CN117654511A - Catalyst and method for preparing 2, 5-tetrahydrofuran dimethanol in water phase by using same - Google Patents
Catalyst and method for preparing 2, 5-tetrahydrofuran dimethanol in water phase by using same Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 24
- YCZZQSFWHFBKMU-UHFFFAOYSA-N [5-(hydroxymethyl)oxolan-2-yl]methanol Chemical compound OCC1CCC(CO)O1 YCZZQSFWHFBKMU-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 51
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 43
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 12
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
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- 238000003756 stirring Methods 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000012043 crude product Substances 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- TVYABKWHFSGGMF-UHFFFAOYSA-N [2-(hydroxymethyl)oxolan-3-yl]methanol Chemical compound OCC1CCOC1CO TVYABKWHFSGGMF-UHFFFAOYSA-N 0.000 description 39
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
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- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- SOGYZZRPOIMNHO-UHFFFAOYSA-N [2-(hydroxymethyl)furan-3-yl]methanol Chemical compound OCC=1C=COC=1CO SOGYZZRPOIMNHO-UHFFFAOYSA-N 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a high-activity catalyst and a method for preparing 2, 5-tetrahydrofuran dimethanol by one-step hydrogenation of 5-hydroxymethylfurfural in a water phase by using the catalyst. According to the catalyst disclosed by the invention, nickel salt is directly and uniformly introduced into furfuryl alcohol urea-formaldehyde resin, and then the obtained resin is calcined under the hydrogen atmosphere to obtain the metallic nickel-based catalyst, so that the catalyst has excellent affinity with HMF, the high-selectivity preparation of THFDM (THFDM) by the HMF can be realized under the relatively mild reaction condition in a water phase, and the THFDM yield is up to 93%. The catalyst disclosed by the invention is simple in preparation process, mild in hydrogenation reaction condition, high in THFDM yield, capable of taking HMF crude product water solution as a substrate, and good in industrial application prospect. In addition, the HMF has good water solubility, and the water is used as a reaction medium in consideration of the principles of green and sustainable chemistry, so that compared with an expensive organic solvent, the post-treatment cost can be greatly reduced.
Description
Technical Field
The invention belongs to the technical field of catalysts and organic synthesis, and particularly relates to a catalyst and a method for preparing 2, 5-tetrahydrofuran dimethanol by one-step hydrogenation of 5-hydroxymethylfurfural in a water phase by using the catalyst.
Background
5-Hydroxymethylfurfural (HMF) is one of the ten most valuable bio-based chemicals listed by the U.S. department of energy and can be used as a platform compound for preparing a series of derivatives for various fields of energy, chemical industry, agriculture, medicine and the like. Tetrahydrofuran dimethanol (THFDM) is a thermochemical stable dihydric alcohol, can be used as a monomer for preparing polyester compounds, fuel additives, paint additives and the like, and can also be used for synthesizing high-added-value compound monomers such as 1, 6-hexanediol, 1, 5-hexanediol, 1,2, 6-hexanetriol and the like.
HMF selective preparation THFDM is typically carried out in an organic solvent and is based on a noble metal catalyst. There are few reports of highly selective preparation of THFDM from HMF in pure water, such as Nakaga wa and Tomishige using Pd-Ni/SiO 2 Catalyst, achieving 96% THFDM yield in pure water phase at 40 ℃ and 80bar hydrogen atmosphere (Catalysis Communications,2010,12 (3), 154-156); when Pd-Ir/SiO is used 2 In the presence of a catalyst, the THFDM yield reaches 95 percent under the optimal condition (ACS catalyst 2014; 4:2718-26); chen et Al synthesized Pd/MIL-101 (Al) -NH 2 The catalyst, with water as solvent, achieves 96% high yield preparation of THFDM at near room temperature (30 ℃) and mild pressure (10 bar). Noble metal catalysts were used in the above. In noble metal catalytic systems, it is possible to use a relatively mild H 2 High selectivity conversion of HMF is achieved under conditions. However, since the noble metal reserves are low, the price is high, and the supply relationship is greatly affected by market fluctuation, the development and practical industrial application of the noble metal catalyst are limited. In addition, under relatively harsh conditions, non-noble metal catalyst systems can also achieve efficient conversion of HMF and yield high yields comparable to noble metal catalysts. However, HMF is susceptible to various side reactions such as hydrogenolysis, ring opening, polymerization, etc. under severe conditions, which presents a great challenge for obtaining THFDM in high yields and selectivities.
The preparation of THFDM from non-noble metal highly selective catalytic HMF in pure water phase and under reaction conditions is still a challenging research direction. Patent CN 113773284A discloses a Ni-Co/SiO in aqueous phase 2 The method for preparing THFDM by catalyzing HMF has the THFDM yield reaching 83% under the hydrogen pressure of 30bar at 110 ℃; but the reaction temperature is relatively high, and a bimetallic catalyst is adoptedThe preparation process is complex, and in addition, the yield is low. Therefore, the development of a non-noble metal catalyst and the high-selectivity catalysis of HMF to prepare THFDM under the mild reaction conditions in pure water phase have important practical significance.
Disclosure of Invention
Aiming at the situation of the problems, the invention provides a catalyst and a method for preparing 2, 5-tetrahydrofuran dimethanol in a water phase by using the catalyst, and solves the main technical problems that the preparation of THFDM by selective hydrogenation of 5-hydroxymethylfurfural is generally carried out in an organic solvent, and the problems of harsh reaction conditions and low selectivity exist under the catalysis of non-noble metal. In order to solve the technical problem, the invention adopts furfuryl alcohol urea resin as a carrier, the similar furan carrier structure and the introduction of nitrogen element in the urea resin enhance the adsorption effect of substrate HMF and catalyst active site in the water phase, thereby realizing the high-selectivity preparation of THFDM in the water phase, and the THFDM yield is more than 90% under the relatively mild hydrogenation condition.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a high-activity catalyst is prepared by the following process: dissolving nickel salt in formaldehyde solution, adding urea, stirring for 0.5-2H, adding furfuryl alcohol with certain mass, stirring, heating to 90-150deg.C, performing polymerization reaction for 6-24H to obtain furfuryl alcohol urea-formaldehyde resin material Ni-UFF containing nickel ion precursor, and adding the obtained furfuryl alcohol urea-formaldehyde resin material Ni-UFF into H at certain temperature 2 Calcining in Ar mixed gas for 4-12h to obtain the catalyst Ni-UFC.
Further, in the process, the molar ratio of formaldehyde to urea is 0.5-2:1, a step of; the molar ratio of the nickel salt to the urea is 0.01-0.1:1.
further, in the process, the mass ratio of furfuryl alcohol to urea is 0.1-3:1.
further, in the process, the calcination temperature of the furfuryl alcohol urea resin material Ni-UFF is 300-700 ℃, H 2 H in Ar gas mixture 2 The ratio is 10%.
The invention also provides a method for preparing 2, 5-tetrahydrofuran dimethanol in the water phase by using the catalystThe method comprises the following steps: adding 5-hydroxymethylfurfural, deionized water and the catalyst in a certain proportion into a high-pressure reaction kettle, replacing air in the reaction kettle by hydrogen, and filling H 2 ，H 2 The pressure is 5-40bar, the high-pressure reaction kettle is placed in a constant-temperature water bath for reaction, the reaction kettle is cooled to room temperature after reaching the reaction time, the residual hydrogen is discharged, the reaction liquid is filtered, and the filtrate is collected to obtain the product.
Further, in the process, the adding amount ratio of the 5-hydroxymethylfurfural to the deionized water to the catalyst is as follows: 5-50mmol:10-20g:50-200mg.
Further, the temperature of the constant-temperature water bath is 30-80 ℃, and the reaction time is 1-12h.
Further, the collected filtrate was fixed in volume with water, and the yield of 2, 5-tetrahydrofuran dimethanol was quantitatively measured using high performance liquid chromatography.
The invention has the following beneficial effects:
according to the invention, nickel salt is directly and uniformly introduced into furfuryl alcohol urea-formaldehyde resin, and then the obtained resin matrix is calcined under hydrogen atmosphere to obtain the metallic nickel-based catalyst, so that the catalyst has excellent affinity with HMF, the high-selectivity preparation of THFDM by HMF can be realized under relatively mild reaction conditions, and the THFDM yield is up to 93%. The catalyst provided by the invention has the advantages of very simple preparation, mild hydrogenation reaction conditions, high THFDM yield, capability of taking HMF crude product water solution as a substrate, and good industrial application prospect. In addition, the HMF has good water solubility, and the water is used as a reaction medium in consideration of the principles of green and sustainable chemistry, so that compared with an expensive organic solvent, the post-treatment cost can be greatly reduced.
Drawings
FIG. 1 is a liquid-phase differential chromatogram of the reaction solution in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
1. And (3) preparing a catalyst:
0.64g of Ni (NO 3 ) 2 ·6H 2 O is dissolved in 4.1g of 37% formaldehyde solution, 3g of urea is added and stirred for 1h, then 3g of furfuryl alcohol is added, after stirring for 1h, the temperature is raised to 100 ℃ and polymerized for 12h, and the furfuryl alcohol urea formaldehyde resin material (Ni-UFF) containing nickel ion precursors is obtained. The obtained Ni-UFF material is subjected to 10% H at 500 DEG C 2 Calcining in Ar mixed gas for 4 hours to obtain the Ni/UFF-500 catalyst, and sealing and preserving the catalyst in nitrogen for standby.
2. Preparation of THFDM in aqueous phase (catalyst performance evaluation):
1.26g of HMF, 15g of water and 50mg of Ni/UFF-500 catalyst are added into a 50mL high-pressure reaction kettle, and after three times of air in the kettle is replaced by hydrogen, 20bar H is filled 2 The kettle was placed in a 40 ℃ constant temperature water bath for reaction for 5h, cooled to room temperature after the reaction time was reached, the remaining hydrogen was removed, the reaction solution was filtered, the filtrate was collected with water to a constant volume of 25mL, and the THFDM yield was quantitatively detected using high performance liquid chromatography differential (as in fig. 1).
The conversion of the starting material and the THFDM yield of the product were determined by liquid chromatography external standard method, and the average value of three tests was taken.
HMF conversion and THFDM yield of product were calculated according to the following formula:
equation 1: conversion [ mol ]]＝(n 0 -n)/n 0 ×100％；
Equation 2: yield [ mol ]]＝n i /n 0 ×100％。
Wherein n is 0 Initial charge of molar quantity [ mol ] for HMF]；
n is the residual molar weight [ mol ] of HMF after reaction;
n i molar amount [ mol ] of THFDM as a product of the reaction]。
The calculation showed that the HMF conversion was 98% after the reaction in this example and the THFDM yield was 90%.
Examples 2 to 6
In other examples of the present invention, to verify the effect of catalyst calcination temperature on catalyst activity, the reaction conditions of example 1 were adjusted: the reaction conditions were the same as in example 1, except that the catalyst was different. The reaction results are shown in Table 1 below.
| Examples | Catalyst | HMF conversion | THFDM yield |
| Example 2 | Ni/UFFC-300 | 83％ | 74％ |
| Example 3 | Ni/UFFC-400 | 96％ | 87％ |
| Example 4 | Ni/UFFC-400a | >99％ | 92％ |
| Example 5 | Ni/UFFC-600 | 99％ | 86％ |
| Example 6 | Ni/UFFC-700 | 95％ | 79％ |
a represents that the calcination time is prolonged to 12 hours;
from the above table, it is clear that as the calcination temperature increases, the activity of the resulting Ni/UFFC catalyst tends to increase and then decrease, and that lower calcination temperatures result in incomplete reduction of higher nickel ions to the metallic state, and thus lower activity. The HMF conversion rate of the calcined catalyst at 300 ℃ is 83%, and the THFDM yield is 74%; along with the improvement of the calcination temperature, the HMF conversion rate and the THFDM yield are obviously increased, the THFDM yield is 87% when the calcination temperature is 400 ℃, the calcination time is further prolonged to 12 hours, the catalyst activity is further improved after the nickel ions are fully reduced, the HMF conversion rate is more than 99%, and the THFDM yield is 92%; however, as the calcination temperature further increases the HMF conversion and THFDM yield gradually decrease, it is hypothesized that too high a calcination temperature results in aggregation of the metallic nickel particles resulting in reduced activity.
Examples 7 to 9
In other examples of the invention, to verify the effect of urea introduction on catalyst activity, the conditions for catalyst preparation in example 1 were adjusted: the conditions were the same as in example 1 except that the urea introduction amount was different. The reaction results are shown in Table 2 below.
| Examples | Urea introduction/g | HMF conversionRate of conversion | THFDM yield |
| Example 7 | 0 | 49％ | 32％ |
| Example 8 | 0.75 | 75％ | 63％ |
| Example 9 | 1.5 | 97％ | 87％ |
As can be seen from table 2, the catalyst activity was very low, HMF conversion was only 49%, THFDM yield was 32% and the main byproduct was furandimethanol, as a blank comparison, without urea introduction. With increasing urea incorporation, the catalyst activity increased significantly, and the catalyst selectivity was comparable to example 1 when urea and formaldehyde were equal in quality (example 9), and transmission electron microscopy analysis indicated that the incorporation of nitrogen was beneficial to the dispersion of nickel metal and stability during calcination, which was also responsible for the relatively high activity.
Examples 10 to 15
In other examples of the invention, to examine the effect of catalytic reaction conditions on THFDM yield, the reaction conditions in example 1 were adjusted: the procedure of example 1 was repeated except that the reaction conditions were different. The reaction results are shown in Table 3 below.
As can be seen from Table 3, the reaction proceeds relatively slowly when the hydrogen pressure is too low, and the main by-product is intermediate 2, 5-furandimethanol, the THFDM selectivity is still low even if the reaction temperature is increased, for a prolonged reaction time (examples 10-13); when the hydrogen pressure was raised to 30bar, the HMF was substantially completely converted after 3 hours of reaction, the THFDM yield was comparable to that of reaction 5 hours at 20bar (example 14vs example 1); when the hydrogen pressure was further increased to 40bar, the THFDM yield reached a maximum of 93% at 30 c for 1h, indicating that the relatively low reaction temperature and high hydrogen pressure helped to increase the THFDM selectivity.
Example 16
3g of fructose is dissolved in 20mL of deionized water, 1g of HND-587 super solid acid catalyst is added, and the mixture is heated to 120 ℃ in a 50mL reaction kettle for reaction for 1h. After the reaction was completed, the reaction mixture was cooled to room temperature, and the catalyst was removed by filtration, whereby the yield of HMF was 61% as measured by taking the filtrate. Taking filtrate as HMF crude product, adding 50mg of Ni/UFF-500 catalyst into a 50mL high-pressure reaction kettle, replacing air in the kettle with hydrogen for three times, and filling 40bar H 2 The kettle was placed in a 30 ℃ constant temperature water bath for reaction for 1h, cooled to room temperature after reaching the reaction time, the residual hydrogen was removed, the reaction solution was filtered, the filtrate was collected with water to a constant volume of 25mL, and the THFDM yield was quantitatively detected using high performance liquid chromatography differential. The results indicated 87% conversion of HMF after the reaction and 77% yield of THFDM product. This example shows that when crude HMF is used as a substrate, the catalyst still has excellent catalytic selectivity, but the presence of impurities affects the activity of the catalyst, resulting in a relatively slow reaction.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. The catalyst is characterized by being prepared by the following process: dissolving nickel salt in firstAdding urea into aldehyde solution, stirring, adding furfuryl alcohol with certain mass, stirring, heating to a preset temperature, performing polymerization reaction to obtain furfuryl alcohol urea formaldehyde resin material Ni-UFF containing nickel ion precursor, and placing the obtained furfuryl alcohol urea formaldehyde resin material Ni-UFF under H at a certain temperature 2 Calcining in Ar mixed gas to obtain the catalyst Ni-UFC.
2. The catalyst according to claim 1, wherein the molar ratio of formaldehyde to urea in the process is 0.5-2:1, a step of; the molar ratio of the nickel salt to the urea is 0.01-0.1:1.
3. the catalyst according to claim 2, wherein in the process, the mass ratio of furfuryl alcohol to urea is 0.1-3:1.
4. a catalyst according to claim 3, characterized in that the process is in particular: dissolving nickel salt in formaldehyde solution, adding urea, stirring for 0.5-2H, adding furfuryl alcohol with certain mass, stirring, heating to 90-150deg.C, performing polymerization reaction for 6-24H to obtain furfuryl alcohol urea-formaldehyde resin material Ni-UFF containing nickel ion precursor, and adding the obtained furfuryl alcohol urea-formaldehyde resin material Ni-UFF at 300-700deg.C under H 2 Calcining in Ar mixed gas for 4-12H to obtain the catalyst Ni-UFC, wherein H is 2 H in Ar gas mixture 2 The ratio is 10%.
5. A process for the preparation of 2, 5-tetrahydrofurandimethanol in aqueous phase using a catalyst according to any of claims 1 to 4, characterised in that it comprises the following processes: adding a certain proportion of 5-hydroxymethylfurfural, deionized water and the catalyst into a high-pressure reaction kettle, replacing air in the reaction kettle by hydrogen, and filling H 2 ，H 2 The pressure is 5-40bar, the high-pressure reaction kettle is placed in a constant-temperature water bath for reaction, the reaction kettle is cooled to room temperature after reaching the reaction time, the residual hydrogen is discharged, the reaction liquid is filtered, and the filtrate is collected to obtain the product.
6. The method for preparing 2, 5-tetrahydrofuran dimethanol in aqueous phase according to claim 5, wherein in said process, the addition ratio of 5-hydroxymethylfurfural, deionized water, said catalyst is: 5-50mmol:10-20g:50-200mg.
7. The method for preparing 2, 5-tetrahydrofuran dimethanol in aqueous phase according to claim 5, wherein the constant temperature water bath temperature is 30-80 ℃ and the reaction time is 1-12h.
8. The method for preparing 2, 5-tetrahydrofurandimethanol in an aqueous phase of claim 5, wherein the collected filtrate is fixed in volume with water and the yield of 2, 5-tetrahydrofurandimethanol is quantitatively determined using high performance liquid chromatography.
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2023
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