CN109513462A - A kind of catalyst and its preparation method and application adding hydrogen for 5 hydroxymethyl furfural - Google Patents

A kind of catalyst and its preparation method and application adding hydrogen for 5 hydroxymethyl furfural Download PDF

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CN109513462A
CN109513462A CN201811356768.7A CN201811356768A CN109513462A CN 109513462 A CN109513462 A CN 109513462A CN 201811356768 A CN201811356768 A CN 201811356768A CN 109513462 A CN109513462 A CN 109513462A
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CN109513462B (en
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仇茉
漆新华
王晓琦
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Agro Environmental Protection Institute Ministry of Agriculture
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
    • B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium

Abstract

A kind of catalyst and its preparation method and application adding hydrogen for 5 hydroxymethyl furfural.The present invention utilizes the product AlPO after aluminum phosphate roasting4Induction occupation time process success pure phase MIL-100 (Al) is loaded into SiO in a short time2In (or MCM-41, SBA-15 etc.) Inorganic material carrier, MIL-100 (Al)@SiO has been obtained2Equal complex carriers；Palladium chloride is packaged in the cage of MIL-100 (Al) using incipient impregnation method later, has obtained high activity and highly selective 5 hydroxymethyl furfural hydrogenation catalyst with ammoniated treatment by further restoring.This method can substantially reduce the particle size of MIL-100 (Al), shorten the mass transfer and diffusion path of reaction molecular, greatly improve the utilization efficiency of precious metal palladium, while also solve the problem that catalyst is separated from liquid phase.

Description

A kind of catalyst and its preparation method and application adding hydrogen for 5 hydroxymethyl furfural
Technical field
The invention proposes a kind of catalyst and its preparation method and application for adding hydrogen for 5 hydroxymethyl furfural, belong to life Physical resources catalytic conversion technique field.
Background technique
Metal-organic framework materials (MOFs) are compared with conventional porous materials, because of its, hole very high with specific surface area Rate is big, structure and duct Modulatory character and the advantages that Chemical Diversity, receives the fervent concern of researchers.Result of study Show MOFs the storage and separation of gas, catalysis, absorption, sensing, light, electrically and magnetically learn and in terms of suffer from Good application prospect.Wherein, MIL-n (Al) material of aluminium system, because its hydrothermal structural stability is high, in many catalysis reaction All it is used as the carrier of catalyst.Wherein, MIL-96 (Al) and MIL-100 (Al) are due to secondary structure list having the same Easily there is mixed phase in the synthesis process in member.Result of study discovery, MIL-96 (Al) is a kind of thermodynamically stable phase, and MIL- 100 (Al) be a kind of dynamics interphase (N.A.Khan, et al.Micropor.Mesopor.Mater., 2012,152: 235–239.).MIL-100 (Al) is more difficult to synthesize than MIL-96 (Al).However, MIL-100 (Al) has than MIL-96 (Al) Bigger specific surface area and more Lewis acidic sites, therefore application value is higher.The MIL- of traditional liquid phase method synthesis 100 (Al) partial sizes are universal larger (about 200nm), although partial size is conducive to greatly it from the separation in liquid phase, your gold encapsulated It is unfavorable for the mass transfer diffusion of reaction molecular when belonging to as catalyst；So as to cause large-sized MIL-100 (Al) enclosed inside Most of noble metal nano particles can not effectively play a role.How MIL-100 (Al) partial size substantially to be reduced, together When be also easy to from liquid phase by separation be the problem that such material is faced in terms of catalytic applications.
Summary of the invention
The technical problem being lost the invention aims to solve above-mentioned activity of hydrocatalyst component, while further The selectivity of activity and target product of the catalyst in 5 hydroxymethyl furfural hydrogenation reaction is improved, the invention proposes a kind of use In 5 hydroxymethyl furfural plus the catalyst of hydrogen and its preparation method and application.
The present invention utilizes the product AlPO after aluminum phosphate roasting4Induction occupation time process success in a short time by pure phase MIL-100 (Al) loads to SiO2In (or MCM-41, SBA-15 etc.) Inorganic material carrier, MIL-100 (Al)@SiO has been obtained2 Equal complex carriers；Palladium chloride is packaged in the cage of MIL-100 (Al) using incipient impregnation method later, by further Reduction and ammoniated treatment have obtained high activity and highly selective 5 hydroxymethyl furfural hydrogenation catalyst.This method can be with substantially The particle size for reducing MIL-100 (Al), shortens the mass transfer and diffusion path of reaction molecular, greatly improves the benefit of precious metal palladium With efficiency, while catalyst is also solved from the separation problem in liquid phase.
The technical solution adopted by the present invention is as follows:
A kind of preparation method for the catalyst adding hydrogen for 5 hydroxymethyl furfural comprising the steps of:
(1) it is stirred at room temperature under state, phosphate is dissolved in deionized water, aluminum nitrate is added after its dissolution, continues 10-30min is stirred, nitric acid solution is added dropwise later, adjusts the pH value of solution in 2~3 ranges, continues stirring at least Above-mentioned solution is impregnated into carrier using equi-volume impregnating after 30min, later by impregnated of the carrier of mixed liquor at 80 DEG C Then dry at least 5h is warming up to 120 DEG C until drying again；Then sample is put into Muffle furnace under 500 DEG C of air atmospheres At least 2h is roasted, precursor A is obtained；Wherein the molar ratio of phosphate and aluminum nitrate is 1:1；
(2) it is stirred at room temperature under state, aluminum nitrate and trimesic acid is dissolved into deionized water and obtain solution B；It stirs It mixes and precursor A is added after at least 30min, stir after at least 10min the ultrasonic disperse at least 10min under ultrasound condition again, obtain Slurries C；Wherein aluminum nitrate: trimesic acid: the molar ratio of deionized water is 1.2:1:350-500；Precursor A and solution B Mass ratio is 0.05~0.2:1；
(3) slurries C is transferred in the microwave reaction pipe of quartz, is subsequently placed in microwave synthesizer, control microwave power For 200W, pressure 50-150psi, 150 DEG C are warming up to the heating rate of 20 DEG C/min, is maintained after 5min again with 10 DEG C/min Heating rate be warming up to 190 DEG C, cool down after the reaction was continued 10-20min, product filtered separate later, obtained solid is used Deionized water is sufficiently washed, and the solid after washing is dried to obtain sample D at 120 DEG C later；
(4) palladium chloride solution is impregnated into sample D using equi-volume impregnating, sealing and standing at least 3h, later 120 It dries, is then transferred in tube furnace at DEG C, restore at least 1h at 300~350 DEG C of hydrogen atmosphere, be then cooled to 150 DEG C, In 10%NH3At least 3h is handled under/Ar gaseous mixture, is then swept in Ar air-blowing and is dropped to room temperature and obtain required catalyst.
Carrier described in above-mentioned steps (1) is MCM-41, SBA-15 or SiO2One or more of.
The phosphate is ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate or di(2-ethylhexyl)phosphate One or more of hydrogen sodium.
The mass ratio of palladium chloride and sample D in palladium chloride solution described in above-mentioned steps (4) is 0.1%~3%:1.
Invention also provides a kind of catalyst prepared by the above method for adding hydrogen for 5 hydroxymethyl furfural.
The present invention also provides the application of catalyst described in more than one, which is applied to autoclave hydrogenator It is interior, it is catalyzed 5 hydroxymethyl furfural hydrogenation reaction, catalytic reaction condition are as follows: temperature range is 120~250 DEG C, Hydrogen Vapor Pressure 0.5 ~3.0MPa, catalyst amount account for the 0.3%~3% of liquid charging stock quality.
The advantages of the present invention:
(1) pass through infusion process for aluminum phosphate impregnation to SiO2On equal inorganic carriers, the product after being roasted using aluminum phosphate AlPO4Induction occupation time process, using microwave process for synthesizing success pure phase MIL-100 (Al) is loaded into SiO in a short time2(or MCM-41, SBA-15 etc.) in Inorganic material carrier, obtain MIL-100 (Al)@SiO2Deng serial complex carrier.
(2) preparation method proposed in the present invention can substantially reduce the particle size of MIL-100 (Al), shorten reaction point The mass transfer and diffusion path of son, are substantially improved the utilization efficiency of precious metal palladium, while also solving catalyst from point in liquid phase From problem.
(3) present invention proposes that catalyst is cooled to 150 DEG C after hydrogen reducing, then in 10%NH3Under/Ar gaseous mixture At least 3h is handled, which is to carry out ammoniated treatment to the ligand trimesic acid on the surface MIL-100 (Al)；It can be enhanced pair Raw material 5 hydroxymethyl furfural and its adsorption capacity for adding hydrogen intermediate, so as to improve product 2,5- dihydroxymethyl tetrahydrofuran (DHMTHF) selectivity.
Detailed description of the invention
Fig. 1: catalyst CAT-1 prepared by embodiment 1 (i.e. Pt/MIL-100 (Al)@SiO2) XRD diagram.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, with reference to the accompanying drawing to the present invention It is described in further detail.It should be noted that following embodiments are merely to the explanation present invention, should not be construed as limiting Fixed practical range of the invention.Any changes and modifications in accordance with the scope of the present application should still belong to this hair Within bright patent covering scope.
Embodiment 1:
(1) it is stirred at room temperature under state, 1.32g (0.01mol) diammonium hydrogen phosphate is dissolved in 25g deionized water, to it 3.75g (0.01mol) aluminum nitrate (ANN aluminium nitrate nonahydrate) is added after dissolution, continues to stir 10min, it is molten that nitric acid is added dropwise later Liquid, the pH value for adjusting solution is 2, continues using equi-volume impregnating above-mentioned solution to be impregnated into 5g gas phase after stirring 30min SiO2In carrier, in 80 DEG C of dry 5h, 120 DEG C then will be warming up to again until drying impregnated of the carrier of mixed liquor later；So Sample is put into Muffle furnace afterwards and roasts 2h under 500 DEG C of air atmospheres, obtains precursor A；
(2) it is stirred at room temperature under state, 7.7g aluminum nitrate and 3.6g trimesic acid is dissolved into 108g deionized water Obtain solution B；Precursor A is added after stirring 30min, is stirred after 10min the ultrasonic disperse 10min under ultrasound condition again, is obtained Slurries C；
(3) slurries C is transferred in the microwave reaction pipe of quartz, is subsequently placed in microwave synthesizer, control microwave power For 200W, pressure 50psi, 150 DEG C are warming up to the heating rate of 20 DEG C/min, is maintained after 5min again with the liter of 10 DEG C/min Warm rate is warming up to 190 DEG C, cools down after the reaction was continued 10min, filters product separate later, by obtained solid deionized water Sufficiently washing, is dried to obtain sample D for the solid after washing later at 120 DEG C；
(4) use equi-volume impregnating palladium chloride solution is impregnated into sample D (mass ratio of palladium chloride and sample D for 0.1%:1), sealing and standing at least 3h is dried at 120 DEG C later, is then transferred in tube furnace, at 350 DEG C of hydrogen atmosphere Lower reduction 1h, is then cooled to 150 DEG C, in 10%NH33h is handled under/Ar gaseous mixture, is then swept in Ar air-blowing and drops to room temperature Obtain required catalyst, number CAT-1.
Embodiment 2
Preparation step is same as Example 1, only by gas phase SiO2Carrier is changed to MCM-41 molecular sieve carrier, and gained is urged Agent number is CAT-2.
Embodiment 3
Preparation step is same as Example 1, only by gas phase SiO2Carrier is changed to SBA-15 molecular sieve carrier, and gained is urged Agent number is CAT-3.
Embodiment 4
Preparation step is same as Example 1, and the quality of aluminum nitrate in step (2) is only changed to 5.4g and trimesic acid Quality be changed to 2.5g, gained catalyst number is CAT-4.
Embodiment 5
(1) it is stirred at room temperature under state, 1.32g (0.01mol) diammonium hydrogen phosphate is dissolved in 25g deionized water, to it 3.75g (0.01mol) aluminum nitrate (ANN aluminium nitrate nonahydrate) is added after dissolution, continues to stir 10min, it is molten that nitric acid is added dropwise later Liquid, the pH value for adjusting solution is 2, continues using equi-volume impregnating above-mentioned solution to be impregnated into 5g gas phase after stirring 30min SiO2In carrier, in 80 DEG C of dry 5h, 120 DEG C then will be warming up to again until drying impregnated of the carrier of mixed liquor later；So Sample is put into Muffle furnace afterwards and roasts 2h under 500 DEG C of air atmospheres, obtains precursor A；
(2) it is stirred at room temperature under state, 1.9g aluminum nitrate and 0.9g trimesic acid is dissolved into 27g deionized water and obtained To solution B；Precursor A is added after stirring 30min, is stirred after 10min the ultrasonic disperse 10min under ultrasound condition again, is starched Liquid C；
(3) slurries C is transferred in the microwave reaction pipe of quartz, is subsequently placed in microwave synthesizer, control microwave power For 200W, pressure 50psi, 150 DEG C are warming up to the heating rate of 20 DEG C/min, is maintained after 5min again with the liter of 10 DEG C/min Warm rate is warming up to 190 DEG C, cools down after the reaction was continued 10min, filters product separate later, by obtained solid deionized water Sufficiently washing, is dried to obtain sample D for the solid after washing later at 120 DEG C；
(4) use equi-volume impregnating palladium chloride solution is impregnated into sample D (mass ratio of palladium chloride and sample D for 0.1%:1), sealing and standing at least 3h is dried at 120 DEG C later, is then transferred in tube furnace, at 350 DEG C of hydrogen atmosphere Lower reduction 1h, is then cooled to 150 DEG C, in 10%NH33h is handled under/Ar gaseous mixture, is then swept in Ar air-blowing and drops to room temperature Obtain required catalyst, number CAT-5.
Embodiment 6
Preparation step is same as Example 5, and the quality of aluminum nitrate in step (2) is only changed to 1.4g and trimesic acid Quality be changed to 0.6g, gained catalyst number is CAT-6.
Embodiment 7
Preparation step is same as Example 5, is only 1%:1, institute by the mass ratio of palladium chloride and sample D in step (4) Obtaining catalyst number is CAT-7.
Embodiment 8
Preparation step is same as Example 5, and diammonium hydrogen phosphate in step (1) is only changed to 1.64g (0.01mol) phosphoric acid Sodium, gained catalyst number is CAT-8.
Comparative example 1
It is intended to indicate that do not have MIL-100 (Al) to exist in carrier, only gas phase SiO2When doing carrier, catalyst The selectivity of activity and product.
Palladium chloride solution is impregnated by gas phase SiO using equi-volume impregnating2(palladium chloride and gas phase SiO in carrier2Carrier Mass ratio be 0.1%:1), sealing and standing at least 3h is dried at 120 DEG C, is then transferred in tube furnace, later in hydrogen 1h is restored at 350 DEG C of atmosphere, is then swept in Ar air-blowing and is dropped to room temperature and obtain required catalyst, number CAT-9.
Table 1 gives 7 kinds of different catalysts according to prepared by embodiment 1-6 and comparative example 1 in identical evaluation condition Under to 5 hydroxymethyl furfural hydrogenation activity and to the selectivity of DHMTHF product (evaluation condition: in autoclave hydrogenator, catalysis Agent use temperature range is 180 DEG C, and Hydrogen Vapor Pressure 3.0MPa, catalyst amount accounts for the 1% of liquid charging stock quality, reaction time 2h)。
Table 1
Catalyst number 5 hydroxymethyl furfural conversion ratio (%) DHMTHF selectivity (%)
CAT-1 50.1 56.8
CAT-2 53.2 57.2
CAT-3 55.2 57.9
CAT-4 42.8 51.5
CAT-5 38.2 49.3
CAT-6 34.7 46.8
CAT-7 51.4 55.3
CAT-8 43.7 51.6
CAT-9 28.9 6.9

Claims (6)

1. a kind of preparation method for the catalyst for adding hydrogen for 5 hydroxymethyl furfural, it is characterised in that comprise the steps of:
(1) it is stirred at room temperature under state, phosphate is dissolved in deionized water, aluminum nitrate is added after its dissolution, continues to stir Nitric acid solution is added dropwise in 10-30min later, adjusts the pH value of solution in 2~3 ranges, continues after stirring at least 30min Above-mentioned solution is impregnated on carrier using equi-volume impregnating, will be dried at least impregnated of the carrier of mixed liquor at 80 DEG C later Then 5h is warming up to 120 DEG C until drying again；Then sample is put into Muffle furnace and is roasted at least under 500 DEG C of air atmospheres 2h obtains precursor A；Wherein the molar ratio of phosphate and aluminum nitrate is 1:1；
(2) it is stirred at room temperature under state, aluminum nitrate and trimesic acid is dissolved into deionized water and obtain solution B；Stirring is extremely Precursor A is added after few 30min, stirs after at least 10min the ultrasonic disperse at least 10min under ultrasound condition again, obtains slurries C；Wherein aluminum nitrate: trimesic acid: the molar ratio of deionized water is 1.2:1:350-500；The quality of precursor A and solution B Than for 0.05~0.2:1；
(3) slurries C is transferred in the microwave reaction pipe of quartz, is subsequently placed in microwave synthesizer, control microwave power is 200W, pressure 50-150psi are warming up to 150 DEG C with the heating rate of 20 DEG C/min, maintain after 5min again with 10 DEG C/min's Heating rate is warming up to 190 DEG C, cools down after the reaction was continued 10-20min, filters product separate later, obtained solid is spent Ionized water sufficiently washs, and the solid after washing is dried to obtain sample D at 120 DEG C later；
(4) palladium chloride solution is impregnated into sample D using equi-volume impregnating, sealing and standing at least 3h, later at 120 DEG C Drying, is then transferred in tube furnace, restores at least 1h at 300~350 DEG C of hydrogen atmosphere, be then cooled to 150 DEG C, 10%NH3At least 3h is handled under/Ar gaseous mixture, is then swept in Ar air-blowing and is dropped to room temperature and obtain required catalyst.
2. preparation method according to claim 1, which is characterized in that the carrier is MCM-41, SBA-15 or SiO2In One or more.
3. preparation method according to claim 1, which is characterized in that the phosphate be ammonium phosphate, diammonium hydrogen phosphate, One or more of ammonium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate or sodium dihydrogen phosphate.
4. preparation method according to claim 1, it is characterised in that palladium chloride and sample D in the palladium chloride solution Mass ratio is 0.1%~3%:1.
5. a kind of catalyst for adding hydrogen for 5 hydroxymethyl furfural, which is characterized in that using described in 4 any one of Claims 1 to 4 Preparation method be made.
6. a kind of application of catalyst described in claim 5, it is characterised in that the catalyst is applied in autoclave hydrogenator, Be catalyzed 5 hydroxymethyl furfural hydrogenation reaction, catalytic reaction condition are as follows: temperature range be 120~250 DEG C, Hydrogen Vapor Pressure be 0.5~ 3.0MPa, catalyst amount account for the 0.3%~3% of liquid charging stock quality.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111777578A (en) * 2020-07-15 2020-10-16 烟台大学 Method for preparing 2, 5-dihydroxymethyl tetrahydrofuran by hydrogenation of 5-hydroxymethylfurfural
CN114082451A (en) * 2021-11-25 2022-02-25 西安交通大学 Preparation method of MOF-derived nano-reactors with different structures

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