CA1202016A - Crystalline silicoaluminophosphates - Google Patents

Abstract

CRYSTALLINE SILICOALUMINOPHOSPHATES

A B S T R A C T

Crystalline microporous silicoalumino-phosphates used as adsorbents and catalysts and their process of preparation are disclosed.

Description

CRYSTALLINE SILICOALUMINOP~OSPHATES
BAC~GROUND OF THE INVENTION
Field of the Invention ~ he present invention ~elates to a novel class of csys~alline microporous silicoalumino-phosphat~s, o the methoa for their preparation, and to their use as adsorsents ana catalysts. Th~se compositions are prepared hydro~hermally fro~ gels containing reactiv~ phosphorus~ silicon and aluminu~
compounds ana organic templa~ing agents whicn function in par~ to determine tne course o~ tne crystallization ~echanism and hence the structure of the crystalline product.
Description of the Prior Art Molecular siev~s of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synth~tic compositions. In general the crys~all-ne zeolites are forme~ from corner-sharing Al02 and 5iO2 tetrahedra and characterized by having pore openings of uniform dimensions, having a significant ion~xchange capacity and b2ing capable of reversibly desorbing an adsort~d phase which i5 disperqed ~hroughout the internal voids of tne crys~al withou~ displaciny any ~toms whicn make up the permanent crystal s~ructure.
Oth~r crystall~ne microporous compositions wh~ch ar~ not zeolitic, i.e. do not contain ~12 t~trahedra as essen~ial fram~work consti~uents, but wnich exhibit ~he ion-excbange a~d/or adsorption characteristics of ~he zeolites are also known.
Metal organosilicates whicn are said to po3sess D-13,443 lon-exchange properties, have uni~orm pores and are capable o~ reversibly adsorbing molecules having molecular diameters of abDut 6A or less are reported in U.S~ Patent No. 3,941,871 issued March 2, 1976 to Dwyer et al. Also a pure silica polymorph, silicali~e, having molecular sieving prop~rties and a neutral framework containing neither cations nor cation site~ is disclosed in U.S. Patent No.
4,061,724 issued Decem ~r 6, 1977 to R.W. Grose et al.
The most recently reported class of microporous compositions and the first framework oxide molecular sieves syn~hesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Patent No. 4,310,440 issued January 12, lg82 to Wilson et al. These materials are formed from A102 and PO2 tetranedra and have electro~alently neutral frameworks as in the case o~
silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparen~ly due to the difference in electronegativity ~etween aluminum and phosphorus.
Th~ir intracrystalline pore volumes and poré
dlameters are comparable to those known for zeolites and silica molecular sieves.
Several years ago, when the syn~hesis of zeoli~ic aluminosilicates had become established as a signi~icant ~ield ~or research, a num ~r of attempts ~ various investigators were made to isomotphously replace a portion o~ the SiO2 tetrahedra.of zeolites with PO2 tetrahedra during the synthesis proces~. Barrer et ai. (J. Chem. Soc.

D-1~,443 1965, pgs. 6~16-6628) attempted ~o synthesize the mineral viseite, which contains A102, SiO2 and P02 ~etrahedra, by hydrothermal crystallization from reaction mixtures containing silica, phosphorus and aluminum compounds along with the oxides of sodium ana/or calcium. Although a number oE
aluminosilicates and phosphates were formed, no eviaence of isomorphous su ~titution of phosphorus for silicon was found. Wacks et al. (U.S~ Ratent No. 3,443, 892, issued May 13, 1969) reported the preparation of a faujasite-type zeolite naving the formula:
0.5-l.lNa20:A1203:0 0.2P205

2.3-3.3SiO2:0-7.2~20 It is not 5tated whether there was any isomorphous substitution of phosphorus int~ the zeolite lattice.
Su ~tantial success in prepar ing zeolite analogues containing pbosphorus was reported by Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, ~ashing~on, D.C. (1~71), using a synthesis technique utilizing gel crystallization involving controlled copolymerization and coprecipitation of all ~he ~ramework component oxides, aluminate, silicate and phosphate into a relatiYely homogeneous gel phase, with su ~equent crystallization at 80C to 210C.
This technique resulted in the production of a1uminosilicophosphates with the following types of zeolite ~rameworks; analcime, chabazite, pnillipsite- harmo~ome, Type A zeolite, Type L
zeolite and Type B zeoli~e, all of which contained significant amounts of phosphorus (5-25 wt.-~P205) incorporated into the c~ystal ~ramework.
Insofar as is presently known, none of the heretofore synthesized phosphorus-cont~ining zeolite D-13, 443 !

analogues have been utilized commercially.
The substitution of phosphorus for silicon did not appear to impart any beneficial properties to the substituted compositions not possessed by their aluminosilicate analogues with the possible exception that the individual crystals tended to be significantly larger.
To the contrary, many of the physical and chemical properties of the phosphorus-substi-tuted analogues were inferior to those of the unsubstituted species. The substitution of phosphorus in the framework structure of a Type L
zeolite resulted in approximately a 50~ reduction in its adsorption capacity and also a reduction in apparent pore size from about 10A to 6-7A.
Phosphorus-substituted Type B was not stable toward thermal activation, and several of the cation forms of other of the phosphorus-substituted compositions prepared by Flanigen and Grose were not as stable as their aluminosilicate analogues. There are no knowm reports on observed differences in catalytic activity resulting from any phosphorus substitution which may have been achieved by prior known techniques.

SUMMARY OF THE INVENTION
In the drawings, Fig. 1 and Fig. 2 are ternary diagrams showing the molar proportions of silicon, aluminum and phosphorus in the compositions of this invention. The broad range of proportions is shor,m in Fig. 1 whereas the preferred range is shoT,m in Fig. 2.
Fig. 3 is a ternary diagram showing the rela-tive molar proportions of silicon, aluminum and phosphorus in the reaction mixtures used to prepare the compositions of the present invention.
There has now been discovered a novel class of silicon-substituted alum:inophosphates which are both crystalline and microporous and exhibit properties which are characteristic of both the D-13,443 ~Z~20~

aluminosilicate zeolites and the more recently discovered aluminophosphates of Wilson et al., supra. Mem ~rs of this novel class of silicoaluminophosphate materials have a three-dimensional microporous crystal framework structure of PO2, A102 and SiO2 tetrahedral units, and whose essential empirical chemical compssition on an anhydrous basis is:
mR : (SixAl~Pz)02 wherein ~R~ represents at least one organic templating agent present in the intracrystalline pore system: ~m" represents the moles of "R" present per mole of (SiXAlyPz)02 and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoalumino-phospnate species involved, "xn~ "y" and nZ~
represent the mole ~ractions of silicon, aluminum and phosphorus, respectively, presen~ as tetrahedral oxides, said mole ~ractions being such that they are within ~he pentagonal compositional area defined ty points A B C D and E of the ternary diagram which is Fig. 1 of the drawings, the said points ~ B C D and E representing the following values for "x", "y" and nzll Mole Fraction Point _ __~ _ A 0.01 0.47 0.52 B 0.94 0.01 0.05 C 0.~8 0.01 0.01 D 0.39 0.60 0.01 ~ 0.01 a~60 0.39 D 13,443 20~i When synthesized in accordance wi~h the novel process of the present invention, the minimum value of ~m" in the formula above is 0.02. In a preferred 5U ~class of tne silicoaluminophosphates of this invention, ~he values of ~xn, "y" and ~z" in the formula atove are confined to those within the pentagonal compositional area defined by ~he poin~s a b c d and e of the ternary diagram which is Fig. 2 of the drawings, the said points a ~ c d and e representing the ~ollowing values for ~xH, ~yl- and nzn Mole Fraction Point _ __~ _ a 0.02 0.49 0.49 b 0.25 0.37 0.38 c 0.25 0.48 0.27 d 0.13 0.60 0.27 e 0.02 0.60 0.38 The ~erm "essential empirical chemical composition" is meant to include the crystal framework an~ can include any organic templa~ing agent present in the pore system, but does no~
include alkali metal or other cations which can be present by virtue of being contained in the reaction mixture or as a resul~ of post-syn~hesis ion-exchange. Such cation species, when present, function as charge-balancing ions for A102 tetrahedra not associated wi~h a PO2 tetrahedron or an organic ion derived from the organic templating agent. Thus, f or example, in the prepara~ion of SAPO-20 disclosed hereinafter in .ample 28, sodium aluminate was employed as the ~-13,44~

~ ~J~

~ou~ce of aluminum in the reaction mixture, and accordingly the as-~yntnesized SAP0-20 product was found to contain 0.5 moles Na20 per mole o~
A1203 in addition to 0.3 moles (T.~A) 2 per mole of A1203. Th~ overall composition of the as-synthesized SAP0-20, calculated uRing the ~hemical analysis da~a and expressed in terms of molar oxide ratios was:
0.3(TMA)20:0.5Na20:2.7SiO2:A1203:0.31P205:0.8H20 The essential empirical as-synthesized formula on an anhydrous casis is, howeYer:
0.1131~MA): (sio 51A10.38P0.12)2 using the aforementioned formula form of . mR : (5iXAlyPz~02 Tnis essential empirical as-synthesized formula is readily computed ~rom the molar oxide ratio expression in wbich the components R~TMA), Si, Al and P are present in the molar ratio o~:
0.6R : 2.7 Si : 2.0 Al : 0.62 P
The sum (Si ~ Al ~ P~ ~(2.7 + 2.0 ~ 0.62) - 5.3~ i5 normalized to (~i + Al ~ P) ~ 1.00 by dividing each term by 5.32, thusly: m ~ (0.6/5.32) - 0.113;
X 8 t2~7/5.32) ~ 0.51; y - (2.9/5.32) ~ 0038; and Z 3 (0.62/5.32) ~ 0.12.
Th~ aforesaid novel silicoaluminophosphates are ~yn~hesized by hydrothermal crystallization ~som a reac~ion mixture containing r~active sources of silica, alumina and phosphate, an organic templating, i.e., ~tructure^directing, agent, prefera ~y a compound of an element of Group VA of the Periodic Table, and optionally an alkali metal.
The reactisn D-13,443 mixture is placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetra~luoroethylene and heated, preferably under autogenous pressure at a ~empera~ure of at leas~ ~boutlO0C, and preferably between 100C and 250C, until crystals of ~he silicoaluminophosphate product are ob~ained, usually a period of from 2 hours to 2 weeks. The product is recovered by any convenient method 6uch as cen'crifugation or filtration.
DETAI LED DESCRI PTI ON OF T~E I NVENTI ON
In synthesizing the 5A~O compositions of the presen~ invention, it is preferred that the reaction mixture t~ essentially free of alkali metal catlons, an~ accordingly a preferred reaction mixture composition expresse~ in terms of molar oxide ratios is as follows:
a~20: (Si~AlyPz)02 : bH2 wherein ~R" is an organic templating agen~4 "a" has a value great enough to constitute an effective concentration of ~R~ and ~s within the range of ~ 0 to 3; ~ has a value of from zero ~o 500, preferably 2 to 30; ~x", ~Y"
and ~z~ represent the mole fractions, respectively of silicon, aluminum ana phosphorus in the ~SiXAlyPz)02 constituent, and each has a value of at least 0.01. In this expression the r~action mixture composition is normalized with respect to a 'cotal of (Si ~ A1 ~ P) ~ (x ~ y ~ z) -1.00 mole, whereas in many of ~h~ working examples appearing hereinafter the reaction mix~u:res are expressed in terms of molar oxide ratios normalized to 1.00 ~ole of A1~03. ~he procedure for co~Yerting this latter ~orm to the ormer is the same as that illustra'ced hereinabov0 for ~ne product D 13,443 ~2~

compositions. Thus, or example, in a reaction mixture expressed in terms of molar oxide ratios as 0.8A12O3:P2o5:o-4sio2~tTpA~2o 5 2 the molar ratios of Si, Al and P are 0.4 Si~: 1.6 Al : 2.0 P
and (Si + Al + P) ~ 4.~. the mole fractions of x, y and z are thus computed by dividing each coefficient by 4.0 resulting in :
1.0/4.0(TPA)2O:(sio.4/4.o~ll.6/4.o~2.o/4.o)o2 50/4.0 ~O, or 0.25(TPA)20:(S io lA10.4Po.s)O2 1 2 ~ hen alkali metal cations are optionally present ~n the reaction mixture it is preferred to ~orm an aluminophosphate gel, or a~ least an aluminophosphate protogel, by admixing at least a portion of each of ~he aluminum and phosphorus sources in the ~ubstantial absence of the silicon sourc~ so that the procedure is avoided where ~ the phosphorus source is added to a highly ~asic aluminosilicate gel, as was done in most o~ the prior art attempts to substitute isomorphously P02 tetrahedra for SiO2 tetrah~dra in known zeolite structures. Although the reaction mechanism is no mean.~ clear at ~his time, it appears tha~ the templating function of the organic species favors tne incorpora~ion of PO2 and AlO2 tetrahedra in the tramework ~tructures of the crystalline products witb SiO2 tetrahedra isomorphously replacing PO2 ~etrahedra. This i~ consistent with the present finding that several of the new silicoalumino-phosphate compositions appear to be struc~urally related to prior known AlPO~ composition5 or D-~3,443 $

which there are no known aluminosilicate structural analogues. Moreover, certain of the known zeolites which have structures similar to certain of the present silicoaluminophosphates also have structural counterparts among the known AlP04 materials.
Still further, in at least one instance in which two compositions having similar X-ray diffraction patterns, one being prepared in the organic-containing system of the present invention and tne other being prepared in an aLkali mstal-containing system free of an organic templating agent, it is found that the hydrothermal and thermal stability of the two phases is not at all the same, the foxmer being sub6tantially more stable. Whether this is an inaication of fundamental structural difference or simply a difference in the degree of defect structure has not yet been determined. It is quite apparent, however, that the presence of the organic templating agent in the reaction mixture, and consequently in the as-synthesized composition, is highly beneficial both with respect to enabling the production of a much larger number of different structures and in enhancing their physical and chemical properties.
In any event, the preferred synthesis procedure when alkali metals are not e~cluded from the reaction mixtur~ i5 to prepare a reaction mixture having a composition expressed in terms of molar oxide ratios as follows.
aR2 2 ( x y z) 2 2 wherein "Rn is an organic templating agen~; "al has a value great enough ~o constitute an ef~ective con-entration of ~R" and is within the range ~0 to

3; ~Mt~ iS an alkali metal; "bl has a value of zero D-13,443 to 2.5; ~c~ has a value o~ f~om ~ero to 500, preferably 2 to 3C; ~xn ~
~y~ an~z~ represen~ the mole fractions, respec~ively, of silicon, aluminum and phosphorus in the ~Six~ly~z)02 constituent, and each has a value of at least 0_01 ana being within the quadrilateral compositional area defined ty points f g h and i whi~h is Fig. 3 o the drawings, the said poin~s f g h and i representing the following values ~or ~x~, ~y~ and z~:

Mole Fraction Point x y z f 0.010.9Q 0.01 g 0.010.01 0.~8 n 0.320.24 0.44 i. 0.980.01 0.01 ;
sald reaction mixture having been formea ~
combining at least a portion of each o~ ~he aluminum and phosphorous sources in the substantial absence of the silicon source and thereafter combining the resulting mixture with the remaining constituents to form the complete reaction mixtur~.
Although alkali metal silicates can ~
~mployed 35 the silica source in reaction gels ~o produce certain of the present SAPO compositions, the high alkali metal content and concomitant high p~ conditions necessarily imparted to gels where high molar SiO2/A1~03 ratios are desired, results 1n a marked ~en~ency ~o produce extraneous aluminophosphates which appear to be dense, i.e., non-microporous, composltions. ~hile the high p~
conditions can be avoided ty the in situ neutralization of the alkali witb an acid and the consequent formation o~ a precipitated silica, this D-13,443 is, in efrect, the u5e of silica as a reagent rather ~han an alkali metal silicate. Accordingly it is pre~erred that if alkali metal silicate is employed a~ a reagent, it is used in conjunction with a form of silica and lS a minor proportion of the overall silica source. In that event, the reaction mixture should have the same composition expressed in terms o mole ratios of oxides a~ ~et forth hereinahove when alkali metals are not excluded, and in addition comply with the proviso ~hat at least the major source of silica be a form of sllica with ~he alkali metal silicate comprising a minor propor~ion, i.e~, less than half, of the silica source.
In formihg the reaction mixture from which the present silicoaluminophosphates are crystallized the organic templating agent can be any of ~hos~
heretofore proposed for use in the synthesis of conven~ional zeolitic aluminosilicates and microporous aluminophosphates. In general these compounds contain elements of Group VA of the Periodic Table o~ Elements, particularly nitrogen~ -phosphorus, arsenic and antimony, preferably N or P
and most preferably N, which compounds al50 con~ain a~ least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly pre erred nitrogen-containiny compounds for use as templating agents are the amines and quat~rnary ammonium compounds, the latter being represented generally by the forMula R4N wherein each R is an alkyl or aryl group containing from 1 to 8 carbon a~oms.
Polymeric quaternary ammonium salts such as ~(C14~32N2~(OH)2]X wherein "x" has a value o~ at least 2 are also suitably employed. Both mono-, di- and tri-amines are advantageously D- 13 , 4 4 3 ~ 13 -utilized, either a}one or in combination with a quaternary ammonium compound or other templating c~ d. Mixture o~ t~o or more templating agen~s can either produce mixtur~s of the desired silicoal~ inophosphates or the ~ore 3trongly directing templating speci~s may control the course of ~he reaction with the other templating species ~erving pri~arily to establish the pH conditions of the reaction gel. Representative ~empla~ing agents include tetra~ethylammonium, tetrae~hylammonium, t~trapropylammonium o~ tetrabutylammonium ions;
di~n~propylamine; tripropylamine; triethylamine;
triethanolamine; piperidine; cyclohexylamine;
2-methylpyridine; N,N-dimethylbenzylamine;
N,N-diethylethanolamine; dicyclohexylamine;
N,N-dimethylethanolamine; choline;
N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2) octane; N-methyldiethanolamine, N-methyl-ethanolamine; N-metbylpiperidine; 3-methyl-piperidine; N-methylcyclohexylamine; 3-methyl-pyridine; 4-methylpyridine; quinuclidine;
N,N'-dimethyl 1,4-diazabicyclo ~2,2,2) octane lon;
di-n-butyla~ine, neopentylamine; di-n-pentylamine;
isopropylamine; t-butylamine; e~hylenediamine;
pyrrolidine; ~nd 2-imidazolidone. As will be r@adily apparent from the illustrativ~ Examples set forth hereinafter, not every templating agent will direct the formation of every species of ~ilicoaluminophosphate ~SAPO), i~e. a single templ~ting agent can, with proper manipul~tion sf the r~action conditions, direct the ~ormation o~
several SAPO compositions, and a given SAPO
composition can te produced using several differen~
templatin~ agents.

~-13,443 Though not necessary, alkali metal usually introduced as the hydroxides, may ~acilitate the crys~allization of particular SAPO phases. Ordinarily when such cations as Na ; or K+ are present in the reaction gels, these cations also appear in the SAPO
produc~s, either as merely occluded (extraneous) compounds or, as stated hereinbefore, as structural c~tions balancing ne~ negative charges at various sites in the crystal lattice if such should happen ~o exist. It will be understood that although the essential empirical chemical rormulae for the SAPO
compositions do not specificaily recite such constituents, it is not inkended that they be excluded in the same sense that hydrogen cations and/or hydroxyl groups are no~ specifically provided for in the conventional empirical formulae o~
zeolitic al~minosilicates.
The most suitable phosphorus source yet found for the present process is phosphoric acid, but organic phosphates such as triethyl phosphate have been found satisfactory; and so also have crystalline or amorphou~ aluminophospates such as the AlPO4 composition of U.S.P. 4,310,440O
Organo~phosphorus compounds, such as tetrabutylphosphonium bromide do not, apparently, ~erve as reac~ive sources of phosphorus, but these compounds do ~unction as templating agent~.
Conventional phosphorus salts such as sodium ~etaphosphate, may be used; at least in part, as the phosphoru~ source, but are not preferred~
2h~ preferred aluminum source is either an aluminurn alkoxide, such as aluminum isoproproxide, or p~eudotoebmite~ The crystalline or amorphous D-13,443 aluminophospnates which are ? suitable source of pnosphorus are, o~ course, also suitable sources of aluminum. Other sources of alumina used in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are not preferrea.
Silica is preferably introduced into the reaction system as either a silica sol or as fumed silica, but other conventional sources of silica used in zeolite synthesis procedures can be employed, for example, a reactive solid amorphous precipitated silica, silica gel, alkoxides of silicon, silicic acid or alkali metal silicate, the last two named b2ing not pre~erred.
While not essential to tAe syn~hesis of SAPO compositions, it has been found that in ganeral stirring or other moderate agitation of the reaction mixture and~or seeding the reaction mixture with seed crystals of either the SAPO species to ~
produced or a topologically similar aluminophosphate or aluminosilicate composition, facilitates the crys~allization procedure.
After crystallization the SAPO product is isolated and advantageously washed with water and dried in air. The as-synthesized SAPO contains within its 1nternal pore system at leas~ one form of the templating agent e~ployed in i~s formation.
Most co~monly the organic moiety is an occluded molecular species, bu~ it is possible, steric considera~ions permitting, that at least some of the templating agent is present as a charge-balancing cation as is commonly the case wi~h as-synthesized zeolites prepared from organic-containing systems~
As a general rule the templating agent, and hence ~-13,443 ~3Z ~ ~

the occluded organic species, is too large to move freely through the pore system of the SAPO product and must be removed bv calcining the SAPO at temperatures of 200C to 700C to thermally degrade the organic species. In a few instances the pores of the S~PO product are sufficiently large to permit transport of the temp~ating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal the~eof can be accomplished by conventional desorption procedures such as carried out in the case of zeoli~es. It will be understood that ~he term ~as-synthesized~ as used herein and in the claims does not include the condition of the SAPO phase wherein the organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystallization process has been reduced ~y post-synthesis treatment such that the value of "m" in the composition formula mR (SiXAlyPz)O2 has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an all in alkoxide is employed as the source of aluminum, the corres-ponding alcohol is necessarily present in the reaction mixture since it lS a hydrolysis produc~ of the alkoxide. It has not been determined whether this alcohol par~icipates in the syntheses process as a templating agent. For the purposes of ~his application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it is present in the as-synthesized SAPO material.
Since the presen~ SAPO composi~ions are formed from AlO2, PO2 and S1O2 ~e~rahedral units which, respective~y~ have a ne~ negatiYe D-13,443 (3~ O ~ -charge, a net positive charge and electrical neutrality, the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there i5 a stoichiometric relationship between A102 tetrahedra and charge-balancing cations. In the SAPO compositions, an A102 tetrahedron can be ~1Anced electrically ei~her ~y associa~ion with a PO2 tetrahedron or a simple ca~ion such as an alkali metal cation or an organic cation derived from the templating agent, or both. It has also been pos~ula~ed that non-adjacent A102 and P02 tetrahedral pairs can be ~1Anced ~y Na+
and OH respectively (Flanigen and Grose, supra).
The apparent departure from the Loewenstein rule [W.
Loewenstein, Am. Mineral, 39, 92-6(1954)] in such SAPO species as ~hose having compositions in ~he near proximity of the line D-E in the ternary diagram of Fig. 1 may simply be attributed to inadequate analytical capabilities, or may reflect more fl~n~A -ntal considerations such as the presence f (~32) tetrahedral units which are not ~aken into account in the composition formulae.
In any event, all o~ the SAPO compositions of the present invention examined to date have exnibited cation-~xchange capacity, in some cases to a signiicant degree, when analyzed using ion-exchange ~echni~ues heretofore employed with zeolitic aluminosilicates. All ~ave uniform pore diameters which are inherent in the lat~ice structure of each species and which are at least about 3A in diameter. Ion exch~nge is ordinarily possible only after the organic moiety present as a resul~ of synthe3is has ~en removed from the pore D-13,443 systemu Dehydration to remove water present in the as-synthesized SAP0 compositions can usually be ~cc_ lished, to some d~gree a~ least, in the usual manner without removal of the organic moiety, but the absence of the organic species greatly ~acilitates adsorption and desorption procedures.
As illustrated hereinafter, the SAP0 materials have various degrees of hydrothermal and thermal stability, some being quitQ remarkable in this regard, and function well as molecular sieve adsorbents and hydrocarbon conversion catalys1s or catalyst ba5~s.
~ he invention is illustrated by the following Examples:
Example l (Preparation of SAP0-5) A reaction mixture was prepared oy combining 7.69 grams of 85 wt.% orthophosphoric acid (H3P04) and 33.29 grams of water, ~o which was added 4.58 grams of a hydrated aluminum oxide, (a psue~o-boehmite phase, 74.2 wt.~ Al203, 25.B
wt.~ ~2)' and stirred until homogeneous. To this mixture was first added 1.08 gramsof 37 wt.% ~Cl, and then 2.16 grams of a fumed silica (92.8 wt.
SiO2, 7.2 wt.~ ~2) and the mixture stirred until nomogeneous. Finally there was added 16.30 grams of an aqueous solution o 40 wt.~
tetraethylammonium hydroxide (TEA0~) and the mixture stirred until homogeneous. The composi~ion of th~
final reaction mixture in molar oxide ratios was:
A~2~3 : P205 : 0-565 (TEA)20:SiO2: 0.33 ~C1:80 ~2 In terms of molar proportio~ in which the silicon, aluminum and phosphorus ~ources are expressed as ~-13,443 f~3 T02, i.e., (SiXAlyPz)o, units, the reaction mixture can ~ expressed as:
0.27(TEA): (sio ~oA~ opo~40) 2 2 A por~ion of this reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and hea~ed in an oven at 150C at autogenous pressure for 168 hours. The solid r~action product was recovered by fil~ration, washed with water, and dried in air overnight at room ~emperature. The composition of the as-synthesi2ed solid product was determined in accordance with th~ law of mass balance using data from the chemical analysis of the mother liquor, specifically:
Al23 0.94 mgs./ml P205 24.6 mgs./ml SiO2 l.ll m~s./ml Na20 0.15 mgsO/ml C 65 mgs~/ml N 9.3 mgs./ml Cl 7.2 mgs./ml The (TEA~20 content was calculated rom the carbon analysis, and ~he H20 content was determined by difference. The as-synthesized composi~ion, denominated 5APO-5, thus had a chemical composition (anhydrous ~Si5):
0.05(TEA) O (Sio.22~l~.45Po.33) ~
The chemical composition in terms of mole ratios of oxiaes wa3:
0 985 Al203: 0.716 P20S : 0.97 SiO2 : 2 A portion of tbe solids was analyzed chemically and found to contain 6.9 wt.-% C, l.O'wt.-~ N, 16.3 2' 28.9 wt.-~ Al203, 38.3 wt.-~P205 and 14.4 wt.-% LOI~ giving a product compositon in Molar oxide ratios o~:

D-13~443 1.0 A1203:0-95 P205:0.96 SiO2 0.13 (TEA)20 0-8 ~2 whicn corresponds to the formula (anhydrous basis):
0.053 (TEA) (sio.2Alo.4lpo.39)o2 The x-ray powder difXraction pattern of tbe SAPO-5 product was characterized by the following data:
Table A
d 100 x I/Io 7.5 11.~ 100 lZ.9 b . 86 12 15.0 5.91 26 19.9 4.46 61 21.1 4.21 53 22.45 3.96 77 24.8 3.59 5 26.0 3.43 30 29.1 3.07 17 30.15 2.96 19 33.65 2.66 5 34.65 2.5g 16 This X-ray pattern and all other X-ray patterns appearing hereinafter were obtained using standard X-ray powder diffraction techniques. The radiation source was a high-intensity, copper target, X-ray ~u ~ operated at 50 Kv and 40 ma~ The diffraction pattern fro~ the copper X~ radiation and graphite monochromator i5 suita~ly recorded by a~ X-ray spec~rometer scintillation coun~er, pulse heigh~
analyzer and strip chart recorder. Flat compressed powder samples a~e scanned a~ 2 (2 theta) per minute, using a two second time constant.
In~e~planar spacings (d) in Angstrom units are ob~ained irom the position of the diffraction peaks expressed as 20 where ~ i5 the Bragg an~le as ob6er~ed on the strip chart. Intensitles were D-13~443 ~2~ 0~

determined from the heights of diffraction p~aks arter subtracting background, ~Io~ being the intensi~y of the strongest line or peak, and "I n being th~ in ensity of each of the other peaks.
As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about +0.4 on each reported value of 2 theta. This uncertainty is, of course, also manifested in th~
reported values of th~ d-spacings, which are calulated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from tne compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by ~he nota~ions vs, s, m, w and vw which represent very strong, strong, medium, weak and very weak, respectivelyO
Example 2 (Preparation of SAPO-5) ~ a~ A reaction mixture was prepared ~
combining 11.50 grams of 85 wt.% orthophosphoric acid (~3PO4) and 1.37 grams of a hydrated aluminum oxide (a pseudo-boehmite pha~e, 74.2 wt.
A12O3, ~5.8 wt.~ ~2) and stirring until homogeneous. To this mixture was added slowly and with stirring 88.50 grams of an aqueous solution of 23 ~t.~ tetra-n-propyl-ammonium nydroxide ~TPAOH).
Lastly tnere was added 71.30 grams of an aqueous silica ssl containing 33.7 wt.~ SiO2, and the m~xture stirred until homog~neous. The composition ~-13,443 ^ 22 ~

of ~he final reaction mixture in molar oxide ratios was: -2 0 5 P2~5 0-1 A12O3 0.5(TPA) 2 65 ~2 A portion of the reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluorethylene and heated in an oven at 200C at autogenous pressure for 168 nours. The solid reaction product was separated and recovered ~y centri~ugation and filtering, suspending in water and decanting to eliminate easily suspended amorphous material, then drying in air at room temperature. A portion of the solids was su~mitted for X-ray analysis. The above product was impure, but the ~ajor crystalline phase had an X-ray powder di~fraction pattern characterized ~y the da~a of Ta~le A, ~E~ The major phase was thus established to ~e SAPO-So (b) A reaction mixture having the same relative concentration of reagents as in part (a~ of tnis Example 2 was prepared ~y using five times the quantity of each lngredient and changing the or~er of admixture so ehat the phosphoric acid and the ~lumina were fisst admixe~, followed by admixture with the silica sol and finally with the TPAO~. The reaction mixture was crystallized in a sealed reactor at 200C for 24 hours. Part sf the larger, denser crystalline particles in the product were concentrated by elutriation with an upflow o~
water. ~his portion of the solid~ was submitted ~or X-ray analyis and had an X-ray powder di~fraction pa~rern essentially iden~ical to that in Example 1.
(c) A sample of ~he solids o~ part (b) _upra were examined using a scanning elec~ron D-13,443 microscope which showea the presence of hexagonal tablet-shaped crystals (a morphology found common to SAPO-5 preparations) with some plate-like growths attached, along with what appear2d to ~ amorphous dried gel par~icles. Certain of tne hexagonal ta~lets were subjected to energ~ dispersive analysis X rays ( DAX) and wer~ found ~o contain abou~ 90 percent silicon and tne balance aluminum and phosphorus in approximately equal proportio~s.
Example 3 ~Preparation of SAPO 5) A reaction mixture was prepared b~
combining 9.6 grams of a hydrated aluminum oxide (a pseudo-boehmite phase, 74.2 wt. ~ A12O3, 25.8 wt. ~ ~2) and 16. 2 grams of 85~ H3PO4 and mixing until homogeneous. To this mix~ure was added 125.1 grams of an aqueous sol containing 33.7 w~.
SiO2, and the mixture stirred until homogeneous.
To this mixture was adaed 1~o3 grams o~
tri-n-propyiamine (~r3N) ana tne resulting mixture stirred until homogeneous. Th* composition of the final reaction mixture in molar oxide ratios was:
10.0 SiO2 Pr3N A12O3 P2O5 2 A por~ion of the reaction mixture was sealed in a stainless steel pressure vessel Lined witn polytetrafluoroetnylene and heated in an oven at 200C at autogenous pres~ure for 96 hrs. Tne solid reaction product wa~ recovered by filtration, wa~hed with H2O and dried in air at room temperature.
portion of the solids was submitted for x-ray analysis. The product was impure bu~ the major crystalline phase had an X-ray dif~raction pa~tern essentlally identical to that in Example 1.

D-13,443 Example 4 (Preparation of SAPO-5) Another portion of the gel prepared in Example 1 was similarly digested but at 125C for 2 weeks. The X-ray di~fxaction pattern of the washed, filtered, room temperature dried solid was essentially iaentical to that of Example 1 with the exception of a minor amount of crystalline impurity.
Example 5 (Preparation of SAPO-5) A ~irst mixture was prepared by combining 80.1 grams of an aqu~ous silica sol (30 wt. %
SiO2) with 176.0 grams of an aqueous solution of 23 wt. % tetra-n-propylammonium hydroxide (TPAO~) and heating to boiling with loss of 37.0 grams of water. A second mixture was prepared by combining 27.5 grams of a hydrated aluminum oxide (pseudo-boehmite, 74.2 wt. ~ A12O3, 25.8 wt~ ~
H2O) with 46.1 grams of 85 wt. % orthophosphoric acid and 143.6 grams of water and stirring until homogeneous. The two reactions mixtures were mixed ~ogether, and the resultant mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxiae ratios was:
(T A)20 : 2.0 SiO2 : A1~03 : P205 : 90 H20 A portion of the reaction mix~ure was sealea in a stainless steel pressure vessel having an inert liner, ana heated ln an oven at 200C at autogenous pressure for 22 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at 100C. A portion of the solids was subjected to X-ray analysis. The product was impure ~ut the major phase had an X-ray powder diffraction pattern corresponding essentially to that in Example 1.

D-13,443 Example 6 (Preparation of SAPO-5) A reaction mixture was prepared by combining 90.7 grams of aluminum isopropoxide (Al~OC3H7)3) and 100 grams of water, to which was added 46.2 grams of 85 wt. ~ orthophosphoric acid (~3P04) and 11 grams of water. To this mixture was added 1.33 grams of a fume silica (95%
SiO2, 5% LOI) and ~he mixture stirred until homogeneous. To one third by weight of this mixture was added 27.2 grams of an aqueous solution of 40 wt. % tetraethylammonium hydroxide (TEAO~), and the mixture stirred until homogeneous. The composition o~ the final reaction mixture in molar oxide ratios was:
0.5 (TEA)20 : 0.1 SiO2 : A1203 : 0.9 P205 42 ~2 The reaction mixture was placed in a stainless steel pressure vessel lined with an inert plastic material ~polyte~rafluoroethylene) and heated in an oven at 150C at autogeneous pressure for 45 hours. The solid reactlon product was recovered by centrifugation, washed With water, and aried in air at room temperature. A portion of ~he solids was subjected to X-ray analysis. The above product (SA~0-5) was impure but the major phase had an X-ray powder diffraction pattern characterized ~ the data in Table B, below.

D-~3,443 ~z~z~

~ 26 ~

TA~LE B

d 100 X I/Io 7~50 11.8 100 12.9' 6~84 12 *
15~0~ 5~91 23 19~9( ~o~6 56 20~9~ 4~24 52 *
22~5~ 3~95 68 ~4~7~ 3060 2 26.1 3~40 29 28~9l 3~9 8 30~2~ 2~95 17 33~7~ 2~6 3 34~8l 2~5~ 12 37~1~ 2~42 2 37~7~ 2~39 7 41~81 2~16 42~6l 2~12 2 48.ll 1.89 2 *
52~ 76 2 * col .ains impurity peak Example 7 (Pr~ ~aration of SAPO-5) A re~ tion mixture was prepared by combining 57.~ grams of 85 wt. ~ orthophosphoric acid (~3PO4) ~ .d 29~5 grams of water with 102.1 grams aluminw isopropoxide tAl(OC3~7) 3), The well-stirr2d I xture was added ~o 30~1 grams of an aqueous silic. sol containing 30 wt. % SiO2, and grams of wat2: and the resulting mixture s~irred until homogent U8. To 58.5 grams of this mixture was aade~ 5~.: grams of an aqueous solution of 25 wt. % tetra-n ropylammonium hydroxide (TPAO~), and the mixture s rred until homogeneous~ The composition o: the final reac~ion mixture in terms of molar oxia~ ra~ios was:

D-:L3, 443 ~2~3~V~

~ 27 -0 5 ~TPA)2O 0-6 SiO2 ~ A123 P2O5 : 2 In terms of molar proportions in which the silicon, aluminum and phosphorus sources are expressed as TO2, i.e., (SiXAlyPz)O2, units, the reaction mixture can be expressed as:
0.22(TPA): ~sio 13A10.43Po.43)o2 2 A portion of the rea¢tion mixture was placed in a stainless steel pressure vessel having an inert liner, and heated in an oven at 2~0C at autogeneous pressure for 48 hours. The solid reaction product was r~cover~d ~y centrifugation, washed witb water, and dried in air at 100C. As indicated ty X-ray analysis the above product was impure but the major phase (SA~O-S) nas an X-ray powder diffraction pattern essentially iden~ical to that in Example 6.
Example 8 (Preparation of SAPO-5) A first mixture was pr~pared by combining 57.7 g-ams of 85 wt. % orthophosphoric acid (H3PO4~ ~nd 15.0 grams of water and adding to 102.1 grams of aluminum isopropoxide (Al(OC3~7)3) and mixing well. A solution of 6.0 grams of NaO~ in 11.8 grams of ~ater was mixed into 30.1 grams oI an aqueous sol containing 30 wt.
~ SiO2 stabilized with a small amount of NaOH, to form a second mixture. The ~wo mixtures were com~ined and stirred until homogeneous. To 71.0 grams of this third mixture were added 24.6 grams of an aqueous solu~ion of 40 wt. ~ tetraethylammonium hydroxide (TEAO~) and 26.0 grams o~ water, and the mixture ~tirred until homogeneous. The chemical D-13,443 ~20~6 composition of the ~inal reaction mix~ure in terms of molar oxide ratios was:
0 5 (~EA)2O 0 3 Na2O A123 P2O5 :0.6 SiO2 60 ~2 A portion oi the reaction mixture was placed in a seainless steel pressure vessel lined with polytetra~luoroetAylene and heated in an oven at 200C at autogenous pressure for 48 hours. The solid reaction proauct was recovered by centrifugation, washed with water, and dried in air at L00C. The above product was impure but a major crystalline phase had an X-ray powder diffraction pattern essentially identical to tnat in Example 6.
The produc~ was designated SAPO-5.
Example 9 (Preparation of SAPO 5) (a) A reac~ion mixture was prepared by combining 18.44 grams of 85 wt. ~ orthophosphoric acid (~3PO4) and 11.56 grams of water, to wnich was added 11.04 grams of hydrated aluminum oxide (a pseudo-boehmite phase, 74.2 wt. % A1203, 25.8 w~ 2)~ and stirred until homoge~eous. To this mixture was added a dispersion of 2.08 grams of a ~umed silica (92.8 wt. % SiO2, 7.2 wt. ~ H2O), in 81.64 grams of an aqueous solution of 40%
t~tra-n-propylammonium hydroxide (TPAO~), and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
A12O3 : P2O5 : 0.4 SiO2 : (TPA)2O : 50 ~2 A portion o~ tne reaction mixture was sealed in a stainless steel pressure vessel lined with an inert plaa~ic material and heated in an oven at 225C at D-13,443 V3L~

autogeneous pressure for 24 hours. The solid reaction product was recovered by centrifuging and washing with water, and driea in air at roOJQ
temperature. The above product has an X-ray powder dif~raction ~attern characterized by the ~ollowing data:
TABLE C
d 100 X I/Io 7.4 11.95 100 12.9 6.86 11 14.9 5.95 25 19.7 4~51 51 21.1 4.21 67 22.3 3.99 92 24.a 3.59 5 25.8 3.453 37 28.9 3.089 21 ~9.9 2.988 22 33.~ 2.667 5 34.4 2.6~7 16 36.8 2.442 3 37.6 2.3g2 9 ~1.5 2.176 ~
42.2 2.141 5 42.8 2.113 3 43.5 2.0~30 3 44.9 2.019 3 47.6 1.910 Chemical analysis established that the solids ~product) comprisea 8.0 wt. ~ C, 0.97 w~. ~ N.~7.22 2' 33-5 wt. ~ A12O3, 44.5 Wt.
P2O5, 12.8 wt. ~ LOI, giving a product composition in terms of molar oxide ratios of.
0.085 (~PA)2O: 9.37 SiOz: 1.0 A12O3: 0.96 P2O5O 0.2~ ~2 In terrQs of moles of organic constituent per average ~-13,443 mole f ~2 units, the composition was (anhydrous basis):
0.040 (TPA) : (sio.o8Alo.47po.45)o2 (b) A portion of solid crystalline product was calcined in air at abou~ 600C for 1 hour. The calcined product had an X-ray powder dif~raction pattern characterized by the following data:
TABLE D
d 100 X I/Io 7.5 11.79 100 13.0 6.81 27 lS.0 5.91 11 19.9 ~.46 42 21.3 ~.17 62 22.6 3.93 96 25.0 3.56 4 2~.0 3.427 44 29.2 3.058 23 30.2 2.959 23 33.8 2.652 6 3~.6 2.592 17 (c) Adsorption capacities were measured on the calcined product of part ( b), supra using a stand~rd McBain-Bakr gravimetric adsorp~ion apparatus. The following data were ot~ained on a sample activated a~ 350C.
Kinetic Pressure, Temp., ~t. ~
Diameter, ~ ~orr ~C Adsorbed 2 3.46 100 -183 14.5 2 3.46 750 -183 19.8 Cyclohexane 6.0 60 24 10.9 Neopentane 6~ 2 743 24 7.6 H2O 2.65 406 24 14~7 H2O 2.65 20.0 24 31.3 ~he pore size of the calcined product is greater D- 13 ~ 44 3 q~7~

than 6.2A, as shown by adsorption of neopentane, kinetic diameter of 6.2A.
(d) Ion-exchange studies were carried out on 1.0 gram of the product o~ part (a) calcined in air for 2 hours at 600C. Tne sample was stirred at room temperature for 10 minutes with 25 cc of a saturated NaCl solution containing 1.0 gram o~
NaHCO3. After being washad with 1 liter of hot water and then 1 li~er of cold water, the product was dried in air at 100C ror 2 hours. Chemical analysis o~ the product showed 29.5 wt.
A12O3, 39.0 wt. ~ P2O5, 7.6 wt. ~ SiO2, 3.3 wt. % Na2O corresponding to a product composition in molar oxide ratios of 1.0 A12O3: 0.95 P2O5: 0.44 SiO2: 0.18 Na2O
Example 10 ~Preparation-of S~PO-5) Using a procedure essentially the same as in Example 9(a) suPra~ and using aluminum isopropoxide as the alumina source, phosphoric acid as the P2O5 source, a fumed silica as the silica source and a 25~ aqueous solution of tetra-n-butylammonium hydroxide (TB~O~) as the templating agent, the ~ollowing gel composition was prepared in terms o~ mole ratios sf oxides:
2 3 P2O5 0 4 SiO2 (TBA)2o 100 H O
The gel was digested and crystallized for 72 hours under autogenous pressure in a sealed reac~or at 200C~ SAP0-5 was produced as evidenced by the X-ray powder dif~ract1on pattern of the solid proauc~.

D-13,443 ~v~

Example 11 (Preparation of SAPO-5) Using essentially ~he same procedure as in Example 9(a3 supra, and using a pseudo-boemite as the alumlna source, triethylphosphate as the P2O5 source, a fumed silica as the SiO2 source and a mixture of tetra-n-propylammonium hydroxide and tetra~.ethylammonium hydroxide as the templating agents, the following gel co~posi~ion was prepared in ~erms of mole ratios o~ oxides.
A12O3: P2O5:0.4 SiO~:0..5 ~TPA)~O:O.Ol(TMA)2O:50 ~2 The gel was digested and crystallized under autogenous pressure in a ~ealed reactor for 24 hours at 200C. SAPO-5 was produced as evidenced b~ the X-ray powder diffraction pattern of the solid product.
Example 12 (Preparation o~ SAP0-5) (a) A reaction mixture was prepared ~y combining 40.9 yrams aluminum isopropoxide (Al(OC3~7)3) and 44.1 grams H2O to which was added 23.1 grams of 85 wt. ~ orthophosphoric acid (~3PO4) and 5 yrams ~2 and the mixture stirred well~ Then 60.7 grams o~ an aqueous sol containing 30 wt. ~ SiO2 was added to ~he mixture which was s~irred until homogeneous. To this mixture was added Z8.7 gr~ms of tri-n-propylamine (Pr3N), and the mixture stirred until homogeneous. The composition of the f inal reaction mix~ure in molar oxide ratios was:
2.0 Pr3N: 0.3 SiO2: AlzO3: P2O5 2 A portion of ~he reaction ~ixture was sealed in a s~ainless steel pre~sure vessel lined with pol~etxafluorethylene and heated in an oven at D- 13 , 443 ~3;Z~

15~C at auto~enous pressure tor 168 hours. The solid reaction proauct was recovered by centri~ugat~on, washed with water and dried in air at 100C~ The proauct bad an X-ray powder diffraction pattern essentially identical to that in Example 6, and was designated SAPO-5. Chemical analysis showed 5.5 wt. % C, 0.~ wt. % N, 35~3 wt.
~ A12O3, 46.2 wt. ~ P2O5, 1.6 wt. ~ SlO2, 15.1 wt. ~ LOI, glving a product compostion (anhydrous ~sis):
0.038 Pr3N (slo D 02Al0.51 0O47 2 The composition in terms of mole ratios of oxides is:
3 A123 0-94 P2O5: 0-08 Si2 1-3 ~ O
EDAX (energy dispersive analysis by X-ray) microprobe analysis, performed in conjunc~ion wi~h SEM (scanning electron microscope) study, on relatively clean crystals having a crystal morphology characteristic of SAPO-5 gives the following analysis, based on relative peak helghts:
Si 0.2 Al 1.0 P 0.9 The product was calcined ln air at about 550C ~or ~3 hours. ~he calcined product had an X-ray powder diffraction pat~ern essentially dentical to that in Example 6.
(b) Adsorption capacities were measurea on the calcined product of part (a) using a standard ~cBain-Bakr gravimstric adsorption apparatus. The olLowing data were obtained on a sample activated at 350C.

D-~3,443 Rinetic Pressure Temp., Wt. ~
Diameter, A Torr C Adsor~ed 2 3.46 102 -183 12.0 2 3.46 7~3 -183 14.9 Cyclohexane 6.0 52 24.6 7.8 Neopentane 6~2 99 24.8 5.0 ~2 2.65 4.6 23.3 6.8 ~2 2.65 20.2 23.2 22.1 The pore size o~ the calcined product is greater than 6.2A, as shown by adsorption of neopentane, kinetic diameter of 6~2A.
(c) 5APO-5 was also produced using the mixing procedure of part (a~ supra and using as the templating agent choline hydroxide [(CH3)3NCH2C~2OH]O~ in proportions with the other reagents to form a reaction gel having a composition in terms o~ mole ratios:
1 0 Choline hydroxide: A12O3: P2O5: ~ 2 when the gel was crystallized at 200C ~or 43 hours.
Example 13 (Preparation o~ SAPO-5) (a) A reaction mixture was prepared by combining 23.06 grams of 85 wt. % orthophosphoric acid (~3PO4) and 82.47 grams of water, to which was added 13.81 grams of hydrated aluminum oxide, ~74.2 wt. ~ A12O3, 25.8 wt. % H2O) and stirred until homogeneous. To this mixture was added a dispersion of 2.59 grams of ~umed silica (9208 wt.
SiO2, 7.2 wt. ~ ~2) in 29.41 grams of tri-n-propylamine ~Pr~N), and the mixture stirred until homogeneous. The composition of the rinal reaction Mixture in molar oxide ratios was:

A123 P2O5 0-4 SiO4 : 2.0 Pr3N 50 ~ O
The reaction mixSure was sealed in a stainless s~eel D-13,443 - 35 - .

pressure vessel lined with an inert plastic material and heated in an oven at 200C at autogenous pressure for 24 hours. The solid reaction product was recovered by centrifuging, washing with water, and drying in air at room temperature. The product was impure but the major phase had an X-ray powder diffraction pattern characterized by the following data.
TA~LE E
d 100 X I/Io 7.4 11.~5 88 12.8 6092 14 14.8 5.99 21 13.6 4.53 47 20.9 ~.25 61 22.2 g.00 100 24.6 3.62 5 25.9 3.44 33 2~.9 3.08~ 23 30.0 2.979 21 33.5 2.675 5 34.4 2.607 16 36.8 2.442 7 37.5 2.398 14 40.6 2.222 2 41.4 2.181 3 42.0 2.151 5 42.6 2.122 5 43.5 2.080 3 47.6 1.910 7 Chemical analysis established that the SAPO-5 product had a composition (anhydrous basis):
0.042 Pr3N ~Sio 095A10.47Po.43s) 2 which corresponds, in terms of mole ratios of oxides (anhydrous ~a5 i5 ) A12O3: 0.92 P2O5: 0.4 SiO2: 0.18 Pr3N
(b) Adsorption capacities were measured on the calclned product (600~ for 1 hour in air) using D-13,443 a standard NcBain-Bakr gravimetric adsorption apparatus. ~he followin~ data were obtained on a sample ac~lvated at 350Co Kinetic Pressure, Temp., ~t. ~.
Diameter, A Tvrr C Adsorbed 2 3.46 100 -183 13.2 2 3.46 750 -183 18.1 Neopentane 6.2 750 24 7.3 H2O 2.65 4.6 24 11.0 ~2 2.65 21.0 24 27.2 The pore size of the calcined product is greater than.6.2A, as shown by adsorption of neopentane, kinetic diameter of 6.2A.
~ c) Ion-exch~nge studies were carried out on 1.0 gram of the product of part (a) calcined in air for 2 hours at 600C. The sample was slurried at room-~emperature for lG minutes with 25 cc of a saturated NaC1 solution containing 1.0 gram of Na~CO3. After ~ing washed with 1 liter of hot water and 1 liter of cold water, the product was dried in air at 100C for 2 hours. Chemical analysis of the ion-exchanged material showea 0.96 wt-% Na20 and a composition in terms of molar ratios to ~:
~i2/A123 = 0 49 P25/A123 = 0.98 ~a2/A12~3 2 0.055 Bxample 14 (Preparation of SAPO-5) Diethylethanolamine, (DEA) was employed ~o templa~e the formation of SAP0-5 in a reaction mixtu~e prepared by combining 204.3 grams of alumin~m isopropoxide with a solution of 115.3 grams of 8 wt-% ~3PO4 ln 385.5 grams of water and stirring un~il homogeneous. Silica in ~he form of an a~ueous 801 (30 wt-~ SiO2) was then added in an ~-13,443 amount of 30.1 grams. To one fourth ~ weight of the resulting composition was added 14.6 grams of ~he templating agent to form a ~inal reaction mix~ure having tbe following composition in terms o~
mole ratio-~ of oxides~
(DEA) 0 3 SiO2 A123 P205 2 A~er aigestion ~nd crystallization of the reaction mixture a~ auto~enous pressure at 200C for 168 hours, the resulting SAPO-5 was found to have a chemical compo~ition in terms of mole ratios o~
oxides of 0-11 (DEA)20:0.15 SiO2:A1203:0.92 P205 2 The species SAPO-5 as re~erred to herein is a silicoaluminophosphate material having a three-dim~nsional microporous crystal framework structure of PO2 7 A102 and SiO2 tetrahedral units, and whose essential empirical cnemical composition on an anhydrous basis is:
mR : (SiXAlyPz)02 whereln "R" represents at least one organic templating agent present in the intracrystalline pore ~ystem; "m" represents the moles of "R~ present per mole of ISlxAlyP2)02 and has a value of from zero to 0.3, ~xn, ~y" and "z" represent respectively, the mole rractions of silicon, aluminum and phospho~us present in ~he oxide moiety, said mole ~ractions teing within the compositional area bounded ~y points A, B, C, D and E on the ternar~f diagram whlch is Fig~ 1, or pre~erably ~ithin the area bounded ~y points a, b, c, d and e on the ~ernary diagram which is Fig. 2, said silicoaluminophosphate having a characteris~ic X~ray D-13,443 ~Z~

powder di~fraction pattern which contain~ at least the d-spacings set ~orth below in Table I. In the form as synthesized in accordanc~ with the process of tnis invention, "m~ has a value of from 0.02 to 0.3.
Table I

Relative d Intensity 7.35 - 7.6512.0 - 11.56 m - vs 19.6 - 19.954.53 - 4.46 m 20.9 - 21.34.25 - 4.17 m - vs 22.3 - 22.63.99 - 3.93 m - vs 25.85 - 26.153.46 - 3.40 w - m All of the as-synthesized SAPO-5 compositions for which x-ray powder diffraction data have presently been obtained have patterns which are within the generalized pattern o~ Table II below:
Table II

d 100 x I/Io 7.35 - 7.6512.0 - 11.56 52 - 100 12.75 - 13.16.94 - 6.76 7 - 18 14.8 - 15.15.99 - 5.91 13 - 25 19.6 - 19.954.53 - 4.47 31 - 56 20.~ - 21.34.25 - ~.17 30 - 100 2~.3 - 22.63.99 - 3.93 44 - 100 24.6 - 24.~3.62 - 3.59 2 - 5-25.8 - 26.153.453 - 3.~08 19 - 37 28.9 - 29.253.089 - 3.053 8 - 21 29.9 - 30.252.998 - 2.954 11 - 22 33.3 - 33.852.691 - 2.648 2 - 5 34.4 - 34.~2.607 - 2.578 9 - 1 36.8 - 37.22.442 - 2.417 2 - 3 37.5 - 37.92.398 - 2.374 6 - 13 40.6 - 41.~2.222 - 2.201 0 - 1 41.4 - 41.82.181 - 2.161 1 - 3 42.1 - 42.4~.146 - 2.~32 2 - 5

4~.6 - 42.g2.122 - 2.10~ ~ - 4 D-13,443 Table II (con'td) d 1~0 x IJIo 43.5 - 43.6 2.080 - 2.076 1 - 3 44.~ ~ ~5.0 2~019 - 2.014 0 - 3 47.55 - 4~.1 l.gl2 - 1.892 3 - 8 51.4 - 51.65 1.778 - 1.773 0 - 2 51.8 - 52.1 1.765 - 1.755 0 - 2 55.4 - 55.8 1.658 - 1.6~7 1 - 4 I~ will be no~ea in the case of SA~0-5 that the essential d-spacings of Table I are common to the X-ray pattern~ of all of the as-synthesized forms, i.e., template-containing, and those calcined forms of SAP0-5 which contain no tamplating agent.
It has been found, however t that in the case of the X-ray patterns of several other SAPO species, there can be an apparent substantial difference in the posi~ion and intensities of certain d-spacings ~tween ~he as-synthesized and the calcined form.
These dif~erences are not believed to be indicative of a fund~ -ntal structure change as a consequence of calcination, but ra~her indicate a relaxation of lattice distortion caused by the presence of organic templating agents iA the in~racrystalline pore system which are too large to be accommodated wiShout some bond-s~retching within ~he S~PO crystal lattica. Upon calcination, the removal o tAe organic ~pecies by thermal destruction permi~s ~he struc~ure to relax to its normal con~i~ion. Thus it may be po~sible o utilize a templating agent in the preparation sf SAPO-5 or any SAPO speci~s of this i~ven~ion which is large enough to change the position of one or more d-spacings wi~h respect to the X-ray patterns presented in this application for D-13,443 ~z~

such species while not creating a distinct silicoaluminophosphate crystal structure.
Example 15 (Preparation of SAPO-ll) (a) A reaction mixture was prepared by combining 160 grams of water and 90.7 grams of aluminum isopropoxide (Al(OC3~7)3) to which was added 51.3 grams of ~5 Wt. ~ orthophosphoric acid (~3PO4) and the mixture stirred well. To this was added 1.4 grams of a fumed silica (95 wt.
SiO2; 5 wt. % ~2) and then, after stirring, 7.4 grams o~ di-n-propylamine (Pr2N~) was adde~ to one-third by weight of the above mixture. The final mixture was stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
Pr2NH:O.1 SiO2:A1203:P205:4~! H20 In terms of molar proportions in which the silicon, alumlnum and phosphorus sources are expressed as TO2, i.e., (SiXAlyPz)O2, units, the reaction mixture can be expressed as:
( 2 H) (sio . 02A1oO49sio 49~O2:10.2~2o The reaction mlxture was sealed in a s~ainless steel pressure vessel lined with polytetrafluoroethylene and h0ated in an oven at 150~C a~ autogenous pressure ~or 133 hours. The soli~ reaction product was recovered cy centrifugation, washed with water, and dried in air at room temperature. Chemical analysis established the composition to comprise 3.5 wt.-~ C, 0.65 wt.-~ N, 38.2 wt.-~ A12O3, 35.9 wt. ~ P2O5, 2.9 wt. ~ 5iO2, 17.7 wt.-~ LOI, giving a product composition (anhy~rcus ~a51S) for the SAPO-ll as ~ollows:

D-13,443 0.037 Pr2NH: (sio. 04Alo.S7P0.39)O2 or, in terms of mole ratios of oxides:
0.13Pr2N~:A1203:0.68P205:0.13SiO2:2.1~20 The as-synthesized composition had an x-ray powder diffraction pattern cAaracterized by the following data: , Table F
d 100 ~ I/Io 8.~5 10~98 20 9.4 9.41 36 13.1 6.76 13 15.65 5.66 23 16.3 5.44 3 18.95 4.68 5 20.4 4.35 36 21.0 4.23 10 22.1 ~.02 54 22.5 3.95 ~ 56 22.7 sh* 3.92 r 23.15 3.84 66 24.5 3.63 ~ 8 24.7 3.60 26,4 3.38 19 27.2 3.28 28.6 3.121 14 29.0 3.079 3 29.45 ~.033 6 31.5 2.~40 8 3~.8 2.730 13 34.1 2.629 8 35.75 2.512 3 35.3 2.475 3 37.5 2-3~8 37.8 2.380 ~ 10 39.3 2.292 3 40.3 2.23a 2 ~2.~ 2.113 6 44.9 2.019 4 46.8 1.941 48.7 1.870 2 50.5 1.807 3 54.6 1.684 4 *sh ~ shoulder D-13,443 - ~2 -(b) A portion of the product of part (a) was calcined in air at 500C for 1 hour, then at 600C ~or 1 hour. The calcined proauct has an x-ray powder di~fraGtion pattern characterized by the rollowing data:

2~ d 100 x I/Io 8.1 10.9 54 ~.6 9.2 53 12.8 6.92 13.~ 6.78 ~ 18 15.85 5.59 16.1 (sh)5.50 ~ 46 19.4 (sh)4.58 20.3 4.37 ~ 30 21.3 4.17 100 21.9 (sh)4.06 39 22.3 3.99 75 22.9 (sh)3.88 41 23~3 3.82 60 24.1 3.69 9 24.9 3.58 5 26.35 3.3~ 20 28.9 3.089 12 2g.5 3.028 11 30.3 2.950 5 31.7 2.823 9 32.75 2.734 14 34.0 2.637 4 34.55 2.596 5 36.2 2.4~1 7 37.1 2.423 2 37.8 ~.380 10 39.4 2.287 2 41.0 2.201 43.Z 2.09~ 3 44.7 2.027 3 48.3 1.884 51.2 1.784 2 * sh ~ shoulder (c~ Adsorption capacities were measured on this calcined product using a standard McBain-Bakr gravimet~ic adsorption apparatus. The following data were obtained on a sample activated at 350C.

D-13,443 ~2~ ~

- 43 ~

Kinetic Pressure, Temp, Wt. %
Diameter, A T - C Adsorbed 2 3.46 102 -183 7.3 2 3.46 743 -183 15.3 Cyclohexane 6.0 52 24.6 6.9 Neopentane 6.2 300 24.8 1.7 ~2 2.65 4.6 23.9 11.4 ~2 2.65 20.2 23.2 18O0 The pore size of the calcined product is ~6O0A and ~6.2A as show~ by adsorption o~
cyclobexane, kinetic diameter of 6.0A and negligible adsorption of neopentane, kinetic diameter of 6.2A.
Example 16 (Preparation of SAPO-ll) SAPO-ll was crystallized ~rom a reaction system containing a mixture of two organic templating agents prepar2d by combining an aqueous solution consisting of 11.53 grams of 85 wt-~orthophosphoric acia and 22.0 grams of water with 6.9 grams of a hydrated all- 1nur oxide (a pseudo-boehmite, 74.2 wt-~ A1203, 25.8 wt-%
~2) and s~irring until homogeneous~ To this mixture was added a mixture of 1.3 grams of a ~umed silica (92.8 wt.~ Si02, 7.2 wt.-~ ~2) in 32.46 grams o~ an aqueous solution of 40.0 wt.-%
tetra-n-butylammonium hydroxide (TBAOH)~ ~his mix~ure was stirred until homogeneous, and then 5.10 grams of di-n-propylamine (Pr2N~) was added with stirring until again homogeneous. Th~ composi~ion of the final reaction mixture in molar oxide ratios ~as:
2 ( ~2 2 3 2 5 Si 2 5 ~he reaction miY.ture was crystallized at 200C under autogenous pressure ~or 24 hours in a reactor lined D-13,443 with polytetrafluoroethylene~ X-ray analyses of a portion of tne crystalline product indicated the product to have an X-ray pow~er di~fraction pattern essentially identical to the SAPO-ll product of Example 15~a) su~ra.
Example 17 ~Preparation of SAPO-ll) A reac~ion mixture was prepared by combining 23.06 grams of 85 wt.-% orthophosphoric acid (~3PO4) and 23.06 grams of water, to which was added 13.81 grams of a hydrated aluminum oxide (a pseudo boehmite phase, 74.2 wt~-% A1203, 25.8 w~ 2) and stirred until homogeneous. To this mixture was added a mixture o~ 3.90 grams of a fumed silica (92.8 wt.-~ SiO2, 7.2 wt.-% ~2) in 103.5 grams of a solution of 25.0 wt.-~tetra-n-butylammonium hydroxide (TBAO~) in methanol. This mixture was stirred untll homogenous and then 20.41 grams of di^n-propylamine was added with stirring un~il a homogeneous mixture was obtained. The composition of the final reaction mixture in molar oxide ratios was:
2 0 Pr2NH 0.5 (TBA)20 A1203 P205 0-6 Si2 2 3 A portion of the reaction mixture was placed in a stainless ste~l pressure vessel lined with an inert pla~tic ma~erial and heated in an oven at 209C at autogenous pressure for 48 hours. The solid reaction proauct was recovered ~ centriruging and washing with water, and dried in air at room temperature. A portion of the solids was submitted for X-ray and chemical analysis~ The above product was impure, but the major constituent had an X ray powder diffraction pattern essentially identical to D-13,443 ~20~0~6 ~ 45 -that of the SAPO-ll composition of Example 15(a) supra. By chemical analysis, the compositon was found to ce 31.5 wt.-% A1203, 40.9 wt.-~P205, 12.0 wt.-~ Si02o 8.1 wt.-~ ~, 1.2 wt.-%
N, ~nd 13.9 wt~-~ LOI.
Example 18 (Prepara~ion o~ SAPO-ll~
A reaction mixture was prepared by com~lning 57.8 grams of 85 wt. ~ orthophosphoric acid (~3PO4) and 29.5 gr~ms o~ water, which was added to 102.1 gram~ aluminum i~oprspoxide (Al(OC3~7)3) and the mixture stirred well.
The mixture ~as added to 30.1 grams of an aqueous sol containing 30 wt. ~ SiO2, and 4 grams of water and the mixture stirred until homogeneous. To 65.7 grams of this mixture was added 6.7 grams of di n-propylamine (Pr2N~), and the mixture qtirred until homogeneous. The composition of the final reactlon mixture in molar oxide ratios was:
0.9 P~2NH:0-6 SiO2;A12O3 P2O5 5~ ~2 Part of the reaction mixture was sealed in a stainless steel pressure vessel llned with an in~rt plastic material and heated in an oven a 200C at autog~nous pressure ror 48 houss. The solid reaction product was recovered by centrirugation, washed with water, and aried in air a~ room temperature. X-ray analysis and chemical analysis e~tablisned tne product to be SAPO-ll. The product had an x-ray powde~ dif~raction pattern essentially identical to tnat in Example 15(a). In accordance with the data from ~he chemical analysis, ~he composition consisted of 4.9 w~. ~ C, 0.9 wt. % N, 36-9 wt- ~ A123~ 46-3 wt. ~ P2 5 ~-13,443 ~3 SiO2, 9.4 wt. % LOI, giving a product composition (anhydrous basis) of:
n . 047 Pr2N~: (sio, 062Alo.4~Po.44)O2' or in te~ms of mole ratlos of oxldes:
0.19 Pr2~:1.00 A1203:90 P20540.25 Si02:0.38 ~2 Example l9 (Preparation of SAPO-11) A reac~ion mix~ure was prepared in the sam~
way as in Example 18. Part of the reac~ion mixture was placed in a s~ainless steel pressure ves~el lined wi~h polytetrafluoroethylene and heated in an oven at 20noc at autogenous pressure for 168 hours~
The solid reaction product was recovered by cent~ifugation, washed with water/ and dried in air at 100C. A portion of the solids was submitted for x-ray and infrared analysis. The SAPO-ll product had an x-ray powder diffraction pattern essentially identical to that in Example l5(a)O
Example 20 (Preparation of SAPO-ll) (a) A re~ction mixture was prepared in essentialiy ~he same way as in Example 19. One half o~ tne reaction mixture was sealed in a stainless steel pressuxe vessel lined with an inert plas~ic material and heated in an oven at 200C at autogenous pressure fox 168 hours. The solid reaction product was recovered by centrifugation, washed with water, and dried in air at 100C.
Chemical analysis of the SAPO-ll product showed 37.0 wt.-~ A12~3r 44.6 wt- ~ P2O5' SiO2, 9 3 wt.-~ LOI, ~C and N were not determined) giving a non-volatile product composi~ion in solid molar oxide ratios of:
0~35 SiO2 : 1400 A12O3 : 0.87 P2O5 D-13, 443 ~-z(~2~6 The above product had a~ x-ray powder diffraction pattern essentially identical to that in Example 15(~.
(b) A portion of the above product was calcined in alr at abDut 550C for 7 hours. The ca1cined produc~ had an x-ray powder dif~raction pattern characterized by the following data:

Table J

23 d 100 x I/Io 8.1 10.92 25 ~.85 8.98 48 11.7 7.56 4 1~.8 6.92 21 13.6 6.51 3 14.7 6.~3 3 16.1 5.50 63 17.6 5.04 2 19.55 4.54 10 20.0 4.44 26 20.8 4.27 9 21.95 4.05 100 22.3 3.99 ~ 52 22.5 3.95 J
23.5 3.786 56 24.1 3.693 17 24.3 3.663 8 25.8 3.453 19 26.8 3.326 9 ~7.~5 3.273 12 27.7 3.220 14 2~.6 3.121 3 2g.7 3.008 27 30.4 2.g40 16 31~8 2.814 6 32.7 2.739 19 34.1 2.629 5 34.6 2.592 3 35.65 2.51~ 7 37.3 ~.411 5 D-13,443 - 48 ~

Table J (Cont'd) d 100 x I/Io 380~ 2.344 2 38.8 2.321 11 ~1.05 2.199 5 ~3.6 2.076 2 ~4.7 2.027 3 45.45 1.996 2 ~9.2 1.852 7 53.7 1.707 2 54.6 1.681 (c) Adsorption capacities were measured on this calcined product using a standar~ McBain-Bakr gravimetric adsorption appara~us. The following data were o ~ained on a sample activated at 350C.
Kinetic Pressure, Temp., Wt. ~
Diame~er, A Torr C Adsorbed 2 3.46 102 -183 8.~
~2 3.~6 743 -183 10.9 Cyclohexane 6.0 52 24.6 4.5 Neopentane 6.2 300 24.8 0.8 H20 2.65 4.6 2309 10.5 ~2 2.65 20.2 23.2 15.4 The pore size of the calcined product is ~6.0A and ~5.2A as shown by adsorption of cyclohexane, kinetic diamet2r of 6.OA and nil adsorption o neopentane, kinetic diameter of 6.2A.
(d) Another portion o the solid crystalline produc~ obtained in part (a) was calcined in air on a programmed run from 100C to 600C for 8 hours. The calcined product had an x-ray powder dif~raction pattern essentially identical to that in ~xample 15(b).
(e~ Adsorp~ion capacities were measured on ~his calcined product of par~. (d) using a standard McBain~akr gravi~e~ric adsorp~ion apparatus. The D-13,443 2~

ollowing data were obtained on a sample activated at 350C.
Kinetic Pressure, Temp., Wt. ~
Diameter, A T_ C Adsorbed 2 3.46 102 -183 8.1 2 3.46 743 -183 11.2 Cyclohexane 6~0 52 24.6 4.6 Neopentane 6.2 300 24.8 0.7 ~2 2.65 4.6 23.9 10.6 ~2 2.65 20.2 23.2 15.~
The pore size of the calcined product is >6.0A and ~6.2A as shown by adsorption o~
cyclohexane, kinetic diameter of 6.0A and nil adsorption o~ neopentane, kine~ic diameter of 6.2A.
Example 21 (Preparation of SAP0-11) A reaction mixture was prepared by combining 23.1 grams of 85 wt. ~ orthophosphoric acid (~3P04) and 60 ~rams of water, which was added to 40.9 grams of aluminum isopropoxide (Al(OC3~7)3) and 5.0 grams o~ water and the mixture stirred well. To this mixture was added 6~9 grams of an aqueous sol containing 30 wt. ~ SiO2, and then 5 grams of water and stirred until homogeneous. To this mixture were added 10.1 grams of diisopropylamine (i-Pr2NH) and 5.0 grams of water, and the mixture stirred until homogeneous.
The composition of the final reaction mixture in molar oxide ratios was:
1.0 i-Pr2NH:A1203:P205:0.3 SiO2 2 Part of the reaction mixture was placed in a stainles~ ~teel pressure vessel lined with an inerS
plastic material and heated in an oven at 200C at autog~nous pressure for 48 hours~ The solid reaction product was recoverea by centrifugation, D-13,443 ~02(~

washed with water, and dried in air at 100C. The SAPO-ll product was impure but the major phase had an X-ray powder diffraction pattern essentially identical to that in Example 15 (a).
Example 22 (Preparation of SAP~ 11) To a reaction mixture having the composition (in terms of oxide mole ratios):
3 7)2N~:Al2o3 P2~s 0-6 Si2 50 H20 and ~ormed from di-n-propylamine~ aluminum isoproproxide, silica sol, phospnoric acid and water, was added 10 wt.-~ SAPO-ll seed crystals (~ased on tne solids content of tne gel), and the mixture crystallized ln a stirred reactor under autcgenous pressure at 150C for 19 hours. The SAPO-ll product had an X-ray powder diffraction pattern essentially identical to the product of Example 15(a) above.
The species SAPO-ll as referred to herein is a silicoaluminopbosphate material having a three-dimensional rnicroporous crystal framework structure of PO2 , A102 and SiO~
tetrahedral uni~s, and whose essential empirical chemical composition on an anhydrous basis is:
mR : (SiXAlyPz)02 wherein "R~ represents at least one organic templating agent present in the intracrystalline pore systern; ~m" represents the moles of "~ present per mole of (SiXAlyP2)02 and has a value from zero to 0.3, ~x~, ~y" and ~z~ represent respectively, the mole fractions of silicon, ali- in~ and pbosphorus present in the oxide moiety, D-13,443 lZ~

said mole fractions being within the compositional area b~unded by points A, B, C, D and E on the ternary diagram which is Fig. 1 or preferably within the area bounded by points a, b, c, d and e on the ternary diagram which is Fig. 2, said silicoaluminophosphate having a characteristlc X-ray powder diffraction pattern which contains at lea~t the d-spacings ~et ~orth below in Table III. In the form as synthesized in accordance with the process of this invention, ~m" has a value of from 0.02 to 0.3.

Table III

Relative d Intensity 9.4 - 9.65 9.41 - 9.17 m 20.3 - 20.6 4.37 - 4.31 m 21.0 - 21.3 4.23 - 4.17 vs 22.1 - 22.35 4.0Z - 3.99 m 22.5 - 22.9 (doublet) 3.95 - 3.92 m 23.15 - 23.35 3.84 - 3.81 m - s All of the as-synthesized 5AP0-11 compositions for which x-ray powder dif~raction data have presently been obtained have patterns which are within the generalized pattern o~ the Table IV below.

TABLE IV

d 100 x I/I~
8.05 - 8.3 10.~8 -10.65 20 - 42 9.4 - 9.65 9.41 - 9017 36 - 58 13.1 - 13.4 6.76 - 6.61 12 - 16 15.6 - 15.85 5.68 - 5.59 23 - 38 16.2 - 1~.4 5,47 - 5.4Q 3 - 5 1~.95 - 19.2 4.68 - 4.62 5 - 6 2U.3 - 20.6 4~37 - 4.31 36 - 49 ~1.0 - 21.3 4.23 - 4.17 100 D-13,443 ~02(~

TABLE IV (Cont.) d 100 x I/Io 22.1 - 22.35 4O0~ - 3~99 47 - 59 2205 - 22.9 (doublet~ 3.~5 - 3.92 55 - 60 23.15 - 23.35 3.8~ - 3.81 64 - 74 24.5 - 24.9 (doublet) 3.63 - 3.58 7 - 10 26.4 - 26.8 (doublet) 3.38 - 3.33 11 - 19 27.2 - ~7.3 3.28 - 3027 0 - 1 28.3 - 28.5 (~houlder) 3.15 - 3.13 ~ 17 28.6 - 2~.~5 3.121 - 3.094 J
29.0 - 29.2 3.079 - 3.058 0 - 3 29.45 29.65 3.033 - 3.013 5 - 7 31.45 - 31.7 2.8~6 - 2.823 7 - 9 32.8 ~ 33.1 ~.730 - 2.706 11 - 14 34.1 - 34.4 2.629 - 2.607 7 - 9 35.7 - 3600 2.515 - 2.495 0 - 3 36.3 - 36.7 2.475 - 2.449 3 - 4 37.5 - 38.0 (doublet) 2.398 - 2.368 10 - 13 39.3 - 39.55 2.292 - 2.279 2 - 3 40.3 2.238 0 - 2 4~.2 - 42.4 2.141 ~ 2.13~ 0 - 2 42.8 - 43.1 2.113 - 2.099 3 - 6 44.8 - 45.2 (doublet) 2.023 - 2.006 3 - 5 45.9 - 46.1 1.977 - 1.969 0 - 2 46.8 - 47.1 1.941 - 1.929 0 - 1 48.7 - 49.0 1.870 - 1.859 2 - 3 50.5 - 50.8 1.807 - 1.797 3 - 4 54.~ - 54.8 1.681 - 1.67S 2 - 3 55.4 - 55.7 1.658 - 1.650 0 - 2 Example 23 (Prepara~,ion of SAPO-16) A reacrion mixture was ~repared ~
combining ~6.0 grams o~ 85 wt. % orthophosphoric acid and 100 grams of water which was added to 81.7 grams of aluminum isopropoxide (Al(OC3H7)3) and 5.0 grams of water and th2 mixture stlrred well. ~o the above mixture were added 12.0 grams of an ~ueous sol containing 30 wt. % Si92, and 5.0 additional gra~s of water, and the mixture stirred until homogeneous. To one-hal~ (by weight) of ~his ~ixture were ad~ed 11.1 grams of quinuclidine, D-13,443 ~z~z~

C7~13N,(Q) and 21.9 grams of water, and the mixture stirred until homogeneous. The composition o~ tne sinal reactlon mixture in molar oxiae ratios was:
1-0 Q A12O3 P2O5 0-3 Si2 5 ~2 Part of the reaction mixtur~ was sealed in a stainles~ steel pressure vessel having an inert plas~ic liner and heated in an oven at 200C at autogenous pres~ure for 48 hours. The solid reaction product, denominat~d SAPO-16, was recovered by centri~ugation, washed with water, and dried in air at 100C. X-ray analysis was performed on a portion of the solids which passed through 100 mesh sieve. T~e SAPO-16 product had an x-ray powder diffractlon pattern characterized by the following data:
Table K
29 d 100 x I/Io 11.45 7.73 54 17.35 5~11 4 18.8 4.72 51 22.05 4.03 100 26.65 3.345 20 29.2 3.05~ 6 29.85 2.993 25 32.7 2.739 3 34.8 2.578 4 38.~5 2.365 8 39.9 2.259 3 44.4 2.0~0 2 48.5 1.~77 49.0 1.859 52.4 1.746 2 54.8 1.675 2 ~xample 24 (Preparatisn o~ SAPO -16) A reaction mixture was prepared ~y com~ining 132 grams of water and 132.8 grams of D-13,443

5~ -aluminum isopropoxide (~ltOC3~7)3) to which was added 45.0 grams of water and 30.1 grams of an aqueous sol containing 30 w~. ~ SiO2, and the mixture stirred well~ To this mixture was added 57.7 gram~ o$ 85 wt. % orthophosphoric acid, and the mixture stirred until homogeneous. To this mixture were added an aqueou~ solution containing 27.8 grams of quinuclidine, C7~13N, tQ) and 45 grams of water, and then 5 addi~ional grams of water, and the mixture stirred until homogeneousO The composition of ~he final reaction mixture in molar oxide ratios was-1.4 Q:1.3 ~12O3:P2os;o~6 5iO2 60~2OPart of the reac~ion mix~ure was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 200C at autogenous pressure for 338 hours. The solid reaction product was recovered by centrifugation, washed with water, and dried in air at 100C. The SAPO-16 product had an x-ray powder diffraction pat~ern essentially identical to that in Example 23. ~y chemical analysis, the composition of the SAPO-16 product was found to be 12.2 wt. % C, 1.9 wt. 4 ~, 7.8 wt. ~ SiO~, 3406 wt. % A12O3, 32.1 wt. ~ P2O5, 24.6 wt. % LOI, c~rresponding ~o the formula (anhydrous basis) 0.116 QuinuClidine: (Sio . loA10.54Po.36)O2 In terms o~ mole ratios of oxides, the composition was:
0.215Q2O:A12O3:0.38SiO2:0.67P2O5:1.4H2O
The species SAPO-16 as reerred to herein is a ~ilicoaluminophosphate mater ial ~aving a three-dimen~ional microporou.s crystal framework structure of PO~ , A10 and SiO tetrahedral D- 1 ~ , 443 3~

units, and whose essen~ial empirical chemical composition on an anhydrous basis is:
mR : (SiXAlyP2~02 whereln "R" represents at least one organic templating agent present in the intracrystalline pore system; "m~ represents the moles of ~R~ present per mole of ~SiXAlyP~)02 and has a value of from zero to 0.3, ~x~, ~y" and ~z" represent resp~ctively, the mole fractions of silicon, aluminum and phosphorus present in the oxide moiety, said mole ~rac~ions being within,the compositional area bounded by points A, ~, C, D and E on ~he ternary diagram which is Fig. 1, or preferably within the area bounded ~y points a, b, c, d and e on the ternary diagram which is Fig. 2, said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which con~ains at least the d-spacings set forth below in Table V. In the form as syn~hesized in accordance with the process of this invention, nm" has a value of from 0.02 to 0.3.
Table Y
Relative d Intensity 11.3 - 11.5 7.83 - 7~69 m 18.7 - 18.9 4.75 - 4.70 m 21.g - 22.3 4.06 - 3.99 vs 26.5 - 27.0 3.363 - 3.302 w - m 29.7 - 30.05 3.008 - 2.974 w ~ m All of the as-synthesized SAPO-16 composi~ions for which X-ray powder di~fraction data have ~resently ~een o ~ained ha~e patterns which are within the generalized pattern of Table VI, below.

D-13,443 3~2f~Z~

Ta ~e Vl d 100 x I/Io 11.3 - 11.5 7.83 - 7.69 52 - 66 17.0 - 17.5 5.2~ - 5.07 ~ ~ 4 18.7 - 1~.9 4.75 - 4.70 50 - 58 2109 - 22.3 4.06 - 3.99 100 26.5 - 27.0 3.363 - 3.30215 - 23 29.L - 29~4 3.069 - 3.0385 - 13 29.7 - 30.05 . 3.008 - 2.97423 - 26 32.7 - 3~.9 2.739 - 2.722 0 - 3 34.4 - 3~8 2.607 - 2.~7~ 2 - 4 38.0 - 38.3 2.3~8 - 20 3507 - 9 39.9 - 4~.3 ~.259 - 2.~38 0 - 7 44.3 - 44.~5 2.045 - 2.038 0 - 4 ~8.5 - ~8.7 1.877 - 1.87~ 6 - 8 49.0 - ~9.4 1.859 - 1.845 0 - 2 52.3 - 52.5 1.749 - 1.743 0 - 2 54.8 - 54.9 1.675 - 1.672 0 - 2 Example 25 (Preparation o~ SAPO-17) SAP0-17 was crystallized from a reaction mixture ~ormed by combining 57.7 grams of 85 wt. ~
orthophosphoric acid and 130~0 grams of water with 132.8 grams of aluminum isopropoxide (Al(OC3H7)3) and mixing well. To this mixture were added 47.0 grams of wa~er and 30.1 grams of an aqueous sol containing 30 wt. ~ SiO2, and the mixture stirred until homogeneousO To this mixture was added a solution of 27.8 grams of quinuclidine, C7H13N, (Q) in 50.0 grams of water, and the mixture stirred until homogeneous. The composition o~ th~ ~inal reaction mixture in molar oxide ratios was:
~ :0.6 SiO2:1.3 A12O3:P2O5:60 H2O
Part of ~he reaction mixture was placed in a st~lniess ~teel pressure vessel lined with an inert plastic material and heated :in an oven a~ 200~C at D-13,443 :12~3~0~6 autogenous pres ~re for 338 hours. The solid reaction produc was recov\ered by centrifugation, washed with wat :, and dried in air at 100C. The SAP0-17 product ~as impure but the minor phase had an X-ray powder ~iffraction pa~-tern characterized by the following d :a:
Ta ble L
d 100 x I/Io 7.75* 11.4 100 9.8 9.03 5 13.4* 6.61 ~0 15.55* 5.70 65 16.7 5.31 5 18.0 4.93 . 25 19.7 4.51 10 20O6* 4.31 100 21.4 (sh~ 4.15 23.4 3.80 20 25.~ 3.507 15 27.0 3.302 24 27.4 3.255 5 28.7 ~.110 5 30.6 (sh) 2.921 31.35 2.853 10 32.0 2.797 20 33.4 ~.683 5 36.05 2.491 10 ' 36.45 2.465 10 40.0**) 2.254 1 40 40.3**~ 2.238 r 45.9 1~977 5 49.7 1.834 5 52.3** 1.749 15 53.g 1.701 5 55.5 1.656 5 * probably c Itains peak from another phase ** contains p ~k from another phase Example 26 (Pre Iration of SAPO-17) ~ a) A 3ubstantially purer SAPO-17 composition was ?repared using cyclohexylamine ~instead of the ~uinuclidlne of Ex. 25 Bu~ra) as the D-13,443 3 ~3~

templating agent and decreasing the relative proportion of silica in the g~l. This superior reactlon mlxture was prepared ~y combining 81.7 grams of aluminum isopropoxide [Al(OC3~)3]
with a solution of 46 1 grams of 85 wt. ~
orthophosphoric acid (H3PO4) in 159.6 grams of ~2' stirring until homogeneou~,, and then adding 4.0 grams of an aqueous silica sol containing 30 w -~ sin2~ The resulting mixture was stirred until it was homogeneous. To this mixture was added 19.8 grams of cyclohexylamine (CHA), and the mixture stirrsd until homogeneous. The composition of the final reaction mixtuxe in molar oxide ratios was:
1~0 C~A:0.1 SiO2:A12O3:P2O5:50 ~2O
A portion o~ the reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafl~oroetnylene and heated in an oven at 2~0C at autogenous pressure for 50 hours. The solid reaction product was recovered ~ filtration, washed with water, and aried in air at 100C. By chemical analysis, the composition of the product was found to be 9.5 wt.-~ C; 1.6 w~.-% SiO2; 37.8 wt.-~ Ai203; 3~q9 wt.-~ P20 an~ 19.8 wt.-%
LOI, corresponding to the formula (anhydrous ~sis):
0.103 ~A:(sio.o2Al~.56po.42;o2/
or in terms of molar oxide ratios:
0.18 (C~A~20:A1203:0.76 P205:0.07 Si02 Tbe SAPO-17 product was impure and had an x-ray powder dirfrac~ion pattern characterized by the following data:

D-13.443 ~ ~(3~

Table M
d 100 x 7.7 ll.S 100 9.8 9.03 36 10.9* 8.12 9 11.8 7.50 13.4** 6.61 95 14.2 6.24 6 15.5 5.72 37 16.6 5.34 19 17.4* S.10 8 18.0 ~93 18 19.65 4.52 39 2n . 5 4.33 80 ~1.4** 4.15 35 22.0* 4.~4 16 22.5 3~95 7 23.3** 3.82 38 23.8 3.74 32 25.4 3.507 38 27.0** 3.30~ 49 27.4 3.255 9 28.7** 3.110 la 30.6 2.9~1 5 31,3 2.858 20 31.85 2.810 48 32,2* 2.780 sh 33.55 2.671 19 34.6* 2.592 3~.9** 2.501 8 3~.4 2.468 4 37.4 2.404 2 37.9 2.374 2 39.8 2.2~5 3 40.3 2.238 40.9 2.206 42.1 2.14~ 2 42.6 ~.122 43.7 2.071 11 45.6 1.9~9 46.5 1.953 2 47.8 1.903 48.7 1.870 49.3 1.848 sh 49.6 1~838 15 52.0 1.759 10 53.8 1.704 2 55.45 1.657 11 **~ontains peak ~rom another pnase *Peak rrom another phase D-13, 443 ~ 3~0~

(b) The product was calcined for 4 hours at 550C in alr. The calcined product had an x-ray powder diffra~tion pattern characte~ized by the following data (known lmpurity peaks have been omitted):
Table N

2~ d 100 x I/Io 7.7 11.5 92 .65 9.17 32 11.5 7.69 10 13.5* 6.56 100 13.9 ~.37 21 15.6 5.68 11 16.65 5.32 22 19.0 4.67 7 19.4 4.58 6 20.7 4.29 22 21.45* 4.14 13 23.5 3.79 19 23.7 3.75 sh 24.5 3~63 19 27.L5 3.285 17 28.0 3.187 5 3~.1 2.g69 ~0.6 2~921 3 31.25 2.862 14 l2.0 2.797 9 33.55 . 2.671 6 35.0 2.564 2 36.2 2.481 3 39.4 2.287 2 40.2 2.243 41.3 Z.186 2 41.g 2.156 42.6 2.122 3 43.5 2.080 ~6.0 1.973 46.4 1.957 47.1 1.929 2 47.9 1.899 2 S0.1 1.~21 5 51.2 1.784 5 52.7 1O737 55.2 1.664 2 *cont~in~ peak ~rom anothe~ phase D-13,443 (c) Adsorption capacities were measured on th2 caLcined product of part (b3 supra using standard McBain-Bakr gravimetric adsorption apparatus. The following data were obtained on a sample activated at 350C.:
Kinetic Pressure, Temp., Wt. ~
Diameter, A Torr C Adsorbed 2 3~46 9~.5 -183 21.5 2 3.46 740 -lR3 29.4 n-hexane 4.3 53.5 24 10.3 ~2 2.65 4.6 23 25.2 H29 2.65 19.4 2~ 35.0 isobutane 5.0 400 24 1.1 the por~ slze of the calcined produc~ is ~4.3A
and <5.OA as shown by the adsorption of n-hexane, kinetic diameter of 4.3A, and ne~ligi~le adsorption of isobutane, kinetic diameter of 5.OA.
The species SAPO-17 as referred to herein is a silicoaluminophosphate material having a three dimensional microporous crystal framework structure of P02 , A102 and SiO2 tetrahedral units, and whose essential empirical chemical compositon on an anhydrous ~asis is:
mR (SiXAlyPz)02 wherein "~ represents at least one organic templating agent present in the intrac~ystalline psre system; ~m" represents the moles of ~R" present per mole o~ (SiXAlyPz) 2 and has a value o~
from æero to 0~3, ~x~, ~y" and ~z" represent respectively, the mole fractions of silicon, aluminum and phosphorous present in the oxide moie~y, said mole fractions ~ing within the compositional area bounded by poi~ts ~, B, C, D and E on the ternary diagram which is Fig. 1, or preferably within the area b4unded by points a, b, c, d and e on the ~ernary diagram which is Fig. 2, said ~ilicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least th~ d-spacings set ~ort.h ~low in Table VII.

D~13,443 - 62 ~

In the form as synthesized in accordance with the process of this invention, ~m" has a value of fr~m 0.02 to 0.30.
TABLE VII
Relative d Intensity 7~70 ~ 7~75 lloS ~ 1104 YS
13~4 6~61 s ~ vs 15~5 ~ 15~55 5~72 ~ 5~70 s 19~65 ~ 19~7 4~52 ~ 4~51 w ~ m 2~5 - 2~6 4~33 4.31 vs 31~85 ~ 32 2.810 - 2~797 w ~ m All o~ the as-synthesized SAP0-17 compositions for which x-ray powder diffractlon data have presently been obtained hav~ patterns which are within the generalized pattern of Table VIII below.
Table VIII
d 100 x I/Io 7~70 11~5 ~ 11~45 100 9~8 9~03 5 ~ 36 11~8 7~50 13. 4 6~61 60 ~ 95 14~2 6~24 6 15~5 5~7~ ~ 5~70 ~7 ~ 65 16~6 5~34 19 18~0 4O93 18 ~ 25 19.65 - 19.7 4.52 - 4.51 10 - 39 20~5 ~ 20~6 4~33 ~ 4~31 80 ~ 1~0 21~4(sh) 4~15 2~5 3~g5 7 23~ - 23~4 3~82 - 3~80 20 - 3a Z3.8 3~74 32 25~4 3~507 15 ~ 38 ~7~0 3~30~ 25 ~ 4g 27~4 3~255 5 ~ 9 28.7 3.110 S ~ 18 30~6(8h~ 2~921 sh - 5 31.3 - 31~35 2~858 ~ 2~853 10 ~ 20 D-13,443 ;~2~3~

Table VIII (Cont.) 2~ d 100 x I/Io 31~85 ~ 32~0 2~810 ~2~797 20 - 48 33~4 ~ 33~i5 ;~o683 - 2.. 671 5 ~ 19 35~9 ~ 36~05 2~501 2~91 8 ~ 10 36~4 ~ 36~45 2~46~ ~2~465 4 ~ 10 40 ~ 3 2~ 238 43 ~ 7 2 ~ 071 11 ~5 ~ 9 1~ 977 5 4~ ~ 6 ~ 49~ 7 1 ~ 838 ~ 1 ~ 834 5 ~ 15 52~ 0 ~ 5i~ 3 1~ 70~ 749 10 ~ lS
53 ~ 8 ~ 53~ 9 1~ 704 ~ 1 ~ 701 2 ~ S
5~ ~ 45 ~ 55 ~ 5 1~ 6571 ~ 65~i 5 11 Example ~7 (Preparation of SAPO-20~
(a) SAPO-20 was crystallized from a gel prepared by combining a solution of 57 ~ 6 grams o~ 85 wt. ~ ortnophosphoric acid (~3PO4~ in 60.2 grams of water with 34.4 grams o~ a hydrated aluminum oxide (a pseudo-boehmite phase, 74~2 wt~ ~
A12O3 25-8 w~ 2) To tnis mixture was added 50.1 grams o~ an aqueous silica sol containing 30 wt.-% SiO2, and after s~irring well, was combined wi~h 68 grams of tetrametnylammoniumhydroxide pentahydrate (TMAO~ 5 ~2) and 70 grams of water, and the mixture stirred unt~l ho~ogeneous. The composition of ~he ~inal reaction mlxture in molar oxiae ratios was:
0 75 (TMA)2O:5iO~:A12O3:P2O5:50 ~2 Part of the reaction mixture wa~ placed in a stainless steel pressure vessel lined wi~h polytetra-~luoroe~hylene and heated in an oven at 125C a~
autogenous pressure ~or 68 hours~ The solid reac~ion produc~ was recovered by centrifuga~ion, wasned with water, and dried ln air at L00C~ The D-13,443 ~z~o~

SAPO-20 product had an x-ray powder diffraction pattern charac~erized by the following data:
Table N
d 100 x I/Io 14.1 6.28 40 1~.9 4.46 41 22.2 4.00 5 24.4 3.65 100 28.2 3.16~ 13 31.5 . 2.840 -11 34.7 2.585 14 37.5 2.39~ 2 40.2 2.243 4 42.85 2.110 .6 47.65 1.908 5 52.0 1.759 10 By chemical analysis, th~ composition of the SAPO-20 was 9.9 wt. ~ C, 2.9 w~. % N, 11.3 wt. ~ SiO2, 203! 35-7 wt- ~ P205, 21.6 wt.
% LOI, giving a product CQmpOSitiOn in molar oxide ratios ~f:
0.35 (TMA)20:0.63 SiO2: A1203: 0.85 P205: 0 53 ~2 which corresponds to the ~ormula (anhydrous basis~
O. 16 (TMA): (sio lsA10.47Po-38)~2 (b) A por~ion of the product of part (a) a~ove was calcined in air at 500C for 2 hours.
Sometime thereafter adsorption capacities o~ the calcined product were determined using a standard McBain-Bakr gravimetric adsorption apparatus. rrhe following data were obtained on a sample activated at 350C.
Kinetic Pressure, Temp~, Wt. ~
Diameter, A Torr C Adsorbed 2 3.46 100 -183 3.2 2 3.46 761 -183 12.8 H20 2.65 4.6 25.1 14.6 H20 2.65 20.0 25.0 25.1 D-13,443 zo~

The pore size of ~he calcined product is greater than 2.65A and less than 3.46A, as shown by adsorption of water, kine~ic diameter of 2~65A, and low aasorption of oxygen at 100 torr, kinetic diameter of 3.46A. X-ray analysis of the SAP0-20 sample usea in the adsorption studies establis~ed ~hat the x-ray powder diffraction pattern was essentially unchanged as a result of the calcination and subsequent contact with the adsorbate ~pecie~.
Example 28 (Preparation of SAPO-20) ~ his pr~paration utilizes a reaction mix~ure which contains a significant amount of intentionally added sodium in the form of sodium aluminate. A first mixture was formed by combining a solu~ion of 76.9 grams of 85 wt. ~ orthophosphoric acid (H3P04) in 60.1 grams o~ water with 45.8 grams of a hydrated aluminum oxide (a pseudo-boehmite phase, 74,2 wt~ % A1203, 25.8 wt. ~ H20) and stirring until homogeneous. To this mixture was added a solu~ion o~ 192.3 grams of tetrame~hylammonium hydroxide pentahydrate (TMAOH 5 ~0) in 121.1 grams of water and the mixture stirred until homogeneous. A s~cond mixture was prepared by com~ining a solution of 23.5 grams of so~ium aluminate (1,21 Na20 A1203 '3.2 ~2) in 38.0 grams of water wi~h 80.1 grams of an aqueous sol of 30 wt. % SiO2 and 8.2 additional grams of wa~er. To this mixture was added 98.7 grams of the first-prepared mixture, and the resulting composition stirred until homogeneous.
The composition of the ~inal mixture in molar oxide D-13,443 ~ ~3;~ 6 ratios was:
l-l(T ~ 0 4-~ sio2:l.66 A1203 0,66 P205 l.2 ~a20 95 ~2 ~ar~ of the reaction mixture ~as placed in a stainless steel pressure vessel lined with an inert plastic materlal and heated in an oven at 200~C at autogenous pressure for 168 hours. The solid reaction product was recovered by centrifugation, washed with water, and dried in air at 100C. ~he SAPO-20 product had an x-ray powaer airfraction pattern essentially identiral to that shown in Example 27 for the as-synthesized materialO
~hemical analysis showed 6.9 wt.-~ C, 1.6 wt.-% N, 8.0 wt.-% Na20, 39.6 wt.-~ SiO2, 2~.7 wt.-%
~12O3, 1~-5 wt.-~ P2O5, 16.6 wt.-% LOI, giving a product composition in molar oxide ratios of:
0.3(TMA)20:0~5 Na20:2.7 SiO2:A1~03:0.31 P205:0.8 ~2 whlch corresponds to the formula (anhydrous basis):
0.113(TMA~ (0-19 Na~ (sio.slAlo.3gpo.l2)o2 Example 29 ~Preparation of SAPO-20) SAPO-20 was produced in about g5~ purity from a reaction mixture templated with tetramethylammonium bydroxide using aluminum isopropoxide as the source of alumina and a ~umed silic~ as the cilica qource. The overall reaction miY.ture composition, in terms o~ molar oxide ratios, was:
0.5(~MA~2O:o-lsio2 Al23 o 9P2O5 49 ~2 C~ystallization was carried out at 150C for 133 hours unaer au~ogenous pressure. The X-ray powder D-13,443 pattern of the major product phase was essentially ldentical to that in Example 27(a). Tbe chemical composition of the product was 8.0 wt.-~ C, 2~23 wt.-~ N, 3.3 wt.-~ SiO2, 34.9 wt.-~ A1203, 34.0 wt.-~ P205, 21.5 wt.-~ LOI, giving a product composi~ion in molar oxide ratios or:
0.24(T~A)20 0.16SiO2:A1203:0.70P205:1.1~20 wnich corresponds ~o th~ formula (anhydrous basis) 0.13(TMA) : (sio.o5Alo.56 0.39 Example 30 ~Preparation of SAP~-20) (a) A reaction mixture was prepared by adding 1.03 grams of a reactive amorphous precipitated silica (91.4 wt.-~ SiO2, 8.6 wt.-~~2) to a solution of 14.50 grams of tetramethylammonium hydroxide pentahydrate (TMA0~-5 ~2) in 20.0 grams of water, and mixed until homogeneous. To this mix~ure were added 6.12 grams of a nydrated aluminum oxlde (a pseudoboehmlte phase~ 74.2 wt.-% ~1203, 25.8 wt.-~ H20) and 9.55 grams of 85~ orthophosphoric acid (H3P04) and 6.21 grams of water and the mix~ure stirred until homogeneous. The composition of the f inal reaction mixture in molar oxide ratios was:
1.1 A1203 1-P25 l (TMA)2~ 2 2 Part of the reaction mixture was placed in a s~ainless .steel pressure vessel with an inert plastic liner ana heated in an oven a~ 200C at autogenous pressure for 24 hours. '~he solid reaction product was recovered by filtering, washed wlth water, and dried in air at room temperature.
The SAP0-20 product had an x-xay powder dif~raction pattern characterized ~y the rollowing data:

D-13,443 ~z~

Table P
d lO0 x I/Io 14.1 6.28 39 19.8 4.4~ 49 2~.2 4.00 6 24. 3 3 . 66 100 ;28.1 3.175 11 31.7 2.822 12 34. 7 2. 585 16 37.5 2039R
~0. 2 2. 243 5 42.7 2.117 6 47.5 1.914 6 Sl.9 1.762 12 (b1 Adsorption capacities were measured on this calcined (500C for one hour) product using a s~andard McBain-Bakr gravimetric adsorption apparatus. The following data were obtained on a sample activated at 350C in vacuum.
Klnetic Pressure, Temp Wt. ~
Diameter, A Torr C Adsorbed 2 3. 46 100 -183 0 2 3.46 750 -L83 0 H20 2.65 4.6 2432.1 H20 2, 65 20 2439 . 8 The pore size of the calcined product is greater than 2~65A as shown by adsorption of ~2~
kinetic ~iameter 2.65A, and less than 3 . 46A, as shown ~y no adsorption of 2~ kinetic diameter 3.46A.
(c) The above product, after calcination and Mc~ain adsorption studies, had an X-ray powd~r diffraction pattern charac~eristic of SAP0-20 (short scan).

D-13,443 .3~6 ~ 69 -d 100 x I/Io 14.0 6.33 100 l9.B 4.48 38 22.2 4.00 8 24.. 3 3.663 95 28.2 3.16~. 23 31.5 2.849 18 34.6 2.592 20 ~ d) EDAX (energy dispersive analysis by X-ray) microprobe analysis performed in conjunction with SEM (scAnning ~l~c~ron microscop~) study, on clean crystals having a crystal morphology characteristic of SA~0-20 gives the following analysis, based on relative peak heights:
Ar~a Average of Range Scan Spot Probes Si 0.4~ 0.40 0.36 - 0.43 Al 1.0 1.0 1.0 P 0.77 0.79 0.76 - 0.85 Example 31 (Preparation o~ SAPO-20) SAPO 20 was successfully prepared using pyrrolidine as ~he templating agen~ in a reaction mixture containing alu~inum isopropoxide and an aqueous silica sol as the source o~ alumina and silic~ respectively. Orthophosphoric aeid was ~he phosphorus source. The overall reaction gel composition in terms of molar oxide ratios was:
C4HgN:0.3SiO2:A1203:P205:39~20 The gel was crys~allized at 200C for 48 hours.
Chemical analysis showed 10.0 wt. % C, 2.2 w~. ~ N,

6.4 wt. ~ SiO2, 32.6 wt. % A1203, 41-0 wt-P205, 18.7 wt. % LOI, giving a product composition in molar oxide ratios of:

0 325(C HgN)20 0~33 SiO2 : A1203: 0.90 P2 S 2 which corresponds to the ~ormula (anhydrous ~a5is) ~-13,4~.3 ~2~ 6 0.l6(c4HgN) : ~sio.o8Alo.48po.44)o2 The species SAPO-20 as referred to herein is a silicoaluminophosphate material having a three-dimensional microporous crystal framework structure of PO2, AlO2 and SiO2 tetrahedral units, and whose essential empirical c~emical composition on an anhydrous basis is:
mR : (Si~AlyPz)O2 wherein WR" represents at least one organic templatiny agen~ present in the intracrystalline pore system; ~mn represents the moles of "R" present per mole of (SiXAlyPz)O2 and has a value of from zero to 0.3, ~x~, ny" and ~z~ represent respectively, the mole fractions of silicon, aluminum and phospnorus present inthe oxide moiety, said mole fractions being within the compositional area bounded ~ points A, B, C, D and E on the ternary diagram which is Fig. 1, or pre~erably within the area bounded by poin~s a, b, c, d and e on the ternary diagram which is Fig. 2, said silicoaluminophosphate haviny a characteristic X-ray powder di~fraction pattern whiCh contains at least the d-spacings set forth below in Table IX. In the form as synthesized in accordance with the process of this invention, Um~ has a value of from 0.02 to 0.3.

Table IX
Relative d Intensity 13.7 - 14.25 6.46 - ~.22 19.55 - 20.0 4.54 - 4.44 w - m 24.05 - 24.45 3.700 - 3.641 vs 34.35 - 35.0 2.611 - ~.564 w 42.5 - 43.0 2.127 - 2.103vw - w D-1-~,443 All of the as-synthesized SAP0-20 compositions for which X-ray powder diffraction data have presently ~en obtained have patterns which are within the generalized pa~tern of Table X, below.

Table X
d 100 x I/Io 13.7 - 14.25 ~o46 - 6.22 38 - 63 l9.S5 - 2~.0 4.54 - 4.44 25 - 58 21.9 - 22.35 ~06 - 3.98 0 - 9 24.05 - 24.45 3.7~0 - 3.641 100 27.85 - 28.55 3.203 - 3.126 8 - 17 31.~5 - 31.8 2.862 - ~.814 S - 16 34.35 - 35.~ 2.611 - 2.56412 - 22 37.3 - 37~5 2.411 - 2.398 ~ - 3 39.9 - 40.4 2.259 - 2.233 2 - 6 4~.5 - 43.0 2.127 - 2.103 3 - 24 47.25 - 47.8 1.924 - 1.9~3 2 - 8 51.6 - 52~ 1,771 - 1.752 2 - 17 ~xampLe 32 (Preparation of SAP0-34) In the preparation of SAP0-34, a reaction mixture was formed by combining 28.8 grams of 85 wt.~ orthophosphoric acid ~3P04) with a mixture of 17.2 grams of a hydrated aluminum oxids (a pseudo-boehmite phase, 74.2 wt.~ A1203, 25.8 wt.% H20) in 18.4 grams of wa~er~ To this mix~ure was added lSl.7 grams o~ an aqueous solution of 40.7 wt.~ tetraethylammonlum hydroxide (TEA0~) and ~he mixture stirred until homogeneou To 81.9 grams of ~his mixture was added a solution of 11.7 grams of sodium aluminate (A1203:1.21 Na20:3.2 H20) in 23.0 grams of water and 40.0 grams of ~n aqueous 501 0~ 30 wt.~ SiO2, and the mixture stirred untLl homogeneous. The composition of the final reac~ion mixture in molar oxide ratios was:
1.6 ~TEA)20:1.2 Na20:4 SiO~:2 A1~03:P205:112 ~2 D-13,443 ~L~v~

~ 72 -Part ~f the reaction mixture was sealed in a stainless steel pressure vessel having an inert plastic liner, and heated in an oven at 200 C at autogenous pressure for 168 hours. The solid rea::tion product was recovered ~y filtration, washed with water, arld dried in air at 110C. The crys alline product was impure but the major phase, SAP0-34, had an X-ray powder diffraction pattern characterized by the following data:
TABLE Q
28 d 100 X I/I O
9.6 9.2i 100 13.0 6.81 17 14.05 6.30 ;~3 16.1 5.50 33 17.85 4.97 75 19.0 4.67 2 20.7 4.29 ~9 ~2.05 4.03 d, 23.1 3,85 10 24.95 3.57 76 26.0 3.43 19 ;27.7 3.220 3 28.15 3.170 12*
29.4 3.038 4 30.7 2.91~ 67 31.05 2.8~0 28 32.4 2.763 33.4 2.6B3 6 34.55 2.596 14 36.0 2.495 11 39.7 2.270 4 43.4 2.085 3 47.6 1.910 6 48.8 1.866 7 49.2 1.852 5 50.65 1.802 53.2 1.722 6 ~4,25 1.691 a, 55.9 1.645 4 * contains peak from an impurity.

D-13,443 ~z~

~y chemical analysis, the composition of the solids product was established to be 2.8 wt.% C, O.5 wt.
N, 37.0 wt.4 SiO2, 27.6 wt~ A1203, 12.2 wt.%
P205, 704 wt.~ Na20, 15.9 wt.~ LOI, giving an overall product composition in molar oxide ratios o~:
0005 (TEA~20:2.3 SiO2:0.4 Na20:A1203:0.3 P205:2.4 ~2' Example 33 (preparation of SAP0~34) SAPO-34 exhib~ting an X-ray powder diffraction pattern essentially identical With that set forth in Example 32, supra and having a chemical composition in terms of mole ratios of oxides 0.1 (TEA)~O : 0.17 SiO2 : A1203: 0069 P245: 1.5 ~2 and a formula (anhydrous basis) o.O6(TEA~:(Sio.osA10.56 0.39 2 was prepared as ~ollows: A mixture of ~0.7 grams o aluminum isopropoxide (Al(OC3~7)3~ and 160 grams of water was combined with 51.3 grams of 85 wt.~ orthophosphoric acid (H3P04) while stirring. To this mixture was added 1.4 grams of fumed silica (.35 wt.~ SiO2, 5 wt.% wa~er) and the mixture stirred until bomogeneous. To one third by weight of this mix~ure was added 27.2 grams of an aqueous solution of 40 wt.~ tetraetnylammonium hydroxide (TEAOH), and the mixture stirred until nomogeneous. The composition of the inal reaction mixture in molar oxide ratios was:
0.5 (TEA)20:0.1 SiO2:A1203:P205: 2 The gel was crystallized at 150C for 133 hours at autogenous pressure, the product recovered by centri~ugat~on, washed with water and ~ried in air at room temperature~

D-13,443 Exampie 34 (Preparation o~ SAPO 34) (a) Using the same reagents in Example 33, suPra, except that ~he silica source was an aqueous silica sol rather than fumed sllica, a reaction mixture was prepared having the composition:
( )2 SiO2 A123 P2O5 52~20 Thi~ composition was crystallized under autogenous pressure at 200C for 48 hours to yield SAP0-34 as evidenced by its X-ray powder di~raction pattern which was characterized by the following data:

T~3LE R

d 100 X I/Io 9.5 9.31 100 12.9 6.86 11 14.05 6.30 10 16.05 5.52 50 18.0 4.93 11 20.6 4.31 73 22.3 3.99 2 23.1 3.85 3 25.2 3.53 1~
25.85 3.446 14 27.6 3.232 2 ~8.3 3.153 29.5 3.0~8 4 30.55 2.92~ 24 31.2 2.867 18 32.35 2.767 2 33.8 2.652 34.4 2.607 4 36.35 2.471 2 38.8 2.3~1 1 39.6 2.276 3 43.3 2.090 3 47.5 1.914 2 49.0 1.859 6 50.2 1.817 51.0 1.7gl 3 53.05 1.726 3 54.45 1.685 5~.8 1.647 4 D-13,443 3 ;~ 6 EDAX (energy dispersive analysis ty X-ray) microprobe analysis, performed in conjunction with SEM (scannlng electron microscope) stu~y, on clean crystals having a crystal morphology characteristic of SAPO-34 gives tne ~ollowing analysis based on relative peak heigntsO
Si 0.3 Al 1.0 (b~ A substantially identical reaction mixture composi~ion as in part ~a) above, formed ~rom the same reagents and crystallized at 150C for 336 hours yielded a SAPO-34 p~oduc~ having the chemical composition 10.2 wt.% C, 1.5 wt.% N, 34.4 wt.% A12O3, 38~3 wt.~ P2O5, 7.7 wt.% SiO2 and 19.9 wt.% LOI. This corresponds to a composition in terms of molar oxide ratios of 0.16 (TEA)2O : 0.38 SiO2 : A12O3 : 0.80 P2O5 : 0.70 H2O
which in turn corresponas to the ~ormula (anhyqrous basis) 0.08 (TEA) (sio.loAlo~5opo.4o)o2 Example 35 (Preparation of SAPO-3~) (a) A reaction mixture was prepared combining 81.7 grams of aluminum isopropoxide (Al(OC3H7)3) with a solution of 46.1 grams of 85 wt.% orthophosphoric acid in 104.9 grams of water, while stirring. To this mixture were added 12 grams o~ an aqueous sol of 30 w~.% SiO2 and 5 gra~s of water, and the mixture stirred until ho~ogeneous. To this mixture was added 73.7 grams of an aqueous solution o~ 40 Wto % tetraethyl-ammonium hydroxide (TEAOH). One half by weight o~
tnis mix~ure was combinea with 36.8 grams of 40%

D-13,443 zv~

TEAOH, and th~ ~ixture stirred until homogeneous.
The compositic of the final reaction mixture in molar oxide rc ios was:
( )~ 0.3 sio2:A123:P2os 5o o H2O
The reaction n xture was placed in a stainless steel pressure vess~ lined with an iner~ plastic ma~erial (poLy~etrarluc ~ethylene) and heated in an oven at 200C at autoc neous pressure for 120 hours. Tne solid reactior ;~roduct (SAPO-34) was recovered by centri~ugatior washed with water, and dried in air at 100~. By ~emical analy5is, the product was established tc _omprise 10.5 wt.~ ~, 1.6 wt.% N, 34.1 wt.~ A12C , 39.2 wt.~ P2O5, 6.8 w~.%
SiO2 and 19.2 t.% LOI, giving a proauct composition in nolar oxide ratios of:
0.17(TEA)~O : .33 SiO2 : A12O3:0.82 P2O5 0-40 H2O, which correspo ~s to tne formula (anhydrous basis) 0.09 (TEA)-(Sio 03A1o 51Po 41)2 The above prod ~t had an X-ray powder diffraction pattern essent ~lly iden~ical to that in Example 32.
( D) portion of the solid crystalline SAP0-34 of par (a) was calcined in air at 550C ~or 2 hours. Adso ?tion capacities were measured on this calcined ~oduct u~ing a standard ~cBain-Bakr gravime~ric ad ~rption apparatus. ~he following data were obta led on a sample activated a~ 350~C.
K letic Pressure, Temp., wt.%
D Imeter, A Torr C Adsor ~d 2 3.46 104 -183 25.1 2 3.~6 746 -183 36.6 n-Hexane 4.3 46 ~3.~ 11.0 H2O 2.65 4.623.0 30.1 H2O 2~65 19.522.8 42~3 D-13,443 o~

The pore size o~ the calcined product is greater than 4.3A, ~s shown by adsorption of n-hexane, kinetic diameter of 4.3~.
(c) Th2 product a~ter McB~in adsorption studi~s had an X-~ay powder diffrac~lon pattern characterized by the foLlowing data:
TABLE S
d 100 X I/Io 9.45 9.36 100 12.95 6.84 25 14.0 6.33 ' 5 16.1 5.50 27 16,9 5.25 3 17.7 5.01 9 19.05 4.66 3 20.75 ~.28 55 21.25 4.18 22.0 4.04 3 22.55 3.9g 2 23.15 3.84 4 24.8 3.59 21 25.05 3.555 11 27.8 ~ 3.209 ~ 4 28.1 (sh) ~ 3.175 ~
29.6 3.018 3 30.8 2~903 26 31.6 2~831 2 32.3 2.772 2 33.3 2.691 2 34.7 2.585 4 35.85 2.505 4 3806 2.332 39.85 2.262 2 42.7 2.118 2 43.5 2.080 2 47.05 1.932 47.9 1.899 2 4~.8 l.a66 4 50.5 1.807 3 51.9 1.762 53.4 1.716 2 54.15 1.~9~ 2 54.6 1.681 D-13,443 ~2(~0~

Example 36 ~Preparation of SAPO-34) (a) Isopropylamine (i-PrNH2~ was success~ully employed to template the tormation of SAPO-34 in a reaction mlxture having the composition:
i-PrN~2 : 0.6 SiO2 : A12O3 : P2O5 2 and formed from aluminum isopropoxide, an aqueous silica ~ol, orthophosphoric acid and water. The reac~ion gel was crystallized at 200C ~or 51 hours at autogenous pressure. X-ray analysi~ confirmed the ~ormation of SAPO-34.
(b) A por~ion of the solid crystalline product of pa~t (a) above was calcined in air ~or 3.5 hours at abou~ 600Co The major species of the calcined product had an X-ray powder diffraction pattern essentially iden~ical with that o~ Example 34(a)-(c) Adsorption capacities were measured onthe calcined product of part (b) using a standard McBain~Bakr adsorption apparatus. ~he following data were obtained on a sample activted at 350C.
Kinetic Pressure, Temp.,~t.%
Diameter, A Torr C Adsor ~d 2 3.4698 -183 15.0 2 3.46746 -183 21.7 n-hexane 4.3 97 24 3.7 isokutane 5.0 402 26 0.2 H2O 2.65 4.6 22 18.7 H2O 2.6519.4 24 23.7 The pore side of the calcined product is ~4.3 and ~5.0A as ~hown by tne adsorption o~ n-hexane, kinetic diameter of 4.3A, ~nd negligible adsorption of ~sobutane, kinetic diameter of 5~0A.

D-13,443 Example 37 (Preparation of SAPO-34) (a~ SAPO-34 was crystallized from a system containing a mixture of two organic templating agents by combining orthophosphoric acid, a hydrated aluminum oxide, a ~umed silica, water, tetraethylammonium hy~roxide and di-n-propylamine to form a r~action mixture having a composition in terms of molax ratios of oxides of:
A1203 P205 0.6SiO2 0.5(TEA) 20 1.5(Pr2N~1) 50H20 After digestion and crystallization at 200C for 24 hours, the recovered produc~ was identified ~y X-ray analysis to be ess~ntially SAPO 34 and to have a chemical composition of 33.0 w~ A12O3~ 34.4 wt.-~ P2O5, 10.3 wt.~% SiO2, 11.1 wt.-~ C, 1.7 wt.-% N and 21.3 wt.-% loss on ignitibn (LOI).
(b) A portion of the product of part (a) su~ra was calcined at 600C ~or 1 hour, and adsorption capacities determined using a s~andard Mc~ain-Bakr gravimetric adsorption apparatus. The following data were obtained on a sample activated at 350C.
Kinetic Pressure, Temp.,Wt~
Diameter, A ~orr C Adsor ~d 2 3.46 100 183 25.5 2 3.46 753 -lR3 34. 8 Cyclohexane 6.0 58 24.4 2.0 Neopentane 6.2 745 24.5 1.7 ~2 2.65 ~.6 24.2 28.6 ~2 2.65 2~.0 24.2 34.9 n-~exane 4.3 45.0 24.4 11.9 ~-13,443 ~.~f3~

Example 38 (Preparation of SAPO-34) . SAPO-34 was crys~allized from a reaction system containing both $oaium ana TEA ions prepared by combining 66.4 yr~ms of aluminum isopropoxide with a solution of 28.8 grams of 85 wt.-~orthophosphoric acid in 70.1 grams f ~2 To ~his mixture was aaded a mix~ure of 15.0 grams of an aqueous silica sol (30 wt.-~ SiO2) and a solu~ion of 3.0 grams of NaOH in 10.0 grams ~2 Thereafter 46.0 grams of an aqueous solution of 40 wt.-% ~etraethylammonium hydroxide was added and the mixture stirred until homogeneous. 'rhe composition of the final mixture was:
9.5(TEA)20: 0.3 Na2O:1.3 A12O3:0.6 SiO2: P2O5: 60 H2O
Af~er crystallization in a sealed reactor at 200C
for 1~7 hours, the SAPO-34 product (identlfied by X-ray analysis) had a chemical composition: 4.5 wt.-% C, 37.7 wt.-~ A12O3, 2~.9 wt.-% LOI, 29.5 wt.-~ P~O5, 4.9 wt.-~ Na2O and 4.5 wt.-%
sio2.
Tne species 5APO~34 as referred to herein is a silicoaluminophosphate material having a three-dimensional microporous crystal framework structure of PO2, AlO2 and SiO2 tetrahedral units, and whose essential empirlcal chemical composition in ~he as-synthesized form and on an annydrous basis is:
mR : (SiXAlyPz~O2 wherein ~R" represents at least one organic templa~ing agent present in the intracrystalline pore sy3tem; ~m" represents the moles of UR" present per mole of (SiXAlyPz)O2 and has a value of fro~ 0.02 to 0.3, ~xU~ ~y" and ~z" represent respectively, the mole fractions of siLicon, D-13,443 ~.Z~3~

aluminum and phosphorus present in the oxide moiety, said mole ~ractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is Fig. 1, or prererably within the area bounded by points a, b, c, d and e on the ternary diagram which is Fig. 2, said silicoaluminophosphate having a characteristic X-ray powder di~raction pattern which contains at least tne d-spacings s~t ~orth below in Table XI.
TABLE XI

. Relative d Intensity 9.45 - ~.65 9.36 - 9.17 s - vs 16.0 - 16.2 5.54 -- 5.47 w - m 17.85 - 18.15 4.97 - 4.89 w - s 20.55 - 20.9 4.32 - 4.25 m - vs 24.95 - 25.4 3.57 - 3.51 30.5 - 30.7 2.931 - 2.912 All of the as-synthesiz~d 5APO-34 compositions ~or which X-ray pow~er diffraction aata have presently been obtained have patterns which are within the generalized pattern of Table XII, below.

TA~LE XI I
~ d 100 X I/~o 9.45 - 9.65 ~.36 - 9.17 81 - 100 12.8 - 13.05 6.~2 - 6.78 ~ - 20 13.95 - 14.2 6.35 -6.24 8 - 23 16.0 - 16.2 5.54 - 5.47 25 -54 17.85 - 18.15 4.97 -4.89 11 - 76 19.0 4.67 0 - 2 20.55 - 20.9 4.32 - 4.25 44 - 100 22.05 - 22.5 4.~3 -3.95 0 ~ 5 23.0 - 23.15 3.87 - 3.84 2 - 10 24.95 - 25.4 3.57 -3.51 12 - 87 25.8 - 26.0 3.45 - 3.43 14 -26 D-13,443 3,~

~ABL~ XII (Con~.) 2~ d 100 X I/Io 27.5 - 27.7 3.243 - 3.220 1 - 4 28.05 - 2~.4 3.181 - 3.1431 - 12 29.2 - 29.6 3.0~8 - 3.018 3 - 9 30.5 - 30.7 2.931 - 2.912 19 -75 31.05 - 31.4 2.880 - 2.8~915 - ~8 32.2 - 32.4 ~.780 - 2.763 1 - 5 33.4 - 33.85 2.6~3 - 2.648 0 - 6 34.35 - 34.~5 2.611 - 2.5894 - 15 36.0 - 36.5 2.495 - 2.462 2 - 11 38.8 - 38.9 2.321 - 2.315 0 - 2 39.6 - 39.7 2.276 - 2.270 2 - 4 ~3.1 - 43.5 2.0~9 - 2.080 3 - 6 47.4 - 47.7 1.918 - 1.907 2 - 6 48.B - 4~o2 1.866 - 1.852 4 - 7 49.g - 50.45 1.~28 - 1.809 0 - 2 ~0.65 - 51.3 1.802 - 1.7811 - 8 53.0 - 53.25 1.728 - 1.720 2 - 7 54.25 - 54.7 1.691 - 1.678 0 - 4 55~ 7 ~ 55 ~ 9 lo 650 ~ 1~ 645 2 - 5 Example 39 (Preparation of SAPO-35) SAPO-35 was synthesized ~rom a reaction mixture which contained quinuclidine as the templatlng agent and which had an overali composition in terms of molar oxide ratios:
4.0 C7~13N : 0.3 SiO2 A123 ~25 2 Tnis reaction mixture was prepared ~y combining 46.1 grams of 85 w~.% orthophosphoric acid t~3PO4) and 60.9 grams of water with 81. 7 grams o~ aluminum isopropoxid~ (Al(OC3~7)3) while stirring. To this mixture were added 12 grams of an aqueous sol o~ 30 wt.~ SlO~ and 5 grams of water, and the mixture stirred until homogeneous. To 87.4 grams of t~is mixture were added 37.8 grams of quinuclidine, C7~13N, (Q), and 75.1 grams ~2' and the mixture stirred until homogeneous. A portion of the reaction mix.ture was sealed in a stainless steel D-13,443 r~action vessel having an iner~ liner and heated in an oven at 200C at autogeneous pressure ~or 168 hours. The solid reaction product ~as recovered ~y centrifugation, washed with water, and dried in air at 100C. The product had an X-ray powder diffraction pa~tern characterized by the ~ollowing data:
TA~LE T
d 100 X I/I~
8.7 10.1 18 11.05 8.01 47 11.9 7.44 2 13.4 6.. 61 23 16.0 5.54 12 17.4 ~ 5.10 ~ 83 17.7 (sh) J 5.01 17.9 4.96 14 21.25 4.18 55 22.0 4.04 100 2~.8 3.90 5 23.3 3.82 18 23.7 3~75 6 25.2 3.53 5 26.0 3.427 26.9 3.314 18 28.55 3.126 26 28~65 3.116 13 29.1 3~069 6 32.15 2.7R4 40 34.65 2.589 9 3~.7 2.515 3 37.8 2.380 2 39.3 2.292 2 40.8 2.212 2 42.1 2.146 4 42.4 2.132 43.15 2.0g6 4 44.4 2.0qO 2 48.5 1.877 7 49.~ ~.8~5 51.5 L.774 7 55.2 1~664 7 D-13, 443 ( b~ EDAX (energy dispersive analysis ~
X-ray) microprobe analysis, perrormed in conjunction with SE~ ( canning electron microscope) study, on clean crystals of SAPO-35 gives the ~ollowing analysis based on relative peak heights:
Si 0.2 ~1 1.0 P 0.7-0.8 Example 40 (Preparatisn of SAP0-35) (a) A reaction mixture was prepared by combining 132 grams of water with 132.8 grams of aluminum isopropoxide (Al(OC3H7)3) and then adding 30.1 grams of an aqueous sol containing 30 w~.% SiO2 and 45 grams of water. To this mixture was added 57.7 grams of 85 wt.% orthophosphoric acid (~3PO4) and ~he mixture stirred untll homogeneous. To this mixture was added a solution of 27.8 grams of qulnuclidine, C7H13N, (Q) in 50 grams o~ water, and the mixture stirred u~til homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
1.0 Q:0.6 SiO2:1.3 A12O3:P2O5:60 ~2 Part of ~he reaction mixture was placed in a stalnless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 150C at autogenous pressure for 48 hours. The solid reaction product was recovsred by centri~ugation, washed in water, and dried in air at 100C. The above product was impure but the major phase had an X-ray powder di~fraction pattern essentially identical to that in Example 39.
(b) A portion o~ the solid crystalline D- 13 , 4 4 3 product was calcined in air at about 600C ~or 2 hours. The wniter portion of the calcined product had an X-ray powder pattern characterized by the following data:
TABLE U
d 100 X I/Io 6.8 13.0 2 8.2 10.78 2 8.7 10.16 14 11.0 8.04 100 11.4 7.7~ 17 13.55 6.53 89 16.1 5.50 4 L7.4 5.10 24 18.7 4.75 3 21.0 4.23 29 22.2 - ~.00 63 23.0 3.~7 4 23.6 3.77 15 25.05 3.555 13 26.0 3.427 9 27.3 3.267 20 28.6 3.121 42 29.5 3.028 10 30.6 2.921 2 31.75 2.818 6 32.4 sh 2~763 ~ 32 32.6 2.747 ~
34.6 20592 7 35.4 2.536 4 36.3 2.475 2 47.~ 1.899 2 51.7 1.768 3 (c) A~sorption capacities were measured on this calcined product using a standard McBain-Bakr g~avimetric adsorption apparatus. The following da~a were obtained on a sample activated at 350C:

D-13,4~3 zo~

Kinetic Prassure, Temp.,Wt.%
Diameter, A Torr C Adsor ~d 2 3.46 98 -183 15.3 2 3.46 74~ -183 30.3 isobutane 5.0 101 25 0.7 n-hexane 4.3 48 24 10.2 H20 2.65 4.6 22 22.2 ~2 2.65 19 24 47,7 The pore siz~ of the calcined product is >4.3A and ~S.OA as shown by adsorption of n-hexane, kinetic dia~eter of 4.3A, and negligibls adsorption of isobutane, kinetic diameter of 5.0A.
Example 41 (Preparation of SAP0-35) (a) A reaction mixture was prepared ~
.combining 66.4 grams of aluminum isopropoxide and 67.8 grams H~O, to which was added a mixture of 15.0 grams of an aqueous silica sol (30 wt.-%
SiO2) and a solution of 3~0 grams NaOH in 20 grams ~2 and the mixture stirred until homogeneous. To this mixture was added 28.8 ~rams of 85 wt.~%
ortnophosphoric acid to wnich had been adaed a solution o~ 13.9 grams of quinuclidine (C7~13N) in 25 grams f ~2 The ~in~l homogeneous reaction mixture had a chemical composition in terms of molar oxide ratios of:
0.5(C7H13M) 20:0.3Ma20:0.60 SiO2:1.3 A1203:P2C15:60 H20 The reaction mixture was cryst~llized a~ 150C under autogenous pressure in a sealed reactor for 137 hours. The X-ray pattern of the recovered D-13,4~3 ~z~z~

crystalline SAPO-35 product was essentially identical to that of the SAPO-35 composition of Example 40, supra. Chemical analysis showed 3.7 wt.-% C, 4.4 wt.-% SiO2, 4.8 wt.-~ Na2O, 39.5 23' ~8-4 wt. ~ P2O5, 22.5 wt.-%
LOI, giving a composition in terms of molar oxide ratios of:
5(C7~13N) 2o 2Na2 A123 19si2 52P25 2 52~2 which Gorresponds to an essential empirical formula (anhydrous b~sls) of:
0.o3~c7Hl3N : ~sio.o6Alo.62po.32) 2 (b) Using the same reagents as in part (a) above, except that soaium was omitted, a reaction mixture was prepared ha~in~ a composition in terms of molar oxide ratios:

7 13 )2 0 4 SiO2: 1.2 Al2O3: P2O5: 60 ~ O
This mixture was digested and crystallized for 160 nours at 150C in a sealed reactor~ The X-ray powder diffraction pattern of the recovered product was essentially identical to that of the product of part (a) a ~ve. The chemical composition of the product was (anhydrous basis):
0.4 C7~13N : 0.23 SiO2 : Al2O3 : 0.64 P2O5 corresponding to an essential empirical formula of:
o.11C7~13N : (si~.07Alo.57po~36) 2 The species SAPo-35 as re~erred to herein i8 a silicoaluminophospAate material having a three-dimensional microporous crystal framework stLucture o~ PO2, AlO2 and SiO2 tetrahearal units, and whose essen~ial emplrical chemical composition on an anhydrous basis i5:
mR : (SixAlyPz)O2 D-13,443 l~J2V~Ç~

wAerein "R~ represents at least one organic templating agent present in the intracrystalline pore system; "m~ represents the moles of NR~ present per mole of (SiXAlyPz)O2 and has a value o from zero to 0.3, ~x~, "y" and ~z~ represent respectively, the mole ~ractions of silicon, all j n and phosphoru~ present in the oxide moiety, said mole ~rac~ions being within the compositional area bounded ~y points A, B, C, D and E on the ternary diagram which is Fig. 1, or preferably within the area bounded ~y points a, b, c, d and e on the ternary diagram which is Fig. 2, said silicoaluminophosphate having a characteristic X-ray powaer di~raction pa~tern wh~ch ~ontai~s at least the d-spacings set forth below in Table XIII. In the form as synthesized in accordance with the process of this invention, "m" has a value of from 0.02 to 0~3.

TABLE XIII
Relative d Intensity 10.9 - 11.058.12 - 8.01 m 17.2 - 17.4~ 5.16 - 5.10 ~ s 17.4 - 17.7 (sh)~ 5.10 - 5.01 ~
21.0 - ~1.25 4.23 - 4.18 m 21.8 - 22.0 4.08 - 4.04 vs 32.0 - 32.15 2.797 - 2.784 m All of the as-synthesized SAPO-35 compositions for which X-ray powder diffraction data have presently ~en obtained have patterns which are within the generallzed pattern of Table XIV, below.

D-13,~43 ~3~

TABn~ XIV
d 100 X I/Io

8.5 - 8.710.4 -10.113 - lB
10.9 - 11.05~.12 - ~.013~ - 48 11.6 - 11.97.63 - 7.44~ - 3 13,2 - 13.46.71 - 6.6123 - 24 15.75 - 16.05.~2 - 5.5~7 - 12 17.2 17.4~ 5.16 - 5.10 166 - 83 17.4 - 17.7 (sh)~ 5.10 - 5.01 ~
17.6 - 17.95.~4 - 4.9~9 - 18 21.0 - 21.254.23 - 4.1847 - 56 21 8 - 22.0~o08 - ~.04 100 23 0 ~ 23.33.87 - 3.8214 - 18 23.55 - 23.753.78 - 3.75 6 24.9 - 25.23.5~ 3.533 - 6 25.85 - 26.0 3.446 - 3.427 0 - 2 26.7 - 26.9 3.339 ^ 3.31416 - 19 28.4 - 28.55 3.143 - 3.12622 - 2 28.65 - 2~.85 3.116 - 3.09513 - 20 29.0 - 29.1 3.079 - 3.069 4 - 6 32.0 - 32.15 2.797 - 2.78433 - 47 34.55 - 34.7 2.596 2.585 ~ - 9 35.6 - 35.8 ~.52~ - 2.508 3 - 4 37.7 - 37.8 2.386 2.380 2 ~ 3 39.2 - 39.3 2.298 - 2.292 40.7 - 40.8 2.217 - 2.212 0 - 2 41.gS - ~2.~ 2.154 - 2.146 3 - 5 42.4 - 42.55 2.132 2.125 2 - 4 42.95 - 43.2 2.106 - 2.~94 2 -~4.4 - 44.5 2.~0 - 2.036 1 2 48.4 - 48.55 1.881 - 1.875 7 - 8 49.3 - 49.45 1.848 - 1.843 6 - 8 5~.4 - 51.5 1.77~ - 1.774 5 8 55.2 - 55.25 1.664 - 1.6~3 4 - 7 Example 42 (Preparation of SAPO 37) A SAPO-37 was synthesized from a reaction mix~ure pr~pared ~y combining 9.2 grams of 85 wt.%
orthophosphoric acid (~3PO4) and 5.8 yrams of water, to which was added 5.5 grams of hydrated aluminum oxide (a pseudo-boehmite phase, 74.2 wt.%
A12O3, ~5.8 wt.% ~2)~ and stirred until homogeneous. To this mixture was added a ~ispersion D-13,443

- 9~ -~

of i.o gram of fumed silica (92.8 wt.% SiO2, 7.2 wt.~ ~2) in 40.8 grams of an aqueous solution of 40~ tetra-n-propylammonium hydroxide (TPAO~). The mixture was stirred until homogeneous. The composition of the final reaction mix~ure in molar oxide ra~ios was:
A12O3 P2O5 0-4 S12 (TPA)2 2 A portion o~ this mixture was crystallized a~ 200C
for 24 hours under autogeneous pressure in a sealed reactor lined with an inext plastic material. The solid reaction product was recovered by centri~uging and washing with water, and dried in air at room temperature. The SAPO-37 product was impure but the major phase (~80%) had an X ray powder diffraction pattern characterized by the following data:
TABLE VA
2~ d 100 X I/I~
6.24 14.17 100

10.17 8.69 22

11.93 7.42 4 15.69 5.65 33 18.73 ~.74 ~
2~.405 4.35 13 21.~8 4.21 5 22.84 3.89 8 23.69 3.75 24 24.67 3.61 25.85 3.45 6 27.09 3.29 14 27.84 3.204 2 2g.69 3.009 3 30.80 2.903 5 31.45 ~.844 12 32.50 2.755 3 33.14 2.703 L

D- 13 , 443 ~z~

TABLE VA (cont'd) d 100 X I/Io 34.14 2.626 5 34.45 2.603 2 37.94 2.371 3 40.61 2.221 41~46 2~178 43.29 ~.089 44.10 2.054 2 By chemical analysis the composition of the SAPO-37 product was founa to be 12.1 wt.% C, 1.43 wt.~ N, 8~98 wt.~ SiO2, 33.08 wt.% A1203, 33-69 wt.~
P205, 24.25 wt.~ LOI (by difference), giving a product composition in molar oxide ratios of:
0.13(TPA)20 : 0~46 SiO2: A1203: 0.74 P205: 1.23 ~2 which corresponds to the formula (anhydrous basis) 0.066(TPA) : (Sio.l2A10.51PO.37)02 EDAX (energy dispersive analysis by X-ray) microprobe analysis, performed in conjunction with SEM (sc~nn;~g electron microscope) study, on clean crystals having a crystal morphology characteristic of SAPO-37 gives the following analysis based on relative peak heights:
Range Average Si 0.43-0.47 0.45 Al 1.0 1.0 P 0.76-0.82 0.795 ~xample 43 (Preparation of SAP0-37) (a) SAP0-37 was found to be suitably templated by a mixture of tetra-n-propyla~nonium ions and tstrame~hylammonium ions in a reaction rnixture formed ~ combining 27.7 gram~ of 85 wt.%

D-13,443 orl ophosphoric acid (~3PO4) and 30.5 grams of wat r, to which was added 16.6 grams of hydrated all inum oxide (a pseudo-boehmite phase, 74.2 wt.
Al; 3, 25.8 wt.~ ~2)' and stirred until hol geneous. To this mixture was added a dispersion of .1 grams of a ~umed silica (92.8 wt.~ SiO2, 7.~ wt.% ~2) and 1~1 gram o tetrame~hylammonium hy~ oxide pentahydrate (TMAO~ 5 ~20) in 115.98 grc s of an aqueous solutlon of 40 wt.%
tet a-n-propylammonium hydroxide (TPAOH) and the ~i, ure stirred until homogeneous. The composition of he final reaction mixture in molar oxide ratios wa~
A1203~P205:0.4 SiO2:(TPA)2O:0.0~5 (TMA~O:50~2O
A ~ rtion of the reaction mixture was placed in a st~ nless steel pressure vessel lined with po tetrafluoroethylene and neated in an oven at 20l C at autogenous pressure for 24 nours. The so d reaction product was recovered by centrifuging an~ washing with water, and dried in air ~t 100C~
Th above product had an X-ray powder diffraction pa- ern characterized by the following data:
T~3LE W
d 100 X I/Io 6.2 14.25 1~0 10.1 8.74 22 11.9 7~4~ 5 15.6 5.68 42 18.5 4.80 34 20.2 4.40 16 21.2 4019 4 22.7 3.92 11 23.5 3.79 39 24.8 3.59 25.7 3.47 6 ~6.9 3.314 27 D- , , 44 3 ~'~Q~016 TABLE w (cont'd) d 100 X I/Io 27.6 3.232 2 29.4 3.038 7 30.6 2.921 9 31.2 2.867 1~
32.2 2.780 5 33.0 2.714 2 33~ 2.6~4 7 34.4 2.607 3 37.8 2.380 6 40.4 2.233 2 41.2 2.191 2 43.1 2.09~ 1 43.9 2.062 3 The chemical composition of the SAPO-37 product was determined to be 31.8 wt.% A12O3, 31.4 wt.%
P2O5, 9.2 wt.% SiO2, 14.2 wt.4 C, 1.8 wt.~ N
and 26.1 wt.~ LOI, corresponding to a product composition in molar oxide ratios of:
1.0 A12O3 0 71 P2O5:0 4~ Si2 ( 2 (TMA)2O:0.89 ~2' and thus had the formula (anhydrous ba~is):
0.10(TPA ~ TMA): (Sio .125A10.51Po.365) 2 (b) A portion of the solid crystalline product of part (a) was calcined in air at a ~ut 600C ~or 1 hour. The calcined product had an X-ray powder diffraction pat~ern characterized by ~he data shown in the following table:
TABLE Y
d 100 X I/Io 6.2 14.25 100 10.3 8.59 19

12 1 7.37 11 15 9 5~57 20 D-13,443 - g4 -TABLE Y (cont'd~
d 100 X I/Io 18.6 4.77 7 20.4 4.35 9 21.5 4.13 22.9 3.88 3 23.8 3.74 13 25.0 3.56 25.8 3.45 27.0 3.30 7 27.7 3.22 29.5 3.03 2 30.7 ~.g2 4 31.4 `2.85 7 32.4 2.76 2 33.0 2.71 3~.0 2.63 3 3~.6 2.59 37.9 2.37 2 40.5 2.~3 41.2 2.19 43.1 2.10 44.0 ~.06 (c) Adsorption capacities were measured on this calcined produc~ using a standard ~cBain-~akr gravimetric adsorption apparatus~ The following data were obtained on a sample activated at 350C in vacuum.
Kinetic Pressure, Temp,, ~t. %
Diameter, A Torr CAdsor~d 2 3.46 100 183 35.0 2 3.46 750 ~183 42.9 Cyclo- 6.0 60 2~ 23.2 nexane ~eopentane 6.2 743 24 14.8 ~2 2.65 ~.6 24 35.3 D-13,443 ~2{:~2~

The pore size of the calcined product is greater than 6.2A, as shown by adsorption of neopentane, kinetic diameter of 6.7A.
(d) EDAX (energy dispersive analysis ~
X-ray) microprobe analysis, performed in conjunc~ion with SE~ (scanning electron microscope) study, o~
clean crystal~ having a crystal morphology characteristic of SAPO-37 gives the following analysis ~ased on relative peak heights:
~i 1 Al 3 P
(e) Mixtures of tetramethylammonium nydroxide with tri-n-propylamine and with tetra-n-butylammonium hydrox'de were also found to faclli~ate tne formation of SAPO-37.
Example 44 (Preparation of SAPO-37) Using the same general procedure and reagents as in ~xample 42, supra, ~t using a mixture of tetramethylammonium hydroxide and tetrapropylammonium hydroxide as the templating Igent, a reaction mixture was prepared having the following composition in terms o~ molar oxide ratios:
~ )2O:l.O(TPA)2O:A12O3:P2O5: 2.0 SiO2: 50 ~2 Upon crys'callization at 200C in a sealed reactor for 72 hours, the product was found to contain principally SAPO-37 in combination with abou~ 20 wt.-~ o~ the crystalline solids ~ing identified as SAPO-5 and about 10 wt.-~ SAPO-40.
The species SAP0-37 as re~erred to nerein i5 ~ silicoalu~inophosphate having a microporous cry~talllne ~ramework structllre and whose essentlal empirical chemical composition in the as-s~nthesized D-13,443 3LZ~)2~

form and on anh~ rous basis is:
mR:(sixAlypz)o2 wherein R repre~ nts at least one organic templating agent present ir the intracrystalline pore system, ~mH has a ~alue f from 0.02 to 0.3, "xn, ~y" and ~z" represent, ~ spectively, the mole fraction of silicon, alumin- and phosphorus present in the oxide moiety, t~ value of x, y and z being within the compositionc area bounded by points A, B, C, D
and E on the te~ ary diagram which is Fig. 1, or preferably withi the area bounded ~y points a, br c, d and e on t~ ternary diagram which is Fig. 2, said silicoalumi ophosphate having a characteristic X-ray powaer di~ raction pattern which contains at least the d-spac ngs set forth below in Table XV:
~ABLE XV
Relative d Intensity ~.1 - 6.3 14.~9 - 14.03 vs 15.5 - 15.7 5.72 - 5.64 w - m 18.5 - 18.8 4.80 - 4.72 w - m 23.5 - 23.7 3.79 - 3.75 w - m 26.9 - 27.1 3.31 - 3.29 w - m All of the as-s~ thesized SAPO~37 compositions for which X-ray pow~ r dif~raction data have presently ~een o~tained h~ e pa~terns which are within the generalized pat1 rn of Table XVI, below.
TABLE XVI
d 100 X I/Io ~.1 - 6.3 14.49 - 14.03 100 10.1 - 10.3 8.76 - 8.59 22 - 30 11.8 - 12.0 7.50 - 7.37 4 - 10 15.5 - 15.7 5.72 - 5.64 30 - 6Q
18.5 - 18.8 4.80 - 4.72 20 - 5 ~-13,443 TABLE XVI ~Cont'd) 2~ d 100 X I/Io 20.2 - 20.4 4.40 - 4.35 12 26 21.0 - 21.2 4.23 - 4.19 4 - 10 22.7 - 22.9 3.~2 - 3.88 8 - 21 23.5 - 23.7 3.79 - 3.75 2g - 59 24.6 - 24.9 3.62 - 3.58 1 - 3 25.6 - 25.8 3.48 - 3.45 5 - 11 26.9 - 27.1 3.31 - 3.29 14 - 42 27.6 - 27.9 3.232 - 3.198 2 - 4 29.4 - 29.7 -- 3.038 - 3.008 ~ - 11 30.6 - 30.8 2.921 - 2.903 5 - 18 31.2 - 31.5 2.867 - 2.840 12 - 32 3202 - 32.5 2.780 - 2.755 3 - 11 33.0 - 33.2 ~.714 - 2.698 1 - 3 33.9 - 3~.2 2O6~4 - 2.622 4 - 14 34.3 - 34.5 2.614 - 2.600 2 - 6 37.7 - 3~.0 2.3~6 - 2.3~8 3 - 9 40.4 - 40.7 20232 - 2.217 1 - 5 41.2 - 41.5 2.191 - 2.176 1 - 7 43.1 - 43.3 2.099 - 2.089 1 - 7 43.9 - 44.1 2.062 - 2.053 2 - 8 Example 45 (Pr~paration of $APO-40~
(a) A reaction mixture was prepared by combining 9.22 grams of 85 wt.% orthophosphoric acid (H~PO4) and 5.78 grams of water, to which was added 5.52 grams of a hydrated aluminum oxide, ~a pseudo-boehmite phase, 74.2 wto% A12O3, 25.8 wt ~ ~ H2O), and st~rred until homogeneous. To this mixture was added a dispersion o~ lo 04 grams of a fumed silica (92.8 wt.~ SiO2, 7.2 wt.% ~2) in 40.82 grams of an aqueous solution of 40 wto %
tetra-n-propylammonium hydroxide (~PAOH), and the mixture stirred until homogeneous7 The composi~ion of the f inal reaction mixture in molar oxide ratios was:
A12O3:P2Os:0.4 SiO~ PA)2O:5O H2O

D-13,443 .3~03~

The gel was crystallized at 200C $or 24 hours under autogenous pressure to yield a crystalline product containing SAPO-40 which was recovered by centrifuging, washing with water, and drying in air at room temperature. The solids were subjected to X ray analysis. The results indicate the presence of a minor proportion of SAPO-40 in admixture with other known SAPO phases. After removing peaks corresponding to other phases from the X-ray powder di~raction pattern, a pattern remained representing a minor component and characterized by the following data:

TABLE ~
d 100 X I/Io 8.061 10~97 85 12.46 7.10 100

13.711 6.46 42

14.044 6.31 30 17.632 5.~3 17 21.899 4.06 22 ~4.020 3.70 15 (b) EDAX (energy dispersive analysis by X-ray) microprobe analysis, performed in conjunction with SEM (scanning electron microscope) study, on clean crystals of 5APO-40 gives the following analysis ~ased on relative peak h0ights:
Si 0.08 Al 1.0 P 0.~7 D-13, 443 ~.2S..3'~6 Example 46 (Preparation of SAPO-40) (a~ SAPO-40 was also produced by crystallizing a~ 200C for 96 hours under autogenous pressure a reaction mixture containing both sodium hydroxide and TPAO~ in addition to phosphoric acid, a hydrated aluminum oxide, ~ater and a fumed silica in proportions such that ~he reaction mixture had the composition:
A12O3:P2O5:0.4 SiO2:(TPA)2O:0.01 Na2O:5O ~2 A portion o~ the recovered solids was analyzed with X-radiation to produce a powder diffraction pattern characterized by the following data (peaks resulting solely from a minor SAPO-5 impurity have been omitted):

TABLE ~A
2B cl 100 X I/Io 7.60 11.63 18*
8.03 11.01 100 12.~3 7.12 18 13.68 6~47 43 1~.02 6.32 12 16.12 5.50 17.36 5011 7 18.50 4.80 14 19.72 4.50 6 20.39 4036 13 21.40 4.15 10 21.68 4.10 6 22.93 3.88 4 23.74 3.75 19 24.21 3.68 5 24.62 3.61 27.32 3.264 22 D-13,443 ~2~2~

TABLE AA (Cont'd) 2~ d 100 X I/Io 27.%4 3.204 15 28.10 3.176 4 28.59 3~:123 30.34 ~.946 3 30.61 2.920 2 31.07 2.878 3 31.76 2.~17 4 32.33 2.769 3 33.28 ~.692 2 33.77 2.654 2 35.07 2.559 2 35.82 2.507 3 * Contains peak from impurity Chemical analysis indicated ~he product contained 8.9 wt.% C, 1.0 wt.% N, 34~4 w~.% A12O3, 40.4 wt.~ P2Os, 6.9 wt.~ SiO2, 0.7 wt.% Na2O, 17.5 wt.~ LOI, giving a product composi~ion in molar oxide ratios of:
0.092(TPA)~0:0.034 Na20:1.00 A12O3:O.85 P20s:0.34 SiO2:0.81 ~2~ and a formula (anhydrous basis) [o.o45(TpA)~o.ol7 ~a]: tsio . 08SA10.495Po.42)o2 (~) A portion of the produc~ of part (a) supra was calcined in air at 700C for 1 hour. The X-ray pattern of the calcined material was characterized by the following data after subtraction of peaks contributed by identified impurities:

D-13, 443 TABL~ BB
d 100 X I/Io 7.60 11063 78 7.95 11.19 100 12.55 7.08 14 13.60 6.51 13 14.20 6.24 13 16.00 5.~4 3 17~40 5.10 9 le.60 4.77 15 20.40 4.35 7 21.~5 4.11 4 22.75 3.92 3 23.70 3.75 . - 3 27.15 3.290 15 2~00 3.186 12 30.65 2.921 3 31q70 2O~22 3 32.~0 2.763 2 (c~ Adsorption capacities were measured sn this calcined product using a standard McBain-~akr gravimetric adsorp~ion apparatus. ~he ~ollowing data were obtained on a sample activated at 350C in vacuum.
Kine~icPressure, Temp., Wt %
Dia~eter, A Torr CAdsorbed 2 3.46 100 -18321.8 0~ 3.46 750 -18324.4 Cyclohexane 6.0 60 24 8.0 Neopentane 6.2 743 24 5.1 ~2 2.65 4.6 2422.7 ~2 2.65 20 2431.5 Isobutane 5.0 697 24 7.0 SF6 5.5 400 2411.6 The pore size of the calcined product appears to be greater than 6.2A, as shown by adsorption of neopentane, kinetic diameter 6.2A. It snould be noted, however, that the sample contained D-13,443 ~ ~3~

substantial amounts or SAPO-5, which adsorbs molecules as large as neopentane.
(d) EDAX (energy dispersive analysis by X-ray) microprobe analysis7 performed in conjunction with SEM (scanning electron microscope) study, on clean crys~als having a crystal morphology characteri tic of SAPO-40 gives the following analysis ba~ed on relative peak heights:

Si 0.14 Al 1.0 P 0.95 Example 47 (Preparation of SAPO-40) A reaction mixture was prepared by combining, in a manner to obtain a homogeneous composition, 6.90 grams of a hydrated aluminum oxide (74.~ wt.-~ A12O3, 25.8 wt.-~ H2O) with 11.53 grams of 85~ orthophosphoric ~cid, and a solution of O.38 gram a~monium acetate (NH4AC) in 11.16 grams ~2~ and finally with a mixture o~ 1.30 grams of a fumed silica (92.8 wt.-~ SiO2) in 50.9 grams of 40~ aqueous tetra-n-propylammonium hydroxide 301ution (TPAOH). ~he composition of the reaction ~ixture was:
0-1NH4Ac : (TPA)2O : ~12O3 : 0.4 SiO2 : P2O5 : 5~2 After digestion and crystallization in a sealed reactor ac 200C for 24 hours, a SAPO-40-containing produc~ was recovered. The SAPO-4~ component exhibited an X-ray powder dif~raction pattern essentially identical to that of Example 46.
The ~pecies SAPO-40 as referred to herein is a silicoaluminophosphate ma~erial having a three-dimensional microporou~ crystal ~ramework D-13,443 s~ructure of PO2, AlO2 and SiO2 tetrahedral units, and whose essential empirical chemical composition on an anhydrous basis is:
mR : (SiXAlyPx)O2 wherein ~R~ represent at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles o~ "R" present per mole of (SiXAlyPz)O2 and has a value of from zero to 0.3, "x~, "y~ and "z" represent respectively, the mole fractions of silicon, aluminum and phosphorus present inthe oxide moiety~
said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is Fig. 1, or preferably within the area bounded by points a, b, c, d and e on the ternary diagram which is Fig. 2, said silicoaluminophosphate haviny a characteristic X-ray powder dif~raction pattern which contains at least the d-spacings set ~orth below in Table XVII. In the form as synthesized in accordance with the process o~ this invention, ~m~ has a value of f~om 0.02 to 0.3.

TABLE XVII

Relative 2~ d Intensity 7.5 - 7.711.79 - 11.48 VW - M
8.0 - 8.111.05 - 10.94 S - VS
12.4 - 12.5 7.14 - 7.08 W - YS
13.6 - 13.8 6.51 - 6~42 M - S
14.0 - 14.1 6.33 - 6.28 W - M
27.8 - 28.0 3.209 - 3.18 W - M

D-13,443 All of the as-synthe ized SAPO-40 compo~itions for which X-ray powder diffraction data have presently ~en obtained have pattern~ which are within the generalized pattern of Table XVIII, below.

~ABLE XVIII

d 100 X I/Io 7.5 - 7.7111.79 -- 11.4~ 6 - 51 8.0 - ~.11 11.05 - 10.94 85 - 100 12.4 - 12.5 7.14 - 7.08 15 - 100 13.6 - 13.8 6.51 - 6.42 43 - 62 14.0 - 14.1 6.33 - 6.28 12 - 3 16.1 - 16.3 5.50 - 5.44 1 - 2 17.3 - 17.7 5.13 - 5.01 6 - 17 18.5 - 1~.6 4.80 - ~.77 14 - 30 ~9.7 ~ 20.0 4.51 - 4.~4 6 - 22 20.3 20.5 4.37 - 4.33 12 - 19 ~1.3 21.5 4.17 - 4,13 10 - 19 21.6 - 21.9 ~ 4.06 6 - 22 22.9 - 23.2 3.88 ~ 3.83 4 - 9 23.7 - 23.8 3.75 - 3.74 19 - 30 24.0 - 24.3 3.71 - 3.66 0 - 5 ~4.6 - 24.7 3.62 - 3.60 1 - 17 27.3 - 27.5 3.267 - 3.24 22 - 29 ~7.8 - 28.0 3.209 - 3.18 15 - 33 28.0 - 28.2 3.187 - 3.164 0 - 4 28.5 - 28.7 3.132 - 3.110 0 - 2 29.2 - 29.3 3.058 - 3.0~8 0 9 30.3 - 30.4 2.950 - 2.g40 0 - 3 30.6 - 30.7 2~g21 - 2.912 0 - 2 31.0 - 31.2 2.885 - 2.867 0 - 3 31.7 - 31.9 2.8Z3 - 2.805 ~ - 5 32.3 - 32.5 2.772 - 2.755 3 - 5 33.2 - 33.4 2.698 - 2.6~3 1 - 2 33.7 - 33.8 2.660 - 2.652 2 - 3 35.0 - 35.2 2.564 - 2.550 2 - 3 35.8 - 35.9 2.508 - 2.501 2 - 3 ~xample 48 (Yreparation of SAPO-42) (a~ SAPO-42, which appears to be structurally similar to the aluminosilicate zeolite D-13,443 ~Lzf~z~3~L6 A, is found to be produced by the extended aging at lower temperatures of a gel composition which otherwise yields SAP0-20, a silicoaluminophosphate wbich has structural similarity to the aluminosilicate sodalite. The gel involved was prepared as ln Example 28 supra and had a composition in molar oxide ratios of:
1.2 Na20:1.1(TMA)20:400 SiO2:1.66 A1203:0.66 P205:95 H20 Part of the reaction mixture was placed in a sealed iner plastic container and heaked in an oven at 100C at autogenou~ pressure for 480 hours. The solid r~action product was recovered by centri~ugation, washed wi~h water, and dried in air at 100C. The above product had an X-ray powder dif~raction pattern characterized by the following data:

TABLE CC

d 100 X I/Io 7.4 11.9 71 10.4 8.51 55 12.7 6.97 61 13l9 6.37 7 16.35 5.42 31 17.9 4096 13 21.6 ~sh) ) 4.13 ~ 68 21.9 ~ ~.06 23.1 3.85 17 24.25 3.67 100 26.4 3.376 29 27.4 3.255 83 3~.25 2.955 75 31.1 2.876 15 32.9 2.722 19 33.7 2.660 34.45 2.603 37 36.05 2.4gl 19 D-13,443 TABLE CC (Cont) 2~ d 100 X I/Io 36.9 2.436 5 38.35 2.347 5 40.5 2~227 7 41.85 2.158 11 42.55 2,1,~5 6 43.15 2.096 3 43.~5 2.065 44.5 2.036 9 47.7 1.907 8 ~8.3 1.884 4 49.~ 1.859 ~9.5 1.841 6 50.05 1.~22 4 52.4 ~.74~ 3 53.0 1.728 16 53.6 1.710 2 54.65 1~679 16 55.2 1.664 2 By chemicsl analysis, ~he composition o~ the crystalline product was found to be 11.3 wt.
Na20, 38.3 wt.% SiO~, 25.6 wt.~ A1203, 1.6 wt.-% C, 0.43 wt.~ N, 4.4 wt.~ P205, 19.9 wt.~ LOI, giving a product composition in molar oxide ratios of:

O.07(TMA)20:2.5 SiO2:0.7 Na20:A1203:0.1 P~05:3.7 ~2 which corresponds in turn to the essen~ial formula (anhydrous basis):
0.03 (TMA): ~sio . 53 AlO.42 0.04 2 (b) A portion of the SAPO-42 part (a~
su~ra was calcined in air at 550~C for 2 hours, Adsorptio~ capacities were measured on this calcined sa~ple using a standard McBain-Bakr gravimetric ~dsorp~ion apparatus. The following data were o~tain~d on a ~ample activated at 350C.

D-13,443 Kinetic Pressure, Temp.,~t.~
Diameter, A Torr C Adsorted 2 3.46g8.5 -183 12.6 2 3.46740. -183 17.0 n-~exane 4.353.5 24 7.4 Isobutane 5.0 7510 24 1.0 ~2 ~ 4.6 23 15.5 ~2 2.6519.4 24 21.0 .The pore si2e of the calcined product is ~ 4.3A, as shown by the adsorption of n-hexane.
Example 49 (Preparation of SAP0-42) A reaction mixture ha~ing the composition, in terms of molar oxide ratios of:
4.2(TEA)2O:SiO2:2.0A12O3:P2O5:129H2O
was prepared, using as the reagents, water, a hydrated alumina, orthophosphoric acid, te~raethyla~monium hydroxide (TEAO~) and a silica sol. In the preparation, an aluminophosphate gel was firs~ prepared ~y combining 17.2 grams of the hydrated alumina (74.2 w~ A12O3) with 18.4 grams H2O, 28.8 grams of 85 wt.-~ orthophosphoric acid and 151.7 grams of a 40.7 w~. ~ aqueous solution of the TEAO~. A second mixture formed by combining the remaining alumina, TEAOH and the silica sol was then added to the initially prepared gel. The ~inal reac~ion mixture was crystallized at 200C for 168 hours in a sealed reactor. X-ray analysis of the isolated produc~ established that SAPO-42 had ~en produced.

D-13,443 A

~3~0 The species SAPO-42 as referred to herein is a silicoaluminophosphate having a microporous crystalline framework structure and whose empirical chemical composition in the as-synthesized form and an anhydrous basis:
mR:(SiXAlyPz)O2 wherein R represents at least one organic templating agent yresent in the intracrystalline pore system, nm~ has a value of ~rom 0.02 to 0.3 nxn, ny~ and "z" represen~, respectively, the mole fraction o~
silicon, aluminum and phosphorus present in the oxide moiety, the value of x, y an~ z being within the compositional aEea bounded by points A, B, C, D
and E on the ternary diagram which is Fig. 1, or preferably witnin the area bDunded ~ points a~ b, c, d and e on the ternary diagram which is Fig. 2., said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth below in Table XIX:

TABLE XIX
Relative d Intensity 7.15 - 7.4 12.36 - 11.95 M VS
12.5 -12.7 7.08 - 6.97 M ~ S
21.75 -21.9 4.086 - 4.058 ~ - S
24.1 -24.25 3.69 - 3.67 VS
27.25 -27.4 3.273 - 3.255 S
30.05 -30.25 2.974 - 2.955 M - S

All of ~he as-syn~hesized SAPO;42 compositions for wnich X-ray powder dif~rac~ion data have presently Deen o ~ained have patterns which are within the generalized pattern of Table XX, below:

D-13,443 ~n ~ Ul ~n Ul ~ P P ~ ~ P ~ P ~ ~ ~ W W ~ W W W W ~ f~
~~ ~n w ~D W ~ C X ~ ~ ~ ~ w ~ D W Ul a~ o o ~I ~ ~ 1--W ~ Ul O ~I C~

Ul ~n Ul Ul ~n P P ~ ~ .P ~ .P P ~P ~ ~ W W W W ~ W ~ ~ ~ ~ ~ ~ ~ ~ ~~ ~ ~~ i~ ~I a~
~n ~ ~ ~ O ~ ~ I ~ W ;~ ~ ~~ O ~0 O~ ~ ~ W ~ ~ O ~ ~ w ~ w t~; o -~1 O ~ O ~n O W ~ D O ~ ~ J .P tn .. ..................... ... s.... .... O........ ~3 1 O O O 1~ i~ ~ W ~ ~ P ~ ~ O 1-- 0 ~ ~ O a~ W o ~ ~b n ~ ~ ~- w m ~ W W l- W ~
O o W X

~ Q O O O 1' ~ ~ ~ ~ ~ ~ ~ ~ ~ w a~ ao o ~-- ~D .P W
a~J ~u-wowcrcD~-n~w~0~3n ~n~~ n~nt~
~ ao ) cr~ ~ ~--~D ~ ~I ~ ~ ~ ~ d~ ~I ~I a~ 1--w o ~ a ~ Ul ~ o o c~ ~n o o ~ o 1--o c:~ ~n o w ~ a~ o o ~ n w W ~ ~ c~ O ~ o w ~ 1~ r o ~ co ~ 1~ ~ O

W C~ O ~ r~ w ~ w t~ O ~ ~I ~D O O ~ ~ ~ 1 ~J O ~ ~n o b~ O

Example 50 (Preparation of SAPO-44) A SAPO species which has no known structural counterpart in the AlPO4 or zeolite series, SAPO~44, is prepared ~ combining 23.1 grams of 85 wt.~ orthophosphoric acid (~3PO4) and 57.
grams of water with 40.9 grams of aluminum isopropoxide (Al(OC3~7)3~ and 5.0 grams of water and the mixture stirred until homogeneous. To this mixture were added 12~0 grams of an aqueous sol of 30 wt.~ SiO2 and 5.0 grams of water and the mix~ure stirred until homogenous. To this mixture were added 9.9 grams of cyclohexylamine (C6~11N~2) and 5.0 grams o~ water, and the mixture stirred until homogenous. The composition of the final reaction mixture in molar oxide ratios was:
C6HllNH2 : 0.6 SiO2 : A12O3 : P2O5 2 Part of the reac~ion mix~ure was placed in a stainless steel pressure vessel lined with an iner~
plastic material and heated in an oven at 200C at autogenous pressure for 52 hours. The solid reaction product was recovered by centrifuga~ion, washed with water, and dried in air at 100C. The above product was impure but the major phase (SAPO-44) had an X-ray powder diffraction pa~tern characterized by the ~ollowing data:

T~BLE DD
a 100 X I/Io 7.5* 11.8 2 9.5 9.31 100 10.~5 ~.0~ 4 13.0 6.~1 31 13.3 6.66 13.75 6~4~ 3 ~-13,4~3 ~4~Z~

TABLE DD tCont ' d) 28 d 100 X I /I O
14.9* 5.95 16.15 5.49 51 17.4 5.10 9 19.0 4.67 6 19.7* 4.51 20.85 4.26 21.1 (sh) * 4.21 T 98 21.9 4.06 25 22.5 tsh)* 395 22.7 3.92 ~ 7 23.1 3.85 12 24.55 3.626 55 25.9 (sh) * 3.440 1 26.2 3.401 ~ 22 26.9 3.314 27.9 3,198 10 28.5 3.132 2 2~ .0* 3.079 29.7 3.008 4 30O 2* 2.959 18 30.9 2.894 80 31.6 2.831 32.15 2.784 2 32.55 2.751 3 33.0 2.714 5 33.6* 2.667 34.8~ 2.578 3 35.6 2.522 11 38.5 2.338 3~.2 2.298 39.9 20259 2 42.3 2.137 ~
42.6 ( sh) 2.122 J 4 43.7 2.071 3 44.4 2.040 45.2 2.006 ~6.2 1.965 47.3 1.922 2 ~8.2* 1.8~8 6 4~.8 1.866 5 50.5 1.807 9 51.2 1.784 52.2 1.75~ 2 54.0 1.698 8 * Possi bly contains peak of another phase D-13,443 ~z~

Chemical analysis indicated the composition of the product SAPO-4~ to be 6 11 H2) ~47 SiO2 A~2O3 0-85 P2O5 0.64 H o This corresponds to an essential empirical formula (anhydrous basis) of 0.14 ~C6~11NH2) : (Sio . llA10~48PoO41)O2 (b) A por~ion of the solid crystalline product obtained by heating a portion of the above reaction mixture at 200C for 168 hours and exhibiting an X-ray powder diffraction pattern essentially identical ~o that above was calcined in air at about 550C for 2 hou.rs. The calcined product had an X-ray powder diffraction pattern cnaracterized ~y the ~ollowing d ta:
TABLE EE
d 100 ~ I/Io 7.4* 11.9 1~.9 8.12 3 12.95 6.84 46 13.4 ~.61 3 13.9 6.37 3 16.1 5.50 22 17.8 ~.98 22 19.1 4.65 3 20.75 4.28 5~
22.1 4.02 5 22.65 3.925 23.2 3.834 11 24.9 3.576 ~3 26.1 3.~14 18 ~7.2 3.278 L
27.8 3.209 3 28.2 3.164 7 29.2 3.058 .75 3.003 3 30.8 2.903 ~0 31.2 2.~67 16 D-13,443 /~

3~3 (TABLE EE (Cont) 2~ d 100 x I/Io 31.8 2.814 32.5 2.755 2 33.6* 2.667 3 34.8* 2.578 5 35.2 2.550 36.2 2.~81 3 43.0 2.103 48.2* 1.888 49.2 1.852 2 51.1 1.787 2 53.8 1.704 54.6 1.681 *possibly contains peak from another phase (c) Adsorption capacities were measured on this calcined product using a standard McBain-Bakr gravimetric adsorption apparatus. The following data were obtained on a sample activated at 350C:
Kinetic Pressure, Temp., Wt%
Diameter Torr C Adsorbed 2 3.4 98 -183 25.5 2 3.4 746 -183 32.3 n-hexane 4.3 48 23.9 3.6 isobutane 5.0 101 25.4 0 The pore size of the calcined product is ~4.3A
and ~5.0A, as shown by adsorption of n-hexane, kinetic diameter of 4.3A and nil adsorption of isobutane, kinetic diameter of 5.OA.
The ~pecies SAYO-44 as referred to herein is a silicoaluminophosphate material having a three-dimensional microporous crystal framework structure of PO~, A102 and SiO2 tetra'nedral units, and whose essential empirical chemical composition on an anhyd rous basis is:
mR : (SiXAlyPx)O2 wherein "R" represents at least one or~anic templating agent present in ~he in~racrystalline pore system; "m" represen~s the moles of 'IR" present per mole of (SiXAlyPz)O2 and has a value of from zero to 0.3, Rx~, nyn and nzn represent respectively, the mole fractions of silicon, aluminum and phosphorus present inthe oxide moiety, said mol~ ~ractions being within the compositional area ~ounded by points A, B, C, D and E on the ternary diagram which is Fig. 1, or preferably within th~ area bounded by points a, b, c, d and e on the tarnary diagram which is Fig. 2, said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set ~orth below in Table XXI. In the form as synthesized in accordance with the process of tnis invention, "m" has a value of ~rom g.03 to 0.3.

TABLE XXI
Relative d Intensity 5.4 - 9.55 9.41 9.26 VS
13.~ - 13.1 ~.81 - 6.76 W - ~
16.1 - 16.2 5.50 - 5.47 W - M
20.75 20.85 4.28 ~ 5 - vS
30.85 - 30.95 2.898 - 2.889 All of the as-syn~hesized SAPO-44 compositions ~or which X-ray powder di~fraction data have presently ~en o ~ained have pa~terns which are wi~hin the generalized pattern of Table XXIT, below:

D-13,443 ~ 115 -TABLE XXI I
d 100 X I/Io 9.4 - 9.5 9.41 ~ 9.26 97 - 100 10.95 ~ .08 4 - 12 13.~ - 13.1 6.81 - 6.76 15 - 31 13.3 - 13.~ 6.66 - 6.61 1 - 6 13.75 - 13.8 6.44 - 6.42 3 16.1 - 16.2 5.50 - 5.47 31 - 55 17.35 - 17.4 5.11 - 5 O 1~ 9 - 16 19.0 4.67 6 20.75 - 20.85 ~.28 - 4.26 ~68 - 100 210 0 - 21.1 (sh)4.23 - 4.21 21.8 - 21.9 4.~8 - 4.06 25 22.6 - 22.7 3.93 - 3.92 3 - 7 23.1 3.85 7 - 12 24.45 - 24.55 3.641 ~ 3.626 55 - 74 26.15 - 26.2 3.40B - 3.401 16 - 22 ~6.9 3.314 1 - 2 27.8 - 27.9 3.209 - 3.198 7 - 10 28.5 3.132 2 - 7 2~ .7 3.008 3 - 4 30.2 2.959 18 - 20 30.85 - 30.95 2.898 - 2.889 45~ 50 31.6 - 31.65 2.831 - 2.R27 32.15 - 32.2 2.784 - 2.780 2 - 7 32.55 - 32.6 2.751 - 2.747 1 - 3 33.0 2.714 5 3~.8 2.578 1 - 3 35.6 2.522 8 - 11 38.5 - 38.6 2.338 - 2.332 39.2 2.298 39~ 9 ~ 40.0 2.259 - 2.25~ 1 - 2 42.2 - 42.3 2.1~1 - 2.137 L
42.6 (sh)2.122 ~ 4 42.9 (sh)2.108 4 43.6 - 43.72.076 - 2.071 2 - 3 44.3 - 44.42.045 - 2.040 45.1 - 45.22.010 - 2.006 46~1 - 46.21.969 - 1.965 47.2 - 47.31.926 - 1.922 2 48.15 - 48.2 1.890 - 1.888 6 - 7 48.7 - 48.81.870 - 1.866 5 50.4 - 50.51.811 - 1.807 7 ~9 51.2 - 51.31.78~ - 1.781 52.1 - 52.21.755 - 1.752 2 53.9 - 54.01.701 - 1.698 6 - 8 D- 13,443 3'Zg~

Example 51 (Preparation of SAPO-31) SAPO-31 was crystallized from a reaction mixture prepared by combining 81.7 grams of aluminum isopropoxide (Al(OC3B7)3) wi~ 46.1 grams of 85 wt. ~ or~hophosphoric acid (~3PO4) and 85.0 grams of w~ter and stirring until homogeneous. To this mixture were added 24.0 grams of an aqueous sol of 30 wt. ~ SiO2 and 42.8 grams of water, and the mixture stirred until homogeneous. To this mixture were added 20.2 grams of di-n-propylamine ~Pr2NH) and 34~0 grams of wat~r, and the mixture stirred until homogeneous. To this mixture was added 5.8 grams of AlPO4-31 seed crystals and the mixture stirred until homogeneous. The composition of the rlnal reaction mixture in molar oxide ratios was:
Pr2NH : 0.6 SiO2 : A12O3 : P2O5 2 and contained 10 wt. % AlPO4-31 seed crystals oased on the soiids content. A portion of this reaction mix~ure was placed in a stainless steel pressure vessel lined with an inert plastic material and heated in an oven at 200C at autogenous pressure ~or 24 hoursO The solid reaction product was recovered by ~iltration, washed with waterl and aried in air at 100C. The chemical composition o~
the S~PO-31 product in ~erms of molar oxide ra~ios ~anhydrous ~sis) was:
0-16 (Pr2N~) : A12O3: 0.15 SiO2: 0.83 P2O~
wnich corresponds to the formula:
0.04Pr2N~: (sio . 04~10,53Po 43~2 The x-ray powder diffrac~ion pattern of ~he ~APO-31-containing p~oduct was charac~erized by ~he following data:

D-13,443 TABLE EF
2~ d 100 X I/Io 7.25* 12O193 tsh) 8.53g 10.355 72 9.530~ 9O2~0 14 13.279* 6.66~ 4

15.77~* 5.618 8 17.104 5.184 6 18.380 ~.827 3 20~280 4.379 43 20.5~ 4.332 (8h) ~1.15~* 4.200 22 22.033 4.034 2 22.662* 3.92~ 100 23.316 3.815 14 25.145 3.542 3 25.718 3.464 3 26.566* 3.355 3 26.701 3.339 4 27.9~6 ~.189 9 28.810* 3.0~9 4 ~9.797 ~.gg8 6 31.760 2.~17 16 33.~16 2.713 3 34.367* 2.609 2 35.215 ~.5~9 , 8 36.090 2.489 2 37.777* 2.381 3 37.938* 2.372 3 38.113 ~,361 3 39.402 2.287 3 39.641 2.274 2 40.195 2.24~ 2 44.891* 2.019 2 45.34S 2.0~0 2 ~6.708 ~.94S 2 51.674 1.769 3 * contains impurity peak The X-ray powder diffraction pat~rn of the SAPO-31-containing product after calcination in air ~or 7 hours at 550C was characterized by the following data:

D-13,443 3~ZO~

TAB LE FF
2~ d 100 X I/Io 7.7 11.5 (shJ
8.5 10.4 . 100 8.9 9.94 (sh) 9.~ 9.21 (sh) 9.~ 9.03 3 S 6.89 14.7 6~03 7

16.1 5.50 3

17.05 5.20 1~

18.45 4.81 2 20.3 ~.37 34 21.4 4.15 (sh) 22.05 4.03 37 2206 3.93 81 23.35 3.81 3 25.1 3.548 3 25.7 3 466 4 27.9 3 198 11 29.7 3.008 8 31.0 2.885 3107 2.~23 18 32.4 2.763 35.1 2.557 7 36.2 2.481 37.2 2.417 2 37.6 2.392 2 38.3 2 350 2 3~-3 2 292 3 39.6 2.276 40.3 ~.238 3 43.2 2.094 44.0 2.058 45~0 2.014 2 ~7.1 1.929 3 47~6 1.910 2 48.6 1.873 2 4~.~ 1.852 50,8 1.797 51.6 1.771 4 55.6 1.~53 (b) Adsorption capacities were measured on tne pro~uct of part(a). The ~ollowing data were obtained on a sample ac~ivated at 350C in vacuum.

D - 13 , 4 43 ZO~

Kinetic Pressure Temp., Wt. %
Diameter, A Torr ~C Adsor ~d 2 3.46 ~9 -1838.8 2 3.467~0 -18315.4 ~2 2.654,6 23 6.g ~2 2.6519.4 2421.1 Cyclohexane 6.0 49 25 7,2 Neopentane 6.2 400 24 5.9 It is apparent from these data that the pore size of SAPO-31 is greater than 6.2A.
Example 52 (Preparation of SAPO-31) SAP0~31 was produced using a different source of silica from a reaction mixture prepared by combining 81.6 yrams of aluminum isopropoxide (Al(OC3H7)3) and 100 grams o~ water with 51.3 grams of 85 wt. % orthophosphoric acid (~3P~4).
To this mixture was added 1.33 grams of fume silica (95 wt. ~ SiO2, 5 wt. % ~2) and the mixture stirred until homogeneous. To on~ thi~d by weight of thiS mixture were added 16.3 grams of wa~er and 704 grams of di-n-propylamine (Pr2NH), and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
Pr2N~ : 0.1 SiO2 : 0.9 A1203 : P205 : 2 The reaction mixture was placed in a s~ainless s~eel pr0ssure vessel lined with polytetrafluoroe~hylene and heated in an oven at 150C at autog~nous pres ure for 133 hours. The solid reaction product was recovered by centrifugation, washed with water, and dried in air at room temperature. Tne product was impure but the minor phase had an X-ray powder D-13,443 ~o~ ~

diffrac~ion pattern characSerized by the tollo~ing aata:
TABLE GG
d 8.5 1~.4 9.5* 9.31 13.35* 6.63 15.8* 5.61 17.2 5.16 18.4 ~.82 20.3 4.37 21~1* 4.21 ~1.9 (sh) 4.06 22.65* 3.926 25.6 3.480 27.9 3.198 28.4 2.143 31.6* 2.831 35.05 2.560 * contains peak from another pbase Example 53 (Preparation of SAPO-31) A homogeneous mixture was prepared by combining 306.4 grams of aluminum isoproproxide with a solution of 173.0 grams of 85 wt. ~
orthophosphoric acid in 5~5.3 grams of water.
Tnereafter were added in sequence, with intermittant stirring to achieve homogeneity after each addition, (a) 90.2 grams of an aqueous silica sol (30 wt.
SiO~ ) 75.9 grams o~ din-propylamine (n-C3H7)2NH, and (c) 21.0 grams of AlPO~-31 s~ed crystals, The compositio~ of the final reaction mixture, in ~erms o~ molar oxide ratios, was (exclusive of the seed crystals).
(n-C3H7)2NH : 0,6 SiO2 A1203 2 5 2 and contained 10 weigh~ percent AlP0~-31seeds based on the overall solids content. The reaction mixture D-13,443 ~.~(3~0~

was placed in a stainless steel pressure reactor lined with an inert plastic material and heated under autogenous pressure for 96 hours at 200C.
The solia reaction product was recovered ~
centrifugation, washed with water, and dried in air at 110C. The product ~as calcined in air using the ~ollowing ramp schedule: (a) raised from room ~emperature ko 230C over the period of 0.5 hour;
~b) held at 230C for 2 hours; (c) increased from 230C to 500~C over ~h~ period of 1 hour; (d) held at 500C for 2 hours; and (e) cooled f~om 500C to room tempera~ure over the period of 4 hours. ~he calcined product nad an X-ray powder diffraction pattern characterized by the following data:
TABLE G~
28 d 100 X I/Io 7.45* 11.87 cl 8.6 10.28 75 9.8~ 9.03 ~1 1408 5.99 5 16.1 5.50 17.lS 5.17 10 1~.1* 4.90 c1 18.4 4.82 4 20.3 ~.37 55 ~1.0* 4.23 <1 22.1 4.02 50 ~2.7 3.92 lOg 23.6* 3.77 ~1 25.Z 3.53 6 25.7~ 3.46 8 25.55* 3.357 ~1 28.0 3.187 14 29.75 3.003 9 31.0 2.885 2 31.8 2.814 31 35.2 2.550 9 36.2 2.481 5 37.3 2.411 3 37.8 2.380 38.2 2.356 3 3~.4 2.287 4 D-13,443 ~2~
- 12~ -TABLE GH
d 100 X I/Io 39.7 2.270 ~1 40.3 2.238 3 43.2 2.0~4 ~L
44.1 2.053 ~1 45.3 2.002 46.2 1.965 ~1 46.~ 1.941 9 47.5 1.914 2 4~.5 1.~77 ~1 48 ~ 7 lo 870 3 49~ 155 50~9 1~794 51.7 10768 6 55.5 1~656 2 * Contains peak from another phase The species SAPO-31 as referred to herein is a silicoaluminophosphate having a three-dimensional microporous crystal ramework structure of PO2, AlO2 and SiO2 tetrahedral units, and whose essential empirical chemical composition on an anhydrous basis is:
m~ : ISix~lyp2) 2 wherein R represents at least one organic templating agent present in the intracrystalline pore system;
"mn represents the moles of "R~ present per mole of ~SiXAlyPz) 2 And nas a value of from zero to 0-3; ~xn, ~y~ and ~Z~ represent respectively, the mole fractions of silicon, aluminum and phospho~us present in the oxide moiety, said mole fractions b~ing within the compositional area bounded by points ~, B, C, D ana E on the ternary ~iagram which is Pig. 1, or preferably within the area bounded by points a, b, c, d and e on the ternary ~iagram which is Pig. 2, said silicoaluminophosphate having a cAaracteris~ic X-ray powder diffraction pattern wnich contains at least the d ~pacings set ~orth D-13, 443 below in Table XXIII. In the form as synthesized in accordance with the process of this invention, ~m"
has a value of from 0.02 to 0.3.

TABLE XXIII
Relative d Intensity 8.5 - 8.6 10.40 - 10.28 M - S
20.2 - 20.34.40 - 4.37 21.9 - 22.14.06 - 4.02 W - M
22.6 - 22.73l93 - 3.92 VS
31.7 - 31.82.823- 2.814 ~ - M
All of the as-synthesized SAPO-31 compositions for which X-ray powder diffraction data have presently been obtained havP patterns which are within the generalized pattern of Table XXIII, below.

TABLE XXIV

d lOO X I/Io 6.1 14.5 0 -8.5 - 8.6*10.40 - 10.28 60 - 72 9.5~ 9.31 7 - 14 13.2 - 13.3*6.71 - 6.66 1 - 4 14.7 - 14.86.03 - 5.99 1 - 2 15.7 - 15.8*5.64 - 5.~ 8 ~7.05- 17.15.20 - 5.19 2 - 4 18.3 - 18.44.85 - ~.82 2 - 3 20.2 - 20.34.40 - 4.37 ~4 - 55 21.1 - 21.2*4.21 - 4~19 6 - 2a 21.g - 22.1*4.0~ - 4.02 32 - 3 22.6 - 22.7*3.g3 - 3.92 100 23.3 - 23.35*3.818- 3.810 2 - 20 25.1* 3.548 3 - 4 25.65- 25.753.~73- 3.460 2 - 3 26.S~ 3.36~ 1 - 4 27.g - 28.03.198- 3.187 8 - 10 28.7~ 3.11~ 0 - 2 29.7 3.008 4 - 5 31.7 - 31.82.823- 2.814 15 - 18 32.9 - 33.0*2~722- 2.714 0 ~ 3 D-13,443 ~o~

TABLE XXIV (cont'd) 2~ d 100 X I/Io 35.1 - 35.2 2.557- 2.550 5 - 8 36~0 - 36.1 2.495- 2.4a8 1 - 2 37.2 2.417 1 - 2 37.9 - 38.1* 2.374- 2.362 2 - 4 39.3 2.2~2 ~ - 3 43.0 - 43.1* 2.103- 2.100 44.8 - 45.2* 2.~23- 2.006 46.6 1.949 1 - 2 47.4 - ~7.5 1.918 ~8.~ - 48.7, 1.873- 1.870 2 50.7 - 50.8 1.~01- 1.7~7 5106 - 51.7 1.771-1.7Ç8 2 - 3 55.4 - 5~.5 1.65~-1.656 ~ Pos~ibly contains peak from minor impurity Example 54 (Preparation of SAPO-41) (a) A reaction mixture was prepared ~
combining ~.22 yrams of 85 wt~ % or~hophosphoric acid (~3P04) and 5.78 grams of water, to which was added 5.52 grams of hydrated aluminum oxide, (a pseudo-boehmite phase, 74.2 wt. % A1203, 25~8 wt. % ~2) and stirred un~il homogeneous. To this mixture wa~ added a mixture of 1.04 grams of a fume silica (92.8 wt. % SiO2, 702 wt. ~ H20) in 41.67 grams of an aqueous solution of 25.9 wt. ~
tetra-n-butylammonium hydroxide (TBAOH). This mixture was stirred until homogeneous and then another 41.67 grams of TBAO~ was slowly added with stirring until a homogeneous mixture was obtained.
The composition of the final reaction mix~ure in molar oxide ratios was:
( BA)20 : A1203 P205 9.4 SiO2 : 98.7 H20 A portion of the reaction mix~ure was sealed in a ~t~inless steel pressure vessel Lined with an inert plastic material and heated in an oven at 200C a~

D~13,443 ~z~

autogenous pressure for 144 hours. The solid reaction product was recovered ~y centrifuging and washing with water, and dried in air at room temperature. The product had an X-ray powder dif~raction patt~rn characterized by the following data:
TABLE H~
2~ d100 X I/Io 6.7 13.19 24 9.6 9~21 25 13.6 6.51 28 18.2 4.87 10 20.~ 4.33 10 21.1 4.21 100 22.1 4.02 82 22.8 3.90 43 23.1 3.85 30 25.3 3.52 20 25.7 3.47 28 2~.3 3.048 23 31.4 2.848 10 33.1 2.706 7 37.6 20392 15 38.1 2.362 7 39.6 2.276 5 43.0 2.103 8 49.1 1~55 8 51.5 1.77~ 8 By ch2mical analysis the composition of ~he SAP0-41 was round to be 5.2 w~. ~ C; 38.1 wt. % A1203;
41.1 wt. % P205; 7.1 wt. % SiO2; and by difrerence, LOI was 13.7 wt. ~; giving a product composition in terms of molar oxide ratios of:
) 20 1- 0 A1203 - 77 P205: 0 . 32 ~iO2 1- 0 ~1 0 which corresponds to the formula 0.02 TBA : (sio~o8Al.o.s2po.4o) 2 (b) A portion of the above solid produc~
was calsined in air at 600C for 2 hour~ and then at D-13,443 ~o~o~

700C or 1 hour. The calcined product had an X-ray powaer dir~raction pattarn characterized by the following data:

TABI.E JJ
d100 X I/Io 6.7 13.19 17 9.7 9.1Z 33 , 13.6 6.51 27 18.4. 4.82 10 20.5 4.33 6 21.3 ~.17 100 22.3 3.99 62 22.8 3.90 38 23.0 3.87 36 25.4 3.52 25 ~5.7 3.466 . 23 28.1 3.175 4 29.4 3.038 19 31.4 2.849 10 33.2 20698 10 36.7 2.449 4 37.g 29374 10 38.4 2.344 4 39.7 2.270 4 43.3 2.089 6 51.5 1.774 2 (c) Adsorption capacities were measured on this calcined product of par~ (b) using a standard McBain-Bakr gravimetric adsorption apparatus. The following data were ob~ained on a sample activated at 350~C.
Kinetic Pressure Temp., Wt. %
Diameter, ~ Torr C Adsorbed 2 3.46100 -183 9.3 2 3.46750 -183 11.8 Cyclohexane 6.0 60 24 4.2 Neopentane 6.2 743 24 1.2 ~2 2.654.6 24 10.4 ~O 2.6520.0 24 ~1.9 D-13,443 The pore size of the calcined product is between 6.0 and 6.2A as shown by adsorption of cyclohexane, kinetic diameter of 6.OA and negliglble adsorption o~ neopentane, kinetic diameter of 6.2A.
EDAX (energy dispersive analysis by X-ray~
microprobe analysis, performed in conjunc~ion with SEM (scanni~g electron microscope) study on crystals having a crystal morpholoyy characteris~ic of SAP0-41 gives the following analysis based on relative peak heights-Rod Agglomerate Si 0.~9 0.11 Al 1.0 1.0 P 0.87 0.74 The species SAPO-41 as referred to herein is a silicoaluminophosphate having a three-dimensional microporous crystal framework structure o~ P02, A102 and SiO2 tetrahedral units, and whose essential empirical chemical composi~ion on an anhydrous basis is:
mR : ~SixAlyPz)02 whereln R represents at least one organic templating agent present in the intracrystalline pore system; "mn represents the moles o~ "R"
present per mole of (SiXAlyPz)02 and has a value of ~rom zero to 0.3; "xn, "y" and "z' represent respectively, the mole ~ractions o~
~ilicon, aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is Fig. 1, or pre~era~ly within the area bounded ~ points a, b, c, d and e on the ternary dia~ram which is Fig. 2 D-13,443 ~v~o~

said silicoaluminophospha~ having a characteristic X-ray powder di~xaction pattern which contains at least the d-spacings set forth below in Table XXV.
In the fo~m as synthesized in accordance with the proc~ss of this inv~ntion, "m" has a value of from 0,02 to 0.3.
TABLE XXV
Relative d In~ensity 13.6 - 13.8 6.51 - 6.42 W - M
20.5 - 20.6 4.33 - 4.31 W - M
21~1 - 21.3 4.21 ~ 4.17 VS
22.1 - 22.3 4.02 - 3.99 M - S
22.8 - 23.0 3.90 - 3.~6 M
23.1 - 23.4 3082 - 3.80 W - M
25.5 - 25.9 3.493- 3.44 W - M
All o~ the as-synthesized SAPO-41 compositions for which X-ray powder diffraction data have presently been obtained have patterns which are within the generalized pattern of Table XXVI, below.

TABLE XXVI

d 100 X I/Io 6.7 - 6.8 13.19 - 12.99 15 - 24 9.6 - g.7 9.21 - 9.11 12 - 25 13.6 - 13.8 ~.51 - 6.42 10 - 28 18.2 - 1~.3 ~.87 - 4.85 8 - 10 20.5 - 20.6 4.33 - 4.31 10 - 32 21.3 4.~1 - 4.17 100 22.1 - 22.3 4.0~ - 3.99 45 - 82 22.8 - ~3.0 3.90 - 3.87 43 - 5 23.1 - 23.4 3.82 - 3.80 20 - 30 25.2 - 25.5 3.53 - 3.49 8 - 20 25.~ - 25.93.493 - 3.~4 12 - 28 ~.3 - 25.5 3.0~8 - 3.02817 - 23 31.4 - 31.62.849 - 2.831 5 - 10 33.1 - 33.320706 - 2.690 5 - 7 37.6 - 37.92.392 - 2.37410 - 15 38.1 - 38~32.362 - 2.350 7 - 10 D-13,443 ~Z(:~2~

TABLE XXVI (Cont.) d 100 X I/Io 39~6 - 39.8 2.276 - 2.265 2 - 5 ~2.8 - 43.0 2.113 - 2.103 5 - 8 49.0 - 4~.3 1.~59 - 1.848 1 - 8 51.5 1.7740 - 8 The present SAPO compositions exhibit novel surrace selectivity characteristics which render them use~ul as ratalyst or catalyst bases in a num~er of hydrocarbon conversion and oxidative combistion reactions. They can be impregnated or otherwise loaded with catalytically active metals by methods well known in the art and used, for example, in fabricating catalysts compositions having silica or alumina bases.
Among the hydrocarbDn conversion reactions catalyzed by SAPO compositions are crackiny, hydrocracking, alkylation of both the aromatic and isopararfin types, isomerization, including xylene isomerization, polymeri~ation, reforming, hydrogenation, dehydrogenation, transalkylation, aealkylation and hydration.
Using SAPO catalysts compositions which contain a hydrogena~ion promotor such as platinum, palladium, tungsten, nickel or molybdenurn, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks can be hydrocracked at temperatures in the range of 400F ~o 825F usiny rnolar ra~ios of hydrogen to hydrocarbon in the range of between 2 an~ 80, pressures between 10 and ~500 p.s.i.g., and a li~uid hourly space velocity ~L~SV) o~ from 0.1 to 20, preferably 1.0 to 10.

D-13,443 3~(3 The SAPO catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at tempera~ures of from about 700F to 1000F, hydro~en pressures of from 100 to 500 p.s.i.g., L~SV values in the range of 0.1 to 10 and hydrogen to nydrocarbon molar ratios in the range of 1 tO 20, preferably between 4 and 12.
These same catalysts, i.e., those containing hydrogenation promoters, are also useful in hydroisomerization processes in which feedstocks such as normal pasa~ins are convertea to saturated branched-chain isomers. ~ydroisomerization is carried out at a temperature of from about 200F to 600F, pre erably 300F to 550F with an L~SV value of from about 0.2 to 1Ø ~ydrogen is supplied to the reactor in admix~ure with the hydrocarbon feedstock in molar proportions (~/~c) of between 1 and 5.
At somewhat higher temperatures, i.e., from about 650F to 1000F, preferably 850F to 950F and usually at somewhat lower pressures within the range of atout 15 to 50 p.s.i.g., the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock compris~s normal paraffins having a carbon number ranye of C7-C20~ Contact time be~ween the feedstock and ~he catalyst is generally relatively short to avoid undersirable side reactions such as olefin polymerization and paraffin cra~king. LHSV
values in the range of 0.1 ~o 10, preferably lqO to 6.0 are suitable.
The unique crystal structure of ~he ~resent SAPO catalysts and their availability in most cases as D-13,443 .3~0~

as-synthesized compositions which have a total lack of alkali metal con~en~, favor their use in the conversion of alkylaromatic compounds, particularly the ca~aly~ic dispropor~ionation of ~oluene, xylene, trimethylbenz2nes, tetramethylbenzenes and the like. In the disproportionation process isomerization and transalkylation can also occur.
Group YIII noble metal adjuvants alone or in conjunction with Group VI-~ metals such as tungsten, molyb~enum and chromium are preferably includea in the catalys~ composition in amounts of from about 3 to 15 weignt-~ of ~he overall composition.
Extraneous hydrogen can, but neeu not be present in the reaction zone which is maintalned at a temperature o~ from about 400 to 750F, pressures in the range o~ 100 to 20Q0 p.s.i.g. and L~SV values in the rànge of 0.1 to 15.
Catalytic cracking processes are preferably carried out with SAPO compositions using ~eedstocks such as gas oils, heavy naphthas, deaspnalted cru~e oil residue etc. with gasoline being the principal desired product~ Temperature condi~ions of 850 to 1100F, L~V values of 0~5 to 10 and pressure conaitions o~ from about 0 to 50 p.s.i.y. are suitable.
Dehydrocycliza~ion reactions employing paraf~inic hydrocar~on feedstocks, preferably normal para~fins having more ~han 6 carbon atoms, to form tenzene, xylenes, toluene and the like are carried out using essentially the same reaction condi~ions as f or catalytlc cracki~g. For these reactions it is pre~erred to use the SAPO catalyst in conjunction with a Group VIII non-noble metal catisn such as co ~lt and nickel.

D-13,443 3ZO~

In catalytic dealkylation wherein it is desirsd to cleave paratfinic side chains from aromatic nuclei without subs~antially hydrogenating the ring structure, relatively high temperatures in the range of about 800F-1000F are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g., other conditions being similar to those described a~ove for ca~alytic hydrocracking.
Preferred catalyst~ are of ~he same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to napnthalene and toluene and/or xylenes to benzene.
In catalytic hydroflning,the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without sutstantially a~'fecting hydrocarbon molecules therein. For this purpose it i5 preferred to employ the sam~ general conditions described above for catalytic hydrocracking, and catalysts o the same general nature described in connection wi~h dehydrocyclization operations. Feedstocks include gasoline fractions, kerosenes, jet ~uel frac~ions, diesel ~ractions, light and heavy gas oils, deasphalted crude oil residua and the like any of wnich may contain up to about 5 weight percent of sulfur and up to about 3 weight-percent of nitrogen.
Similar condi~ions can be employed to effec~ hydrot'ining, i.e., denitrogenation and d~sul~'urization, of hydrocarbon ~eeds containing su~stantial proportions of organoni~rogen and organosultur compounds. It is generally recognized ~-13,443 2~

that the presence of substantial amou~ts of such constituents markedly inhibits th~ activity of catalysts for hydrocracki~g. Consequently, it is necessary to operate at more extreme conditio~s when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatlvely nitrogenous feed than are required with a feed containing less organonitrogen compounds.
Consequently, the conditions under which denitrogena~ion, desulfurization ana/or hydrocrackin~ can be most e~peditiously accomplished in any given situa~ion are necessarily determinea in view of the characteristics of the ~eedstocks in particular the concentration of organonltrogen compounds in the feedstock. As a result of the effect oX organonitrogen compounds on the hydrocracking activity of these compositions it i5 not a~ all unllkely ~hat the conditions most suitable for denitrogenation of a given feedstock havlng a relatively high organonitrogen content wi~h minimal hydrocracking, e.g., less than 20 volume percen~ of fresh feed per pass, miyht ~e the same as those preferred for hydrocrackin~ another feedstock having a lower concentration of hydro~racklng inhibiting constituents e.g., organonitrogen compoun~s. Consequently, it has become the practice in this art to establish the conditions under which a certain feea is to b2 con~acted on tne ~sis of preliminary screening tests with the specific cataly$t and feeastock.
Isomerization reactions are carried out under conditions similar to ~hose described above for reforming, using somewhat more acidic ca~alysts. Olef1ns are preferably isomerized at ~_~3,443 2~

temperatures of 500F - 900F, while paraffins, naphthenes and aikyl aromatics are isomerized at temperatures o~ 700F - 1000F. Particularly desirable isomerization reactions contemplated herein include the conversion of n heptane and/or n-octane to isoheptanes, iso-octanes, ~tane to iso butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to para-xylene, 1-butene to 2-butene and/or isobutene, n-hexene to isohexane, cyclohexane to methylcyclopentene etc.
The preferred cation form i5 a combination of the SAPO with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the SAPO compositions having pores of at least 5A are preferred. When employed for dealkylation of alkyl aromatics, the temperature is usually at least 350F and ranges up to a temperature at WhiCh substantial cracking of the ~eedstock or conversion products occurs, generally up to about 700F. Tne temperature is preferably at least 45~F and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied ~o retain at least the aromatic feed in ~he liquid sta~e. For alkyla~ion the ~emperature can be as low as 250F but is preferably at least 350F. In alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.
The present silicoaluminophospahte compoeitions can be used in the same conventional molecular sieving processes as heretofore have been carrled out using aluminosilicate or D-13,443 12r~0~

aluminopho~phate molecular sieves. For use in these p~ocesses ~he SAPO compositions are pre~erably activated to remove any molecular species which may be presen~ in the intracrystalline pore system as a result of synthesis or otherwise. It is sometimes necessary to thermally d~stroy organic species present in afi-synthesized SAPO's since some are too large to be desorbed by conventional means.
~ s an indication o the catalytic cracking activity of the presen1 class of novel silicoaluminosilicates, cer~ain of the SAPO species wer~ tested for n-butane cracking usin~ a bench-scale appara~us~ The reactor was a cylin~rical quartz tube 254 mm. in length and 10.3 mm. I.~. In each tes~ ~he reactor was loaded with particles of the test SAPO which were 20-40 mesh (U.S. std.) in size and in an amount of from 0.5 to 5 grams, the quantity being selected so that the convession of n-butane was at least 5% and not more t~an 90~ undar ~he test conditions. Most of the SAPO
samples had been previously calcined in air to remove organic materials trom the pore system, and, were activated ~n si~u in the reactor in a flowing stream of helium at 500C ~or one hour. The fe2dstock was a nelium-n-butane mixture containing 2 mole percent n-butane and was passed through the reac~or at a rate of 50 cc./minute. Analysis of the ~eedstock and the reactor effluent were carried out using conventional gas chromatography ~echniques.
The reactor e~fluent was analyzed after 10 minutes o~ on-stream opera~ion. From the analytical data the pseu~o-fir~t-order rate constant (k~) was calculated. Pertinent data is set forth in tabular form below.

D-13,443 S~MPLE SAPOAIR CALCINATION
OF EX. NO.SPECIESBEFORE TEST k(A) 13 51 hr. at bOO~C 1.4 9~a) 5 1 hr. at 600C 7.4 11 1 hr. each at 0.5 500C and 600C
26 174 hrs. at 550C 0.5 51 317 h~s. at 550C 0.2 37 34 1 hr. at 600C 3.0 42 37 none 1.1 43 37 none 1.6 443.5 hrs. a~ 600C 2.4 The SAPO compositions are useful as adsor-bents and are capable of separating mixtures of molecular species both on the basis of molecular size (kinetic diameters) and degree of polarity of the in-volved molecules. In the case of selective adsorption based on molecular size, the SAPO adsorbent is chosen in view of the dimensions of its pores such ~hat at least the smallest molecular specie of the mixtuxe can enter the intracrystalline void space while at least the largest specie i5 excluded. Separations based on degree of polarity, the more hydrophilic SAPO species will preferentially adsorb the more polar molecular species of a mixture having differ~nt degrees of polari~y even though both molecular species can en'cer the SAPO pore system.

D-13,443

Claims (52)

1. Microporous crystalline silicoaluminophosphates the pores of which are uniform and have nominal diameters of greater than about 3 Angstroms and whose essential empirical chemical composition in the as-synthesized and anhydrous form is mR : (SixAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" has a value of from 0.02 to 0.3;
"m" represents the moles of "R" present per mole of (SixAlyPz)O2; "x", "y" and "z" represent the mole fractions of silicon, aluminum and phosphorus respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points ABCD
and E of the ternary diagram which is Fig. 1 of the drawings.

2. Microporous crystalline silicoaluminophosphates according to Claim 1 wherein the mole fractions of silicon, aluminum and phosphorus are within the pentagonal compositional area defined by points a, b, c, d and e of the ternary diagram which is Fig. 2 of the drawings.

3. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table I.

4. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table III.

5. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V.

6. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table VII.

7. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table IX.

8. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XI.

9. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIII.

10. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XV.

11. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XVII.

12. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XIX.

13. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXI.

14. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXIII.

15. Crystalline silicoaluminophosphate according to Claim 1 or Claim 2 having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table XXV.

16. Crystalline silicoaluminophosphate prepared by calcining the compositions of Claim 1 or Claim 2 at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system.

17. Silicoaluminophosphate material having a three-dimensional microporous framework structure of PO+2, AlO-2 and SiO2 tetrahedral units, and whose essential empirical chemical composition on an anhydrous basis is:
mR : (SixAlyPz)O2 wherein R represents at least one organic templating agent present in the intracrystalline pore system;
"m" represents the moles of "R" present per mole of (SixAlyPz)O2 and has a value of from zero to 0.3; "x", "y" and "z" represent respectively, the mole fractions of silicon, aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is Fig. 1, said silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth below in any one of Tables I, III, V, VII, IX, XIII, XVII, XXI, XXIII or XXV.

18. Composition according to Claim 17 wherein the mole frictions of silicon, aluminum and phosphorus are within the pentagonal compositional area defined by points a, b, c, d and e of the ternary diagram which is Fig. 2 of the drawings.

19. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table I.

20. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table III.

21. Composition according to claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table V.

22. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table VII.

23. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction powder containing at least the d-spacings of Table IX.

24. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XIII.

25. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XVII.

26. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XXI.

27. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacing of Table XXIII.

28. Composition according to Claim 17 or Claim 18 which has the characteristic X-ray powder diffraction pattern containing at least the d-spacings of Table XXV.

29. Composition according to Claim 17 or Claim 18 wherein in the formula mR : (SixAlyPz)O2 "m" has a value of zero, said composition having an X-ray powder diffraction pattern essentially as set forth in any one of Tables D, J, N, U, BB, EE, FF, and JJ.

30. Process for preparing a crystalline silicoaluminophosphate of Claim 1 which comprises forming a reaction mixture containing reactive sources of SiO2, Al2O3, and P2O5 and an organic templating agent, said reaction mixture having a composition expressed in terms of molar oxide ratios of:
a R2O : (SixAlyPz)O2 : bH2O

wherein "R" is an organic templating agent; "a" has a value large enough to constitute an effective amount of "R" and is within the range of greater than 0 to 3;
"b" has a value of from zero to 500;
"x", "y" and "z" represent the mole fractions, respectively, of silicon,aluminum and phosphorus in the(SixAlyPz)O2 constituent and each has a value of at least 0.01.

31. Process according to Claim 30 wherein "b" has a value of from 2 to 30.

32. Process for preparing a crystalline silicoaluminophosphate of Claim 1 which comprises forming a reaction mixture having a composition expressed in terms of molar oxide ratios of:
a R2O : b M2 O : (SixAlyPz)O2 : c H2O

wherein "R" is an organic templating agent; "a" has a value great enough to constitute an effective concentration of "R" and is within the range 0 to 1;
"M" is an alkali;
"b" has a value o zero to 2.5; "c" has a value of from zero to 500; "x", "y" and "z"
represent the mole fractions, respectively, of silicon, aluminum and phosphorus in the (SixAlyPz)O2 constituent, and each have a value of at least 0.01 and being within the quadrilateral compositional area defined by points f, g, h and i which is Fig. 3 of the drawings, the said points f, g, h and i representing the following values for "x", "y" and "z":

Mole Fraction said reaction mixture having been formed by combining at least a portion of each of the aluminum and phosphorous sources in the substantial absence of the silicon source and thereafter combining the resulting mixture with the remaining constituents to form the complete reaction mixture.

33. Process according to Claim 30 or Claim 32 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

34. Process according to Claim 32 wherein the source of aluminum in the reaction mixture is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alcoholate, and the source of phosphorus is orthophosphoric acid.

35. Process according to Claim 34 wherein the aluminum alcoholate is aluminum isopropoxide.

36. Process according to Claim 30 or Claim 32 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula R4X+
wherein X is nitrogen or phosphorus and each R is An alkyl or aryl group containing from 1 to 8 carbon atoms.

37. Process according to Claim 30 or Claim 32 wherein the organic templating agent is an amine.

38. Process according to Claim 30 or Claim 32 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion;
tetraethylammonium ion; tripropylamine;
triethylamine; triethanolamine; piperidine;
cyclohexylamine; 2-methyl pyridine; N, N-dimethylbenzylamine; N, N-dimethylethanolamine;
dicyclohexylamine; N, N-dimethylethsnolamine;
choline; N, N-dimethylpiperazine;
1,4-diazabicyclo-(2,2,2) octane;
N-methyldiethanolamine; N-methylethanolamine;
N-methylpiperidine; 3-methylpiperidine;
N-methylcyclohexylamine; 3-methylpyridine;
4-methylpyridine; quinuclidine;
N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
tetramethylammonium ion; tetrabutylammonium ion, tetrapentylammonium ion; tetrapentylammonium hydroxide; di-n-butylamine; neopentylamine;
di-n-pentylamine; isopropylamine; t-butylamine;
ethylenediamine and 2-imidazolidone;
di-n-propylamine; and a polymeric quaternary ammonium salt [(C14H32N2)]+x wherein x is a value of at least 2.

39. Process for separating molecular species from admixture with molecular species having a lesser degree of polarity which comprises contacting said mixture of molecular species with a silicoaluminophosphate composition of Claim 1 or Claim 17 having pore diameters large enough to adsorb of at least one of the more polar molecular species, said silicoaluminophosphate being at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof.

40. Process for separating a mixture of molecular species having different kinetic diameters which comprises contacting said mixture with a silicoaluminophosphate composition of Claim 1 or Claim 17 having pore diameters large enough to adsorb at least one but not all molecular species of said mixture, said aluminosilicate being at least partially activated whereby at least some molecules whose kinetic diameters are sufficiently small can enter the intracrystalline pore system thereof.

41. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a silicoaluminophosphate of Claim 1.

42. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with silicoaluminophosphate of Claim 17.

43. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is cracking.

44. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is hydrocracking.

45. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is hydrogenation.

46. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is polymerization.

47. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is alkylation.

48. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is reforming.

49. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is hydrotreating.

50. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is isomerization.

51. Process according to Claim 41 or Claim 42 wherein the isomerization is xylene isomerization.

52. Process according to Claim 41 or Claim 42 wherein the hydrocarbon conversion process is dehydrocyclization.