CN116351414A - Method for preparing pentanediol by catalyzing furfural hydro-conversion through mesoporous silica bimetallic catalyst - Google Patents
Method for preparing pentanediol by catalyzing furfural hydro-conversion through mesoporous silica bimetallic catalyst Download PDFInfo
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- CN116351414A CN116351414A CN202310360775.9A CN202310360775A CN116351414A CN 116351414 A CN116351414 A CN 116351414A CN 202310360775 A CN202310360775 A CN 202310360775A CN 116351414 A CN116351414 A CN 116351414A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 43
- 238000001354 calcination Methods 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 26
- 238000001291 vacuum drying Methods 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 13
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 13
- 239000005011 phenolic resin Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 238000011068 loading method Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 18
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 18
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 16
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 13
- 229920001992 poloxamer 407 Polymers 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 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
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011701 zinc 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing pentanediol by catalyzing furfural hydrogenation conversion by using a mesoporous silica bimetallic catalyst, which adopts a template method to synthesize SiO with a mesoporous structure 2 The carrier realizes active bimetal loading on the mesoporous carrier, and the furfuraldehyde is catalyzed to be converted into the pentanediol in one step in the hydrogen by the synergistic effect of active metal sites, mesoporous silicon dioxide high pore characteristics and strong interaction between the carrier and the carrier, thereby realizingHigher reaction rate and pentanediol yield.
Description
Technical field:
the invention relates to the field of comprehensive utilization of biomass resources, in particular to a method for preparing pentanediol by catalyzing furfural hydroconversion through a mesoporous silica bimetallic catalyst.
The background technology is as follows:
the synthesis of high value-added chemicals using biomass-based materials is a novel way and a viable solution for comprehensive utilization of biomass resources, wherein the preparation of pentanediol by hydroconversion of furfural is one of the most representative examples. At present, the biomass raw material can be used for preparing the furfural in large quantities on an industrial scale, which provides a premise for converting the furfural into other high-added-value chemicals. Through ring opening and hydrogenation reaction, furfural can be further converted into pentanediol through tetrahydrofurfuryl alcohol (THFA) intermediates, and the pentanediol can be widely applied to the fields of polyester materials, plasticizers, coatings and the like, and has extremely high market application prospects.
The high-efficiency stable hydrogenation catalyst is a main factor limiting the large-scale application of the scheme, and the catalytic activity can be effectively improved by good structural design of the catalyst and loading of active metal sites. CN114073967a discloses an application of a nickel-containing catalyst in preparing 1, 5-pentanediol from furfural, the catalyst uses tungsten oxide-alumina composite oxide as a carrier, the active components are Ni and Pt group metal elements, and one or more of the Ni and Pt group metal elements are combined to form an alloy, so as to prepare the supported nickel-containing alloy catalyst. CN 106732602B discloses a catalyst for preparing pentanediol by catalyzing direct hydrogenolysis of furfural, and the catalyst with Pt supported by a composite oxide carrier of magnesium, cobalt or aluminum can prepare pentanediol with high conversion rate and high selectivity. CN 113318735A also discloses the application of the composite oxide supported Pt catalyst in preparing pentanediol from furfural, which is characterized in that: the composition of the catalyst is Pt/MMgO x X is more than or equal to 2 and less than or equal to 3; wherein the carrier is MMgO x M is any one or more than two of Ti, fe and Ce metals. However, the above-described technique is still further improved.
The invention comprises the following steps:
the invention aims to provide a mesoporous silica bimetallic catalyst for catalyzing furfural hydro-conversionMethod for preparing pentanediol, and template method is adopted to synthesize SiO with mesoporous structure 2 The carrier realizes active bimetal loading on the mesoporous carrier, and the furfuraldehyde is catalyzed to be converted into the pentanediol in one step in hydrogen by means of the synergistic effect of active metal sites, high pore characteristics of mesoporous silicon dioxide and strong interaction between the carrier and the carrier, so that higher reaction rate and pentanediol yield are realized.
The invention is realized by the following technical scheme:
a method for preparing pentanediol by catalyzing furfural hydro-conversion through a mesoporous silica bimetallic catalyst comprises the following steps:
(1) Synthesizing SiO with mesoporous structure by template method 2 A carrier;
(2) Mesoporous SiO 2 Adding carrier and metal nitrate into ethylene glycol, stirring at 45-55deg.C for 4-6 hr, vacuum drying at 115-125deg.C for 10-12 hr, grinding the solid residue, and feeding into a tube furnace, N 2 Calcining at 400-600 ℃ for 2-6h under the atmosphere to obtain a catalyst, and reducing the catalyst for 2-4h at 300-500 ℃ under the hydrogen atmosphere before using the catalyst; the metal nitrate is Pt, cu, ce, zn, ni corresponding to two kinds of nitrate, wherein Pt is necessary;
(3) Adding furfural, the catalyst reduced in the step (2) and a solvent into a reaction kettle, filling argon for three times to exhaust air in the kettle, then filling hydrogen, closing an air outlet valve, stirring and reacting for a period of time at 150-250 ℃, preferably 180-240 ℃, more preferably 220-230 ℃, and collecting a liquid phase product after natural cooling.
In the step (1), a template method is adopted to synthesize SiO with a mesoporous structure 2 The carrier specifically comprises the following steps: adding Pluronic F127 template agent and ethanol into hydrochloric acid solution, stirring at room temperature, adding ethanol solution of tetraethoxysilane and phenol resin precursor, stirring for 2 hr, transferring the mixture into evaporating dish, volatilizing at room temperature, drying in 90 deg.C oven, grinding the solid residue, and N 2 Calcining at 900 ℃ for 3 hours under atmosphere, and then continuously calcining at 550 ℃ for 3 hours in air to obtain mesoporous SiO 2 A carrier.
Preferably, the mass ratio of Pluronic F127 template, tetraethoxysilane to phenolic resin precursor is 8:10.4:5-20, more preferably 8:10.4:10-15.
Preferably, the molar amount of metal nitrate used in step (2) is calculated on SiO 2 The mass ratio of the carrier is 1 to 10mmol/g, most preferably 5mmol/g.
Preferably, the molar ratio of Pt metal nitrate to Cu or Ce or Zn or Ni metal nitrate is from 1:0.25 to 4, more preferably from 1:0.25 to 1, most preferably 1:0.25.
In the step (3), the mass ratio of the catalyst to the furfural is 0.2-2:1.
In the step (3), the solvent is one of water, methanol, ethanol, glycol and isopropanol.
In the step (3), the pressure of the introduced hydrogen is 0.1-2 MPa, and the reaction time is 1-6 h.
Synthesizing SiO with mesoporous structure by template method 2 The carrier realizes active bimetal loading on the mesoporous carrier, has stable property, low cost and good reusability, the mesoporous structure can improve the dispersity of the loaded metal on the surface of the carrier, improve the catalytic activity and utilize mesoporous SiO 2 The unique pore canal structure has remarkable promotion effect on the diffusion of reactants, greatly improves the contact opportunity of the reactants and metal active sites, improves the catalytic activity, and can realize selective hydrogenation to generate pentanediol; meanwhile, the strong interaction between the carrier and the load metal is also beneficial to the hydrogenation catalytic process of the active metal site, active H atoms can be adsorbed by utilizing the hydrogen overflow effect of Pt, the transfer of the active site is realized, the synergistic effect between the bimetal and the carrier is realized, the catalytic hydrogenation reaction is carried out under hydrogen, and the higher reaction rate and the pentanediol yield are obtained.
The beneficial effects of the invention are as follows:
1) Synthesizing SiO with mesoporous structure by template method 2 The carrier has stable property, low cost and good reusability, the mesoporous structure can improve the dispersity of the load metal on the surface of the carrier, improve the catalytic activity and realize selective hydrogenation to generate pentanediol;
2) The invention adopts a hydrogen/hydrogen-rich solvent double reduction strategy, and the low-carbon alcohol used in the experiment can also be used as a reducing agent in the reaction, and can be used for pushing furfuryl alcohol hydrogenation reduction process together with exogenous hydrogen;
3) The one-pot system greatly improves the catalytic reaction rate and effectively reduces the additional cost expenditure caused by factors such as product separation, long reaction time and the like.
In a word, the invention provides a method for preparing pentanediol by catalyzing furfural by a bimetallic-loaded mesoporous silica catalyst, which realizes coupling of furfural ring opening and selective hydrogenation in a hydrogen and low-carbon alcohol system, generates pentanediol with high yield and high selectivity, and provides a new high-efficiency, clean and economic idea for converting biomass into high-added-value chemicals.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 10g phenol resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 5mmol of platinum nitrate and 5mmol of copper nitrate are added into 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent into a tube furnace, N 2 Calcining for 3 hours at 500 ℃ in the atmosphere to obtain 5Pt5Cu@MSi10-500/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 5Pt5Cu@MSi10-500/3 of catalyst and 20mL of methanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 0.5MPa of hydrogen is filled and an air outlet valve is closed, the reaction is stirred for 3 hours at 220 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 52.31%, the yield of 1, 5-pentanediol is 36.41%, and the total yield of 88.72%, and the details are shown in Table 1.
Comparative example 1:
the same as in example 1, except that the catalyst was prepared with the addition of 10mmol of platinum nitrate and no addition of copper nitrate, the final 1, 2-pentanediol yield was 24.76%, and the 1, 5-pentanediol yield was 17.22%, totaling 41.98%.
Comparative example 2:
the same as in example 1, except that 10mmol of copper nitrate was added as the metal salt at the time of catalyst preparation, and that no platinum nitrate was added, the final 1, 2-pentanediol yield was 19.33%, and the 1, 5-pentanediol yield was 12.67%, totaling 32.00%.
Comparative example 3:
the same as in example 1, except that the carrier used in the preparation of the catalyst was a conventional commercially available SiO having no mesoporous structure 2 The final 1, 2-pentanediol yield was 30.79% and the 1, 5-pentanediol yield was 21.01% for a total of 51.80%.
As can be seen from the examples 1, 1 and 2, the synergistic effect of the bimetal can significantly promote hydrogenation of furfural to generate pentanediol; as is clear from example 1 and comparative example 3, siO 2 The mesoporous structure of the carrier remarkably promotes the hydrogenation catalytic activity of the catalyst.
Example 2:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 10g phenol resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 5mmol of platinum nitrate and 5mmol of cerium nitrate are added into 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent into a tube furnace, N 2 Calcining for 3 hours at 500 ℃ in the atmosphere to obtain 5Pt5Ce@MSi10-500/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 5Pt5Ce@MSi10-500/3 of catalyst and 20mL of methanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 0.5MPa of hydrogen is filled and an air outlet valve is closed, the reaction is stirred for 3 hours at 220 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 46.52%, the yield of 1, 5-pentanediol is 32.44%, and the total is 78.96%, and the details are shown in table 1.
Example 3:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 10g phenol resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 5mmol of platinum nitrate and 5mmol of zinc nitrate are added to 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent to a tube furnace, N 2 Calcining for 3 hours at 500 ℃ in the atmosphere to obtain 5Pt5Zn@MSi10-500/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 5Pt5Zn@MSi10-500/3 of catalyst and 20mL of methanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 0.5MPa of hydrogen is filled and an air outlet valve is closed, the reaction is stirred for 3 hours at 220 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 52.36%, the yield of 1, 5-pentanediol is 28.47%, and the total yield is 80.83%, and the details are shown in table 1.
Example 4:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 10g phenol formaldehyde resin precursor solution (dissolved in ethanol, 20 wt.%) were added and stirring was continued for 2h, after which the mixture was transferred to an evaporation dish and after 6h evaporation at room temperature continued at 9Drying in oven at 0deg.C for 24 hr, grinding the solid residue, and N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 5mmol of platinum nitrate and 5mmol of nickel nitrate are added to 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent to a tube furnace, N 2 Calcining for 3 hours at 500 ℃ in the atmosphere to obtain 5Pt5Ni@MSi10-500/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 5Pt5Ni@MSi10-500/3 of catalyst and 20mL of methanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 0.5MPa of hydrogen is filled and an air outlet valve is closed, the reaction is stirred for 3 hours at 220 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 45.87%, the yield of 1, 5-pentanediol is 35.11%, and the total is 80.98%, and the detailed contents are shown in table 1.
Example 5:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 10g phenol resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 8mmol of platinum nitrate and 2mmol of copper nitrate are added into 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent into a tube furnace, N 2 Calcining for 3 hours at 500 ℃ in the atmosphere to obtain 5Pt5Cu@MSi10-500/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 8Pt2Cu@MSi10-500/3 of catalyst and 20mL of methanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 0.2MPa of hydrogen is filled and an air outlet valve is closed, the reaction is stirred for 3 hours at 220 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 53.19%, the yield of 1, 5-pentanediol is 37.64%, and the total yield is 90.83%, and the details are shown in table 1.
Example 6:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 20g phenol formaldehyde resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 2mmol of platinum nitrate, 8mmol of copper nitrate were added to 30mL of ethylene glycol, stirred at 50℃for 6 hours, the solution was then placed in a vacuum oven at 120℃for vacuum drying for 12 hours, the solid residue was ground and fed into a tube furnace, N 2 Calcining for 2 hours at 450 ℃ in the atmosphere to obtain 2Pt8Cu@MSi20-450/2; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 2Pt8Cu@MSi20-450/2 of catalyst and 20mL of methanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 1.0MPa of hydrogen is filled, an air outlet valve is closed, the reaction is stirred for 3 hours at 220 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 42.08%, the yield of 1, 5-pentanediol is 24.33%, and the total yield is 66.41%, and the details are shown in table 1.
Example 7:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 15g phenol resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 8mmol of platinum nitrate and 2mmol of copper nitrate are added into 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent into a tube furnace, N 2 Under the atmosphereCalcining at 650 ℃ for 6 hours to obtain 8Pt2Cu@MSi15-650/6; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 8Pt2Cu@MSi15-650/6 catalyst and 20mL of methanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 1.0MPa of hydrogen is filled and an air outlet valve is closed, the reaction is stirred for 3 hours at 220 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 50.74%, the yield of 1, 5-pentanediol is 35.10%, and the total yield is 85.84%, and the details are shown in Table 1.
Example 8:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 15g phenol resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 8mmol of platinum nitrate and 2mmol of copper nitrate are added into 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent into a tube furnace, N 2 Calcining for 3 hours at 550 ℃ in the atmosphere to obtain 8Pt2Cu@MSi15-550/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 8Pt2Cu@MSi15-550/3 of catalyst and 20mL of methanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 1.0MPa of hydrogen is filled and an air outlet valve is closed, the reaction is stirred for 3 hours at 220 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 58.08%, the yield of 1, 5-pentanediol is 37.45%, and the total content of the 1, 5-pentanediol is 95.53%, and the details are shown in table 1.
Example 9:
(1) 8.0g Pluronic F127 templating agent and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 15g phenol formaldehyde resin precursor solution (dissolved in ethanol, 20 wt.%) were added and stirring was continued for 2h, after which the mixture was transferred to an evaporation dishIn the process, after volatilizing for 6 hours at room temperature, the mixture is dried in an oven at 90 ℃ for 24 hours, and the solid residue is ground and N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 8mmol of platinum nitrate and 2mmol of copper nitrate are added into 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent into a tube furnace, N 2 Calcining for 3 hours at 550 ℃ in the atmosphere to obtain 8Pt2Cu@MSi15-550/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.1g 8Pt2Cu@MSi15-550/3 of catalyst and 30mL of ethanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 1.0MPa of hydrogen is filled and an air outlet valve is closed, the reaction is stirred for 6 hours at 240 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 48.19%, the yield of 1, 5-pentanediol is 29.24%, and the total yield is 77.43%, and the details are shown in table 1.
Example 10:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 15g phenol resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 8mmol of platinum nitrate and 2mmol of copper nitrate are added into 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent into a tube furnace, N 2 Calcining for 3 hours at 550 ℃ in the atmosphere to obtain 8Pt2Cu@MSi15-550/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.05g 8Pt2Cu@MSi15-550/3 of catalyst and 15mL of isopropanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 1.0MPa of hydrogen is introduced, an air outlet valve is closed, stirring is carried out at 180 ℃ for 2 hours, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 41.79%, the yield of 1, 5-pentanediol is 21.60%, and the total yield is 63.39%, and the details are shown in table 1.
Example 11:
(1) 8.0g Pluronic F127 template and 40.0g ethanol were added to 5g HCl solution (0.2 mol/L), after stirring at room temperature for 1h 10.4g Tetraethoxysilane (TEOS) and 15g phenol resin precursor solution (dissolved in ethanol, 20 wt.%) were added, stirring was continued for 2h, the mixture was then transferred to an evaporation dish, after volatilizing at room temperature for 6h it was dried in an oven at 90℃for 24h, the solid residue was triturated, N 2 Calcining at 900 deg.c in atmosphere for 3 hr, and calcining at 550 deg.c in air for 3 hr to obtain mesoporous SiO 2 2g of the catalyst support, 8mmol of platinum nitrate and 2mmol of copper nitrate are added into 30mL of ethylene glycol, stirred for 6h at 50 ℃, then the solution is placed in a vacuum drying oven for vacuum drying at 120 ℃ for 12h, the solid residue is ground and then is sent into a tube furnace, N 2 Calcining for 3 hours at 550 ℃ in the atmosphere to obtain 8Pt2Cu@MSi15-550/3; before use, the catalyst was reduced under a hydrogen atmosphere at 450 ℃ for 3 hours.
(2) 0.1g of furfural, 0.2g 8Pt2Cu@MSi15-550/3 of catalyst and 20mL of isopropanol are added into a reaction kettle, argon is filled and discharged three times to exhaust air in the kettle, then 1.0MPa of hydrogen is introduced, an air outlet valve is closed, stirring reaction is carried out for 3 hours at 230 ℃, liquid phase products are collected for detection after natural cooling, the yield of 1, 2-pentanediol is 60.26%, the yield of 1, 5-pentanediol is 38.35%, and the total yield is 98.61%, and the details are shown in table 1.
Example 12:
the same as in example 11, except that the catalyst was 8Pt2Cu@MSi15-550/3-R1 after one use, the 1, 2-pentanediol yield was 58.40%, the 1, 5-pentanediol yield was 36.72%, and the total was 95.12% under the same reaction conditions, as detailed in Table 1.
Example 13:
the same as in example 11, except that the catalyst was 8Pt2Cu@MSi15-550/3-R3 after 3 uses, the 1, 2-pentanediol yield was 57.37% and the 1, 5-pentanediol yield was 35.85%, amounting to 93.22%, as detailed in Table 1, under the same reaction conditions.
TABLE 1
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (10)
1. The method for preparing pentanediol by catalyzing furfural hydro-conversion by using a mesoporous silica bimetallic catalyst is characterized by comprising the following steps of:
(1) Synthesizing SiO with mesoporous structure by template method 2 A carrier;
(2) Mesoporous SiO 2 Adding carrier and metal nitrate into ethylene glycol, stirring at 45-55deg.C for 4-6 hr, vacuum drying at 115-125deg.C for 10-12 hr, grinding the solid residue, and feeding into a tube furnace, N 2 Calcining at 400-600 ℃ for 2-6h under the atmosphere to obtain a catalyst, and reducing the catalyst for 2-4h at 300-500 ℃ under the hydrogen atmosphere before using the catalyst; the metal nitrate is Pt, cu, ce, zn, ni corresponding to two kinds of nitrate, wherein Pt is necessary;
(3) Adding furfural, the catalyst reduced in the step (2) and a solvent into a reaction kettle, filling argon for three times to exhaust air in the kettle, then introducing hydrogen, closing an air outlet valve, stirring and reacting for a period of time at 150-250 ℃, and collecting a liquid-phase product after natural cooling.
2. The method according to claim 1, wherein the SiO having a mesoporous structure is synthesized by a template method in the step (1) 2 The carrier specifically comprises the following stepsThe steps are as follows: adding PluronicF127 template agent and ethanol into hydrochloric acid solution, stirring at room temperature, adding ethanol solution of tetraethoxysilane and phenol resin precursor, stirring for 2 hr, transferring the mixture into evaporating dish, volatilizing at room temperature, drying in 90 deg.C oven, grinding the solid residue, and N 2 Calcining at 900 ℃ for 3 hours under atmosphere, and then continuously calcining at 550 ℃ for 3 hours in air to obtain mesoporous SiO 2 A carrier.
3. The method of claim 2, wherein the mass ratio of PluronicF127 templating agent, tetraethoxysilane, and phenolic resin precursor is 8:10.4:5-20.
4. The method of claim 2, wherein the mass ratio of PluronicF127 templating agent, tetraethoxysilane, and phenolic resin precursor is 8:10.4:10 "15.
5. The method of claim 1, wherein the molar amount of metal nitrate used in step (2) is calculated from SiO 2 The mass ratio of the carrier is 1-10 mmol/g; the mol ratio of the Pt metal nitrate to the Cu or Ce or Zn or Ni metal nitrate is 1:0.25-4.
6. The method of claim 5, wherein the molar amount of metal nitrate used in step (2) is calculated from SiO 2 The mass ratio of the carrier is 5mmol/g; the mol ratio of the Pt metal nitrate to the Cu or Ce or Zn or Ni metal nitrate is 1:0.25-1.
7. The method according to claim 1, wherein the temperature in step (3) is 180 to 240 ℃.
8. The method of claim 7, wherein the temperature in step (3) is 220 to 230 ℃.
9. The method according to claim 1, wherein in the step (3), the mass ratio of the catalyst to the furfural is 0.2-2:1; the solvent is one of water, methanol, ethanol, glycol and isopropanol.
10. The method according to claim 1, wherein in the step (3), the pressure of the introduced hydrogen is 0.1 to 2MPa and the reaction time is 1 to 6 hours.
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