CN111085203A - Method for preparing 2-methylfuran by catalyzing hydrogenation of furfural - Google Patents
Method for preparing 2-methylfuran by catalyzing hydrogenation of furfural Download PDFInfo
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- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 title claims abstract description 84
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 26
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 26
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 11
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 238000003980 solgel method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical compound CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
- B01J23/72—Copper
-
- B01J35/23—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing 2-methylfuran by catalyzing furfural hydrogenation. Cu/SiO2The catalyst is prepared by a sol-gel method, comprising the following steps: (1) adding a silicate, absolute ethyl alcohol and water into a reaction container, and adding a copper salt solution while stirring to obtain a mixed solution; (2) titrating the mixed solution with alkali liquor until the pH value of the mixed solution is 7, stopping stirring, refluxing, and aging to obtain precipitated colloid; (3) filtering, washing and drying the precipitated colloid, and calcining to obtain a catalyst precursor; (4) reducing the catalyst precursor in a hydrogen atmosphere to obtain Cu/SiO2A catalyst. The invention provides Cu/SiO2The catalyst has the characteristics of large specific surface area, high reaction activity, small catalyst particle size, high dispersibility of active metal Cu and the like, and realizes the conversionFurfural 100% conversion and 2-methylfuran selectivity of 98%.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a method for preparing 2-methylfuran by catalyzing furfural hydrogenation.
Background
With the rapid development of human material civilization, global warming, depletion of fossil energy, deterioration of ecological environment and other problems, the development and utilization of renewable resources are widely concerned by researchers in various countries. The biomass resource has the advantages of abundant reserves, biodegradability, short regeneration period, low cost and the like. Among many biomass resources, the agricultural and forestry biomass resources have a huge content (accounting for about 90% of the fixed energy of the earth), are an excellent choice for replacing fossil resources, and are also main sources for biomass conversion and utilization.
As a big agricultural country, China has abundant agriculture and forestry biomass resources which are abundant in variety, wide in distribution and huge in development and utilization potential. Wherein, various agricultural and forestry wastes generated by production and life, such as straws, wheat straws, bagasse, secondary small firewood and the like, exceed 10 hundred million tons every year. However, these resources have not been fully utilized to date, mainly as direct combustion heat, feed, fertilizer and pulp and paper making raw materials, and the utilization rate is less than 50% of the total amount. Most of agricultural and forestry wastes are directly burned or discarded, which causes pollution to soil and atmosphere and waste of resources. Therefore, the biomass resources in agriculture and forestry are purposefully converted and utilized, the biomass resources are used for developing high-value-added products such as novel materials, high-calorific-value fuels, fine chemical raw materials, drug intermediates and the like, the dependence of human beings on fossil resources can be reduced, the situation of energy shortage can be relieved, increasingly serious environmental problems caused by the use of the fossil resources can be relieved, the harmony and unity of economic and ecological environments are promoted, and the sustainable development is realized.
Furfural, one of the high value platform chemicals, is a raw material for many valuable chemicals, such as furfuryl alcohol, 2-methylfuran (2-MF), tetrahydrofurfuryl alcohol, and 2-methyltetrahydrofuran. More than 50% of furfural is consumed to produce FFA, an important monomer in the polymer industry. 2-MF is considered a promising liquid fuel because it has several excellent properties of comparable energy density, better explosion suppression capability and lower aldehyde emissions. The method for preparing the renewable 2-MF by taking the furfural as the raw material has important significance for optimizing the energy structure of China, improving the increasingly concerned environmental problems and promoting the high-valued utilization of biomass.
Disclosure of Invention
The invention provides a method for preparing 2-methylfuran by catalyzing furfural hydrogenation in Cu/SiO2Preparing 2-methylfuran, Cu/SiO under the action of catalyst2The catalyst is prepared by a sol-gel method, has the characteristics of large specific surface area, high reaction activity, small catalyst particle size, high dispersibility of active metal Cu and the like, and realizes the conversion rate of furfural of 100% and the selectivity of 2-methylfuran of 98%.
The invention aims to provide a Cu/SiO2Catalyst, said Cu/SiO2The catalyst is prepared by a sol-gel method, comprising the following steps:
(1) adding a silicate, absolute ethyl alcohol and water into a reaction container, and adding a copper salt solution while stirring to obtain a mixed solution;
(2) titrating the mixed solution with alkali liquor until the pH value of the mixed solution is 7, stopping stirring, refluxing and aging to obtain precipitated colloid;
(3) filtering, washing and drying the precipitated colloid, and calcining to obtain a catalyst precursor;
(4) reducing the catalyst precursor in a hydrogen atmosphere to obtain Cu/SiO2A catalyst.
Preferably, Cu/SiO in step (1)2The copper loading amount in the catalyst is 10-50%, the mole ratio of the copper salt to the silicon salt is 0.1:1-0.9:1, the silicon salt is ethyl orthosilicate, and the copper salt is copper nitrate.
Preferably, the volume ratio of the silicon salt to the water is 1:1-3:1, and the volume ratio of the absolute ethyl alcohol to the water is 1:1-2: 1.
Preferably, the aging step in step (2) is aging at 80 ℃ for 5h, and the calcining step in step (3) is calcining at 350 ℃ to 450 ℃ for 4 h.
Preferably, the specific steps of step (4) are: reducing the catalyst precursor for 2h at 220-400 ℃ in a hydrogen atmosphere to obtain Cu/SiO2A catalyst.
The invention also provides a method for preparing 2-methylfuran by catalyzing furfural hydrogenation, which takes furfural as a raw material, gamma-butyrolactone as a solvent and the Cu/SiO2The catalyst is used as a catalyst to catalyze furfural to prepare 2-methylfuran through hydrogenation.
Preferably, the furfural and Cu/SiO2The mass ratio of the catalyst is 1:1-10:3, the reaction pressure is 2-5MPa hydrogen, the reaction temperature is 210-250 ℃, and the reaction time is 1-7 h.
Compared with the prior art, the invention has the beneficial effects that:
the Cu/SiO is prepared by a sol-gel method2The catalyst has the characteristics of large specific surface area, high reaction activity, small catalyst particle size, high dispersibility of active metal Cu and the like, realizes the conversion rate of furfural of 100 percent and the selectivity of 2-methylfuran of 98 percent under the conversion action, and has great guiding significance for the utilization of biomass resources.
Drawings
FIG. 1 shows Cu/SiO solid prepared in example 12An X-ray diffraction pattern of the catalyst;
FIG. 2 shows Cu/SiO solid phase prepared in example 12Transmission electron micrograph of catalyst.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1
Cu/SiO2The catalyst is prepared by a sol-gel method, and specifically comprises the following steps:
(1) measuring 30mL of tetraethoxysilane, 20mL of ethanol and 10mL of deionized water into a three-neck flask, stirring, adding 50mL of 0.1mol/L cupric nitrate solution, plugging the flask with a glass plug, and stirring for half an hour;
(2) titrating the solution with ammonia water until the pH value is 7, stopping stirring, building a reflux device, and aging at 80 ℃ for 5 hours;
(3) filtering the obtained precipitation colloid, washing for 5 times by deionized water, putting the precipitation colloid into a 100 ℃ oven for overnight drying, grinding the precipitation colloid into powder, and calcining the powder at 400 ℃ for 4 hours to obtain a catalyst precursor;
(4) reducing the catalyst precursor for 2h at 270 ℃ in a hydrogen atmosphere to obtain 30% Cu/SiO2A catalyst.
Cu/SiO2The X-ray diffraction pattern and transmission electron micrograph of the catalyst are shown in FIG. 1 and FIG. 2, respectively, and only SiO is contained in FIG. 12No Cu peak was found, indicating that Cu/SiO2The medium active metal Cu has a smaller particle size or is in a non-crystalline state, and FIG. 2 illustrates Cu/SiO2The medium active metal Cu has a small particle size and Cu is in a crystalline state, and Cu is highly dispersed.
Examples 2 to 5
Examples 2-5 are the same as example 1 except that examples 2-5 produced Cu/SiO by adjusting the molar ratio of copper nitrate to ethyl orthosilicate2The copper loading in the catalyst was 10%, 20%, 40% and 50%, respectively.
Cu/SiO with different Cu loading amounts2Evaluation of the catalyst performance for conversion of furfural to 2-methylfuran (2-MF):
1g of furfural and 0.3g of Cu/SiO in a high-pressure reaction kettle with a stirring device under the hydrogen pressure of 2MPa2Heating a catalyst with a stirring paddle (700rpm) at 5 ℃/min to 220 ℃ under the stirring condition to react for 5h, collecting the solution in the reaction kettle, filtering, and analyzing the reaction conversion rate and yield. The above Cu/SiO2The catalyst is Cu/SiO prepared in examples 1-52The catalyst, specific experimental parameters and reactant yields are shown in table 1.
TABLE 1 Cu/SiO for different Cu loadings2Evaluation of catalyst Performance
| Examples | Copper loading/% | Conversion rate/% | 2-MF yield/%) |
| 1 | 30 | 100 | 75 |
| 2 | 10 | 100 | 19 |
| 3 | 20 | 100 | 38 |
| 4 | 40 | 100 | 63 |
| 5 | 50 | 100 | 56 |
It can be seen from table 1 that copper with different mass ratios is used as an active site to catalyze furfural to convert into 2-methylfuran, and when the copper content is low, the active site is increased along with the increase of the loading amount, so that the reaction effect is improved. However, when the amount of copper supported is too large, the catalyst is agglomerated, resulting in an increase in the particle size of the catalyst and a decrease in catalytic activity. Therefore, Cu supported at 30% has the best catalytic effect.
Examples 6 to 17
Performance evaluation under reaction temperature, hydrogen pressure and time for catalytic conversion of furfural to 2-methylfuran: Cu/SiO at 30% copper loading2Under the condition of a catalyst, the influence of the reaction temperature, the hydrogen pressure and the reaction time on the yield of the product of converting furfural into 2-methylfuran is examined, wherein the invariable reaction conditions are as follows: 1g Furfural starting Material, 0.3g Cu/SiO2The catalyst was stirred at 700 rpm. For comparison, example 1 is included in the reaction results listed in Table 2. The Cu/SiO obtained by the dipping method2Catalyst comparative example 1A brief preparation of an impregnated catalyst was carried out using copper nitrate, commercial SiO2The catalyst is obtained by stirring, drying, calcining, reducing and the like, and the temperature involved is the same as that of the catalyst prepared in example 1. The reaction temperature, hydrogen pressure and time performance of the catalytic conversion of furfural to 2-methylfuran (2-MF) are evaluated in table 2.
TABLE 2 evaluation of reaction temperature, Hydrogen pressure and time Performance for catalytic conversion of Furfural to 2-MethylFuran (2-MF)
As can be seen from Table 2, the catalytic conversion of furfural to 2-methylfuran has a significant effect under the reaction conditions. Along with the increase of reaction temperature, hydrogen pressure and time, the conversion rate of furfural and the yield of 2-methylfuran are correspondingly improved, but after the saturation point is reached, the corresponding reaction conditions are improved to have little effect on the reaction, and the reaction tends to be stable. In the above examples, the reaction temperature was 240 ℃, the hydrogen pressure was 4MPa, and the reaction time was 5 hours, which was optimal, and 100% furfural conversion and 98% 2-methylfuran yield were obtained.
Examples 18 to 23
Examples 18-23 30% Cu/SiO for different calcination and reduction temperatures2Evaluation of the catalyst performance for conversion of furfural to 2-methylfuran (2-MF):
Cu/SiO at 30% copper loading2Under catalyst conditions, the effect of the calcination and reduction temperatures of the catalyst on the conversion of furfural to 2-methylfuran (2-MF) was examined. Wherein the reaction conditions which are unchanged are as follows: 1g Furfural starting Material, 0.3g Cu/SiO2The catalyst has the reaction temperature of 240 ℃, the reaction time of 5h, the reaction hydrogen pressure of 4MPa and the stirring speed of 700 rpm. The catalyst calcination and reduction temperatures are evaluated for the conversion of furfural to 2-methylfuran (2-MF) in table 3.
TABLE 3 evaluation of catalyst calcination and reduction temperatures for the conversion of furfural to 2-methylfuran (2-MF)
As can be seen from Table 3, the calcination temperature of the catalyst precursor at 350 ℃ to 450 ℃ for 30% Cu/SiO2The effect of the catalyst on the conversion of furfural into 2-methylfuran (2-MF) is little. After calcination, reduction treatment is carried out, and at 220 ℃, the conversion rate of furfural and the yield of 2-methylfuran are relatively low, probably because the reduction temperature is too low, so that copper is not completely reduced into copper simple substance. When the reduction temperature is too high, the particle size of copper increases, and the conversion effect is affected.In the above examples, it is preferable that the calcination temperature is 400 ℃ and the reduction temperature is 270 ℃.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (7)
1. Cu/SiO2The catalyst is characterized in that the Cu/SiO2The catalyst is prepared by a sol-gel method, comprising the following steps:
(1) adding a silicate, absolute ethyl alcohol and water into a reaction container, and adding a copper salt solution while stirring to obtain a mixed solution;
(2) titrating the mixed solution with alkali liquor until the pH value of the mixed solution is 7, stopping stirring, refluxing and aging to obtain precipitated colloid;
(3) filtering, washing and drying the precipitated colloid, and calcining to obtain a catalyst precursor;
(4) reducing the catalyst precursor in a hydrogen atmosphere to obtain Cu/SiO2A catalyst.
2. The Cu/SiO of claim 12Catalyst, characterized in that in step (1) Cu/SiO2The copper loading amount in the catalyst is 10-50%, the mole ratio of the copper salt to the silicon salt is 0.1:1-0.9:1, the silicon salt is ethyl orthosilicate, and the copper salt is copper nitrate.
3. The Cu/SiO of claim 12The catalyst is characterized in that the volume ratio of the silicon salt to the water is 1:1-3:1, and the volume ratio of the absolute ethyl alcohol to the water is 1:1-2: 1.
4. The method of claim 1Cu/SiO of2The catalyst is characterized in that the aging specific step in the step (2) is aging at 80 ℃ for 5 hours, and the calcining specific step in the step (3) is calcining at 350-450 ℃ for 4 hours.
5. The Cu/SiO of claim 12The catalyst is characterized in that the specific steps in the step (4) are as follows: reducing the catalyst precursor for 2h at 220-400 ℃ in a hydrogen atmosphere to obtain Cu/SiO2A catalyst.
6. A method for preparing 2-methylfuran by catalyzing furfural hydrogenation is characterized in that furfural is used as a raw material, gamma-butyrolactone is used as a solvent, and Cu/SiO shown in claim 1 is used2The catalyst is used as a catalyst to catalyze furfural to prepare 2-methylfuran through hydrogenation.
7. The method for preparing 2-methylfuran by catalytic hydrogenation of furfural according to claim 6, wherein the furfural and Cu/SiO2The mass ratio of the catalyst is 1:1-10:3, the reaction pressure is 2-5MPa hydrogen, the reaction temperature is 210-250 ℃, and the reaction time is 1-7 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113457675A (en) * | 2021-05-26 | 2021-10-01 | 郑州大学 | Catalyst for preparing 2-methylfuran through furfural gas-phase hydrogenation and preparation method thereof |
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| GB2482887A (en) * | 2010-08-18 | 2012-02-22 | Johnson Matthey Plc | Catalyst and process for hydrogenation of aldehydes |
| CN103028405A (en) * | 2012-12-27 | 2013-04-10 | 珠海凯美科技有限公司 | Catalyst for preparing 2-methyl furan through selective furfural hydrogenation and preparation method of catalyst |
| CN104923228A (en) * | 2014-03-17 | 2015-09-23 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol by hydrogenation of oxalate and preparation method thereof |
| CN107970934A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of furfural hydrogenation 2- methylfurans method for preparing catalyst and catalyst |
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