CN103788033B - A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural - Google Patents

A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural Download PDF

Info

Publication number
CN103788033B
CN103788033B CN201210435872.1A CN201210435872A CN103788033B CN 103788033 B CN103788033 B CN 103788033B CN 201210435872 A CN201210435872 A CN 201210435872A CN 103788033 B CN103788033 B CN 103788033B
Authority
CN
China
Prior art keywords
group
fructose
hmf
sio
base
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
Application number
CN201210435872.1A
Other languages
Chinese (zh)
Other versions
CN103788033A (en
Inventor
徐杰
石松
陈晨
王敏
贾秀全
郑玺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201210435872.1A priority Critical patent/CN103788033B/en
Publication of CN103788033A publication Critical patent/CN103788033A/en
Application granted granted Critical
Publication of CN103788033B publication Critical patent/CN103788033B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0231—Halogen-containing compounds
    • 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
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

A kind of fructose Dehydration is for the novel method of 5 hydroxymethyl furfural (HMF), and the method, using silicon dioxide base hydrophobic nano solid-acid material as catalyzer, is applied to fructose Dehydration for HMF process.Because this material has surface hydrophobicity and acidic site, be conducive to promoting efficiently carrying out of reaction, obtain high fructose converting rate and HMF selectivity.

Description

A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural
Technical field
The invention belongs to the catalytic applications of nano material, specifically a kind of silicon dioxide base hydrophobic nano solid-acid material is applied in fructose dehydration reaction, in order to efficiently, the acquisition HMF of highly selective.
Background technology
Along with the minimizing day by day of fossil resource, the substitute of development fossil resource is the problem that the mankind pay close attention to jointly.Compared to new forms of energy such as wind and solar energies, biomass resource can be converted into fine chemicals due to it and then replace existing petrochemical industry route and seem particularly important.HMF, i.e. 5 hydroxymethyl furfural are a kind of important platform chemicals that biomass catalyzing transforms in preparative chemistry product route, it can be further converted to 2, the derived product such as 5-furans dicarbaldehyde, FDCA, 2,5-dimethyl furans and maleic anhydride.These derived product can be utilized as the polyester monocase of novel high polymer or bioenergy.Current HMF is mainly obtained by an acidic catalyst catalysis carbohydrate Dehydration.There is the problems such as temperature of reaction is higher, yield is lower, coking is serious.The acid material of Development of Novel improves productive rate and the selectivity of HMF, extremely important.Traditional an acidic catalyst surface is wetting ability, and the water that fructose dehydration produces can be adsorbed on the surface of catalyzer, easily causes the HMF generated degrade or be polymerized to humin substances, hinders the continuation reaction of substrate molecule and reduces selectivity.
Summary of the invention
Transforming generation HMF to realize fructose efficient catalytic, needing invention a kind of for the hydrophobic solid acid Catalysts and its preparation method of fructose catalytic Dehydration for HMF.Under the effect of catalyzer, under mild conditions, efficient for fructose catalytic dehydration is prepared HMF.
According to the present invention, in order to improve the effect of catalyzed reaction, the nano SiO 2 particle that have selected good dispersity is the difunctionalization catalyzer of substrate.Specifically with SiO 2nano particle is substrate, connects sulfonic group in its surface as acid active sites, grafting hydrophobic group regulating catalyst surface catalysis microenvironment; The dehydration of catalysis fructose is carried out by acidic-group, the hydrophobicity on surface is improved by the group introducing nonpolar or low-pole, the water produced in dehydration is departed from from catalyst surface in time, thus avoids the generation of the side reactions such as HMF hydrolytic polymerization, and then improve selectivity and productive rate.Difunctionalization catalyzer its can adopt general formula AcHg-SiO 2(X, Y) represents, Ac is the abbreviation of Acid, is sulfonic acid surfactant base; Hg is the abbreviation of Hydrophobicgroup, is surface hydrophobicity group; Wherein, Ac is one or more in propyl sulfonic acid base, ethylsulfonic acid base, phenylbenzimidazole sulfonic acid base and tetrafluoro phenyl sulfonic group; Hg is one or more in methyl, ethyl, propyl group, vinyl, Chloroallyl, naphthyl, phenyl, trifluoro propyl, phenyl-monofluoride base and pentafluorophenyl group.X is the mass content of acidic-group, and Y is the mass content of hydrophobic group.
Precipitation agent is water miscible, and silane is oil-soluble, in order to synthesize uniform particle diameter, the dispersed high nano SiO 2 particle containing organic group, must make precipitation agent and silane fully and uniform contact, the present invention adopts tensio-active agent and cosurfactant by ammonia soln high dispersive among oil phase, silane is fully contacted, precipitation from homogeneous solution with precipitation agent.
The preparation method of catalyzer can operate according to the following step:
1) by the ammoniacal liquor of tensio-active agent, mass concentration 25-28%, water, organic phase and cosurfactant mixing composition reverse micro emulsion A; Tetraethoxy, hydrosulphonyl silane and hydrophobic silane are silicon source, are mixed and made into solution B; Under the condition stirred, solution B is added in solution A, and aging 2-48h; The mass ratio of the final mixing solutions of gained is 0 ~ 8 tensio-active agent: 1 ~ 4 water: 5 ~ 9 organic phases: 0 ~ 6 cosurfactant: 1 tetraethoxy: 0.05 ~ 1.5 hydrophobic silane: the hydrosulphonyl silane of 0.05 ~ 1.5: 0.01 ~ 2 ammonia.
2) the 1-20 ethanol breakdown of emulsion doubly of silicon source quality is added, collected by centrifugation solid; The tensio-active agent of solid surface, 80-150 DEG C of oven dry are removed in the 5-50 times of alcohol reflux washing adding silicon source quality for 2-6 time.
3) nano material of gained is placed in 20mL ethanol, add silicon source quality 5-50 30% hydrogen peroxide doubly, at room temperature stir 24h, centrifugal, add sulphuric acid soln and the silicon source quality 5-50 ethanol doubly of silicon source quality 5-50 times of 1M, stir 1h, wash three times, 80-150 DEG C of oven dry, finally obtains homogeneous granular nano material.
According to the present invention, in order to realize the microballoon that catalyzer is Nano grade, tensio-active agent used in catalyst preparation process can be that anion surfactant is as linear alkylbenzene sulphonic acid and α-sodium olefin sulfonate, also can be nonionogenic tenside as the organic primary amine of long-chain, Np series and TWEEN Series tensio-active agent, can also be that cats product is as hexadecyl trimethyl ammonium bromide etc.Organic phase is ethanol, hexanaphthene, normal hexane or toluene, and cosurfactant is propyl carbinol, isopropylcarbinol or n-Octanol.The SiO of gained in the present invention 2granular size be 5-150nm.
According to the present invention, the performance of catalyzed reaction is relevant with the kind of the acidic-group on catalyzer, and the acidic-group described in catalyst preparation process is one or more in propyl sulfonic acid base, ethylsulfonic acid base, phenylbenzimidazole sulfonic acid base and tetrafluoro phenyl sulfonic group.
According to the present invention, the performance of catalyzed reaction is relevant with the amount of the acidic components on catalyzer, and acidic site is too low, and can affect the selectivity of catalyzed reaction, consumption is too high, and side reaction increases.The charge capacity of the acidic-group therefore in the present invention is 0.5-40%.
According to the present invention, in order to improve the hydrophobicity of catalyst surface and improve transformation efficiency and the selectivity of catalysis, the hydrophobic grouping in hydrophobic silane described in catalyst preparation process is one or more in methyl, ethyl, propyl group, vinyl, Chloroallyl, naphthyl, phenyl, trifluoro propyl, phenyl-monofluoride base and pentafluorophenyl group.
According to the present invention, the amount of hydrophobic group can affect the catalytic effect of catalyzer, and content too much can make nano silicon spheres irregular, and the hydrophobic performance on the too low then surface of content improves not enough, and catalytic effect is all bad.Therefore hydrophobic group mass content 0.5-40% in the catalyst in the present invention.
According to the present invention, fructose Dehydration is for the reaction of HMF, and its temperature of reaction is 50-200 DEG C, and optimum temps is 80-180 DEG C; Reaction is carried out under nitrogen or air atmosphere; Reaction times is 30-720min, and optimum reacting time is 60-180min; Substrate conversion efficiency is that 6-99%, HMF selectivity reaches more than 95%.
The present invention obtains hydrophobic solid acid material by the organically-modified design on surface, is applied in this reaction, is conducive to water and the timely desorption of HMF of generation, reduce the generation of side reaction, and then be conducive to the absorption of substrate, improve transformation efficiency, thus improve the productive rate of HMF.
Accompanying drawing illustrates:
With SpPh-SiO 2(15,15) be example, the content that this material confirms its acidic site through acid base titration is 25ummol/g, the surface that phenylbenzimidazole sulfonic acid base silane and hydrophobic propyl silane have been coupled to silicon ball is confirmed through FT-IR spectrogram and 29Si-NMR, and contact angle can reach 130 °, it is hydrophobic for describing this acid material.
Fig. 1 SpPh-SiO 2the FT-IR spectrogram of (15,15)
Fig. 2 SpPh-SiO 2the 29Si-NMR spectrogram of (15,15)
Fig. 3 SpPh-SiO 2the contact angle spectrogram of (15,15)
Embodiment
Below by embodiment, method provided by the invention is described in detail, but do not limit the present invention in any form.
Embodiment 1 materials A (SpPh-SiO 2(15,15)) preparation
Get 20gNp-12,25g hexanaphthene, 5g water, 2g ammoniacal liquor (25-28%) and 3g n-Octanol are mixed to get solution A; 0.2g3-mercaptopropyi Trimethoxy silane (presoma of acidic-group), 1g tetraethoxy and 0.2g phenyl triethoxysilane (hydrophobic silane) are mixed to get solution B; With vigorous stirring solution B is added in solution A, aging 8h; Then, add 10mL ethanol, vigorous stirring 30min, centrifugal white powder; 60mL ethanol is added, heated and stirred 15min in this solid, centrifugal; Repeat this step repeatedly, until removal of surfactant is clean; In solid, add 20mL ethanol, 1g mass concentration 30% hydrogen peroxide, stir 2h.Centrifugal, obtain white solid, add 1M sulphuric acid soln 10mL, stir 3h, centrifugal, obtain white solid powder.Add distilled water 30mL wherein, stir 30min, centrifugal, repeat this step repeatedly, until residual sulphuric acid soln is except clean; Dry to obtain final nano material SpPh-SiO for 80 DEG C 2(15,15).
The acidity of this material is 25ummol/g through its acid amount of titration, its FT-IR spectrogram and 29si-NMR spectrogram (Fig. 1 and Fig. 2) proves that the coupling of phenyl and sulfydryl is at silica sphere, and it is 120 ° (Fig. 3) that its contact angle figure shows its hydrophobic angle.
The preparation of embodiment 2 material B-E
The same materials A of preparation method of material B-E, difference is on the contamination of selected organosilane, and the kind of the concrete organosilane adopted is in table 1, and table 1 listed in by the material obtained.
The kind of the organosilane adopted in prepared by table 1 material B-E
Embodiment 3
By the 0.025gSpEt-SiO of synthesis 2the catalyzer of (10,15) joins in 5mLDMSO, adds 0.5g fructose, is heated to 80 DEG C, reacts 5h in air in oil bath, and after reaction terminates, the content HPLC of fructose analyzes, and transformation efficiency is 92%.The yield of HMF comes quantitatively with GC, and yield is 80%.
Embodiment 4
By the 0.2gPcPr-SiO of synthesis 2the catalyzer of (10,20) joins in 50mLDMSO, adds 1g fructose, is heated to 100 DEG C, reacts 2h in nitrogen in oil bath, and after reaction terminates, the content HPLC of fructose analyzes, and transformation efficiency is 99%.The yield of HMF comes quantitatively with GC, and productive rate is 85%.
Embodiment 5
By the 0.05gEtPf-SiO of synthesis 2the catalyzer of (5,10) joins in 10mLDMf, adds 2g fructose, is heated to 120 DEG C, reacts 8h in nitrogen in oil bath, and after reaction terminates, the content HPLC of fructose analyzes, and transformation efficiency is 99%.The yield of HMF comes quantitatively with GC, and productive rate is 70%.
Embodiment 6
By the 0.075gFcMy-SiO of synthesis 2the catalyzer of (15,10) joins in 10mLDMF, adds 1.5g fructose, is heated to 120 DEG C, reacts 5h in nitrogen in oil bath, and after reaction terminates, the content HPLC of fructose analyzes, and transformation efficiency is 87%.The yield of HMF comes quantitatively with GC, and productive rate is 72%.
Embodiment 7
By the 0.1gSpPh-SiO of synthesis 2the catalyzer of (2,10) joins in 10mLDMF, adds 5g fructose in oil bath, is heated to 120 DEG C, react 12h in nitrogen, and after reaction terminates, the content HPLC of fructose analyzes, and transformation efficiency is 93%.The yield of HMF comes quantitatively with GC, and productive rate is 82%.
Embodiment 8
By the 0.1gSpVi-SiO of synthesis 2the catalyzer of (25,10) joins in 10mLDMSO, adds 0.5g fructose, is heated to 120 DEG C, reacts 4h in nitrogen in oil bath, and after reaction terminates, the content HPLC of fructose analyzes, and transformation efficiency is 99%.The yield of HMF comes quantitatively with GC, and productive rate is 83%.
Embodiment 9
By the 0.025gFcPf-SiO of synthesis 2the catalyzer of (30,15) joins in 2mLDMSO, adds 1g fructose in oil bath, is heated to 120 DEG C, react 6h in nitrogen, and after reaction terminates, the content HPLC of fructose analyzes, and transformation efficiency is 87%.The yield of HMF comes quantitatively with GC, and productive rate is 84%.
The present invention obtains hydrophobic solid acid material by the organically-modified design on surface, be applied in this reaction, be conducive to water and the timely desorption of HMF of generation, reduce the generation of side reaction, and then be conducive to the absorption of substrate, thus making transformation efficiency can reach 99%, selectivity reaches as high as 96%, and this shows that this catalyzer is the catalyzer that the dehydration of effective fructose generates HMF.

Claims (5)

1. fructose Dehydration is for a method of 5 hydroxymethyl furfural (HMF), it is characterized in that: the method is with silicon dioxide base hydrophobic nano solid-acid material for catalyzer, and this catalyzer is with SiO 2microballoon is substrate, at its surperficial scion grafting acidic-group and hydrophobic group; Catalyst surface has hydrophobicity and acidic site; Be applied to fructose Dehydration for HMF, this method can improve the transformation efficiency of fructose and the selectivity of HMF;
Silicon dioxide base hydrophobic nano solid-acid material its adopt general formula AcHg-SiO 2(X, Y) represents, Ac is the abbreviation of Acid, is sulfonic acid surfactant base; Hg is the abbreviation of Hydrophobicgroup, is surface hydrophobicity group; X is the mass content of acidic-group, and Y is the mass content of hydrophobic group; AcHg-SiO 2(X, Y) particle diameter is 20-150 nanometer, and the mass content of acidic-group is 0.5-40%, and the mass content of hydrophobic group is 0.5-40%, and all the other components are SiO 2.
2. in accordance with the method for claim 1, it is characterized in that: described fructose Dehydration is for the reaction of HMF, and its temperature of reaction is 80-180 DEG C; Reaction is carried out under nitrogen or air atmosphere; Reaction times is 60-180min.
3. in accordance with the method for claim 1, it is characterized in that: in silicon dioxide base hydrophobic nano solid-acid material, acidic site is one or two or more kinds in propyl sulfonic acid base, ethylsulfonic acid base, phenylbenzimidazole sulfonic acid base and tetrafluoro phenyl sulfonic group, and hydrophobic group is one or two or more kinds in methyl, ethyl, propyl group, vinyl, Chloroallyl, naphthyl, phenyl, trifluoro propyl, phenyl-monofluoride base and pentafluorophenyl group.
4. according to the method described in claim 1 or 2, it is characterized in that: described catalyst levels is the 5%-40% of fructose quality.
5. according to the method described in claim 1 or 2, it is characterized in that: react in liquid phase and carry out, its solvent adopted is DMSO or DMF, and described solvent load is 2-40 times of fructose quality.
CN201210435872.1A 2012-11-05 2012-11-05 A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural Active CN103788033B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210435872.1A CN103788033B (en) 2012-11-05 2012-11-05 A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210435872.1A CN103788033B (en) 2012-11-05 2012-11-05 A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural

Publications (2)

Publication Number Publication Date
CN103788033A CN103788033A (en) 2014-05-14
CN103788033B true CN103788033B (en) 2016-04-06

Family

ID=50664139

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210435872.1A Active CN103788033B (en) 2012-11-05 2012-11-05 A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural

Country Status (1)

Country Link
CN (1) CN103788033B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107185510A (en) * 2016-12-22 2017-09-22 青岛大学 It is catalyzed the preparation of the titanate radical nanopipe of fructose dehydration 5 hydroxymethylfurfurals of generation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106179493B (en) * 2015-05-06 2018-11-13 中国科学院大连化学物理研究所 A kind of hydrophobic solid acid catalyst and preparation and the application in aromatic acid esterification
CN109776459A (en) * 2019-02-27 2019-05-21 天津大学 A kind of method that the fructose dehydration of hydrophobic solid acid catalysis prepares 5 hydroxymethyl furfural

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100029926A1 (en) * 2008-07-29 2010-02-04 Georgia Tech Research Corporation Molecular mass enhancement of biological feedstocks
CN102049298A (en) * 2009-10-29 2011-05-11 中国石油化工股份有限公司 Composite solid acid catalyst as well as preparation method and application thereof in alkylation reaction
CN102153527A (en) * 2011-02-28 2011-08-17 浙江师范大学 Method for preparing 5-hydroxymethylfurfural with fructose
CN102477020A (en) * 2010-11-29 2012-05-30 中国科学院大连化学物理研究所 Method for preparing 5-hydroxymethyl furfural by catalysis of carbohydrate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101217383B1 (en) * 2010-12-29 2012-12-31 코오롱인더스트리 주식회사 METHOD OF PREPARING FURFURAL USING lNORGANIC ACID MODIFED SILICA BEAD
KR101217404B1 (en) * 2010-12-29 2013-01-02 코오롱인더스트리 주식회사 Method of preparing furfural using silica bead

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100029926A1 (en) * 2008-07-29 2010-02-04 Georgia Tech Research Corporation Molecular mass enhancement of biological feedstocks
CN102049298A (en) * 2009-10-29 2011-05-11 中国石油化工股份有限公司 Composite solid acid catalyst as well as preparation method and application thereof in alkylation reaction
CN102477020A (en) * 2010-11-29 2012-05-30 中国科学院大连化学物理研究所 Method for preparing 5-hydroxymethyl furfural by catalysis of carbohydrate
CN102153527A (en) * 2011-02-28 2011-08-17 浙江师范大学 Method for preparing 5-hydroxymethylfurfural with fructose

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Acid-Functionalized SBA-15-Type Periodic Mesoporous Organosilicas and Their Use in the Continuous Production of 5-Hydroxymethylfurfural;Mark H.Tucker et al;《ACS Catalysis》;20120709;第2卷(第9期);第1865-1867、1870、1873页 *
Preparation of 5-hydroymethylfurfural by dehydration of fructose in the presence of acidic ionic liquid;Quanxi Bao et al;《Catalysis Communications》;20080125;第9卷(第6期);第1384、1386-1387页 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107185510A (en) * 2016-12-22 2017-09-22 青岛大学 It is catalyzed the preparation of the titanate radical nanopipe of fructose dehydration 5 hydroxymethylfurfurals of generation

Also Published As

Publication number Publication date
CN103788033A (en) 2014-05-14

Similar Documents

Publication Publication Date Title
CN103801394B (en) A kind of hydrophobic nano solid-acid material of organic decoration and preparation thereof
CN108794756A (en) A kind of preparation method and applications of the covalent organic frame material of nickel ion modification
CN103788033B (en) A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural
CN101927182B (en) Biodiesel catalyst and method for preparing biodiesel by using same
CN102218544B (en) Preparation method and application of metal nanoparticles
Das et al. Development of mesoscopically assembled sulfated zirconia nanoparticles as promising heterogeneous and recyclable biodiesel catalysts
CN103537313A (en) Catalyst for preparing phenol by benzene hydroxylation and preparation method thereof
CN101973554A (en) Method for preparing mesoporous silica material
CN106378160B (en) It is a kind of to prepare CdS/MoS2The method of composite hollow square photochemical catalyst
CN101879459B (en) Preparation method and application of Schiff base functionalized ordered mesoporous PMO material solid supported Cu(I) heterogeneous catalyst
CN104815690B (en) A kind of more sulfonic acid funtionalized mesoporous polymer solid acid catalysts and its preparation method and application
CN107597106A (en) A kind of preparation method and applications of hollow nanometer capsule parcel platinum catalyst
CN107586254B (en) Method for synthesizing ethylene glycol by hydrogenating oxalate
CN105921168A (en) Preparation method of hydrodeoxidation isocatalyst, hydrodeoxidation isocatalyst and application thereof
CN107138169B (en) Two-dimensional sulfide nano-junction hydrogen production photocatalyst, and preparation method and application thereof
CN107858457A (en) A kind of method of high dispersive sulfoxidation graphene catalyzing hydrolysis cellulose
CN104399527A (en) Preparation method of attapulgite/polymerized ionic liquid composite catalyst
CN102755908A (en) Alkene epoxidation method
Liu et al. Core–Shell Dispersed Polymeric Ionic Liquids as Efficient Heterogeneous Catalyst for CO2 Conversion into Cyclic Carbonates
CN111203224A (en) Method for preparing green catalyst by using biomass tar and application
CN111195528A (en) Preparation method of bifunctional Pickering emulsion catalyst
CN113502280B (en) Hydrophobic polyion liquid immobilized lipase catalyst, preparation method and application thereof
CN111744553B (en) Zirconium dodecylbenzene sulfonate catalyst and application thereof in furfuryl alcohol alcoholysis reaction
CN112705261B (en) Preparation method of Pickering emulsion guanidino ionic liquid catalytic system for ester exchange reaction
CN114789064A (en) Catalyst for preparing methanol by partial oxidation of coal bed gas and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant