CN112090434A - Preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol - Google Patents
Preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol Download PDFInfo
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- CN112090434A CN112090434A CN202010972107.8A CN202010972107A CN112090434A CN 112090434 A CN112090434 A CN 112090434A CN 202010972107 A CN202010972107 A CN 202010972107A CN 112090434 A CN112090434 A CN 112090434A
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- furfural
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- selective hydrogenation
- furfuryl alcohol
- nickel phosphide
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 76
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 18
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 16
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 15
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 14
- 238000004817 gas chromatography Methods 0.000 claims description 14
- 239000001307 helium Substances 0.000 claims description 14
- 229910052734 helium Inorganic materials 0.000 claims description 14
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000010935 stainless steel Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 5
- 150000001299 aldehydes Chemical class 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/40—
-
- 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
-
- 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
Abstract
The invention relates to the technical field of selective hydrogenation of biomass unsaturated aldehyde, in particular to a preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol. The catalyst has simple preparation, low cost and good nickel phosphide dispersibility. The catalyst is used for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol, has mild conditions and high activity and selectivity, and is easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of selective hydrogenation of biomass unsaturated aldehyde, in particular to a preparation method of supported nickel phosphide for catalyzing selective hydrogenation of furfural to prepare furfuryl alcohol.
Background
With the increasing depletion of fossil fuel reserves worldwide, the demand for alternative energy sources is rapidly growing. The biomass energy has the advantages of being renewable, rich in raw materials, low in cost, capable of being converted into liquid fuel through various technical means and the like. The utilization of renewable biomass energy sources to replace fossil fuels to produce high value-added chemicals is also an important direction for the development of sustainable chemical industry by human beings in the future. Furfural, a biomass-derived C5 platform compound, is produced primarily from pentosan-rich agricultural feedstocks (e.g., crop straw, corn cobs, and bagasse) by dehydration to form rings. In recent years, the furfural industry in China is in a state of excess capacity, the production of products and the development of the industry are limited by the international market, and the embarrassing situation can be relieved by increasing the development of downstream products. The furfural can be subjected to catalytic selective hydrogenation to obtain the high value-added chemical furfuryl alcohol. Furfuryl alcohol is an important derivative of furfural, and is a main product of furfural deep processing. Two thirds of the total global furfural production is used to produce furfuryl alcohol, which has wide applications in resin manufacturing, pesticide and solvent applications. The key point of the furfural selective hydrogenation for preparing furfuryl alcohol is the catalyst. The current catalyst for selective hydrogenation of furfural comprises noble metals of Pt, Pd, Ru and Au, non-noble metals of Ni, Cu, Co and the like. Although noble metal catalysts possess high reactivity, their industrial application is limited by high preparation costs. The Ni-based catalyst in the non-noble metal catalyst shows higher activity because the Ni-based catalyst can interact with carbonyl and furan rings. Nickel phosphide has attracted much attention as a new type of hydrogenation catalyst. The catalyst has excellent catalytic hydrogenation activity, low price and stable structure, and is a candidate hopeful to replace noble metals. However, the nano nickel phosphide has larger surface energy and is easy to agglomerate and inactivate.
Disclosure of Invention
The invention aims to solve the technical problems that the price of the existing noble metal catalyst for preparing furfuryl alcohol by selective hydrogenation of furfural is high and the performance of the non-noble metal catalyst is not ideal enough, and provides a method for preparing furfuryl alcohol by selective hydrogenation of furfural by taking novel supported nickel phosphide as a catalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of supported nickel phosphide comprises the steps of adding 60mg of graphite oxide into 30mL of polyalcohol solvent, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution with the concentration of 2 mg/mL; and then adding nickel chloride hexahydrate and sodium dihydrogen hypophosphite, fully stirring, placing in an oil bath reflux device for reacting for 1-5 hours at the temperature of 150-170 ℃, fully washing the obtained supported nickel phosphide by using water and ethanol to remove unreacted nickel chloride, generated sodium chloride, sodium phosphate and the like, and carrying out vacuum drying for 3 hours at the temperature of 60 ℃.
Wherein the oxygen content of the graphite oxide is 45 wt.%; the polyalcohol solvent is ethylene glycol, 1, 3-propylene glycol, and glycerol; the mass ratio of the nickel chloride hexahydrate to the graphite oxide is 2: 1-6: 1, and the molar ratio of the nickel chloride hexahydrate to the sodium dihydrogen hypophosphite is 1: 2-1: 5.
A method for preparing furfuryl alcohol by selective hydrogenation of furfural under catalysis of supported nickel phosphide comprises the steps of putting 10-30 mg of supported nickel phosphide, 0.1-1 mL of furfural and 10mL of deionized water into a stainless steel high-pressure reaction kettle, replacing the reaction kettle with helium and hydrogen in sequence, and then reacting for 0.5-2.5 hours at 50-90 ℃ under the hydrogen pressure of 0.3-1.5 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Advantageous effects
In research, the graphene with oxygen-rich groups is used as a carrier to effectively stabilize the nickel phosphide nanoparticles, the preparation method is mild, other reducing agents are not added, the stabilizing effect of the polyol on the nickel phosphide nanoparticles is achieved, the prepared supported nickel phosphide is uniformly dispersed, the particle size is small and is approximately 8-10 nm, and the synthesized nickel phosphide is in an amorphous state. In addition, the reduced graphene oxide obtained after the graphene oxide is reduced contains a large number of defect sites, and the defect sites have a strong adsorption effect on hydrogen molecules and even have certain hydrogen decomposition capacity, so that the hydrogenation rate of the catalyst is improved to a certain extent. Under mild conditions, the supported nickel phosphide has excellent hydrogenation performance, and the catalyst has the advantages of simple synthesis, low cost, mild conditions and easy realization of industrial production.
Detailed Description
The invention will be further described in the following examples, but it is to be understood that these examples are for illustrative purposes only and are not to be construed as limiting the practice of the invention.
Example 1
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then adding 120mg of nickel chloride hexahydrate and 107mg of sodium dihydrogen hypophosphite, fully stirring, placing in an oil bath reflux device for reaction at 150 ℃ for 1h, fully washing the obtained supported nickel phosphide with water and ethanol after the reaction is finished, and drying in vacuum at 60 ℃ for 3 h.
10mg of load type nickel phosphide, 0.1mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, helium and hydrogen are used for replacing the reaction kettle in sequence, and then the reaction is carried out for 0.5h at 70 ℃ under the hydrogen pressure of 0.3 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 2
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 321mg of sodium dihydrogen hypophosphite are added, the mixture is fully stirred and then placed in an oil bath reflux device to react for 2 hours at the temperature of 170 ℃, after the reaction is finished, the obtained supported nickel phosphide is fully washed by water and ethanol, and the mixture is dried for 3 hours under vacuum at the temperature of 60 ℃.
20mg of supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 1h at 70 ℃ under the hydrogen pressure of 0.5 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 3
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 360mg of nickel chloride hexahydrate and 482mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device to react for 2 hours at the temperature of 170 ℃ after being fully stirred, the obtained supported nickel phosphide is fully washed by water and ethanol after the reaction is finished, and the mixture is dried for 3 hours in vacuum at the temperature of 60 ℃.
20mg of supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 1h at the hydrogen pressure of 1MPa and the temperature of 70 ℃. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 4
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 535mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device to react for 2 hours at the temperature of 170 ℃ after being fully stirred, the obtained supported nickel phosphide is fully washed by water and ethanol after the reaction is finished, and the mixture is dried for 3 hours in vacuum at the temperature of 60 ℃.
30mg of supported nickel phosphide, 1mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2 hours at the temperature of 90 ℃ under the hydrogen pressure of 1.5 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 5
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 321mg of sodium dihydrogen hypophosphite are added, the mixture is fully stirred and then placed in an oil bath reflux device to react for 2 hours at the temperature of 170 ℃, after the reaction is finished, the obtained supported nickel phosphide is fully washed by water and ethanol, and the mixture is dried for 3 hours under vacuum at the temperature of 60 ℃.
20mg of supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2.5h at the temperature of 90 ℃ under the hydrogen pressure of 1 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 6
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 535mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device to react for 2 hours at the temperature of 170 ℃ after being fully stirred, the obtained supported nickel phosphide is fully washed by water and ethanol after the reaction is finished, and the mixture is dried for 3 hours in vacuum at the temperature of 60 ℃.
20mg of supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2 hours at 70 ℃ under the hydrogen pressure of 1 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 7
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 535mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device to react for 2 hours at the temperature of 170 ℃ after being fully stirred, the obtained supported nickel phosphide is fully washed by water and ethanol after the reaction is finished, and the mixture is dried for 3 hours in vacuum at the temperature of 60 ℃.
20mg of supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2 hours at 70 ℃ under the hydrogen pressure of 1.5 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 8
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 535mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device to react for 5 hours at the temperature of 170 ℃ after being fully stirred, the obtained supported nickel phosphide is fully washed by water and ethanol after the reaction is finished, and the mixture is dried for 3 hours under vacuum at the temperature of 60 ℃.
30mg of supported nickel phosphide, 1mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2 hours at the hydrogen pressure of 1MPa and the temperature of 70 ℃. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 9
Adding 60mg of graphite oxide into 30mL of glycerol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 535mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device to react for 2 hours at the temperature of 170 ℃ after being fully stirred, the obtained supported nickel phosphide is fully washed by water and ethanol after the reaction is finished, and the mixture is dried for 3 hours in vacuum at the temperature of 60 ℃.
20mg of supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2 hours at 70 ℃ under the hydrogen pressure of 1 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Example 10
Adding 60mg of graphite oxide into 30mL of 1.3-propylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 535mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device to react for 2 hours at the temperature of 170 ℃ after being fully stirred, the obtained supported nickel phosphide is fully washed by water and ethanol after the reaction is finished, and the mixture is dried for 3 hours in vacuum at the temperature of 60 ℃.
20mg of supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2 hours at 70 ℃ under the hydrogen pressure of 1 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Comparative example 1
Adding 240mg of nickel chloride hexahydrate and 535mg of sodium dihydrogen hypophosphite into 30mL of ethylene glycol, fully stirring, placing in an oil bath reflux device for reacting for 2h at 170 ℃, fully washing the obtained non-supported nickel phosphide with water and ethanol after the reaction is finished, and drying in vacuum for 3h at 60 ℃.
20mg of non-supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2h at the temperature of 70 ℃ under the hydrogen pressure of 1 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
Comparative example 2
Adding 60mg of graphite oxide into 30mL of ethylene glycol, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then 480mg of nickel chloride hexahydrate and 1070mg of sodium dihydrogen hypophosphite are added, the mixture is fully stirred and then placed in an oil bath reflux device for reaction for 2 hours at the temperature of 170 ℃, after the reaction is finished, the obtained supported nickel phosphide is fully washed by water and ethanol, and the mixture is dried for 3 hours under vacuum at the temperature of 60 ℃.
20mg of supported nickel phosphide, 0.5mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle together, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2 hours at 70 ℃ under the hydrogen pressure of 1 MPa. After the reaction, the solid particles were separated by centrifugation, the liquid mixture was separated by extraction with dichloroethane, and the product was analyzed by gas chromatography.
The conversion of furfural and the selectivity of furfuryl alcohol obtained in the above examples and comparative examples are shown in table 1. The result shows that the supported nickel phosphide catalyst prepared by taking the graphene oxide as the carrier can effectively catalyze the reaction of preparing furfuryl alcohol by selective hydrogenation of furfural. Under mild reaction conditions, the catalytic reaction can reach 99.9 percent of conversion rate and 99.5 percent of furfural selectivity.
TABLE 1 Furfural alcohol production performance by selective hydrogenation of furfural with supported nickel phosphide catalyst
| Examples | Furfural conversion (%) | Furfuryl alcohol selectivity (%) |
| 1 | 85.4 | 99.7 |
| 2 | 92.7 | 98.9 |
| 3 | 97.5 | 98.6 |
| 4 | 99.9 | 95.8 |
| 5 | 99.7 | 96.3 |
| 6 | 99.9 | 99.5 |
| 7 | 99.9 | 99.1 |
| 8 | 98.1 | 98.3 |
| 9 | 91.4 | 99.0 |
| 10 | 94.6 | 98.9 |
| Comparative example 1 | 43.2 | 99.3 |
| Comparative example 2 | 90.7 | 98.8 |
The catalyst obtained in example 6 was recovered by centrifugation and washed with ethanol and dried for reuse, and the performance of the catalyst was evaluated as shown in Table 2:
table 2 example 6 catalyst multiplexing performance
| Number of times of multiplexing | Furfural conversion (%) | Furfuryl alcohol selectivity (%) |
| 1 | 99.9 | 99.5 |
| 2 | 99.2 | 99.2 |
| 3 | 99.0 | 99.3 |
| 4 | 98.9 | 99.5 |
| 5 | 98.6 | 99.1 |
| 6 | 98.2 | 99.3 |
Table 2 shows that the activity of the catalyst is not significantly reduced after 6 times of use, and the furfural selectivity of more than 99% is always maintained, and the reuse performance is good.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (9)
1. A method for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural is characterized by comprising the following steps:
(1) loading a supported nickel phosphide catalyst, furfural and deionized water into a stainless steel high-pressure reaction kettle, replacing the reaction kettle with helium and hydrogen in sequence, and setting reaction conditions for reaction;
(2) after the reaction is finished, the reaction kettle is naturally cooled to normal temperature, the gas in the kettle is exhausted, the solid catalyst is separated by a high-speed centrifuge, the liquid mixture is separated by extraction, and the product is analyzed by gas chromatography.
2. The method for preparing furfuryl alcohol by catalytic selective hydrogenation of furfural according to claim 1, wherein the supported nickel phosphide catalyst is prepared by a method comprising the following steps:
weighing graphite oxide, adding the graphite oxide into a polyol solvent to enable the concentration of the graphite oxide to be 2mg/mL, and performing ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; and then adding nickel chloride hexahydrate and sodium dihydrogen hypophosphite, fully stirring, placing in an oil bath reflux device for reaction, and washing and drying the obtained solid catalyst after the reaction is finished.
3. The method for preparing furfuryl alcohol by catalytic selective hydrogenation of furfural according to claim 2, wherein the polyhydric alcohol is ethylene glycol, 1, 3-propylene glycol, glycerol, and the oxygen content of graphite oxide is 45 wt.%.
4. The method for preparing furfuryl alcohol by selective hydrogenation of catalytic furfural according to claim 2, wherein the mass ratio of nickel chloride hexahydrate to graphite oxide is 2: 1-6: 1, and the molar ratio of nickel chloride hexahydrate to sodium dihydrogen hypophosphite is 1: 2-1: 5.
5. The method for preparing furfuryl alcohol by catalytic selective hydrogenation of furfural according to claim 2, wherein the oil bath reaction temperature is 150-170 ℃ and the time is 1-5 h.
6. The method for preparing furfuryl alcohol by catalytic selective hydrogenation of furfural according to claim 2, wherein the washing manner is fully washing with water and ethanol in sequence, and the drying manner is vacuum drying at 60 ℃ for 3 h.
7. The method for preparing furfuryl alcohol by selective hydrogenation of catalytic furfural according to claim 1, wherein the amount of the supported nickel phosphide catalyst is 10-30 mg, the amount of furfural is 0.1-1 mL, and the amount of deionized water is 10 mL.
8. The method for preparing furfuryl alcohol by selective hydrogenation of catalytic furfural according to claim 1, wherein the reaction conditions are a hydrogen pressure of 0.3-1.5 MPa, a reaction temperature of 50-90 ℃ and a reaction time of 0.5-2.5 h.
9. The method for preparing furfuryl alcohol by catalytic selective hydrogenation of furfural according to claim 1, wherein the liquid mixture extraction separation method is to extract three times by using dichloroethane as an extract.
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| CN102887809A (en) * | 2012-10-17 | 2013-01-23 | 天津大学 | Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst |
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| CN104437572A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Preparation method of graphene-loaded nano nickel phosphate hydrogenation catalyst |
| CN105964288A (en) * | 2016-06-12 | 2016-09-28 | 常州大学 | Method for preparing mesoporous carbon nitride loaded nano nickel phosphide |
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| CN102887809A (en) * | 2012-10-17 | 2013-01-23 | 天津大学 | Method for hydroisomerizing normal alkane by using supported nickel phosphide catalyst |
| CN104001503A (en) * | 2014-05-23 | 2014-08-27 | 常州大学 | Preparation method of graphene oxide-loaded nano Pd (palladium) hydrogenation catalyst |
| CN104437572A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Preparation method of graphene-loaded nano nickel phosphate hydrogenation catalyst |
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