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WO2012029071A2 - Composition de catalyseur (icat-2) comprenant du métal de terre rare - Google Patents

Composition de catalyseur (icat-2) comprenant du métal de terre rare Download PDF

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Publication number
WO2012029071A2
WO2012029071A2 PCT/IN2011/000102 IN2011000102W WO2012029071A2 WO 2012029071 A2 WO2012029071 A2 WO 2012029071A2 IN 2011000102 W IN2011000102 W IN 2011000102W WO 2012029071 A2 WO2012029071 A2 WO 2012029071A2
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catalyst
organic
icat
rare earth
inorganic
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WO2012029071A3 (fr
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Ganapati Dadasaheb Yadav
Rajesh Vishnudev Sharma
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J31/2252—Sulfonate ligands
    • B01J31/2256—Sulfonate ligands being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional 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
    • 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
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • 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
    • 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
    • B01J2531/37—Lanthanum
    • 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
    • B01J2531/38—Lanthanides other than lanthanum
    • 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
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • 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

Definitions

  • the present invention is related to the process for preparation of a water tolerant heterogeneous acid catalyst (ICaT-2).
  • the catalyst comprises of rare earth metals in the form of trifluromethane sulfonate anchored with hexagonal organic- inorganic functionalized mesoporous silica as a base metal through organic linkage.
  • the said catalyst composition has specific surface area in the range of 200 m 2 /g to 850 m 2 /g and pore diameter in the range of 20-50 A.
  • the catalytic activity tests were carried out for dehydration reactions.
  • the catalyst was found to be highly active and reusable for biomass based chemicals. BACKGROUND OF THE INVENTION
  • Lewis acid catalysts are water sensitive and can be hydrolyzed by water but some Lewis acids, such as group III B and rare earth triflates, are water tolerant and can be used in variety of reactions. Some of the water tolerant Lewis acid catalysts are europium triflates, hafnium triflates, lanthanum triflate and ytterbium triflate etc. These triflates are used as catalyst in several industrially important reactions.
  • US 6352954 discloses synthesis of Lewis acid triflate, encapsulated in the network of polymer gel. This was used in the variety of organic synthesis such as imino-aldol condensation, Mannich-type reactions, Micheal reactions and Friedel-crafts reactions.
  • US 6348631 discloses acylation or sulphonation of aromatics with Lewis acid, such as rare earth triflate.
  • US 6194580 discloses synthesis of esters by reacting a compound containing a tertiary alcohol with acylheteroaromatic ion-based compound in the presence of a lanthanide metal based catalyst.
  • US 5728901 discloses a process for nitrating an aromatics with nitric acid in the presence of metal triflate.
  • This invention relates to the development of heterogeneous solid acid catalyst ICaT-2 (Institute of Chemical Technology, Mumbai).
  • metal trifluromethane sulfonates are coordinated with hexagonal organic - inorganic functionalized mesoporous silica through a chemical bonding.
  • the resulting catalyst has porosity, Bronsted acidic characteristic of organic - inorganic functionalized mesoporous silica, as well as Lewis acidic nature of water tolerant metal triflate.
  • Furfural is exclusively produced by dehydration of D-xylose.
  • Furfural acts as a renewable feedstock for furfuryl alcohol and tetrahydrofuran, which is obtained through hydrogenation of furfural.
  • Furfural and its derivatives are multipurpose intermediates and can replace petroleum based building blocks that are used to make resins, pharmaceuticals, and fine chemicals.
  • Furfural also has applications in the refining of lubricating oil, removing aromatics from diesel, and as fungicide and nematocide.
  • US 7572925 B2 discloses process for converting fructose to 5-hy oxymethylfiirfural (HMF) using biphasic reactor containing a reactive aqueous phase and an organic extracting phase.
  • the acid catalyst is selected from the group consisting of heteropolyacids, HC1, HN0 3 , H 2 S0 4 , H 3 P0 3 , oxalic acid.
  • US 2750394; US 2917520; US 2929823; US 3118912; US 4339387; US 4740605 describe methods to produce HMF.
  • the catalytic activity and recyclability of the ICaT-2 catalyst was tested for the dehydration of carbohydrates to furfurals.
  • the objective of the present invention is to provide a heterogeneous solid acid catalyst with high surface area, water tolerant, high acidity and mesoporosity. Yet further objective of the present invention is to prepare a synergistic heterogeneous solid catalyst having benefit of Bronsted acidic characteristic of functionalized mesoporous sieve and Lewis acidic characteristic of water tolerant rare earth metal triflates.
  • One another objective of the present invention is to anchor the metal trifluromethane sulfonate on the hexagonal organic-inorganic functionalized mesoporous silicon material via organic linkage.
  • One more objective of present invention is based on covalent attachment of rare earth metal trifluromethane sulfonates on the hexagonal organic-inorganic functionalized mesoporous silica support. This attachments is based on adsorption, ion-exchange or tethering of the catalyst.
  • One more objective of the present invention is to design catalyst composition which can be easily separable and reusable.
  • one of the aspects of the present invention is to provide water tolerance Lewis and Brownsted acidic mesoporous synergistic solid catalyst comprising hexagonal organic- inorganic functionalized mesoporous silica having metal triflate selected from the group consisting of lanthanides, actinides, and IIIB group metals and/or mixture thereof.
  • the rare earth metal is selected from the group comprising La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and/or mixture thereof.
  • Yet another aspect of the present invention is to prepare heterogeneous catalyst having a surface area in the range of 200 m /g to 850 m /g, pore volume in the rage of 0.1 ml/g to 0.5 ml/g and pore diameter in the range of 20 to 50 A and XRD peak at 2 theta angle being 0-50.
  • a water tolerant mesoporous solid catalyst "ICaT-2" (Institute of Chemical Technology, Mumbai) is prepared by in situ anchoring of metal trifluromethane sulfonate in the hexagonal organic- inorganic functionalized mesoporous sieves.
  • One more objective of the present invention is to check catalytic activity of ICaT-2 catalyst for dehydration of pentose and hexose sugars.
  • a process for preparation of a heterogeneous solid catalyst possessing high surface area, water tolerant, acidity and mesoporosity is disclosed here.
  • the present invention is directed to provide a synergistic heterogeneous solid catalyst having combination of Bronsted acidic characteristics of functionalized organic- inorganic hexagonal mesoporous sieves and Lewis acidic characteristics of water tolerant rare earth metal triflates.
  • Further aspect of the invention is to anchor the rare earth metal trifluromethane sulfonate on the functionalized organic- inorganic hexagonal mesoporous silicon material via organic linkages.
  • the aspect of the present invention is to provide water tolerant Lewis and Brownsted acidic mesoporous, synergistic solid catalyst comprising of functionalized organic- inorganic hexagonal mesoporous silica having metal trifluromethane sulfonate selected from the group consisting of Lanthenides, Actinides, and IIIB group elements and/or mixture thereof.
  • the catalytically active rare earth metal is selected from the group comprising La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and/or mixture thereof.
  • the present invention is based on the development of water tolerant heterogeneous catalysts (ICaT-2) having a surface area in the range of 200 m 2 /g to 850 m 2 /g, pore volume in the rage of 0.1 ml/g to 0.5 ml/g and pore diameter in the range of 20 to 50
  • IaT-2 water tolerant heterogeneous catalysts
  • Drawing 2 Scanning Electron Microscope images of one of catalyst at various
  • the present invention is related to catalyst composition (ICaT-2) comprising of rare earth metal in the form of trifluromethane sulfonate anchored with hexagonal organic -inorganic functionalized mesoporous silica having surface area in the range of 200-850 m 2 /g; pore volume in the range of 0.1-0.5 ml/g and pore diameter in the range 20-50 A.
  • catalyst composition comprising of rare earth metal in the form of trifluromethane sulfonate anchored with hexagonal organic -inorganic functionalized mesoporous silica having surface area in the range of 200-850 m 2 /g; pore volume in the range of 0.1-0.5 ml/g and pore diameter in the range 20-50 A.
  • Process for production of catalyst composition comprising the following steps of:
  • the hexagonal organic - inorganic functionalized mesoporous silica is prepared by reacting silicate precursor with organofunctionalised silica in the presence of C8-C 14 template.
  • Organic template removed through solvent extraction by using ethyl alcohol and/or by calcination.
  • the rare earth metal is selected from the group comprising La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and/or mixture thereof.
  • the catalyst shows excellent activity for production of biomass based chemicals and the catalyst is used in an amount of 0.1 to 15 % wt/wt of the reaction mixture.
  • the catalyst is easily separable and has excellent reusability.
  • heterogeneous solid catalyst having high surface area, water tolerance, acidity and mesoporosity is prepared.
  • heterogeneous solid acid catalyst comprises of silicon metal as basic backbone having hexagonal mesoporosity.
  • Aforesaid catalyst of the present invention has organic linkage to the silicon backbone.
  • the functionality is incorporated either by co-condensation or post grafting techniques by using thio-containing silane.
  • the mesoporous molecular sieves of the present invention are prepared from alkoxide of silica with primary amine as a templating agent, the said primary amine having carbon atoms from 8 to 14.
  • the heterogeneous catalyst comprises of rare earth trifluromethane sulfonate anchored on organic-inorganic hexagonal mesoporous silica as a support.
  • the metal incorporated in the catalyst is metal ions, selected from rare earth group consisting of La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb in the form of chloride or nitrate.
  • metal ions selected from rare earth group consisting of La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb in the form of chloride or nitrate.
  • One of the embodiments of the present invention is the pore functionalized with sulfonic acid group, as ion-exchanger with the said rare earth chlorides or nitrates, to form corresponding rare earth incorporated sulfonic acid functionalised organic- inorganic hexagonal mesoporous silica.
  • the said rare earth incorporated sulfonic acid functionalized organic- inorganic hexagonal silica is treated with trifluromethane sulfonic acid to form corresponding rare earth metal trifluromethane sulfonate anchored on organic- inorganic hexagonal mesoporous silica.
  • the said ICaT-2 catalyst composition has the specific surface area in the range 200 m 2 /g to 850 m 2 /g.
  • the said ICaT-2 catalyst composition has pore diameter in the range of 20-50 A.
  • the present invention discloses post grafting and co-condensation methods to prepare hexagonal organic-inorganic functionalized mesoporous silica with sulfonic acid pore fictionalization.
  • the active support is prepared by post grafting method.
  • a primary amine is dissolved in aqueous alcohol.
  • Tetraethyl orthosilicate is added under vigorous stirring. The precipitate is separated and template is removed by calcinations to form the hexagonal mesoporous silica. It was further grafted with sulfonic group into active hexagonal organic- inorganic functionalized mesoporous silica as support.
  • active hexagonal organic- inorganic functionalized mesoporous silica is prepared by co-condansation method.
  • a primary amine is dissolved aqueous alcohol.
  • Tetraethyl orthosilicate and thio silane is added under vigorous stirring.
  • the reaction mixture is allowed for aging 5 to 30 h at temperature range 50 to 100 °C.
  • the template was removed to get the active hexagonal organic- inorganic functionalized mesoporous silica support.
  • Lewis acidity was incorporated to the active hexagonal organic- inorganic functionalized mesoporous silica support by metal triflates on it. It leads to the ICaT- 2 catalyst.
  • This ICaT-2 catalyst is characterized by several analytical techniques such as thermogravimetric analysis, NH 3 -temperature programmed desorption (NH 3 -TPD), BET-surface area and pore volume measurements, elemental analysis by energy dispersive X-ray spectroscopy, surface morphology by scanning electron microscope (SEM), X-ray diffraction analysis (XRD).
  • Themogavimetric analysis (TGA) and Differential thermal analysis (DTA) discloses the thermal stability of the ICaT-2 catalyst (Drawing 5).
  • the said catalyst has the thermal stability in the range of 300 °C to 400 °C more. preferably around 350 °C.
  • the NH 3 -TPD profile suggests that ICaT-2 possesses a large number of acid sites with medium acid strength (Drawing 3).
  • Drawing 3 represents the NH 3 -TPD profile of fresh and used ICaT-2 after reaction.
  • the used catalyst also possesses the same acid strength after reaction.
  • ICaT-2 catalyst has good reusability and water tolerance.
  • One more embodiments of the present invention are that the ICaT-2 catalyst, which comprise of rare earth metal ion in the range of 0.1 to 20 mass percentage to the total mass percent of the catalyst.
  • Another aspect of the present invention is to prepare the aforesaid ICaT-2 ecofriendly heterogeneous catalyst having a surface area in the range of 200m 2 /g to 850 m 2 /g, pore volume in the rage of 0.1 ml/g to 0.5 ml/g, a pore diameter in the range of 20 to 50 A and XRD peak at 2 theta angle being 0 to 50.
  • One more embodiment of the present invention involves checking the catalytic activity ICaT-2 catalyst in the field of biomass based chemicals.
  • One more embodiment of the present invention is to check the catalyst activity of ICaT-2 by dehydration of xylose to furfural.
  • furfural is manufactured using ICaT-2 to gives excellent conversion of xylose with high efficiency and selectivity.
  • the ICaT-2 catalyst is easily separable, regenerable and reusable.
  • One of the embodiment of the present invention is the catalyst activity of the ICaT-2 is done for dehydration of fructose to 5-hydroxymethylfurfural (HMF).
  • HMF is the key chemical for the biomass based chemicals and has very huge industrial potential. The excellent conversion of fructose was observed to get excellent yield of HMF.
  • the ICaT-2 has excellent catalytic activity and only 0.1 to 15 % catalyst required to get furfural and 5- hydroxymethylfurfural in excellent yield.
  • the hexagonal organic-inorganic mesoporous silicate was prepared by dissolving 10 g Dodecyl amine in 43 g of ethanol. 60 g of tetraethyl orthosilicte was added under vigorous stirring to it. The reaction mixture was aged for 5 h at 30 °C. White coloured precipitate was dried. The template was removed either by calcining the resulting material at 250 °C in air or by washing the material twice in 150 ml ethanol.
  • ICaT-2 is prepared by a co-condensation sol-gel route.
  • Dodecyl amine was dissolved in ethanol.
  • Mixture of tetraethyl orthosilicate and 3- (mercaptopropyl)trimethoxysilane were added to the above solution. It is treated with lanthanum chloride (400 mg) for 2 h.
  • the slurry was filtered and treated with trifluromethanesulfonic acid at 30 °C for 2 h.
  • the slurry was filtered and washed with water and dried under vacuum to get the active ICaT-2 catalyst.
  • the reusability of the catalyst was tested by conducting four run (Table G). After the reaction catalyst was filter and refluxed in 50 cm 3 of methanol for 30 min, to remove any adsorbed material from the catalyst surface and pores, and then dried at 120 °C for 2 h. reaction was performed by reacting 0.025 mol of xylose, 0.01 g cc of used catalyst, 100 ml water as solvent and reaction was performed at 180 °C for 2 h.
  • the ICaT-2 catalyst has excellent reusability and can make the process efficient.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un catalyseur acide hétérogène hydro-compatible (ICaT-2). Le catalyseur selon l'invention comprend des métaux de terre rare se présentant sous la forme de trifluromethansulphonate ancré avec de la silice mésoporeuse fonctionnalisée organique-minérale hexagonale en tant que métal de base, par l'intermédiaire de liaison organique-minéral. Ladite composition de catalyseur présente une surface spécifique de l'ordre de 200 m2/g à 850 m2/g et le diamètre de pore est de l'ordre de 20-50 Å. Le catalyseur ICaT-2 s'est avéré avoir une activité élevée et pouvoir être réutilisé pour des produits chimiques à base de biomasse.
PCT/IN2011/000102 2010-09-03 2011-02-18 Composition de catalyseur (icat-2) comprenant du métal de terre rare Ceased WO2012029071A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IN2442/MUM/2010 2010-09-03
IN3052MU2010 2010-11-03
IN3052/MUM/2010 2010-11-03
IN2442MU2010 IN268182B (fr) 2010-09-03 2011-02-18

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WO2012029071A2 true WO2012029071A2 (fr) 2012-03-08
WO2012029071A3 WO2012029071A3 (fr) 2012-06-14

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PCT/IN2011/000048 Ceased WO2012038969A1 (fr) 2010-09-03 2011-01-24 Procédé de conversion de fructose en 5-hydroxyméthylfurfural à l'aide d'un catalyseur de silice mésoporeuse imprégné avec des métaux de terres rares
PCT/IN2011/000102 Ceased WO2012029071A2 (fr) 2010-09-03 2011-02-18 Composition de catalyseur (icat-2) comprenant du métal de terre rare

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CN115806535A (zh) * 2021-09-14 2023-03-17 中国科学院大连化学物理研究所 一种5-羟甲基糠醛的制备方法

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CN103028424A (zh) * 2013-01-10 2013-04-10 厦门大学 用于5-羟甲基糠醛合成的固体酸催化剂及其制备方法

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