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• • 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
  • C01B39/30—Erionite or offretite type, e.g. zeolite T
  • C01B39/305—Erionite or offretite type, e.g. zeolite T 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
  • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
• • 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
  • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
  • B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
  • B01J29/54—Noble metals
• • 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
  • B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
  • B01J29/52—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952 containing iron group metals, noble metals or copper
  • B01J29/56—Iron group metals or copper
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/01—Particle morphology depicted by an image
  • C01P2004/03—Particle morphology depicted by an image obtained by SEM
• • 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

• This disclosure relates to new crystalline molecular sieve designated SSZ-98, a method for preparing SSZ-98 using a ,N'-dimethyl-l,4-diazabicyclo[2.2.2]octane dication as a structure directing agent ("SDA”), and uses for SSZ-98.
• SDA structure directing agent
• These materials have the ERI framework type. The method enables control over silica-to-alumina ratio, crystal size, and morphology of these materials.
• 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.
• IZA International Zeolite Association
• framework type molecular sieves and other crystalline microporous molecular sieves for which a structure has been established, are assigned a three letter code and are described in the Atlas of Zeolite Framework Types " Sixth Revised Edition, Elsevier (2007).
• ERI framework type materials are characterized by three-dimensional 8- membered-ring pore/channel systems containing double-six-rings (d6R) and cages.
• Small pore molecular sieves containing d6R building units and cages have shown utility in methanol-to-olefins catalysis and in the selective catalytic reduction of nitrogen oxides (NO x ) to name some of the more important commercial applications.
• ERI framework type molecular sieves are often intergrown with offretite (OFF) framework type molecular sieves, a topologically related molecular sieve.
• Intergrown ERTOFF molecular sieves comprise regions of ERI framework type sequences and regions of OFF framework type sequences.
• Zeolite T is disclosed in U.S. Patent No. 2,950,952 and later discovered to be an ERI/OFF intergrowth (see J.M. Bennett et ah, Nature, 1967, 214, 1005-1006).
• 3,699, 139 discloses the use of a benzyltrimethylammonium cation to synthesize ERTOFF intergrowth molecular sieves.
• U.S. Patent No. 4,086,186 discloses using choline to synthesize ZSM-34 (an intergrowth).
• U.S. Patent No. 4,503,023 discloses molecular sieves designated LZ-220 which are more siliceous forms of the known mineral erionite and its synthetic analog, zeolite T. M.L. Occelli et al. in Zeolites, 1987, 7, 265-271 disclose using templates designated DABCO(I) and DABCO(II) to synthesize ERI/OFF intergrowth molecular sieves.
• U.S. Patent No. 7,344,694 reports synthesizing an essentially pure ERI framework type molecular sieve designated UZM-12.
• UZM-12 is purported to have a Si/Al ratio of greater than 5.5.
• UZM-12 can be prepared as nanocrystallites having an average particle size of about 15 to about 50 nm and a spheroidal morphology.
• UZM-12 is synthesized via a charge-density mismatch approach whereby quaternary ammonium hydroxides are employed to solubilize aluminosilicate species, while crystallization inducing agents such as alkali and alkaline earth metals and more highly charged organoammonium cations are often introduced in a separate step.
• SSZ-98 crystalline molecular sieves with unique properties
• SSZ-98 has the framework type designated "ERI" by the IZA.
• a crystalline ERI framework type molecular sieve having a mole ratio of from 15 to 50 of silicon oxide to aluminum oxide.
• the molecular sieve has either a rod-like crystal morphology or a plate crystal morphology.
• the SSZ-98 molecular sieve has, in its as-synthesized form, the X-ray diffraction lines of Table 3.
• a method for preparing an ERI framework type molecular sieve by contacting under crystallization conditions (1) at least one source of silicon oxide; (2) at least one source of aluminum oxide; (3) one or more sources of one or more elements selected from Groups 1 and 2 of the Periodic Table; (4) hydroxide ions; (5) a N,N'-dimethyl-l,4-diazabicyclo[2.2.2]octane dication; and (6) optionally, 18-crown-6.
• a process for preparing a crystalline molecular sieve by: (a) preparing a reaction mixture containing: (1) at least one source of silicon oxide; (2) at least one source of aluminum oxide; (3) one or more sources of one or more elements selected from Groups 1 and 2 of the Periodic Table; (4) hydroxide ions; (5) a N,N'-dimethyl- l,4-diazabicyclo[2.2.2]octane dication; (6) optionally, 18-crown-6; and (7) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
• the present disclosure includes such a method wherein the crystalline molecular sieve has the ERI framework type and wherein the molecular sieve has, in its as- synthesized form, the X-ray diffraction lines of Table 3.
• the present disclosure further provides a crystalline molecular sieve having a composition, as -synthesized and in its anhydrous state, in terms of mole ratios as follows: wherein (1) Q is a ,N'-dimethyl-l,4-diazabicyclo[2.2.2]octane dication, and Q > 0; (2) A is 18-crown-6, and A > 0; and (3) M is selected from the group consisting of elements from Groups 1 and 2 of the Periodic Table.
• FIG. 1 is a powder X-ray diffraction (XRD) pattern of the as-synthesized molecular sieve prepared in Example 1.
• FIG. 2 is a Scanning Electron Microscopy (SEM) image of the as-synthesized molecular sieve prepared in Example 1.
• FIG. 3 is a powder XRD pattern of the calcined molecular sieve prepared in Example 1.
• FIG. 4 is a SEM image of the as-synthesized molecular sieve prepared in Example 2.
• FIG. 5 is a SEM image of the as-synthesized molecular sieve prepared in Example 3.
• FIG. 6 is a SEM image of the as-synthesized molecular sieve prepared in Example 13.
• the dimethyl DABCO dication is associated with anions which can be any anion that is not detrimental to the formation of the molecular sieve.
• Representative anions include elements from Group 17 of the Periodic Table (e.g., fluoride, chloride, bromide and iodide), hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and the like.
• the molecular sieve is prepared by: (a) preparing a reaction mixture containing (1) at least one source of silicon oxide; (2) at least one source of aluminum oxide; (3) one or more sources of one or more elements selected from Groups 1 and 2 of the Periodic Table; (4) hydroxide ions; (5) a ,N'-dimethyl-l,4-diazabicyclo[2.2.2]octane dication; (6) optionally, 18-crown-6; and (7) water; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
• Q is a ,N'-dimethyl-l,4-diazabicyclo[2.2.2]octane dication, and Q > 0;
• A is 18-crown-6, and A > 0; and
• M is selected from the group consisting of elements from Groups 1 and 2 of the Periodic Table
• the A/Q mole ratio of the reaction mixture is from 0 to 1 (e.g., from 0 to 0.5, from 0 to 0.35, from 0.01 to 1, from 0.01 to 0.5, or from 0.01 to 0.35).
• Sources of silicon oxide useful herein include fumed silica, precipitated silicates, silica hydrogel, silicic acid, colloidal silica, tetra-alkyl orthosilicates (e.g., tetraethyl orthosilicate), and silica hydroxides.
• Sources of aluminum oxide useful herein include aluminates, alumina, and aluminum compounds such as A1C1 3 , A1 2 (S0 4 )3, Al(OH) 3 , kaolin clays, and other molecular sieves.
• Examples of the source of aluminum oxide include LZ-210 zeolite and Zeolyst International's CBV 720 (types of zeolite Y).
• the reaction mixture can be formed using at least one source of one or more elements selected from Groups 1 and 2 of the Periodic Table (referred to herein as M).
• M any M-containing compound which is not detrimental to the crystallization process is suitable.
• Sources for such Groups 1 and 2 elements include oxides, hydroxides, nitrates, sulfates, halides, acetates, oxalates, and citrates thereof.
• M is potassium.
• M is a combination of potassium and strontium.
• the reaction mixture can also comprise seed crystals having a framework type of ERI, KFI, or a combination thereof to facilitate the crystallization process.
• the mole ratio of seed crystals/Si0 2 in the reaction mixture is from 0.001 to 0.1, e.g., from 0.01 to 0.05.
• the molecular sieve reaction mixture can be supplied by more than one source. Also, two or more reaction components can be provided by one source. [031 ] The reaction mixture can be prepared either batch wise or continuously. Crystal size, morphology and crystallization time of the molecular sieve described herein can vary with the nature of the reaction mixture and the crystallization conditions.
• the molecular sieve is prepared by: (a) preparing a reaction mixture as described herein above; and (b) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the molecular sieve.
• the reaction mixture is maintained at an elevated temperature until the molecular sieve is formed.
• the hydrothermal crystallization is usually conducted under pressure, and usually in an autoclave so that the reaction mixture is subject to autogenous pressure, at a temperature between 125°C and 200°C.
• the reaction mixture can be subjected to mild stirring or agitation during the crystallization step.
• impurities such as amorphous materials, unit cells having framework topologies which do not coincide with the molecular sieve, and/or other impurities (e.g., organic hydrocarbons).
• the solid product is separated from the reaction mixture by standard mechanical separation techniques such as filtration.
• the crystals are water- washed and then dried to obtain the as-synthesized molecular sieve crystals.
• the drying step can be performed at atmospheric pressure or under vacuum.
• the molecular sieve can be used as-synthesized, but typically will be thermally treated (calcined).
• the term "as-synthesized” refers to the molecular sieve in its form after crystallization, prior to removal of the structure directing agent(s).
• the structure directing agent(s) can be removed by thermal treatment (e.g., calcination), preferably in an oxidative atmosphere (e.g., air, gas with an oxygen partial pressure of greater than 0 kPa) at a temperature readily determinable by one skilled in the art sufficient to remove the structure directing agent(s) from the molecular sieve.
• the structure directing agent(s) can also be removed by photolysis techniques (e.g., exposing the SDA-containing molecular sieve product to light or electromagnetic radiation that has a wavelength shorter than visible light under conditions sufficient to selectively remove the organic compound from the molecular sieve) as described in U.S. Patent No. 6,960,327.
• photolysis techniques e.g., exposing the SDA-containing molecular sieve product to light or electromagnetic radiation that has a wavelength shorter than visible light under conditions sufficient to selectively remove the organic compound from the molecular sieve
• the molecular sieve can subsequently be calcined in steam, air or inert gas at temperatures ranging from 200°C to 800°C for periods of time ranging from 1 to 48 hours, or more.
• extra-framework cation e.g., K +
• ion- exchange or other known method it is desirable to remove the extra-framework cation (e.g., K + ) by ion- exchange or other known method and replace it with hydrogen, ammonium, or any desired metal-ion.
• the target molecular sieve formed is an intermediate material
• the target molecular sieve can be achieved using post-synthesis techniques to allow for the synthesis of a target molecular sieve material having a higher silica-to-alumina ratio from an intermediate material by acid leaching or other similar dealumination methods.
• the molecular sieves made from the process of the present invention can be formed into a wide variety of physical shapes.
• the molecular sieve can be in the form of a powder, a granule, or a molded product, such as an extrudate having a particle size sufficient to pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh (Tyler) screen.
• the molecular sieve can be extruded before drying, or dried or partially dried and then extruded.
• the molecular sieve can be composited with other materials resistant to temperature and other conditions employed in organic conversion processes.
• Such matrix materials include active and inactive materials and synthetic or naturally occurring molecular sieves as well as inorganic materials such as clays, silica and metal oxides. Examples of such materials and the manner in which they can be used are disclosed in U.S. Patent Nos.
• compositional variables Q, A and M are as described herein above.
• SSZ-98 has the ERI framework topology. It is characterized by its X-ray diffraction pattern.
• the X-ray diffraction pattern lines of Table 3 are representative of as- synthesized SSZ-98 made in accordance with this disclosure.
• the crystallized ERI framework type materials disclosed herein are preferably "substantially free of OFF framework type materials" as determined by X-ray diffraction.
• substantially free of OFF framework type materials means that the ERI framework type materials disclosed herein contain less than 2.5% OFF framework type character, e.g., less than 1% OFF framework type character, less than 0.5% OFF framework type character, or no measurable OFF framework type character.
• Minor variations in the X-ray diffraction pattern can result from variations in the mole ratios of the framework species of the particular sample due to changes in lattice constants. In addition, sufficiently small crystals will affect the shape and intensity of peaks, leading to significant peak broadening. Minor variations in the diffraction pattern can also result from variations in the organic compound used in the preparation. Calcination can also cause minor shifts in the X-ray diffraction pattern. Notwithstanding these minor
• the powder X-ray diffraction patterns presented herein were collected by standard techniques.
• the radiation was CuK a radiation.
• SSZ-98 is useful as an adsorbent for gas separations.
• SSZ-98 can also be used as a catalyst for converting oxygenates (e.g., methanol) to olefins and for making small amines.
• SSZ-98 can be used to reduce oxides of nitrogen in a gas streams, such as automobile exhaust.
• SSZ-98 can also be used to as a cold start hydrocarbon trap in combustion engine pollution control systems.
• SSZ-98 is particularly useful for trapping C3 fragments.
• the resulting product was analyzed by powder XRD and SEM.
• the powder X-ray diffraction pattern for the as-synthesized product is shown in FIG. 1 and indicates that the material is a single phase ERI framework type molecular sieve.
• SEM image (FIG. 2) for the as-synthesized product shows predominantly a rod-like crystal morphology.
• the term "rod-like” refers to a shape which is elongated along one axial direction, and in which the thickness is substantially constant along the longest axis.
• the calcined product was subjected to a micropore volume analysis using 2 as adsorbate and via the BET method.
• the measured micropore volume was 0.15 cm 3 /g.
• the calcined product after ammonium ion-exchange had a micropore volume of 0.20 cmVg.
• the as -synthesized product was analyzed by powder XRD and SEM.
• the X- ray diffraction pattern showed the product to be a single phase ERI framework type molecular sieve.
• the SEM image (FIG. 4) for the as-synthesized product shows
• the plate crystal morphology is such as the width (W) and the thickness (T) are as follows: W/T is > 10 and advantageously ranges from 10 to 100.
• W/T is > 10 and advantageously ranges from 10 to 100.
• the reaction product was analyzed by powder XRD and SEM.
• the X-ray diffraction pattern showed the product to be a single phase ERI framework type molecular sieve.
• the SEM image (FIG. 5) for the as-synthesized product indicates that the crystal sizes are much smaller than the ones made by Examples 1 and 2.
• the product had a S1O2/AI2O 3 mole ratio of 27.0 as determined by ICP elemental analysis.
• Example 1 The procedure of was Example 1 repeated but with the amounts of starting materials being adjusted and/or different Al sources to produce reaction mixtures having the particular mole ratios set forth in Table 5 below. Crystallization was conducted in the same manner as described in Examples 1-4, although in some cases, as shown in Table 5, the crystallization conditions varied somewhat.
• FIG. 6 is a SEM image of the as-synthesized product of Example 13. TABLE 5
• the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.
• the term “comprising” means including elements or steps that are identified following that term, but any such elements or steps are not exhaustive, and an embodiment can include other elements or steps.

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