CA1241943A - Molecular sieve compositions - Google Patents

Abstract

MOLECULAR SIEVE COMPOSITIONS
ABSTRACT
Crystalline molecular sieves having three-dimensional microporous framework structures of MO2, AlO2, and PO2 tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MxAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the amount of "R"
present per mole of (MxAlyPz)O2: "M"
represents at least two elements capable of forming framework tetrahedral oxides, where "M" is at least one element selected from the group consisting of arsenic, beryllium, boron, chromium, iron, gallium, germanium, lithium and vanadium and at least one element selected from the group consisting of cobalt, iron, magnesium, manganese, titanium and zinc; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is disclosed.

Description

b'` - , MOLECULAR SIEVE COMPoS I T I ONS
Field of the Invention The instant invention relates to a novel class of crystalline microporous molecular sieves, to the method of their preparation and to their use as adsorbents and catalyst. The invention relates to novel molecular seives having at least four elements capable of forming framework tetrahedral oxide units. These compositions may be prepared hydrothermally from gels containing reactive compounds of aluminum and phosphorus and at least one element from each of two groups of elements, as hereinafter set forth, capable of forming a framework tetrahedral oxide, and preferably at least one organic templating agent which functions in part to determine the course of the crystallization mechanism and the structure of the crystalline product, Backaround of the Invention Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing A102 and SiO2 tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without displacing anv atoms which make up the permanent crystal structure.

D-14,208 I

- 2 - ~2~

Other crystalline microporous compositions which are not zeolitic, i.e. do not contain only A102 and SiO2 tetrahedra as essential framework constituents, but which exhibit the ion-exchange and/or adsorption characteristics of the zeolites are also known. Metal organo6ilicates which are said to possess ion-exchange properties, have uniform pores and are capable of reversibly adsorbing molecules having molecular diameters of about 6A or less, are reported in U.S. Patent No.

3,941,871 issued March 2, 1976 to Dwyer et al. 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. 4,061,724 issued December 6, 1977 to R.W. Grose et al.
A recently reported class of microporous 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 al. These materials are formed from A102 and P02 tetrahedra and have electrovalently neutral frameworks as in the case of 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, apparently due to the difference in electronegativity between aluminum and phosphoru6.
Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.

D-14,208 -.. ..

In commonly assigned Canadian Patent No.
1,202,016 issued on March 18, 1986, there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensional crystal framework of PO2, AlO2 and SiO2 tetrahedral units and, exclusive of any alkali metal or calcium which may optionally be present, an as-synthesized empirical chemical composition on an anhydrous basis of:
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, 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 silicoaluminophosphate species involved; and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.
In copending and commonly assigned Canadian application Serial No. 450,658, filed March 28, 1984 there is described a novel class of titanium-D-14,208-C

- 4 - 3 containing molecular sieves whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:
mR:(TixAlypz)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 (TiXAlyPz)O2 and has a value of between zero and about 5.0; and "x", "y" and "z"
represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.
In copending and commonly assigned Canadian application Serial No. 458,495, filed July 10, 1984, there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of MO2, AlO2 and PO2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR:(MxAlyPz)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 (MXAlyPz)O2 and has a value of from zero to 0.3; "M" represents at least one metal of the group magnesium, manganese, zinc and cobalt;
"x", "y" and "z" represent the mole fraction of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.
In copending and commonly assigned Canadian application Serial No. 458,914, filed July 13, 1984, D-14,208-C

~L2~

there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO2, A102 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)02 and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fraction of the iron, aluminum and phosphorous, respectively, present as tetrahedral oxides.
The instant invention relates to new molecular sieve compositions comprising at least two elements in the form of "M02n" tetrahedral units, as hereinafter discussed, capable of forming framework tetrahedral oxide units with AlO2 and P02 tetrahedral oxide units.
Description of the Fiaures FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.
PIG. 2 i8 a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.
FIG. 3 is a ternary diagram wherein earameters relating to the reaction mixtures employed ln the preparation of the compositions of this invention are set forth as mole fractions.

D-14,208 .
, . : . - .

3~

Summarv of the Invention The instant invention relates to a new class of crystalline molecular sieves in which at least two elements capable of forming three-d.imensional microporous framework form crystal framework structures of A102, P02+ and M02n tetrahedral oxide units wherein "MOn2"
represents at least two different elements present as tetrahedral units "M02n" with charge "no where "n" may be -3, -2, -1. 0 or +1. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and accordingly find wide use as adsorbents and catalysts. The members of this novel clas6 of compositions have crystal framework structures of A102, P02 and M02n tetrahedral units and have an empirical chemical composition on an anhydrous basis e,xpressed by the formula:
mR : (MXAlyPz)02 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R"
present per mole of (MXAlyPz)02; ~M~
represents at least two elements capable of forming framework tetrahedral oxides; and "x", "y" and "z represent the mole tractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxide. "M" is at least two different elements tMl and M2) such that the molecular sieves contain at least two framework tetrahedral unit6 in addition to A102 and P0+2. "M" is at least one element selected from the group consisting of D-19,208 arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium and is at least one element selected from the group consisting of cobalt, iron, magnesium, manganese, titanium and zinc.
The molecular sieves of the instant invention will be generally referred to herein by the acronym or "ELAP0" to designate elements "M" in a framework of A102, PO2+ and MOn2 tetrahedral units. Actual class member will be identified by replacing the "EL" of the acronym with the elements present as MO2n tetrahedral units.
Eor example, "MgBeAPO" designates a molecular sieve comprised of A102, P02, Mgo2 BeO2 tetrahedral units. To identify various structural species which make up each of the subgeneric classes, each species is assigned a number and is identified as "ELAPO-i" wherein "i" is an integer. The given species designation is not intended to denote a similarity in structure to any other species denominated by a similar identification system.
Detailed DescriPtion of the Invention The instant invention relates to a new cla6s of molecular sieves in which at least two elements capable of forming framework tetrahedral oxides are provided to form crystal framework structures of AlO2, PO2 and MOn2 tetrahedral wherein "M" represents at least two elements capable of forming tetrahedral units "MlO2n" and "M202n" where "Ml" and "M2" are two different elements, where "n" is -3, -2, -1, 0 or ll D-14,20~

and where "Ml" is at least one element selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium and "M2" is at least one element seIected from the group conæisting of cobalt, iron, magnesium, manganese, titanium and zinc. These new molecular sieve6 exhibit ion-exchange, adsorption and catalytic properties and accordingly find wide use a6 adsorbents and catalysts.
The members of this novel class of compositions have crystalline three-dimensional microporous framework structures of A102, P0+2 and M02n tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : ~MXAlyPz)02;
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system: "m" represents the molar amount of ~'R~' present per mole of (MXAlyPz)02 and has a value of zero to about 0.3; "M" represents at least two elements capable of forming framework tetrahedral oxides where "M" i6 at least one element selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and at least one element selected from the group consisting of cobalt, iron, magnesium, manganese, titanium, and zinc.
The relative amounts of elements "M", aluminum and phosphorus are expressed by the empirical chemical formula (anhydrous):
mR : (MXAlyPz)02 D-14,208 . .

3~3 where ~Ix~ y~l and ~zl~ represent the mole fractions of said "M", aluminum and phosphorus. The individual mole fractions of each "My (Ml, M2, M3, etc.) may be represented by "xl'l, "x2l~, "X3", etc. wherein "xl", "x2", and "X3", and etc. represent the individual mole fractions of elements Ml, M2, M3, and etc. for "My as above defined. The value of "xl", "x2", "X3", etc, are as defined for "x", hereinafter, where "xln~"x2"+"x3"...="x" and where xl, x2, X3, etc. are each at least 0,01, The molecular sieves of the instant invention have crystalline three-dimensional microporous framework 6tructures of MOn2, A102 and P0+2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR (MxAlypz)o2 wherein "R" represents at least one organic templating agent pre6ent in the intracrystalline pore system: "m" represents a molar amount of "R"
present per mole of (MXAlyPz)02 and has a value of zero to about 0.3: "M" represents at least two different elements capable of forming framework tetrahedral oxides, as hereinbefore defined, and "x", "y" and "z" represent the mole fraction& of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides; said mole fractions "x", "y"
and "z" being generally defined as within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram which is FIG. 1 of the drawings. The points A, B, C, D and E

D-14,208 . i .
i represent the following values for ~Ix~, llyll, and "z":
Mole Fraction Point x Y z A 0.02 0.60 0.38 B 0.02 0.38 0.60 C 0.39 0.01 0.60 D 0.98 0.01 0.01 E 0.39 0.60 0.01 In a prèferred sub-class of the ELAPOs of this invention, the values of "x", "y" and "z" in the formula above are within the hexagonal compositional area defined by the points a, b, c, d, e and f of the ternary diagram which is FIG. 2 of the drawings, the said points a, b, c, d, e and f representing the following values for "x", "y" and "z":
Mole Fraction Point x Y z a 0.02 0.60 0.38 b 0.02 0.38 0.60 c 0.39 0.01 0.60 d 0.60 0.01 0.39 e 0.60 0.39 0.01 f 0.39 0.60 0.01 The ELAPOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.
LAP0 compositions are generally synthesized by hydrothermal crystallization from a D-14,208 reaction mixture containing reactive sources of the elements "M", aluminum and phosphorus, preferably an organic templating. i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture i8 generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such ag polytetrafluoroethylene and heated, preferably under autogenous presgure at a temperature between 50C and 250C, and preferably between 100C and 200C until crystals of the ELAP0 product are obtained, ugually a period of from several hours to several weeps. Typical crystallization times are from about 2 hours to about 30 days with from about 2 hours to about 20 days being generally employed to obtain cry6tals of the ELAP0 products. The product ,iB recovered by any convenient method such as centrifugation or filtration.
In synthe6izing the ELAP0 compositions of the instant invention, it ig preferred to employ a reaction mixture composition expressed in terms of the molar ratios ag followg:
aR : ~MXAlyPz)02 : bH20 wherein "R" is an organic templating agent; "a" is the amount of organic templating agent ~'R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (01 to about 6; "b" has a value of from zero (0) to about 500, preferably between about 2 and 300: "M" represents at least two elements, ag above aescribed, capable of forming tetrahedral oxide D-14,208 , , framework units, MO2n, with A102 and P02+ tetrahedral units; "n" has a value of -3, -2, -1, 0 or +1; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, "y" and "z" each have a value of a least 0.01 and "x" has a value of at least .02 with each element "M" having a mole fraction of at least 0.01. The mole fractions "x", "y" and "z" are preferably within the pentagonal compositional areas defined by points F, G, H, I, and J which is shown in PIG. 3 of the drawing6, said pointC F, G, H, I, and J representing the following values for "x", "y"
and "z":
Mole Fraction Point x v z F 0.02 0.60 0.38 G 0.02 0.38 0.60 H 0.39 0.01 0.60 I 0.98 0.01 0.01 J 0.39 0.60 0.01 In the foregoing expression of the reaction composition, the reactants are normalized with respect to a total of (M + Al + P) - (x + y + z) =
1.00 mole, whereas in many of the working examples appearing hereinafter the reaction mixtures are expressed in term of molar oxide ratios and may be normalized to 1,00 mole of P205. This latter form i5 readily converted to the former form by routine calculations by dividing the total number of mole6 of "M", aluminum and phosphoru6 into the moles of each of "M", aluminum ad phosphoru6. The moles of template and water are similarly normalized by D-14,208 ~L2~

dividing the total moles of "M", aluminum and phosphorus.
In forming the reaction mixture from which the instant molecular sieves are formed the organic templating agent can be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, pho6phorus, arsenic and antimony, preferably nitrogen or pho6phorus and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms.
Particularly preferred compounds for use as templating agents are the amines, quaternary phosphonium compound6 and quaternary ammonium compounds, the latter two being represented generally by the formula R4~ wherein "X" i8 nitrogen or pho6phorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
Polymeric quaternary ammonium salts such as ~(C14H32N2) (OH) 2]x wherein "x" has a value of at lea6t 2 are also suitably employed. The mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents can either produce mixtures of the de6ired LLAPOs or the more 6trongly directing templating species may control the course of the reaction with the other templating species serving primarily to establi6h the pH conditions of the reaction gel.

D-14,208 Representative templating agents include tetramethylammonium, tetraethylammonium, tetrapropylammonium or tetrabutylammonium ions:
tetrapentylammonium ion; di-n-propylam,ne;
tripropylamine; triethylamine; triethanolamine;
piperidine; cyclohexylamine; 2-methylpyridine;
N,N-dimethylbenzylamine; N,N-dimethylethanolamine;
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:
di-n-butylamine, neopentylamine; di-n-pentylamine:
i~opropylamine; t-butylamine; ethylenediamine;
pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every species of ELAPO, i.e., a jingle templating agent can, with proper manipulation of the reaction condition, direct the formation of several ELAPO
compositions, and a given ELAPO composition can be produced using several different templating agents.
The most suitable pho6phorus source yet found for the present process is phosphoric acid, but organic phosphates such as triethyl phosphate may be sati6factory, and 60 also may crystalline or amorphous aluminophosphates such a6 the AlP04 composition of U,S.P. 4,310,440. Organo-pho~phorus compounds, such as tetrabutylphosphonium bromide, do not apparently serve as reactive sources of pho6phoru~, but these compounds may function as templating agents. Conventional phosphorus salts D-14,208 such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferred.
The preferred aluminum source is either an aluminum alkoxide, 6uch as aluminum isoproproxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of pho6phorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthe6i6, such as gibb6ite, sodium aluminate and aluminum trichloride, can be employed but are not preferred.
The elements "Ml' can be introduced into the reaction 6y6tem in any form which permits the formation in situ of reactive form of the element, i.e,, reactive to form the framework tetrahedral oxide unit of the element. The organic and inorganic salts, of "M" such a6 oxides, alkoxides, hydroxide6, halide6 and carboxylates, may be employed including the chloride6, bromides, iodides, nitrates, 6ulfates, acetates, formate6, ethoxides, propoxides and the like.
While not e6sential to the synthesis of ELAPO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the ELAPO species to be produced or a topologically similar specie6, guch as aluminophosphate, alumino-silicate or molecular sieve compositions, facilitate6 the crystallization procedure.
After crystallization the ELAPO product may be isolated and advantageou61y washed with water and D-14,208 dried in air. The as-synthesized ELAP0 generally contains within its internal poLe system at least one form of the templating agent employed in 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 zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular ELAP0 species. As a general rule the templating agent, and hence the occluded organic species, i6 too large to move freely through the pore system of the ELAP0 product and must be removed by calcining the ELAP0 at temperatures of 200C to 700C to thermally degrade the organic species. In a few instances the pores of the ELAP0 product are 6ufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures such as carried out in the case of zeolites. It will be understood that the term ~as-synthesized" as used herein does not include the condition of the ELAP0 phase wherein the organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystalli2ation process has been reduced by post-synthe6is treatment 6uch that the value of "m"
in the composition formula mR : ~MXAlyPz)02 ha a value of less than 0.02. The other symbols of D-14,20~

the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the source of element "M", aluminum or phosphorus, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol paeticipates 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 is present in the as-synthesized ELAP0 material.
Since the present ELAP0 compositions are formed from M02n, A102, and P02 tetrahedral oxide Units which, respectively, have a net charge of "n", (where "m" may be -3, -2, -1, 0 or +1), -1 and +1, the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular 6ieves in which, ideally, there is a stoichiometric relationship between A102 tetrahedra and charge-balancing cations. In the instant compositions, an A102 tetrahedron can be balanced electrically either by association with a P0+2 tetrabedron or a simple cation such as an alkali metal cation, a proton (H ), a cation of "M" present in the reaction mixture, or an organic cation derived from the templating agent. Similarly an M02n tetrahedron, where "n" is negative, can be balanced electrically by association with P0+2 tetrahedra, a cation of "M" present in the reaction mixture, organic cations derived from the templating agent, a simple cation such as an alkali metal cation, or other divalent or polyvalent metal D-14,20~

cation, a proton (H'), anions or cations introduced from an extraneous source. It has also been postulated tbat non-adjacent A102 and P02 tetrahedral pairs can be balanced by Na+
and OH re6pectively tFlanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, DC
(1971)]
The ELAPO compo6ition6 of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have pore diameters which are inherent in the lattice 6tructure of each 6pecie6 and which are at lea6t about 3A in diameter. Ion exchange of ELAPO
compositions is ordinarily po6sible only after the organic moiety derived from the template, pre6ent as a result of synthesis, ha6 been removed from the pore system. Dehydration to remove water pre6ent in the as-synthesized ELAPO compo6itions can usually be accomplished, to some degree at lea6t, in the usual manner without removal of the organic moiety, but the absence of the organic 6pecies greatly facilitate6 aa60rption and de60rption procedures.
The ELAPO material6 have variou6 degrees of hydrothermal and thermal 6tability, some being quite remarkable in thi6 regard, and function well a6 molecular 6ieve ad60rbent6 and hydrocarbon cohver6ion catalyst6 or catalyst base6.
In preparing the ELAPO compo6ition6, it i6 preferred to u6e a 6tainle66 6teel reaction ve6sel utilized lined with an inert pla6tic material, polytetrafluoroethylene, to avoid contamination of D-14,208 ~L2~il9~3 the reaction mixture. In general, the final reaction mixture from which each ELAP0 composition is crystallized is prepared by forming mixtures of less than all of the reagents and thereafter incorporating into these mixtures additional reagents either singly or in the form of other intermediate mixtures of two or more reagents. In some instances the reagents admixed retain their identity in the intermediate mixture and in other cases 60me or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Further, unless otherwi6e specified, each intermediate mixture as well as the final reaction mixture was 6tirred until 6ubstantially homogeneous.
X-ray patterns of products are obtained by Ray analy6ig, using either: 1) copper K-alpha radiation with Siemens Type K-805 X-ray sources with two computer interfaced Siemens D-500 X-ray powder diffractometers, available from Siemens Corporation, Cherry Hill, N.J.; or 2) 6tandard X-ray powder diffraction techniques. When the standard technique is employed the radiation source is a high-intensity, copper target, %-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator it 6uitably recorded by an X-ray spectrometer scintillation counter, pul6e height analyzer and strip chart recorder. X-ray patterns are obtained using flat compre6sed powder samples which are 6canned at 2 (2 theta) per minute, u6ing a two second time con6tant.
A

D-14,208 ., .~ .

All interplanar spacings Ed) in Angstrom units are obtained from the position of the diffraction peaks expressed as 2e where e is the Bragg angle as observed on the strip chart.
Inten6ities are determined from the heights of diffraction peaks after subtracting background, "Ioll being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.
As will be understood by those skilled in the art the determination of the parameter 2 theta i6 sub3ect 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 the reported vaiues of the d-spacings, which are calculated from the 2 theta values. This impreci6ion is general throughout the art and is not sufficient to preclude the differentiation of the present cry6talline material6 from each other and from the compositions of the prior art. In some of the %-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, 8, m, w and vw which represent very strong, 6trong, medium, weak and very weak, respectively.
In ceetain instances the purity of a synthe6ized product may be assessed with reference to its Ray powder diffraction pattern. Thus, for example, if a 6ample may be stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline D-14,208 - 21 - ~2~ 3 impurities, not that there are no amorphous materials present.
The molecular sieves of the instant invention may be characterized by their x-ray powder diffraction patterns and such may have one of the x-ray patterns set forth in the following Tables A
through V, wherein said x-ray patterns are for both the as-synthesized and calcined forms unless otherwise noted:
TABLE A (ELAP0-51 2~ d(Al Relative IntensitY
7.3 - 7.65 12.1 - 11.56 m - vs 19.5 - 19.95 4.55 - 4.46 m - s 20.9 - 21.3 4.25 - 4.17 m - vs 22.2 - 22.6 4.00 - 3.93 w - V6 25.7 - 26.15 3.47 - 3.40 w - m TABLE B (ELAP0-111 2~ d(A) Relative IntensitY
9.3 - 9.65 9.51 - 9.17 m - s 20.2 - 20.6 4.40 - 4.31 m - s 20.9 - 21.3 4.25 - 4.17 s - vs 22.0 - 22.5 4.04 - 3.95 m - s 22.5 - 22.9 3.95 - 3.92 m - s 23.0 - 23.4 3.87 - 3.80 m - vs TABLE C (ELAPO-14) 2~ d(Al Relative Intensitv 8.6 - 8.9 10.3 - 9.93 v6 13.0 6.81 w 21.9 - 22.2 4.06 - 4.00 w 25.4 3.51 w 27.5 3.24 w 29.7 3.01 w D-14,208 :............... .
, - TABLE D (ELAPO-16) 2~ d(Al Relative IntensitY
11.3 - 11.6 7.83 - 7.63 m - vs 18.7 - 18.9 4.75 - 4.70 w -21.9 - 22.3 4.06 - 3,99 m - vs 26.5 - 27.0 3.363 - 3.302 w - m 29.7 - 30.05 3.008 - 2.974 w - m TABLE E (ELAPO-17) 2~ d(A) Relative Intensity 7.7 - 7.75 11.5 - 11.4 vs 13.4 6.61 s - vs 15.5 - 15.55 5.72 - 5.70 s 19.65 - 19.7 4.52 - 4.51 w - s 20.5 - 20.6 4.33 - 4.31 vs 31.8 - 32.00 2.812 - 2.797 w - s TABLE F (ELAP0-18) 2~ d(A~ _elative IntensitY
9.6 - 9.65 9.21 - 9.16 vs 15.5 - 15.55 5.72 - 5.70 m 16.9 - 17.1 5.25 - 5.19 m 20.15 - 20.25 4.41 - 4.39 m 20.95 - 21.05 4.24 - 4.22 m 31.8 - 32.5 2.814 - 2.755 m TABLE G (ELAPO-20) Z~ d(A) Relative Intensitv 13.7 - 14.25 6.46 - 6.22 m - vs 19.55 - 20.0 4.54 - 4.44 w - s 24.05 - 24.5 3.70 - 3.63 m - vs 34.3 - 35.0 2.614 - 2.564 vw - w 42.5 - 43.0 2.127 - 2.103 vw - w D-14,208 _ 23 -TABLE H tELAP0-31) 2~ dtA) Relative Intensity 8.5 - 8.6 10.40 - 10.28 m - s 20.2 - 20.3 4.40 - 4.37 m 21.9 - 22.1 4.06 - 4.02 w - m 22.6 - 22.7 3.93 - 3.92 vs 31.7 - 31.8 2.823 - 2.814 w - m TABLE J* (ELAP0-33~
2~ d(A) Relative IntensitY
9.25 - 9.55 9.56 - 9.26 w - m 12.5 - 12.9 7.08 - 6.86 vs 16.9 - 17.3 5.25 - 5.13 w - m 20.45 - 20.9 4.34 - 4.25 w - m Z3.85 - 24.25 3.73 - 3.67 w - m 26.05 - 26.35 3.42 - 3.38 w - m 27.3 - 27.6 3.27 - 3.23 vs * as-synthesized form TABLE K* (ELAP0-33) 2~ d(A) Relative Intensitv 13.15 - 13.4 6.73 - 6.61 vs la.05 - 18.35 4.91 - 4.83 m 18.4 - 18.6 4.82 - 4.77 m 26.55 - 26.7 3.36 - 3.34 m 32.0 - 32.1 2.80 - 2.79 m * calcined form TABLE L (ELAP0-34) 2~ d(A) Relative Intensitv 9.4 - 9.65 9.41 - 9.17 6 - VS
15.9 - 16.2 5.57 - 5.47 w - m 17.85 - lB.4 4.97 - 4.82 w - 8 20.3 - 20.9 4.37 - 4.25 m - vs 24.95 - 25.4 3.57 - 3.51 vw - s 30.3 - 30.8 2.95 - 2.90 w - 8 D-14,208 - 2g -TABLE M 5ELAPO-35) 2~ d(A) Relative Intensitv 10.8 - 11.1 8.19 - 7.97 m 17.2 - 17.4 5.16 - 5.10 s - vs 21.0 - 21.25 4.23 - 4.18 m - s 21.8 - 22.0 4.08 - 4.04 vs 31.8 - 32.2 2.814 - 2.788 m TABLE N ELAP0-36) 25~ d(A) Relative Intensitv 7.7 - 7.9 11.5 - 11.2 vs 16.2 - 16.6 5.47 - 5.34 w - m 18.9 - 19. 3 4.70 - 4.60 m - s 20.6 - 20.8 4.31 - 4.27 w - s 21.8 - 22.0 4.08 - 4.04 m 22.2 - 22.5 4.00 - 3.95 w - m TABLE 0 (ELAP0-37) 2~ d(A) Relative IntensitY
6.1 - 6.3 14.49 - 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 TABLE P ~LAPO-39 L
2~ d(A) Relative Intensitv 9.4 - 9.6 9.41 - 9.21 w - m 13.3 - 13.6 6.66 - 6.51 m - vs 18 0 - 18.4 4.93 - 4.82 m 21 2 - 21.5 4.19 - 4.13 m - s 22.5 - 23.0 3.95 - 3.87 8 - V8 30.2 - 30.5 2.96 - 2.93 w - m D-14,208 9~3 .

TABLE 0 (ELAP0-40~
2~ d(A! Relative Intensitv 7.5 - 7.7 11.79 - 11.48 vw - m 8.0 - 8.1 11.05 - 10.94 8 - VS
12.4 - 12.5 7.14 - 7.08 w - vs 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 - 3.187 w - m TABLE R (ELAP0-41) 2~ dual Relative IntensitY
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 - 3.9g m - 8 22.8 - 23.0 3.90 - 3.86 m 23.1 - 23.4 3.82 - 3.80 w - m 25.5 - 25.9 3.493 - 3.440 - m TABLE S (ELAP0-42~
2~ d(A) Relative Intensitv 7.15 - 7.4 12.36 - ll.9S m - vs 12.5 - 12.7 7.08 - 6.97 m - 8 21.?5 - 21.9 4.09 - 4.06 m - 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 TABLE T (ELAP0-44) 2~ d(Al Relative Inten~itv 9.4 - 9.55 9.41 - 9.26 V8 13.0 - 13.1 6.81 - 6.76 w - m 16.0 - 16.2 5.54 - 5.47 w - m 20.6 - 20.85 4.31 - 4.26 8 - VS
24.3 - 24.4 3.66 - 3.65 w - V8 30.7 - 30.95 2.912 - 2.889 w - s D-14,208 TABLE U ~ELAP0-46) 2~ d(A) Relative Inten6itv 7.2 - 8.1 12.3 - 10.9 vs 21.2 - 21.8 4.19 - 4.0~ w - m 22.5 - 23.0 3.95 - 3.87 vw - m 26.6 - 27.2 3.3~1 - 3.278 vw - w 28.5 - 29.0 3.132 - 3.079 vw - w TABLE V (ELAP0-47) 2~ d~A) Relative Intensitv 9.4 9.41 V8 15.9 - 16.0 5.57 - 5.54 w - m 20.5 - 20.6 4.33 - 4.31 8 24.5 - 24.7 3.63 - 3.60 w 25.8 - 25.9 3.45 - 3.44 w 30.4 - 30.5 2.940 - 2.931 w The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:
Example 1 tPreparation of BeMgAP0-5) a) BeMgAP0-5 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
1.0-2.0 TPA : 0.05-0.2 (M)20q : 0.5-1.0 A123 0.5-1.0 P205 40-100 H20 where "TPA" denotes tripropylamine and "9" denotes the oxidation state of "M" tberyllium and magnesium).
The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time until crystals D-14,208 .

of the BeMgAP0-5 product are obtained. Solids are recovered by filtration, washed with water and dried in air at room temperature.
The BeMgAP0-5 product's chemical analysis shows the BeMgAP0-5 product contains beryllium, magnesium, aluminum and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D, and E of PIG. 1.
The x-ray powder diffraction pattern of an BeMgAP0-5 product is characterized by the following data:
2~ d(A) Relative Intensitv 7.3 - 7.6512.1 - 11.56 m - vs 19.5 - 19.954.55 - 4.46 m - s 20.g - 21.34.25 - 4.17 m - vs 22.2 - 22.64.00 - 3.93 w - vs 25.7 - 26.153.47 - 3.40 w - m b) The x-ray powder diffraction pattern for a calcined BeMgAP0-5 is also characterized by the X-ray pattern of part a).
c) When the calcined BeMgAP0-5 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350C in vacuum. The following data are used in the adsorption studies:
KineticPressure Wt. %
Adsorbate Diameter (A) (Torr) -183 Adsorbed 0 3.46 750 -183 10 Neopentane 6.2 700 24 4 H20 2.65 4.3 24 4 H20 2.65 20.0 24 12 *typical amount adsorbed D-14,208 The pore diameter of 9eMgAP0-5 is greater than 6.2 A.
Example 2 (Preparation of CrMgAP0-11) a) CrMgAP0-11 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
1.0-2.0 DPA : 0.05-0.2 (M)20q : 0.5-1.0 AlzO3 0-5-1-0 P2O5 40-100 H2O

where "DPA~ denotes di-n-propylamine and g denotes the oxidation state of "M" (chromium and magnesium).
The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time until crystals of the CrMgAP0-11 product are obtained. Solids are then recovered by filtration, washed with water and dried in air at room temperature.
The CrMgAP0-11 product's chemical analysis show6 the CrMgAP0-11 product contains chromium, magnesium, aluminum and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D, and E of YIG. 1.
The x-ray powder diffraction pattern of an CrMgAP0-11 product is characterized by the following data:
2~ dual Relative Intensitv 9.3 - 9.659.51 - 9.17 m - s 20.2 - 20.64.40 - 4.31 m - s 20.9 - 21.34.25 - 4.17 s - vs 22.0 - 22.54.04 - 3.95 m - z 22.5 - 22.93.95 - 3.92 m - s 23.0 - 23.43.87 - 3.80 m - vs D-14,208 l;3 b) The x-ray powder diffraction pattern for a calcined CrMgAP0-11 is also characterized by the X-ray pattern of part a).
c) When the calcined CrMgAP0-11 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350C in vacuum, The following data are used in the adsorption studies:
KineticPressure Wt. %
Adsorbate Diameter (A) (Torr) Temp, oc Adsorbed*
2 3.46 100 -183 5 2 3.46 750 -183 6 Cyclohexane 6.0 90 24 4 H20 2.65 4.3 24 6 H20 2.65 20 24 8 -typical amount adsorbed The pore diameter of CrMgAP0-11 is about 6A.
ExamPle 3 (Preparation of MgCoVAP0-17) a) MgCoVAP0-17 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
1.0-2.0 QN : 0.05-0.2 ~M)2q : 0.5-1.0 where "Q~" denotes guinuclidine and llqll denotes the oxidation state of ~M~ tmagnesium, cobalt and vanadium).

D-14,208 The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure ves6el and heating it at an effective temperature and for an effective time until crystals of the MgCoVAPO-17 product are obtained. Solids are then recovered by filtration, washed with water and dried in air at room temperature.
The MgCoVAPO-17 product' B chemical analysis shows the MgCoVAP0-17 product contains magnesium, cobalt, vanadium, aluminum and pho6phorus in amounts within the pentagonal compositional area defined by points A, B, C, D, and E of PIG. 1.
The x-ray powder diffraction pattern of an MgCoVAP0-17 product is characterized by the following data:
2~ dtA~ Relative Intensitv 7.7 - 7,75 11.5 - 11.4 vs 13.4 6.61 8 - vs 15.5 - 15.55 5.72 - 5.70 8 19.65 - 19.7 4.52 - 4.51 w - s 20.5 - 20.6 4.33 - 4.31 vs 31,8 - 32.00 2.812 - 2.797 w - B
b) The x-ray powder diffraction pattern for a calcined MgCoVAP0-17 is also characterized by the X-ray pattern of part a).
c) When the calcined MgCoVAP0-17 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatu6 the measurements are made on a sample after activation at 350C in vacuum. The following data are used in the adsorption studies:

D-14,208 Kinetic Pressure We. %
Adsorbate Diameter (A) (Torr) Temp, C Adsorbed*
2 3.46 100 -183 10 2 3.46 750 -183 12 n-butane 4.3 loo 24 4 H20 2.65 4.3 24 13 H20 2.65 20 24 14 typical amount adsorbed The pore diameter of Mg~oVAP0-17 is about 4.3 A.
ExamPle 4 (Preparation of FeAsAP0-31) a) FeAsAP0-31 is prepared from a reaction mixturs having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture. of:
1.0-2.0 DPA : 0.05-0.2 (M~20q : 0.5-1.0 wherein ~DPA: denotes di-n-propylamine and llq' denotes the oxidation state of "M" (iron and arsenic).
The reaction mixture is seeded with cry6tals of AlP04-31 (U.S. Patent No. 4,310,440) and digested by placing the reaction mixture in a 6ealed stainles6 steel pressure vessel and heating it at an effective temperature and for an effective time until crystal6 of the FeAsAP0-31 product are obtained. Solids are then recovered by filtration.
washed with water and dried in air at room temperature.

D-14,208 The FeAsAPO-31 product's chemical analysis shows the FeAsAPO-31 product contains iron, arsenic, aluminum and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1.
The x-ray powder diffraction pattern of an FeAsAP0-31 product is characterized by the following data:
29 d(A~ Relative Intensitv 8.5 - 8.610.40 - 10.28 m - s 20.2 - 20.3 4.40 - 4.37 m 21.9 - 22.1 4.06 - 4.02 w - m 22,6 - 22.7 3.93 - 3.92 vs 31,7 - 31.8 2.823 - 2.814 w - m b) The x-ray powder diffraction pattern for a calcined FeAsAPO-31 is also characterized by the X-ray pattern of part a).
c) When the calcined FeAsAP0-31 of part (b) i6 utilized in adsorption capacity 6tudies using a standard McBain-Bakr gravimetric adsorption apparatu6 the measurement6 are made on a sample after activation at 350C in vacuum. The following data are used in the adsorption studies:
Kinetic Pressure Wt. %
Adsorbate Diameter (A) (Torr) em C Adsorbed*
2 3.46 100 -1~3 4 2 3.46 750 -183 6 Cyclohexane 6.0 90 24 3 Neopentane 6.2 700 24 3 H20 2.65 4.3 24 3 ~2 2.65 20 24 10 * typical amount adsorbed D-14,208 ~2 l The pore diameter of FeAsAPO-31 is greater than about 6.2 A.
Example 5 preparation of GeMgAPO-34) a) GeMgAPO-34 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
1.0-2.0 TEAOH : 0.05-0.2 (M)20q :
0 5-1 0 Al O : 0.5-1.0 P205 : 40-100 H2O
where "TEAOH" denotes tetraethylammonium hydroxide and "q" denote6 the oxidation 6tate of "M"
(germanium and magnesium The reaction mixture i6 dige6ted by placing the reaction mixture in a 6ealed 6tainle6s 6teel pres6ure ve6sel and heating it at an effective temperature and for an effective time until crystals of the GeMgAPO-34 product are obtained. The 601ids are recovered by filtration, washed with water and dried in air at room temperature.
The GeMgAPO-34 product 18 chemical analysis 6hows the GeMgAPO-34 product contains germanium, magne6ium, aluminum and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D, and F of FIG. 1.
The x-ray powder diffraction pattern of a GeMgAPO-34 product i6 characterized by the following data:
2~ d(A~ Relative Intensity 9.4 - 9.659.41 - 9.17 8 - Y
lS.9 - 16.25.57 - 5.47 vw - m 17,85 - 18.44.97 - 4.82 w - 8 20.3 - 20.94.37 - 4.25 m - V8 24,95 - 25.43.57 - 3.51 vw - 8 30.3 - 30.82.95 - 2.90 w - 8 D-14,208 b) The x-ray powder diffraction pattern for a cal~ined GeMgAPO-34 is also characterized by the X-ray pattern of part a).
c) When the calcined GeMgAPO-34 of part ~b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350C in vacuum. The following data are used in the adsorption studies:
Kinetic Pressure Wt. %
Adsorbate Diameter (A) Torn Tom C Adsorbed*
2 3.46 100 -183 13 2 3.46 750 -183 18 n-hexane 4.3 100 24 6 H20 2.65 4.3 24 15 H2O 2.65 20 24 21 *typical amount adsorbed The pore diameter of GeMgAPO-34 is about 4.3A.
Example 6 (Preparation of GeMgCoAPO-44) a) GeMgCoAPO-44 may be prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
1.0-2.0 CHA : 0.05-0.2 (M)20q : 0.5-1.0 A1203 0-5-1-0 P205 40-100 ~2 where "CHA" denotes cyclohexylamine and "q" denotes the oxidation state of "My (germanium, cobalt and magnesium).
The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel D-14,208 .

pressure vessel and heating it at an effective temperature and for an effective time until crystals of the GeMgCoAP0-44 product are obtained. Solids are then recovered by filtration, washed with water and dried in air at room temperature.
The GeMgCoAP0-44 product's chemical analysis shows the GeMgCoAPO-44 product contains germanium, magnesium, cobalt, aluminum and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D, and E of PIG. 1.
The x-ray powder diffraction pattern of an GeMgCoAP0-44 product i5 characterized by the following data:
2~ d~A~ Relative Intensitv 9.4 - 9.55 9.41 - 9.26 V5 13.0 - 13.1 6.81 - 6.76 w - m 16.0 - 16.2 5.54 - 5.47 w - m 20,6 - 20,85 4.31 - 4.26 s - vs 24.3 - 24.4 3.66 - 3.65 w - vs 30.7 - 30.95 2.912 - 2.889 w - 6 b) When the calcined GeMgCoAP0-44 i6 utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350C in vacuum. The following data are used in the adsorption studies:
KineticPressure Wt. S
Adsorbate Diameter (A) (Torr) TemP, C Adsorbed*
2 3.46 100 -183 13 2 3,46 750 -183 16 n-hexane 4.3 100 24 2 H20 2.65 4.3 24 15 H20 2.65 20 24 17 *typical amount adsorbed D-14,208 3'~3 The pore diameter of GeMgCoAPO-44 is about 4.3 A.
PROCESS APPLICAT I ONS
The ELAPO compositions of the present invention are, in qeneral, hydrophilic and adsorb water preferentially over common hydrocarbon molecules such as paraffins, olefir.s and aromatic species, e.g., benzene, xylenes and cumene. Thus, the present ELAPO compositions as a class are useful as desiccants in such adsorption separation/purification processes as natural gas drying, cracked gas drying. Water is also preferentially adsorbed over the so-called permanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen. These ELAPOs are therefore suitably employed in the drying of reformer hydrogen streams and in the drying of oxygen, nitrogen or air prior to llquifaction.
The present ELAPO compositions also exhibit novel surface selectivity characteristics which render them useful as catalyst or catalyst bases in a number of hydrocarbon conversion and oxidative combustion 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 catalyst compositions having silica or alumina bases. Of the general class, those species having pores larger than about 4A are preferred for catalytic applications.
Among the hydrocarbon conversion reactions catalyzed by ELAPO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin types,isomerization including xylene D-14,208 isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.
Using ELAPO catalyst compositions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic 6tocks and other hydrocrackable charge stocks, can be hydrocracked at temperatures in the range of 400F to 825F using molar raeio6 of hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g., and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.
The FLAPO catalyst compositions employed in hydrocracking are also 6uitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 700F to 1000F, hydrogen pressures of from 100 to 500 pig LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of 1 to 20, preferably between 4 and 12.
These 6ame catalysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomerizations proce6ses in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about 200F to 600F, preferably 300F to 550F with an LHSV value of from about 0.2 to 1Ø Hydrogen is supplied to the reactor in admixture with the hydrocarbon feedstoc~ in molar proportions D-14,208 ,, , ~8 (hydrogen/hydrocdrbon) of between 1 and s.
At somewhat higher temperatures, i.e. frGm about 650F to 1000F, preferably 850F to 950F and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g., the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C7-C20. Contact time between the feedstock and the catalyst is generally relatively 6hort to avoid undesireable side reactions such as olefin polymerization and paraffin cracking. LHSV
values in the range of 0.1 to 10, preferably l.o to 6.0 are suitable.
The unique crystal structure of the present ELAP0 catalysts and their availability in a form totally void of alkali metal content favor their ufie in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disproportionation process, i60merization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, molybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall composition.
Extraneous hydrogen can, but need not, be present in the reaction zone which is maintained at a temperature of from about 400 to 750F, pres6ures in the range of 100 to 2000 p.s.i.g. and LHSV values in the range of 0.1 to 15.

D-14,208 - - 39 _ ~2~3~
Catalytic cracking processes are preferably carried out with ELAPO compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline being the principal desired product. Temperature conditions of 850 to 1100F, LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. are suitable.
Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out u6ing essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the ELAP0 catalyst in con3unction with a Group VIII non-noble metal cation such as cobalt and nickel.
In catalytic dealkylation wherein it is de6ired to cleave paraffinic side chains from aromatic nuclei without 6ubstantially hydrogenating the ring structure, relatively high temperatures in the range of about 800-1000P are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g., other conditions being similar to those described above for catalytic hydrocracking.
Preferred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conver6ion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.

D-14,208 2~ 3 In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without ubstantially affecting hydrocarbon molecules therein. For this purpose it it preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the same general nature described in connection with dehydrocyclization operations. Feedstocks include gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy ga6 oils, deasphalted crude oil residua and the like any of which may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.
Similar conditions can be employed to effect hydrofining, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing 6ubstantial proportions of organonitrogen and organosulfur compounds. It is generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of hydrocracking catalysts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatively nitrogenous feed than are required with a feed containing le6s organonitrogen compounds.
Consequently, the conditions under which denitrogenation, desulfurization and/or hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in D-14,208 view of the characteristics of the feedstocks in particular the concentration of organonitrogen compounds in the feedstock. As a result of the effect of organonitrogen compounds on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most 6uitable for denitrogenation of a given feedstock having a relatively high organonitrogen content with minimal hydrocracking, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking another feedstock having a lower concentration of hydrocracking inhibiting constituents e.g., organonitrogen compounds. Consequently, it has become the practice in thi6 art to establish the conditions under which a certain feed is to be contacted on the basis of preliminary screening tests with the specific catalyst and feed6tock.
I60merization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalysts. Olefins are preferably isomerized at temperatures of 500-900F, while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700-1000F. Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptene and/or n-octane to i~oheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, l-butene to 2-butene and/or isobutene, n-hexene to isohexene, cyclohexene to methylcyclopentene etc. The D-14,208 ~l24~

preferred form of the catalyst is a combination of the ELAPO 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 ELAPO 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 feedstock oe conversion products occurs, generally up to about 700F. The temperature is preferably at least 450F and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state. Por alkylation the temperature can be as low as 250P but is preferably at least 350F. In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.

D-14,208 :, :

Claims (59)

1. Crystalline molecular sieves having three-dimensional microporous framework structures of MO2, AlO2, and PO2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
mR : (MxAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R"
present per mole of (MxAlyPz)O2 and has a value of zero to about 0.3; "M" represents at least two elements capable of forming framework tetrahedral oxide units and comprises at least one element selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium and at least one element selected from the group consisting of cobalt, iron, magnesium, manganese, titanium and zinc; "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, and are within the pentagonal compositional area defined by points A, B, C, D and E of Fig. 1.

2. The crystalline molecular sieves of claim 1 wherein "x", "y" and "z" are within the hexagonal compositional area defined by points a, b, c, d, e and f of Fig. 2.

3. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table A.

4. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table B.

5. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table C.

6. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table D.

7. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table E.

8. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table F.

9. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table G.

10. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table H.

11. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table J.

12. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table K.

13. The crystalline molecular sieves of claim 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table L.

14. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table M.

15. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table N.

16. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table O.

17. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table P.

18. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table Q.

19. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table R.

20. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table S.

21. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table T.

22. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table U.

23. The crystalline molecular sieves of claims 1 or 2 having a characteristic x-ray powder diffraction pattern which contains at least the d-spacings set forth in Table V.

24. The molecular sieves according to claims 1 or 2 comprising a three-dimensional microporous framework structure of MO?, AlO? and PO? tetrahedral units where "n"
is -2, -1, 0 or +1.

25. Molecular sieves according to claim 1 wherein "M" is beryllium and magnesium.

26. Molecular sieves according to claim 1 wherein "M" is at least one of the group consisting of arsenic, germanium, chromium and vanadium and at least one of the group consisting of manganese, magnesium, iron and zinc.

27. The molecular sieves according to claim 1 wherein "M" is at least one of boron and gallium and at least one of the group consisting of iron, magnesium, manganese and zinc.

28. The molecular sieves according to claim 1 wherein "M" is magnesium and germanium.

29. The molecular sieves of claim 1 wherein "M" is at least one element selected from the group consisting of beryllium and germanium and at least one element selected from the group consisting of magnesium, manganese, iron and zinc.

30. The molecular sieves of claim 1 wherein "M" is magnesium and cobalt.

31. The molecular sieves of claim 26 wherein "M" is chromium and magnesium.

32. The molecular sieves of claim 26 wherein "M" is iron and arsenic.

3. Process for preparing the crystalline molecular sieves of claim 1 having three-dimensional microporous framework structures wherein said process comprises reacting at an effective temperature and for an effective time a mixture composition expressed in terms of molar oxide ratios as follows:
aR : (MxAlyPz)O2 : bH2O
wherein "R" is an organic templating agent: "a" is the amount of "R" and may be zero or an effective amount greater than zero: "b" has a value of from zero to about 500; "M" represents at least two elements capable of forming a framework tetrahedral oxide where at least one element is selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium and at least one element is selected from the group consisting of cobalt, iron, magnesium, manganese, titanium and zinc; and "x", "y" and "z" represent the mole fractions, respectively, of "M", aluminum and phosphorus in the (MxAlyPz)O2 constituent, "y" and "z" each have a value of at least 0.01 and "x" has a value of at least 0.02, whereby the molecular sieves of claim 1 are prepared.

34. Process of claim 33 where "x", "y" and "z" are within the pentagonal compositional area defined by points F, G, H, I and J of FIG. 3.

35. Process according to claim 33 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.

36. Process according to claim 33 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.

37. Process according to claim 36 wherein the aluminum alkoxide is aluminum isopropoxide.

38. Process according to claim 33 wherein the source of "M" is selected from the group consisting of oxides, alkoxides, hydroxides, halides, nitrates, sulfates, carboxylates and the like.

39. Process according to claim 33 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.

40. Process according to claim 33 wherein the organic templating agent is an amine.

41. Process according to claim 33 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-methylpiperdine;
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 quaternary ammonium salt [(C14H32N2)(OH)2]x wherein x is a value of at least 2.

42. Molecular sieve 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.

43. 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 molecular sieve of claim 1 having pore diameter large enough to adsorb at least one of the more polar molecular species, said molecular sieve being at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof.

44. 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 molecular sieve of claim 2 having pore diameter large enough to adsorb at least one of the more polar molecular species, said molecular sieve being at least partially activated whereby molecules of the more polar molecular species are selectively adsorbed into the intracrystalline pore system thereof.

45. Process for separating a mixture of molecular species having different kinetic diameters which comprises contacting said mixture with a molecular sieve 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 molecular sieve being at least partially activated whereby at least some molecules whose kinetic diameters are sufficiently small can enter the intracrystalline pore system thereof.

46. Process according to claim 43 or 44 wherein the more polar molecular species is water.

47. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a molecular sieve of claim 1.

48. Process for converting a hydrocarbon which comprises contacting said hydrocarbon under hydrocarbon converting conditions with a molecular sieve of claim 2.

49. Process according to claim 47 or 48 wherein the hydrocarbon conversion process is cracking.

50. Process according to claim 47 or 48 wherein the hydrocarbon conversion process is hydrocracking.

51. Process according to claim 47 or 48 wherein the hydrocarbon conversion process is hydrogenation.

52. Process according to claim 47 or 48 wherein the hydrocarbon conversion process is polymerization.

53. Process according to claim 47 or 48 wherein the hydrocarbon conversion process is alkylation.

54.Process according to claim 47 or 48 wherein the hydrocarbon conversion process is reforming.

55. Process according to claim 47 or 48 wherein the hydrocarbon conversion process is hydrotreating.

56. Process according to claim 47 wherein the hydrocarbon conversion process is isomerization.

57. Process according to claim 48 wherein the hydrocarbon conversion process is isomerization.

58. Process according to claim 56 or 57 wherein the isomerization conversion process is xylene isomerization.

59. Process according to claim 47 or 48 wherein the hydrocarbon conversion process is dehydrocyclization.