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WO1997032815A1 - Materiau mesoporeux - Google Patents

Materiau mesoporeux Download PDF

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Publication number
WO1997032815A1
WO1997032815A1 PCT/GB1997/000635 GB9700635W WO9732815A1 WO 1997032815 A1 WO1997032815 A1 WO 1997032815A1 GB 9700635 W GB9700635 W GB 9700635W WO 9732815 A1 WO9732815 A1 WO 9732815A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
composition
pore size
polysilicic acid
mesoporous silica
Prior art date
Application number
PCT/GB1997/000635
Other languages
English (en)
Inventor
Graham John Bratton
Karon Doreen Buck
Timothy De Villiers Naylor
Original Assignee
Graham John Bratton
Karon Doreen Buck
Timothy De Villiers Naylor
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 Graham John Bratton, Karon Doreen Buck, Timothy De Villiers Naylor filed Critical Graham John Bratton
Priority to AU21018/97A priority Critical patent/AU723919B2/en
Priority to EP97906275A priority patent/EP0897373A1/fr
Publication of WO1997032815A1 publication Critical patent/WO1997032815A1/fr

Links

Classifications

    • 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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • 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
    • 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 porous amorphous structures and methods of making them, in particular it relates to compositions with large pore sizes which can contain metal ions and can be used as adsorbents and catalysts.
  • This US Patent discloses a method of forming porous compounds by reacting certain alumino-silicates with an organic directing agent which is a quaternary ammonium compound under specified conditions to precipitate the compound. It is known from an article by S Gontier and A Tuel in 'Zeolites' 15:601-610, 1995 to form titanium containing mesoporous silicas by reacting a solution of tetraethyl orthosilicate with a solution of tetraisopropyi orthotitanate and adding this reaction mixture to a long chain alkylamine as a templating agent to obtain a Ti-containing mesoporous silica with enlarged pore structure.
  • Silica materials are known which are amorphous in the sense that they have no long range order and are characterised with a pore size distribution over a wide range of sizes and have no X-ray diffraction pattern. Their porosity arises form the voids between dense particles of silica.
  • Paracrystalline materials such as the transitional aluminas which have broad X-ray peaks.
  • the microstructure of these materials consists of tiny crystalline regions of condensed alumina phases and the porosity of these materials results from irregular voids between these regions.
  • the pore size variability is typically very wide in these materials.
  • Zeolite membranes are known with a narrow defined pore size range and are commonly referred to as molecular sieves, however these have a pore size below 15 Angstroms and are referred to in detail in US Patent 5,108,725 these materials are described as having a microporous structure.
  • the pore size can be measured by using the technique of bubble point pressure as defined in ISO4003 or by nitrogen adsorbtion using the Polimore Head method.
  • the composition should have a regular pore size with a narrow pore size distribution, e.g. the second and third quartile are within the specified range, the pore size distribution may be measured by a Coulter Porometer (Trademark).
  • the structure of the material can be in the form of a chain of molecules linked together in a linear fashion to form what is substantially a chain or it can be in the form of a substantially planar structure of molecules linked together substantially in one plane or it can be in the form of a three dimensional structure with molecules linked together accordingly.
  • the materials of the invention preferably have a benzene adsorption capacity of greater than 10 grams benzene/ 100 grams at 50 torr and 25 degrees C as measured in US Patent 5, 108,725.
  • the materials of the present invention essentially comprise a series of polysilicic acid units linked together, each unit comprising a polysilicic acid molecule as described in GB Patent Application 9316350.9 and comprising a plurality of three dimensional species linked together with each species either having silicon atom bridges with an oxygen atom between each silicon atom or hydroxyl groups on the silicon atoms. The linking together of these units forms the structure of the compounds of the invention.
  • compositions of the present invention can be formed by the condensation of a polysilicic acid from solution in the presence of a surfactant.
  • the polysilicic acid preferably has a weight average molecular weight of 700 to 2000. This acid is preferably dissolved in an alcohol such as ethanol or butanol to form the solution.
  • the surfactant is thought to act to hold the individual units in a suitable orientation and separation to form the mesoporous compounds of the invention when they are joined together.
  • the surfactant is preferably a compound which is at least partially miscible with silicic acid solution and can be in the form of a suspension or solution, e.g. in an alcohol.
  • the surfactant can be a cationic, anionic or non-ionic.
  • Suitable surfactants include amines, quaternary ammonium compounds and siloxanes.
  • Suitable amines include long chain alkyl amines, e.g. containing 6-25 carbon atoms.
  • Suitable quaternary ammonium compounds include tetra-alkyl ammonium compounds.
  • the composition of the present invention can be formed by adding a solution of the silicic acid to a solution or suspension of the surfactant to form the composition.
  • other silicon containing compounds can be incorporated in the silicic acid solution to modify the structure of the composition obtained.
  • Suitable compounds include silanes, siloxanes, and functionalised silanes and siloxanes, etc.
  • the polysilicic acid solution is mixed with the surfactant solution, preferably with vigorous stirring and the product filtered and dried.
  • the material is preferably calcined, e.g. above 350 degrees C
  • composition of the present invention can incorporate metals in addition to or in place of the silicon atoms to modify the pore structure of the material.
  • Suitable metals include titanium, zirconium and any metal which can form, e.g. an oxide, hydroxide, alkoxide, acetonate or acetyl acetonate and any other functionality which can undergo a condensation reaction and which can form a solution or gel and which can condense to form a polymeric type structure.
  • the pore size of the composition formed by the process of the invention will depend on the conditions and the presence of other metals.
  • compositions of the present invention can be used in filtration, the pore size being larger than in conventional zeolite membranes enables them to be used as filter media for separations which are not possible using zeolite membranes.
  • Their robustness and temperature resistance compared with polymeric membranes enables them to be used in separations which are not possible using polymers.
  • They can also be used as catalyst supports e.g. for preparing polymers such as polyolefins e.g. polyethylene, polypropylene etc. as well as other polymers for example as supports for metallic catalysts such as titanium based catalysts where their pore size enables specific control of the polymer formed to be achieved and in other catalytic processes.
  • Solution A was added slowly to solution B under vigorous stirring conditions for about 15 mins.
  • a white solid was precipitated which was washed several times with distilled water and dried in a fume cupboard for 24 hours.
  • the solid was calcined at 650°C for six hours.
  • the X ray diffraction pattern of the HMS product was taken and was compared with that of HMS fabricated from TEOS as in the S Gontier and A Tuel article referred to above and was found to be identical with a single peak at 3.2°- D- Spacing.
  • a first solution (mixture A) was prepared by adding hexadecylamine (0 027 mol) into a beaker containing distilled water (3 6 mol) and hydrochloric acid (0 002 mol) After the mixture was stirred vigorously for 30 minutes at room temperature, a thick creamy white acidic surfactant mixture was formed
  • a second solution mixture B was prepared by adding silicic acid/n-butanol solution (containing 0 1 mol Si) to absolute ethanol (0 65 mol)
  • the silicic acid/n-butanol solution was prepared by adding 2 gram of sodium silicate powder into 8 35 gram of distilled water with constant stirring for 15 minutes
  • the sodium silicate solution was added slowly into 100ml of cold 3M hydrochloric acid with constant stirring
  • the mixture was stirred vigorously for 2 hours and the silicic acid extracted with n-butanol to form the silicic acid/n-butanol solution

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Analytical Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Il est possible d'obtenir un matériau en silice mésoporeux en condensant un acide polysilicique à partir d'une solution en présence d'un tensio-actif tel qu'une akylamine à chaîne longue. Ces matériaux mésoporeux ont une grosseur de pores importante qui leur permet d'être utilisés en filtration comme support de catalyseur, et dans des procédures de séparation dans lesquelles les zéolites classiques ont une grosseur de pores trop petite.
PCT/GB1997/000635 1996-03-08 1997-03-07 Materiau mesoporeux WO1997032815A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU21018/97A AU723919B2 (en) 1996-03-08 1997-03-07 Mesoporous material
EP97906275A EP0897373A1 (fr) 1996-03-08 1997-03-07 Materiau mesoporeux

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9606002.5 1996-03-08
GBGB9606002.5A GB9606002D0 (en) 1996-03-08 1996-03-08 Mesoporous material

Publications (1)

Publication Number Publication Date
WO1997032815A1 true WO1997032815A1 (fr) 1997-09-12

Family

ID=10790816

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1997/000635 WO1997032815A1 (fr) 1996-03-08 1997-03-07 Materiau mesoporeux

Country Status (5)

Country Link
EP (1) EP0897373A1 (fr)
AU (1) AU723919B2 (fr)
CA (1) CA2248060A1 (fr)
GB (1) GB9606002D0 (fr)
WO (1) WO1997032815A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999052820A1 (fr) * 1998-04-11 1999-10-21 Degussa-Hüls Aktiengesellschaft Procede de production de peroxyde d'hydrogene par synthese directe
WO1999065822A1 (fr) * 1998-06-18 1999-12-23 The Dow Chemical Company Nouveau procede de fabrication de materiaux cristallins mesoporeux et materiaux ainsi fabriques
US6334988B1 (en) * 1998-08-21 2002-01-01 The University Of Vermont And State Agricultural College Mesoporous silicates and method of making same
US6500402B1 (en) * 1998-01-13 2002-12-31 Metallgesellschaft Aktiengesellschaft Catalyst for oxidizing SO2 to SO3 and utilization of the catalyst in a method for producing sulfuric acid
US7018596B2 (en) * 1997-11-21 2006-03-28 Asahi Kasei Kabushiki Kaisha Mesoporous silica, process for the preparation of the same, and use thereof
US8815200B2 (en) 2004-12-02 2014-08-26 The University Of Vermont And State Agricultural College Mesoporous inorganic oxide spheres and method of making same
CN115785948A (zh) * 2022-12-09 2023-03-14 上海海优威新材料股份有限公司 一种在胶膜中能延长转光粉寿限的保护结构
CN117487470A (zh) * 2023-11-14 2024-02-02 苏州易昇光学材料股份有限公司 长效抗老化eva胶膜及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991011390A2 (fr) * 1990-01-25 1991-08-08 Mobil Oil Corp Materiau synthetique cristallin et poreux, et procede de synthese et d'utilisation
US5108725A (en) * 1990-01-25 1992-04-28 Mobil Oil Corp. Synthesis of mesoporous crystalline material
US5143879A (en) * 1991-07-18 1992-09-01 Mobil Oil Corporation Method to recover organic templates from freshly synthesized molecular sieves
GB2269377A (en) * 1992-08-07 1994-02-09 British Petroleum Co Plc Silica gel and process for making it from polysilicic acid
WO1995030625A1 (fr) * 1994-05-10 1995-11-16 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un tamis moleculaire a larges pores

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991011390A2 (fr) * 1990-01-25 1991-08-08 Mobil Oil Corp Materiau synthetique cristallin et poreux, et procede de synthese et d'utilisation
US5108725A (en) * 1990-01-25 1992-04-28 Mobil Oil Corp. Synthesis of mesoporous crystalline material
US5143879A (en) * 1991-07-18 1992-09-01 Mobil Oil Corporation Method to recover organic templates from freshly synthesized molecular sieves
GB2269377A (en) * 1992-08-07 1994-02-09 British Petroleum Co Plc Silica gel and process for making it from polysilicic acid
WO1995030625A1 (fr) * 1994-05-10 1995-11-16 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un tamis moleculaire a larges pores

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7018596B2 (en) * 1997-11-21 2006-03-28 Asahi Kasei Kabushiki Kaisha Mesoporous silica, process for the preparation of the same, and use thereof
US6500402B1 (en) * 1998-01-13 2002-12-31 Metallgesellschaft Aktiengesellschaft Catalyst for oxidizing SO2 to SO3 and utilization of the catalyst in a method for producing sulfuric acid
WO1999052820A1 (fr) * 1998-04-11 1999-10-21 Degussa-Hüls Aktiengesellschaft Procede de production de peroxyde d'hydrogene par synthese directe
WO1999065822A1 (fr) * 1998-06-18 1999-12-23 The Dow Chemical Company Nouveau procede de fabrication de materiaux cristallins mesoporeux et materiaux ainsi fabriques
US6334988B1 (en) * 1998-08-21 2002-01-01 The University Of Vermont And State Agricultural College Mesoporous silicates and method of making same
US8815200B2 (en) 2004-12-02 2014-08-26 The University Of Vermont And State Agricultural College Mesoporous inorganic oxide spheres and method of making same
CN115785948A (zh) * 2022-12-09 2023-03-14 上海海优威新材料股份有限公司 一种在胶膜中能延长转光粉寿限的保护结构
CN117487470A (zh) * 2023-11-14 2024-02-02 苏州易昇光学材料股份有限公司 长效抗老化eva胶膜及其制备方法

Also Published As

Publication number Publication date
CA2248060A1 (fr) 1997-09-12
AU723919B2 (en) 2000-09-07
AU2101897A (en) 1997-09-22
GB9606002D0 (en) 1996-05-22
EP0897373A1 (fr) 1999-02-24

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