CA1238470A - Crystalline ferroaluminophosphates - Google Patents

Abstract

CRYSTALLINE FERROALUMINOPHOSPHATES
ABSTRACT
Novel class of crystalline microporous ferroaluminophosphate compositions containing as lattice constituents in addition to AlO2 and PO2 structural units, ferric and/or ferrous iron in tetrahedral coordination with oxygen atoms. These compositions are prepared hydrothermally using organic templating agents and are suitably employed as catalysts or adsorbents.

Description

CRYSTALLINE FERROALUMINOPHOSP~TES
BACKGROUND OF THE INVE~TIQN
Field of the Invention the present invention relates. to a novel class. ox crystalline micropo~ou~ ferroalumino-: phosphates, to the method for their preparation, and to their use as adsorbent and catalysts. These compositions are prepared hydrothermally from gels containing reactive phosphorus, iron and aluminum compounds and organic templating agents which function in part Jo determine the Corey ox the crystallization mechanism and hence the structure ox' the crystalline product.
Description of the Prior Art Lo Molecular Yes of the crystalline aluminosilicate elite type are jell known in the art and now comprise over-150-species of both I naturally occurring and synthetic compositions. In general the crystalline zealot are formed from .- 20 corner-sharing Aye and Sue tet~ahedra and characterized by having pore openings of uniform . dimensions having a significant ion-exchange capacity and briny capable of reversibly resorbing ? an adsorbed phase which is dispersed throughout the , 25 internal voids ox the crystal without displacing any Jo atoms which make up the permanent crystal structure.
Other cry~tallina micro porous. compositions which ace not zeolitic, i.e. do not contain ~102-tetrahedfa as e~.~ential framework contusions, but , 30 which exhibit the ion-exchange and/or adsorption O
I, D--13, 864 "

Jo characteristics of the zealots are also known.
Metal organosllicates which are said to possess ion-exchange properties, have uniform pores sod are capable of reversibly adsorbing molecules hiving molecular diameters of about PA or less are reported in U.S. Patent No. 3,941,871 issued March 2, 1976 to Dyer et at. Also a pure silica polymorph, silicalite, having molecular sieving properties and a neutral framework containing neither cations nor cation sites is disclosed in U.S. Patent No.
4,061,714 issued December 6, 1977 to R. W. Grove et at.
The most recently reported class of micro porous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Patent No. 4,310,440 issued January 12, 1982 to Wilson et at. These materials are formed from Aye and POX tetrahedral and have electrovalently neutral frameworks as in the case ox silica polymorphs. Unlike the silica molecular sieve, silicate, which is hydrophobic due to the absence ox extra-structural cations, the ~luminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus.
Their intracrystalline pore volumes and pore diameters ore comparable to those known for zealots and silica molecular sieves.
In U.S. Patent No. 4,440,871 issued April 3, 1984 to Lo et at., there is described 8 novel class of silicon-substituted aluminophosphates which are both micro porous and crystalline. The materials have a thee dimensional crystal framework of P02, Aye and Sue tetrahedral units and exclusive of any alkali metal or calcium which may optionally be present, an as-synthe~ized empirical chemical composition on an Andre basis of:
my : (SiXAlyPz)02 wherein "R" represents at feast one organic templating agent present in the intracrystalline pore system: "m" represents the motes of I present per mole of (SiXAlyPz)02 and ha 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 peculiar silicoaluminopho6phate species involved: "x", "y", and "z" represent the mole fraction of silicon.
aluminum and phosphorus, re~pec~ively, prune as tetrahedral ode. The minimum value or each of "x", "y", and "z" it O o Of and preferably ~.02. The maximum value or "x" is 0.9~; for "y" is 0.60; and for 1l2ll is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zealots and aluminophosphates.
A number ox compositions containing compounds of iron, aluminum and phosphorus are known and used a cements, glues coaxings and refractories Such compounds have also been investigated in the field of soil science, and may occur a products in procedures fox removing D-13,864 t I

7~3 .

phosphates from waste water. Crystalline from ` phosphates having the crystal structure of quartz sod tridymite are well known in the art, as ore other dense iron phosphates and iron phosphate .
hydroxides such as Walt [a sodium aluminum iron phosphate disclosed in Mineral. Rec., 4, 131 (1973)]] and ernstite [a manganese iron aluminum phosphate, Nazi Jahrg. Mineral., No. 7, 289 (1970)].
A new class of metal aluminophosphates which are both crystalline and micro porous and in which the metal is at least one of cobalt, zinc, magnesium or manganese is described in U.S. Patent No. 4,56/,029 issued January 28, 1985 to Wilson et at. contemporaneously with the present application.
The crystal structure of certain species of this invention are topological related to certain species of the aforesaid cop ending application.

IN THE DRAWINGS
Fig. l is a ternary diagram showing the compositional parPrneters of the ferroaluminophosphates of this invention in terms of mole fractions of iron, aluminum and phosphorus.

/

:.

, ,, I., , to ~,~

, .

I
-pa-Fig. 2 is a ternary diagram showing the preferred compositional parameters of the ferroaluminophosphates of this invention in terms of mole fractions of iron, aluminum and phosphorus.
Fig. 3 is a ternary diagram showing the compositional parameters of the reaction mixtures used to prepare the ferroaluminophosphstes of this invention in terms of mole fractions of iron, aluminum aloud phosphorus.

Summary of the Invention There has now been discovered a novel class of framework-substituted crystalline micro porous aluminophosphates in which the substituent metal is iron, and which exhibit adsorption, ion-exchange Andre catalytic properties similar to the prior known ~luminosilicate, aluminophosphate and silicoaluminophosphate molecular sieve compositions. Members of this novel class of terroaluminophosphates have a three-dimensional micro porous crystal framework structure of Aye, Foe and P02 tetrahedral units and have an essential empirical chemical composition, on an an hydrous basis of:
my : (FexAlyPz)02 D-13,864 _ 5 I

wherein "R" represent at least one organic emulating agent present in the intracrys~all;ne pore system; "m" reappearance the moles ox "R" present.
per mole of (FexAlyPz)02 and has a value of f Lo zero to O . 3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore ~y6tem of the particular ferroalumino-phogpha~e involved, "x", "y", and "z" represent the mole fractions of iron, aluminum and pho~phoru~, respectively, present as tetrahedral oxides, said mole flaxen being such that they are within thy tetragonal compositional area defined by points I, B, C and D of the ternary diagram which is Fig. 1 of ; 15 the drawing The said joints A, B. C and D
representing the hollowing values for "I", "y", and "2":
Mole Fraction Point x Y
A 0.01 0.60 0.39 8 0.01 0.39 0.60 0.35 0.05 0.60 D 0~35 0.60 0.05 When synthesized in accordance with the novel process ox the prison invention, the minimum value ox "m" in the formula above it 0.02. In a preferred sub-class ox the ferroaluminophogphate~ of this invention, the values of "x", "y" and "I" in the formula above are confined to those within the ~etragonal compositional area defined by the points a, b, c and d of the ternary diagram which is Fig. 2 of the drawing, the said point a, b, c and d D-13,864 : Jo I

representing the hollowing value for "x", "y" and "z":
Cole Fraction Point x my_ z a 0.01 0.52 0.47 b 0.01 0.39 0.60 0.25 . 0.15 0.~0 d 0.25 0.40 0.35 : The iron ox the Foe structural units of the prevent composition can be in zither thy fork or ferrous valence state. depending largely upon the source of the iron in the synthesis gel. Thus an Foe tetrahedron in the tractors can have a net charge of either -1 or -2. While it is believed that the Fe, Al and P framework continuity are prevent in tetrahedral coordination with oxygen (and are referred to herein as ~uch3 it it theoretically pueblo that some minor fraction of eye framework constituents are present in coordination with five or six oxygen Amy. It is not, moreover, necessarily the cave that all of the Fe, Al and/or P
content of any given synthesized product is a pat - of the fame wok in the aforesaid types ox coordination with oxygen. Some of each constituent may be merely occluded or in some a yet undetermined form, and may or may not be structurally significant.
The ferroaluminophospha~e6 ox this new class of compositions exhibit molecular sieving properties, and, in common with zeolitic aluminosilicateæ, are capable of reversibly adsorbing water and other molecular specie. Many , Dow to are capable of reversibly undergoing complete dehydration White 10~6 or change in crystal structure.
For convenience in deficribing the compositions of the present invention in this specification, the "short-hand" acronym "F~P0" is sometime employed hereinafter. To identify the various structural push which maze up the generic class FOP, each species it assigned a number and it identified for example a FOP, FOP, FOP
and so forth.
The term "essential empirical chemical composition" it meant Jo include the crystal framework and can include any organic templating agent present in the pore stem but does no include alkali metal ox other ion which can be present by virtue ox being contained in the reaction mixture or as a result of pofit-~ynthe~is ion-exchange. Such ionic pries when prune : 20 function primarily as charge-balancing ions for Foe and/or Aye tetrahedral Phase tetrahedral a~ociated with P02 toreador ox not associated with P02 ~etrahed~a or an organic ion derived from the organic templating agent.
The aforesaid novel ferroaluminophophates are synthesized by hydrothermal crystallization from a reaction mixture containing reactive source ox -iron oxide, alumina and phosphate, an organic templating, i.e., 6~ructure-directing, agent, pre~srably a compound ox an element ox Group VA of the Periodic Table, and optionally an alkali metal.

D-13,864 .

The reaction mixture is placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure at a temperature of at least 100C, and preferably between 100C and 250C until crystals of the metal alumino~hosphate product are obtained, usually a : period of from 2 hours to 2 weeks. The product is recovered by any convenient method such as centrifugation or filtration.
DETAILED DESCRIPTION OF THE INVENTION
In synthesizing the FOP compositions of the present invention, it is preferred to employ a Jo reaction mixture composition expressed in terms of molar ratios as follows:
; art (Fillips) 2 I
wherein "R" ill an organic templating agent; "a" has a value great enough to constitute an effective concentration of "R" and is Wyeth range of I
to 6; "b" has a value of from err Jo 503, preferably 2 to a; I yell and "z" reprint the mole fractions, respectively. of iron, aluminum and phosphorus in the (~exAlyPz) 2 constituent, : and each has a value of at least 0.01. and being within the hexagonal compositional area defined by points ~,F,G,H,I, and J which is shown in Fig. 3 of the drawings, the said points E,F,G,H,I, and J
representing the following values for "x", "y" and z":
;

D-l3,364 .

I

Mole Fraction Point ox y z_ E 0.01 0.70 0.29 F 0.01 0.29 0.70 & 0.29 0.01 0.70 H 0.40 0.01 0.59 I 0.40 0.59 0.01 J 0.29 0.70 0.01 : In the foregoing expression of the reaction composition, the reactants are normalized with respect Jo a total of foe Al + P) = (x + y + z) =
1.00 mole, whereas in many of the working examples appearing hereinafter the reaction mixtures are expressed in terms of molar oxide ratios normalized to l.00 mole ox POW. This latter o'er it readily converted to the former form by routine calculation.
: In worming the reaction mixture from which the Ryan ferroaluminophosphates are crystallized the organic templating agent can be any of those heretofore proposed for use in the synthesis of Jo conventional zealot aluminosilica~es and micro porous aluminophosphates. In general these compounds contain elements of Group VA of the Periodic Table of laminates, particularly nitrogen, phosphorus arsenic and antimony, preferably N or P
and most preferably N, which compounds also contain I'. at least one alkyd or aureole group having from l to 8 carbon autumn. Particularly preferred , 30 nitrogen-containing compounds or use as templa~ing I
, ~-13.36~

, .

agents era the amine and qua ternary ammonium compound, the latter being represented generally by the formula RUN wherein each R is an alkyd or aureole group containing from 1 to 8 carbon atoms.
Polymeric qua ternary ammonium salt ugh as ( 14 3Z 2) ( ) ox herein x ha a value of at lea 2 are alto suitably employed.
Both moo-, dunned trimness are advantageously utilized, either alone or in combination with a qua ternary ammonium compound or other templating compound. Mixtures of two or more templa~ing agents can either produce mixtures ox the desired metal aluminophosphates or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily Jo establish the pi conditions of the reaction elm Representative templating agents include tetramethylammonium, ~etrae~hylammo~iu~, tetrapropyl~mmonium or tetr~bu~ylammonium ions:
di-n-propylamine;trinpropylamine: triethyla~ine:
t~iethanolamine; piperidine; cyclohe~ylamine;

2-me~hylpyridine; N,N-dime~hylbenxylamine;
N,N-dimethylethanolamine; choline;
; N9N'-dimethyl~iperazine: 1,4-diazabicyclo (2,2,2,) ; 25 octane; N-me~hyldie~hanolamine, N-methylethanolamine; N-methylpiperidine;

3-meth~lpiperidin~; N-methylcyclohexylamine;
3-methylpyridine; 4-me~hylpyridine; quinculidine;
M,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion;
di-n-butylamine, neopentylamine; di-n-pentylamine;
: isopropyl amine: t-butylamine: ethylenediamine:
~yrrolidine; and 2-imidazolidone. As will be D-13,864 readily apparent from the illus~Lative Exemplify set forth hereinafter, not every templating agent will direct the formation of every species of ferroaluminophosphate typo Ida., a jingle templating agent can, with proper manipulation of the reaction conditions, direct the formation of several FOP compositions, and a given FOP
composition can be produced using several different templating agents.
The most suitable phosphorus source yet wound or the present process is phosphoric acid, but organic phosphate such a triethylphospha~e have been found satisfactory, and Jo also have crystalline or amorphous aluminopho~phates such a the Alp composition I U. S . P . 4, 310, 4~0 .
Organo-phosphoru~ communed, such as tet~abutylpho~phonium bromide do no, apparently, serve as Reactive sources ox phosphorus, buy these compound do function as emulating agents.
Conventional phosphorus salt such a sodium metaphosphate, may be used, a least in par, as the phosphorus source, but are not pLe~erred.
The preferred aluminum source is either an aluminum alkoxide, such as aluminum isoproproxide, or ~eudoboehmite. The crystalline or amorphous aluminophospha~es which are a suitable source of phosphorus are, of course, also suitable sources of ! aluminum. Other sources of aluminum used in elite synthesis, such US gibbsite, sodium acuminate and aluminum trichloride, can be employed buy art not preferred.

D-13,86~

I
- lo -Iron can be introduced into the reaction system in any form which permit the formation in situ of reactive ferrous or ferris ions.
Advantageously iron salts, oxides or hydroxides are employed such a iron sulfate, iron acetate, iron nitrate, or the like. Other sources such as a freshly precipitated iron oxide, foe, are alto suitable.
While not essential Jo the synthesis of FOP compositions. it has been found that in general, stirring or other moderate agitation ox the reaction mixture Andy weeding the reaction mixture with seed crystals of either the FOP species to be produced or a ~opologically similar aluminopho~phate or alumino~ilicate commotion, facilitates the ; crystallization procedure.
Awful crystallization, the FOP product is isolated and advantageously washed with water and dried in air. The synthesized FOP contains within its internal pose system at least one form of the templating agent employed it its formation.
Most commonly the organic moiety is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zealot prepared from organic-co~taining reaction system. It it possible, however, thaw some or all of the organic moiety it an occluded molecular specie in a particular FOP species. As a general rule the templating agent, and hence the occluded organic specie, it too large to move freely through the pore system of the FOP product and must be removed D-13,864 by calcinins the APE at temperature of 200C Jo 700~C to thermally degrade the organic species. In a Jew instances the pores of the FOP product are sufficiently large Jo permit transport of the templating agent. particularly it the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desolation procedures such as carried out in the case of zealotry. It will be understood that the term "as-~ynthesi~ed" as used herein and in the claims does not include the condition of the FOP
phase wherein the organic moiety o~cupying.the intracrystalline pore system as a result ox the hydrothecmal crystallization process has been lo reduced by post-synthesis treatment such what the value ox "m" in the composition formula my ex~l~Pz)o~
ha a value of lest ho 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an aluminum alkoxide it employed as the source of aluminum. the corresponding alcohol is necessarily prison in thy reaction mixture since it is a hydrolysis product ox the alkoxide. It has not been determined whether this alcohol pertest in the synthesis process as a templating agent. For the purposes of this application, however, this alcohol is arbitrarily omitted from the class of templating agents, even if it it present in the as-synthesized APE material.
Since the present FOP compositions are Jo _ formed from Aye, P02, Foe Andre Phase units the matter of cation D-13,364 exchangeability is considerably more complicated than in the case of zeolitic molecular sieve in which, ideally there is a 6~0ichiometric relationship between Aloe tetrahedral and charge-balancing cations. In the FOP compositions, an ~10~ tetrahedron can be balanced electrically either by a660ciation with a P02 tetrahedron or a simple cation such as an alkali metal cation, a Fe or Fe cation present in the reaction mixture, Of an organic cation derived from the templating agent. similarly an Foe or Foe tetrahedron can by balanced electrically by association with a P02 tetrahedron, a FQ I or Foe cation, organic cation derived from the templating agent, or other metal cation introduced from an extraneous source.
: It ha also been postulated that non-adjacan~
Aye and P02 tetrahedral pyre can be balanced by Nay and OH respectively [Flanigen and Greece Molecular Sieve Zealot, ALSO
Washington, DC ~1971)~. -In any event, all of the FOP company ox the present invention examined to date have exhibited cation-exchange capacity, in some cases to a significant degree, when analyzed using io~-exchange technique heretofore employed with zeolitic aluminosilicates. All have uniform pore diameter which ace inherent in thy lattice-UC~ULe of each species and which are at least about PA in diameter. Ion exchange it ordinarily possible only aster the organic moiety present as a result ox ~ynthe6is has been removed from the pore D-13,864 Jo I

system. Dehydration to remove water present in the as-6ynthesized FOP compositions can usually be accomplished. to some degree at least, in the usual manner without removal of the organic moiety, but the absence of the organic push greatly facilitates adsorption and duration procedures.
us illustrated hereinafter. the FOP materials have various degree of hydcothermal and thermal stability, Moe being quite repackable in this regard, and function well as molecular sieve adsorb~nts and hydrocarbon conversion catalysts or catalyst bases.
The invention it illu~krated by the following Examples. In each preparation ox a FOP
composition, a reaction gel was prepared by combining sources of iron, aluminum, and phosphorus with water and the gel then crystallized over a period ox several hours in sealed stainless steel reactor line with the inert plastic.
polytetrafluoroethylene. Four methods were employed in mixing the reagents to Norm the reaction mixture. These mud were:
(a) The iron-containing reagent way dissolved or dispersed in a solution prepared by I admixing White with an 85 wt.-% aqueous 601ution of ortho-pho~phoric acid. The resulting Ron and phosphorus-con~aining slurry or solution was then combined with the aluminum source, and thereafter the organic templating agent (R) is added to form the final reaction mixture, (b) The aluminum-containing reagent weft added to a solution preread by admixing water D-13,864 ' ;

with an 85 we.-% agusous ortho-phosphoric acid solution. The iron source was then added, and finally the organic templating agent was incorporated to form the final reaction mixture;
(c) All reagents except the aluminum source were admixed with slight heating and then added to the aluminum Ursa with stirring; and (d) The iron source was dissolved in water and then added to the aluminum source.
Thereafter the phosphorus source was added with stirring followed by the addition of the organic templating agent, also with stirring.
;: In eye example in which a hydrated aluminum oxide is specified, the material employed : 15 was a commercially available pseudo-boehmite phase containing 74~2 we. % Allah and 25.8 wt. % water.
eye reaction products ware subjected Jo . Zoo annul, the X-ray patterns were obtained using standard g-ray powder diffraction techniques.
The radiation source was a high-inten~ity, copper target, Roy tube operated at 50 Xv and I ma. The darken pattern from the copper Kay radiation and graphite monoch~omator it suitably recorded by an X-ray spectLome~er scintillation counter, pulse height analyze and trollop chart recorder. Flat compressed powder sample aye scanned at 2 (2 I; theta) per minute, using a two second time constellate. InterplanaL spacings (d) in Angstrom units are obtained from the position of the diffraction teaks expired as I where is the Bragg angle as observed on the strip char.
Intensities were determined from the height of :`

D-13,B64 .3 I`' : - 17 defection peaks after ~ubteacting background, "It" being the intensity of the stlonge~t line OX
peak, and "I" being the intensity of each of the other peaks.
As will be understood by those skilled in the cot 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, alto manifested in the reported value of the d-spacing6, which are calculated from the 2 theta values. This imprecision it general throughout the art and is not sufficient Jo preclude the differentiation of the prevent crystalline materials from each other and I: from the compositions of the prior art. In some of I- the eye pureness reported, the relative intensities of the d-spacingx are indicated by the notation us, s, my, m, and ow which represent very strong, tong, medium strong, medium, weak and very weak respectively.
In certain instances hereinafter in the illustrative example, the purity of a synthe~lzed product it assessed with euphonize to its Roy powder diffraction pattern. Thus, for example, if a sample of FOPS is stayed Jo be "pure FOP", it it intended only that the Zoo pattern of the sample is free of line attributable to crystalline impurities, not that there are no amoephou6 materials present.
:,~
Jo Exam~l~_L_L~e~___ion of FOP) (a) Using mixing Method (a), a reaction ;,' D-13,864 - I

mixture way prepared having a composition, expressed in terms ox molar oxide ratios, of:
lo TEACH : 0-1 Foe 0~9 ~123 P2Q5 : 40 H20 The reagents employed and the quantity of each were: 0.9 grams on oxyhyd~oxide [ Foe]: 6.2 grams hydrated aluminum oxide, 11.5 grams of aqueous a% o~th~-phospho~ic acid;
18 9 grams waxer 4 gram of a 40% aqueous solution of tetr~e~hylammonium hydroxide (TEACH).
The gel was crystallized at 200C or 24 hour. The solid paddock way subjected Jo Ray and chemical analysis and found Jo camp a major portion of the species FOP and a trace amount of another species, FOP. The chemical ~ompo6ition ox the solid product in terms ox moles of te~raethylammonium hydroxide per Argo TO unit way wound to be:
ooze TAO : (Fez 07~1o,47Po.46~ 2 2 The Roy powder derricks pattern was characterized by the ~ollowi~-data:
TABLE I-I Dow Rio .
7.6 11.63 loo 9.7~ 9.12 4 13.1 6.76 10 15.1 5.87 25 15.7* 5.641 (so) 17.1* 5.19 4 ` 18.0* 4.g3 20.0 4.~4 53 21.2 4.19 60 22.~ 3.93 79 25.0 3.562 3 26.2 3.401 2 .
D-13,864 TABLE A icon I d, PA) lo I/I
- _ o 28.4 3.1~3 2 29.3 3.0~8 1~1 30.4 2.9~0 1 31 . 5*2 . I
32 . 5*2 . 755 33 . 4~2 . 683 3 34 . 02 . ~37 4 34 . 92 . 571 12 3~.8 2.442 6 37.3 2.411 3 t8h) 38.0 2.368 10 I . 12 . ~49 I . 3* -2 . 186 2 41.8 2.161 ~2.6 2.122 2 43.0 2.103 44.~ 2.05~ 1 aye . 21 . 8~8 2 53 . 31 . 719 2 * = line possibly a~ctribu~able to an impurity ( shy = shoulder (b) The FOP 5 composition of pat (a) ox Casey example way calcined irk air at 600C for I' 3 hours. The Roy powder defrock pat~ce~n of he calcined product way charac~eLized by the following data:
TABLE B
I d, AYE Jo I/IQ
7 . 411 . 95 100 9.6~ 9.21 8 12.9 6.86 18 13.4* 6.61 1 (oh) lD~.9 5.95 6 17 . 2~5 . 16 19 . Jo . 48 I

D- 13 , 8 64 .

~31~7~1 Jo --' - TABLE B (keynote I do 100 Rio 21.2 ~.19 38 22.5 3.g5 65 2~.2* 3.68 3 2~.9 3.58 3 Z6.0 3.427 I
~9.1 3.069 12 3G.1 2.969 10 10 33.1~ 2.706 10 33.8 - 2.652 4 (oh) 34.6~ ~.592 8 35.7* 2.515 10 37.1 Z.~Z3 3 37.9 2.374 7 39.4~ 2.~7 40.8~ Z.212 41.7* 2.166 ~2.4 2.~3Z
~3.1 2.~99 ~3.8 2.067 47.~ 1.903 Z
- ~9.4* 1.845 3 .; 54.0 1.698 * = line po6siblr attributable to an impurity (shy = shoulder -I Energy dispersive analysis by - X-ray (DOW) in conjunction with scanning electron microscope studies on a portly of the solid - 30 product of pat (a) having a minimal amount of debris associated herewith had a Fe: P : Al peak height ratio of 0.04 : 1.0 : 0.98.
I' Example 2 (Preparation of APE
(a) Using mixing Method (b), a reaction gel way prepared having a company expressed in terms of molar oxide ratios of:
1.0 TPAOH : 0.2 Foe : 0.8 AYE : PROS
, : 50 Ho I' i`
; D 13,864 The reaction employed and the quantity of each were: 3.6 grams y-iron oxyhydroxide ~yFe(III)OOH]; 11.0 grams of hydrated aluminum oxide: 23.1 gram of 85% aqueous ortho-phosphori~
acid: 16.9 gram of water: and 81.4 gram of a 25%
aqueous solution of tetrapropylammonium hydroxide (TPAOH). The gel was crystallized for 24 hour at 150C. The solid product was identified by X-ray analysis to be principally FOP with a minor proportion of an unidentified crystalline composition and a crystalline material having the s~ructura of variscite.
(b) The procedure of part (a) above was repeated and produced the same products.
Example 3 (Preparation of FOP
(a) Using mixing Method (a), the following reagents were admixed Jo for a elation mixture I gram of iron (II) chloride tetrahydrat~ fake. 4~0]; 12.4 grams of hydrated aluminum oxide; 23.1 gram of an as aqueous or~ho-pho~phoriG acid solution: 36.5 grays of waxer; and 36.8 grams of a 40~ aqueous tetraethylammonium hydroxide 601ution. The composition of the final reaction mixture, in term of molar oxide ratios way:
1.0 TEACH 0.1 Eye I Aye P205 : 40 H20 The gel was crystallized for 24 hours at 150C. The resulting solid product was ground to Dave the : 30 following X-ray powder diffraction pattern which is characteristic of FOP.

D-13,864 '7~1 TABLE C
do 10~ X Rio 7.4 11.95 91 12.8 6.92 10 5 14.8 5.99 I
19.7 4.51 70 21.0 4~23 66 22.4 3.~7 10 aye 3.59 5 1025.9 3.440 34 29.~ 3.07~ 18 30.1 2.96~ 20 : 33.6 2.667 3~.5 Z.600 17 1536.9 2.~36 5 37.7 2~386 14 41.5 ~.176 2 I 2 Z.141 4 I 7 2.118 : 20~3.6 1.076 2 47.7 1.907 6 5~.7 1.650 I) A reaction mixture having the same composition as in par (a) above was prepared using the same reagents and using the tame mixing Mucked (a). The gel was crystallized for lug hours at 150C and the solid product subjected to Roy and chemical analysis. The chemical Gompoæition of the product in ~erm6 of mole ox tetraethylammonium hydroxide per average TO unit way:
o 05 EYE : foe oily pow 2 i The X-ray powder diffraction pattern of the j as-synthesized product way characterized by the following data:

D-13~364 I

TABLE D
I Dow 100 Rio __ 7.4 11.95 100 12.9 6.~6 12 15.0 5.91 23 19.8 4.48 I
.19 - I
2Z.5 3.9~ 98 : 24.8 3.59 26.0 3.4z7 33 27.2~ aye 3 29.0 3.079 18 30.1 Z.9~9 18 : 33.7 2.660 5 34.6 Z.592 17 : 37.1 2.4~3 I 2.380 11 41.0 2.~01 ~1.8 2.161 42.~ 03 2 43.G 2.132 3 43.~ 2.067 45.2 aye I` 45.8 1.981 : 25 47.8 Lc903 5 51.8 ~.76~ 2 : 52.2 1.752 2 * = line possibly attributable to an impurity (c) The a~-~yn~hesized APE
composition part (b) was calcined in air at 600C
for 3 hours and when subjected to aye analysis.
The X-ray powder pattern obtained was characterized ; by the following data:
TAB IF E
I Dow Rio 7.3 12.11 100 12.8 6.92 13 14.8 5.99 S

D-13~864 .

Al r2 3 I -TABLE E keynote I Doyle Rio ~9.6 ~.53 24 I: 21.1 4.21 31 Jo 5 22.3 3.~9 US
.7 3.~0 25.8 3.~53 16 2~.9 3.0~9 8 29.9 2.98~ 8 1033.6 2.667 3 3~.4 ~.607 7 36.9 2.436 2 37.8 2.38~ 5 40.7 2.217 1 1541.3 2.1~6 42.2 l 2 Jo ~3.0 2.103 43.6 2.076 I 2.023 Al : 2045.4 1.998 Al 47.4 l.91~ 3 51.2 1.7~4 52.0 1.759 55.2 1.664 (d) Adsorption capacities were : measured on the callused FOP port (c) I using android McBain-Bakr gravime~ric adoration , apparatus. The hollowing Dow were obtained on a sample activated at 350C.
- kinetic Prowar it. %
I' Ad ornate Diameter Tour my Adsorbed 2 3.4~ 98 -183 1~.3 2 3.46 758 -1~3 19.4 Neopentane 6.2 100 25.85.8 H20 2.65 4.6 22.419.4 H20 2.65 19.4 23.82S.3 (en The procedure of part (b) above was repeated to form a gel having the same chemical D-13,864 - 25 _ ~2~3~

composition a in par (by. This gel was crystallized at 200C for 332 hour. The white : portion of the product solids was subjected Jo chemical and g-ray analysis and found to be principally Fops with a minor portion of Fop and a trace amount of FOP. The chemical composition of the white solids way:
o 07 TEACH : (Foe aye pus 2 (f) Particles in the 20-40 micrometer range taken from the Fop product of part (b) of : this Example were analyzed by ED AX and found to have a Fe : P : Al peak height ratio of 0.06 : lo : 0.96.
Example (Preparation of FOP) (a) Using iron (II) acetate as the ounce of iron, FOP way produced from a reaction mixture prepared using mixing Method (a) and the following proportions of reagent: 3.5 grams of - Andy iron (II) acetate eke]: 12.~
slams of hooded aluminum oxide; 23.1 grams of an 85~ aqueous solution of ortho-phosphoric acid; 37.9 grams ox awry; and 36~8 gramfi of a 40% aqueous solution ox ~etraethylammonium hooded. The reaction mixture had the following chemical company, expressed in terms of molar oxide ratios:
lo TEACH 0.1 Foe 9 ~123 P~05 o 40 Ho : portion of the gel was crewless for 40 hours at 200C. and the solid product found, by Roy analysis, to contain a major proportion of FOP, a minor proportion of FOP and a trace amount of FOP. The chemical composition of a portion of ,;

D-13,864 the solid product was found by chemical analysis to be:
0.07 TEACH : (Foe ape 0 30 2 (b) The Remaining portion of the gel of part (a) above, was crystallized at 150C for 16 hour and found to produce essentially the same solid product as in part (a) except that no FOP
was detected.
The specie YAPO-5 a referred to herein it a feeroaluminopho~phate material hazing a three-dimen~ional MicroPro crystal framework structure of the tetrahedral units P02, Aye and at least one of Foe and Foe. and whose essential empirical chemical composition on an Andre basis it:
my: (FexAlyPz)02 wherein "R" ee~re6ents at least one organic - templa~ing agent present in the intracrystalline pore system; "m" reorients the mule of "R" prune per mole of (FexAlyP~)02 and has a value of from zero to 0.3. "x". "y" and "z-L represent respectively, the mole fractions ox iron, aluminum and phosphorus prevent in the oxide moiety, said mole fractions being within the compositional area bounded by point A, B, C and D on the ternary diagram which is Fig. 1, or preferably within the area bounded by points a, b, c and d on the ternary diagram which is Fig. 2, said Eerroaluminopho~phate having a characteristic X-ray powder diffraction pattern which contains at least the d-s~acings set forth below in Table I. In the form as synthesized in accordance with the process of this invention, "m" has value ox from a . 02 to 0.3.

D-13,864 ' Table I
Relative d AYE Intensity 7.3 - I 12.1 - 11.6 us 14.8 - 15.1 5.99 - 5.87 w-m 19.6 - 20.0 4.53 - 4044 my 21.0 - 21.2 4.23 - 4.19 m-s 22.3 - ~2.6 3.99 - 3.93 so 25.9 - 26.Z 3.453 - 3.401 m All of the synthesized Fop composition for which Roy powder diffraction data have presently been obtained have petunia which are within the' generalized porn of Table II below:
TABLE. II
I Dow 100 7.3 - 7.6 12.1 - 11.63 91 - 100 12.3 - 13.1 6.92 - 6.~6 10 - 18 14.8 - 15.1 ~.99 - 5.87 5 - I
19 6 - 2~.0 4.53 2 - 70 21 0 - 21.2 ~.23 - 4.1~ 31 - 6 22.3 - I I - 3.g3. 46 - 10 ~4,2 - 25.~ 3.68. - 3.56 1 - 5 25.8 - 26.2 3.~53 - 3.401 16 - 34 : 28.9 - 29.3 3.08~ - 3.04~ 12 - 18 29.9 - 30.4 ~.998 - 2.9~0 8 - 2 33.6 - 34.0 2.667 - ~.637 3 - 5 34.4 - 3~.9 2.607 - 2.571 7 - 17 36.9 - 37.3 2.436 - 2.411 2 - 5 37.7 - 38.0 2.3B6 - foe 5 - 14 40.7 - 41.0 2.217 - 2.2~1 0 - 4 41.3 - 41.~ 2.1~6 - 2.1~ 2 42.2 - 42.6 2.1~ - 2.122 1 -- 42.7 - 43.1 2.118 - 2.099 0 - 2 43.~ - 4~.0 2.076 - 2.05~ 1 - 2 ~4.8 - 45.~ 2.003 - 2.00~ 0 - 1 45.4 - ~5.8 1.~98 - 1.981 0 - 1 47.4 - I 1.~18 - 1.888 2 - 6 51.2 1.78~ 0 - 1 51.~ - 52.0 1.76~ - 1.759 0 - 2 D-13,864 3~7~

:
TABLE II keynote I do 100 I/I
5~.2 1.752 0 - 2 54.0 1.698 0 -55.2 1.66~ 0 - 1 55.7 1.550 0 -sample 5 (Preparation ox FOP
pa) Using mixing Method (a), a reaction mixture was prepared having a composition, 0 expired in term Of molar oxide ratio, of:
1.0 P~2NH : 0.1 Foe : 0.9 AYE :

The reagents and the amount thereof utilized in forming the reaction mixture were: 7.0 gram of Andre iron tip) acetate [Fake: 24.7 grams of a hydrated aluminum oxide: 46.1 grams of an 85% aqueous ortho-pho6phoric acid solution; 120 grams of water and 20.2 gram of di-n-propylamine.
A potion of the rusting gel was crystallized at 200C for 24 hours. The recovered solid product us subjected to Zoo and chemical-analy~i6 and fund to comprise FOP a the principal constituent along with a trace amount of FOP. The chemical company of the solid product, in terms of moles of Prune pew average To unit, way 0,04 Prune : (Foe pow) 2 The Slay powder diffraction pattern of the solid product was characterized by the following data:

.
"

it D-13,864 , .

.

:
I' ~.~3~7~
I

TAO: E
2~3d, (A) 100 g Rio .1 10.~2 34 8.5* 10.4033 (oh) 9.5 9.3144 13.2 6.71lZ
13 . I 6 46 4 lo . 7 5 . 64 23 1~.2 5.47 2 18.3t 4.8~ 7 19 . 0 4 . 67 20.3 4.3752 21 . 1 4 . 21 92 22 . 2 4 . 00 67 ( oh) . 6 3 . 93 100 23 . 2 3 . 83 64 ( oh) 24.8 3.59 6 25 . 8* 3 . 453 5 26 . 4 3 . 376 16 27 . 0 3 . 302 6 I . 0* 3 . 187 10 I . 7 3 . 110 I
29:1 3.0~93 29 . 6 3 . Ova 31. 6 . 2 . 831 llj 32 . 9 2 . 722 lo 34 . 2 2 . 622 6 35 . 1* 2 . 557 3 36.~ 2.~L62 37 . 8 2 . I
39.4 aye 42 . 9 . 108 2 44 . 8 2 . 023 5 46 . 6 1. 9g9 I 1.873Z
50.5 1.8072 51 . I 1 . 778 2 54.6 1.6~12 55 . 3 1 . 661 2 *, line possibly attributable Jo an impurity ash) = shoulder r .
D-13,864 '7~3 (b) Particle of the solid FOP
product of pat I in the size range of 5-35 micrometer were analyzed by ED AX (energy dispersive analysis by X-ray) and found to have a ye : P : I
peak height ratio of 0.07 : 1.0 : 0.87.
(c) The remaining portion of the gel from pelt (a) above way catalyzed at 150C fox 48 hours. The crystalline product exhibited essentially thy same Zoo powder defection pattern as the product of part aye and was thus established to be FOP.
(do The idea product of par (c) way calcined in air at 550C for 7 hours. The Roy powder diffraction pattern of the calcined product was characterized by the following data:
; TABLE G
; I Dow Rio 8.2 10.7831 (oh) 8.5~ 10.40 54 9.7 9.12 I
aye ~.92 17 L3.5 foe 14.8~ 6.99 .16.1 5.50 39 17.0* 5.22 18.4* 4.B2 19.5 4.5515 ash) Z0.0* 4.4g29 ho 20.3 4.37 53 21.6 4.1122 (so) 21.9 ~.06 93 22.5 3.95100 23.~ 3.80 55 24.0~ 3.71 24.3~ US 1 25.2 3.53~ 7 25.7~ 3.46617 26.5 3.363 9 D-13,864 - 31 _ I 7 TABLE G keynote 2~3 d, (A) 100 Rio 27.2* 3.278 I
27.8~ 3.239 16 29.6 3.018 I
30.3* 2.950 9 31.7 2.~23 2Z
32.5 2.755 14 33.9* 2.644 3 34.4 2.~07 35.1* 2.557 8 35.5 2.529 37.2~ 2.417 8 38.2 ~.356 8 : 15 3~.6* 2.332 8 39.3 2.292 43.7* 2.0~1 1 45.0 2.01~ 1 49.1 l.BS5 2 * = line pueblo attributable to an impurity (shy = shoulder (e) The sample used in part (d) upper was cay Ed it sir at 500C fox 5 hours and then at 600C for 2 I hours.. Adsorption Asia were the measured, The data obta nod it a follows:
KinetisPressure Wt. %
Adsorb ate Diame~Qr~ A Torn Temp.,C Adsorbed I 3~4~100 -183 I
2 3.~6750 -18311.7 Nixon 4.3 97 23.55.9 butane 5.0 740 24.63.9 Neopentane 6.2 101 24.1 1.2 Ho 2.654.6 24.414.2 ~2 2.651~.9 24.52~.2 .

D-13,864 , The species FAP0-ll as Levered to herein it a ferroaluminophosphate material having a three-dimensional micro porous crystal framework structure of the tetrahedral unit P02, Aye and a least one of Foe and Foe and whose essential empirical chemical composition on an Andre basis it:
my: (Fe~lyPz)Oz wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "I" present per mole of (FaxAlyP2)~2 and has a value ox from zero Jo 0.3, "x", "y" and "z" represent respectively, the mole fraction of iron, aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C and D on the ternary diagram which it Fig. l. o ~eferably within the I; area bounded by points a, b. c and d on the ternary diagram which is Pig. 2. said ferroaluminopho~phate hiving a characteristic a power diffraction pattern which contains a least the spacings set worth below in Table III. In the form as synthesized in accordance with the process ox this invention, "m" has a value of prom 0.02 Jo 0.3.
Table III
Relative d (A) Intensity 30~.1 - 8.2 1~.9~ - 10.78 9.5 - 9.7 9.31 - 9.12 m 20.~ 4.37 m 21.1 - 21.6 4.21 - 4.11 m-vs ~1.9 - 22.2 4.06 - ~.00 5-V5 I, ., . D-13,86~

Lo Relative I Intensity Z2.5 - 22.6 3.g5 - 3.93 us 23.2 - 23.4 3.83 - 3.80 m-s ~11 ox the as-synthe~ized FOP compositions for which aye powder Daphne data have presently been obtained have patterns which are within the generalized pattern of Table IV below.
TABLE IV
I Dow 100 X Rio 8.1 - 8.2 10.9Z - 10.78 31 - 3 8.5 10.40 ho 9.5 - 9.7 9.31 - 9.12 I - 54 13.2 - 13.5 6.71 - 6.56 12 - I
15.7 - 16.1 5.6~ - 5.50 23 - 39 1~.2 5.~7 o - Z
19.0 - 19.5 4.67 - 4.55 4 - I
20.3 4.37 52 - 53 21.1 - 21.6 4.21 - 4.1~ 22 - 92 21.9 - 22.2 ~.06 - 4.00 67 - 9 22.5 - ~2.6 3.9~ - 3.93 100 23.2 - ~3.4 3.83 - 3.~0 I - 64 2~.8 - 25.2 3.59 - 3.5~ 6 7 25.4 - 26.5 3.376 - 3.363 9 - 16 27.0 - I 3.302 - 3.196 0 - 6 29.7 3.110 0 - 12 I .069 0 - 3 29.6 3.01~ 6 - 22 31.6 - 31.7 Allah - 2.823 16 - 22 I 5 - 32.9 2.755 - 2.722 12 - 14 I, 34 2 - 34.~ 2.622 - 2.607 1 - 6 35 5 2.529 0 - 8 36 5 2.~62 0 - Z
37.8 - 38.~ 2.3~ - 2.35~
39.3 - 3g.4 2.Z92 - 2.287 1 - 4 .9 2.108 0 - 2 go - 45.0 2.0~1 - 2.023 1 -46.6 1.949 0 - 1 ~8.6 1.~73 0 - 2 :;
D--13,864 _ 34 _ I

TABLE IV (keynote I do 100 IJIo 4g.1 1.~55 0 - 2 50.5 1.807 0 - 2 54.~ 1.6~1 0 - 2 55.3 1.661 0 - Z
Example 6 preparation of FOP) (a) Using mixing Method (b), a reaction mixture was prepared from: US grams of Audrey iron (II) acetate [Fake]: 30.6 grams of aluminum isopropo~ide Alec:
19.2 grams ox an 85% aqueous oetho-phosphoric acid solution: 67.7 gram ox wow; and 9.3 grams of quinuclidi~e (C7H13N). The composition of the reaction mixture, in term of molar oxide ratios, way:
~7~13N eye I ~123 A portion of the resulting vet way crystallized a 150C for 52 hours. The solid product as subjected to Roy analysis and was found to be principally FOP. The Roy powder diffraction petunia ox thy solid product was characterized by the following data:
TALE H
I Dow) 100 Rio 7.4* 11.95 6 9.2~ 9.61 3 ~1.4 7.76 I
~4.8~ 5.99 Z
16.1~ 5.50 17.4 S.10 3 1~.8 ~.72 52 D-13,864 ., _ 35 I

TABLE H Jo keynote I Dow Rio ~9.8~ ~.48 3 20.6* 4.31 3 21.1* 4.213 ash) 22.0 4.0~ 100 22.9 3.882 (so) 25.9~ 3.4401 ho 26.6 3.351 25 Z7.1~ 3.290 3 : 2900 3.079 8 29.4* 3.038 z 29.7 3.008 Z8 31.4~ 2.849 2 32.7 2.739 5 34.7 2.585 5 37.9 2.374 9 39.~ Z.26~ 2 ~4.2 2.049 3 48~4 l.B81 5 Jo 5~.4 1.746 53.7* 1.707 5~.6 1.681 2 = line possibly a~ribu~able to an impurity (so) = shoulder (by A end portion of the reaction gel of cart (a) above, was cry tallied at 150~C fox 175 hours. The solid product was alto established by it Roy powder diffraction pattern to be FOP, and was omit more pure than the pLod~ct ox part (a). Thy chemical composition of the product, in term of mole of quinuelidine per average T02 units was 0.12 C7H13N (Phyla 0.50 Z
0.58 H20 The X-ray powder diffraction pattern of the product way characterized by the following data:

I- 13 , 8 64 ~3~7~

TABLE J
2Ç~ d, (Pi) 100 Rio 9.2 g.61 11.57.69 58 13 . 1*6 . 7 6 2 14.8*5.99 17.45.10 3 18.84.72 58 20.6*4.31 2 22 . 04 . 04 100 23 .13 . 85 5 ( fix) I . 63 . 351 Z3 29.13.069 8 29 . 82 . 998 27 32 . I . 730 4 34. 82 . 578 7 ~5.7*~ . 515 2 3~.02.36û 10 39 . 72 . 270 2 I . 42 . 040 3 48.51.877 8 52.~1.7D~6 3 5~.81.675 3 * -. line possibly attributable to an impurity I, ( fix) = shoulder I, Jo (c) Thy a~-syn~hesized FOP
product of part (by above was calcined in air or 2 hours at 600C. The X-ray powder diffraction pattern of the Colorado mozzarella was characterized by the followiIlg data:
TABLE K
? I d, (A) 100 _ o 9.2~9.61 Z
' 11 . 3 7 . 03 100 13 . 1* 6 . 7 6 7 Jo 18 . 6 4 . 77 I
21 . 9 4 . 06 So .0 D- 13 , 0 64 . .

I

TABLE K (can't) I Dow X Rio 22.9 3.~lZ
26.5 3.363 21 5 29.0 3.079 6 29.7 3.~0~ 36 32.6 2.747 B
34.6 2.592 10 37.9 2.374 6 10 I ~.0~9 2 I 1.881 4 52.2 1.752 5~.8 1.675 2 * = line possibly attributable to an impurity (d) A portion ox the product of part (a) above was heated under vacuum at 350C for 16 hours in a standard McBain-Bakr gravim~tric appa~atuæ, and thereafter the following adsorption data obtained:
Cook Presort %
Adso~ba~e imp Torn Tempt Adsorbed 2 3.4~ Lowe 2.3 2 owe 734 -1~3 7.9 H20 ~.65 4.624.4 18.2 H20 2.65 18.524.0 25.1 (do A third portion of the gel of Hart (a) above way crystallized at 200C fox 52 hours. my Roy analysis, the resulting Solid product was found to be principally FOP with a minor amount of an impurity phase having Rome ~imilaritr to F~P0-17.
(e) Using mixing Method (a), 5.8 grams of iron (II) acetate, 61.3 grams of aluminum isopropoxide, 38.4 grams of 85% aqueous D-13,864 - 3 a 3~(~'7C3 ortho-phosphoric acid and 135.4 grams of water were admixed and the resulting mixture divided into two portion of equal weight. To one portion 9.3 gram of quinuclidine (C7~113N) was added to form a reaction mixture having a composition in terms of molar oxide Roy ox:
1.0 C7H13N : 0.1 Foe : 0.9 Aye :
P205 : 50 ~2 The reaction mixture was crystallized at ~25~C for 98 hours. By Roy analysis the resulting solid product was wound to comprise a major proportion of FOP in combination with a minor proportion of FOP.
The pus FOP as referred to herein is a ferroaluminopho6phate material having a three dimensional micropo~ous cly6tal framework structure ox the tetrahedral unit Pi Aye and at least one of Foe and Foe, and whose essential empirical chemical composition on an an hydrous basis is:
my : fox Any Pi) I
wherein "R" represents at least one organic templating agent prevent in the intracrystalline Gore system; "m" represents the Poles of "R" prevent : 25 per mole ox (Fillip and has a value of from zero Jo 0.3, "x", "y" and "z" represent respectively, ho mole fractions of iron, aluminum and phosphorus prevent in the oxide moiety, said mole rickshaws being within the compositional area bounded by points A, B, C and D on the ternary diagram which it Fig. 1, or preferably within the area bounded by points a, b, c, and d on the ternary D-13,864 ~23~

diagram which is jig. 2, said ferroaluminophosphate having a characteristic aye pod diffraction pattern which contain at least the spacing eye forth below in Table V. In the form as synthesized in accordance with the process of this invention, "m" ha a value of prom 0.02 Jo 0.3.
Table V
Relative 23 d SAL Intones : 10 11.3 - 11.5 7.~3 - 7.69 m-vs 1~.6 - Lowe ~.77 - 4.72 m . 21~9 - 2Z.0 4.06 - 4.0~ m-vs 26.5 - 26.6 3.363 - 3.351 m 29.7 - 29. a 3.008 - 2.998 m All ox the synthesized FOP compositions or which X-ray powder diffraction data Dave presently ; been obtained have patterns which aye within the generalized pattern of Table VI below.
YALE VI
I do 100 Rio _ __ 11.3 - 11.5 7.83 - 7.69 58 - 10 : 17.4 5.10 3 18.6 - 18.8 ~.77 - ~.72 21 - 58 21.9 - 22.0 ~.06 - I 50 - Lou 22.9 - 23.1 3.88 - 3.85 2 - 12 (so) 26.5 - 26.6 3.~40 ~.363 21 - 25 2g.0 - 29.1 3.079 - 3.069 6 - 8 29.7 - 29.~ aye - 2.9~8 28 - 36 32.6 - I Z.747 - 2.730 4 8 3~.6 - 3~.8 2.592 - 2.578 5 - 10 37.9 - 3~.0 2.37~ - 2.368 6 - 10 39.7 - 39.8 2.270 - 2.265 2

4~.2 4~.4 2.0~9 - 2.0~0 2 - 3 - 4~.4 - 48.5 1.8~1 - 1.877 - 8 52.2 - 52.~ 1.752 - 1.4~6 2 - 3 54.6 - 54.8 Allah - 1.675 2 - 3 D-13,864 ,, .
.

- Jo -Example 7 (Preparation of FAPO-17L
pa) 8.3 grams of cyclohexylam;ne was added to the remanning half of the reaction mixture from Example I. The resulting mixture had a composition of:
1. n Clowns : 0.1 Foe : 0~9 ~1203 o P205 : 50 H20 One halt of this new reaction mixture was c ystal-lized at 200C for 112 hours, and the other half crystallized at 200C for 276 howls. After 112 hours thy product way found by X-ray analysis to comprise principally APE along with some unidentified cry~alline impurity. After 276 hour the product way principally FOP along with unidentified crystalline impurity. A relatively pure FOP was physically separated from the mixture.
(by Energy dispersive analysis by X-ray (EDDY) in connection with scanning electron microscope studies ox a particle of the relatively pure FOP product of part (a) above having a minimal amount of debris associated therewith established what the Fetal peak height ratio ox the composition was 0.4:1.0:0.82. The X-ray powder diffraction pattern of the predominantly FOP
product was characterized by the hollowing data:
TABLE L
pa do 100 X Rio I 11.33 100 ; 30 go 9.03 23 11.6 7.63 13.4 I 74 ; 14.2 6.24 4 15.~ 5.75 45 D 13,864 I

TABLE L (cowl to 29 d, PA) loo Rio _ 16 . 65 . I
17.0~5.~2 2 18.0 40g3 6 19 64 . 53 I
20 I . 35 91 ~1.3 ~.17 3g 21.B~ 4.08 7 oh 22 . 4 3 . 97 4 23 . 2 3 . 83 30 23 . 7 3 . 75 25 25 . 3 . 3 . 520 1~1 26 . 8 3 . 326 31 27 . I 3 . 267 15 28.1~ 3.17~ 3 28 . 7 3 . 110 11 ~0.5 2.931 7 (so) 31.1 2.876 30 31.7 . 2.823 I
33 4 2 . ~83 18 35 1* 2 . ~57 35 . 8* 2 . 508 9 36.2 2.481 2 (oh) 37 . 9* . 37~ 2 : 3g.2~ 2.298 3 ~9.7* 2.270 4 4~.3 2,238 . 2 I 2.2:t2 ~12.~ 2.}51 42 . 6* 2 . 1~2 ~30~ 2.076 4 . 3* 2 . 045 aye . 6 1 . go 3 46 . I 1. 953 2 ISLE 5* 1 . 914 48 I 1. 873 go . 5 1 . 8~1 11 49.B 1.831 2 oh 50 . 3* 1 . 81~ 2 52 . 0 1 . 75g 5 53 . 8 1 . 70~ 2 55, 3 1. ~61 9 ; * = line possibly attributable to an impurity (so) = shoulder ' ' D~13,864 ;, -I Adsorption capacities were measured on the product of part (a) after calcination in air fox 2 hour at 600C using a standard McBain-Ba~r gravimet~ic adsorption apparatus. The following data were obtained on a sample activated it 350C:
Kinetic Pressure Wt. %
Ad~orbate diameter, A Torn Tempo ~dsorhed 2 3.~6101 -183 13.3 2 3.~6739 -183 13.9 nooks 4.3 53 2~.813.0 ~2 2.654.6 23.914.1 H20 2.6519 24.315.5 (d) The as-syntheæi2ed 276 hour digested FOP product of part (a) swooper way calcined in air for 2 hour a 600C. The Roy powder diffraction pattern of the calcined product way characterized by the following data:
TABLE
I Dow Rio 7.7 11.48 6 9.7 9.12 43 11. By . 50 12 13.4 6.61 100 14.1 6.2~ 30 I 6.07 3 15.4 5.7~ 16 16.5 5.37 17.~ 4.98 4 19.5 4.55 10 20.4 4.35 57 21.3 ~.17 21 21.7* 4.10 4 (ah) 22.4 3.97 3 OWE 3.82 3 (oh) ~3.7 3.75 Z9 D-13,8fi4 .

: TABLE M keynote Dow : 2~.1*3.69 3 : 2~.7*3.~0 12 25.03.~2 12 25.9*3.440 9 26.93.314 18 28.03.187 I
~8.63.121 16 29.4~3.~38 13 29.8~2.99~ 1 31.~2.867 23 31.~2.~31 I
33.4~.683 8 3~.6~.592 3 35.8*2.508 8 oh : 36.12.~88 8 (so) : 38.62.332 40.82.210 41.62.171 Jo 47.21.9~ 3 48.31.884 48, R1 . 866 4 I . ~31 3 ` 52.~1.7~4 ,: 55 . 6 1. 653 . 6 , * , line pueblo attributable to an impurity s . .
Pi Shea = shoulder The specie FOP as referred to Hun it a ferroaluminopho~pha~e material having a thLee-di~ensional micro porous Shelley framework structure of the tetrahedral units, POX, Aye and at least one of Foe and Phase, and whose essential empirical chemical composition on an an hydrous byway is ; OR : fillips wherein "R" cepresen~6 a least one organic I!
':
I: D-13,864 I.

~.23~
- 44 _ templating agent present in the intracrrstalli~e pore system; "m" reprints the mower of "R" present per mole of (FexAlyP~)02 and ha a value of from zero to 0.3, "x", "y" and Lucille represent respectively, the mole fractions ox iron, aluminum ; - and phosphorus prevent in the oxide moiety, said mole fractions Borg within the compositional area bounded by points A, B, C, D and E on the ternary diagram which it Fig. 1, or preferably within the area bounded by point a, b, I, d and e on the ternary diagram which it Fig. 2, said ferroaluminophosphate having a characteristic Roy powder diffraction pattern which contains at least the spacings eye worth below in Table VII. In the form as synthesized in accordance with the prows ox this invention, "m" has a value of from 0.02 to 0.30.
.
Table VII
Relative 20_ I Allah__ Intensity 7.7 - 7.8 11.48 - 11.33 my 9.7 - 9.8 9.12 - 9.03 m 13.4 6.61 m-vs 15.4 5.75 wow 19.4 - 19.7 4.58 - 4.51 w-m - 20.~ 4.35 ~-~
21.3 4.17 m , 31.6 - 31.7 2.814 - 2.822 m All of the as-synthesized FOP composition fox ; which Roy powder diffraction data have presently been obtained have patterns which are within the generalized pattern of Table Vile below.

D-13,864 ~L23~

Table VIII
2 Dow 100 Rio 7.7 - 7.8 11.48 - 11.33 68 - 10 9.7 - 9.8 9.12 - 9.03 23 - I
11.~ 11.8 7.63 - 7.50 1 - 12 13.4 6.61 74 - 100 14.1 - 1~.2 6.28 - 6.24 4 - 30 14.6 6.07 0 - 3 15.4 5.75 16 - 45 16.5 - 16.S 5.37 - 5.34 - 21 17.8 - 18.0 4.9~ - 4.93 4 - 6 19.5 - 19.6 4.55 - ~.53 10 - 26 20.4 4.35 57 - 91 21.3 4.17 21 - 39 21.7 - 21.8 4.10 - 4.08 4 _ 7 (oh) 22.~ 3.97 3 - 4 23.2 - 23.3 3/83 - 3.82 3 - 30 23.7 3.75 25 - Z9 25.0 - 2~.3 3.562 - 3.520 12 - 18 26.8 - 2~.9 3.326 - 3.314 I - 31 27.3 3.2~7 0 - 15 28.0 - 28.1 3.187 - 3.175 3 - 21 28.6 - 2~.7 sly - 3.110 11 - 16 29.4 3.03~ - 13 29.~ 2.998 0 - 14 30.5 2.931 7 (oh) 31.1 - 31.2 2.8~6 - 2.8~7 23 - 30 31.6 - 31.7 2.B31 - 2.823 23 - 47 : 33.4 2.683 8 - 1 3~.6 2.592 - 3 Jo 35.1 2.557 - 1 35.8 2.508 8 - g 36.1 - 36.2 2.488 - 2.481 2 - 8 (6h3 37.9 2.374 0 - 2 38.6 2.332 0 - 1 39.2 2.2g8 0 - 3 39.7 2.270 0 - 4 40.3 2.23~ 0 - 2 40.8 2.212 0 - 1 42.0 2.151 0 - 1 4~.6 2.122 0 - 1 43.6 2.076 0 - 4 44.3 2.045 0 - 1 45.6 1.989 0 - 3 46.5 l.g53 0 2 ~7.2 - 47.5 1.926 - l.gl4 1 - 3 /
j D-13,864 Table VIII (con I do 100 Rio : 4~.3 1.88~ 0 - 1 48.6 - 48.H 1.~73 - 1.866 1 - 4 ~9.5 1.~1 0 - 11 49.8 1.~31 2 - 3 50.3 - 50.8 1.814 - 1.797 - 3 5Z.0 1.759 0 - 5 53. a 1 . 704 o - 4 55.6 1.653 0 - 6 Example 8 tpre~aeation of F~PO-182 (a) Using Method (a), a reaction gel was prepared having a composition. expressed in terms of molar oxide ratio, of:

: 40 H20 The reagent employed and quantity of each were:
2.2 gram iron oxyhyd~oxide fudge;
15.5 Guam hydrated aluminum oxide; 28.8 grams ox 85~ aqueous o~ho-phosphoric acid: 47.2 grams waler and 46.0 grams ox 40% aqueous solution ox te~raethylammonium hydroxide (TAO. The gel was divided into two equal potions. One pow was crystallized for 25.5 hours at 200C and the other I portion fox 25.5 hours at 150C. By Roy annul.
the solid product resulting from the 200C
crystallization was substantially pure FOP
whereas the product ox the portion crystallized a 150C was principally FOP with only a trace amount of F~PO-lB. By chemical analysis the chemical composition ox the FOP product was:
OOZE TAO : foe 06Alo.5opo.4g) 2 ~2 , .
Jo , .
D-13,864 I

The Era powder diffraction pattern ox this product way characterized by the following data:
TABLE: O
d, Aye I/I
9 . 7 9 . 12 loo 10.6 8.35 lo 11.2 7.90 5 13.3 6.~6 5 14.2 6.24 5 14.9 5.95 lo 15 . 7 5 . I 30 17.2 5.16 1~.0 4.93 25 19.6 ~.53 10 Jo . 3 4 . 37 40 21.2 4.19 us I . 2 4 . 00 15 23 . 6 3 . 77 5 24.1 3.S9 5 : 20 I. 6 3 . 62 10 25 . 1 3 . Do 5 I . 7 3 . ~66 5 26.4 . 30376 20 26.6 3.3~ 10 ho 27 . 0 3 . 302 I
pa . 2 3 I 20 go . I 3 . ~58 5 - 30 . 2 . 959 - - 25 31 . 85 I
31, do 2 . 849 15 31.9 ~.805 I
32 . 6 2.747 25 33 . 2 . 6~3 lo 34.8 2.578 10 36 . 2 2 . ~81 5 (oh) 36 . I* 2 . 442 2 40 . 2 2 . 243 5 41.3 2.186 5 g3.1 2.100 5 * = line pueblo att~ibutablQ to aft impurity ( oh) - Shea don D-1~,864 .

- I -(b) A portion of the a~-~yn~hesized FOP product of part pa) was calcined at 500C
for 2.75 hours in a nitrogen atmosphere. The X-ray powder diffraction pattern of the calcined product way characterized by thy following data:
TABLE P
I 100 Rio 9.5179.29~8 100.0 90~74*~.8681 22.9 ` 10.~13~.3352 12.8 lZ.929~.8~71 10.
13.4g2*6.5625 ~.~
14.0126.3202 2.0 ; 1&.0895.5085 7.9 16.9155.241~ 15.7 17.1975.1562 12.2 19.079*~.~517 2.3 : 19.6~8~.~181 2.5 20.0204.4349 3.4 20.68Z~4.2g46 7.8 ~1.35~ 01 7.5 23.~0g3.7~17 I
26.0183.~2~6 I
.2633.3932 gas ~7.~1230~077 3.5 30.G682.9720 2.7 ago I
30.7~92.9067 I
31.1482.B713 4.7 32.1~~. aye 5.2 : 32.5262.75~7 2.1 : 32.7022.75~3 3.1 : 33.1892.6992 I
33.572*2.6693 1.5 35.6962.5152 6.8 .779*2.21~7 1.6 78*2.1972 1.6 Allis 2.0 49.L14*1.8549 2.6 Allah 2.3 guy 2.6 49.900*1.~275 1.8 I' .
D-13,864 I

I
I Dow loo Rio 50.~05* 1.8171 300 54.086 1.6955 1~7 54.183 l.S9Z7 I
* = line possibly attributable to an impurity (c) A potion of the calcined material of part (b) upper was utilized in adsorption capacity Swede using a standard McBain-Bakr gravimetric adsorption apparatus.
: Measurement were made ox a sample after vacuum activation at 350C. The following data were obtained:
Kinetic Prowar it.
15Ad60cbate Diameter Atari Temp.,C Adsorbed 2 3.46 1~3 -1~3 ~8.9 I 3.4~ 733 -183 ~5.2 Nixon 4.3 I 23.48.8 i-Butane 5.0 100 23,02.0 ' 20 H20 2.65 I 22.92306 I H20 2~65 19~5 23~03502 , Example 9 Lyre ration ox APE) (a) A reaction mixture having a company, episode in term ox molar oxide ; 25 ratios. of:
ZOO Tao 0.2 Foe ORB Aye Pi 5 o 121 Ho was prepared by combining, using mixing Method (d), - 3.5 gram of an hydrous icon (II) acetate [Fake]: 16.4 grams ox aluminum isopropoxide; 11. 6 gramfi of an 85~ aqueous ortho phosphoric acid: 40.0 grams of water and 36.8 :

D-13,864 I

grams of a 40% aqueous solution of tet~aethylammonium hydroxide. A portion of the gel was crystallized at 150C for 42 hours. By Zoo analysis the solid product was determined to be substantially pure FApo-la. The Roy powder diffraction pattern was characterized by thy hollowing data:
TABLE
I do 100 X I/I
9.6 sly loo L0.4 8.51 7 11.0 8.0~ 9 13.2 6.71 5 : ~4.1 I 8 14.9 5.95 9 15.6 5.68 lo 17.0 5.22 26 17.9 4.96 11 (so) 18 . 3*4 . By 5 ( 8h3 Lo . 6*4 . 77 4 shy 20.2 4.~0 24 21 . 04 . 23 44 22~ I 13 23.3 3.82 3 ~3.9 3.72 3 24.4 3.65 9 24 . 93 . 58 3 I 3 . 506 3 2~.1 3.414 11 ;26 . 53 . 363 5 I . I . 326 9 ~7.4-~3.255 28.1 3.175 7 ~9.1~3.069 2 30 . 02. 979 14 30. 82 . 903 11 31.3 2.8S8 11 31. 82 . 814 2 (oh) : 32 7 ~42. 763 4 33 . I . EYE 3 34.5 2.600 3 35 . ~12 . 508 3 ~-13, 361~

I

TABLE Q ( curl ' 29 Dow) 100 Rio 3~.2 2.48~ 3 : 40.0 2.25~ 1 ~3.0 2.103 5 ` glue* 2.053 47.B 1.983 49.4 1.845 3 : ~9.9 1.8~8 Jo 10 51.0 1.791 4 4.2 1.692 55.2~ 1.664 2 * = line possibly attributable to an impurity Shea) = shoulder by A portion of the as-syn~hesized : product of part (a) above way colonnade in air at ~OOGC fox 2.75 hour. The Zoo powder diffraction pattern of the calcined product indicated that . 20 partial decomposition ox the sample had occurred with the probable formation ox cry~tallina ;. impurities. The X-ray petunia characterized by the following data:
I, - TABLE R
I, ' 25 20 do 100 X Rio 1, '- 9.4 9.~1 100 9.9*8.93 67 Shea 10~3 3.59 6 (oh) I: I 6.92 lug 13.7 6.46 10 15.7 5.64 13 ` 16.9 5.~5 26 . 18.0 4,93 : 20.5 4.33 16 21.6 4.11 lo 22.2 4.00 22. aye '. 4 Dow .

,' ;

TABLE R (keynote I data) 100 Rio ~3.6 3.77 19 2~.3 3.66 10 I 3.59 4 : 26.1 3.414 16 27.1 3.290 3 2~.6 3.121 30.4 2.~40 16 31.5 2.84~ 16 32.1 2.7~8 13 33.0 2.71~ 13 : 35.7 2.515 3 ; 41.0* 2.201 43.~ 2.103 7 4~.9* 1.863 13 SUE* 1.~24 55.2* 1.6Ç4 8 - line possibly attributable to an impurity t8h) = shoulder (c) The remaining portion of the gel from part (a) way crystallized at ZOO for 107 hours and way found by Roy analysis to have pcodu~ed FOP in admixture wow trace amount of APE. The chemical composition of the a~-~ynthesi~ed product it terms of moles of TAO
per average T02 unit, was: -0.06 TEACH : (Foe ogA1o~-44Po~47)02 2 The species F~PO-18 as referred to herein is $erroalumino~hosphate material having a . three-dimen~ional micro porous crystal ELamework structure ox the tetrahedral unit P02, Aye and a least one of Foe and Foe, and whose essential empirical chemical composition on an Andre basis is:
my : (Fillips D-13,864 ~3~7~

wherein "R" represent at least one organic templating agent present in the intrac~ystalline pore system: "m" represents the mole ox "R" prevent per mole of (Fillips and has a value of from awry Jo 0.3~ "x", "y" and "z" represent respectively, the mole fractions of iron, aluminum and phosphorus present in the oxide moiety, said mole tractions being within the compssi~ional 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 it Fig. 2, said ferroaluminophosphate having a characteristic X-ray powder diffraction pattern which contains a least the spacings jet forth below in Table It. In the form as synthesized in accordance with the process of this invention, "m" ha a value of Tom 0.02 to 0.30.
Table Relative 29 _ _ d AYE ~nLi~Y
.4 - 9.7 9.41 9.1~ V8 15.6 - 16.1 5.6~ - ~.51 wow 16.9 - 17.2 5.25 - 5.16 wow 2520.~ - 20.7 ~.40 - 4.29 w-m 21.0 - 21.6 4.23 - ~.11 w-m All of the as-6ynthesized FOP ~omposi~iorls for which Ray powder diffraction data have presently been obtained have pattern which are within the generalized pattern ox Table T below:

D-13,864 -- I --TABLE X
I do (A) 100 X Rio 9 . 4 9 . 7 1 1 - 9 . 1 2 100 10~3 1(:~.6 8.59 - 8~34 6 7 11.0 - Liz 8.04 - 7.90 o - 9 12.8 - 13.3 6.92 - 6.6~ 5 - 19 13.7 - 1~.2 60~6 - 6.24 14.9 5.~5 0 - 9 15.6 - 16.1 5.68 - 5.51 8 - 30 : 10 16.9 - 17.2 5.25 - 5.16 0 - 26 17.9 - 1~.0 ~.96 - 4.93 0 - Z5 19.6 - 20.0 ~.53 - 4.43 3 - 1 20.2 - 20.7 4.4~ - ~.2g 16 - 4 21~ 0 21 6 4 . 23 4 2Z.1 - 22.Z OOZE - 4.00 0 - 15 23~3 23~6 3~82 3.77 3 - 19 : 23.9 - Z4.1 3.72 - 3.69 3 - 8 2~.3 - 2~.6 3.66 - 3.62 0 - 10 24~8 oily 3.590 - 3.5~8 0 - 5 25.~ - 25.7 3.506 - 3.466 0 - 5 26.0 - 2~.1 3~425 - 3.~14 0 - lo 26.3 - 26.5 3.393 - 3.363 0 - I
27.8 - pa 2 3.20~ - 3.164 0 - 20 :- 30.0 - 30.~ 2.~79 - ~.~40 3 - 25 30.~ - 31.Q 2.907 - ago 2 - 15 31.1 - 31.5 ~.~71 - I 5 - 16 31.~ - 3~.2 2.~1~ - 2.780 2 - 13 32.~ - 32.~ 2.. 7~3 - 2.747 - 25 3~7 33~0 2~738 2~715 0 1.3 33 2 I . AL 2 6g9 2 6~3 0 15 34.5 - 34.8 2.600 - 2~57B O - 10 , 35.7 - 36.2 2.508 - 2.~81 5 - 7 ~0.0 ~0.2 I 2.24~ 0 - 5 41.3 2.186 43.0 - ~3.1 2.103 - 2.100 - 7 . 47.8 1.903 : 49.4 - ~9.5 1. I 1.~41 3 51.0 1.791 4 5g.1 - 54.2 1.696 - 1.692 3 - 4 .; 40 (a) A reaction gel consisting of 23.Z
grams of an hydrous iron (II) acetate ~FetII)(OAc)2], 108~9 grams ox aluminum ;, , , " .
DOW

.,.

I

isopropoxide, 76.9 grams of 85~ aqueous o~tho-pho~phoric acid, 123.7 grams of water and 245.5 grams of a 40% aqueous solution of tet~aethylammonium hydroxide (TEACH) was prepared using mixing Method (c). The composition of the reaction mixture in term of molar oxide ratio was:
2.0 TEACH : 0.2 F203 O. a Aye 2 5 Halt of the gel was crystallized at 200C for 117 hour. By chemical analysis the recovered idea product way found to have a chemical composition in term of mole of TAO per average T02 unit of:
0 07 TAO : (Foe pow) 2 Z
The X-ray powder diffraction pattern ox the as-synthesized product way characterized by ho hollowing data:
TABLE S
; I data) 10~
7.3* 12.~1 1 .6 9.21 10~
12.9 6.8~ 11 14.2 6.24 11 16.1 5.50 23 18.2 ~.87 15 : 20.7 4.29 59 22.~ 3.97 3 23.3 3.B2 : 25.5 3.~93 16 : 26.1 3.~14 13 27.2~ 3.27~ 4 27.7 3.220 2 28.6 3.121 2 29.8 2.998 3 (oh) 30.7 2.912 20 31.~ ~.8~0 14 34.6 2.~92 5 36.5 2.~2 2 39.8 2.265 2 ~3,7* 2.071 3 D-13,864 - So -TABLE S (Connally 29 do 100 Rio I 1.903 2 49.4 1.845 4 50.7 1.801 2 51.4 1.778 2 53.3 1.719 2 * = line possibly attributable Jo an impurity (so) should (by The remaining portion of the gel from part (a) of this Example was crystallized or 117 hour a lZ5~C. By X-ray analysis the solid product was found to be FOP having an X-ray : powder pat~eLn essentially identical to that ox Table S, swooper.
(c) A portion ox the FOP
composition of part (a) was colonnade for 2 hours at 450C in a nitrogen atmosphere. The ray powder diffraction pattern ox the caLcin~d product aye characterized by the oiling data:
I' TABLE T
I do (Pi 100 X Rio 9 ~9L9 41 100 10 ~1*8 76 2 r shy 12.8 6~92 20 13~13 6.4Z Z
So 1:2 16~9~ 5~25 1 (oh) L7.7 5.01 7 Jo 30 18.g 4.7~ 2 L9.6 4.53 2 (so) 20.5 ~.06 21 :: 2L.9 4.33 22.3 3.99 I, !
D-13,B64 ' ,.

~Z3~
Jo - 57 -. TABLE T keynote) I Dow Rio 23.0 3.~7 2 I: 24.0~ 3.711 (oh) 24.9 3.58 6 25.8 3.~53 6 27.4 3.255 2 28.0 3.187 29 I 3.079 I; 10 29 5 3.0~
30.5 2.93113 30.9* 2.8944 (so) 31.5 2.8401 (so) : 32.2 ~.780 33.3 2.691 34.4 2.607 2 : 35.9 2.501 2 3~.5 ~.33~ 1 3~.9 2.315 3g.5 2.281 42.7 2.~lB
43.3 2.090 47.5 1.914 4~.7 1.~70 2 50.6 1.~04 2 53.~ 1.7~8

5~.2 1.692 55.~ 1.6~7- 1 ., * = line possibly attributable Jo an impurity (so) = shoulder I,, (do Adsorption capacities were measured on a portion of part (a) which had been calcined fox 1.25 hours at ~00C. A sundered ; ~cBain-Bakl gravimetric adsorption apparatus was employed. The hollowing data were obtained on a sample activated at 350C:

I' I' D-13,364 I
- I -Kinetic Pressure Jut %
Adso~bate Diameter, A Torn Topeka Adsorbed oxygen 3.46100 -183~2.8 Oxygen 3.4673~ -18332.3 Nixon 4.3 51 24.310.4 Hz0 2.654.6 24.428.3 H20 2.S518.5 24.032.7 Exile 11 (Preparation ox FOP
Using mixing Method (c), 5.6 grams of ferrous sulfate heptahydrate tFe(SO~). 7 HO]:
16.4 grays ox aluminum isopropoxide; 11.6 grams of an 85% aqueous ortho-pho6phoric acid solution: 35 : grams of water: and 36.8 grams ox a 40% aqueous tetraethylammonium hydroxide solution (TAO) were combined to form a reaction mixture having the hollowing company in term of muter oxide ratio:
2.0 TEACH : 0.2 Foe : 0.8 AYE : POW
: 68 Sue 2G The reaction mixture way catalyzed a 200~C for 42 hours. Thy solid product way found Jo haze an Roy powder duration pattern essentially identical to that of Table S, swooper.
The species APE as referred to herein is a felloalumino~hQsphate material having a three-dimen~ional MicroPro crystal framework structure of the tetrahedral units POX, Aloe and a least one of Foe and Phase and whose essential empirical chemical composition on an an hydrous basis is:
my : (Fox Any Pi) 2 wherein "R" reprint at least on organic : tem~lating agent runt in thy intracry~talline pore system: "m" reprint the mole of "I" resent :`

D-13~864 Lo pus mole of (~exAlyP~)02 and has a value ox from zero to 0.3, , "ye and I represent respec~ivsly, the mole laxness of iron, aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C and D on the ternary diagram which is Fig. 1, or preferably within the area bounded by points a b, c, and d on the ternary diagram which i& Fig. 2, said ferroaluminophospha~0 having a characteristic Roy powder diffraction pattern which contains at least the dozing jet forth below in Table I. In the Norm as synthesized in accordance with top process ox this inve~ion, "m" has a value of from 0.02 Jo 0.3.
Table I
Elaine ____~ __ d PA) Intensity 9.4 - 9.6 ~9.21 12.8 - 12.~ guy wow 2015.9 - 16.1 5.57- 5.50 wow 20.5 - 20.7 4.~3- 4.29 m 30.5 - 30~8 2.931 - 2.903 my All ox the as-synthesized FOP compositions or which Roy powder di~fraction-data have presently been obtained have patterns which are within the ; generalized pattern ox Table XII below:
TABLE IT
I do 100 X Rio I - 9.6 g.41 - 9.21 100 30lZ.8 - lZ.9 6.92 - 6.86 11 - 20 13.8 14.2 6.42 - 6.Z~ 2 - 11 15.9 - 16.1 5.57 - 5.50 12 - 23 I`
D-13,86 -- I --TABLE XI I ( con to I d, (A 100 Rio 17.7 - lB.25.01 - 4.87 7 - 15 18.9 ~.70 0 - 2 19 . 6 4 . 53 2 (oh) 52~ . 5 - Zoo . 74 . 33 - 4 . 29 2g - 5 21.9 ~.06 0 - 1 22 . 3 - 22 . 43 . 99 3 . 97 I - 3 23.0 - 23.33.87 - 3.82 1 - 3 24 . 9 - Z5 . 53 . 58 - 3 . 493 6 - I
1025 . 8 - I . 13 . 4s3 - 3 . ~14 - 13 27 . 4 - 27 . 73 . 255 - 3 . Z20 2 28 . 0 - 28 . 63 . 1~7 - 3 . 121 Z
2g.s - 29.83.028 - 2.998 I - 3 oh) 30 . 5 - 30 . 82 . 912 - 2 . 903 13 - 20 1531.5 2.840 1 - 14 oh) 32 . 2 2 .7~0 o - 1 33 . 3 2 . 691 o -34 . 4 - 34 . 62 . 607 - 2 . 592 2 - 5 9 - 36 . 52 . 501 - 2 . 46Z 2 253~ . 5 . 338 0 - 1 38.9 2.315 o - 1 39 . 5 - 3 . 98Z . 2~1 - 2 . 265 1 - Z
42 . 7 2 . 118 0 - 1 I . 3 - 43 . I . 09~ - 2 . 0~5 3047 . 5 - 47 . ~14 - 1. 9~3 1 - 2 ,7 - Lowe - L.8~5 Z - 4 5û . - 50 . I I 1 2 51~4 1.778 2 53.~ - 53.~ 1.72~- 1-.7~9 1 - 2 355~ . 2 - ED . 1. I 75 I - 2 55.8 1.647 Q - 1 ( shy - shoulder I e en (a Using mixing Method (a), a raccoon mixture having thy composition ( in terms of molar oxide ratios of:
Kiwi o .1 Foe : o- 9 Aye P205: 60 H20 was prepared by combining 3 . 5 grams ox an hydrous D-13, 864 I

iron (II) acetate; 37.8 grams of aluminum i~oplopoxide, 23.1 gram ox 85% ox~ho-phosphoric avid, 46.6 gram of water and 57.1 grams of 25.1 %
aqueous me~hylquinuclidine (Clown). Half of the resulting gel was crystallized at 150C for 66 hour. The resulting solid product (F~P0-35) had a chemical composition of 8 16~ (Phyla 47P0 49)2 : 0.41 H20 and an X-ray odor defection pattern characterized by the hollowing data:
TABLE U
I Dow Rio 8.0* 11.05 15 8.7 lolls 13 : I 9.8* 9.03 11.0 8.04 52 11.4 7.764 (so) 13 ~.56 29 15 7 . 5.64 16.1 5.5~ 8 17.5 ~.07 70 18.0 4.9310 Shea Lowe 4.75 18 20.6~ 4.3110 oh 21.1 4.21--- 32 22.1 ~.02 10~
23.4 3.8029 (so) Jo 25.2 3.534 : 25.5* 3.493 4 26.5~ 3.3634 (so) 27.1* 3.290 33 2~.7 ~.110 39 29.4~ 3.038 I
32.0 2.9794 (so) 32.5 2.755 34 34.7 2.5~5 6 36.0 2.~95 3 3~.0 ~.36~ 3 D-13,864 I

ALIBI
I d, (A) loo Rio ___ I 1.8~ 3 49 . Ox . I so 51 . 91 . 762 3 * = line possibly attributable to an impurity ( shy = shoulder (b) The remaining half of the gel from part (a) of this Example way c~ystalli2ed for 66 hours at 200C and resulted in a FOP
eompositioA having essentially the same X-ray pattern a in Table U, swooper.
(c) A sample of F~P0-35 prepared in essentially the same manner a jet forth in part (a) above except or a crystallization period of 22B
hour, way calcined at 500C f or 2 hours in a nitrogen atomizer. The cry powder diffraction pattern of ache calcined product was characterized by the following Dick 2 0 TABLE: W
2~d9 AYE 100 X Rio . owe . 05 11 I 10.28 22 9.5~ ~.31 10. I . 12 83 Ll.4 7.76 5 (so) L2.3* 7.20 Z
13.4 6.61 59 15 . US . 61 9 16 . 0*5 . 54 3 17.~ 5.10 I
17.~ 4.9û 3 18 . 6~4 . 77 4 I . I . 70 7 D- 1 3 , 3 64 I -TABLE W (keynote pa d,tA3 100 Rio 20.9 I I
22.1 4.02 1 ~2.9 3.8~
23.4 3.~0 35 ~4.9 ~.58 28 25.4 3.506 12 26.6 3.351 16 27.1* 3.290 20 I 3.1~3 38 29.3* 3.04~ 9 31.~ 2~849 8 32.3 Z.772 37 3~.8 2.730 3 3~.3 Z.614 35.1 2.557 6 3~.0 2.495 9 : 37.8 2.380 38.3 2.350 2 39.7 2.270 2 ~0.3 2.23~ 1 ~1.2 2.191 2 42.0 2.151 5 42.~ 2.12~
I 2.023 2 : I . 1.945 - 3 47.3 1.9~2- 3 4~.6 1.~73 5 49.8 }aye 51.~ }.78~ 6 5~.7 1.650 * = line possibly attributable Jo an impurity oh = old The species FOP as rearward to herein it a ~er~oaluminopho~phate material having a the dimensional micro porous crystal framework structure ox the tetrahedral unit P02, Aye and at least one ox Foe and ; 40 Foe, and whose essential empirical chemical ' ~-13,864 I

composition on an Andre basis my: (F~XAlyP%)O2 wherein "R" reprint at least on@ organic templating agent errant in the in~racrystalline pore ~yst0m: my reprint the moles of "R" prevent per mole of (Fillips and ha a value of prom zero to 0.3, "x", "y" and "2" represent respectively, the mole fractions of iron, aluminum : and phosphorus present in the oxide moiety, said molt fractions being within the compositional area : bounded by point A, B, C and D on the ternary diagram which it Fig. 1, or preferably within the area bounded by points a, b, c and d on the ternary diagram which it Fig 2, said ferroaluminophospha~e having a char~c~eEistic g-ray powder diffraction pattern which Canaan at least the d-spacings jet forth below in Table ~III. In the form as synthesized in a~ordan~e with the process ox hi invention. "m" ha a value of from 0.02 Jo 0.3.
Table XIII
Jo Relative I d (a elm 10.9 - 11.0 8.12 - I
13.4 - 13.5 6.61 - h.56 m 17.4 - 17.5 5.10 - 5.07 8 I. 2520.9 - 21~1 4.25 - 4.21 m Jo 22.1 4.~2 TV
~8.4 - 28.7 3.143 - 3.110 m 32.3 - 32.5 2.775 - 2.77Z
All of the as-~yn~he~ized FAPV-35 compositions or which Zoo powder diffraction data have presently bee obtained have patterns which are within the generalized pattern of Table XIV below , D-13,864 I

TABLE IVY
I do 100 X Rio 8.6 - 8.7 10.28 - 1~.16 13 - 22 10.9 - 11.0 8.12 - 8.04 52 - I
11.4 7.76 0 - 5 oh) 13.~ - 13.5 6.61 - 6.56 2g - 5g 15.7 - 15.8 5.64 - 5.61 -17.4 - 1~.5 5.10 - 5.07 I - 70 17.8 - 18.0 4.98 - 4.93 3 - 10 (oh) 2~.9 - 21.1 ~.25 - 4.21 32 - 42 22.1 I 10~
22.9 3.88 0 - g AYE 3.~0 29 - 35 ash) : 2~.9 - 25.2 3.58 - 3.53 7 - 28 25.4 - 25.5 3.~6 - 3.~93 4 - 12 26.5 - 26.6 3.363 - 3.351 4 - 16 oh) 27.1 3.29~ 20 - 33 2~.4 - 28.7 3.143 - 3.110 38 - 39 29.3 - 29.4 3.0~8 - 3.034 0 - 16 :: 20 31.4 2.~9 0 - a 32.0 2.979 U - 4 32.3 - 32.5 2.772 - 2.755 34 - 37 32.8 ~.730 . 0 - 3 34.3 3~.7 2.614 - 2.585 S - 8 35~1 2.557 0 -:: 36.0 2.4g5 3 - 9 : 37.~ - 38.0 ~.380 - 2.~368 3 3~.3 2.350 0 2 ; 39.7 2.~7~ 0 - 2 I 2.23~ 0 -, 4 1 . t I . 1 9 1 O -- 2 queue 2.151 0 ` 5 ~'12 . a 2 0 - 4 ~14 . 3 2 . 02:~ 0 -- 2 I 1.9~5 0.-7 . 3 l . g 2 2 0 3 4~1 . 2 -- 41~ . 6 I. . 3}~0 -- 1 . 673 -- 5 I 9 . 0 1 . I 5 9 0 -- 4 51.~ isle await 1.761 3 - 6 go . 7 1.650 5 ;

DOW

`
;

- I _ X

A an indication ox the catalytic activity, particularly the cracking activity, of the present class of novel ferroaluminophosphates organosilicate~, certain of the FOP species were tested for n-butane cracking using a bencil-scale apparatus&. The reactor was a cylindrical quartz : tube 254 mm. in length and 10.3 mm. I.D. In each : test the reactor was loaded with particles of the test FOP which were 20-40 mesh (US. to in size and in an amount ox from 0.5 Jo 5 grams, the quantity being selected so that the conversion of n-butane was at least I and not more than 90% under the test conditions. The FOP samples had been previously calcined Jo remove organic material from the pore system, and were activated in Sue in the reactor in a slowing stream ox helium at 500C fox one hour. The feed~tock was a helium-n-butane mixture containing 2 mole percent button and was passed through the reactor at a rate of 50 cc./minute. Analyzes of the feed~tock and the reactor effluent were carried out using conventional gay chromatography techniques. The reactor effluent was analyzed after lo minute of stream operation. From the analytical data the pseudo-first-order rate constant (Kay was calculated. Pertinent data is sex forth in tabular form below.
Sample of Calcination Example No. Species Before Test Kay 3tb) FOP 600C, 3 his. 0.~5 I FAP0-ll 550, 7 his. OOZE

; D-13,864 Sample ofCalcination Example No. Species fore Test pa I ~P0-16600C, 2 his. 0.6 I FAP0-17600C, 2 his. 0.09 : 5 Lola) FAP0-34~00C, 1.25 his. 006 I've FOP compositions of the present invention are, in general, hydrophilic and adsorb water preferentially over common hydrocarbon molecules such as paraffins, ol~fins and benzenoid aromatic species e.g., Bunsen, zillions and cumin. Thus the present metal aluminophosphates as a class are uphill as desiccants in such adsorption : separation/purification processes as natural gas drying, and cracked gas drying. Water is also p~efereneially adsorbed over the occlude permanent gases such as carbon dioxide, Norwegian oxygen and hydrogen. These metal aluminophosphates are therefore suitably employed in the drying of reformer hydrogen stream and lo the drying of oxygen. nitrogen ox air prior to liquefac~lon. In this respect thy adsorptive properties of the Jo present metal alumino~hosphates appear Jo be quite similar to those of the low silica aluminosilicate zealots, despite the fact what they exhibit, at best, a mode fit io~-exchange capacity.
The present FOP compositions Allah exhibit ; novel surface selectivity characteristics which render them useful as catalyst or catalyst base in a number of hydrocarbon conversion and oxidative combustion reactions. They can be impregnated or otherwise loaded with catalytically active metals by D-13,864 .1 methods well known in the art and used for example, in fabcica~ing catalyst compositions having silica : or alumina bases. Of the general class, those species having sores larger than about I are preferred or catalytic applications.
Among the hydrocarbon conversion reactions catalyzed by FOP compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparafPin type6,iso~erization including zillion isome~ization, polymerization, reforming, Lo hydrogenation, dehydrogena~ion, transalkylation, dealkylation, hydrodecycliza~ion and dehydrocyclization.
Using FOP catalyst composition which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge jocks can be hyd~ocrasked at templates n the range ox 400~F
to 825 using molar ratios ox hydrogen to hydrocarbon in the range of between and I
pressures between 10 and 3500 pug and a liquid hourly space velocity (LH5V) of from 0.1 to 28 preferably lo to lo The APE catalyst compositions employed in hydrocracking are Allah suitable for use in reforming processes in which the hydrocarbon feed~tocks contact the catalyst at temperatures of from aback 700F to 1000F, hydrogen pressures of from lo Jo : 500 p . 8 . i . g ., LIST values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of l to 20, preferably between 4 and 12.

D-13,864 , .

These same koalas, i.e. those containing hydrogenation promoter, are also useful in hydroisomerization~ processes in which feeds tucks such as normal pureness are converted to Seward branched chain isomers. Hydroisomerization it carried out arc a temperature ox from aback 200 to 600F, preferably 30ûF to 550F with an LHSV value : of prom about 0 . 2 to 1. 0 . hydrogen it supplied to the reactor in admixture with the hydrocarbon feed sock in molar proportions (H/HC~ of between 1 ; and 5.
At somewhat higher temperatures, i.e. prom about 650F to 1000P, preferably 850F Jo 950 and usually at somewhat lower pressures within the Lange of about 15 to 50 prig the Amy catalyst compositions aye used Jo hydroisomeriz2 normal paraffin. Preferably the paraffin ~eed~tock comprises normal paraffins having a carbon number range ox C7-C2~. Contact time between the feed stock and the catalyst is generally relatively short to avoid undesirable side reactions such as olsfin polymerization and paraffin cracking. LHSV
values in the range ox 0.1 to 10, preferably 1.0 to

6.0, aye suitable.
The unique crystal ~ucture oath present FOP catalysts and their availability in a form totally void of alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic di6proportionation of Tulane, ethylene, trim ethyl benzenes, tetrame~hyl benzenes and the like. In the disproportionation prows isomerization anal transallsylation can alto : D-13,864 .

I

occur. Group VIII noble metal adjuven~s alone or in conjunction with Group VI-B metals such as tung~en, molybdenum and chromium are preferably included in the catalyst composition in amount of from about 3 to 15 weight-% of the overall composition.
Extraneous hydrogen can, but need not, be resent in the sicken zone which is maintained at a temperature of from about 400 to 750F, prosier in the range of loo to 2000 p. 8 . i . g. and L~SV values in the range ox 0.1 to 15.
Catalytic cracking processes are preferably carried out with FOP compositions using feed stock such as gas oils, heavy naphthas, disaffiliated crude oil no idea etch with gasoline being the principal desired product. Temperature conditions of 850 to 1100F, LHSV values ox 0.5 to 10 and pressure conditions of from about 0 to 50 prig aye MU i table.
Dehydrocyclization reactions employing paraEfinic hydrocarbon Ed socks preferably normal puffs hazing more than 6 carbon atom, Jo form Bunsen, zillions, Tulane and the like are carried out using essentially the save reaction conditions as for cowlick cracking. For these equines it is reflowered to use the FOP catalyst in conjunction with a Group VIII non-noble metal cation such as cobalt and nickel.
In catalytic dealkylation wherein it is desired to cleave ~ara~finic side chains from aromatic nuclei without substantially hydrogenating the lying structure, relatively high tempe~atuces in the range of about 800-1000F are employed at .

D-13,864 I to moderate hydrogen pressure of about Lowe prig other conditionfi bring similar Jo those described above for catalytic hydrocracking.
Preferred catalyst are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and ~oluene and/or zillion to Bunyan.
In catalytic hydro~ining, the primary objective is to promote the selective hydrodecomposition of organic sulfur Andre nitrogen compounds in the feed, without substantially affecting hydrocarbon molecule therein. For this purpose it it preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts ox the same general nature described in connection with dehydrocycliza~ion operations. Fee docks include gasoline fractions. kerns, jet fuel tractions, diesel fusion. light and heavy gas oil, deasphal~ed crude oil Rudy and the like any ox which may contain up to about 5 weight-percent of sulfur and up to about 3 w0ight-percent of nitrogen.
Similar condition can be employed to eject hydrofining. Leo denitrogenation and desul~urization, of hydrocarbon feed containing substantial proportion of organonitrogen and organo~ulfur compoundfi. It it generally recognized that the pliancy of substantial amounts ox such con6tituentfi markedly inhibits the activity ox catalysts ox hydrocrackinq. Consequently, it is D-13,864 I
- I -necessary to operate at more exclaim Canadian when it it desired to obtain the same degree of hydrocracking conv0~sion pew pass on a relatively nitrogenous iced than are Required with a feed containing lass orga~onitrogen compound.
Consequently, the conditions under which denitrogenation, desulfurization anger hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in view of the characteristic ox the ~eed~tocks in particular the concentration of organonitroge~
compounds in the feed~tock. As a result of the effect of organonitrogen compounds on the hydrocracking activity ox these compositions it it not at all unlikely what the conditions most suitable for deni~rogenation of a given feed~tock having a revisal high organonitrogen content with minimal hydrocracking, e.g., let Han 20 volume percent ox fresh feed per pas~,-m}ght be the same as whose preferred fox hydroc~a~king another feed stock hiving a lower concentration hydrocracking-inhibiting consents e.g., organoni~rogen compounds. Consequently, it has become the practice in this art to establish the conditions under which a certain feed it to be contacted on the basis ox preliminary screening essays with the specific catalyst and feed stock.
I~omerization reactions are carried out under conditions similar to those described above fox reforming, using somewhat move acidic catalyst. Olin are preferably immersed at temperatures of 500-900F, while paraffins D-13,~64 :
naphthene~ and alkyd aromatic are isomerized at tem~eratuLe~ of 700-1000F. Particularly desirable isomeIization reactions contemplated herein include the conversion ox Newton Andy n-octane to iso~eptanes, i60-octane~, butane to iso-bu~ane, methylcyclopentane to cyclohexane, meta-xylene and to ortho-xylene to paraxylene, l-bu~ene Jo button and/or isobutene, Nixon to isohexene, cyclohexene to methylcyclopentene etc. The preferred cation Norm it a combination of the FOP
with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metal. For alkaline and dealkylation processes the FOP composition having pores of at least PA
:; 15 are preferred. When employed for dealkyla~ion of alkyd aromatics, the temperature is usually at least 350F and range up to a temperature at which substantial cracking Ox the feed sock or conversion predate occurs, generally up to about 700F. The temperature is preferably a least 450F and not - greater than the critical temperature of the compound undergoing dealkyla~ion. Pressure Canadian are applied to retain at least the "
aromatic feed in the liquid state. For alkylation the temperature can be as low as 250F but it preferably at least 350F. In alkylation ox Bunsen, Tulane and zillion, the preferred :, alkylating agents are olefins such as ethylene and propylene Jo D-13,864 :

Claims (33)

1. Crystalline ferroaluminophosphate having a three-dimensional microporous framework structure of FeO2, AlO2 and PO2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula mR: (FexAlyPz)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 (FexAlyPz)O2 and has a value of from zero to 0.3, "x", "y and "z" represent the mole fraction of the iron, aluminum and phosphorus respectively present as tetrahedral oxides, said mole fractions being such that they are within the tetragonal compositional area defined by points A, B, C and D of the ternary diagram which is Figure 1 of the drawings.

2. Crystalline ferroaluminophosphate according to claim 1 wherein the mole fractions of iron, aluminum. and phosphorus present as tetrahedral oxides are within the tetragonal compositional area defined by the points a, b, c and d of the ternary diagram which is Figure 2 of the drawings.

3. Composition according to claim 1 wherein "m" has a value of from 0.02 to 0.3.

4. Crystalline ferroaluminophosphate 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.

5. Crystalline ferroaluminophosphate 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.

6. Crystalline ferroaluminophosphate 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.

7. Crystalline ferroaluminophosphate 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.

8. Crystalline ferroaluminophosphate 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.

9. Crystalline ferroaluminophosphate 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.

10. Crystalline ferroaluminophosphate 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.

11. Process for preparing ferroaluminophosphate which comprises providing a reaction mixture composition expressed in terms of molar oxide ratios as follows:

aR2O: (FexAlyPz)O2: bH2O
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 of greater than zero to 3; "b" has a value of from zero to 500; "x", "y" and "z" represent the mole fractions, respectively, or iron, aluminum and phosphorus in the (FexAlyPz)O2 constituent, and each has a value of at least 0.01, and being within the hexagonal compositional area defined by points E, F, G, H, I and J of the ternary diagram which is Figure 3 of the drawings.

12. Process according to claim 11 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

13. Process according to claim 11 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group of pseudo-boehmite and aluminum alkoxide.

14. Process according to Claim 13 wherein the aluminum alkoxide is aluminum isopropoxide.

15. Process according to claim 11 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.

16. Process according to claim 15 wherein the organic templating agent is an amine.

17. Process according to claim 15 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-diethylethanolamine:
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: di-n-butylamine:
neopentylamine: di-n-pentylamine; isopropylamine;
t-butylamine; ethylenediamine, pyrrolidine, 2-imidazolidone; di-n-propylamine; and a polymeric quarternary ammonium salt [(C14H32N2)]?
wherein x is a value of at least 2.

18. Crystalline ferroaluminophosphate prepared by calcining the compositions of claim 1 or claim 2 or claim 3 at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system.

19. Process for separating molecular species from admixture with molecular species having a lesser degree of polarity which comprises contacting said mixture ofmolecular species with a ferroaluminophosphate composition of claim 1 or claim 2 having pore diameter large enough to adsorb at least one of the more polar molecular species, said ferroaluminophosphate being at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof.

20. Process for separating a mixture of molecular species having different kinetic diameters which comprises contacting said mixture with a ferroaluminophosphate composition of claim 1 or claim 2 having pore diameters large enough to adsorb at least one but not all molecular species of said mixture, said ferroaluminophosphate being at least partially activated whereby at least some molecules whose kinetic diameters are sufficiently small can enter the intracrystalline pore system thereof.

21. Process according to claim 19 wherein the more polar molecular species is water.

22. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a ferroaluminophosphate of claim 1.

23. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a ferro-aluminophosphate of claim 2.

24. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is hydrocracking.

25. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is hydrogenation.

26. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is polymerization.

27. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is alkylation.

28. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is reforming.

29. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is hydrotreating.

30. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is isomerization.

31. Process according to claim 22 or claim 23 wherein the isomerization conversion process is xylene isomerization.

32. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is dehydrocyclization.

33. Process according to claim 22 or claim 23 wherein the hydrocarbon conversion process is cracking.