CN112090434B - Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural - Google Patents
Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural Download PDFInfo
- Publication number
- CN112090434B CN112090434B CN202010972107.8A CN202010972107A CN112090434B CN 112090434 B CN112090434 B CN 112090434B CN 202010972107 A CN202010972107 A CN 202010972107A CN 112090434 B CN112090434 B CN 112090434B
- Authority
- CN
- China
- Prior art keywords
- reaction
- furfural
- furfuryl alcohol
- selective hydrogenation
- nickel phosphide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 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 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 86
- 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
- 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
- 239000000203 mixture Substances 0.000 claims description 27
- 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 17
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 239000007789 gas Substances 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
- 239000002245 particle Substances 0.000 description 14
- 238000005119 centrifugation Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 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
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 corncobs Substances 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 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
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 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
- 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 preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural. The catalyst has simple preparation, low cost and good nickel phosphide dispersibility. The method 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 preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural.
Background
With the increasing depletion of global reserves of fossil fuels, the demand for alternative energy sources is rapidly growing. 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 use of renewable biomass energy sources instead of fossil fuels to produce high value-added chemicals is also an important direction for the development of sustainable chemical industry by humans in the future. Furfural, a C5-platform compound derived from biomass, is mainly prepared from agricultural raw materials rich in pentosans (such as crop straws, corncobs, bagasse and the like) through dehydration into rings. In recent years, the furfural industry in China is in a state of surplus productivity, the production of products and the development of industries are limited by international markets, and the embarrassing situation can be relieved by increasing the development force of downstream products. Furfuraldehyde can be subjected to catalytic selective hydrogenation to obtain high-added-value chemical furfuryl alcohol. Furfuryl alcohol is an important derivative of furfural and is a main product for deep processing of furfural. Two-thirds of the total global furfural yield is used to produce furfuryl alcohol, which has wide use in the resin manufacturing industry, pesticides and solvent applications. The key point of furfuryl alcohol is the catalyst. The current catalyst for selective hydrogenation of furfural comprises noble metals such as Pt, pd, ru, au, non-noble metals such as Ni, cu, co and the like. Noble metal catalysts, while possessing relatively high reactivity, have limited industrial applications due to the high cost of preparation. The Ni-based catalyst in the non-noble metal catalyst shows higher activity because of the interaction with carbonyl and furan rings. Nickel phosphide has attracted attention as a novel class of hydrogenation catalysts. The catalyst has excellent catalytic hydrogenation activity, low price and stable structure, and makes the catalyst a candidate for replacing noble metals. However, the nano nickel phosphide has larger surface energy and is easy to agglomerate and deactivate.
Disclosure of Invention
Aiming at the problems that the existing noble metal catalyst for preparing furfuryl alcohol by selective hydrogenation of furfural is high in price and the performance of the non-noble metal catalyst is not ideal, the invention 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 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 a polyalcohol solvent, and carrying out ultrasonic treatment to obtain a stable dispersed graphene oxide mixed solution with the concentration of 2 mg/mL; then adding nickel chloride hexahydrate and sodium dihydrogen hypophosphite, fully stirring, placing in an oil bath reflux device for reaction for 1-5 h at 150-170 ℃, fully washing the obtained supported nickel phosphide by using water and ethanol after the reaction is finished to remove unreacted nickel chloride, generated sodium chloride, sodium phosphate and the like, and vacuum drying for 3h at 60 ℃.
Wherein the oxygen content of the graphite oxide is 45wt.%; 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.
The method for preparing furfuryl alcohol by catalyzing furfural through selective hydrogenation with supported nickel phosphide comprises the steps of loading 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 h 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 the research, the graphene rich in oxygen groups is adopted as a carrier, so that the nickel phosphide nano particles can be effectively stabilized, the preparation method is mild, other reducing agents are not added additionally, the stabilizing effect of the polyalcohol on the nickel phosphide nano particles is achieved, the prepared supported nickel phosphide is uniformly dispersed, the particle size is small and is about 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 a certain hydrogen decomposition capacity, so that the hydrogenation rate of the catalyst is improved to a certain extent. Under milder conditions, the supported nickel phosphide has excellent hydrogenation performance, and the catalyst has simple synthesis, low price and mild conditions, and is easy to realize industrial production.
Detailed Description
The invention will be further illustrated with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not 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 stable 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 for 1h at 150 ℃, fully washing the obtained supported nickel phosphide by using water and ethanol after the reaction is finished, and vacuum drying for 3h at 60 ℃.
10mg of supported nickel phosphide, 0.1mL 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 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 stable dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 321mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device for reaction for 2 hours at 170 ℃, and after the reaction, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 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, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 1h at 70 ℃ under the pressure of 0.5MPa of hydrogen. 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 stable 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 for reaction for 2 hours at 170 ℃, after the completion, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 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, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 1h at 70 ℃ under the pressure of 1MPa of hydrogen. 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 stable 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 for reaction for 2 hours at 170 ℃, and after the completion, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 60 ℃.
30mg of supported nickel phosphide, 1mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2 hours at 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 stable dispersed graphene oxide mixed solution; then 240mg of nickel chloride hexahydrate and 321mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device for reaction for 2 hours at 170 ℃, and after the reaction, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 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, the reaction kettle is replaced by helium and hydrogen in sequence, and then the reaction is carried out for 2.5 hours at 90 ℃ under the pressure of 1MPa of hydrogen. 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 stable 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 for reaction for 2 hours at 170 ℃, and after the completion, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 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, 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 pressure of 1MPa of hydrogen. 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 stable 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 for reaction for 2 hours at 170 ℃, and after the completion, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 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, 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 stable 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 for reaction for 5 hours at 170 ℃, and after the completion, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 60 ℃.
30mg of supported nickel phosphide, 1mL of furfural and 10mL of deionized water are put into a stainless steel high-pressure reaction kettle, 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 pressure of 1MPa of hydrogen. 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 stable 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 for reaction for 2 hours at 170 ℃, and after the completion, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 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, 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 pressure of 1MPa of hydrogen. 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 stable and 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 for reaction for 2 hours at 170 ℃, and after the completion, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 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, 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 pressure of 1MPa of hydrogen. 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
240mg of nickel chloride hexahydrate and 535mg of sodium dihydrogen hypophosphite are added into 30mL of ethylene glycol, the mixture is placed in an oil bath reflux device for reaction at 170 ℃ for 2h after being fully stirred, and the obtained non-supported nickel phosphide is fully washed by water and ethanol after the completion of the reaction, and is dried in vacuum at 60 ℃ for 3h.
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, 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 pressure of 1MPa of hydrogen. 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 stable dispersed graphene oxide mixed solution; then 480mg of nickel chloride hexahydrate and 1070mg of sodium dihydrogen hypophosphite are added, the mixture is placed in an oil bath reflux device for reaction for 2 hours at 170 ℃, after the completion, the obtained supported nickel phosphide is fully washed by water and ethanol, and is dried in vacuum for 3 hours at 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, 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 pressure of 1MPa of hydrogen. 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 milder reaction conditions, the catalytic reaction can reach a conversion rate of 99.9% and a furfural selectivity of up to 99.5%.
TABLE 1 Supported Nickel phosphide catalytic Furfural Selective hydrogenation furfuryl alcohol preparation Performance
| 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 prepared in example 6 was subjected to multiplexing performance investigation, and the catalyst was centrifugally recovered and reused after washing and drying with ethanol, and the performance is shown in table 2:
TABLE 2 multiplexing Properties of the catalyst of example 6
| Multiplexing times | 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 obviously reduced after 6 times of use, and the furfural selectivity of over 99% is always maintained, so that the reusability is good.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (6)
1. A method for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural, which is characterized by comprising the following steps:
(1) Loading the 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, naturally cooling the reaction kettle to normal temperature, exhausting gas in the kettle, separating a solid catalyst by adopting a high-speed centrifuge, extracting and separating a liquid mixture, and analyzing a product by adopting gas chromatography;
the preparation method of the supported nickel phosphide catalyst comprises the following steps:
weighing graphite oxide, adding the graphite oxide into a polyalcohol solvent to enable the concentration of the graphite oxide to be 2mg/mL, and carrying out ultrasonic treatment to obtain a stably dispersed graphene oxide mixed solution; then adding nickel chloride hexahydrate and sodium dihydrogen hypophosphite, fully stirring, placing the mixture in an oil bath reflux device for reaction, and washing and drying the obtained solid catalyst after the reaction is finished;
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;
the oil bath reaction temperature is 150-170 ℃ and the time is 1-5 h.
2. The method for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural according to claim 1, wherein the polyalcohol is ethylene glycol, 1, 3-propylene glycol, glycerol, and the oxygen content of graphite oxide is 45wt.%.
3. The method for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural according to claim 1, wherein the washing mode is to fully wash with water and ethanol in sequence, and the drying mode is to dry in vacuum at 60 ℃ for 3 hours.
4. The method for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural according to claim 1, wherein the dosage of the supported nickel phosphide catalyst is 10-30 mg, the dosage of furfural is 0.1-1 mL, and the dosage of deionized water is 10mL.
5. The method for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural according to claim 1, wherein the reaction condition is hydrogen pressure of 0.3-1.5 MPa, reaction temperature of 50-90 ℃ and reaction time of 0.5-2.5 h.
6. The method for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural according to claim 1, wherein the liquid mixture extraction and separation method is to use dichloroethane as an extraction liquid for three times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010972107.8A CN112090434B (en) | 2020-09-16 | 2020-09-16 | Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010972107.8A CN112090434B (en) | 2020-09-16 | 2020-09-16 | Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112090434A CN112090434A (en) | 2020-12-18 |
| CN112090434B true CN112090434B (en) | 2023-05-23 |
Family
ID=73759665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010972107.8A Active CN112090434B (en) | 2020-09-16 | 2020-09-16 | Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112090434B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105964288A (en) * | 2016-06-12 | 2016-09-28 | 常州大学 | Method for preparing mesoporous carbon nitride loaded nano nickel phosphide |
-
2020
- 2020-09-16 CN CN202010972107.8A patent/CN112090434B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105964288A (en) * | 2016-06-12 | 2016-09-28 | 常州大学 | Method for preparing mesoporous carbon nitride loaded nano nickel phosphide |
Non-Patent Citations (2)
| Title |
|---|
| 磷化镍催化剂的制备及其对生物油模型化合物加氢性能研究;罗昊;《中国优秀硕士学位论文全文数据库：工程科技Ⅰ辑》;20180215(第2期);第35-38页 * |
| 罗昊.磷化镍催化剂的制备及其对生物油模型化合物加氢性能研究.《中国优秀硕士学位论文全文数据库：工程科技Ⅰ辑》.2018,(第2期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112090434A (en) | 2020-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109603819B (en) | Graphene-loaded PdRu bimetallic catalyst and preparation method and application thereof | |
| CN107442177B (en) | Method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural | |
| CN109225254B (en) | PtNi/C bimetallic catalyst and preparation method thereof | |
| CN106622327A (en) | N-doped porous carbon supported metal catalyst, and preparation method and application thereof | |
| CN108620127B (en) | Catalyst for preparing 1, 5-pentanediol through hydrogenolysis of tetrahydrofurfuryl alcohol, preparation method and application thereof | |
| CN108409692B (en) | Method for preparing gamma-valerolactone by catalyzing levulinic acid hydrogenation with sulfur-doped carbon material-loaded ruthenium catalyst | |
| CN112194577A (en) | Method for preparing cyclopentanone compounds from furfural and furfural derivatives through aqueous phase hydrogenation rearrangement | |
| CN111875566A (en) | Method for preparing 2, 5-dimethylfuran | |
| CN114573429A (en) | Preparation method of 2-methoxy-4 methylphenol based on selective hydrodeoxygenation of vanillin | |
| CN113754514A (en) | Method for preparing pentanol from 2-methylfuran at room temperature by adopting supported catalyst | |
| CN111499603B (en) | Method for preparing furfuryl alcohol by catalytic conversion of furfural | |
| CN114163404A (en) | Method for synthesizing gamma-valerolactone by catalytic hydrogenation of levulinic acid | |
| CN112961123B (en) | Method for preparing 3- (2-furyl) -2-methyl-2-acrolein by catalyzing oxidation condensation of furfural and n-propanol | |
| CN111215090A (en) | Application of oxygen-rich vacancy tungsten oxide supported catalyst in lignin depolymerization | |
| CN112090434B (en) | Preparation method of supported nickel phosphide for preparing furfuryl alcohol by catalyzing selective hydrogenation of furfural | |
| KR20120094555A (en) | Novel metal catalyst supported on activated carbon aerogel, production method thereof and decomposition method of lignin compound using said catalyst | |
| KR101799932B1 (en) | Process for selective hydrogenation of hydroxymethylfurfural using Ru nanoparticles supported catalysts | |
| CN112295571B (en) | PtNi cage catalyst and application thereof in furfuryl alcohol preparation by catalyzing selective hydrogenation of furfural | |
| CN114849755B (en) | Nitrogen-doped mesoporous carbon supported alloy nano catalyst and application thereof | |
| CN114939438B (en) | Method for selective hydrogenation of olefinic unsaturated carbonyl compound and catalyst thereof | |
| CN111135828A (en) | Catalyst and application, preparation and performance test methods thereof | |
| Song et al. | Recent advance in selective hydrogenation reaction catalyzed by biomass-derived non-noble metal nanocomposites | |
| CN111689933B (en) | Synthetic method of 5- [ (phenylamino) methyl ] -2-furancarbinol | |
| CN111389395B (en) | Ruthenium iridium catalyst, preparation method thereof and application of ruthenium iridium catalyst in hydrogenolysis reaction of 5-hydroxymethylfurfural | |
| CN102240564A (en) | Catalyst for preparing crotyl alcohol from gas-phase crotonaldehyde through selective hydrogenation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |