CN109776628B - Mesoporous zirconium tannate catalyst and application thereof in catalyzing furfural hydrogenation - Google Patents
Mesoporous zirconium tannate catalyst and application thereof in catalyzing furfural hydrogenation Download PDFInfo
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Abstract
The invention discloses a mesoporous zirconium tannate catalyst and application thereof in catalyzing furfural hydrogenation, and belongs to the field of heterogeneous catalysis. The mesoporous zirconium tannate catalyst is prepared by using tannic acid as a ligand of metal zirconium, and is used for catalyzing furfural hydrogenation to prepare furfuryl alcohol; the reaction temperature is only 120 ℃, the yield of the furfuryl alcohol can reach 98.16% after reaction for 80min, the catalytic effect is still good after 8 times of circulation, and the yield of the furfuryl alcohol is still 91.36% in the catalytic process.
Description
Technical Field
The invention relates to a mesoporous zirconium tannate catalyst and application thereof in catalyzing furfural hydrogenation, and belongs to the field of heterogeneous catalysis.
Background
With the rapid development of society, the problems of energy and environment are more and more prominent, and the traditional production process can cause the problems of energy waste, environmental pollution and the like. In order to solve the contradiction between energy and environment, the search for novel, green and renewable energy sources is receiving wide attention. Biomass is not only a renewable resource, but also the most widely distributed, numerous and varied energy sources on earth, and has attracted considerable attention from many researchers. The production of high value-added compounds from these basic materials is increasing through the basic material platform of biomass, so the development of new production technologies, production routes, and the production of high value-added compounds have a profound impact on the actual production and the development of the modern industry.
The furfural is used as a basic platform substance of biomass, is a five-carbon compound, is derived from agricultural products such as wheat, corncobs and the like, has abundant reserves and has wide application. The furfural serving as an important compound derived from a furan ring system can be used as a basic raw material to synthesize a plurality of compounds with high additional value, wherein furfuryl alcohol is an important compound with high additional value, and the furfuryl alcohol can be used for producing resins, fuels, synthetic fibers, rubber, plastics, pesticides and the like, so the furfuryl alcohol can be widely applied to the industrial industry.
However, at present, the industrial production method still uses furfural hydrogenation at high temperature and in a hydrogen environment to prepare furfuryl alcohol as a main production route, uses noble metals as catalysts for catalytic hydrogenation, has harsh reaction conditions, generally needs to be carried out at high temperature and high pressure, and needs to use a large amount of traditional fossil energy derived from petroleum, so the production method brings great burden on energy and economy. In recent years, reports that a coordination noble metal catalyst catalyzes furfural to synthesize furfuryl alcohol from a raw material have been appeared, but the reaction conditions for synthesizing furfuryl alcohol in the reports are still harsh, many methods are still needed to carry out the reaction under hydrogen pressure, and the reaction time is generally 2-10 h.
Disclosure of Invention
[ problem ] to
The method aims to solve the problems of poor cycle performance and overlong reaction time of the catalyst in the existing process of catalyzing furfural to synthesize furfuryl alcohol.
[ solution ]
The invention synthesizes a mesoporous zirconium tannate catalyst with high-efficiency catalytic capability, which is used for the conversion from furfural hydrogenation to furfuryl alcohol. The catalyst is simple in preparation method, can have high catalytic activity under mild reaction conditions, is easy to recycle, and tannic acid is a natural compound and fulfills the aim of green sustainable development.
The invention firstly provides a preparation method of a mesoporous zirconium tannate catalyst, which comprises the following steps:
taking a certain amount of tannic acid and ZrCl4Respectively dissolving the ZrCl into DMF, respectively treating the DMF in ultrasonic waves for 5-20 min, and carrying out ultrasonic treatment on the ZrCl4Placing the solution in a reaction kettle, and dropwise adding the tannic acid solution subjected to ultrasonic treatment within 5-20 min; after the solutions are uniformly mixed, uniformly mixing the solutions with a glacial acetic acid solution, then reacting for 4-24 h at 120-160 ℃ in a reaction kettle, and cooling to room temperature after the reaction is finished; washing the mixture with DMF and ethanol respectively for at least three times, drying the mixture in vacuum drying at 70-100 ℃ for 8-12 hours, and grinding the dried mixture into powder.
In one embodiment of the invention, the reaction vessel is a polytetrafluoroethylene reaction vessel.
In one embodiment of the present invention, the ZrCl4The concentration of the solution is 0.025-0.25 mol/L, and the concentration of the tannic acid solution is 0.003-0.25 mol/L.
In one embodiment of the invention, the tannic acid and ZrCl4The molar ratio of (a) to (b) is 0.0625-1: 2
In one embodiment of the invention, the tannic acid and ZrCl4Preferably 0.125: 2.
In one embodiment of the present invention, the frequency of the ultrasonic wave is 40 to 60 kHz.
The second purpose of the invention is to provide the mesoporous zirconium tannate catalyst prepared by the method.
The third purpose of the invention is to provide a method for preparing furfuryl alcohol by catalyzing furfural hydrogenation, wherein mesoporous zirconium tannate prepared by the method is used as a catalyst, furfural is used as a substrate, the catalyst is added according to 0.05-0.25 g of mesoporous zirconium tannate/mmol of furfural, and the reaction is carried out at 110-140 ℃ for 60-100 min, wherein isopropanol is used as a hydrogen source, and the addition amount is 5-10 mL/mmol of furfural.
In one embodiment of the present invention, the amount of the mesoporous zirconium tannate added is preferably 0.2g mesoporous zirconium tannate/mmol furfural.
In one embodiment of the present invention, the reaction temperature is preferably 120 ℃ and the reaction time is preferably 80 min.
In one embodiment of the invention, the reaction is carried out under magnetic stirring.
In an embodiment of the invention, after the catalyst reacts, the catalyst is separated from the product, washed by DMF and ethanol respectively, and dried, so that the catalyst can be used for catalyzing furfural hydrogenation to prepare furfuryl alcohol again.
Compared with the prior art, the invention has the following advantages and effects:
(1) the catalyst used in the invention is mesoporous zirconium tannate, which not only has good catalytic effect on catalyzing the conversion of furfural into furfuryl alcohol, but also has mild reaction conditions, the reaction temperature is only 120 ℃, the yield of furfuryl alcohol can be up to 98.16% after the reaction is carried out for 80min, and the energy consumption is greatly reduced.
(2) The raw material tannic acid selected by the catalyst is of a polyphenol structure, so that the tannic acid has super-strong coordination capacity, is successfully coordinated with zirconium ions, and can provide a good microenvironment for catalytic hydrogenation reaction, thereby improving the yield and the selectivity of furfuryl alcohol.
(3) The mesoporous zirconium tannate is heterogeneous, the catalyst can be recovered and used for the next reaction through simple filtration after the reaction is finished, the catalyst still has good catalytic effect after 8 cycles, the yield of furfuryl alcohol in the catalytic process is still up to 91.36%, and the green chemical policy is reflected.
(4) According to the invention, glacial acetic acid is added in the process of preparing mesoporous zirconium tannate, so that the catalytic performance of the catalyst is obviously improved, and when zirconium tannate prepared without acetic acid is used for catalyzing furfuryl alcohol to be converted into furfuryl alcohol, the yield of furfuryl alcohol is only 75.27%, which is obviously lower than that of the mesoporous catalyst prepared by the invention.
Drawings
FIG. 1 is a graph of furfuryl alcohol yield and furfural conversion for catalytic hydrogenation of furfural at various temperatures using a mesoporous zirconium tannate catalyst in example 4.
FIG. 2 is a graph of furfuryl alcohol yield and furfural conversion for catalytic hydrogenation of furfural over different times for the mesoporous zirconium tannate catalyst of example 5.
FIG. 3 is a graph of furfuryl alcohol yield and furfural conversion for catalytic hydrogenation of furfural with mesoporous zirconium tannate catalyst at different catalyst dosages for example 6.
Detailed Description
Method for determining furfural by Gas Chromatography (GC): the ratio of the peak areas of furfural (FF) and Furfuryl Alcohol (FA) was used for calculation, with naphthalene as a reference.
Calculation formula of conversion:
the calculation formula of the yield is as follows:
calculation formula of selectivity:
the present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Taking ZrCl4And tannic acid are respectively dissolved in DMF, and the molar ratio of the two is 2:0.125, and respectively treating in ultrasonic waves for 10min to obtain the ultrasonically treated ZrCl4Solutions ofPlacing in a reaction kettle, and dropwise adding the tannic acid solution subjected to ultrasonic treatment within 20 min; after the solutions are uniformly mixed, dropwise adding a glacial acetic acid solution, reacting the reaction kettle at 140 ℃ for 16 hours, and naturally cooling to room temperature after the reaction is finished; washing with DMF and ethanol for three times, drying at 80 deg.C for 12 hr, and grinding into powder to obtain mesoporous zirconium tannate.
Example 2
According to ZrCl4And tannic acid at a molar ratio of 2:0.0625, 2:0.25, 2:1, 1:2, 0.5:2, 0.25:2, respectively, different mesoporous zirconium tannins were prepared in the same manner as in example 1, and the catalysts prepared in examples 1 and 2 were subjected to a catalytic performance test:
(1) weighing 200mg of mesoporous zirconium tannate in 25mL of polytetrafluoroethylene lining, and adding quantitative naphthalene (wherein the naphthalene is a reference sample and is the same as below) and 5mL of isopropanol;
(2) weighing 1mmol of furfural, adding into the reaction system in the step (1), putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120 ℃ under magnetic stirring, reacting for 3 hours, after the reaction kettle is cooled to room temperature, separating solid from liquid by using a centrifugal machine, and taking a liquid phase test sample;
(3) mu.L of the reaction solution obtained in step (2) was transferred by a syringe and the yield of furfuryl alcohol was measured by gas chromatography.
The results are shown in Table 1, and it can be seen that when ZrCl is used4When the molar ratio of tannic acid to tannic acid is 2:0.125 (example 1), the catalyst obtained has good performance, and therefore ZrCl is selected4And tannic acid at a molar ratio of 2/0.125.
TABLE 1 ZrCl in different proportions4Catalytic performance of the catalyst prepared according to the molar ratio of tannic acid
| Ratio of | 2/0.0625 | 2/0.125 | 2/0.25 | 2/0.5 | 2/1 | 1/1 | 1/2 | 0.5/2 | 0.25/2 |
| |
100 | 91.94 | 63.9 | 100 | 38.85 | 13.7 | 23.78 | 18.42 | 21 |
| YFA | 43.73 | 58.06 | 48.13 | 53.27 | 38.85 | 13.7 | 3.26 | 0 | 0 |
| SFA | 43.73 | 63.15 | 75.32 | 53.27 | 100 | 100 | 13.71 | 0 | 0 |
Wherein, CFFDenotes the conversion of furfural, YFARepresents the yield of furfuryl alcohol, SFAIndicating the selectivity of furfuryl alcohol.
Example 3
ZrCl in example 14Respectively exchanged into AlCl3、SnCl4、TiSO4、NiCl2、CoCl3、FeCl3And different catalysts were prepared according to the procedure of example 1: aluminum tannate (Al-TA), tin tannate (Sn-TA), titanium tannate (Ti-TA), nickel tannate (Ni-TA), cobalt tannate (Co-TA), iron tannate (Fe-TA), and further, tannic acid alone or ZrCl alone4The catalyst tannic acid and ZrCl were prepared according to the preparation method of example 1 as the raw material4。
Weighing 200mg of different catalysts in 25mL of polytetrafluoroethylene lining, and adding quantitative naphthalene and 5mL of isopropanol; heating to 120 ℃ under magnetic stirring, reacting for 80min, cooling the reaction kettle to room temperature, separating solid and liquid in the reaction kettle by using a centrifugal machine, and taking a liquid phase test sample; 0.2L of the reaction solution obtained in step (3) was transferred by a syringe and the yield of furfuryl alcohol was measured by gas chromatography.
The results of the measurements are shown in Table 2, and the results are shown in aluminum tannate (Al-TA), tin tannate (Sn-TA), titanium tannate (Ti-TA), nickel tannate (Ni-TA), cobalt tannate (Co-TA), iron tannate (Fe-TA), and zirconium tannate (Zr-TA)Example 1), tannic acid and ZrCl4The yields of furfuryl alcohol for catalytic hydrogenation of furfural by the catalysts were 16.28%, 1.57%, 2.12%, 4.31%, 0, 26.95%, 98.16%, 0.78%, and 3.26%, respectively. It can be seen that the catalytic performance of the catalysts with different metal active sites is very different, and when zirconium is used as the active site, the catalytic performance is the best.
TABLE 2 Activity of different tannates on the conversion of furfural hydrogenation to furfuryl alcohol
| Catalyst and process for preparing same | Al-TA | Sn-TA | Ti-TA | Ni-TA | Co-TA | Fe-TA | Zr-TA | TA | ZrCl4 |
| CFF | 19.64 | 3.16 | 6.15 | 4.31 | 0 | 33.81 | 100 | 7.62 | 8.74 |
| YFA | 16.28 | 1.57 | 2.12 | 4.31 | 0 | 26.95 | 98.16 | 0.78 | 3.26 |
| SFA | 82.89 | 49.68 | 34.47 | 100 | 0 | 79.71 | 98.16 | 10.24 | 37.3 |
Wherein, CFFDenotes the conversion of furfural, YFARepresents the yield of furfuryl alcohol, SFAIndicating the selectivity of furfuryl alcohol.
Example 4
(1) Weighing 200mg of mesoporous zirconium tannate prepared in example 1 into a 25mL polytetrafluoroethylene lining, and adding a certain amount of naphthalene and 5mL of isopropanol;
(2) weighing 1mmol of furfural, adding into the reaction system in the step (1), putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 110 ℃, 120 ℃, 130 ℃ or 140 ℃ under magnetic stirring, reacting for 80min, after the reaction kettle is cooled to room temperature, separating solid from liquid by using a centrifuge, and taking a liquid phase test sample;
(3) mu.L of the reaction solution obtained in step (2) was transferred by a syringe and the yield of furfuryl alcohol was measured by gas chromatography.
As a result of the measurement, as shown in FIG. 1, when the reaction temperature distribution was 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, the yield of furfuryl alcohol was 82.17%, 98.16%, 89.75%, 83.38%, respectively, and it was found that the increase of the reaction temperature allowed the conversion rate of furfuryl alcohol to reach 100%, but the by-product was generated due to the excessively high temperature (more than 120 deg.C), and thus the yield of furfuryl alcohol was decreased.
Example 5
(1) Weighing 200mg of the mesoporous zirconium tannate catalyst prepared in example 1 into a 25mL polytetrafluoroethylene lining, and adding quantitative naphthalene and 5mL of isopropanol;
(2) weighing 1mmol of furfural, adding into the reaction system in the step (1), putting a polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120 ℃ under magnetic stirring, carrying out distribution reaction for 20min, 40min, 60min, 80min and 100min, after the reaction kettle is cooled to room temperature, carrying out solid-liquid separation by using a centrifugal machine, and taking a liquid phase as a sample to be detected;
(3) mu.L of the reaction solution obtained in step (2) was transferred by a syringe and the yield of furfuryl alcohol was measured by gas chromatography.
As a result of measurement, as shown in fig. 2, when the reaction time is 20min, 40min, 60min, 80min, and 100min, respectively, the yield of furfuryl alcohol is 22.92%, 58.03%, 91.72%, 98.16%, and 91.13%, respectively, it can be seen that when the reaction time is less than 80min, the yield of furfuryl alcohol increases with the increase of time, but when the reaction time is too long, a side reaction occurs instead, so that the yield of furfuryl alcohol decreases, and therefore, the reaction time is preferably 80 min.
Example 6
(1) 50mg, 100mg, 150mg, 200mg or 250mg of the mesoporous zirconium tannate catalyst prepared in example 1 was distributed and weighed in a 25mL polytetrafluoroethylene lining, and quantitative naphthalene and 5mL isopropanol were added;
(2) weighing 1mmol of furfural, adding into the reaction system in the step (1), putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120 ℃ under magnetic stirring, reacting for 80min, and cooling the reaction kettle to room temperature after the reaction is finished;
(3) mu.L of the reaction solution obtained in step (2) was transferred by a syringe and the yield of furfuryl alcohol was measured by gas chromatography.
As a result, as shown in FIG. 3, the yields of furfuryl alcohol were 85.37%, 87.37%, 90.62%, 98.16%, 90.97% when the amounts of the catalysts were 50mg, 100mg, 150mg, 200mg, and 250mg, respectively.
Example 7
(1) Weighing 200mg of the mesoporous zirconium tannate catalyst prepared in example 1 into 25mL of a polytetrafluoroethylene lining, adding a certain amount of naphthalene, and respectively adding 5mL of solvents of methanol, ethanol, n-amyl alcohol, 2-butanol, n-butanol, isobutanol, tert-butanol, cyclohexanol or isopropanol;
(2) weighing 1mmol of furfural, adding into the reaction system in the step (1), placing the polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120 ℃ under magnetic stirring, reacting for 80min, cooling the reaction kettle to room temperature, separating solid from liquid by a centrifuge, and taking the liquid as a sample to be detected
(3) mu.L of the reaction solution obtained in step (2) was transferred by a syringe and the yield of furfuryl alcohol was measured by gas chromatography.
As a result, as shown in table 3, when the reaction solvent is methanol, ethanol, n-pentanol, 2-butanol, n-butanol, isobutanol, t-butanol, cyclohexanol or isopropanol, the yields of furfuryl alcohol were 0%, 10.79%, 44.92%, 54.75%, 22.75%, 33.8%, 0, 2.12% and 98.16%, respectively, and thus, isopropanol was selected as the solvent and hydrogen source for the catalytic reaction in the present invention.
TABLE 3 Effect of different solvents on the catalytic hydrogenation of Furfural to methanol
| Solvent(s) | Methanol | Ethanol | N-pentanol | 2-Butanol | N-butanol | Isobutanol | Tert-butyl alcohol | Cyclohexanol | Isopropanol (I-propanol) |
| CFF | 79.63 | 68.59 | 67.12 | 60.8 | 43.64 | 65.36 | 1.36 | 99.34 | 100 |
| YFA | 0 | 10.79 | 44.92 | 54.75 | 22.75 | 33.8 | 0 | 2.12 | 98.16 |
| SFA | 0 | 15.73 | 66.92 | 90.04 | 52.13 | 51.71 | 0 | 2.1 | 98.16 |
Wherein, CFFDenotes the conversion of furfural, YFARepresents the yield of furfuryl alcohol, SFAIndicating the selectivity of furfuryl alcohol.
Example 8
Example 7 after the reaction, the catalyst was separated by filtration when the reaction solvent was isopropanol, washed and dried, and then put into a 25mL polytetrafluoroethylene liner again, to which quantitative naphthalene and 5mL isopropanol were added; weighing 1mmol of furfural, adding the furfural into the reaction system, placing a polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120 ℃ under magnetic stirring, reacting for 80min, cooling the reaction kettle to room temperature after the reaction is finished, and recycling, wherein the yield of furfuryl alcohol is still 91.36% after the mesoporous zirconium tannate is recycled for 8 times through experimental calculation, and no obvious activity loss exists.
Comparative example 1
When 1,3, 5-benzenetriol is used as a ligand, a catalyst is prepared: 1.0g of 1,3, 5-benzenetriol and 1.4g of ZrCl were added respectively4Dissolving in DMF solvent, adding 3mL triethylamine as buffer, reacting at room temperature for 4h, aging for 4h, washing with DMF and ethanol for three times, drying to obtain solid precipitate which is 1,3, 5-benzenetriolA zirconium catalyst.
(1) Weighing 200mg of 1,3, 5-zirconium benzenetrisphenoxide catalyst into 25mL of polytetrafluoroethylene lining, and adding quantitative naphthalene and 5mL of isopropanol;
(2) weighing 1mmol of furfural, adding into the reaction system in the step (1), putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120 ℃ under magnetic stirring, reacting for 80min, after the reaction kettle is cooled to room temperature, separating solid from liquid by using a centrifugal machine, and taking the liquid phase as a sample to be detected;
(3) mu.L of the reaction solution obtained in step (2) was transferred by a syringe and the yield of furfuryl alcohol was measured by gas chromatography.
The results show that the catalytic effect of the zirconium 1,3, 5-benzenetrisphenoxide catalyst is that the conversion rate of furfural is 92% and the yield of furfuryl alcohol is only 81.25%.
Comparative example 2
Taking ZrCl4And tannic acid are respectively dissolved in DMF, and the molar ratio of the two is 2:0.125, and respectively treating in ultrasonic waves for 10min to obtain the ultrasonically treated ZrCl4Placing the solution in a reaction kettle, and dropwise adding the tannic acid solution subjected to ultrasonic treatment within 20 min; after the solutions are uniformly mixed, reacting the reaction kettle at 140 ℃ for 16 hours, and naturally cooling to room temperature after the reaction is finished; washing with DMF and ethanol for three times, drying at 80 deg.C for 12 hr, and grinding into powder to obtain mesoporous zirconium tannate.
(1) Weighing 200mg of mesoporous zirconium tannate catalyst in 25mL of polytetrafluoroethylene lining, adding quantitative naphthalene, and respectively adding 5mL of isopropanol as a solvent;
(2) weighing 1mmol of furfural, adding into the reaction system in the step (1), placing the polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120 ℃ under magnetic stirring, reacting for 80min, cooling the reaction kettle to room temperature, separating solid from liquid by a centrifuge, and taking the liquid as a sample to be detected
(3) 0.250. mu.L of the reaction solution obtained in step (2) was transferred by a syringe and the yield of furfuryl alcohol was determined by gas chromatography.
The results show that when no acetic acid is added, the catalytic effect of the mesoporous zirconium tannate is as follows: the conversion of furfural was 94.77% and the yield of furfuryl alcohol was only 75.27%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (13)
1. A preparation method of a mesoporous zirconium tannate catalyst is characterized by comprising the following steps:
taking a certain amount of tannic acid and ZrCl4Respectively dissolving the ZrCl into DMF, respectively treating the DMF in ultrasonic waves for 5-20 min, and carrying out ultrasonic treatment on the ZrCl4Placing the solution in a reaction kettle, and dropwise adding the tannic acid solution subjected to ultrasonic treatment within 5-20 min; after the solutions are uniformly mixed, uniformly mixing the solutions with a glacial acetic acid solution, then reacting for 4-24 h at 120-160 ℃ in a reaction kettle, and cooling to room temperature after the reaction is finished; washing the mixture with DMF and ethanol respectively for at least three times, drying the mixture in vacuum drying at 70-100 ℃ for 8-12 hours, and grinding the dried mixture into powder.
2. The method for preparing the mesoporous zirconium tannate catalyst according to claim 1, wherein the ZrCl is4The concentration range of the solution is 0.025-0.25 mol/L, and the concentration of the tannic acid solution is 0.003-0.25 mol/L.
3. The method for preparing the mesoporous zirconium tannate catalyst according to claim 2, wherein the tannic acid and ZrCl are4The molar ratio of (a) to (b) is 0.0625-1: 2.
4. the mesoporous zirconium tannate catalyst prepared by the preparation method of the mesoporous zirconium tannate catalyst according to any one of claims 1 to 3.
5. A method for preparing furfuryl alcohol by catalyzing furfural hydrogenation is characterized in that the mesoporous zirconium tannate catalyst of claim 4 is used as a catalyst, furfural is used as a substrate, the catalyst is added according to 0.05-0.25 g of mesoporous zirconium tannate/1 mmol of furfural, and the reaction is carried out for 60-100 min at 110-140 ℃, wherein isopropanol is used as a hydrogen source, and the addition amount of isopropanol is 5-10 mL/1mmol of furfural.
6. The method for preparing furfuryl alcohol by catalytic hydrogenation of furfural according to claim 5, wherein the mesoporous zirconium tannate catalyst is added in an amount of 0.2g mesoporous zirconium tannate per 1mmol of furfural.
7. The method for preparing furfuryl alcohol by catalytic hydrogenation of furfural according to claim 5 or 6, wherein the reaction temperature is 120 ℃.
8. The method for preparing furfuryl alcohol by catalytic hydrogenation of furfural according to claim 5 or 6, wherein the reaction time is 80 min.
9. The method for preparing furfuryl alcohol by catalytic hydrogenation of furfural according to claim 7, wherein the reaction time is 80 min.
10. The method for preparing furfuryl alcohol by catalytic hydrogenation of furfural according to any one of claims 5, 6 or 9, wherein the catalyst is separated from the product after reaction, washed with DMF and ethanol respectively, and dried before being used again for preparing furfuryl alcohol by catalytic hydrogenation of furfural.
11. The method for preparing furfuryl alcohol by catalytic hydrogenation of furfural according to claim 7, wherein the catalyst is separated from the product after the reaction, washed with DMF and ethanol respectively, and dried before being used again for preparing furfuryl alcohol by catalytic hydrogenation of furfural.
12. The method for preparing furfuryl alcohol by catalytic hydrogenation of furfural according to claim 8, wherein the catalyst is separated from the product after the reaction, washed with DMF and ethanol respectively, and dried before being used again for preparing furfuryl alcohol by catalytic hydrogenation of furfural.
13. The application of the method for preparing furfuryl alcohol by catalytic hydrogenation of furfural according to any one of claims 5 to 12 in the fields of dye synthesis, rubber synthesis, medicines, pesticides and casting industry.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435658A (en) * | 2013-08-24 | 2013-12-11 | 北京化工大学 | Preparation and nitrile rubber hydrogenation application of tannic acid rhodium coordination catalyst |
| WO2017066328A1 (en) * | 2015-10-12 | 2017-04-20 | The University Of Chicago | Stabilization of active metal catalysts at metal-organic framework nodes for highly efficient organic transformations |
| CN106928167A (en) * | 2017-03-14 | 2017-07-07 | 中国科学院广州能源研究所 | A kind of method that utilization hydrogen transfer reaction catalysis furfural prepares furfuryl alcohol |
| CN108067304A (en) * | 2016-11-17 | 2018-05-25 | 南京农业大学 | A kind of mesoporous function hybrid material and preparation method and application |
| CN108276364A (en) * | 2018-01-29 | 2018-07-13 | 江南大学 | A kind of preparation and application of porous hexa metaphosphoric acid Zr catalyst |
| CN108484360A (en) * | 2018-04-04 | 2018-09-04 | 中国科学技术大学 | A kind of preparation method of alcohol compound |
-
2019
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435658A (en) * | 2013-08-24 | 2013-12-11 | 北京化工大学 | Preparation and nitrile rubber hydrogenation application of tannic acid rhodium coordination catalyst |
| WO2017066328A1 (en) * | 2015-10-12 | 2017-04-20 | The University Of Chicago | Stabilization of active metal catalysts at metal-organic framework nodes for highly efficient organic transformations |
| CN108067304A (en) * | 2016-11-17 | 2018-05-25 | 南京农业大学 | A kind of mesoporous function hybrid material and preparation method and application |
| CN106928167A (en) * | 2017-03-14 | 2017-07-07 | 中国科学院广州能源研究所 | A kind of method that utilization hydrogen transfer reaction catalysis furfural prepares furfuryl alcohol |
| CN108276364A (en) * | 2018-01-29 | 2018-07-13 | 江南大学 | A kind of preparation and application of porous hexa metaphosphoric acid Zr catalyst |
| CN108484360A (en) * | 2018-04-04 | 2018-09-04 | 中国科学技术大学 | A kind of preparation method of alcohol compound |
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