Unlted States Patent [19]
`Zones
`
`[11] Patent Number:
`[45] Date of Patent:
`
`4,544,538
`Oct. 1, 1985
`
`4,331,643 5/1982 Rubin et al. ....................... .. 423/329
`
`2311133 32332 is???"
`
`1335352
`
`208/111
`
`[54] ZEOLITE ssz-13 AND ITs METHOD OF
`
`PREPARA'HON
`
`[75] Inventor: Stacey I- Zones, San Francisco, Calif-
`
`.
`[73] Amgnee: Chew?“ ReseaFch C‘m‘P‘mY’ San
`Franclsco, Callf-
`[21] APPI- N°-= 519,954
`[22] Filed=
`Aug- 3, 1983
`
`[63]
`
`Related US. Application Data
`Continuation-impart of Set. NO. 397,007, Jul. 9, 1982,
`abandoned_
`4
`
`---------------------------------
`
`. .
`
`. .................................. ..
`;
`;
`423/329; 502/60; 502/61; 502/62; 502/77
`[58] Field of Search ..................... .. 423/328, 329, 326;
`502/6Q_62
`
`[56]
`
`_
`References C1ted
`U.S. PATENT DOCUMENTS
`
`""""""""""""" "
`11321:?
`502/6O
`3’248’17O 4/1966 Kvetinskas'
`::::''423/329
`3:649:178 3/1972 Wang et 61.‘:
`3,950,496 4/1976 Ciric .................. .. 423/328
`4,061,717 12/1977 Kerr et a1. ......................... .. 423/329
`
`, , 4,419,220 12/1983 LaPierre 6161. O Otal 0 at a . ..
`
`
`
`
`
`
`
`.. 502/77
`4,431,746 2/1984 Rollmann .......... ..
`585/640
`4,496,786 1/1985 Santilli et a1. ..... ..
`4,503,024 3/1985 Bourgogne et a1. .............. .. 423/328
`FOREIGN PATENT DOCUMENTS
`868846 5/1961 United Kingdom .............. .. 423/329
`
`OTHER PUBLICATIONS
`R- M; Farm et ‘11-’ “The Hydl'9themalphemistl'y 0f
`the S111cates: Part VII* Synthetlc Potassmm Alurmno
`silicates”, J. Chem. 800., pp. 2882-2903 (1956).
`W. H. Meier and P. H. Olson Atlas of Zeolite Structure
`T es, 1978 ,1
`. 257 69’ 9O_93, 95_99.
`y?’
`(
`) ‘7p
`Prmwnv hammer-John D911
`Assistant Examiner-Jackson Leeds
`Attorney, Agent, or Firm-S. R. LaPaglia; W. K. Turner;
`V_ J‘ Cavalieri
`[57]
`
`ABSTRACT
`
`A crystalline zeolite, SSZ-13, is prepared from organic
`nitrogen-containing cations derived from l-adamanta
`mine’ 3'quinuclidinol’ and z'em'aminomrmmane’
`
`10 Claims, 1 Drawing Figure
`
`""2
`
`1110-1313
`
`l-ADAMANTAMINE
`
`TEMPLATE A
`
`+CH3
`
`E-OUINUCLIDINOL
`
`TEMPLATE B
`
`@8112
`
`when“
`
`Z-EXO-AMINONORBORNME
`
`TBJPLATE C
`
`m
`
`Umicore AG & Co. KG
`Exhibit 1016
`Page 1 of 10
`
`Exhibit 2035.001
`
`

`

`U.S. Patent
`
`Oct. 1,1985
`
`4,544,538
`
`FIG. I.
`
`NH2
`
`l-ADAMANTAMINE
`
`TEMPLATE A
`
`N @OH
`
`CH +N3
`
`OH
`
`3- QUINUCLIDINOL
`
`TEMPLATE B
`
`+
`
`@(Mcn-gg
`
`Z-EXO-AMINONORBORNANE
`
`TEMPLATE C
`
`Umicore AG & Co. KG
`Exhibit 1016
`Page 2 of 10
`
`Exhibit 2035.002
`
`

`

`4,544,538
`2
`ZSM-S using l-alkyl, 4 aza, 1-azonia-bicyclo(2,2,2)oc
`tane, 4-oxide halides.
`Chabazite is a natural zeolite with the approximate
`formula Ca6Al12Si24O72. Three synthetic forms of cha
`bazite are described in “Zeolite Molecular Sieves”, by
`D. W. Breck, published in 1973 by John Wiley & Sons,
`the complete disclosure of which is incorporated herein
`by speci?c reference. This publication is referred to
`herein as “Breck”. The three synthetic forms reported
`by Breck are: Zeolite “K-G”, described in J. Chem.
`800., p. 2822 (1956), Barrer et a1; Zeolite D, described in
`British Patent No. 868,846 (1961); and Zeolite R, de
`scribed in U.S. Pat. No. 3,030,181 (1962). Chabazite is
`also discussed in “Atlas of Zeolite Structure Types”
`(1978) by W. H. Meier and D. H. Olson.
`The K-G zeolite material reported in the J. Chem.
`Soc. article by Barrer et al is a potassium form having a
`silicazalumina mole ratio of 2.3:1 to 4.15:1. The zeolite D
`material reported in British Patent No. 868,846 is a
`sodium-potassium form having a silicazalumina mole
`ratio of 4.5:1 to 4.9:1. The zeolite R material reported in
`U.S. Pat. No. 3,030,181 is a sodium form which has a
`silicazalumina mole ratio of 3.45:1 to 3.65:1.
`Citation No. 93:66052y, in Volume 93 (1980) of
`Chemical Abstracts, concerns a Russian Language arti
`cle by Tsitsishrili et al in Soabsch. Akad. Nauk. Gruz.,
`SSR 1980, 97(3) 621-4.
`This article teaches that the presence of tetramethyl
`ammonium ions in a reaction mixture containing
`K2O—Na2O—SiO2—Al2O3—H2O promotes the crys
`tallization of chabazite. In the absence of the tetra
`methylammonium ion in the reaction mixture, phillip
`site is obtained. The zeolite obtained by the crystalliza
`tion procedure has a SiO2:A1iO3 mole ratio of 4.23. The
`article states that the tetramethylammonium ion has a
`great in?uence on the direction of crystallization of the
`reaction mixture, although it may not even enter into
`the composition of the zeolites.
`
`30
`
`5
`
`10
`
`15
`
`25
`
`35
`
`1
`
`ZEOLITE SSZ-13 AND ITS METHOD OF
`PREPARATION
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`This application is a continuation-in-part of my co
`pending application Ser. No. 397,007, ?led on July 9,
`1982 now abandoned, the disclosure of which is incor
`porated herein by speci?c reference.
`TECHNICAL FIELD
`Natural and synthetic aluminosilicates are important
`and useful compositions. Many of these aluminosilicates
`are porous and have de?nite, distinct crystal structures
`as determined by X-ray diffraction. Within the crystals
`are a large number of cavities and pores whose dimen
`sions and shapes vary from zeolite to zeolite. Variations
`in pore dimensions and shapes cause variations in the
`20
`adsorptive and catalytic properties of the zeolites. Only
`molecules of certain dimensions and shapes are able to
`?t into the pores of a particular zeolite while other
`molecules of larger dimensions or different shapes are
`unable to penetrate the zeolite crystals.
`Because of their unique molecular sieving character
`istics, as well as their potentially acidic nature, zeolites
`are especially useful in hydrocarbon processing as ad
`sorbents, and, as catalysts, for cracking, reforming, and
`other hydrocarbon conversion reactions. Although
`many different crystalline aluminosilicates have been
`prepared and tested, the search for new zeolites which
`can be used in hydrocarbon and chemical processing
`continues.
`I have discovered a novel family of crystalline alumi
`nosilicate zeolites, hereinafter designated “Zeolite SSZ
`13” or simply “SSZ-l3”, and methods for their prepara
`tion and use.
`In recent years, many crystalline aluminosilicates
`having desirable adsorption and catalytic properties
`have been prepared. Typically, zeolites are prepared
`from reaction mixtures having sources of alkali or alka
`line earth metal oxides, silica, and alumina. More re
`cently, “nitrogenous zeolites” have been prepared from
`reaction mixtures containing an organic species, usually
`a nitrogen compound. Depending upon the reaction
`conditions and the composition of the reaction mixture,
`different zeolites can be formed even if the same organic
`species are used. For example, zeolites ZK-4, ZSM-4,
`faujasite and PHI, have all been prepared from solutions
`containing tetramethylammonium cations.
`Although most experiments reported as producing
`nitrogenous zeolites have used fairly simple organic
`species such as tetraalkylammonium cations or al
`kylenediamines, several experiments are reported as
`using more complex organic species. U.S. Pat. No.
`3,692,470, Ciric, Sept. 19, 1972, discloses preparing
`ZSM-10 from 1,4-dimethyl-1,4-diazoniabicyclo[2.2.
`2]octane. U.S. Pat. No. 3,832,449, Rosinski et al., Aug.
`27, 1974, discloses preparing ZSM-lZ from the reaction
`products of alkylene dihalides with complex amines or
`nitrogen heterocycles. U.S. Pat. No. 3,950,496, Ciric,
`Apr. 13, 1976, discloses preparing ZSM-l8 from “tris”
`ammonium
`hydroxide
`(l,3,4,6,7,9-hexa.hydro
`2,2,5,5,8,8-hexamethyl-2H-benzo-[l,2-C:3,4-C’:5,6
`C”]tripyrolium trihydroxide). U.S. Pat. No. 4,018,870,
`Whittam, Apr. 19, 1977, discloses preparing A65 and
`A66 using nitrogenous basic dyes. And, U.S. Pat. No.
`4,285,922, Audeh, Aug. 25, 1981, discloses preparing
`
`45
`
`50
`
`TECHNICAL DISCLOSURE
`My invention is a zeolite having a mole ratio of an
`oxide selected from silicon oxide, germanium oxide, and
`mixtures thereof to an oxide selected from aluminum
`oxide, gallium oxide, and mixtures thereof greater than
`about 5:1 and having the X-ray diffraction lines of Table
`1. The zeolite further has a composition, as synthesized
`and in the anhydrous state, in terms of mole ratios of
`oxides as follows: (0.5 to 1.4)R;O:(0 to 0.5O)M2O:W2O3:
`(greater than 5)YO2 wherein M is an alkali metal cation,
`W is selected from aluminum, gallium, and mixtures
`thereof, Y is selected from silicon, germanium and mix
`‘ tures thereof, and R is an organic cation. SSZ-l3 zeo
`lites can have a YO2:W2O3 mole ratio greater than
`about 5:1. As prepared, the silicazalumina mole ratio is
`typically in the range of 8:1 to about 50:1; higher mole
`ratios can be obtained by varying the relative ratios of
`reactants. Higher mole ratios can also be obtained by
`treating the zeolite with chelating agents .or .acids to
`extract ‘aluminum from the zeolite . lattice. The
`s'ilicazalumina mole ratio can also be increased by using
`silicon and carbon halides and similar compounds. Pref
`erably, SSZ-13 is an aluminosilicate wherein W is alu
`minum and Y is silicon.
`My invention also involves a method for preparing
`SSZ-l3 zeolites, comprising preparing an aqueous mix
`ture containing sources of an organic nitrogen-contain
`ing compound, an oxide selected from aluminum oxide,
`
`65
`
`Umicore AG & Co. KG
`Exhibit 1016
`Page 3 of 10
`
`Exhibit 2035.003
`
`

`

`4,544,538
`4
`The X-ray powder diffraction patterns were deter
`mined by standard techniques. The radiation was the
`K-alpha/doublet of copper and a scintillation counter
`spectrometer with a strip-chart pen recorder was used.
`The peak heights I and their positions, in degrees,.20,
`where 0 is the Bragg angle, were read from the spec
`trometer chart. From these measured values, the rela
`tive intensities, 100 I/IQ, where 10 is the intensity of the
`strongest line or peak, and d, the interplanar spacing in
`Angstroms corresponding to the recorded lines, can be
`calculated. The X-ray diffraction pattern of Tables 1
`and 2 is characteristic of all species of SSZ-l3 family
`compositions. The zeolite produced by exchanging the
`metal or other cations present in the zeolite with various
`other cations yields substantially the same diffraction
`pattern as is given in Table 2, although there can be
`minor shifts in interplanar spacing and variations in
`relative intensity. Minor variations in the diffraction
`pattern given in Tables 1 and 2 can also result from
`variations in the organic compound used in the prepara
`tion and from variations in the silica-to-alumina mole
`ratio from sample to sample. Notwithstanding these
`minor perturbations, the basic crystal structures for the
`as-prepared condition and the calcined condition re
`main substantially unchanged.
`SSZ-l3 zeolites can be suitably prepared from an
`aqueous solution containing sources of an alkali metal
`oxide, an organic compound, an oxide of aluminum or
`gallium, or mixture of the two, and an oxide of silicon or
`germanium, or mixture of the two. The reaction mixture
`should have a composition in terms of mole ratios of
`oxides falling within the following ranges:
`
`25
`
`3
`gallium oxide, and mixtures thereof, and an oxide se
`lected from silicon oxide, germanium oxide, and mix
`tures thereof, and having a composition, in terms of
`mole ratios of oxides, falling within the following‘
`ranges: YO2/W2O3, 5:1 to 350:1; and R2O/WzO3 0.5:1
`to 40:1; wherein Y is selected from silicon, germanium,
`and mixtures thereof, W is selected from aluminum,
`gallium and mixtures thereof, and R is an organic cat
`ion; maintaining the mixture at a temperature of at least
`100° C. until the crystals of said zeolite are formed; and
`recovering said crystals.
`-
`In a preferred embodiment, the SSZ-l3 contains sil
`ica, and is prepared from a reaction mixture which
`includes colloidal silica. I have found that use of an
`aqueous colloidal suspension of silica in the reaction
`mixture to provide a silica source allows production-of
`SSZ-l3 having a relatively high silica:alumina mole ‘
`ratio, and that use of colloidal silica in the reaction
`mixture also allows a relatively smaller concentration of
`20
`hydroxide ion to be present in the reaction mixture.
`Preferably, the silica source is an aqueous silica suspen
`sion such as Ludox AS-30, a commercially available
`colloidal silica suspension.
`Uncalcined SSZ-13 zeolites, as prepared (with the
`organic templating component present in the crystal
`structure), have a crystalline structure whose X-ray
`powder diffraction pattern shows the characteristic
`lines shown in Table I below:
`TABLE 1
`d(A)
`9.24
`6.30
`5.46
`4.98
`4.26
`4.01
`3.91
`3.56
`3.589
`2.885
`2.859
`
`30
`
`35
`
`20
`9.57
`14.06
`16.23
`17.82
`20.87
`22.14
`22.72
`25.01
`26.30
`31.00
`31.29
`
`100 1/ 10
`61
`21
`80
`24
`100
`9
`8
`69
`18
`47
`21
`
`The X-ray diffraction pattern of 552-13 is com
`pletely indexed on a rhombohedral lattice. SSZ-13 has
`been found to possess the crystal structure of chabazite.
`The rhombohedral unit cell of SSZ-l3 shows signi?cant
`change between the as-prepared condition (with the
`organic templating component present in the structure)
`and the condition after calcination. The rhombohedral
`lattice provides appreciable ?exibility. With the organic
`templating species present in the crystal structure, the
`volume of the unit cell is 7 cubic Angstroms (one per
`cent) larger than the volume of the unit cell after calci
`nation. Calcined SSZ-13 zeolites have a crystal struc
`ture whose X~ray diffraction pattern shows the charac
`teristic lines shown in Table 2 below:
`TABLE 2
`d(A)
`9.19
`6.79
`5.46
`4.93
`4.26
`3.808
`3.530
`3.394
`2.883
`2.846
`
`29
`9.62
`13.04
`16.22
`18.00
`20.87
`23.36
`25.23
`26.26
`31.02
`31.44
`
`100 l/IQ
`100
`32
`18
`16
`50
`6
`18
`11
`27
`13
`
`45
`
`60
`
`65
`
`YO2/W2O3
`M20/W2O3
`R2O/W2O3
`MCI/W203
`
`Broad
`
`5-350
`0.5-20
`0.5-40
`20-200
`
`Preferred
`
`12-200
`1—l7
`5-25
`50-150
`
`wherein R is as disclosed below, Y is silicon, germanium
`or both, and W is aluminum, gallium or both. M is an
`alkali metal, preferably sodium or potassium. Typically,
`an alkali metal hydroxide or alkali metal halide is used
`in the reaction mixture; however, these components can
`be omitted so long as the equivalent basicity is main
`tained. The organic compound can provide hydroxide
`ion. The OH"/Y Oz mole ratio to produce SSZ-l3 hav~
`ing silicazalumina mole ratios of less than about 20:1 is
`above about 0.95 and is preferably in the range of 0.95 to
`1.10. To prepare high silica content SSZ-l3, the OH"
`/YO2 mole ratio is below about 0.95.
`The organic component of the crystallization mixture
`is typically a bicyclo heteroatom compound. The het
`eroatom is preferably nitrogen. The preferred organic
`species are derivatives of either l-adamantamine, 3
`quinuclidinol, or Z-exo-aminonorbornane. The quater
`nary lower alkylammonium cation derivatives of these
`compounds are especially preferred. Methyl and other
`lower alkyl derivatives can be made using standard
`synthetic procedures.
`The reaction mixture is prepared using standard zeo
`litic preparation techniques. Typical sources of alumi
`num oxide for the reaction mixture include aluminates,
`alumina, and aluminum compounds such as AlCl3 and
`Al2(SO4)3. Typical sources of silicon oxide include
`silicates, silica hydrogel, silicic acid, colloidal silica,
`tetraalkyl orthosilicates, and silica hydroxides. Gallium
`
`Umicore AG & Co. KG
`Exhibit 1016
`Page 4 of 10
`
`Exhibit 2035.004
`
`

`

`4,544,538
`6
`5
`physically intimately admixed with the zeolite using
`and germanium can be added in forms corresponding to
`their aluminum and silicon counterparts. Salts, particu
`standard methods known to the art. And, the metals can
`be occluded in the crystal lattice by having the desired
`larly alkali metal halides such as sodium chloride, can
`metals present as ions in the reaction mixture from
`be added to or formed in the reaction mixture. They are
`disclosed in the literature as facilitating the crystalliza
`which the SSZ-l3 zeolite is prepared.
`Typical ion exchange techniques involve contacting
`tion of zeolites while preventing silica occlusion in the
`lattice.
`the synthetic zeolite with a solution containing a salt of
`the desired replacing cation or cations. Although a wide
`The reaction mixture is maintained at an elevated
`temperature until the crystals of the zeolite are formed.
`variety of salts can be employed, chlorides and other
`The temperatures during the hydrothermal crystalliza
`halides, nitrates, and sulfates are particularly preferred.
`Representative ion exchange techniques are disclosed in
`tion step are typically maintained from about 100° C. to
`a wide variety of patents including US. Pat. Nos.
`about 235° C., preferably from about 120° C. to about
`200° C. and most preferably from about 130° C. to about
`3,140,249; 3,140,251; and 3,140,253. Ion exchange can
`165° C. The crystallization period is typically greater
`take place either before or after the zeolite is calcined.
`than 3 days and preferably from about 7 days to about
`Following contact with the salt solution of the de
`50 days.
`sired replacing cation, the zeolite is typically washed
`The hydrothermal crystallization is conducted under
`with water and dried at temperatures ranging from 65°
`C. to about 315° C. After washing, the zeolite can be
`pressure and usually in an autoclave so that the reaction
`mixture is subject to autogenous pressure. The reaction
`calcined in air or inert gas at temperatures ranging from
`about 200° C. to 820° C. for periods of time ranging
`mixture can be stirred during crystallization.
`Once the zeolite crystals have formed, the solid prod
`from 1 to 48 hours, or more, to produce a catalytically
`active product especially useful in hydrocarbon conver
`uct is separated from the reaction mixture by standard
`mechanical separation techniques such as ?ltration. The
`sion processes.
`Regardless of the cations present in the synthesized
`crystals are water-washed and then dried, e.g., at 90° C.
`form of the zeolite, the spatial arrangement of the atoms
`to 150° C. for from 8 to 24 hours, to obtain the as syn
`thesized, SSZ-l3 zeolite crystals. The drying step can
`which form the basic crystal lattice of the zeolite re
`mains essentially unchanged. The exchange of cations
`be performed at atmospheric or subatmospheric pres
`has little, if any, effect on the zeolite lattice structure.
`sures.
`During the hydrothermal crystallization step, the
`The SSZ-l3 aluminosilicate can be formed into a
`wide variety of physical shapes. Generally speaking, the
`SSZ-13 crystals can be allowed to nucleate spontane
`ously from the reaction mixture. The reaction mixture
`zeolite can be in the form of a powder, a granule, or a
`molded product, such as extrudate having particle size
`can also be seeded with SSZ-l3 crystals both to direct,
`sufficient to pass through a 2-mesh (Tyler) screen and
`and accelerate the crystallization, as well as to minimize
`the formation_ of undesired aluminosilicate contami
`be retained on a 400-mesh (Tyler) screen. In cases
`where the catalyst is molded, such as by extrusion with
`nants. If the reaction mixture is seeded with SSZ-l3
`crystals, the concentration of the organic compound
`an organic binder, the aluminosilicate can be extruded
`before drying, or, dried or partially vdried and then ‘ex
`can be greatly reduced or eliminated, but it is preferred
`to have some organic compound present, e.g., an alco
`hol.
`The synthetic SSZ-l3 zeolites can be used as synthe
`..sized or can be thermally treated (calcined). Usually, it
`is desirable to remove the alkali metal cation by ion
`exchange and replace it with hydrogen, ammonium, or
`any desired metal ion. The zeolite can be leached with
`chelating agents, e.g., EDTA, or dilute acid solutions to
`increase the silica:alumina mole ratio. I have found that
`SSZ-l3 synthesized with a relatively high silica:alumina
`mole ratio is more active for a cracking activity micro
`test than SSZ-l3 synthesized with a relatively lower
`silica:alumina mole ratio and subsequently acid leached
`with HCl to raise its silica:alumina mole ratio to the
`same relatively high level. The zeolite can also be
`steamed; steaming stabilizes the crystalline lattice to
`attack from acids. The zeolite can be used in intimate
`combination with hydrogenating components, such as
`tungsten, vanadium, molybdenum, rhenium, nickel,
`cobalt, chromium, manganese, or a noble metal, such as
`palladium or platinum, for those applications in which a
`hydrogenation-dehydrogenation function is desired.
`Typical replacing cations can include metal cations,
`e.g., rare earth, Group HA and Group VIII metals, as
`well as their mixtures. Of the replacing metallic cations,
`cations of metals such as rare earth, Mn, Ca, Mg, Zn,
`Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, Fe and Co are particu
`larly preferred.
`The hydrogen, ammonium, and metal components
`can be exchanged into the zeolite. The zeolite can also
`be impregnated with the metals, or, the metals can be
`
`truded.
`'
`The zeolite can be composited with other materials
`resistant to the temperatures and other conditions em
`ployed in organic conversion processes. Such matrix
`materials include active and inactive materials and syn
`thetic or naturally occurring zeolites as well as inor
`ganic materials such as clays, silica and metal oxides.
`The latter may occur naturally or may be in the form of
`gelatinous precipitates, sols or gels including mixtures
`of silica and metal oxides. Use of an active material in
`conjunction with the synthetic zeolite, i.e., combined
`therewith, tends to improve the conversion and selec
`tivity of the catalyst in certain organic conversion pro
`cesses. Inactive materials can serve as diluents to con
`trol the amount of conversion in a given process so that
`' products can be obtained economically without using
`other means for controlling the rate of reaction. Fre
`quently, zeolite materials have been incorporated into
`naturally occurring clays, e.g., bentonite and kaolin.
`These materials, i.e., clays, oxides, etc., function, in part,
`as binders for the catalyst. It is desirable to provide a
`catalyst having good crush strength, because .in petro
`leum re?ning the catalyst is often subjected to rough
`handling. This tends to break the catalyst down into
`powder-like materials which cause problems in process
`mg.
`Naturally occurring clays which can be composited
`with the synthetic zeolites of this invention include the
`montmorillonite and kaolin families, which families
`include the sub-bentonites, and the kaolins, in which the
`main mineral constituent is halloysite, kaolinite, dickite,
`
`20
`
`25
`
`30
`
`40
`
`45
`
`55
`
`60
`
`65
`
`Umicore AG & Co. KG
`Exhibit 1016
`Page 5 of 10
`
`Exhibit 2035.005
`
`

`

`5
`
`15
`
`20
`
`25
`
`4,544,538
`8
`7
`Hydrocarbon cracking stocks can be catalytically
`nacrite, or anauxite. Fibrous clays such as sepiolite and
`cracked using SSZ-l3 at liquid hourly space velocities
`attapulgite can also be used as supports. Such clays can
`from 0.5 to 50, temperatures from about 260° F. to 625°
`be used in the raw state as originally mined or can be
`F., and pressures from subatmospheric to several hun
`initially subjected to calcination, acid treatment or
`dred atmospheres.
`chemical modi?cation.
`SSZ-l3 can be used to dewax hydrocarbonaceous
`In addition to the foregoing materials, the SSZ-l3
`feeds by selectively removing straight chain paraf?ns.
`zeolites can be composited with porous matrix materials
`The process conditions can be those of hydrodewaxin
`and mixtures of matrix materials such as silica, alumina,
`titania, magnesia, silica-alumina, silica-magnesia, silica
`g—a mild hydrocracking-or they can be at lower
`zirconia, silica-thoria, silica-beryllia, silica—titania, ti
`pressures in the absence of hydrogen. Dewaxing in the
`absence of hydrogen at pressures less than 30 bar, and
`tania-zirconia as well as ternary compositions such as
`preferably less than 15 bar, is preferred as signi?cant
`silica-alumina-thoria,
`silica-alumina-zirconia,
`silica
`alumina-magnesia and silica~magnesia-zirconia. The
`amounts of ole?ns can be obtained from the cracked
`paraf?ns.
`matrix can be in the form of a cogel.
`The SSZ-l3 zeolites can also be composited with
`SSZ-13 can also be used in reforming reactions using
`other zeolites such as synthetic and natural faujasites
`temperatures from 315° C. to 595° C., pressures from 30
`(e.g., X and Y), erionites, and mordenites. They can also
`to 100 bar, and liquid hourly space velocities from 0.1 to
`be composited with purely synthetic zeolites such as '
`20. The hydrogen to hydrocarbon mole ratio can be
`those of the ZSM series. The combination of zeolites
`generally from 1 to 20.
`can also be composited in a porous inorganic matrix.
`The catalyst can also be used to hydroisomerize nor
`SSZ-13 zeolites are useful in hydrocarbon conversion
`mal paraf?ns, when provided with a hydrogenation
`reactions. Hydrocarbon conversion reactions are chem
`component, e.g., platinum. Hydroisomerization is car
`ical and catalytic processes in which carbon containing
`ried out at temperatures from 90° C. to 370° C., and
`compounds are changed to different carbon containing
`liquid hourly space velocities from 0.01 and 5. The
`compounds. Examples of hydrocarbon conversion reac
`hydrogen to hydrocarbon mole ratio is typically from
`tions include catalytic cracking, hydrocracking, and
`1:1 to 5:1. Additionally, the catalyst can be used to
`ole?n and aromatics formation reactions. The catalysts
`isomerize and polymerize ole?ns using temperatures
`are useful in other petroleum re?ning and hydrocarbon
`from 0° C. to 260° C.
`conversion reactions such as isomerizing n-paraf?ns and
`Other reactions which can be accomplished using the
`naphthenes, polymerizing and oligomerizing ole?nic or
`catalyst of this invention containing a metal, e.g., plati
`acetylenic compounds such as isobutylene and butene-l,
`num, include hydrogenation-dehydrogenation reac
`reforming, alkylating, isomerizing polyalkyl substituted
`tions, denitrogenation and desulfurization reactions.
`aromatics (e.g., ortho xylene), and disproportionating
`SSZ-l3 can be used in hydrocarbon conversion reac
`aromatics (e.g., toluene) to provide a mixture of ben-=
`tions with active or inactive supports, with organic or
`zene, xylenes and higher methylbenzenes. The SSZ-l3
`inorganic binders, and with and without added metals.
`catalysts have high selectivity, and under hydrocarbon
`These reactions are well known to the art as are the
`conversion conditions can provide a high percentage of
`reaction conditions.
`‘ desired products relative to total products.
`SSZ-l3 can also be used as an adsorbent, a ?ller in
`SSZ-l3 zeolites can be used in processing hydrocar
`paper products, and as a water-softening agent in deter
`bonaceous feedstocks. Hydrocarbonaceous feedstocks
`gents.
`contain carbon compounds and can be from many dif
`ferent sources, e.g., virgin petroleum fractions, recycle
`petroleum fractions, shale oil, lique?ed coal, tar sand
`oil, and in general any carbon containing ?uid suscepti
`le to zeolitic catalytic reactions. Depending on the
`type of processing the hydrocarbonaceous feed is to
`undergo, the feed can be metal containing or without
`metals, it can also have high or low nitrogen or sulfur
`impurities. It can be appreciated, however, that in gen=
`eral processing will be more ef?cient (and the catalyst
`more active) the lower the metal, nitrogen or sulfur
`content of the feedstock.
`The conversion of hydrocarbonaceous feeds can take
`place in any convenient mode, for example, in fluidized
`bed, moving bed, or ?xed bed reactors depending on
`the types of process desired. The formulation of the
`catalyst particles will vary depending on the conversion
`process and method of operation.
`Using SSZ-l3 catalysts which contain hydrogenation
`components, heavy petroleum residual stocks, cyclic
`stocks, and other hydrocrackable charge stocks can be
`hydrocracked at temperatures from 175° C. to 485° C.
`using molar ratios of hydrogen to hydrocarbon charge
`from 1 to 100. The pressure can vary from 0.5 to 350 bar
`and the liquid hourly space velocity from 0.1 to 30. For
`these purposes, the SSZ-l3 catalyst can be composited
`with mixtures of inorganic oxide supports as well as
`with faujasites such as X and Y.
`
`FIGURE
`FIG. 1 illustrates the three primary sources of or
`ganic species for solutions from which SSZ-l3 is pre
`pared, and their trimethyl ammonium cations as pre
`pared in the Examples.
`EXAMPLES
`Example 1
`Preparation of Organic Template Species
`(a) N,N,N-trimethyl-l-adamantammonium iodide
`l-Adamantamine (Aldrich Chemical Company), 10 g,
`was dissolved in 60 ml of dimethyl formamide. 29 g of
`tributylamine was added; 28.4 g of methyl iodide was
`added dropwise while the reaction was stirred in an ice
`bath. The next day, large plate-like crystals had formed.
`These were ?ltered after 5 days and washed with di
`ethyl ether. Microanalysis for C, H, and N showed the
`product to be the trimethyl derivative, N,N,N-trimeth
`yl- l-adamantammonium iodide.
`(b) N-methyl-3-quinuclidinol iodide
`3-Quinuclidinol (Aldrich Chemical Company), 20 g,
`was dissolved in 150 ml of CHC13 (reagent grade). The
`solution was cooled in an ice bath and 25.56 g of methyl
`iodide was added dropwise with stirring. Copious solids
`were produced which were ?ltered the next day and
`washed with diethyl ether. Microanalysis for C, H, and
`
`30
`
`35
`
`50
`
`55
`
`60
`
`65
`
`Umicore AG & Co. KG
`Exhibit 1016
`Page 6 of 10
`
`Exhibit 2035.006
`
`

`

`10
`TABLE 3-continued
`X-RAY DIFFRACTION PATTERN
`OF PRODUCT OF EXAMPLE 2
`d/n
`100 1/10
`3.20
`7
`3.17
`12
`3.15
`10
`2.89
`54
`
`20
`27.90
`28.18‘
`28.30
`30.92
`
`‘Attributed to small amount of impurity - cubic zeolite P
`"Believed to be extraneous to 582-131 structure
`
`TABLE 4
`X-RAY DIFFRACTION PATTERN
`- OF CALCINED PRODUCT OF EXAMPLE 2
`20
`d/n
`100 [/10
`9.55
`9.26
`123
`13.00
`6.81
`39
`14.08
`6.29
`13
`15.90“
`5.57
`23
`16.17
`5.48
`32
`17.88
`4.96
`29
`20.75
`4.28
`100
`23.31
`3.82
`13
`25.14
`3.54
`32
`26.16
`3.41
`35
`26.66‘
`3.34
`48
`27.90
`3.20
`10
`28.36
`3.15
`13
`30.93
`2.891
`61
`
`"Believed to be extraneous 10 552-13 structure
`‘Attributed to quartz
`
`25
`
`30
`
`4,544,538
`9
`N con?rmed the formation of the quaternary ammo~
`nium salt, N-methyl-3-quinuclidinol iodide.
`(c) N,N,N-trimethyl-Z-ammonium exonorborane
`2-Exoaminonorbornane (Aldrich Chemical Com
`pany), 11.1 g, was dissolved in 50 cc dimethyl form
`amide, and 37.1 g of tributylamine was stirred in.
`Methyl iodide, 42.6 g, was added dropwise while the
`reaction mixture was kept in an ice bath. After 5 hours
`of stirring, the reaction was ?ltered and the ?ne crystals
`were washed with acetone. Microanalysis for C, H, and
`vN gave a good analysis for N,N,N-trimethyl~2
`ammonium exonorbornane.
`Example 2
`The following procedure illustrates the preparation
`of SSZ-l3, using N,N,N-trimethyl-l-adamantam
`monium iodide as the organic templating species.
`Into a 23 ml Te?on cup designed to ?t into a stainless
`steel pressure reactor (Parr Chemical Company). a ?rst
`solution was prepared by adding 5 g of sodium silicate
`20
`solution (0.45 g NaZO, 1.46 g SiOz, 3.10 g H20), 6 m1 of
`H20, and 1.56 g of N,N,N-trimethyl-l-adamantam
`monium iodide. A second solution prepared using 0.24 g
`of A12(SO‘4)3.16H2O and 0.67 g of concentrated (50%
`by weight) NaOH solution in 6 ml of water was added
`to the ?rst solution. The reactants were stirred until a
`homogeneous milky solution was obtained. The reactor
`was closed and heated for 6 days at 140° C. and autoge
`nous pressure. Upon cooling, the contents of the Te?on
`cup were poured into a ?lter and the resulting solids
`were washed ?ve times with deionized H2O followed
`by once each with methanol and acetone. The X-ray
`diffraction pattern for the air-dried zeolite is shown in
`Table 3. The pattern for the calcined zeolite is shown in
`Table 4.
`
`TABLE 3
`X-RAY DIFFRACTION PATTERN
`OF PRODUCT OF EXAMPLE 2
`‘V11
`1001/10
`
`20
`
`35
`
`Examples 3-9
`Using the procedure of Example 2, a series of experi
`ments was performed to make SSZ-13. In Examples 3,
`4, and 7-9, the organic templating species was N,N,N
`trimethyl-l-adamantammonium iodide; in Example 5,
`N-methyl-3-quinuclidinol iodide; and in Example 6,
`N,N,N-trimethyl-Z-ammonium exonorbomane. The
`quantities of reactants used are given in Table 5. The pH
`of the reaction mixture was above 12.
`
`TABLE 5
`Examnle
`6
`
`5
`
`4
`
`3
`
`7
`
`8
`
`9
`
`§21“_ti‘£1_.
`Sodium Silicate, g
`H20, ml
`Template, g
`Solution 2
`H10, 1111
`Al2(S04)3.16l-I2O, g
`Conc. NaOH, g
`Time, days
`Temperature, "C.