CN115318288A - Catalyst for preparing furfuryl alcohol by furfural liquid phase hydrogenation, preparation and application thereof - Google Patents
Catalyst for preparing furfuryl alcohol by furfural liquid phase hydrogenation, preparation and application thereof Download PDFInfo
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- CN115318288A CN115318288A CN202110506055.XA CN202110506055A CN115318288A CN 115318288 A CN115318288 A CN 115318288A CN 202110506055 A CN202110506055 A CN 202110506055A CN 115318288 A CN115318288 A CN 115318288A
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- furfuryl alcohol
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 239000007791 liquid phase Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000012065 filter cake Substances 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 239000000443 aerosol Substances 0.000 claims abstract description 7
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 239000011148 porous material Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 230000000711 cancerogenic effect Effects 0.000 abstract 1
- 231100000315 carcinogenic Toxicity 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000012258 stirred mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- -1 carbonate modified copper Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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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 provides a catalyst for preparing furfuryl alcohol by furfural liquid-phase hydrogenation, and preparation and application thereof. The preparation method of the catalyst provided by the invention comprises the following steps: preparing a copper ammonia solution; (b) Adding silica hydrosol or aerosol into the solution, and stirring and mixing uniformly; (c) Heating the mixture system to remove ammonia in the system; (d) filtering the mixture to obtain a filter cake after the pH of the mixture is close to neutrality; (e) The filter cake is freeze-dried and calcined to obtain the catalyst. The invention has the advantages that the catalyst is simple in component and free of toxic and carcinogenic Cr, the catalyst is easy to disperse in a liquid system and has large specific surface area and pore volume, and the catalyst is endowed with excellent reaction activity for preparing furfuryl alcohol by furfural liquid phase hydrogenation.
Description
Technical Field
The invention belongs to the technical field of biomass conversion and catalysis, and particularly relates to preparation and application of a catalyst for preparing furfuryl alcohol through furfural liquid-phase hydrogenation.
Background
The growing contradiction between energy supply and demand and the increasingly stringent environmental requirements have promoted the research on the conversion and utilization of renewable biomass resources. Furfural is a chemical raw material mainly derived from wood biomass such as agricultural and forestry waste. China is the biggest furfural producing country in the world, but has very limited high-value utilization of furfural. The furfural can be used for preparing furfuryl alcohol with high added value through selective hydrogenation reaction. Furfuryl alcohol is an extremely important chemical raw material, and is widely used for producing sand core binders, high temperature resistant phenolic resin binders, plasticizers with excellent cold resistance, synthetic fibers, polyurethane foams, tetrahydrofurfuryl alcohol and the like, pesticides, spices and intermediates of medicines. Therefore, the research on the selective hydrogenation of furfural to prepare furfuryl alcohol is receiving extensive attention from both academia and industry.
Patent CN107952444B discloses a catalyst for preparing furfuryl alcohol by liquid-phase hydrogenation of Cu-Cr-Zr-based furfural, and the presence of a Cr component limits the application of the catalyst. Patent CN106807423B discloses a copper-based catalyst for furfuryl alcohol preparation by furfural hydrogenation, which uses calcium carbonate as a carrier and an alkali metal compound or an alkaline earth metal compound as an auxiliary, and the catalyst composition is relatively complex. Patent CN109731596B discloses an alkali carbonate modified copper-based catalyst for liquid phase hydrogenation of furfural to prepare furfuryl alcohol, which has high copper content and high cost.
Based on the analysis, the invention develops the aerogel catalyst which is simple in composition, free of Cr and environment-friendly and is suitable for the reaction of preparing furfuryl alcohol by furfural liquid-phase hydrogenation, the catalyst consists of copper and silicon oxide, and the catalyst shows high low-temperature reaction activity in the reaction of preparing furfuryl alcohol by furfural liquid-phase hydrogenation.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a catalyst for preparing furfuryl alcohol by furfural liquid-phase hydrogenation and preparation and application thereof, wherein the catalyst and the application can realize one or more of the following steps: the catalyst has the advantages of (1) uniform particles which are beneficial to dispersion in a liquid phase medium, (2) simple catalyst composition, (3) high specific surface area and pore volume of the catalyst which promote mass transfer, (4) avoiding using toxic Cr, and (5) improving the activity of the catalyst.
The invention provides a preparation method of a furfuryl alcohol catalyst prepared by furfural liquid-phase hydrogenation, which comprises the following steps:
(a) Dissolving copper salt in deionized water, wherein the concentration of copper ions is 0.05-0.5 mol/L (preferably 0.1-0.4 mol/L, more preferably 0.15-0.3 mol/L), adding ammonia water or introducing ammonia gas to prepare a copper ammonia solution, and the molar ratio of ammonia to copper ions is more than 4 (preferably 6-10, more preferably 6-8);
(b) Adding silica hydrosol (the mass content of silica is 25-40%, preferably 25-35%, more preferably 25-30%) and/or silica aerosol into the solution, and stirring and mixing uniformly;
(c) Heating the mixed system at 80-95 ℃ for 2-10 h to remove ammonia in the system;
(d) Filtering the mixture to obtain a filter cake after the pH value of the mixture reaches 6.5-7;
(e) The filter cake is freeze-dried and calcined to obtain the catalyst.
In a preferred embodiment, the metal component, copper, comprises 5.0 to 40.0% by weight of the total catalyst.
In a preferred embodiment, the freeze-drying conditions in step e) are: drying at-90-10 deg.c for 2-120 hr with vacuum degree of 0.01-0.5mbar.
In a preferred embodiment, the calcination conditions in step e) are: 350-650 ℃ and 1-48 h.
The invention also provides application of the catalyst in catalyzing furfural liquid-phase hydrogenation to prepare furfuryl alcohol.
In a preferred embodiment, the application is carried out under the following conditions: the temperature is 100-250 ℃, the pressure is 0.5-15 MPa, and the molar ratio of furfural to hydrogen is 1.
In a preferred embodiment, the catalyst is activated before use in a hydrogen atmosphere at a temperature of 150 to 500 ℃ for a time of 0.5 to 24h.
Detailed Description
The invention is further illustrated by the following specific examples, wherein the amounts and percentages are by mass.
Example 1
20Cu/SiO 2 Preparation and use of catalysts
5.7g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 50ml of deionized water, and adding 9ml of ammonia water (the mass concentration is 25-28%) to obtain a copper ammonia water solution. 6g of silica aerosol (A200 from Windsor Industrial group) was weighed at room temperatureStirred for 4h. And transferring the uniformly stirred mixture system into a water bath at 90 ℃, continuously stirring for 4 hours to remove ammonia gas in the mixture, and removing the mixture out of the water bath to cool after the pH value of the system is reduced to 7. And after the system is cooled to room temperature, filtering to obtain a filter cake. Freezing the filter cake in a refrigerator to solid, transferring into a freeze dryer, drying at-40 deg.C under 0.12mbar for 48h, and calcining at 450 deg.C for 4h, wherein the sample is marked as A. The catalyst loading was 0.05g, and the catalyst was reduced in hydrogen at 250 ℃ for 2 hours before use. The activated catalyst is transferred into a 100ml reaction kettle, 2g of furfural and 30ml of 1, 4-dioxane are added, and the pressure of hydrogen is increased to 4MPa (the molar ratio of the furfural to the hydrogen is 6). After 1.5 hours of reaction at 120 ℃, samples were taken for analysis. Specific surface area of A449 m 2 G, pore volume 1.87ml/g, average pore diameter 14.3nm. The conversion rate of the furfural is 76 percent, and the selectivity of the furfuryl alcohol is 100 percent.
Example 2
40Cu/SiO 2 Preparation and application of catalyst
15.2g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 50ml of deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas (the molar ratio of ammonia to copper ions is 7) after the pH value of the system is not increased any more, and stirring the obtained solution system for 20min. 24g of silica hydrosol (Shandong ocean chemical JA-25) was weighed and stirred at room temperature for 6 hours. And transferring the uniformly stirred mixture system into a water bath at 75 ℃, continuously stirring for 6 hours to remove ammonia in the mixture, and removing the mixture out of the water bath to cool after the pH value of the system is reduced to 7. And after the system is cooled to room temperature, filtering to obtain a filter cake. The filter cake is frozen into solid in a refrigerator and then transferred into a freeze dryer, the filter cake is dried for 72h at minus 30 ℃ and 0.10mbar and roasted for 4h at 450 ℃, and the sample is marked as B. The catalyst loading was 0.05g, and the catalyst was reduced in hydrogen at 200 ℃ for 5 hours before use. The activated catalyst is transferred into a 100ml reaction kettle, 2g of furfural and 30ml of 1, 4-dioxane are added, and the hydrogen pressure is increased to 5MPa (the molar ratio of the furfural to the hydrogen is 7.5). After 1 hour of reaction at 130 ℃, samples were taken for analysis. Specific surface area 537m of B 2 Pore volume 1.62ml/g, average pore diameter 12.7nm. The conversion rate of furfural is 100 percent, and the selectivity of furfuryl alcohol is 100 percent.
Example 3
30Cu/SiO 2 Preparation and use of catalysts
8.2g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 40ml of deionized water, adding 15ml of ammonia water (the mass concentration is 25-28%), and stirring the obtained solution system for 20min. 20g of an aqueous sol having a silica content of 25% were added and stirred at room temperature for 3h. And transferring the uniformly stirred mixture system into a water bath at 90 ℃, continuously stirring for 5 hours to remove ammonia in the mixture, and removing the mixture from the water bath to cool after the pH value of the system is reduced to 7. And after the system is cooled to room temperature, filtering to obtain a filter cake. The filter cake is frozen into solid in a refrigerator and then transferred into a freeze dryer, dried at minus 50 ℃ for 24h under 0.10mbar and roasted at 450 ℃ for 4h, and the sample is marked as C. The catalyst loading was 0.05g, and the catalyst was reduced in hydrogen at 300 ℃ for 1 hour before use. The activated catalyst is transferred into a 100ml reaction kettle, 4g of furfural and 30ml of 1, 4-dioxane are added, and the hydrogen is pressurized to 6MPa (the molar ratio of the furfural to the hydrogen is 4.5). After 1 hour at 150 ℃, samples were taken for analysis. Specific surface area of C502 m 2 G, pore volume 1.7ml/g, average pore diameter 13.2nm. The conversion rate of furfural is 100 percent, and the selectivity of furfuryl alcohol is 100 percent.
Example 4
20Cu/SiO 2 Preparation and application of catalyst
9.5g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 100ml deionized water, adding 30ml ammonia water (mass concentration is 25-28%), and obtaining the copper ammonia water solution. 10g of silica aerosol (A300 from Windsor Industrial group) was weighed and stirred at room temperature for 6 hours. And transferring the uniformly stirred mixture system into a water bath at 85 ℃, continuously stirring for 4 hours to remove ammonia gas in the mixture, and removing the mixture out of the water bath to cool after the pH value of the system is reduced to 7. And after the system is cooled to room temperature, filtering to obtain a filter cake. The filter cake was frozen in a freezer to a solid and transferred to a freeze dryer, dried at-40 ℃ for 24h at 0.12mbar and calcined at 450 ℃ for 4h, sample labeled D. The catalyst loading was 0.1g, and the catalyst was reduced in hydrogen at 220 ℃ for 3 hours before use. Transferring the activated catalyst into a 100ml reaction kettle, adding 4g of furfural and 30ml of 1, 4-dioxane, and pressurizing hydrogen to 10MPa (the molar ratio of the furfural to the hydrogen is 7).5). After 1 hour of reaction at 140 ℃, samples were taken for analysis. Specific surface area of D460 m 2 Pore volume 1.82ml/g, average pore diameter 13.9nm. The conversion rate of the furfural is 99 percent, and the selectivity of the furfuryl alcohol is 100 percent.
Example 5
The catalyst D was used. The catalyst loading was 0.2g, and the catalyst was reduced in hydrogen at 400 ℃ for 3 hours before use. The activated catalyst is transferred into a 100ml reaction kettle, 2g of furfural and 30ml of 1, 4-dioxane are added, and the hydrogen is pressurized to 5MPa (the molar ratio of the furfural to the hydrogen is 7.5). After 2 hours of reaction at 180 ℃, samples were taken for analysis. The conversion rate of furfural is 100 percent, and the selectivity of furfuryl alcohol is 100 percent.
Example 6
The catalyst used was D. The catalyst loading was 0.5g, and the catalyst was reduced in hydrogen at 250 ℃ for 4 hours before use. The activated catalyst is transferred into a 100ml reaction kettle, 1g of furfural and 30ml of 1, 4-dioxane are added, and the hydrogen pressure is increased to 8MPa (the molar ratio of the furfural to the hydrogen is 24). After 4 hours of reaction at 120 ℃ a sample was taken for analysis. The conversion rate of furfural is 99 percent, and the selectivity of furfuryl alcohol is 98 percent.
Comparative example 1
20Cu/SiO 2 Preparation and application of conventional catalyst
5.7g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 50ml of deionized water, and adding 9ml of ammonia water (the mass concentration is 25-28%) to obtain a copper ammonia water solution. 6g of silica aerosol (A200 from Windsor Industrial group) was weighed and stirred at room temperature for 4 hours. And transferring the uniformly stirred mixture system into a water bath at 90 ℃, continuously stirring for 4 hours to remove ammonia gas in the mixture, and removing the mixture out of the water bath to cool after the pH value of the system is reduced to 7. And after the system is cooled to room temperature, filtering to obtain a filter cake. And drying the filter cake in an oven at 120 ℃ for 12h, and roasting at 450 ℃ for 4h, wherein a sample is marked as E. The catalyst loading was 0.05g, and the catalyst was reduced in hydrogen at 250 ℃ for 2 hours before use. The activated catalyst is transferred into a 100ml reaction kettle, 2g of furfural and 30ml of 1, 4-dioxane are added, and the pressure of hydrogen is increased to 4MPa (the molar ratio of the furfural to the hydrogen is 6). After 1.5 hours of reaction at 120 ℃, samples were taken for analysis. E specific surface area 416m 2 Pore volume 0.82ml/g, average pore diameter 6.6nm. The conversion rate of furfural is 55 percentThe furfuryl alcohol selectivity was 100%.
Comparative example 2
40Cu/SiO 2 Preparation and application of block catalyst
15.2g of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in 50ml of deionized water, introducing high-purity ammonia gas into the solution in a pulse mode, stopping introducing the ammonia gas (the molar ratio of ammonia to copper ions is 7) after the pH value of the system is not increased any more, and stirring the obtained solution system for 20min. 24g of silica hydrosol (Shandong ocean chemical JA-25) was weighed and stirred at room temperature for 4 hours. And transferring the uniformly stirred mixture system into a water bath at 80 ℃, continuously stirring to remove ammonia gas in the mixture, and removing the mixture from the water bath to cool after the pH value of the system is reduced to 7. And after the system is cooled to room temperature, filtering to obtain a filter cake. The filter cake is dried in an oven at 120 ℃ for 12h and roasted at 450 ℃ for 4h, and the sample is marked as F. The catalyst loading was 0.05g, and the catalyst was reduced in hydrogen at 250 ℃ for 2 hours before use. The activated catalyst is transferred into a 100ml reaction kettle, 2g of furfural and 30ml of 1, 4-dioxane are added, and the pressure of hydrogen is increased to 4MPa (the molar ratio of the furfural to the hydrogen is 6). After 1 hour of reaction at 120 ℃, samples were taken for analysis. Specific surface area 472m of F 2 Pore volume 0.71ml/g, average pore diameter 6.1nm. The conversion rate of the furfural is 80 percent, and the selectivity of the furfuryl alcohol is 100 percent.
Comparative example 3
20Ni/SiO 2 Catalyst preparation and use
6.2g of nickel nitrate hexahydrate is dissolved in 50ml of deionized water, and 20ml of ammonia water (mass concentration 25-28%) is added to obtain a nickel-ammonia aqueous solution. 5g of silica aerosol (A300 from the Ministry of Industrial science) was added and stirred at room temperature for 12 hours. Heating to 90 deg.C, removing ammonia in the system, and stopping heating when pH of the system is reduced to 7. Filtering to obtain a filter cake, washing, drying at 120 ℃ for 5h, and roasting at 500 ℃ for 4h to obtain the catalyst G. 0.05g of the calcined catalyst was taken and reduced at 500 ℃ for 4 hours in a hydrogen atmosphere. The activated catalyst is transferred into a 100ml reaction kettle, 2g of furfural and 30ml of 1, 4-dioxane are added, and the hydrogen is pressurized to 4MPa (the molar ratio of the furfural to the hydrogen is 6). After 1.5 hours at 120 ℃ a sample was taken for analysis. The conversion rate of furfural is 25%, and the selectivity of furfuryl alcohol is 95%.
Comparative example 4
20Cu/Al 2 O 3 Catalyst preparation and use
5.7g of Cu (NO) 3 ) 2 ·3H 2 O was dissolved in 50ml of deionized water, and 6g of alumina was added. The mixture system was transferred to a water bath at 90 ℃ and heated to remove water from the system. And after the system is cooled to room temperature, filtering to obtain a filter cake. The filter cake is dried at 100 ℃ for 12h and roasted at 350 ℃ for 4H, and the sample is marked as H. The catalyst loading was 0.05g, and the catalyst was reduced in hydrogen at 250 ℃ for 2 hours before use. The activated catalyst is transferred into a 100ml reaction kettle, 2g of furfural and 30ml of 1, 4-dioxane are added, and the pressure of hydrogen is increased to 4MPa (the molar ratio of the furfural to the hydrogen is 6). After 1.5 hours at 120 ℃ a sample was taken for analysis. The conversion rate of furfural is 35%, and the selectivity of furfuryl alcohol is 99%.
From the above results, it can be seen that the catalyst of the present invention has a large specific surface area, pore volume and average pore diameter as compared with the conventional catalyst. The catalyst shows excellent reaction performance in the reaction of preparing furfuryl alcohol by furfural liquid phase hydrogenation, and the reaction activity and/or furfuryl alcohol selectivity are superior to those of the conventional silicon oxide supported copper catalyst, silicon oxide supported nickel catalyst and aluminum oxide supported copper catalyst.
From the above results of comparative analysis it can be concluded that with the catalyst of the invention one or more of the following can be achieved: the catalyst has the advantages of (1) uniform particles which are beneficial to dispersion in a liquid phase medium, (2) simple catalyst composition, (3) high specific surface area and pore volume of the catalyst which promote mass transfer, (4) avoiding using toxic Cr, and (5) improving the activity of the catalyst.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (8)
1. A preparation method of a furfuryl alcohol catalyst prepared by furfural liquid-phase hydrogenation is characterized by comprising the following steps:
(a) Dissolving copper salt in deionized water, wherein the concentration of copper ions is 0.05-0.5 mol/L (preferably 0.1-0.4 mol/L, more preferably 0.15-0.3 mol/L), adding ammonia water or introducing ammonia gas to prepare a copper ammonia solution, and the molar ratio of ammonia to copper ions is more than 4 (preferably 6-10, more preferably 6-8);
(b) Adding silica hydrosol (the mass content of silica is 25-40%, preferably 25-35%, more preferably 25-30%) and/or silica aerosol into the solution, and stirring and mixing uniformly;
(c) Heating the mixed system at 80-95 ℃ for 2-10 h to remove ammonia in the system;
(d) Filtering the mixture to obtain a filter cake after the pH value of the mixture is 6.5-7;
(e) The filter cake is freeze-dried and calcined to obtain the catalyst.
2. The method for preparing a catalyst for preparing furfuryl alcohol by liquid-phase hydrogenation of furfural according to claim 1, wherein the metal component copper accounts for 5.0 to 40.0% (preferably 10 to 30%, more preferably 15 to 25%) of the total weight of the catalyst.
3. The method for preparing a furfuryl alcohol catalyst by liquid phase hydrogenation of furfural according to claim 1, wherein the freeze-drying conditions in step e) are: drying at-90 to-10 deg.c (preferably-50 to-30 deg.c, more preferably-40 to-35 deg.c) for 2-120 hr (preferably 24-72 hr, more preferably 50-60 hr) and vacuum degree of 0.01-0.5mbar (preferably 0.05-0.25 mbar, more preferably 0.08-0.15 mbar).
4. The method for preparing a furfuryl alcohol catalyst by liquid phase hydrogenation of furfural according to claim 1, wherein the roasting conditions in step e) are: 350-650 deg.C (preferably 400-600 deg.C, more preferably 450-550 deg.C); 1 to 48 hours (preferably 4 to 20 hours, more preferably 4 to 6 hours).
5. A catalyst obtained by the production method according to any one of claims 1 to 4.
6. Use of the catalyst of claim 5 in the catalytic liquid phase hydrogenation of furfural to furfuryl alcohol.
7. Use according to claim 6, characterized in that it is carried out under the following conditions: the temperature is 100-250 ℃ (preferably 100-200 ℃, more preferably 120-150 ℃); hydrogen pressure of 0.5 to 15MPa (preferably 3 to 10MPa, more preferably 4 to 6 MPa); the molar ratio of furfural to hydrogen is 1 to 1 (preferably 1.
8. Use according to claim 6 or 7, characterized in that the catalyst is activated before use under a hydrogen atmosphere at a temperature of 150 to 500 ℃ (preferably 200 to 300 ℃, more preferably 220 to 260 ℃); the time is 0.5 to 24 hours (preferably 1 to 5 hours, more preferably 2 to 3 hours).
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| CN116351416A (en) * | 2023-01-17 | 2023-06-30 | 郑州大学 | Non-noble metal catalyst for preparing furfurether by etherification of furfuraldehyde, and preparation method and use method thereof |
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