CA1329798C

CA1329798C - Crystalline molecular sieve

Info

Publication number: CA1329798C
Application number: CA 586337
Authority: CA
Inventors: Roland Von Ballmoos; Eric Gerard Derouane; Cynthia Ting-Wah Chu; Michael Eugene Landis
Original assignee: Mobil Oil Corp
Current assignee: ExxonMobil Oil Corp
Priority date: 1987-12-21
Filing date: 1988-12-19
Publication date: 1994-05-24
Anticipated expiration: 2011-05-24
Also published as: WO1989005775A1; EP0393138A4; EP0393138A1; JPH03504372A; NZ227383A; AU2924089A; DK150590A; DK150590D0

Abstract

CRYSTALLINE MOLECULAR SIEVE

ABSTRACT

A synthetic crystalline molecular sieve composition comprises at least 70% by weight of a crystalline material having the following X-ray diffraction lines:

Description

F-4690~47b5) ~L32~7~8 This invcn~ion relates to a syn~l)etic ~ystalline molecular sievc ¢ompos;tion and in particular to a composition oorltainlng a fra~cwolk +3 Yalence elemcnt, e.g. aluminum, a fra~work +5 valence element, e.g. phos~horous, and prefera~ily a frcimc~ork ~4 val~nce element, e.g. si~;c.on.
Zeolit;~. mc~terials, both na~.ural and syTthetic, have been dcmonstrated ln t~ic past ~o have c~talytic propertie~ for vario types of hydrocarbon co~version. Certain zeoli~ic materials are ordered, porous crystalline aluminosi~icates havlng a deinite ~rystfllline struc~l~re as det~rmined by X-ray diffrac.~.;on, within which thcre are cavities which may be interconnected by channels or pores. Th~s~ cavities and pores are ~niform in size within a spec.lfic zeoliti~ materia~. Sinc~ the dim¢n~ions of these pores are ~uc.~ a.~ ~ accept for adsorption molccule,s Or cert~ln di~ensions while rejectin~ ~ho~e o larger dimension.s, thesc materials haivc come to be known as "molecular sie~es" and ~re ut.~lized in a variety of ways to take advant~igc of thesc properties.
Suc.h niolecular sieves, both natural and synthetic., ~nclude a ~ide variety of po~itive ion-containing crystall~ne ~luminosili~ates. ~cse alu~inosilicatc~ ~an ~ie described as rigid three-dimcnsionail ~rameworks of S;04 and ~04 ln whi~h th~
tetrahedra are cross-linked by the shclring of oxygen atoms whcreby the r~tio of the total al-lniin~im ~r~id silicon atoms to oxygen atonls is 1:2~ The electrov~lcnce of the tetrahedrci contc~Jiining alum;num i$
balanced by the inclusion in tle ~.ryst~l o~ a ~ation, ~or example an ~lkali metal or aT~ alin~ earth mctal c~tion~ This can be exprcssed whercin the ratio of alulninum ~o the numl~er o~ rarious cations, such as Ca/Z, Sr/2? ~ ~ or Li, Is equal to ~ y. ~e type of ~2tion may be e~lcl)al ged either entirely or partially with ~nother l;ype of c.ation utilizil~ ion e~change techniqu~s in a .
:' ~

' . , . ~ ~, , . , :, .~' ' . .

~ ~2~7~
F-4690(4765) --2--conventional manner. By means of such cation exchange, it has been possible to vary the properties of a given aluminosilicate by suitable selection of the cation.
Prior art techniques have resulted in the formation of a great variety of synthetic zeolites. The zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U.S. Patent 2,882,243), zeolite X (U.S. Patent 2,882,244), zeolite Y (U.S. Patent 3,130,Q07), zeolite ZK-5 (U.S.
Patent 3,247,195), zeolite ZK-4 (UOS. Patent 3,314,752), zeolite ZSM-5 (U.S. Patent 3,702,8~6), zeolite ZSM-ll (U.S. Patent 3,709,979), zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite 2SM-20 (U.S. Patent 3,972,983), zeolite ZSM-35 (U.S. Patent 4,016,245), ; zeolite ZSM-38 (U.S. Patent 4,0~6,859), and zeolite ZSM-23 (U.S.
Patent 4,076,842).
Aluminum phosphates are taught in, for example U.S.
Patents 4,310,440 and 4,385,994.
Silicoaluminophosphates o various structure are taught in U.S. Patent 4,440,871. U.S. ~tent 4,363,748 describes a combination of silica and aluminum-calcium-cerium phosphate as a low l, 20 acid activity catalyst for oxidati~e dehydrogenation. Great Britain -~ Patent 2,068,253 discloses a combination of siliça and aluminum-calcium-tungsten phosphate as a low acid activity catalyst for oxidative dehydrogenation. U.S. Patent 4,228,036 teaches an alumina-aluminum phosphate-silica matrix as an amorphous body to be mixed with zeolite for use as cracking catalyst. U.S. Patent 3,213,035 teaches improving hardness of aluminosilicate catalysts by treatment with phosphoric acid. The catalysts are amorphous.
-~ The present invention resides in a novel synthetic crystalline molecular sieve composition comprising at least 70% by weight of a crystalline material having the X-ray diffraction lines listed in ~able IA below:

:~

:.
- : , . .
, , , , ~. . -, . . .
, ........................................ .

~29798 F-4690(4765) --3--Table lA
Interplanar d-Spacings (A) Relative Intensity 16.4 1 O.Z YS
8.2 -+ 0.1 w 6.19 + 0.07 w 5.48 + 0.05 w 4-7~ + 0-05 w and more specifically the following X-ray diffraction lines:
Table lB
Interplanar d-Spacings (A) Relative Intensity 16.4 + 0.2 vs 8.2 + 0.1 w 6.19 + 0.07 w ; 5.48 + 0.05 w 4.74 ~ 0.05 w 4.10 + 0.04 w 4.05 + 0.04 w 3 96 + 0 04 w 3.76 ~ 0.03 w 3.28 + 0.03 w These X-ray diffraction data were collected with ' conventional X-ray systems, using copper K-alpha radiation. Thepositions of the peaks, expressed in degrees 2 theta, where theta is the Bragg angle, were determined by scanning 2 theta. The interplanar spacings, d, measured in Angstrom units (A), and the relative intensities of the lines~ I/Io, where Io is one-hundredth of the intensity of the strongest line, including subtraction of the background, were derived. The relative intensities are given in terms of the symbols vs = very strong ~ 30 (75-100%), s = strong (50-74%), m = medium (25-49%) and w = weak - (0-24~). It should be understood that this X-ray diffraction pattern is characteristic of all the species of the present . . : . ., ~ . . , ~- . ..
; -, ., :

:, , : ~ . , .:
"' ' ' ~ " ' ' ' ~32~7~
F-4690(4765~ --4--compositions. Ion exchange of cations with other ions results in a composition which reveals substantially the same X-ray diffracti~
pattern with some minor shifts in interplanar spacing and variatiDn in relative intensity. ~elative intensity of individual lines ma~
also vary relative the strongest line when the composition is chemically treated, such as by dilute acid treatment. Other variations can occur, depending on the composition of the partic~ar sample, as well as its degree of thermal treatment. The relative intensities of the lines are also susceptible to changes by facta~s such as sorption of water, hydrocarbons or other components in t~
channel structure. Further, the optics of the X-ray diffraction equipment can have significant effects on intensity, particularly in the low angle region. Intensities may also be affected by prefe~ed crystallite orientation. In addition, the line at a d-spacing of 6.19 _ 0.07A is believed to be a doublet at 6.21 + 0.05A and 6.17 ~_ 0.05A but in many cases the doublet is difficult to resolve.
The X-ray diffraction lines in Tables lA and lB identify a cryst~l framework topology exhibiting large pore windows of 18-membered ring size. The pores are at least 12 Angstroms, e.g.
12-13 Angstrom, in diameter.
The crystalline framework of the composition of this invention has the general chemical formula:
;

~XO ) :(YO ) 2 l-y 2 l-x 2 x+y wherein X is a +3 valence element, Y is a l5 valence element, Z i~
an optional ~4 valence element, and x and y are each greater than -l and less than fl, with anions and/or cations being present as necessary for electrical neutrality. Preferably, the element Z i5.
p~esent and x and y satisfy the further relationships:
(1) if x is 0, then y is not 0, (2) if y is 0, then x is not 0, and (3) x + y is greater than 0.001 and less than 1.

; . . . .
.. : . .
. . ~, .
' . :

~32~7~
F-4690(4765) --5--In the above composition, the +3 valence element x is preferably selected from aluminum, iron, chromium, vanadium, molybdenum, arsenic, antimony, manganese, ~allium and boron; the +4 valence element Z is preferably selected from silicon, germanium and titanium; the +5 valence element Y is preferably selected from phosphorous, arsenic, antimony and vanadium. Most preferably, X is aluminum, Y is phosphorus and Z is silicon.
In the composition above, depending on the values of x and y, the composition can be a cation exchange material with potential use as an acidic catalyst, or it can be an anion exchange material with potential use as a basic catalyst.
The composition of the present invention is prepared by providing a reaction mixture comprising sources of X oxide, Y oxide and ~ oxide, water, an organic directing agent D, inorganic cations M and anions N, the components of said reaction mixture having the following relationship:

( )a (M2o)b (x2o3)c (zo2)d:(y2os)e:(N)g:(H2o)h where a, b, c, d, e, f, g, and h are numbers satisfying the following elationships:
~' ~- d/(~+2c+2e) is up to 0.2 (preferably 0.05 to 0.2) a/(d+2c+2e) is 0.2 to 0.4, and preferably the additional relationships: b/(c+d+e) is less than 2, c e g/~c+d~e) is less than 2, and h/(c+d~e) is from 3 to 150, ` The initial pH of the reaction mixture should be 4-6. The mixture is heated with agitation to a temperature of 130 to 155C and maintained at this temperature until crystals of oxide material are formed.
The pH is controlled durin~ the reaction so that the final pH is 6-7 and the reaction to produce at least 70%, and preferably " ~

, ., . ~ ,:

F-4690(4765) --6-- ~ 3 2 9 7 9 at least ~ of the c~n~osi.tion of the invent.ion (based on tho ~ei~ht o~ the total cry5tal~ine phase) i~ no~nally complete ~fter 4-20 ho~irs. The crystal]ine produc~ i~ recovcred by separating s~nle from the reactlon n~dilJm, such as by ~ooling th~ whole to room temperaturel filtering and ~ashing with wat~r before dryin~.
In som~ cases it may bc desirable to employ a t~o-phase react.ion ~ixture, in which at least one of the X~ Y and Z o~ldes is dissolved or dispersod in an organi~ solvent.
The ~hove reaction mixture ~on~pos~ion can be prep~red from ~ny suita1~1e malerl~ls whicll su~ply the appropriat~ componcnts.
U~cful sotlrc.es o ~3 v~lenc.e elemcnt, e.~, ~luln;n~lm, include any known form of o~lde or hydroxide, org~nic or ino~ganic salt or ~ompo~lnd. Useflll sourc.es of 14 valence element, e.g. silicon, include, any known form of dio~ide or silicic ~cid, alkoxy- or other co~pounds ~f sueh elclnent. Useful sources of ~5 val.enc~ elernçnt, e.g. phosphorus~ includc, any ~nown form of phosphorus acid~ or phosphoru~ o~ides, p~los~hates and phosphites, and organic der~vatives of sur.h elcment.
The ol~anic. solvent is a C5-C10 alcohol or any oth~r liqllid co~l~olmd substanti~ly ilr~ cible ~it.h w~ter.
The organic tlirecting ag~:nt ~an be an organic mono- or dialkylamine, ~ith a~kyl being of 3 or 4 ~arbon atoms, or an onil3m coln~o~mds having the followin~ for~ula:
R4M X or ~R~l 3 2 wherein R or R' is alkyl of fro~ 1 to 20 carbon atoms, or ~onlhinations thereof; ~1 is a tetr~oordinate e]cment (e.g. nitro~en, phosphorus, arscni~, antinlony or bisnmth); and X is an anion (e.g.
fluoride, chloride, bromide, iodide, hydroxid~ etate, sulfate, car~oxylate), Partiell~arly prcferred directing agents inc.lude tetraethylammonium hydro~de, tetrapro~ylammoniu~ bromide or ~ost preferably tetrapropylammonillm ~ydroxide and dialkylamines wherein alkyl is butyl or most prefcrahly prnpyl.

..:.. ,`

~29798 F-4690(4765) --7--In order to avoid the production of unwanted crystalline phases, the temperature must be carefully controlled within the 130 - 155C range specified abaove. The preferred temperature within this range depends on the directing agent employed, so that with dipropylamine the preferred temperature is 135 - 155C, most preferably about 150C, whereas with tetrapro wlammonium hydroxide the preferred temperature is 130 - 145C, preferably about 135C.
In its synthesized form the present composition will also contain occluded organic directing agent and water molecules, entrapped during the synthesis and filling the microporous voids.
; However, these can be removed by heating.
The original cations of the as-synthesized present composition can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations.
~ 15 Preferred replacing cations include metal ions, hydrogen ions, ; hydrogen precursor, e.g. ammonium, ions and mixtures thereof.
Particularly preferred cations are those which render the composition catalytically active or control catalytic activity, especially for hydrocarbon conversion. These include hydrogen, rare earth metal and metals of Groups IA, I~A, IIIA, IVA, IB, IIB, III~, IVB, VIB and VIII of the Periodic Table of the Elements.
~ A typical ion exchange technique would be to contact the `j synthetic present composition with a salt of the desired replacing cation or cations. Examples of such salts include the halides, e.g.
chlorides, nitrates and sulfates.
` The crystalline composition of the present invention can be `~ beneficially thermally treated, either before or after ion exchange. This thermal treatment is performed by heating the 1 composition in an atmosphere such as air, nitrogen, hydrogen, steam, etc., at a temperature of from 300C to 1100C, preferably from 350C to 750C, for from 1 minute to 20 hours. While subatmospheric : or superatmospheric pressures may be used for this thermal treatment, atmospheric pressure is desired for reasons of convenience.

~3297~8 F-4690(4765) --8--.~

It may be desirable to incorporate the new composition with another material, i.e. a matrix, resistant to the temperatures and other conditions employed in various organic conversion processes.
Such materials include active and inactive material and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides, e.g. alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Catalyst compositions containing the present composition will generally comprise from 1% to 90~ by weight of the present composition and from 10% to 99~ by weight of the matrix material. More preferably, ; such catalyst compositions will comprise from 2~ to 80% by weight of the present composition and from 20% to 98~ by weight of the matrix.
Use of a material in conjunction hith the new composition, ; 15 i.e. combined therewith, which is active, tends to alter the conversion and/or selectivity of the overall catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g.
bentonite and kaolin, to improve the crush strength of the catalyst ~.;
under commercial operating conditions. Said materials, i.e. clays, oxides, etc., function as binders for the catalyst. It may be desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay binders have been employed normally only for the purpose of improving the crush strength of the overall catalyst.
` 30 Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or 1~297~
F-4690(4765) --9--anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
In addition to the foregoing materials, the present composition can be composited with a porous matrix material such as aluminum phosphate, silica-alumina, silica-magnesi~, silica-zirconia, silica-thoria, silica-beryllia~ silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia. The relative proportions of finely ; divided crystalline material and inorganic oxide gel matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of 2 to 80 weight percent of the composite.
Employing a catalytically active form of the present composition as a catalyst component, said catalyst possibly containing additional hydrogenation components, reforming stocks can j be reformed employing a temperature of 370C to 540C, a pressure of 100 psig to ~000 psig (791 to 6996 kPa), preferably from 200 psi~ to 700 psig (1480 to 4928 kPa), a liquid hourly space velocity is of 0.1 to 10, preferably 0.5 to 4, and a hydrogen to hydrocarbon mole ratio of 1 to 20, preferably 4 to 12.
A catalyst comprising the present composition can also be used for hydroisomerization of normal paraffins, when provided with a hydrogenation component, e.g. platinum. Such hydroisomerization is carried out at a temperature of 90C to 375C, preferably 145C
' to 290C, with a liquid hourly space velocity of 0.01 to 2, preferably 0.25 to 0.50, and with a hydrogen to hydrocarbon mole ratio of 1:1 to 5:1. Additionally, such a catalyst can be used for olefin or aromatic isomerization, employing a temperature of 200C
to 480C.

~' - . :, . .. . . . .
' '. ' ~: ' , ' .

- -F-4690(4765) --10-- 1 3 2 9 7 9 8 ~ uch ~ cata~yst c.~n a3so be ~sed for redueing th~ poUr poi~t of gas oi~s. l~is re~c.tion i~ carried out at a liquld hourly space velocity o 10 to 30 alld at a temperature o~ 425G to 59~C.
Other reac.t;ons which can be a~complislled ~mploying ~
catalyst ~omprising the composition of this inYen~ion containin~ a metal, e.g. platinum, include hy~rogen~tion-dehydrogenation reacti~s and dçsulLurjzation reactions9 olef;n polymerization (o~igomeriz~tion) and ot}ler or~anic conlpolmd conversions~ s~ch as the conYersion o~ alGohol~ (e.g. methanol) or eth~rs (e.g.
dimethylether~ to hydroc~rbons, and the ~Ikylation of arornati~s (e.g. ben~ene) in the presence of an alkylati~ agent (e.g.
etllylenc)~
The invent;on wi]l now bc more part;cularly described ~i~h reEcrence to the ~xamples and the acc.on1panying drawin~s, in which:
Fi~re 1 sh~ws the X-r~y diffraction patt~rn of the as-synthe$ized Example 1 product;
Fi~ure 2 sho~s the X-ray diffractlon pattern o~ the calcined Px~ple 1 ~rodu~ nd ~ lgure 3 s}l~ws the X-r~y diffra~ion p~ttern of the as-synthesi~d ~xample 3 product; and Figure 4 shows the X-r~y diffraction pattern o~ the ~lcincd F.x~nlple ~ pr~luct.

AMP~ 1 A two-phase syn~hcsis r~action mixture wa~ prepared wlth the org~nic phase ~olnprisin~ ~Og Si ~OC2~5)4 and 60g l-h~x~nol, ~n~ th~ aqueou.S ph~se comprising 23g H3~04 ~85%), 14g ~1203, l~g d~-n-~ropy~amine (DP~) an~ 60g o~ H20. Thc . reaction mixture as a whole had t~e ollowin~ approximate composition:

~ Si/Si~ P - 0.1 `~ DPA/Si~Al~P - 0.2 F-4690t476$) ~ 3 2 ~

l~le reaction mi~ture had a startiTl~ p~ of 5,5 and having been stirred without he~ting for lS minutes, was hea~cd at 5ûC p~r hour to 150C and ma~nta;ned at that ~emperatur~ for 24 hours whilc b~ing stirrcd at 800 rpn until crys~.als of silic.ophosphoaluminate fornK~d. Thc final pH was 7.
Ihe ~ryst~lline product was scparated from thc reacti.on nixture by filtration, washed with tolllen~ and ether and then dried. A s~n~plc of ~he product was then su~lnittcd for X-ray analysis and found to ~e a crystalline composition exhihiting ~he dîffraction lines shown in Tal-~e 2A. ~e X-ray dirfraction pattern of this sampl~: is shown in Fi~ure 1. ~is product, ~fter ca~cinatio~ ~ 450C in nitro~en and ~ir for four hours each, ~ras fo~md to have the ~-ray pattern shown in T~ble 2~ and ~gure 2.

~-46~0(4765) --12--I 3 ~ :~ 7 ~ ~

Tabl.e ~A
Int~rplanar ~bscrve~dRelative Intensities d-~ac;n~ (A~ ~ x l~ota _~_ * 16,3 5,4~ lO0 lO.B 8 15 2 * 8 18 10.81 10 6 68 13~24 5 64ll4 31 4 * 5.46 16.24 4.g3317.98 4 B42l8 32 2 ~, 2'~622o 45 2 4.08~Z1.74 7 * 4.~572l.gO

3,82823. 23 3 ~* 3.636~4,47 3.5gO~4.86 * ~.41926.06 * 3.3~6Z6.24 3 08~2~.9~ 3 3 .0~92~. 4~ l *diffrac~ion lines identiying a c.rystal framework topo~ogy having pore windo~s formed by 18 tetrahedral ~emhe~ s .
~diffrac.tion lines of * plus additional intensity contri~ution fro~ oth~r crysta11ine ~ihase.
**~ douhlet.

'' ., ~ ' .

, F-46~0(~1765) --13-- 13 2 ~ 7 ~ 8 T~l e 2~
~b r ed ~elat1ve Intensities Interpl~nar ~e v III
d~S~ac.in~ (A~ ~ _ Q _ 7, * 15,4 5,37 lOn 3-4 8.2 3.2l 10 78 14 4,917 ~8,0 ~,092 21.71 3 ~65 22 ~11 6 3 ~34 23 lg ** 3 767 23,61 3.6fJ8 24.Z6 3~633 2~.50 3 581 ~4.R6 ~ 365 ~6.48 3,328 26 7~ 1 ~ 3 ~77 27.20 9 3 054 2a.2 *dif~raction lin~s identifyin~ a crysta~ fTam~:~4r~
topology having pore windows formed by 38 tetrahedral m~mbers .
**diffraction ~inoS of * plus additional intensity çontrlbl~tinn froln other crystal~ ine pl ase.
~** douhlet.

.
~ , ~ .. . . .
: : ~ , . . . .
.
~ ' .: ' '' ~3297~
F~4690(4765) --14--Analysis of the X-ray data of the as-synthesized and calcined products showed the the crystalline phase contained in excess of 80% by weight of the crystalline material of the invention having the X-ray lines listed in Tables 1~ and lBo The process of Example 1 was repeated but with the reaction mixture being heated at 50C/hour to 130C, maintained at this temperature for 24 hours, heated to 200~C, and then maintained at this temperature for 24 hours. In this case, although the composition having the X-ray lines listed in Tables lA and B was present, it constituted less than 70% by ~eight of the overall crystalline product.

Ex~ple 3 A mixture containing 38.3 g of 85~ orthophosphoric acid (H3P04) in 50 g water was mixed with 22.97 g hydrated aluminium oxide (Kaiser A1203). The mixture was heated to 80C with i stirring for 1/2 hour. To this mixture was added 108.8 g ; 20 tetrapropylammonium hydroxide (TPAO~ 25%). Crystallization in an autoclave was at 135C at autogenous pressure for 16 hours. The solid product was filtered, washed and dried. Figure 3 shows the X-ray diffraction pattern of the as-synthesized material and Figure 4 shows that of the calcined material (calcined at 53~C in N2 for 2 hours). Tables 3 and 4 show X-ray powder diffraction data of the as-synthesized and calcined samples, respectively.
Analysis of the X-ray information indicated that the crystalline product of this example contained in excess of 90% by weight of a material having the X-ray lines of Tables 1~ and lB.

' , , , :, : ~ : .

F-4690(4765) --15-- 13 %

Tal)le 3 ~nterpl~nar ~bservcd R~lative d-Spacin~s (A~ 2xl~eta Intens1ties (I/I
_ - 16.3 5-43 lûO
13,4 6.5~ 2 12.0 7'3g 4 11.4 7.7~ ~
g.3 9,47 ~l 8.10 10.92 11 6.85 12.92 < 1 6.l5 1~.40 5.~7 14.85 ~ 1 5.3~ 16~44 2 ~70 lg.00 5 4. 4~ .75 2 4,3~4 20.2~ 1 q 241 ~0.~4 2 4 143 Z].45 g 4.0~6 ~1,86 10 4.014 22.15 8 3.946 22 . 53 10 3.707 24,01 10 3.531 25 . 22 3.~31 ~5.97 2 3 ~88 26.31 3 Z46 27.47 3. ~04 2% .7~ 3 3.045 2!~,~3 . .
' ..

' ,, ; -, ~\
F-4690( ~1765 ) - -16 - -~ 32979~
Tabl e 4 Interplan~ ~bscrved Relative d-~pacin~s tA) ZxThctaInt~nsities (J/Io) 16.5 5.36 lOn 12.0 7.~58 9~5 9.32 8 . Zl 10 .78 12 6.17 14.35 3 .47 16.~1 ~
4.729 1~.76 5 4.28~ ~),75 4.081 21.78 11 3.959 Z2.~6 8 3.840 23.16 3 . 760 23 . 66 7 3.638 24.46 3~57~ ~4.88 2 3.40g ~6.14 3. ~74 27 . 2~ 8 3.155 28.Z8 ~082 2~.97 3 3.Q2g 2g.49 ;

.

.~ ..

, .

,.~
- . .

Claims

1. A synthetic crystalline molecular sieve composition comprising at least 70% by weight of a crystalline material having the X-ray diffraction lines in Table 1A below by weight of the crystalline phase:

2. The composition of claim 1 wherein said material has the X-ray diffraction lines listed in Table 1B:

3. The composition of claim 1 wherein the crystal framework of said material has the following composition:
(XO2)?-y :(YO2)?-x :(ZO2)x+y wherein X is a +3 valence element, Y is a +5 valence element, Z is a +4 valence element, and x and y are each greater than -1 and less than +1.

4. The composition of claim 3 wherein x and y satisfy the further relationships (i) if x is 0, then y is not 0, (ii) if y is 0, then x is not 0, and (iii) x + y is greater than 0.001 and less than 1.

5. The composition of claim 3 wherein X is aluminum, Y is phosphorus and Z is silicon.

6. A method of producing the composition of claim 3 comprising the step of providing a reaction mixture comprising water, sources of oxides of the elements X, Y and Z, an organic directing agent D, inorganic cations M and anions N is the following molar relationship (D)a:(M2O)b:(X2O3)c:(ZO2)d:(Y2O5)e:(Solvent)f:(N)g:(H2O)h wherein a/(d+2c+2e) is up to 0.2 d/(d+2c+2e) is 0.2 to 0.4 and heating the mixture to a temperature of 130 - 155°C for 4 - 20 hours.

7. The method of claim 6 wherein the mixture obeys the following additional relationships:

a/(d+2c+2e) is 0.05 to 0.2, b/(c+d+e) is less than 2, c e, g/(c+d+e) is less than 2, and h/(c+d+e) is from 3 to 150,

8. The method of claim 6 wherein the directing agent is dipropylamine and said temperature is 135 - 155°C.

9. The method of claim 6 wherein the directing agent is a tetrapropylammonium compound and said temperature is 130 - 145°C.

10. The method of claim 6 wherein the initial pH of said mixture is 4 - 6.

11. The method of claim 10 wherein the final pH of the mixture is 6-7.

12. The method of claim 6 wherein the mixture comprises an aqueous phase and an organic phase, at least one of said oxides being dispersed or dissolved in the organic phase and the mixture being agitated to admix the phases during the heating .
step.