CN117700379A - Preparation method of 2, 5-tetrahydrofuran dimethanol - Google Patents
Preparation method of 2, 5-tetrahydrofuran dimethanol Download PDFInfo
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- CN117700379A CN117700379A CN202311346493.XA CN202311346493A CN117700379A CN 117700379 A CN117700379 A CN 117700379A CN 202311346493 A CN202311346493 A CN 202311346493A CN 117700379 A CN117700379 A CN 117700379A
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- YCZZQSFWHFBKMU-UHFFFAOYSA-N [5-(hydroxymethyl)oxolan-2-yl]methanol Chemical compound OCC1CCC(CO)O1 YCZZQSFWHFBKMU-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 35
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- -1 nickel-based metal organic framework compound Chemical class 0.000 claims abstract description 10
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 239000013110 organic ligand Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010812 external standard method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 239000005715 Fructose Substances 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
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 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
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of 2, 5-tetrahydrofuran dimethanol, which is characterized by comprising the following steps: 1) Forming a nickel-based metal organic framework compound by using non-noble metal nickel salt and an organic ligand, and calcining in a nitrogen atmosphere to obtain a nickel-based catalyst for later use; 2) The method comprises the steps of mixing a solution containing 5-hydroxymethylfurfural raw materials with the nickel-based catalyst prepared in the step 1), and reacting in an atmosphere containing hydrogen to obtain the 2, 5-tetrahydrofuran dimethanol to be prepared.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of 2, 5-tetrahydrofuran dimethanol.
Background
5-Hydroxymethylfurfural (HMF) is an important biomass-based platform compound that can be obtained by catalytic conversion of fructose, glucose, cellulose and various biomass carbohydrates. The reactive functional groups (-CHO and-CH 2 OH) in the HMF structure are capable of undergoing various chemical reactions such as hydrogenation, oxidation, amination, condensation, etherification, esterification, hydrogenolysis, etc. Among them, the preparation of 2, 5-tetrahydrofuran dimethanol (THFDM) by catalytic hydrogenation of HMF is a very potential research direction, because THFDM is a thermochemical stable dihydric alcohol, and can be used as a monomer for preparing polyester compounds, and can also be used for synthesizing 1, 6-hexanediol, 1, 5-hexanediol, 1,2, 6-hexanetriol and the like.
At present, THFDM is prepared from HMF with high selectivity, which is mainly based on noble metal catalyst mainly because noble metal has high catalytic activity, low reaction temperature and good selectivity. Fulignati et al tested HMF hydrogenation to THFDM using three commercial catalysts, ru/C, pd/C and Pt/C, and found that Ru/C had the best catalytic effect with a THFDM yield of 95% (appl. Catalyst., A2019,578,122-133). J.Chen et Al use Pd/MIL-101 (Al) -NH under optimal conditions 2 The catalyst achieves 96% of the highest yield of THFDM at low reaction temperatures of 30 ℃ (ACS catalyst.2015, 5, 722-733). R. Alamillo et al at CeO 2 Ruthenium loading gave the highest THFDM yield of 91% (Green chem.2012,14, 1413-1419). Although noble metal catalysts have a good catalytic effect, their high cost is a major barrier to commercial applications. The use of non-noble metal catalysts to catalyze the conversion of HMF to THFDM with high selectivity remains a challenge. Ni-based catalysts are a very potential class of furan compound deep hydrogenation non-noble metal catalysts, such as pores et al, using Raney Nickel to hydrogenate HMF to give 88.5% yield of THFDM (RSC adv.,2014,4,60467-60472); patent CN 113773284A discloses a Ni-Co/SiO 2 In the method for preparing THFDM by hydrogenating HMF, the THFDM yield reaches 83% under the hydrogen pressure of 30bar at 110 ℃, and the catalyst can be separated magnetically after reaction; patent CN 116571263A discloses a preparation method of a silica supported nickel-based catalyst and application thereof in hydrogenation of 5-hydroxymethylfurfural, the THFDM yield is 88% at 30 ℃, however, the reaction needs to be carried out under 40bar hydrogen pressure, in the method, nickel metal and ligand of the nickel-based catalyst need to form a metal organic framework compound, then a carrier precursor is added, and the preparation process of the catalyst is relatively complicated.
According to the invention, the nickel-based organic metal organic framework compound is directly calcined to obtain different nickel-based catalysts, no additional carrier is needed, THFDM is obtained by catalyzing HMF under relatively mild reaction conditions with high selectivity and yield, the catalyst is simple to prepare, the reaction conditions are mild, and the method has wide industrial application prospect.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a preparation method of 2, 5-tetrahydrofuran dimethanol, and the catalyst can realize high selectivity and yield of THFDM under relatively mild conditions.
The technical scheme of the invention is as follows:
a preparation method of 2, 5-tetrahydrofuran dimethanol comprises the following steps:
1) Forming a nickel-based metal organic framework compound by using non-noble metal nickel salt and an organic ligand, and calcining in a nitrogen atmosphere to obtain a nickel-based catalyst for later use;
2) Mixing a solution containing 5-hydroxymethylfurfural raw material with the nickel-based catalyst prepared in the step 1), and reacting in an atmosphere containing hydrogen to obtain the 2, 5-tetrahydrofuran dimethanol to be prepared.
Further, the specific process for preparing the nickel-based catalyst in step 1) is as follows:
first, ni (NO) 3 ) 2 ·6H 2 O, trimesic acid and polyvinylpyrrolidone are dissolved in ethanol solution, the solution is stirred to form green transparent solution, then the solution is poured into a 1L polytetrafluoroethylene container with good sealing, heating is carried out for 12-24 hours at 130-180 ℃, when the reactor is cooled to room temperature, filtering is carried out, distilled water and ethanol are used for washing filter cakes for multiple times, drying is carried out for 12-24 hours at 60-100 ℃, finally, the obtained green Ni-MOF material is calcined under nitrogen atmosphere, and the Ni@C-x catalyst can be obtained.
Further, the Ni (NO 3 ) 2 ·6H 2 The mass ratio of O to trimesic acid to polyvinylpyrrolidone to ethanol solution is 1:0.4-0.8:0.3-0.6:50-150, the mass unit is g, and the volume unit is mL.
Further, the calcination temperature is 300-700 ℃ and the calcination time is 2-12h.
Further, the specific process of step 2) is as follows:
will be originalAdding HMF, solvent and nickel-based catalyst prepared in step 1) into a 500mL high-pressure reaction kettle, and carrying out H for three times 2 After the air is replaced by the gas, H of 1-20bar is continuously introduced 2 Starting the reaction kettle, heating to 80-130 ℃ for reaction for 0.5-5.0h, cooling the reaction kettle to room temperature after the reaction is finished, releasing the gas pressure in the reaction kettle, and filtering to separate out filtrate, namely the 2, 5-tetrahydrofuran dimethanol to be prepared.
Further, the mass ratio of the raw material HMF to the solvent to the nickel-based catalyst prepared in the step 1) is 1:4-20:0.05-0.2.
Further, the solvent is one or more of isopropanol, methanol, ethanol, tetrahydrofuran and acetonitrile.
Compared with the prior art, the invention has the following beneficial effects:
1) Firstly, forming a nickel-based metal organic framework compound by using non-noble metal nickel salt and an organic ligand, calcining under the nitrogen atmosphere to obtain a nickel-based catalyst, mixing a solution containing 5-hydroxymethylfurfural raw materials with the nickel-based catalyst, and reacting in the atmosphere containing hydrogen to obtain the 2, 5-tetrahydrofuran dimethanol to be prepared;
2) According to the invention, a nickel-based metal organic framework compound with high specific surface area and porosity is formed by adopting non-noble metal nickel salt and an organic ligand, and then the nickel-based carbon material catalyst is obtained by calcining under different temperatures in a nitrogen atmosphere, and the obtained catalyst can realize THFDM with high selectivity of 99% of HMF and high yield of 91% under a relatively mild condition;
3) The invention has simple, safe and efficient reaction and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to the above.
Example 1
6.37g of Ni (NO) was stirred magnetically 3 ) 2 ·6H 2 O, 2.56g of trimesic acid and 2.5g of polyvinylpyrrolidone were dissolved in 700mL of ethanol solution and stirred for 1h to form a green transparent solution. Then, the solution was poured into 1LIn a well-sealed polytetrafluoroethylene container, heating at 150 ℃ for 24 hours. When the reactor was cooled to room temperature, it was filtered, and the filter cake was washed several times with distilled water and ethanol and dried at 60 ℃ for 24h. Finally, calcining the obtained green Ni-MOF material at the temperature of 500 ℃ in a nitrogen atmosphere to obtain the Ni@C-500 catalyst.
Adding 1.26g of HMF, 15g of isopropanol and 126mg of Ni@C-500 catalyst into a 50mL high-pressure reaction kettle, replacing air in the kettle with hydrogen for three times, then filling 10bar H2, heating to 100 ℃ for reaction for 2 hours, and cooling to room temperature after the reaction time is reached; the reaction solution was filtered, and the organic phase was collected and analyzed quantitatively by gas chromatography and qualitatively by gas mass spectrometry. The product THFDM was confirmed by gas phase mass spectrometry and comparison with a standard. The conversion of the starting material and the THFDM yield of the product were determined by the gas phase external standard method and the average value of the 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 after the reaction, the HMF conversion was >99% and the product THFDM yield was 89%.
To verify the effect of catalyst calcination temperature and solvent type on HMF hydrogenation to THFDM, the reaction conditions of example 1 were adjusted: the reaction conditions were the same as in example 1, except that the catalyst and the solvent were different. The reaction results are shown in Table 1 below.
| Examples | Catalyst | Solvent(s) | HMF conversion% | THFDM yield% |
| Example 2 | Ni@C-300 | Isopropyl alcohol | 79％ | 65％ |
| Example 3 | Ni@C-400 | Isopropyl alcohol | 90％ | 73％ |
| Example 4 | Ni@C-600 | Isopropyl alcohol | >99％ | 86％ |
| Example 5 | Ni@C-700 | Isopropyl alcohol | >99％ | 80％ |
| Example 6 | Ni@C-500 | Methanol | >99％ | 87％ |
| Example 7 | Ni@C-500 | Ethanol | >99％ | 89％ |
From the above table, with increasing calcination temperature, the activity of the obtained ni@c catalyst tends to increase and then decrease, the activity of the calcined catalyst at 300 ℃ is low, the HMF conversion rate is only 79%, and the THFDM yield is 65%, which is probably caused by the fact that the organic matters in the catalyst cannot be fully carbonized at the calcination temperature and the active sites of the catalyst cannot be fully exposed; with the increase of the calcination temperature, the HMF conversion rate and the THFDM yield are increased, and the THFDM maximum yield reaches 89% when the calcination temperature is 500 ℃; however, with further increases in calcination temperature, the HMF conversion is >99%, and the THFDM yield gradually decreases, meaning that THFDM selectivity decreases, and it is likely that too high calcination temperature results in agglomeration of metallic nickel particles, resulting in a decrease in catalytic activity. The HMF conversion and THFDM yield were not significantly different when the solvent was methanol or ethanol than when isopropanol was the solvent.
Example 8
7.7g NiCl under magnetic stirring 2 ·6H 2 O, 5.78g of 3, 5-pyridinedicarboxylic acid and 1.54g of KOH were dissolved in 700mL of water, stirred at room temperature for 2 hours, then left to stand for 24 hours, the solid precipitate was centrifugally separated, then washed with distilled water several times, and dried at 60℃for 24 hours. Finally, calcining the obtained green Ni-MOF material at the temperature of 500 ℃ in a nitrogen atmosphere to obtain the Ni@CN-500 catalyst.
1.26g of HMF, 15g of isopropanol, 126mg of Ni@CN-500 catalyst were charged into a 50mL autoclave, and 10bar H was charged after the air in the autoclave was replaced three times with hydrogen 2 Heating to 100 ℃ for reaction for 2 hours, and cooling to room temperature after the reaction time is up; the reaction solution is reactedThe organic phase was filtered, collected and analyzed quantitatively by gas chromatography and qualitatively by gas mass spectrometry. The product THFDM was confirmed by gas phase mass spectrometry and comparison with a standard. The conversion of the starting material and the THFDM yield of the product were determined by the gas phase external standard method and the average value of the three tests was taken. The calculation results show that after the reaction, the HMF conversion rate>99%, the product THFDM yield was 91%.
Example 9
2.88g of Ni (NO) was stirred magnetically 3 ) 2 ·6H 2 O, 4.98g of terephthalic acid was dissolved in 600mL of N, N-dimethylformamide and stirred for 1h to form a transparent solution. A solution of 6ml of 0.4mol/L sodium hydroxide was added dropwise to the above-mentioned transparent solution, and a white flocculent precipitate was formed during the course. Then, the solution was poured into a 1L polytetrafluoroethylene container with good sealing, and heated at 100℃for 8 hours. When the reactor was cooled to room temperature, it was filtered, and the filter cake was washed several times with N, N-dimethylformamide and dried at 60 ℃ for 24h. Finally, calcining the obtained green Ni-MOF material at the temperature of 500 ℃ in nitrogen atmosphere to obtain the Ni@Cd-500 catalyst.
1.26g of HMF, 15g of isopropanol, 126mg of Ni@Cd-500 catalyst were added to a 50mL autoclave, the air in the autoclave was replaced three times with hydrogen, and 10bar H was charged 2 Heating to 100 ℃ for reaction for 2 hours, and cooling to room temperature after the reaction time is up; the reaction solution was filtered, and the organic phase was collected and analyzed quantitatively by gas chromatography and qualitatively by gas mass spectrometry. The product THFDM was confirmed by gas phase mass spectrometry and comparison with a standard. The conversion of the starting material and the THFDM yield of the product were determined by the gas phase external standard method and the average value of the three tests was taken. The calculation results show that after the reaction, the HMF conversion rate>99%, the product THFDM yield was 80%.
From examples 8-9, it is clear that the Ni@C catalyst calcined from different Ni-based MOF materials can also have good catalytic activity, and the variety of MOF materials is widened for preparing the Ni@C catalyst.
Claims (7)
1. The preparation method of the 2, 5-tetrahydrofuran dimethanol is characterized by comprising the following steps:
1) Forming a nickel-based metal organic framework compound by using non-noble metal nickel salt and an organic ligand, and calcining in a nitrogen atmosphere to obtain a nickel-based catalyst for later use;
2) Mixing a solution containing 5-hydroxymethylfurfural raw material with the nickel-based catalyst prepared in the step 1), and reacting in an atmosphere containing hydrogen to obtain the 2, 5-tetrahydrofuran dimethanol to be prepared.
2. The preparation method of 2, 5-tetrahydrofuran dimethanol as claimed in claim 1, wherein the specific process of the preparation of the nickel-based catalyst in step 1) is as follows:
first, ni (NO) 3 ) 2 ·6H 2 O, trimesic acid and polyvinylpyrrolidone are dissolved in ethanol solution, the solution is stirred to form green transparent solution, then the solution is poured into a 1L polytetrafluoroethylene container with good sealing, the temperature is between 130 and 180 ℃ and is heated to 12 to 24h, when the reactor is cooled to room temperature, the filtration is carried out, distilled water and ethanol are used for washing filter cakes for multiple times, the filter cakes are dried to 12 to 24h at the temperature of between 60 and 100 ℃, and finally, the obtained green Ni-MOF material is calcined under nitrogen atmosphere, thus obtaining the Ni@C-x catalyst.
3. The method for producing 2, 5-tetrahydrofurandimethanol of claim 2, wherein said Ni (NO 3 ) 2 ·6H 2 The mass ratio of O to trimesic acid to polyvinylpyrrolidone to ethanol solution is 1:0.4-0.8:0.3-0.6:50-150, the mass unit is g, and the volume unit is mL.
4. The method for preparing 2, 5-tetrahydrofuran dimethanol according to claim 2, wherein the calcining temperature is 300-700 ℃ and the calcining time is 2-12h.
5. The method for preparing 2, 5-tetrahydrofuran dimethanol as claimed in claim 1, wherein the specific process of step 2) is as follows:
adding the raw material HMF, the solvent and the nickel-based catalyst prepared in the step 1)To 500mL of high-pressure reaction kettle, three times of H 2 After the air is replaced by the gas, H of 1-20bar is continuously introduced 2 Starting the reaction kettle, heating to 80-130 ℃ for reaction for 0.5-5.0h, cooling the reaction kettle to room temperature after the reaction is finished, releasing the gas pressure in the reaction kettle, and filtering to separate out filtrate, namely the 2, 5-tetrahydrofuran dimethanol to be prepared.
6. The method for preparing 2, 5-tetrahydrofuran dimethanol as claimed in claim 5, wherein the mass ratio of the raw material HMF, the solvent and the nickel-based catalyst prepared in step 1) is 1:4-20:0.05-0.2.
7. The method for preparing 2, 5-tetrahydrofuran dimethanol as claimed in claim 6, wherein said solvent is one or more of isopropanol, methanol, ethanol, tetrahydrofuran and acetonitrile.
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