US20080159950A1 - Preparation of molecular sieve ssz-13 - Google Patents
Preparation of molecular sieve ssz-13 Download PDFInfo
- Publication number
- US20080159950A1 US20080159950A1 US11/863,005 US86300507A US2008159950A1 US 20080159950 A1 US20080159950 A1 US 20080159950A1 US 86300507 A US86300507 A US 86300507A US 2008159950 A1 US2008159950 A1 US 2008159950A1
- Authority
- US
- United States
- Prior art keywords
- ssz
- oxide
- reaction mixture
- mixture
- cation
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the present invention relates to a process for producing the crystalline zeolite designated SSZ-13 from a reaction mixture.
- Molecular sieves are a commercially important class of crystalline materials. They have distinct crystal structures with ordered pore structures which are demonstrated by distinct X-ray diffraction patterns. The crystal structure defines cavities and pores which are characteristic of the different species.
- SSZ-13 is a known crystalline CHA material. It is disclosed in U.S. Pat. No. 4,544,538, issued Oct. 1, 1985 to Zones, which is incorporated by reference herein in its entirety.
- SDA structure directing agent
- this SDA is costly, which makes the synthesis of SSZ-13 using this SDA costly. This cost can limit the usefulness of SSZ-13 in commercial processes. Thus, it would be desirable to find a way to synthesize SSZ-13 without having to use the costly N,N,N-trimethyl-1-adamantammonium cation SDA.
- SSZ-13 can be prepared using benzyl trimethylammonium cation (“BzTMA cation”) in the absence of a 1-adamantammonium cation, such as N,N,N-trimethyl-1-adamantammonium cation.
- BzTMA cation benzyl trimethylammonium cation
- U.S. Pat. No. 5,558,851 issued Sep. 24, 1996 to Miller, discloses a method for preparing a crystalline aluminosillicate zeolite from a reaction mixture containing only sufficient water so that the reaction mixture may be shaped if desired. In the method, the reaction mixture is heated at crystallization conditions and in the absence of an external liquid phase, so that excess liquid need not be removed from the crystallized material prior to drying the crystals.
- U.S. Pat. No. 5,558,851 is incorporated by reference herein in its entirety.
- a molecular sieve having a composition, as synthesized and in the anhydrous state, comprising (1) a tetravalent oxide or mixture of tetravalent oxides (e.g., silicon oxide, germanium oxide or mixtures thereof), (2) optionally, a trivalent oxide or mixtures of trivalent oxides (e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof) arid (3) benzyl trimethylammonium cation, wherein the as synthesized SSZ-13 does not contain a 1-adamantammonium cation.
- a tetravalent oxide or mixture of tetravalent oxides e.g., silicon oxide, germanium oxide or mixtures thereof
- a trivalent oxide or mixtures of trivalent oxides e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof
- benzyl trimethylammonium cation wherein the as synthesized SSZ-13 does not contain a 1-
- the present invention relates to a method of preparing small pore zeolite-13.
- small pore zeolite refers to zeolites having a pore size of less than 5 Angstroms, including those in which the pores have 8 membered rings.
- the small pore zeolite SSZ-13 can have a mole ratio of (1) a tetravalent oxide or mixture of tetravalent oxides (e.g., silicon oxide, germanium oxide or mixtures thereof) to a (2) trivalent oxide or mixtures of trivalent oxides (e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof) in the zeolite framework of greater than 12, including mole ratios of 200 or more.
- a tetravalent oxide or mixture of tetravalent oxides e.g., silicon oxide, germanium oxide or mixtures thereof
- trivalent oxide or mixtures of trivalent oxides e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixture
- the reaction mixture from which and in which the small pore zeolite SSZ-13 is crystallized comprises at least one active source of a tetravalent oxide or mixture of tetravalent oxides (e.g., silicon oxide, germanium oxide or mixtures thereof) and at least one trivalent oxide or mixtures of trivalent oxides (e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof), a structure directing agent (“SDA”) capable of forming the SSZ-13 zeolite, and an amount of water not substantially in excess of the amount required to cause and maintain crystallization of zeolite SSZ-13.
- active source of a tetravalent oxide or mixture of tetravalent oxides e.g., silicon oxide, germanium oxide or mixtures thereof
- trivalent oxide or mixtures of trivalent oxides e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof
- SDA structure directing agent
- the term “not substantially in excess of the amount required to cause and maintain crystallization” means the minimum amount of water required is that which causes and maintains Crystallization of zeolite SSZ-13. This amount of water is considerably less than that required in conventional processes for preparing zeolites. While an amount slightly in excess of this minimum amount may be employed (especially if it is required to allow the reaction mixture to be thoroughly mixed and/or kneaded), the amount of water employed in the reaction mixture should not be so great that the reaction mixture turns into a solution or fluid gel.
- the amount of liquid required in the reaction mixture of the present invention is that amount which is needed to adequately blend the mixture.
- a reaction mixture is prepared by mixing water with active sources of SSZ-13 zeolite to form a uniform mass that can be, for example, in the form of a heavy paste-like consistency or in the form of a powder or granules.
- the active sources will be in a form which can be easily blended into a uniform mass, and may be, for example, powders, hydrated particles, or concentrated aqueous solutions. Sufficient water is added to wet all the powders during mixing and/or kneading of the reaction mixture.
- the powders may be kneaded into a uniform and generally homogeneous, self-supporting mixture. It is not necessary that all of the active sources be readily soluble in water during kneading, since the water added to the active sources will be insufficient to make a fluid-like mixture.
- the amount of water added depends on the mixing apparatus and on the active sources employed. Those familiar with the art can readily determine without undue experimentation the amount of liquid required to properly mix active sources of the zeolite. For example, hydrated sources of the zeolite may require relatively less water, and dried sources may require relatively more. Though it is preferred that the mixture be blended and/or kneaded until the mixture has a uniform, homogeneous appearance, the length of time devoted to kneading the mixture is not critical in the present invention.
- the water content of the reaction mixture after blending and/or kneading may be further adjusted, for example, by drying or by the addition of water so that the reaction mixture has the desired consistency.
- the amount of water present in the reaction mixture as prepared for the crystallization step be sufficient to cause and maintain crystallization of said SSZ-13, but not so much that the water forms a liquid phase external to the reaction mixture, or transforms the reaction mixture into a solution or fluid gel.
- the reaction mixture will be in the form of granules, a powder or a self-supporting mass. While it is not a requirement to form the reaction mixture into shaped particles before the reaction mixture is subjected to crystallization conditions, it may be desired in many cases to do so.
- the amount of water used in the reaction mixture of this invention is less than the amount of water required in conventional processes for preparing zeolites.
- the amount of water present in the reaction mixture is insufficient to cause the reaction mixture to collapse or “melt”, i.e., once the reaction mixture is formed (including any adjustment in the liquid content that may be needed), the resulting mass is self-supporting.
- self-supporting refers to a reaction mixture that does not collapse or “melt” under its own weight. This term includes the case where the reaction mixture is comprised of individual granules in which each granule is self-supporting or a powder in which each particle in the powder is self-supporting.
- the solids content of the reaction mixture will depend on the particular composition of the SSZ-13 desired.
- SSZ-13 zeolites having a very high mole ratio of tetravalent oxide to trivalent oxide are within the scope of the process, including zeolites having a mole ratio of tetravalent oxide (e.g., silicon oxide, germanium oxide or mixtures thereof) to trivalent oxide (e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof) of greater than 12, including zeolites having such a mole ratio of 200 and higher.
- SSZ-13 zeolites which are essentially free of the trivalent oxide(s) such as aluminum oxide, i.e.; the oxides in the zeolite are essentially all tetravalent oxide (e.g., all silicon oxide).
- aluminum is almost always present to a greater or lesser degree.
- aluminum free is meant that no aluminum is intentionally added to the reaction mixture, e.g., as an alumina or aluminate reagent, and that to the extent aluminum is present, it occurs only as a contaminant in the reagents.
- Other metallic components which may be added to the reaction mixture include, for example, active sources of germanium oxide, aluminum oxide, boron oxide, gallium oxide, iron oxide and mixtures thereof.
- Typical sources of silicon oxide (SiO 2 ) include silicates, silica hydrogel, silicic acid, colloidal silica, fumed silica, tetraalkyl orthosilicates silica hydroxides, precipitated silica and clays.
- Typical sources of aluminum oxide (Al 2 O 3 ) when used in the reaction mixture include aluminates, alumina, and aluminum compounds such as AlCl 3 , Al 2 (SO 4 ) 3 , aluminum hydroxide (Al(OH 3 )), kaolin clays, and other zeolites.
- Germanium, boron, gallium and iron can be added in forms corresponding to their aluminum and silicon counterparts.
- Salts, particularly alkali metal halides such as sodium chloride can be added to or formed in the reaction mixture. They are disclosed in the literature as aiding the crystallization of zeolites while preventing silica occlusion in the lattice.
- the reaction mixture also comprises one or more active sources of alkali metal oxide.
- Sources of lithium, sodium and potassium, are conveniently employed with sodium being a typical alkali metal. Any alkali metal compound which is not detrimental to the crystallization process is suitable. Non-limiting examples include alkali metal oxides, hydroxides, nitrates, sulfates, halogenides, oxalates, citrates and acetates.
- reaction mixture depending on the consistency of the reaction mixture, it may be able to form the reaction mixture into a desired, self-supporting shape before the crystallization step (referred to herein as the “preforming step”), thereby reducing the number of process steps required to prepare catalytic materials containing the zeolite prepared in the mixture.
- preforming step Prior to forming the reaction mixture, it may be necessary to change the liquid content of the reaction mixture, either by drying or by adding more liquid, in order to provide a formable mass which retains its shape.
- water will generally comprise from about 20 percent to about 60 percent by weight, and preferably from about 30 percent to about 50 percent by weight of the reaction mixture.
- the reaction mixture can be formed into shaped particles.
- Methods for preparing the particles are well known in the art, and include, for example, extrusion, spray drying, granulation, agglomerization and the like.
- the particles are preferably of a size and shape desired for the ultimate catalyst, and may be in the form of, for example, extrudates, spheres, granules, agglomerates and prills.
- the particles will generally have a cross sectional diameter between about 1/64 inch and about 1 ⁇ 2 inch, and preferably between about 1/32 inch and about 1 ⁇ 4 inch, i.e. the particles will be of a size to be retained on a 1/64 inch, and preferably on a 1/32 inch screen and will pass through a 1 ⁇ 2 inch, and preferably through a 1 ⁇ 4 inch screen.
- the shaped particles prepared from the reaction mixture will contain sufficient water to retain a desired shape. Additional water is not required in the mixture in order to initiate or maintain crystallization within the shaped particle. Indeed, it may be preferable to remove some of the excess water from the shaped particles prior to crystallization.
- Convention methods for drying wet solids can be used to dry the shaped particles, and may include, for example drying in air or an inert gas such as nitrogen or helium at temperatures below about 200° C. and at pressures from subatmospheric to about 5 atmospheres pressure.
- Naturally occurring clays e.g., bentonite, kaolin, montmorillonite, sepiolite and attapulgite, are not required, but may be included in the shaped particles prior to crystallization to provide particles having good crush strength.
- Such clays can be used in the raw state as originally mined or can be initially subjected to calcination, acid treatment or chemical modification.
- Microcrystalline cellulose has also been found to improve the physical properties of the particles.
- zeolite SSZ-13 is crystallized either within the reaction mixture or within the shaped particles made from the reaction mixture.
- the composition of the reaction mixture from which the SSZ-13 is formed has the following molar composition ranges:
- the liquid present in the reaction mixture may be a combination of aqueous and organic liquids, so long as the amount of water present is sufficient to cause and maintain crystallization of the SSZ-13 zeolite, while at the same time optionally keeping the reaction mixture self-supporting.
- the total liquid content may affect, for example, the physical strength of any shaped particles made from the reaction mixture, it is preferred that the total volatiles content of the reaction mixture during crystallization be in the range of between about 20% and about 60% (w/w), and preferably between about 30% and about 60% (w/w), where the total volatiles content is the measure of total volatile liquid, including water, in the reaction mixture. It is a feature of the present process that no additional liquid beyond that required to cause and maintain crystallization of the SSZ-13 is required for crystallization of the SSZ-13 within the reaction mixture.
- crystallization of the zeolite takes place in the absence of an external liquid phase, i.e., in the absence of a liquid phase separate from the reaction mixture.
- it is not detrimental to the present process if some liquid water is present in contact with the reaction mixture or with the shaped particles during crystallization, and it can be expected that some water may appear on the surface of the reaction mixture during crystallization.
- the present method provides a method of synthesizing SSZ-13 which requires no additional water for crystallization beyond a sufficient amount of water required to cause and maintain crystallization of the SSZ-13, while at the same time optionally keeping the reaction mixture self-supporting. Indeed, under certain conditions, liquid water present during crystallization may alter the form of the reaction mixture or shaped particles, and, in extreme circumstances, may cause the reaction mixture or shaped particles to lose their integrity or to dissolve.
- Crystallization is conducted at an elevated temperature and usually in an autoclave so that the reaction mixture is subject to autogenous pressure until the small pore zeolite crystals are formed.
- the temperatures during the hydrothermal crystallization step are typically maintained from about 140° C. to about 200° C.
- the crystallization of the SSZ-13 is frequently accelerated relative to conventional crystallization methods.
- the crystallization time required to form crystals will typically range from about 1 hour to about 10 days, and more frequently from about 3 hours to about 4 days.
- the SSZ-13 is crystallized within the reaction mixture, which comprises amorphous, non-crystalline reagents. Crystals of SSZ-13 (i.e., “seed” crystals) are added to the mixture prior to the crystallization step, and methods for enhancing the crystallization of zeolites by adding “seed” crystals are well known.
- the seed crystals are employed in amounts from about 1 to about 10 wt. % of the weight of silicon oxide (calculated from the amount of active silica source) in the reaction mixture.
- the crystals may be water-washed and then dried, e.g., at 90° C. to 150° C. for from 8 to 24 hours.
- the drying step can be performed at atmospheric or subatmospheric pressures.
- the present invention also includes SSZ-13 made by the process of this invention in its as-synthesized state.
- the term “as-synthesized” refers to the SSZ-13 in its form prior to removal of the BzTMA cation by thermal treatment (e.g., calcination) or other methods.
- the as-synthesized SSZ-13 has a composition comprising (1) a tetravalent oxide or mixture of tetravalent oxides (e.g., silicon oxide, germanium oxide or mixtures thereof), (2) optionally, a trivalent oxide or mixtures of trivalent oxides (e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof) and (3) BzTMA cation, wherein the as-synthesized SSZ-13 does not contain a 1-adamantammonium cation.
- a tetravalent oxide or mixture of tetravalent oxides e.g., silicon oxide, germanium oxide or mixtures thereof
- a trivalent oxide or mixtures of trivalent oxides e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof
- BzTMA cation e.g., aluminum oxide, boron oxide, gallium oxide, iron oxide or mixtures thereof
- the SSZ-13 zeolite may be used in catalysts (such as for converting methanol to light olefins such as ethylene and propylene), in separations (such as in mixed matrix membranes for separating CO 2 from methane), and in environmental applications (such as adsorption of CO and light hydrocarbons).
- catalysts such as for converting methanol to light olefins such as ethylene and propylene
- separations such as in mixed matrix membranes for separating CO 2 from methane
- environmental applications such as adsorption of CO and light hydrocarbons.
- the SSZ-13 pore zeolite can be composited with other materials resistant to the temperatures and other conditions using techniques such as spray drying, extrusion and the like.
- Hi-Sil 233 source of silicon oxide
- Reheis F-2000 alumina 1.7 grams was dissolved in 5 grams of a 50% aqueous NaOH solution and then added to the Hi-Sil 233 in the vessel. The resulting mixture is mixed thoroughly.
- To the resulting mixture was added 1 gram of SSZ-13 seed crystals, and the mixture thoroughly mixed again for 5 minutes.
- 23.3 Grams of a 2.36 mmole/gram solution of benzyl trimethylammonium hydroxide was added slowly to the mixture while mixing.
- 8 Grams of D.I. water was added slowly and the resulting mixture mixed thoroughly for 1 hour.
- the resulting mixture was in the form of slightly wet granules with a volatiles content of 59.6%.
- the molar composition of the synthesis mix was:
- the resulting reaction mixture was divided into two parts (parts A and B), each part was placed in separate 3.5 inch pipe autoclaves and crystallized at 160° C. for 2 days (for Part A) and 4 days (for part B).
- the products were washed with pH 12.5 water twice, then once with plain D.I. water.
- the products were filtered and dried in a vacuum oven at 120° C. overnight, then calcined at 1100° F. for 6 hours.
- Hi-Sil 233 source of silicon oxide
- Reheis F-2000 alumina 1.7 grams was dissolved in 7.9 grams of a 50% aqueous NaOH solution and then added to the Hi-Sil 233 in the vessel. The resulting mixture is mixed thoroughly.
- To the resulting mixture was added 1 gram of SSZ-13 seed crystals, and the mixture thoroughly mixed again for 5 minutes.
- 23.3 Grams of a 2.36 mmole/gram solution of benzyl trimethylammonium hydroxide was added slowly to the mixture while mixing.
- 8 Grams of D.I. water was added slowly and the resulting mixture mixed thoroughly for 1 hour.
- the resulting mixture was in the form of slightly wet granules with a volatiles content of 61%.
- the molar composition of the synthesis mix was:
- the resulting reaction mixture was placed in a 3.5 inch pipe autoclave and crystallized at 170° C. for 2 days.
- the product was washed with pH 11 water twice, then once with plain D.I. water.
- the product was filtered and dried in a vacuum oven at 120° C. overnight, then calcined at 1100° F. for 6 hours.
- Hi-Sil 233 source of silicon oxide
- 1.2 grams of Barcroft 250 alumina (52% Al2O3) was dissolved in 7.9 grams of a 50% aqueous NaOH solution and then added to the Hi-Sil 233 in the vessel.
- the resulting mixture is mixed thoroughly.
- To the resulting mixture was added 1 gram of SSZ-13 seed crystals, and the mixture thoroughly mixed again for 5 minutes.
- 23.3 Grams of a 2.36 mmole/gram solution of benzyl trimethylammonium hydroxide was added slowly to the mixture while mixing.
- 6 Grams of D.I. water was added slowly and the resulting mixture mixed thoroughly for 1 hour.
- the resulting mixture was in the form of slightly wet granules with a volatiles content of 60%.
- the molar composition of the synthesis mix was:
- the resulting reaction mixture was placed in a 3.5 inch pipe autoclave and crystallized at 170° C. for 2 days.
- the product was washed with pH 11 water twice, then once with plain D.I. water.
- the product was filtered and dried in a vacuum oven at 120° C. overnight, then calcined at 1100° F. for 6 hours.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/863,005 US20080159950A1 (en) | 2006-12-27 | 2007-09-27 | Preparation of molecular sieve ssz-13 |
CN2007800484544A CN101573293B (zh) | 2006-12-27 | 2007-12-21 | 分子筛ssz-13的制备 |
AU2007339946A AU2007339946B2 (en) | 2006-12-27 | 2007-12-21 | Preparation of molecular sieve SSZ-13 |
JP2009544212A JP5576124B2 (ja) | 2006-12-27 | 2007-12-21 | 分子篩ssz−13の製造 |
EP07869698.6A EP2118009B1 (en) | 2006-12-27 | 2007-12-21 | Preparation of molecular sieve ssz-13 |
CA002671677A CA2671677A1 (en) | 2006-12-27 | 2007-12-21 | Preparation of molecular sieve ssz-13 |
BRPI0720639-9A2A BRPI0720639A2 (pt) | 2006-12-27 | 2007-12-21 | Método para a preparação de zeólito cristalino, e, peneira molecular |
KR1020097014541A KR101428120B1 (ko) | 2006-12-27 | 2007-12-21 | 분자체 ssz-13의 제조방법 |
PCT/US2007/088478 WO2008083048A1 (en) | 2006-12-27 | 2007-12-21 | Preparation of molecular sieve ssz-13 |
MX2009006822A MX2009006822A (es) | 2006-12-27 | 2007-12-21 | Preparacion de tamiz molecular ssz-13. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US88201006P | 2006-12-27 | 2006-12-27 | |
US11/863,005 US20080159950A1 (en) | 2006-12-27 | 2007-09-27 | Preparation of molecular sieve ssz-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
US20080159950A1 true US20080159950A1 (en) | 2008-07-03 |
Family
ID=39584261
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/863,005 Abandoned US20080159950A1 (en) | 2006-12-27 | 2007-09-27 | Preparation of molecular sieve ssz-13 |
US11/863,017 Active 2030-06-02 US8007764B2 (en) | 2006-12-27 | 2007-09-27 | Preparation of molecular sieve SSZ-13 |
US13/220,481 Abandoned US20110311441A1 (en) | 2006-12-27 | 2011-08-29 | Preparation of molecular sieve ssz-13 |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/863,017 Active 2030-06-02 US8007764B2 (en) | 2006-12-27 | 2007-09-27 | Preparation of molecular sieve SSZ-13 |
US13/220,481 Abandoned US20110311441A1 (en) | 2006-12-27 | 2011-08-29 | Preparation of molecular sieve ssz-13 |
Country Status (10)
Country | Link |
---|---|
US (3) | US20080159950A1 (zh) |
EP (1) | EP2118009B1 (zh) |
JP (1) | JP5576124B2 (zh) |
KR (1) | KR101428120B1 (zh) |
CN (1) | CN101573293B (zh) |
AU (1) | AU2007339946B2 (zh) |
BR (1) | BRPI0720639A2 (zh) |
CA (1) | CA2671677A1 (zh) |
MX (1) | MX2009006822A (zh) |
WO (1) | WO2008083048A1 (zh) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7597874B1 (en) * | 2008-06-23 | 2009-10-06 | Chevron U.S.A. Inc. | Preparation of zeolites using novel structure directing agents |
JP2010163349A (ja) * | 2008-12-17 | 2010-07-29 | Tosoh Corp | N,n,n−トリメチル−ベンジルアンモニウムイオンを用いたチャバザイトの製造方法 |
JP2011121859A (ja) * | 2009-11-10 | 2011-06-23 | Mitsubishi Chemicals Corp | アルミノシリケートの製造方法 |
WO2014123610A1 (en) * | 2013-02-08 | 2014-08-14 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-85 |
WO2015053821A1 (en) * | 2013-10-11 | 2015-04-16 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-96 |
US9643899B2 (en) | 2015-08-24 | 2017-05-09 | Sabic Global Technologies B.V. | SSZ-13 as a catalyst for conversion of chloromethane to olefins |
CN109665545A (zh) * | 2019-02-14 | 2019-04-23 | 正大能源材料(大连)有限公司 | 一种可控形貌ssz-13分子筛的合成方法 |
WO2019145869A1 (en) * | 2018-01-23 | 2019-08-01 | Sud Chemie India Pvt. Ltd. | Process for synthesizing zeolite ssz-13 |
US11247911B2 (en) | 2018-05-03 | 2022-02-15 | Sabic Global Technologies B.V. | SDA-free synthesis of chabazite (CHA) zeolite and uses thereof |
Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8057782B2 (en) * | 2006-12-27 | 2011-11-15 | Chevron U.S.A. Inc. | Preparation of small pore molecular sieves |
JP2010116349A (ja) * | 2008-11-13 | 2010-05-27 | Tosoh Corp | 新規なn,n,n−トリメチル−1−アダマンタンアンモニウムメチルカーボネート |
JP5428501B2 (ja) * | 2009-04-28 | 2014-02-26 | 東ソー株式会社 | ゼオライト製造用の構造指向剤 |
US8992884B2 (en) * | 2009-11-30 | 2015-03-31 | Chevron U.S.A. Inc. | Preparation of X zeolite |
CN102614908A (zh) * | 2012-03-16 | 2012-08-01 | 北京工业大学 | 用于氨选择性催化消除NOx的SSZ-13负载Cu-Fe催化剂的制备方法 |
RU2627399C2 (ru) * | 2012-06-04 | 2017-08-08 | Басф Се | Цеолитные материалы типа сна и способы их получения с применением циклоалкиламмониевых соединений |
US9636667B2 (en) | 2012-06-04 | 2017-05-02 | Basf Se | CHA-type zeolite materials and methods for their preparation using cycloalkyammonium compounds |
RU2643969C2 (ru) * | 2012-12-12 | 2018-02-06 | Хальдор Топсеэ А/С | Однореакторный способ синтеза cu-ssz-13, соединение, полученное с помощью способа, и его использование |
US9296620B2 (en) | 2013-08-09 | 2016-03-29 | Chevron U.S.A. Inc. | Preparation of high-silica cha-type molecular sieves using a mixed template |
CN103599813B (zh) * | 2013-12-04 | 2015-10-14 | 北京化工大学 | 一种用于低温scr脱硝的分子筛基催化剂及其制备方法 |
CN103601211B (zh) | 2013-12-04 | 2015-07-22 | 北京化工大学 | 一种合成分子筛ssz-13的方法 |
EP3152162B1 (en) | 2014-06-05 | 2018-12-12 | Basf Se | Cha type zeolitic materials and methods for their preparation using combinations of cyclohexyl- and tetramethylammonium compounds |
CN105645426B (zh) * | 2014-11-18 | 2017-09-01 | 中触媒有限公司 | 一种ssz‑13分子筛的合成方法 |
US9708192B2 (en) * | 2014-11-25 | 2017-07-18 | Chevron U.S.A. Inc. | Method for preparing aluminosilicate molecular sieves having the CHA framework type |
ES2574500B1 (es) | 2014-12-17 | 2017-03-31 | Consejo Superior De Investigaciones Científicas (Csic) | Síntesis de la zeolita con la estructura cristalina CHA, procedimiento de síntesis y su uso en aplicaciones catalíticas |
ES2589059B1 (es) | 2015-05-05 | 2017-08-17 | Consejo Superior De Investigaciones Cientificas | SÍNTESIS DIRECTA DE Cu-CHA MEDIANTE LA COMBINACIÓN DE UN COMPLEJO DE Cu Y TETRAETILAMONIO, Y APLICACIONES EN CATÁLISIS |
CN105170178B (zh) * | 2015-08-21 | 2017-12-26 | 宁波海越新材料有限公司 | 一种丙烷脱氢制丙烯催化剂及其制备方法 |
US9610534B1 (en) * | 2015-09-10 | 2017-04-04 | Chevron U.S.A. Inc. | Process for gas separations using zeolite SSZ-13 |
CN106824260B (zh) * | 2015-12-03 | 2019-08-06 | 中国石油化工股份有限公司 | Co-SSZ-13催化剂、制备方法及其用途 |
KR20240058939A (ko) | 2015-12-09 | 2024-05-07 | 바스프 코포레이션 | Cha-형 제올라이트 물질 및 사이클로알킬- 및 에틸트라이메틸암모늄 화합물의 조합을 사용하는 이의 제조 방법 |
CN106925340A (zh) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | 甲醇制烯烃催化剂及其制备方法 |
CN107282096B (zh) * | 2016-04-01 | 2020-09-25 | 中触媒新材料股份有限公司 | 一种ssz-13分子筛催化剂及其制备方法与应用 |
JP6786876B2 (ja) * | 2016-05-23 | 2020-11-18 | 東ソー株式会社 | Cha型ゼオライトの製造方法 |
CN106276953B (zh) * | 2016-08-26 | 2018-02-06 | 天津南化催化剂有限公司 | 一种ssz‑13分子筛的制备方法 |
KR101891003B1 (ko) * | 2016-12-12 | 2018-08-24 | 전남대학교산학협력단 | 벤질기를 포함하는 구조유도물질을 이용한 제올라이트 제조방법 및 이로부터 제조된 제올라이트 |
ES2874654T3 (es) * | 2017-06-19 | 2021-11-05 | Sachem Inc | Catión de amonio cuaternario a base de morfolinio y zeolita de tipo AEI fabricada con el mismo |
KR101940409B1 (ko) * | 2017-08-14 | 2019-01-21 | 전남대학교산학협력단 | 합성 모액의 조성을 조절하여 알루미늄 함량이 제어된 제올라이트의 제조방법 |
CZ2017832A3 (cs) * | 2017-12-21 | 2018-12-19 | Unipetrol výzkumně vzdělávací centrum, a.s. | Způsob výroby zeolitu SSZ-13 |
JP2019142753A (ja) * | 2018-02-22 | 2019-08-29 | いすゞ自動車株式会社 | Ssz−13及びssz−13の製造方法 |
JP7083021B2 (ja) * | 2018-03-09 | 2022-06-09 | シェブロン ユー.エス.エー. インコーポレイテッド | *mre骨格型モレキュラーシーブの合成 |
CN108751221A (zh) * | 2018-05-03 | 2018-11-06 | 浙江大学 | 晶种辅助无氟合成富硅ssz-13沸石分子筛的方法 |
WO2020039074A1 (en) | 2018-08-24 | 2020-02-27 | Umicore Ag & Co. Kg | Method for the preparation of a molecular sieve of the cha-type |
EP3898513A1 (en) | 2018-12-19 | 2021-10-27 | Basf Se | Cha type zeolitic materials and methods for their preparation |
CN109775723B (zh) * | 2019-03-26 | 2020-11-24 | 山东国瓷功能材料股份有限公司 | 一种预处理原料在制备ssz-13分子筛中的应用 |
CN111592008A (zh) * | 2020-06-12 | 2020-08-28 | 浙江浙能技术研究院有限公司 | 一种原位水热合成Fe-SSZ-13分子筛的方法 |
JP2023536498A (ja) | 2020-08-03 | 2023-08-25 | シェブロン ユー.エス.エー. インコーポレイテッド | ゼオライトssz-13の低圧合成 |
KR102416759B1 (ko) * | 2020-09-14 | 2022-07-05 | 희성촉매 주식회사 | Cha 제올라이트 제조방법 및 이로부터 제조된 거대입자의 cha 제올라이트 |
CN114538461B (zh) * | 2020-11-26 | 2023-08-08 | 中国科学院大连化学物理研究所 | 一种ssz-13硅铝分子筛及其制备方法与应用 |
WO2023223027A1 (en) | 2022-05-17 | 2023-11-23 | Johnson Matthey Public Limited Company | A cha type zeolite and the method of synthesising said zeolite |
CN114832645B (zh) * | 2022-05-26 | 2023-10-20 | 江西师范大学 | 一种无氟无铝凝胶中ssz-13分子筛膜的制备方法与应用 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3699139A (en) * | 1969-10-16 | 1972-10-17 | Mobil Oil Corp | Synthetic crystalline aluminosilicate |
US4481173A (en) * | 1982-11-22 | 1984-11-06 | Mobil Oil Corporation | Manufacture of low sodium zeolite |
US4544538A (en) * | 1982-07-09 | 1985-10-01 | Chevron Research Company | Zeolite SSZ-13 and its method of preparation |
US5057296A (en) * | 1990-12-10 | 1991-10-15 | Mobil Oil Corp. | Method for synthesizing mesoporous crystalline material |
US5558851A (en) * | 1992-12-16 | 1996-09-24 | Chevron U.S.A. Inc. | Preparation of aluminosilicate zeolites |
US5783167A (en) * | 1993-06-15 | 1998-07-21 | Consejo Superior Investigaciones Cientificas | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides: its synthesis and utilization for the selective oxidation of organic products |
US7597874B1 (en) * | 2008-06-23 | 2009-10-06 | Chevron U.S.A. Inc. | Preparation of zeolites using novel structure directing agents |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3140249A (en) * | 1960-07-12 | 1964-07-07 | Socony Mobil Oil Co Inc | Catalytic cracking of hydrocarbons with a crystalline zeolite catalyst composite |
BE612554A (zh) * | 1961-12-21 | |||
US3140253A (en) | 1964-05-01 | 1964-07-07 | Socony Mobil Oil Co Inc | Catalytic hydrocarbon conversion with a crystalline zeolite composite catalyst |
US3783124A (en) * | 1969-10-16 | 1974-01-01 | Mobil Oil Corp | Hydrocarbon conversion with novel zeolite |
US4665110A (en) * | 1986-01-29 | 1987-05-12 | Chevron Research Company | Process for preparing molecular sieves using adamantane template |
US4931266A (en) * | 1986-10-22 | 1990-06-05 | Union Oil Company Of California | Crystalline galliosilicate with the erionite-type structure |
US4963337A (en) * | 1989-07-07 | 1990-10-16 | Chevron Research Company | Zeolite SSZ-33 |
US5028406A (en) * | 1989-11-29 | 1991-07-02 | Union Oil Company Of California | Crystalline galliosilicate with the mordenite structure |
US5785947A (en) | 1991-12-18 | 1998-07-28 | Chevron U.S.A. Inc. | Preparation of zeolites using organic template and amine |
US5316753A (en) * | 1992-10-09 | 1994-05-31 | Chevron Research And Technology Company | Zeolite SSZ-35 |
EP0746529B1 (en) * | 1994-02-18 | 2000-01-05 | Chevron Chemical Company LLC | Zeolite ssz-42 |
US5707600A (en) | 1995-03-17 | 1998-01-13 | Chevron U.S.A. Inc. | Process for preparing medium pore size zeolites using neutral amines |
US5707601A (en) | 1995-03-17 | 1998-01-13 | Chevron U.S.A. Inc. | Process for preparing zeolites having MTT crystal structure using small, neutral amines |
US5785945A (en) | 1996-07-31 | 1998-07-28 | Chevron Chemical Company Llc | Preparation of zeolite L |
US6419894B1 (en) * | 2000-12-22 | 2002-07-16 | California Institute Of Technology | Process for preparing zeolites having MEL structure using 2,2-diethoxyethyltrimethylammonium structure directing agent |
US6632415B2 (en) | 2001-04-09 | 2003-10-14 | Chevron U.S.A. Inc. | Methods for making molecular sieves |
US6626980B2 (en) | 2001-09-21 | 2003-09-30 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Mixed matrix membranes incorporating chabazite type molecular sieves |
US7166146B2 (en) | 2003-12-24 | 2007-01-23 | Chevron U.S.A. Inc. | Mixed matrix membranes with small pore molecular sieves and methods for making and using the membranes |
US7022308B1 (en) | 2004-09-22 | 2006-04-04 | Chevron U.S.A. Inc. | Preparation of molecular sieve SSZ-33 |
US7837978B2 (en) * | 2006-10-13 | 2010-11-23 | Chevron U.S.A. Inc. | Process for preparing aluminum-containing molecular sieve SSZ-26 |
US8057782B2 (en) * | 2006-12-27 | 2011-11-15 | Chevron U.S.A. Inc. | Preparation of small pore molecular sieves |
-
2007
- 2007-09-27 US US11/863,005 patent/US20080159950A1/en not_active Abandoned
- 2007-09-27 US US11/863,017 patent/US8007764B2/en active Active
- 2007-12-21 AU AU2007339946A patent/AU2007339946B2/en not_active Ceased
- 2007-12-21 CA CA002671677A patent/CA2671677A1/en not_active Abandoned
- 2007-12-21 WO PCT/US2007/088478 patent/WO2008083048A1/en active Application Filing
- 2007-12-21 CN CN2007800484544A patent/CN101573293B/zh not_active Expired - Fee Related
- 2007-12-21 JP JP2009544212A patent/JP5576124B2/ja not_active Expired - Fee Related
- 2007-12-21 KR KR1020097014541A patent/KR101428120B1/ko not_active IP Right Cessation
- 2007-12-21 MX MX2009006822A patent/MX2009006822A/es active IP Right Grant
- 2007-12-21 EP EP07869698.6A patent/EP2118009B1/en not_active Not-in-force
- 2007-12-21 BR BRPI0720639-9A2A patent/BRPI0720639A2/pt not_active Application Discontinuation
-
2011
- 2011-08-29 US US13/220,481 patent/US20110311441A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3699139A (en) * | 1969-10-16 | 1972-10-17 | Mobil Oil Corp | Synthetic crystalline aluminosilicate |
US4544538A (en) * | 1982-07-09 | 1985-10-01 | Chevron Research Company | Zeolite SSZ-13 and its method of preparation |
US4481173A (en) * | 1982-11-22 | 1984-11-06 | Mobil Oil Corporation | Manufacture of low sodium zeolite |
US5057296A (en) * | 1990-12-10 | 1991-10-15 | Mobil Oil Corp. | Method for synthesizing mesoporous crystalline material |
US5558851A (en) * | 1992-12-16 | 1996-09-24 | Chevron U.S.A. Inc. | Preparation of aluminosilicate zeolites |
US5783167A (en) * | 1993-06-15 | 1998-07-21 | Consejo Superior Investigaciones Cientificas | Structure material of the zeolite type with ultralarge pores and a lattice comprised of silicone and titanium oxides: its synthesis and utilization for the selective oxidation of organic products |
US7597874B1 (en) * | 2008-06-23 | 2009-10-06 | Chevron U.S.A. Inc. | Preparation of zeolites using novel structure directing agents |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7597874B1 (en) * | 2008-06-23 | 2009-10-06 | Chevron U.S.A. Inc. | Preparation of zeolites using novel structure directing agents |
JP2010163349A (ja) * | 2008-12-17 | 2010-07-29 | Tosoh Corp | N,n,n−トリメチル−ベンジルアンモニウムイオンを用いたチャバザイトの製造方法 |
JP2011121859A (ja) * | 2009-11-10 | 2011-06-23 | Mitsubishi Chemicals Corp | アルミノシリケートの製造方法 |
WO2014123610A1 (en) * | 2013-02-08 | 2014-08-14 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-85 |
WO2015053821A1 (en) * | 2013-10-11 | 2015-04-16 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-96 |
US9539545B2 (en) | 2013-10-11 | 2017-01-10 | Chevron U.S.A. Inc. | Processes using molecular sieve SSZ-96 |
US9643899B2 (en) | 2015-08-24 | 2017-05-09 | Sabic Global Technologies B.V. | SSZ-13 as a catalyst for conversion of chloromethane to olefins |
WO2019145869A1 (en) * | 2018-01-23 | 2019-08-01 | Sud Chemie India Pvt. Ltd. | Process for synthesizing zeolite ssz-13 |
US11247911B2 (en) | 2018-05-03 | 2022-02-15 | Sabic Global Technologies B.V. | SDA-free synthesis of chabazite (CHA) zeolite and uses thereof |
CN109665545A (zh) * | 2019-02-14 | 2019-04-23 | 正大能源材料(大连)有限公司 | 一种可控形貌ssz-13分子筛的合成方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20090097932A (ko) | 2009-09-16 |
BRPI0720639A2 (pt) | 2014-01-07 |
US20110311441A1 (en) | 2011-12-22 |
US8007764B2 (en) | 2011-08-30 |
WO2008083048A1 (en) | 2008-07-10 |
AU2007339946A1 (en) | 2008-07-10 |
EP2118009B1 (en) | 2016-12-14 |
CA2671677A1 (en) | 2008-07-10 |
MX2009006822A (es) | 2009-08-28 |
US20080159951A1 (en) | 2008-07-03 |
AU2007339946B2 (en) | 2012-08-09 |
CN101573293A (zh) | 2009-11-04 |
KR101428120B1 (ko) | 2014-09-23 |
JP5576124B2 (ja) | 2014-08-20 |
JP2010514663A (ja) | 2010-05-06 |
EP2118009A1 (en) | 2009-11-18 |
EP2118009A4 (en) | 2011-11-09 |
CN101573293B (zh) | 2013-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8007764B2 (en) | Preparation of molecular sieve SSZ-13 | |
US8057782B2 (en) | Preparation of small pore molecular sieves | |
KR101626183B1 (ko) | 캐버자이트형 제올라이트 및 그 제조 방법 | |
US7824658B2 (en) | Method of making ultrasmall crystal MTT molecular sieves | |
EP3030522B1 (en) | Preparation of high-silica cha-type molecular sieves using a mixed template | |
US20110117007A1 (en) | Method for making mfi-type molecular sieves | |
EP3027559B1 (en) | Zeolite ssz-70 having enhanced external surface area | |
EP2340230A1 (en) | Method of preparing ssz-74 | |
JP2020502023A (ja) | モレキュラーシーブssz−41の合成 | |
JP4882202B2 (ja) | 高シリカモルデナイトの合成方法 | |
US9868642B2 (en) | Synthesis of DDR framework-type molecular sieves | |
JP4639713B2 (ja) | 高純度ハイシリカモルデナイトの合成方法 | |
KR101489009B1 (ko) | 작은 공극 분자체의 제조방법 | |
JP4470003B2 (ja) | 高シリカモルデナイトおよびその合成方法 | |
KR102667235B1 (ko) | 분자체 ssz-63을 제조하는 방법 | |
KR20090094028A (ko) | 초소형 결정 mtt분자체의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: EXPRESSLY ABANDONED -- DURING EXAMINATION |