzymatic hydrolysis lignin, alkali extraction lignin, sulfate lignin, organic solvent lignin or ground wood lignin.
Preferably, the preparation method of the glucose-based hydrothermal organic carbon comprises the following steps:
mixing glucose with water, carrying out hydrothermal reaction, washing and drying the obtained precipitate to obtain the glucose-based hydrothermal organic carbon.
Preferably, the concentration of the glucose in the water is 50-100g/L, the hydrothermal reaction temperature is 160-220 ℃, and the hydrothermal reaction time is 6-24h.
Preferably, the mass ratio of the inorganic salt containing metal ions to the lignin and/or the glucose-based hydrothermal organic carbon is 1:2-2:1.
Preferably, the concentration of the lignin and/or glucose-based hydrothermal organic carbon in the solvent is 5-25g/L.
Preferably, the reaction temperature is 100-160 ℃, and the reaction time is 12-48h.
The coordination polymer is applied to the oriented synthesis of 5-hydroxymethylfurfural to 2,5-furandimethanol.
Preferably, the application further comprises the following steps:
adding a coordination polymer catalyst, 5-hydroxymethylfurfural and low-carbon alcohol into a reaction kettle, and carrying out Meerwein-Ponndorf-Verley transfer hydrogenation reaction at a certain reaction temperature and stirring speed to obtain 2,5-furandimethanol.
Preferably, the lower alcohol is one of ethanol, isopropanol, n-butanol or sec-butanol.
Preferably, the dosage of the 5-hydroxymethylfurfural is 1-5wt% of that of the lower alcohol, and the dosage of the coordination polymer catalyst is 10-50wt% of that of the 5-hydroxymethylfurfural.
Preferably, the reaction temperature is 100-150 ℃ and the reaction time is 1-6h.
Advantageous effects
1) The invention uses natural lignin and/or glucose-based hydrothermal organic carbon with abundant natural content in nature to replace expensive organic phenolic acid, carboxylic acid and phosphonic acid as ligands to prepare the novel metal carbon-based coordination polymer catalyst only containing Lewis acid sites and Lewis basic sites. 2) The novel metal carbon-based coordination polymer catalyst prepared by the invention has higher acid-base strength and more acid-base sites, and the synergistic effect of the catalyst and the acid-base sites can not only ensure that 5-hydroxymethylfurfural is directionally converted into 2,5-furandimethanol, but also can effectively avoid the implementation of other side reactions such as etherification, ring opening and the like. 3) The novel metal carbon-based coordination polymer catalyst prepared by the invention has the advantages of wide source of preparation raw materials, simple and controllable preparation process, easy separation, recovery and cyclic utilization after use, and excellent catalytic activity, catalytic selectivity and catalytic stability. 4) The low-carbon alcohol adopted by the invention not only can be used as an in-situ hydrogen donor, avoids the use of molecular hydrogen and increases the safety of the reaction process, but also can be used as a reaction solvent, reduces the introduction of exogenous substances, simplifies the separation process of a target product and reduces the corresponding production cost. 5) The metal carbon-based coordination polymer catalyst can also catalyze various carbonyl compounds such as furfural, n-butyl aldehyde, benzaldehyde, cyclohexanone, levulinic acid, levulinate ester and the like to be directionally converted into corresponding products with high added values, has strong substrate universality, and shows good market application value and industrialization prospect.
Drawings
FIG. 1 is an FT-IR spectrum of Zr-EHL-1 prepared in example 1 (1 is catalyst, 2 is lignin).
FIG. 2 is a Py-IR spectrum of Zr-EHL-3 prepared in example 3.
FIG. 3 is NH of Zr-EHL-3 prepared in example 3 3 -a TPD profile.
FIG. 4 is CO of Zr-EHL-3 prepared in example 3 2 -a TPD profile.
FIG. 5 is an SEM image of the HTC-1 prepared in example 11.
FIG. 6 is an SEM photograph of Zr-HTC-1 prepared in example 11.
FIG. 7 is a Py-IR spectrum of Zr-HTC-2 prepared in example 12.
FIG. 8 is NH of Zr-HTC-2 prepared in example 12 3 -a TPD profile.
FIG. 9 is CO of Zr-HTC-2 prepared in example 12 2 -a TPD profile.
FIG. 10 is an FT-IR spectrum (1 is amorphous carbon obtained by hydrothermal treatment, 2 is catalyst) of Zr-HTC-3 prepared in example 13.
Detailed Description
The technical idea of the invention is to replace expensive organic carboxylic acid, phenolic acid or phosphonic acid with lignin rich in phenolic hydroxyl or glucose-based hydrothermal organic carbon rich in carboxyl and phenolic hydroxyl as ligand, to prepare a novel metal carbon-based coordination polymer catalyst by carrying out solvent thermal self-assembly coordination reaction with metal chloride, wherein M in M-O-C formed in the coordination process n+ Capable of providing a Lewis acid site, O 2- Can provide Lewis basic sites, and the combined action of the Lewis basic sites can ensure that the 5-hydroxymethylfurfural is directionally converted into 2,5-furandimethanol.
When lignin is used as a ligand, the reaction mechanism is: the surface of lignin contains a large number of phenolic hydroxyl groups, in a deprotonation solvent, the phenolic hydroxyl groups can undergo a deprotonation reaction, then oxygen on the phenolic hydroxyl groups can undergo a coordination reaction with metal ions to form a coordination bond so as to generate a lignin-metal chelate, and self-assembly polymerization is further performed under the solvothermal reaction condition, so that the metal lignin-based coordination polymer is finally obtained. The more specific technical scheme comprises the following steps:
the preparation method of the metal lignin-based coordination polymer provided by the invention comprises the following steps: respectively adding metal chloride and lignin into a dimethylformamide solvent according to a certain proportion, and stirring for 30min under the assistance of ultrasound; slowly adding the metal chloride solution into the lignin solution, and continuously stirring for 2 hours at room temperature; transferring the mixed solution into a reaction kettle, and reacting for a period of time at a certain temperature and autogenous pressure to generate gel solid precipitate; filtering and separating the solid precipitate, and repeatedly washing with absolute ethyl alcohol and deionized water until chloride ions cannot be detected; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12h to obtain the metal lignin-based coordination polymer only containing Lewis acid sites and Lewis basic sites.
Wherein the metal chloride is one of magnesium dichloride, cerium trichloride, tin tetrachloride, zirconium tetrachloride, hafnium tetrachloride or titanium tetrachloride, and is preferably zirconium tetrachloride.
The lignin is one of enzymatic hydrolysis lignin, alkali extraction lignin, sulfate lignin, organic solvent lignin or ground wood lignin, and is preferably enzymatic hydrolysis lignin.
Wherein the mass ratio of the metal chloride to the lignin is 1:2-2:1.
Wherein the reaction temperature is 100-160 ℃, and the reaction time is 12-48h.
When the glucose-based hydrothermal organic carbon is used as a ligand, the reaction mechanism is as follows: the surface of the glucosyl group hydrothermal organic carbon contains a large amount of carboxyl and phenolic hydroxyl, in a deprotonation solvent, the carboxyl and phenolic hydroxyl can undergo a deprotonation reaction, then oxygen on the carboxyl and phenolic hydroxyl can undergo a coordination reaction with metal ions to form a coordination bond so as to generate a hydrothermal organic carbon-metal chelate, and further self-assembly polymerization is carried out under the condition of solvothermal reaction, so that the metal organic carbon coordination polymer is finally obtained. The more specific technical scheme comprises the following steps:
the synthesis method of the metal organic carbon coordination polymer catalyst comprises the following steps: (1) Stirring and mixing a certain amount of glucose and deionized water uniformly, adding the mixture into a reaction kettle, and reacting for a period of time at a certain temperature and autogenous pressure to generate solid precipitate; filtering and separating the solid precipitate, and repeatedly washing with absolute ethyl alcohol and deionized water until the filtrate is clear; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the glucose-based hydrothermal organic carbon. (2) Adding a certain amount of glucose-based hydrothermal organic carbon and metal chloride into dimethylformamide, ultrasonically stirring and uniformly dispersing, then transferring into a reaction kettle, and reacting for a period of time at a certain temperature and under autogenous pressure to generate solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the metal organic carbon coordination polymer catalyst.
Wherein in the step (1) for synthesizing the metal organic carbon coordination polymer catalyst, the concentration of glucose is 50-100g/L, the reaction temperature is 160-220 ℃, and the reaction time is 6-24h.
In the step (2) for synthesizing the metal organic carbon coordination polymer catalyst, the metal chloride is one of magnesium dichloride, cerium trichloride, tin tetrachloride, zirconium tetrachloride, hafnium tetrachloride and titanium tetrachloride, and preferably zirconium tetrachloride; the concentration of the metal chloride in the dimethylformamide is 5-25g/L; the concentration of the glucose-based hydrothermal organic carbon in the dimethylformamide is 5-25g/L; the reaction temperature is 100-160 ℃, and the reaction time is 12-48h.
The application of the metal carbon-based coordination polymer prepared by the method in the 2,5-furandimethanol directional synthesis comprises the following steps: adding a certain amount of metal carbon-based coordination polymer catalyst, 5-hydroxymethylfurfural and low-carbon alcohol into a reaction kettle, and carrying out Meerwein-Ponndorf-Verley (MPV) transfer hydrogenation reaction for a period of time at a certain reaction temperature and stirring speed to obtain 2,5-furandimethanol.
Wherein the lower alcohol is one of ethanol, isopropanol, n-butanol or sec-butanol, preferably isopropanol or sec-butanol.
Wherein the dosage of the 5-hydroxymethylfurfural is 1-5wt% of the dosage of the lower alcohol, and the dosage of the metal carbon-based coordination polymer catalyst is 10-50wt% of the dosage of the 5-hydroxymethylfurfural.
Wherein the reaction temperature is 100-150 ℃, the reaction time is 1-6h, and the stirring speed is 300-500 rpm.
The metal carbon-based coordination polymer catalyst only contains Lewis acid sites and Lewis basic sites, and the synergistic effect of the Lewis acid sites and the Lewis basic sites has the effects of improving the product yield and the product selectivity, reducing the reaction temperature and shortening the reaction time.
The application of the metal carbon-based coordination polymer catalyst in selective reduction reaction of carbonyl-containing compounds.
Preferably, the carbonyl-containing compound is selected from furfural, n-butyraldehyde, benzaldehyde, cyclohexanone, levulinic acid ester or the like.
Example 1
4g of enzymolyzed lignin and 2g of zirconium tetrachloride were added to 250mL of dimethylformamide respectivelyStirring for 30min under the assistance of ultrasound; slowly adding a zirconium tetrachloride solution into an enzymolysis lignin solution, and continuously stirring for 2 hours at room temperature; transferring the mixed solution into a reaction kettle, and reacting for 36 hours at the autogenous pressure of 100 ℃ to generate gelatinous solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; drying the washed solid precipitate in a vacuum drying oven at 100 deg.C for 12 hr to obtain zirconium lignin-based coordination polymer catalyst (figure 1), abbreviated as Zr-EHL-1. By Py-IR, NH 3 TPD and CO 2 As can be seen from the TPD characterization analysis, the Lewis acid site content of the Zr-EHL-1 is 0.235mmol/g, and the Lewis basic site content is 1.788mmol/g. Then, 0.5g of 5-hydroxymethylfurfural, 0.15g of Zr-EHL-1 and 25g of isopropanol are added into a reaction kettle, the temperature is raised to 150 ℃ under the stirring speed of 500rpm, and the 2,5-furandimethanol can be obtained after MPV reduction reaction for 2 hours. The detection of a gas chromatograph shows that the conversion rate of the 5-hydroxymethylfurfural can reach 100 percent, and the yield of 2,5-furandimethanol can reach 96.7 percent. In addition, the Zr-EHL-1 was separated from the reaction solution, washed and dried, and then subjected to the next MPV reduction reaction under the above reaction conditions, and the results showed that: after the Zr-EHL-1 is recycled for five times, the conversion rate of the 5-hydroxymethylfurfural and the yield of 2,5-furandimethanol can still reach 97.9 percent and 95.1 percent respectively.
Example 2
Respectively adding 3.5g of enzymatic hydrolysis lignin and 3.5g of zirconium tetrachloride into 150mL of dimethylformamide, and stirring for 30min under the assistance of ultrasound; slowly adding a zirconium tetrachloride solution into an enzymolysis lignin solution, and continuously stirring for 2 hours at room temperature; transferring the mixed solution into a reaction kettle, and reacting for 24 hours at the autogenous pressure of 120 ℃ to generate gelatinous solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the zirconium lignin-based coordination polymer catalyst, which is abbreviated as Zr-EHL-2. By Py-IR, NH 3 TPD and CO 2 The Lewis acid site content of the Zr-EHL-2 is 0.254mmol/g and the Lewis acid site content is known by TPD characterization analysisThe is alkaline site content is 1.841mmol/g. Then, 0.5g of 5-hydroxymethylfurfural, 0.2g of Zr-EHL-2 and 25g of isopropanol are added into the reaction kettle, the temperature is raised to 140 ℃ under the stirring speed of 400rpm, and the 2,5-furandimethanol can be obtained after MPV reduction reaction for 4 hours. The detection of a gas chromatograph shows that the conversion rate of the 5-hydroxymethylfurfural can reach 100 percent, and the yield of 2,5-furandimethanol can reach 98.9 percent. In addition, the Zr-EHL-2 was separated from the reaction solution, washed and dried, and then subjected to the next MPV reduction reaction under the above reaction conditions, and the results showed that: after the Zr-EHL-2 is recycled for five times, the conversion rate of the 5-hydroxymethylfurfural and the yield of 2,5-furandimethanol can still reach 98.1 percent and 96.3 percent respectively.
Example 3
Respectively adding 3g of enzymatic hydrolysis lignin and 4.5g of zirconium tetrachloride into 200mL of dimethylformamide, and stirring for 30min under the assistance of ultrasound; slowly adding a zirconium tetrachloride solution into an enzymolysis lignin solution, and continuously stirring for 2 hours at room temperature; transferring the mixed solution into a reaction kettle, and reacting for 18 hours at the autogenous pressure of 130 ℃ to generate gelatinous solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the zirconium lignin-based coordination polymer catalyst, which is abbreviated as Zr-EHL-3. By Py-IR (FIG. 2) and NH 3 TPD (FIG. 3) and CO 2 As can be seen from the characterization analysis of-TPD (FIG. 4), the Lewis acid site content of Zr-EHL-3 is 0.321mmol/g, and the Lewis basic site content is 1.856mmol/g. Then, 0.5g of 5-hydroxymethylfurfural, 0.2g of Zr-EHL-3 and 25g of sec-butyl alcohol are added into a reaction kettle, the temperature is raised to 130 ℃ under the stirring speed of 500rpm, and the 2,5-furandimethanol can be obtained after MPV reduction reaction for 5 hours. The detection of a gas chromatograph shows that the conversion rate of the 5-hydroxymethylfurfural can reach 100 percent, and the yield of 2,5-furandimethanol can reach 99.1 percent. In addition, the next MPV reduction reaction was carried out under the above reaction conditions after separating Zr-EHL-3 from the reaction solution and then washing and drying it, and the results showed that: after the Zr-EHL-3 is recycled for five times, the conversion rate of the 5-hydroxymethylfurfural and the yield of 2,5-furandimethanol can still reach 99 respectively.2% and 96.8%.
Example 4
Respectively adding 2.5g of enzymatic hydrolysis lignin and 5g of zirconium tetrachloride into 300mL of dimethylformamide, and stirring for 30min under the assistance of ultrasound; slowly adding a zirconium tetrachloride solution into an enzymolysis lignin solution, and continuously stirring for 2 hours at room temperature; transferring the mixed solution into a reaction kettle, and reacting for 12 hours at the autogenous pressure of 140 ℃ to generate gelatinous solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the zirconium lignin-based coordination polymer catalyst, which is abbreviated as Zr-EHL-4. By Py-IR, NH 3 TPD and CO 2 As can be seen from TPD characterization analysis, the Lewis acid site content of Zr-EHL-4 is 0.267mmol/g, and the Lewis basic site content is 1.838mmol/g. Then, 0.5g of 5-hydroxymethylfurfural, 0.25g of Zr-EHL-4 and 25g of sec-butyl alcohol are added into a reaction kettle, the temperature is raised to 120 ℃ under the stirring speed of 400rpm, and MPV reduction reaction is carried out for 6 hours to obtain 2,5-furandimethanol. The detection of a gas chromatograph shows that the conversion rate of the 5-hydroxymethylfurfural can reach 100 percent, and the yield of 2,5-furandimethanol can reach 98.7 percent. In addition, the following MPV reduction reaction was carried out under the above reaction conditions after separating Zr-EHL-4 from the reaction solution and then washing and drying it, and the results showed that: after the Zr-EHL-4 is recycled for five times, the conversion rate of the 5-hydroxymethylfurfural and the yield of 2,5-furandimethanol can still reach 98.0 percent and 95.4 percent respectively.
The following examples are the catalytic effects of Zr-EHL-3 prepared in the above example 3 on selective hydroconversion of other carbonyl compounds such as furfural, n-butyraldehyde, benzaldehyde, cyclohexanone, levulinic acid esters, and the like, with the specific results shown in Table 1.
TABLE 1
Example 11
Adding 5g of glucose into 100mL of deionized water for dissolving, stirring and mixing uniformly, transferring into a reaction kettle, and reacting for 24 hours at 160 ℃ under the autogenous pressure to generate solid precipitate; filtering and separating the solid precipitate, and repeatedly washing with absolute ethyl alcohol and deionized water until the filtrate is clear; drying the washed solid precipitate in a vacuum drying oven at 100 deg.C for 12 hr to obtain glucose-based hydrothermal organic carbon (abbreviated as HTC-1) (FIG. 5). Then, adding 3g of HTC-1 and 3g of zirconium tetrachloride into 200mL of dimethylformamide, ultrasonically stirring and uniformly dispersing, then transferring into a reaction kettle, and reacting for 48 hours at 100 ℃ under the autogenous pressure to generate solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; the washed solid precipitate is dried in a vacuum drying oven at 100 ℃ for 12h to obtain the zirconium organic carbon coordination polymer catalyst, which is abbreviated as Zr-HTC-1 (figure 6). By Py-IR, NH 3 TPD and CO 2 As shown by TPD characterization analysis, the Lewis acid site content of the Zr-HTC-1 is 1.579mmol/g, and the Lewis basic site content is 1.642mmol/g. Then, 0.25g of 5-hydroxymethylfurfural, 0.05g of Zr-HTC-1 and 25g of isopropanol are added into a reaction kettle, the temperature is raised to 110 ℃ under the stirring speed of 300rpm, and the 2,5-furandimethanol can be obtained after MPV reduction reaction for 5 hours. The detection of a gas chromatograph shows that the conversion rate of the 5-hydroxymethylfurfural can reach 100 percent, and the yield of 2,5-furandimethanol can reach 98.1 percent. In addition, the Zr-HTC-1 was separated from the reaction solution, washed and dried, and then subjected to the next MPV reduction reaction under the above reaction conditions, and the results showed that: when the Zr-HTC-1 is recycled for five times, the conversion rate of the 5-hydroxymethylfurfural and the yield of the 2,5-furandimethanol can still reach 100 percent and 96.5 percent respectively.
Example 12
Adding 10g of glucose into 100mL of deionized water for dissolving, stirring and mixing uniformly, transferring into a reaction kettle, and reacting for 10 hours at the autogenous pressure of 180 ℃ to generate solid precipitate; the solid precipitate is filtered and separated for useRepeatedly washing the absolute ethyl alcohol and the deionized water until the filtrate is clear; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the glucose-based hydrothermal organic carbon, which is abbreviated as HTC-2. Then, adding 4g of HTC-2 and 4g of zirconium tetrachloride into 400mL of dimethylformamide, ultrasonically stirring and uniformly dispersing, then transferring into a reaction kettle, and reacting for 24 hours at the autogenous pressure of 120 ℃ to generate solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the zirconium organic carbon coordination polymer catalyst, which is abbreviated as Zr-HTC-2. By Py-IR (FIG. 7) and NH 3 TPD (FIG. 8) and CO 2 As a result of characterization analysis of-TPD (FIG. 9), the Lewis acid site content of Zr-HTC-2 was 1.823mmol/g, and the Lewis basic site content was 1.681mmol/g. Then, 0.5g of 5-hydroxymethylfurfural, 0.2g of Zr-HTC-2 and 25g of isopropanol are added into the reaction kettle, the temperature is raised to 120 ℃ under the stirring speed of 400rpm, and MPV reduction reaction is carried out for 4 hours to obtain 2,5-furandimethanol. The detection of a gas chromatograph shows that the conversion rate of the 5-hydroxymethylfurfural can reach 100 percent, and the yield of 2,5-furandimethanol can reach 99.6 percent. In addition, the Zr-HTC-2 was separated from the reaction solution, washed and dried, and then subjected to the next MPV reduction reaction under the above reaction conditions, and the results showed that: after the Zr-HTC-2 is recycled for five times, the conversion rate of the 5-hydroxymethylfurfural and the yield of 2,5-furandimethanol can still reach 100 percent and 97.1 percent respectively.
Example 13
Adding 6g of glucose into 100mL of deionized water for dissolving, stirring and mixing uniformly, transferring into a reaction kettle, and reacting for 8 hours at the autogenous pressure of 200 ℃ to generate solid precipitate; filtering and separating the solid precipitate, and repeatedly washing with absolute ethyl alcohol and deionized water until the filtrate is clear; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the glucose-based hydrothermal organic carbon, which is abbreviated as HTC-3. Subsequently, 4g of HTC-3 and 4g of zirconium tetrachloride were added to 300mL of dimethylformamide, ultrasonically stirred to disperse uniformly, transferred to a reaction vessel, and subjected to autogenous pressure at 140 ℃Reacting for 16 hours to generate solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; the washed solid precipitate was dried in a vacuum oven at 100 ℃ for 12 hours to obtain a zirconium organic carbon coordination polymer catalyst, abbreviated as Zr-HTC-3 (FIG. 10). By Py-IR, NH 3 TPD and CO 2 As shown by TPD characterization analysis, the Lewis acid site content of the Zr-HTC-3 is 1.718mmol/g, and the Lewis basic site content is 1.577mmol/g. Then, 0.5g of 5-hydroxymethylfurfural, 0.15g of Zr-HTC-3 and 25g of sec-butyl alcohol are added into a reaction kettle, the temperature is raised to 120 ℃ under the stirring speed of 500rpm, and the 2,5-furandimethanol can be obtained after MPV reduction reaction for 5 hours. The detection of a gas chromatograph shows that the conversion rate of the 5-hydroxymethylfurfural can reach 100 percent, and the yield of 2,5-furandimethanol can reach 96.8 percent. In addition, the Zr-HTC-3 was separated from the reaction solution, washed and dried, and then subjected to the next MPV reduction reaction under the above reaction conditions, and the results showed that: after the Zr-HTC-3 is recycled for five times, the conversion rate of the 5-hydroxymethylfurfural and the yield of 2,5-furandimethanol can still reach 100 percent and 96.2 percent respectively.
Example 14
Adding 8g of glucose into 100mL of deionized water for dissolving, stirring and mixing uniformly, transferring into a reaction kettle, and reacting for 6 hours at the autogenous pressure of 220 ℃ to generate solid precipitate; filtering and separating the solid precipitate, and repeatedly washing with absolute ethyl alcohol and deionized water until the filtrate is clear; and (3) drying the washed solid precipitate in a vacuum drying oven at 100 ℃ for 12 hours to obtain the glucose-based hydrothermal organic carbon, which is abbreviated as HTC-4. Then, 2.5g of HTC-1 and 2.5g of zirconium tetrachloride are added into 500mL of dimethylformamide, the mixture is transferred into a reaction kettle after being stirred and dispersed uniformly by ultrasonic, and the mixture reacts for 12 hours at the autogenous pressure of 160 ℃ to generate solid precipitate; repeatedly washing the solid precipitate with absolute ethyl alcohol and deionized water after filtration and separation until no chloride ion is detected; and (3) drying the washed solid precipitate in a vacuum drying oven for 12 hours at 100 ℃ to obtain the zirconium organic carbon coordination polymer catalyst, which is abbreviated as Zr-HTC-4. By Py-IR, NH 3 TPD and CO 2 Characterization of TPDAs a result of analysis, the Lewis acid site content of Zr-HTC-4 was 1.646mmol/g, and the Lewis basic site content was 1.685mmol/g. Then, 0.75g of 5-hydroxymethylfurfural, 0.375g of Zr-HTC-4 and 25g of sec-butyl alcohol are added into a reaction kettle, the temperature is raised to 130 ℃ under the stirring speed of 500rpm, and the 2,5-furandimethanol can be obtained after MPV reduction reaction for 3 hours. The detection of a gas chromatograph shows that the conversion rate of the 5-hydroxymethylfurfural can reach 100 percent, and the yield of 2,5-furandimethanol can reach 97.4 percent. In addition, the Zr-HTC-4 is separated from the reaction solution, washed and dried, and then subjected to the next MPV reduction reaction under the above reaction conditions, and the results show that: after the Zr-HTC-4 is recycled for five times, the conversion rate of the 5-hydroxymethylfurfural and the yield of 2,5-furandimethanol can still reach 100 percent and 95.8 percent respectively.
The following examples are the catalytic effects of Zr-HTC-2 prepared in the above example 12 on selective hydroconversion of other carbonyl compounds such as furfural, n-butyraldehyde, benzaldehyde, cyclohexanone, levulinic acid esters, and the like, with specific results as shown in Table 2.
TABLE 2
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made without departing from the spirit and scope of the invention. Any simple modification or equivalent changes made to the following embodiments according to the technical essence of the present invention, without departing from the technical spirit of the present invention, fall within the scope of the present invention.
Claims (4)
1. The application of the metal carbon-based coordination polymer in the 5-hydroxymethylfurfural oriented synthesis of 2,5-furandimethanol is characterized in that the metal carbon-based coordination polymer takes lignin and/or glucose-based hydrothermal organic carbon as an organic ligand and takes zirconium as a metal center;
the preparation method of the metal carbon-based coordination polymer comprises the following steps:
step 1, mixing inorganic salt containing metal ions with lignin and/or glucose-based hydrothermal organic carbon, and reacting in a solvent; the mass ratio of the inorganic salt containing metal ions to the lignin and/or glucose-based hydrothermal organic carbon is 1:2-2:1, and the concentration of the lignin and/or glucose-based hydrothermal organic carbon in a solvent is 5-25g/L; the reaction temperature is 100-160 ℃, and the reaction time is 12-48h;
step 2, washing and drying the reaction precipitate to obtain a metal carbon-based coordination polymer;
the metal ion is selected from metal ions of zirconium; the inorganic salt is selected from chloride salt and nitrate;
the application also comprises the following steps: adding the metal carbon-based coordination polymer, 5-hydroxymethylfurfural and low-carbon alcohol into a reaction kettle, and carrying out Meerwein-Ponndorf-Verley transfer hydrogenation reaction at a certain reaction temperature and stirring speed to obtain 2,5-furandimethanol.
2. The use of claim 1, wherein the lignin is one of enzymatic lignin, alkali extracted lignin, kraft lignin, organosolv lignin or ground wood lignin.
3. The use according to claim 1, wherein the method for preparing the glucose-based hydrothermal organic carbon comprises the following steps: mixing glucose with water, carrying out hydrothermal reaction, washing and drying the obtained precipitate to obtain glucose-based hydrothermal organic carbon; the concentration of the glucose in water is 50-100g/L, the hydrothermal reaction temperature is 160-220 ℃, and the hydrothermal reaction time is 6-24h.
4. The use according to claim 1, wherein the lower alcohol is one of ethanol, isopropanol, n-butanol or sec-butanol; the dosage of the 5-hydroxymethylfurfural is 1-5wt% of that of the lower alcohol, and the dosage of the metal carbon-based coordination polymer is 10-50wt% of that of the 5-hydroxymethylfurfural; the reaction temperature in the Meerwein-Ponndorf-Verley transfer hydrogenation is 100-150 ℃, and the reaction time is 1-6h.
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