US20150118151A1 - Seeded synthesis of aluminosilicate molecular sieves - Google Patents

Seeded synthesis of aluminosilicate molecular sieves Download PDF

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US20150118151A1
US20150118151A1 US14/065,581 US201314065581A US2015118151A1 US 20150118151 A1 US20150118151 A1 US 20150118151A1 US 201314065581 A US201314065581 A US 201314065581A US 2015118151 A1 US2015118151 A1 US 2015118151A1
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seeds
reaction mixture
molecular sieve
wppm
phosphorus
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Guang Cao
Matu J. Shah
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Assigned to EXXONMOBIL RESEARCH AND ENGINEERING COMPANY reassignment EXXONMOBIL RESEARCH AND ENGINEERING COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CAO, GUANG, SHAH, MATU J.
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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
    • C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • 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
    • 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
    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • 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
    • 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

Definitions

  • This invention relates to the synthesis of crystalline aluminosilicate molecular sieves using seed crystals.
  • molecular sieve materials both natural and synthetic, have been demonstrated in the past to be useful as adsorbents and to have catalytic properties for various types of hydrocarbon conversion reactions.
  • Certain molecular sieves such as zeolites, silicoaluminophosphates (SAPOs), aluminophosphates (AlPOs), and mesoporous materials, are ordered, porous crystalline materials having a definite crystalline structure as determined by X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • cavities which may be interconnected by channels or pores. These cavities and pores are uniform in size within a specific molecular sieve material. Because the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as “molecular sieves” and are utilized in a variety of industrial processes.
  • Such molecular sieves include a wide variety of positive ion-containing crystalline silicates.
  • These silicates can be described as three-dimensional frameworks of SiO 4 tetrahedra and oxides of Group 13 elements (e.g., AlO 2 ) of the Periodic Table.
  • the tetrahedra are cross-linked by the sharing of oxygen atoms with the electrovalence of the tetrahedra containing the Group 13 element (e.g., aluminum) being balanced by the inclusion in the crystal of a cation, for example a proton, an alkali metal or an alkaline earth metal cation.
  • framework-type zeolites and other crystalline microporous molecular sieves are assigned a three letter code and are described in the “Atlas of Zeolite Framework Types”, eds. Ch. Baerlocher, L. B. McCusker, D. H. Olson, Elsevier, Sixth Revised Edition, 2007, which is hereby incorporated by reference.
  • seeding is a term commonly used to describe the effect of a minor amount of a product phase (present either through intentional addition or via cross-contamination) in assisting the crystallization of larger quantities of the same material. Seeding can be used effectively for the control of phase purity and crystal size, as well as to accelerate synthesis and reduce or obviate the need for an organic structure directing agent.
  • WO 00/06493 discloses that a colloidal suspension of seeds of a molecular sieve of the LEV framework type, such as Levyne, NU-3, ZK-20, ZSM-45 and SAPO-35, can be used to manufacture phosphorus-containing molecular sieves, particularly SAPOs and AlPOs of the CHA framework type.
  • LEV framework type such as Levyne, NU-3, ZK-20, ZSM-45 and SAPO-35
  • aluminosilicate molecular sieves can be seeded with silicoaluminophosphate (SAPO) and aluminophosphate (AlPO) molecular sieves.
  • SAPO silicoaluminophosphate
  • AlPO aluminophosphate
  • the invention resides in a process for producing an aluminosilicate molecular sieve, wherein the process comprises: (a) crystallizing a reaction mixture comprising water, a source of silica, and seeds of a silicoaluminophosphate and/or an aluminophosphate molecular sieve; and (b) recovering an aluminosilicate molecular sieve product substantially free of framework phosphorus.
  • the reaction mixture comprises at least 500 wppm of said seeds, e.g., from about 1000 wppm to about 50000 wppm or from about 2000 wppm to about 25000 wppm.
  • reaction mixture can also comprise an organic directing agent effective to direct the synthesis of said aluminosilicate molecular sieve product.
  • organic directing agent effective to direct the synthesis of said aluminosilicate molecular sieve product.
  • the reaction mixture may additionally or alternately comprise a source of fluoride ions.
  • the aluminosilicate molecular sieve product can include a CHA framework
  • the seeds can comprise a silicoaluminophosphate molecular sieve and/or an aluminophosphate having double 6-membered rings as a structural building unit.
  • the seeds may comprise a silicoaluminophosphate and/or an aluminophosphate molecular sieve having a framework type selected from the group consisting of ERI, LEV, AFX, CHA, AEI, and mixtures and intergrowths thereof.
  • FIG. 1 compares the X-ray diffraction patterns of the products of the unseeded syntheses of Examples 1 and 2 with those obtained using the SAPO seeds of Examples 3-7.
  • FIG. 2 compares the X-ray diffraction patterns of the products of the unseeded syntheses of Examples 1 and 2 with those obtained using the SAPO seeds of Examples 8-10.
  • FIG. 3 compares the Scanning Electron Microscopy images of various types of SAPO seeds (top) and their corresponding chabazite products (Examples 3-7, bottom).
  • Described herein is a process for the synthesis of crystalline aluminosilicate molecular sieves using seeds of silicoaluminophosphate (SAPO) and/or aluminophosphate (AlPO) molecular sieves.
  • SAPO silicoaluminophosphate
  • AlPO aluminophosphate
  • the crystalline product can be substantially free of framework phosphorus (e.g., can contain less than 0.5 wt % framework phosphorus, less than 0.2 wt % framework phosphorus, less than 0.1 wt % framework phosphorus, less than 500 wppm framework phosphorus, less than 200 wppm framework phosphorus, less than 100 wppm framework phosphorus, or no measurable framework phosphorus).
  • framework phosphorus e.g., can contain less than 0.5 wt % framework phosphorus, less than 0.2 wt % framework phosphorus, less than 0.1 wt % framework phosphorus, less than 500 wppm framework phosphorus, less than 200 wppm framework phosphorus, less than 100 wppm framework phosphorus, or no measurable framework phosphorus).
  • the SAPO and/or AlPO seeds can be added to an aqueous reaction mixture comprising a source of silicon, optionally an additional source of aluminum (separate from the SAPO and/or AlPO seeds), and typically also an organic structure directing agent effective to direct the synthesis of the desired aluminosilicate molecular sieve product.
  • the reaction mixture can be substantially free of phosphorus, apart from the phosphorus contained by said seeds.
  • the term “substantially free of phosphorus” means that the reaction mixture can contain less than 0.5 wt % phosphorus, less than 0.2 wt % phosphorus, less than 0.1 wt % phosphorus, less than 500 wppm phosphorus, less than 200 wppm phosphorus, less than 100 wppm phosphorus, or no measurable phosphorus), except for the phosphorus from the seeds.
  • the amount of SAPO and/or AlPO seeds added to the reaction mixture can vary significantly, but, in one embodiment, sufficient seeds can be added so that reaction mixture can comprise at least 500 wppm of the SAPO and/or AlPO seeds, e.g., from about 1000 wppm to about 50000 wppm or from about 2000 wppm to about 25000 wppm.
  • the reaction mixture may additionally or alternately comprise a source of fluoride ions, e.g., such that an F ⁇ /SiO 2 molar ratio of the reaction mixture can be from about 0.4 to about 0.8.
  • the pH of the reaction mixture can be less than 9, e.g., less than 8, from about 5 to about 9, or from about 5 to about 8.
  • Crystallization of the desired aluminosilicate molecular sieve from the seeded reaction mixture can be carried out at either static or stirred conditions in a suitable reactor vessel (e.g., polypropylene jars or TeflonTM-lined or stainless steel autoclaves) at a temperature from about 80° C. to about 220° C. (e.g., from about 100° C. to about 200° C.) for a time sufficient for crystallization to occur at the temperature used (e.g., from about 0.5 days to about 100 days or from 1 day to about 20 days). Thereafter, the aluminosilicate crystals can be separated from the liquid and recovered.
  • a suitable reactor vessel e.g., polypropylene jars or TeflonTM-lined or stainless steel autoclaves
  • a time sufficient for crystallization to occur at the temperature used e.g., from about 0.5 days to about 100 days or from 1 day to about 20 days.
  • the crystal structure of the SAPO and/or AlPO molecular sieve employed as the seeds in the present process can be determinative of the crystal structure of the final aluminosilicate product and/or can influence the crystal morphology of the aluminosilicate product.
  • SAPO and/or AlPO molecular sieves can include those having the ERI framework type (such as SAPO-17), the LEV framework type (such as SAPO-35), the AFX framework type (such as SAPO-56), the CHA framework type (e.g., SAPOs having the CHA framework type and made with N,N-dimethylcyclohexylamine, such as EMM-4, and/or those containing fluoride, such as EMM-5), and/or the AEI framework type (such as SAPO-18).
  • ERI framework type such as SAPO-17
  • LEV framework type such as SAPO-35
  • SAPO-56 the AFX framework type
  • the CHA framework type e.g., SAPOs having the CHA framework type and made with N,N-dimethylcyclohexylamine, such as EMM-4, and/or those containing fluoride, such as EMM-5
  • AEI framework type such as SAPO-18.
  • the present invention can include one or more of the following embodiments.
  • a process for producing an aluminosilicate molecular sieve comprising: (a) crystallizing a reaction mixture comprising water, a source of silica and seeds of a silicoaluminophosphate and/or an aluminophosphate molecular sieve; and (b) recovering an aluminosilicate molecular sieve product substantially free of framework phosphorus.
  • reaction mixture comprises at least 500 wppm of said seeds, e.g., from about 1000 wppm to about 50000 wppm or from about 2000 wppm to about 25000 wppm.
  • reaction mixture also comprises a source of fluoride ions.
  • reaction mixture has a pH no more than 9, e.g., from about 5 to about 9.
  • reaction mixture further comprises an organic directing agent effective to direct the synthesis of said aluminosilicate molecular sieve product.
  • said aluminosilicate molecular sieve product has a CHA framework
  • said seeds comprise a silicoaluminophosphate and/or an aluminophosphate molecular sieve having double 6-membered rings as a structural building unit.
  • said seeds comprise a silicoaluminophosphate and/or an aluminophosphate molecular sieve having a framework type selected from the group consisting of ERI, LEV, AFX, CHA, AEI, and mixtures and intergrowths thereof.
  • a reaction mixture suitable for the synthesis of a high-silica aluminosilicate zeolite having a CHA framework type and using dimethylethylcyclohexylammonium hydroxide (DMECHA + OH ⁇ ) as an organic structure directing agent was prepared by mixing ⁇ 58.6 grams of tetraethylorthosilicate (TEOS) and ⁇ 214 grams of an aqueous solution ( ⁇ 11.4 wt %) of DMECHA + OH ⁇ . The mixture was placed on a shaker at room temperature ( ⁇ 20-25° C.) for three days, to ensure complete hydrolysis of the TEOS.
  • TEOS tetraethylorthosilicate
  • the resultant mixture was divided into 10 approximately equal ⁇ 7-gram portions. To the first ⁇ 7-gram portion, no seeds were added. The mixture was sealed inside a ⁇ 23-mL TeflonTM-lined Parr autoclave. The autoclave was heated in an oven at ⁇ 150° C. for about four days before being taken out and cooled, and the solid product was isolated on a filter and washed with deionized water. The solid appeared to be a largely amorphous product containing some chabazite and zeolite beta as crystalline phases. The X-ray diffraction pattern of the product is shown in FIG. 1 .
  • Example 2 To one of the remaining nine ⁇ 7-gram portions of the reaction mixture of Example 1 was added an aqueous solution of Al(NO 3 ) 3 as an aluminum source and the excess water was evaporated prior to sealing of the Parr autoclave before crystallization. The mixture had a Si/Al ratio of ⁇ 83. Again, the product appeared to be largely amorphous, with a very small amount of chabazite being discernible from the X-ray diffraction pattern (see FIG. 1 ). This Example was included to show that merely providing aluminum from a non-SAPO seed source did not lead to the formation of a substantial chabazite product phase.
  • Example 1 To five of the remaining eight ⁇ 7-gram portions of the reaction mixture of Example 1 were each added ⁇ 0.5 wt % of the SAPO seeds as listed in Table 1 below, and the individual mixtures were thoroughly mixed prior to crystallization.
  • the X-ray diffraction patterns of the products are shown in FIG. 1 , and in each case appeared to demonstrate a highly crystalline product composed predominantly of a CHA framework type aluminosilicate. No phosphorus was observed in the products.
  • the Al and Si contents, as well as the Si/Al ratio, of the reaction mixtures are also listed in Table 1.
  • Example 2 To the remaining three ⁇ 7-gram portions of the reaction mixture of Example 1 were each added ⁇ 0.5 wt % of the SAPO seeds as listed in Table 2 below, and the individual mixtures were thoroughly mixed prior to crystallization.
  • the X-ray diffraction patterns of the products are shown in FIG. 2 , and in each case appeared to demonstrate a largely amorphous product with some minority chabazite and zeolite beta phases present.

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US9643852B2 (en) 2017-05-09
CN104837770A (zh) 2015-08-12
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JP6267225B2 (ja) 2018-01-24
CN104837770B (zh) 2017-04-26
JP2016500360A (ja) 2016-01-12
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KR101960567B1 (ko) 2019-03-20
EP2928824B1 (en) 2017-08-09

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