WO2006030741A1 - シリカ多孔体結晶の製造方法 - Google Patents
シリカ多孔体結晶の製造方法 Download PDFInfo
- Publication number
- WO2006030741A1 WO2006030741A1 PCT/JP2005/016769 JP2005016769W WO2006030741A1 WO 2006030741 A1 WO2006030741 A1 WO 2006030741A1 JP 2005016769 W JP2005016769 W JP 2005016769W WO 2006030741 A1 WO2006030741 A1 WO 2006030741A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- crystal
- silicon
- porous silica
- balta
- concentration region
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
Definitions
- the present invention relates to a method for efficiently producing a porous silica as a large single crystal.
- Zeolite which is known as a compound having a crystalline microporous structure, that is, an aluminosilicate having a composition represented by the following general formula, contains a large amount of ion-exchangeable cation and has a three-dimensional network structure. It has the shape and size of cavities and pores unique to the crystal.
- Ml is a monovalent cation such as Na + 'K +
- M2 is a divalent cation such as Ca ++ , Sr ++, etc.
- m ⁇ n is indefinite
- the microporous crystals such as zeolite described above have unique functions such as adsorption and ion exchange as characteristics based on the structure and chemical composition of the cavities, and molecular sieves and clusters that screen molecules according to size. In addition, it is used for applications such as confinement of catalysts or catalyst carriers, and other engineering applications are also being attempted in various fields such as electronic devices and sensors.
- the silica porous crystal of the present invention is a kind of the above-mentioned zeolite, and is a crystal composed only of silicon and oxygen, and a representative example thereof is silicalite.
- the above zeolite has regular nano-sized pores, and by synthesizing a semiconductor, a conductive polymer, etc. inside the pores, it has physical properties that are quantumally unique as an electronic device or an optical device. Can be expressed. When used as a sensor, high selectivity and high responsiveness can be expected.
- zeolite or the like usually has a crystal size of several / zm or less, and it is difficult to regularly arrange crystals in parallel. When used for semiconductor elements, etc., it is important to arrange them regularly, and it is also necessary to arrange individual sizes. On the other hand, if the zeolite has a crystal size of 0.5 mm, preferably several mm, an element with a side of 0.5 mm or more can be easily manufactured and processed into any size or shape.
- the selectivity is such that the outer surface having no adsorption selectivity can be reduced. Therefore, if a large crystal of 0.5 mm or more having a much smaller outer surface ratio can be used, the selectivity can be expected to increase dramatically.
- Patent Document 1 a section of a fused quartz tube is used as a Baluta body, and this is filled in a pressure-resistant reaction vessel to cause a hydrothermal reaction.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2000-34188
- An object of the present invention is to improve these points and to provide a method for efficiently synthesizing a porous silica crystal of 0.5 mm or more with reproducibility.
- the method for producing a porous silica crystal of the present invention is a method for synthesizing a porous silica crystal by a hydrothermal reaction, wherein a high concentration region of silicon is formed in a part of a hydrothermal synthesis vessel, and As a source of a part or all of the skeleton constituent elements of the body crystal, a Balta body made of a compound containing this element and subjected to a surface smoothing treatment so that at least a part thereof is in the high concentration region of silicon.
- the hydrothermal reaction is carried out in the presence of
- a porous silica crystal can be efficiently synthesized as a large-sized single crystal useful for applications such as molecular sieves, electronic devices, and sensors.
- FIG. 1 is a diagram showing one embodiment in which a high concentration region of silicon is formed in a part of a hydrothermal synthesis vessel.
- FIG. 2 is a photomicrograph showing a single crystal formed on a Balta body in Example 1. BEST MODE FOR CARRYING OUT THE INVENTION
- the Balta body in the present invention has a relatively large size unlike a fine powder (about 10 ⁇ m or less, usually submicron order) used as a raw material for conventional hydrothermal synthesis reaction, and has a volume of 'It means a solid body with a small specific surface area relative to the weight.
- the bulk body serves as a growth substrate for porous silica crystals and a source of crystal composition.
- the Balta body needs to have a size that does not dissolve at least in the reaction solution.
- the large porous single crystal of porous silica grows on the surface of the Balta body. If the Balta body dissolves, only a lump of fine crystals is formed at the bottom of the container. Can not. Therefore, it is necessary that the size of the nore body is such that it does not dissolve in the solution, and can support a large single crystal.
- the shape of the Balta body is arbitrary, and various forms such as a spherical body, a massive crushed material, a plate body, a rod or wire body, and a tubular body can be used. There is no upper limit on the size of the Balta body, and it can be used arbitrarily as long as it does not hinder the accommodation in the reaction vessel.
- the material of the Balta body is not particularly limited as long as it has silica power.
- a surface smoothed surface treatment is used as the Balta body.
- This surface smoothing treatment is a treatment to prevent the sharp-cut portion from being present on the cut surface of the Balta body, and can be a method that can smooth the surface such as melting treatment, polishing treatment, cutting treatment, etc. However, it is not limited to these. Among these surface smoothing treatments, melting treatment is preferably used because it is relatively simple.
- the most suitable material for the Balta body is quartz glass.
- a material obtained by coating a material other than silica with silica can be used as a Balta body.
- the Balta body serves only as a base for crystal growth.
- the source of the crystal composition may be only the nodal body, but it is not always necessary to use the whole body as the Balta body.
- a supply source other than the Balta body may be provided.
- powder silica such as colloidal silica, which has been conventionally used conventionally, is used.
- Raw materials can be used.
- a material obtained by coating a material other than silica with silica can be used as a Balta body.
- the Balta body serves only as a crystal growth substrate, it is necessary to add silica powder or a silica nano body as a crystal composition source.
- the present invention it is necessary to form a high concentration region of silicon in a part of the hydrothermal synthesis vessel.
- the purpose of this is to promote crystal formation by creating a partial supersaturation.
- a small container 2 is installed in the hydrothermal synthesis container 1 as shown in FIG.
- body 3 or powdered raw material is added. This is because by adding a small container to form a double structure, a portion having a higher silicon concentration is generated in the small container, particularly in the bottom of the small container, than in the entire reaction container.
- the hydrothermal reaction is carried out by allowing at least a part of the Baltha body to exist in the high concentration region of silicon formed in this manner so that at least a part of the Baltha body is in the high concentration region of silicon.
- a porous silica single crystal is formed on the surface of the Balta body in the high concentration region of silicon.
- the porous silica seed crystal 4 is placed in a high concentration region of silicon, the porous silica crystal is easily formed.
- the porous silica polycrystal is formed in a high-concentration region of silicon, such as the bottom of a small container, but the polycrystal is formed. Therefore, it is preferable to fix the Balta body so that it does not contact the bottom of the small container. When the Balta body is fixed so as not to contact the bottom, only the porous silica single crystal is formed on the surface of the Balta body.
- the force Balta body that forms the polycrystal of the porous silica crystal is fixed away from the bottom force of the small container, so the polycrystal does not cover the Balta body.
- the nano-sized porous silica constituent material formed at the bottom of the small container or the like adheres to the Balta body, from which a porous silica crystal is formed.
- the crystals grow apart from each other. It becomes a single crystal.
- a crystallized silica porous crystal is used as the seed crystal.
- the size of the crystal is not particularly limited, but it is preferably used after being pulverized.
- the porous silica crystal is considered to dissolve after being added to the hydrothermal reaction liquid.
- the porous silica crystal is based on the crystal structure. It is thought that it is easy to form. In particular, when a Balta body is used as the silicon source material, crystals are difficult to form. Therefore, adding a seed crystal has an effect of promoting the formation of a silica porous body crystal.
- the small container used to form the high-concentration region of silicon is a material that can withstand the presence of temperature, the presence of fluorine ions, acidic or alkaline conditions, and contamination of impurity metal ions.
- Tetrafluoroethylene is preferred, but other grease materials can be used as long as they are strong and free from harmful substances.
- the presence of fluorine ions in the hydrothermal synthesis vessel promotes crystal growth, and a single crystal having a large size is obtained with good reproducibility.
- the fluorine ion is not particularly limited as long as it is a compound that becomes a fluorine ion in an aqueous solution, such as hydrogen fluoride and ammonium fluoride.
- an aqueous solution such as hydrogen fluoride and ammonium fluoride.
- silicon is dissolved even in a neutral or acidic solution, and a porous silica crystal can be synthesized.
- the concentration of fluorine ions present in the hydrothermal synthesis container is 0.1 to 1.0 in terms of molar ratio with respect to silicon dioxide dissolved in the container, and 0.2 to 0.8 is more preferred. If this molar ratio is less than 0.1, the effect of fluorine addition is insufficient, and a large single crystal is obtained. It becomes difficult.
- a fused quartz tube section (outer diameter 10 mm, outer diameter 12 mm, height 25 mm) and melted to the extent that the cut surface is smooth (no acute angle part) as a Balta body in a small container made of polytetrafluoroethylene (Thickness lmm, length 25mm) 1. Prepare 5g fixed so that it does not stick to the bottom. Silicalite seed crystal 0. Olg was placed in the bottom of the small container.
- Example 2 Under the same conditions as in Example 1, eight reaction vessels were set for synthesis. As a result, MFI-type zeolite single crystals were formed in all eight reaction vessels.
- the cut surface is melt-processed while being cut as a Balta body in a small container made of polytetrafluoroethylene having an inner diameter of 12 mm and a height of 25 mm, and a fused quartz tube section (outer diameter of 10 mm, wall thickness of 1 mm, length) 25mm) 1.
- a small container made of polytetrafluoroethylene having an inner diameter of 12 mm and a height of 25 mm, and a fused quartz tube section (outer diameter of 10 mm, wall thickness of 1 mm, length) 25mm) 1.
- 5g part of Baltha body on bottom of small container.
- Umuhidorokishido 25 mass 0/0 aqueous solution 7. 27 g of distilled water 10 was diluted with 17g, and the solution was added 46% hydrofluoric acid 0. 63 g to this, the small container The reactor was filled in a pressure-resistant reaction vessel and kept at 200 ° C for 240 hours in a hot air circulating thermostat.
- the Balta body was taken out and washed thoroughly with distilled water. Dry at 20 ° C. On the surface of the Balta body, a crystalline product was formed at an acute angle portion of the cut surface. Most of the crystalline products on the Balta body were MFI-type zeolites. Single crystals with a crystal size of 0.5 mm to l.5 mm are almost adjacent to each other. It was difficult.
- Umuhidorokishido 25 mass 0/0 aqueous solution 7. 27 g was diluted with distilled water 10 17 g, melting and solution plus 46% hydrofluoric acid 1. 08G thereto, the switching section as Balta body A treated fused silica tube section (outer diameter 10mm, wall thickness lmm, length 25mm) 1.5g was filled in a pressure-resistant reaction vessel and kept at 200 ° C for 240 hours in a hot air circulating thermostat.
- the Balta body was taken out, washed thoroughly with distilled water, and dried at 120 ° C. There was no crystalline product on the Balta body surface, only unreacted quartz tubes.
- the cut surface is melt-processed while being cut as a Balta body in a small container made of polytetrafluoroethylene having an inner diameter of 12 mm and a height of 25 mm, and a fused quartz tube section (outer diameter of 10 mm, wall thickness of 1 mm, length) 25mm) 1.
- a small container made of polytetrafluoroethylene having an inner diameter of 12 mm and a height of 25 mm, and a fused quartz tube section (outer diameter of 10 mm, wall thickness of 1 mm, length) 25mm) 1.
- Silicalite seed crystal 0. Olg was placed in the bottom of this small container.
- Comparative Examples 1 and 4 using a fused silica tube section polycrystals were formed on the cut surface, and in particular, it was thought that single crystals could be easily obtained because the amount of crystal formation was small due to the use of seed crystals.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/662,059 US7763223B2 (en) | 2004-09-13 | 2005-09-12 | Method for manufacturing porous silica crystal |
EP05778555A EP2031102B1 (en) | 2004-09-13 | 2005-09-12 | METHOD FOR Manufacturing porous SILICA CRYSTAL |
CA2580391A CA2580391C (en) | 2004-09-13 | 2005-09-12 | Method for manufacturing porous silica crystal |
CN2005800307752A CN101052753B (zh) | 2004-09-13 | 2005-09-12 | 二氧化硅多孔晶体的制造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004265859A JP4719835B2 (ja) | 2004-09-13 | 2004-09-13 | シリカ多孔体結晶の製造方法 |
JP2004-265859 | 2004-09-13 |
Publications (1)
Publication Number | Publication Date |
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WO2006030741A1 true WO2006030741A1 (ja) | 2006-03-23 |
Family
ID=36059994
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2005/016769 WO2006030741A1 (ja) | 2004-09-13 | 2005-09-12 | シリカ多孔体結晶の製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US7763223B2 (ja) |
EP (1) | EP2031102B1 (ja) |
JP (1) | JP4719835B2 (ja) |
KR (1) | KR100893165B1 (ja) |
CN (1) | CN101052753B (ja) |
CA (1) | CA2580391C (ja) |
WO (1) | WO2006030741A1 (ja) |
Families Citing this family (1)
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CN105712356A (zh) * | 2016-01-12 | 2016-06-29 | 西南科技大学 | 一种快速高效功能化改性介孔材料的方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000034188A (ja) * | 1998-07-13 | 2000-02-02 | Japan Chemical Innovation Institute | ミクロ多孔体結晶の製造方法 |
JP2001002410A (ja) | 1999-06-16 | 2001-01-09 | Japan Chemical Innovation Institute | 結晶性ミクロ多孔体の製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5599520A (en) * | 1994-11-03 | 1997-02-04 | Garces; Juan M. | Synthesis of crystalline porous solids in ammonia |
US6350312B1 (en) * | 1999-03-15 | 2002-02-26 | Memc Electronic Materials, Inc. | Strontium doping of molten silicon for use in crystal growing process |
CN1207447C (zh) * | 2002-07-17 | 2005-06-22 | 刘盛浦 | 光学级低腐蚀隧道密度石英晶体的生长工艺 |
-
2004
- 2004-09-13 JP JP2004265859A patent/JP4719835B2/ja not_active Expired - Fee Related
-
2005
- 2005-09-12 US US11/662,059 patent/US7763223B2/en not_active Expired - Fee Related
- 2005-09-12 WO PCT/JP2005/016769 patent/WO2006030741A1/ja active Application Filing
- 2005-09-12 EP EP05778555A patent/EP2031102B1/en not_active Expired - Fee Related
- 2005-09-12 CA CA2580391A patent/CA2580391C/en not_active Expired - Fee Related
- 2005-09-12 CN CN2005800307752A patent/CN101052753B/zh not_active Expired - Fee Related
- 2005-09-12 KR KR1020077005776A patent/KR100893165B1/ko not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000034188A (ja) * | 1998-07-13 | 2000-02-02 | Japan Chemical Innovation Institute | ミクロ多孔体結晶の製造方法 |
JP2001002410A (ja) | 1999-06-16 | 2001-01-09 | Japan Chemical Innovation Institute | 結晶性ミクロ多孔体の製造方法 |
Non-Patent Citations (5)
Title |
---|
KIDA T. ET AL.: "Synthesis of large silicalite-1 single crystals from two different silica sources.", CERAMICS INTERNATIONAL, vol. 30, no. 5, 2004, pages 727 - 732, XP004515578 * |
KIDA T. ET: "Synthesis of large silicate-1 single crystals from two different silica sources", CERAMICS INTERNATIONAL, vol. 30, no. 5, 2004, pages 727 - 732 |
See also references of EP2031102A4 * |
SHIMIZU S. AND HAMADA H. ET AL.: "Synthesis of giant zeolite crystals by a bulk material dissolution technique.", MESOPOROUS MATERIALS., vol. 48, no. 1-3, 1 November 2001 (2001-11-01), pages 39 - 46, XP004311194 * |
SHIMIZU S.; HAMADA H. ET AL.: "Synthesis of giant zeolite crystals by a bulk material dissolution technique", MESOPOROUS MATERIALS, vol. 48, no. 1-3 |
Also Published As
Publication number | Publication date |
---|---|
US7763223B2 (en) | 2010-07-27 |
KR20070067088A (ko) | 2007-06-27 |
KR100893165B1 (ko) | 2009-04-17 |
CA2580391C (en) | 2011-05-24 |
CA2580391A1 (en) | 2006-03-23 |
JP2006076866A (ja) | 2006-03-23 |
US20070248524A1 (en) | 2007-10-25 |
JP4719835B2 (ja) | 2011-07-06 |
EP2031102A4 (en) | 2009-03-04 |
EP2031102B1 (en) | 2012-12-19 |
CN101052753B (zh) | 2012-01-04 |
EP2031102A1 (en) | 2009-03-04 |
CN101052753A (zh) | 2007-10-10 |
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