WO2004069747A1 - Procede de production d'un silicate mesoporeux tridimensionnel hautement regulier - Google Patents

Procede de production d'un silicate mesoporeux tridimensionnel hautement regulier Download PDF

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Publication number
WO2004069747A1
WO2004069747A1 PCT/JP2004/001204 JP2004001204W WO2004069747A1 WO 2004069747 A1 WO2004069747 A1 WO 2004069747A1 JP 2004001204 W JP2004001204 W JP 2004001204W WO 2004069747 A1 WO2004069747 A1 WO 2004069747A1
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WO
WIPO (PCT)
Prior art keywords
producing
mesoporous silicate
highly ordered
silicate
basic catalyst
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PCT/JP2004/001204
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English (en)
Japanese (ja)
Inventor
Masahiko Matsukata
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Waseda University
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Publication of WO2004069747A1 publication Critical patent/WO2004069747A1/fr

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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites

Definitions

  • the present invention relates to a method for producing a three-dimensional highly ordered mesoporous silicate having mesopores having a uniform diameter and usable as an adsorbent, a catalyst carrier, a reaction field of a catalytic reaction, and the like.
  • Mesoporous silicate is a porous material having a large specific surface area and has large pores as compared with zeolite.
  • pores having a pore size of 20A or less such as zeolite are called micropores
  • pores having a pore size of 20 to 500A such as silica gel are called mesopores.
  • the pore size of mesoporous silicate has less variation than silica gel or activated carbon known as mesoporous material. For this reason, it has attracted much attention as a reaction field for selective catalytic reactions involving large molecules to some extent, not limited to the use of conventional porous materials such as adsorption, separation, and catalyst carriers.
  • Mesoporous silicate can be synthesized from an aqueous solution containing a silica source, an organic template, and a catalyst for adjusting pH.
  • the aqueous solution containing the sily power source is stirred and gelled, and the obtained gel is kept at 100 ° C or more for one to several days. Then, the product is sintered at 550 ° C for about 6 hours to obtain mesoporous silicate.
  • a method for producing mesoporous silicate using tetraethoxysilane, using a quaternary ammonium salt as an organic template, and using a strong base such as sodium hydroxide or a strong acid such as hydrochloric acid as a catalyst is disclosed.
  • Mesoporous silicate can be synthesized by a short reaction time, and three types of mesoporous silicates, hexagonal, cubic, and lamellar, can be selected by controlling the type of organic template, reaction temperature, and mixing ratio of raw materials.
  • strong acids or strong bases can be used as catalysts. Requires the use of corrosion-resistant reaction vessels
  • Japanese Patent Application Laid-Open No. Hei 10-17319 discloses that sodium silicate as an aqueous solution of silica is added little by little to an aqueous solution of hexadeciridirubinium chloride adjusted to about pH 7 with hydrochloric acid, and the resulting gel is cooled at room temperature.
  • the method discloses a method for producing a mesoporous silicate by drying after stirring for 3 hours at a temperature of 550 ° C. for about 6 hours.
  • an object of the present invention is to provide a method for producing a three-dimensional highly ordered mesoporous silicate by a simple process without using a strong acid or a strong base. Disclosure of the invention
  • the present inventor has found that by gradually adding a silica source such as tetraethoxysilane to an aqueous solution containing a weakly basic catalyst such as ammonia and an organic template, the silicon source is The present inventors have found that silicates having mesopores which are decomposed and regularly oriented are formed, and arrived at the present invention.
  • a silica source such as tetraethoxysilane
  • a weakly basic catalyst such as ammonia and an organic template
  • the method for producing a mesoporous silicate according to the present invention is characterized in that a mixture of a silica source, an organic template, a basic catalyst, and water is gelled, dried and calcined to obtain a three-dimensional highly regular mesoporous silicate.
  • the method for producing a silicate is characterized in that the basic catalyst is weakly basic.
  • the mixture to which the sily power source is gradually added by dropping or the like preferably has a pH of 7.5 to 12.
  • the drying temperature of the gel is preferably between 40 and 100 ° C, more preferably between 70 and 90 ° C. Also, it is preferable that the basic catalyst disappears when the gel is dried! / ,.
  • the firing temperature of the dried gel is preferably from 400 to 600 ° C.
  • the basic catalyst is preferably at least one selected from the group consisting of ammonia, amines and salts thereof, and more preferably ammonia.
  • the silica source is tetraethoxysilane or tetramethoxysilane.
  • the organic template is a quaternary ammonium salt.
  • the quaternary ammonium salt is an alkyltrimethylammonium salt, and the alkyl group in the ammonium salt preferably has 8 to 18 carbon atoms.
  • FIG. 1 is a chart showing the X-ray diffraction patterns of the gel prepared in Example 1 and its dried product.
  • FIG. 2 is a chart showing the X-ray diffraction pattern of the fired body of the gel and the mesoporous silicate prepared in Example 1.
  • FIG. 3 is a chart showing an X-ray diffraction pattern of the mesoporous silicate prepared in Example 2.
  • FIG. 4 is a chart showing an X-ray diffraction pattern of the mesoporous silicate prepared in Example 3.
  • a raw material is a silicon source, an organic template and a basic catalyst.
  • the silica source is not particularly limited as long as it is hydrolyzed by a basic catalyst in an aqueous solution to form a silicate, and a general silica source can be used.
  • a general silica source can be used.
  • Specific examples include silicon alkoxides such as tetraethoxysilane (tetraethyl orthosilicate, TEOS) and tetramethoxysilane (tetramethyl orthosilicate, TMOS), colloidal silica, fumed silica, and water glass.
  • a silicon alkoxide is preferable.
  • Organic template is not particularly limited as long as it functions as a type of mesopore when the mesoporous silicate is formed, and can be decomposed and removed from the mesopore when heated to about 500 to 550 ° C.
  • General substances such as a surfactant, an alcohol and the like can be used.
  • the surfactant is preferably a quaternary ammonium salt, and the quaternary ammonium salt is preferably an alkyltrimethylammonium salt.
  • the alkyl group in the alkyltrimethylammonium salt preferably has 8 to 18 carbon atoms. Specific examples include cetyltrimethylammonium, myristyltrimethylammonium, decyltrimethylammonium, and derivatives thereof.
  • Alcohols having about 4 to 10 carbon atoms and moderate polarity are preferred. Examples include 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, and 2-methyl-1-pentanol.
  • the basic catalyst a catalyst exhibiting weak basicity in an aqueous solution is used. Further, those having a buffering effect in an aqueous solution and having an effect of maintaining the aqueous solution to be weakly basic are more preferable.
  • the weakly basic catalyst is preferably at least one selected from the group consisting of ammonia, amines and salts thereof. Amines include nitrogen-containing heterocyclic compounds such as pyridine and piperidine.
  • Rinmins may be primary amine, secondary amine or tertiary amine. Specific examples include triethylamine, ethylenediamine, trimethylamine, methylpirididine, N-methylpyridine, ethylenediamine and the like.
  • ammonium salt examples include ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium sulfide, ammonium bromide, ammonium carbonate, and ammonium hydrogen carbonate.
  • CTAB bromide cetyltrimethylammonium
  • the aqueous solution preferably has a pH of about 9 to about 12, and more preferably about pH 11.
  • the concentration of CTAB is preferably about 2.5 to 5% by mass.
  • tetraethoxysilane To this aqueous solution is added tetraethoxysilane. What is necessary is just to add so that the mixture after addition of tetraethoxysilane may become uniform, for example, it is dripped, stirring an aqueous solution.
  • the dropping rate is not particularly limited, but is preferably 1 g / min or less per 10 g of the aqueous solution.
  • the amount of tetraethoxysilane to be dropped is preferably about 10 to 30% by mass based on water.
  • the mesoporous silicate of the present invention has a structure in which micropores having extremely uniform pore sizes are arranged in a hexagonal manner. Such a microporous structure has excellent three-dimensional high regularity.
  • the aqueous solution gelles After the end of the dropping, the stirring of the mixture in which the gel was started is stopped, and the mixture is kept still at room temperature (aging). During aging, the gelation of the mixture proceeds as the silicate synthesis reaction proceeds, and the pH of the mixture changes slightly toward neutral. For example, when the pH of the mixture at the end of the dropping of tetraethoxysilane is 11, the mixture after aging has a pH of about IO.
  • the temperature of the drying step is preferably from 40 to 100 ° C, more preferably from 70 to 90 ° C.
  • the method for drying is not particularly limited, and includes a method of heating using a heater, a method of using a rotary pump to deaerate the inside of the container containing the mixture, and the like. These methods may be used together.
  • the gelled mixture is heated to about 80 ° C by a heater and kept for about one hour, the ammonia odor disappears and the pH of the mixture becomes approximately 7. This is probably due to the evaporation of ammonia in the mixture. 2.5 to 3 hours drying time Then, a white solid precipitates.
  • the precipitated solid is a porous body having hexagonal mesopores. The pore size of this mesoporous body is about 30 to 50A.
  • the mesoporous silicate is prepared by firing the obtained mesoporous body and removing CTAB, unreacted silica source, and the like. It is preferable to bake in a furnace heated to 500 to 550 ° C for about 6 hours. In order to prevent the organic substances taken into the mesoporous material from burning locally and destroying the structure of the mesopores, at least at the beginning of the firing temperature raising process, at least up to about 320 ° C, the inside of the furnace should be argon or the like. It is preferable to use an inert gas atmosphere.
  • mesoporous silicate manufacturing methods such as hydrothermal synthesis
  • the mesopores after firing are smaller than before firing, whereas in the manufacturing method of the present invention, the pore diameter changes before and after firing.
  • a mesoporous silicate having a relatively large pore diameter of 30 to 50 A can be produced.
  • a nitrogen-containing compound such as ammonia as the basic catalyst can prevent the catalyst from breaking the mesoporous silicate during firing.
  • Mesoporous silicates with large pore diameters are suitable as catalytic reaction sites because relatively large molecules as well as small molecules can be introduced into the pores. Further, since the production method of the present invention does not include steps such as filtration and washing with water, all the steps can be performed in one pot, which is excellent in terms of simplifying the steps.
  • CTAB (manufactured by Merck-Schchart, purity: 99%) was dissolved in 5.2 mol of purified water, and 2.4 mol of aqueous ammonia (29% aqueous solution, manufactured by Kanto Chemical Co., Ltd.) was added to prepare an alkaline aqueous solution. While stirring this aqueous solution, 1 mol of tetraethoxysilane (manufactured by Merck-Schchart, purity 98%) was added dropwise. Then, the mixture containing tetraethoxysilane was aged for about 1 hour to gel the mixture.
  • FIGS. 1 and 2 show the X-ray diffraction patterns of the gelled mixture, its dried product, and its fired product.
  • A is the gel after aging
  • B is the gel after drying at 80 ° C for 1 hour
  • C is the gel after drying for 2 hours
  • D is the dried body after keeping it at 80 ° C for about 3 hours. Show.
  • a represents a fired body of A
  • a fired body of B c represents a fired body of C
  • a fired body of D a fired body of D.
  • FIG. 3 shows the X-ray diffraction pattern of the dried product.
  • Figure 3 indicates that lamellar mesoporous silicate was formed. Also, when the X-ray diffraction pattern of the fired body was measured, it was found that the diffraction peak had disappeared, indicating that the lamellar structure had disappeared by firing.
  • FIG. 4 shows the X-ray diffraction pattern of the dried product.
  • Figure 4 shows that lamellar mesoporous silicate is formed.
  • a weakly basic catalyst was used as the basic catalyst, and while the aqueous solution containing the basic catalyst and the organic template was stirred, a sili force source was gradually added to gel the aqueous solution to obtain a gel.
  • the silicic acid source is hydrolyzed by the action of the medium, forming silicate while incorporating the organic template. Therefore, a three-dimensional highly ordered mesoporous silicate can be produced at room temperature without using a strong acid or a strong base.
  • the production method of the present invention does not require a step of purifying the reaction intermediate and Z or the final product by filtration, washing with water, and the like, so that the steps are simple.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Silicon Compounds (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production d'un silicate mésoporeux tridimensionnel hautement régulier, selon lequel on forme en gel avec un mélange d'une source de silicium, d'un groupe structurant organique, d'un catalyseur basique et d'eau, on sèche le gel et on le brûle, lequel procédé est caractérisé en ce que le catalyseur basique est faiblement basique.
PCT/JP2004/001204 2003-02-06 2004-02-05 Procede de production d'un silicate mesoporeux tridimensionnel hautement regulier WO2004069747A1 (fr)

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JP2003029044A JP2004262677A (ja) 2003-02-06 2003-02-06 三次元高規則性メソポーラスシリケートの製造方法
JP2003-029044 2003-02-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101961641A (zh) * 2010-10-21 2011-02-02 上海烟草（集团）公司 多孔氧化物干凝胶吸附材料及其制备方法

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JP4956112B2 (ja) * 2006-09-22 2012-06-20 三菱自動車工業株式会社 Ｈｃトラップ触媒の調製方法
JP5512984B2 (ja) * 2009-02-19 2014-06-04 花王株式会社 メソポーラスシリカ粒子の製造方法
CN111807380B (zh) * 2020-07-24 2023-06-27 山东科技大学 一种一锅制备三维多级结构碱式硅酸镍催化剂的方法
CN114572989B (zh) * 2022-05-06 2022-09-16 北洋研创(天津)科技有限公司 二氧化硅纳米片及其制备方法与叠层结构

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHENG C-F. ET AL: "Optimal parameters for the synthesis of the mesoporous molecular sieve [Si]-MCM-41", J. CHEM. SOC., FARADAY TRANS., vol. 93, no. 1, 1997, pages 193 - 197, XP000642852 *
WANG L. ET AL: "Synthesis of mesoporous silica material with sodium hexafluorosilicate as silicon source under ultra.low surfactant concentration", J. MATER. SCI. LETT., vol. 20, no. 3, 2001, pages 277 - 280, XP002979567 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101961641A (zh) * 2010-10-21 2011-02-02 上海烟草（集团）公司 多孔氧化物干凝胶吸附材料及其制备方法

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