CA1168220A - Crystalline metallophosphate compositions - Google Patents

Abstract

ABSTRACT OF DISCLOSURE

A novel family of crystalline, microporous aluminophosphate compositions is synthesized by hydro-thermal crystallization at elevated temperatures of aluminophosphate gels containing a molecular structure-forming template. The family comprises a number of distinct species, each with a unique crystal structure.
Calcination removes volatile extraneous matter from the intracrystalline void space and yields microporous crystalline adsorbents with uniform pores, the dimensions of which vary, along the individual species, from about 3A to 10A in diameter. The compositions represent a new class of adsorbents of the molecular sieve type, and also exhibit properties somewhat analogous to zeolitic molecular sieves which render them useful as catalysts or catalyst bases in chemical reactions such as hydro-carbon conversions.

Description

The present invention relates in general to a novel ~amily of crystalline compositions and to the method i.or their synthesis. More particularly it relates to crystalline microporous aluminophosphate compositions and ~o hydrothermal processes for preparing same.
Molecular sieves of the crystalline zeolite type are well known in the art and now comprise over 150 species of both naturally occurrin~ and synthetic compositions. In general the crystalline æeolites are aluminosilicates whose frameworks are formed from A104 -and Si04 tetrahedra joined by the sharing of oxygen atoms and 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 through the internal voids of the crystal without displacing any at~ms which make up the permanent crystal structure.
Other cry~talline microporous phases which are not zeolitic, i.e. do not contain A104 - tetrahedra as essential framework constituents, but which exhibit the ion exchange and/or adsorption characteristics of the zeolitic phases are also known. 2~etallorganosilicates 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.P. 3,941,871 issued March 2, 1976 to Dwyer et al. Also a pure silica polymor~h having molecular sieving properties and a neutral framework

- 2 -, i .

containing no cations or cation sites is defined in U.S.P.
4,061,724 issued December 6, 1977 to R.W. Grose et al.
We have now discovered a new class of molecular sieve materials which are microporous three-dimensional crystalline aluminophosphate phases havin~ uniform pore dimensions ranging from about 3A to about 10 A and capable of making size selective separations of molecular species.
The chemistry of aluminum phosphates has been reviewed by J.H. Morris et al. (Chem. Soc. Rev., 6, 173 (1977) ). lhe phosphates:with an A1203:P205 molar ratio of 1:1 are thé most common, and have been the most widely studied. Anhydrous AlP04 is -isoelectronic and isostructural with silica and exists in quartz (as berlinitej, tridymite, and cristobalite forms possessing frameworks of alternat-ing A104 and P04 tetrahedra. In addition to these, F.D'Yvoire lBull. Soc. Chim. France, 1762 (1961)] has described five anhydrous crystalline AlP04 forms which have no silica analogs.
- Two hydrates of AlP04 with the stoichiometry AlP04.2 H20, metavariscite and variscite, occur in natural and synthetic forms. Their structures were determined by Kniep and coworkers (Acta Crysta., B29, 2292 (lg73); ibid., B33 263 (1977), and both can be described as frameworks of alternating octahedral A104(H20)2 and tetrahedral P04 units. In both the metavariscite and variscite structures the H20 is chemically bound to the Al and, although small amounts of this water can be r~moved reversibly, complete ~ .

dehydration is irre~ersible and leads to significant structural changes and the formation of anhydrous AlPO4 phases.
In addition to these, six crystallographically unique, ~etastable hydrates have been sy~thesized by F. D'Yvoire (ibid.). Of these, four are reported to be reversibly dehydrated under mild conditions to yield anhydrous phases, but in each case significant changes in framework topology occurred. These changes were reported to be re~ersible by rehydration. It is possible therefore that the interaction between water and these aluminophosphate phases results in chemical bondin~, such as the formation of A104(H20)2 octahedra, rather than physisorption.
The hydrothermal synthesis of aluminosphosphates in the presence of various alkali metal, alkaline earth, and NH4 cations has been reported by Haseman and coworkers (Soil Sci. Soc. Proceed., 76 (1950); Soil Sci., 70, 257-271 (1950) ), by Cole and Jackson ( J. Phys. Chem.J, 54, 128-142 (1950) ), and by Golub and Boldog (Russ. Jour, Inorg, Chem., 21, 45 (1976) ). A variety of known minerals (e.g. palmierite, taranakite, wavellite, variscite) and many novel crys~alline materials were obtained. Virtually all of these materials hat Al/P ra~ios different from 1Ø
Although most of the products had appreciable H20 content only o~e product was exa~ined by X-ray powder diffraction after dehydration. This product, taranakite, became amorphous at 125C. The stability of the other phases is .

Z~

unknown.
R~M. Barrer and D.J. Marshall (J. Chem. Soc., 6616 (1965) ) attempted to substitute P for Si during hydrothermal crystallization of mixed frameworks analogous to aluminosilicates. The crystalline products obtained from synthesis mixtures containing sources of Al, Si, and P were predominately aluminosilicates (e.g. montmoril-lonite, analcite, and cancrinite) and phosphates (e.g.
hydroxyapatite). Several unidentified crystalline solids were observed, characterized solely by their X-ray powder diffraction patterns. Evidence for phosphorus incorporation in the aluminosilicate structures or silicon incorporation in the hydroxyapatites was not obtained, however.
G. Kuehl has used phosphate as a complexing ion for aluminum in the hydrothermal synthesis of certain zeolites (Proceedings of the Lonton Conf. on Molecular Sieves, April 1967, p. 85; Inorg. Chem., 10, 2488 (1971) ).
Presumably the phosphate complexes some of the aluminum, lowering the effective concentration of the re reactive hydroxoaluminate species in the reaction mixture and, thereby, increases the ratio of silicate to hydroxoalu-minate. The zeolite products had a higher Si/Al ratio than normal and presumably no incorporation of P into the zeolite frameworks was observed. In one case, a high-silica form of zeolite A contained phosphate inter-calated in the sodalite cages.
In an attempt to isolate the aluminophosphate . ~.

~ . ?~ 2~1~
species formed when phosphate is added to a zeolite synthesis mixtu~e, G. Kuehl prepared the crystalline p [(CH3)4N]3tAl(PO4)2] X H20 where X = 10 4, and 1.5. They were characterized by X-ray powder diffraction, thermal, and elemental analysis, and were described as salts containing isolated Al~P04)2(0H2)x3 units. Removal of all the H20 caused the decomposition of these compoùnds (U.S. Patent, No. 3,3~6,801 (1968);
J. Inorg. Nucl. Chem., 31, 1943 (1969) ).
The novel generic class of alu~inoph~sphates of the present invention have an essential crystalline framework structure whose chemical composition expressed in terms of molar ratios of oxides, is A1203 : 1.0 + 0.2 P205 said framework structure being micro~orous in which the pores are uniform and in each species have nominal diameters within the range of from 3 to 10 Angstroms; an intra-crystalline adsorption capacity for water at 4.6 torr and 24C of at least 3.5 weight percent, the adsorption of water being completely reversible while retaining the same essential framework topology in both the hydrated and dehydrated state. By the term "essential framework topology" is meant the spatial arrangemene of the primary Al-O and P-0 bond linkages. No change in the framework topology indicates that there is no disruption of these primary bond linkages.
The present aluminophosphates are prepared by hydrothermal crystallization of a reaction mixture prepared by combining a reactive source of phosphate, alumina and water and at least one structure-directing or templating agent which can include an organic amine and a quaternary ammonium salt. In the as-synthesized form the structure-directing agent is contained ~.~t;~ V

within the framèwork structure of the aluminophosphate in amounts which vary from speci~s to species but usually does not exceed one mole per mole of A1203 thereof.
This structure-directing agent is readily removed by water washing or calcination and does not appear to be an essential c~onstituent of the product aluminophosphate as evidenced by e~sentially complete absence of ion-exchangeability of the as-synthesized compositions and also the absence of any internally-contained organic molecules in the as-synthesized.form of at least one species of the generic class. Evidence that a structure-directing agent is a critical constituent is contained in certain of the illustrative examples appearing hereinafter, wherein reaction mixturés otherwise identical to those which yield products of the present invention except for the presence of templating agents, yield instead the previously known alt~inophosphate phases AlP04 ~
1.3 H20, AlPO4 - tridymite, AlP04 - qtlartz and AlP~4 -: cristobalite.
Broadly the preparaeive process comprises . forming a reaction mixture which in terms of molar ratios of oxides is 23 1 + 0.5 P205 7 - 100 H 0 and containing from about 0.2 to 2.0 moles of templating agent per mole of Al203. The reaction mixture is placed in a reaction vessel inert toward the reaction system and heated at a temperature of at least about 100C., preferably between 100C and 300C., until crystallized, usually a period from 2 hours to 2 weeks.
The solid crystalline reaction product is then recovered by any convenient method, such as filtration or centrifuga-tion, washed with water and dried at a temperature between ambient and 110C in air.
In a preferred crystallization method the source of phosphate is phosphoric acid, and source of alumina is a pseudo-boehmite hydrated aluminnm oxide, the temperature is 125C to 200C, and the crystallization time is from one to seven days. The preferred ratio of oxides in the reaction mixt~re is A1203 : 0.8 - 1.2 P205 : 25-75 H20 In general the most preferred reaction mixture contains per mole of A1203 from about 0.5 - 1.5 moles of templating agent, from 40-50 moles of water and about 1.0 mole of P205 ~
Not all templating agents suitably e~loyed in the prepara~ion of certain species of aluminophosphates of this invention are suitable for the preparation of all members of the generic class. The relationship of specific templating agents to the individual product species is apparent from the illustrative Examples set forth hereinafter.
The method of preparation and the physical and chemical properties of the.various members-of the pre-sent class of novel aluminophosphates are illustrated and characterized, respectively, in the following examples.
The species compounds are denominated as AlP04 - n wherein "n" is a number specific to each individual member.

~ 3 EXAMPLE 1. Preparation of AlPO4-S
A rea~tion mixture w~s prepared by combining 46.1 grams of 85~/~ orthophsophoric acid (H3PO4) and 100.0 grams of water, to which was added 27.5 grams of a hydrated alu~inum oxide (a pseudo-boehmite phase, 74.2 wt% A1203, 25,8 wt,% H20, a commercial product available under the trademark CATAPAL SB of the Conoco Chemicals Division of Continental Oil Company, USA.) and stirred until homogeneous. To this mixture was added 176.8 grams of an aqueous solution of 23 wt.% tetrapropylammonium hydroxide (TPAOH), and the mixture stirred until ho -geneous. The composition of the final reaction mixture ln lar oxide ratios was:
o.S (TPA?20:Al2o3:p2o5 73H2o The reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 150C at autogenous pressure for 43 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The major phase in the product had an X-ray powder diffraction pattern characterized by the following data wherein "I" is the intensity and "d"
the interplanar spacing. The product also contained a minor amount of another crystalline impurity.

_ 9 _ ~i .

J ~ v 2e d _ lOOx I/I~

7.50 11.8 10 12.95 6.84 11 14.95 5.93 28 19.75 4.50 ` 66 20.95 4.24 63 22.4 3.97 94 24.65 3.61 5 26.00 3.43 37 28.95 3.08 21 30.05 2.97 22 33.50 2.67 5 34.50 2.60 19 36.95 2.43 5 37.50 2.40 13 40.75 2.21 41.60 2.17 4 42.45 2.13 4 43.65 2.07 3 44.95 2.02 2 47.70 1.91 6 This X-ray pattern and all other X-ray patterns appearing herein-after were obtained using standard X-ray powder diffraction techniques, The radiation source was a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K~ radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compresset powder samples are scanned st 2 (2 theta) per minute, using a two second time constant. Interplanar spacings (d) are obtained from the position of the diffraction peaks expressed as 2~ where ~ i8 the Bragg angle as observed on the strip chart. Intensities are tetermined from the heights of diffraction peaks after ~ubtracting background.

. . .

EXAMPLE 2. Preparation of AlP04-5 ta) A reaction mixture ~as prepared by combining 23,1 grams of 85% orthophosphoric acid (H3P04) and 44.0 grams of water, to which was added 13.7 grams of the same hydrated aluminum oxide employed in Example 1, and stirred until pomogeneous~ To this mixture was added 35.1 grams of an aqueous solution of 58 wt.% tetrapropyl-am~omium hydroxide (TPAOH), and the mixture stirred until ho geneous. The composition of the final reaction mixture in molar oxide ratios was:
O-5 (TPA)2O : A12O3 : P~Os : 4O H2O
The reaction mixt~re was sealed in a stainless steel pressure vessel lined with polytetrafluoroethyle~e and heated in an oven at 150C at autogenous pressure for 65 hours.
The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature.
A portion of the solids was submitted for X-ray analysis and chemical analysis.
Chemical analysis showed 7.5 wt.% C, 0.67 wt.%
N, 34.2 wt.% A1203, 46.5 wt.% P205, 17.7 wt.% LOI (~oss on Ignition at 1000C for 4 hr ) givin~ a product composition in molar oxide ratios of:
0.08 (TPA)20 1-A123 0 98P2o5 1-3 2 The above product had an X-ray.powder diffraçtion pattern essentially identical to that of the major phase in Example 1, and contained no crystalline impurities. This product was designated AlPO4-5.
(b) A portion of the solid crystalline product obtained from a similar procedure as in part (a) above.

Z20 ~'"`~ I

and exhibiting àn X-ray powder diffraction pattern essentially identical to that in Example 1 was calcined in air at about 500C fo:r 2 hours. The calcined product had an X-ray powder diffraction pattern essentially identical to that in Example 1.
EXAMPLE 3. Preparation of AlP04-S
(a) A reaction mixture was prepared by combining 46.1 grams of 85% orthophosphoric acid (H3P04) and 118.6 grams of water, to which was added 27.5 grams of a pseudo-boehmite phase (74.2 wt.% A1203, 25,8 wt.% H20), and stirred until homogeneous. To this mixture was added 29.2 grams of tripropylamine (Pr3N) and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
1.0 Pr3N:Al203:p2os 40 H20 The reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 150C at autogenous pressure for 70 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. Chemical analysis showed 5.7 wt.% C, 0.72 wt.% N, 34.0 wt.% A1203, 48.1 wt.% P205, 16.4 wt.%
LOI, giving a product composition in molar oxide ratios of:
Pr3N:l~ooAl2o3:l.o2p2o5:l.5H2o The aboveproduct had an X-ray powder diffracti~n pattern virtually identical to that of the major phase set forth in Example 1 and contained no crystalline impurities.

. l (b) A portion of the solid crystalline product obtained above.was calcined in air at ab~ut 600C for 2 hours. The calcined product had an X-ray powder diffraction pattern essentialiy the same as that of the as-synthesized product of part (a) above.
EXAMPLE 4. Preparation of AlP04-5 A reaction mixture was prepared by combining 23.1 grams of 85% orthophosphoric acid (H3P04) and 59.6 grams of water, tc which was added 13.7 grams of a hydrated aluminum oxide, (74.2 wt.Z A1203, 25.8 wt.% H20~, and stirred until homogeneous. To this mixture was added 8.6 grams of tripropylamine (Pr3N) and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
0.6 Pr3N:Al203;p2os 4o H20 The reaction mixture was sealed in a stainless steel pressure vessel lined with an inert plastic material and heated in an oven at 150C at autogenous pressure for 4 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. The X-ray powder diffraction pattern of this product showed the crystall~ne AlP03-5 product of example 3 as the major phase, with a minor amount of a crystalline impurity being also present.

X

11t;~22Q

E~AMPLE 5. Prepar~tion of AlP04-5 A reaction mixture was prepared by combining 46.1 grams of 85% orthophosphoric acid (H3P04) and 119.2 grams of water, to which was added 27.5 grams of a hydrated aluminum oxide (74.2 wt.% A1203, 25.8 wt.% H20), and stirred until pomogeneous. To this mixture was added 30.4 grams of triethylamine (Et3N~, and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
1.5 Et3N;Al2o3 P205 4o H20 The reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 200C at autogenous pressure for 27 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. Chemical analysis of the product indicated the presence of 4.8 wt.% C, 0.97 wt.% N, 35.3 wt.% A1203, 49.7 wt.% P205 and 13.6 wt.% LOI, giving a product composition in molar oxide ratios of:
0.19 Et3N 1 00A1203 1 01P205;1 1H20 The above product had an X-ray powder diffraction pattern essentially identical to that of the AlP04-5 product of example l and contained no crystalline impurities.

2 2 ~

EXAMPLE 6. Preparation of AlP04-5 (a) A reaction mixture was prepared by combining 18.5 grams of 85% orthophosphoric acid (H3PO4) and 45.9 grams of water, to which was added 13.7 grams of a pseudo-boehmite phase (74.2 wt.~ Al203, 25.8 wt.% H20), and stirred until homogeneo~s. To this mixture was added 25.9 grams of an aqueous solution of 57 wt.%
tetrapropylammonium hydroxide (TPAOH), and the mixture in molar oxide ratios was:
0.5 (TPA)20:A1203:0.8 P205:40 H20 The reaction mixture was placed in a stainless steel pressure vessel lined with an inert plastic material and heated ~n an oven at 150C at autogenous pressure for 72 hours. The solid reaction product was recovered by repeated centrifugation and washing with water, followed by filtration, washing, and drying in air at room tempera-ture. The X-ray powder diffraction pattern of the dried product showed the major phase to be identical to AlPO4-S of example l.

~ 2 0 (b) A reaction mixture free of a structure-:
directing agent was prepared by combining 46.1 grams of 85% orthophosphoric acid (H3P04) and 120 grams of water, to which was added 27.5 grams of the same hydrated aluminum oxide as in part (a) above, and stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:

The reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 150C at autogenous pressure for 72 hours.
The solid reaction product was recovered by filtration, washed with water, and dried in air at 110C. The resulting product had an X-ray powder diffraction pattern indicat-ing a mixture of known AlP04 phases: AlP041.1-1.3H20, and two structural analogs of crystalline silica, namely AlP04 (quartz) and AlP04 (tridymite). An identical reaction mixture heated at 200 for 24 hours produced a mixture of the same known AlP04 phases, the major products being AlPO4(quartz) and AlP04 ~tridymitej. No microporous AlP04 phases of the present invention were o~served.

, .

o EXAMPLE 7. Preparation of AlP04-5 A reaction mixture was prepared by combinin~
37.8 grams of 85% orthophosphoric acid (H3PO4) and 177 grams of water, to which was added 67 grams of aluminum isopropQxide and stirred until homogeneous. The mixture was filtered and washed with water. To this mixture was added 145 grams of an aqueous solution of 23 wt.%
tetrapropylammonium hydroxide (TPAOH), and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
0 5 (TpA)2~;Al2o3:p2o5:xH2o The reaction mixture was placed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 150C at autogenous pressure for 276 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at 110C. The dried product was AlP04-5 as indicated by an X-ray powder diffraction pattern which was essen-tially the same as the AlP04-5 in example 1.

2~0 EXAMPLES 8 - 26; Preparation of AlPO4-5 A procedure similar to that in example 3 was followed except where indicated in Table A ~elow. The composition of each final mixture in molar oxide ratios was:
1.0 R:A12O3:P205:4OH20 except where noted in Table A. A portion of the ~olid product from each reaction was examined by X-ray analysis and in each case a phase characterized by an X-ray powder diffraction pattern essentially the same as the AlPO4-5 phase in example 1 was observed alone or ~n admixture with other products.

T~BLE A
EXAMPLE R REACTION REACTION
# TIME (Hrs.) TE~.,(C) 8 (C2Hs)4NOH(tetra_ 24 200 ethyla~nmoni hydroxide) 9 N(CH CH20H) 72 150 ( trie2~hanola3~ine ) piperidine 24 150 - 11 2-methylpyridine 168 150 12 cyclohexylamine 168 150 13 N,N-dimethyl- 168 150 - benzylamine 14 N,N-diethyl- 24 200 ethanolamine dicyclohexylamine 24 150 16 N-N-dimethyl- 24 150 ethanolamine ~r EXAMPLE R REACTION REACTION
# _ TIME(Hrs.) TEMP.,(C) 17 [(CH3)3NCH2CH2OH)OH 52 150 18 N,N - dimethyl- 24 200 piperazinel . I
19 1,4-diazabicyclo 192 200 (2,2,2~ octane .
DABCO
N-methyl-diethanol- 24 200 aminel 21 N-methyl-ethanol- 24 200 amine 22 N-methylpiperidine 24 200 23 3-methylpiperidine 168 150 24 N-methylcyclohexyl- 24 200 amine

3-methylpyr~dine 24 150 26 4-methylpyritine 168 150 1 The final reaction mixture contains 50 H20.
2 The final reaction mixture contains 0.5 DABCO.

~.

Z~O

The species AlP04-5 as herein referred to is a crystalline metallophosphate whose essential frame-work structure has a chemical composition, expressed in terms of molar ratios of oxides, is A1203 : 1.0 + 0.2 P205 and having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 2, below:

2~ d 100 x I/Io 7.4 - 7.6 11.9 - 11.6 100 14.8 - 15.3 5.97 - 5.83 13 - 43 19.7 - 20.1 4.51 - 4.42 39 - 92 20 8 - 21.2 4.27 - 4.19 37 - 87 22 3 - 22.7 3.99 - 3.93 62 -118 25.9 - 26.3 3.44 - 3.39 22 - 35 All of the AlP04-5 compositions for wh~ch the X-ray powder tiffraction data has presently been obtained have patterns that are within the generalized pattern o$
Table 3, below:

2~ d lO0 x I/Io 3 _ ~z 7 ~ sl _ ~ 2 j -118 24 55 - 24 9 3 63 - 3.58 4 - 8 25.9 - 26.25 3 09 - 3 06 -~22 - 32 36.9 - 37 2 2 60 - 2 Ss 1l - 17 , ~;, ~. . ~

l lt;~2() (TABLE 3 cont ' d) 42.25 - 42.5 2.14 - 2.13 0 - 4 42.7 - 42.8 2.12 - 2.11 0 - 3 43.6 - 44.0 2.08 - 2.06 0 - 2 45 0 - 45.4 2.01 - 2.00 0 - 2 46 2 1.96 0 -47.8 1.90 0 - 4 48 0 - 48 4 1 97 ~ 1 77 0 - 2 52.0 1.76 0 - 2 55.8 - 56.0 1.65 - 1.64 ~ - 2 EXA~PLE 27. Preparation of AlP04-8 (a) A reaction ~nixture was prepared by combining 8.9 grams of 85% orthophosphoric acid (H3P04) and 6 grams of water, to which was added 5.3 grams o~' a hydrated aluminum oxide ~ pseudo-boehmite phase, 74.2 wt.% A1203, 25.8 wt.% H20), and 6.0 grams of water, and stirred until homogeneous. To this mixture was added 27.2 grams of an aqueous solution of 37 wt.% tetrabutylammonium hydroxide ¢BAOH), and 2.0 grams of water and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratio was:
0.5 (TBA)20 Al2o3 P25;52 H20 The reaction mixture was sealed in a stainless steel pressure vessel lined with an inert plastic material and heated in an oven at 150C at autogenous pressure for 145 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at 115C. Chemical analysis showed the product to contain 0.2 wt.% C, <0.05 wt.% N, 34.7 wt.Z A1203, 46.6 wt.Z
P205, 18.4 wt.% LOI, giving a product composition in molar oxide ratios of:
1.00 A12o3:0.97P205:3.00H20 `. ~il The major phase in the above product had an X-ray powder diffraction pattern characterized by the following data wherein "I" is the intensity and "d" the interplanar spacing; the product also contained a minor amount of a crystalline impurity.
29 d 100 x I/IO

10 0 8.84 17 10.8 8.19 2 14.6 6.07 4 16.1 5.56 16 18.8 4.72 2 lg.8 4.48 20 2 4.40 12 21 25 4.19 82 21.9 4.06 18 22.4 3 97 39 22.7 3.92 (sh~
23.55 3.77 3 24.15 3.68 11 24.9 3.58 11 27.1 3.29 2 28.2 3.16 5 31.35 2.a53 4 32.9 2.722 3 34 2 2.622 35 6 2~522 3 38 0 2 364 3 (sh)*
43.2 2.094 2 46.9 1.937 49.5 1.841 3 * shoshoulder This product was designated AlPO4-8. It is to be noted that only trace a unts of the tetrabutylamm~nium templating compound were present in the reaction product solids. This may indicat~ that a templating mechanism different from that in most other species of this invention is involvet.
(b) A portion of the solid crystalline product obtained above was calcined in air at about 600C for 2 hours. The calcined product had an X-ray powder diffraction pattern essentially the same as that of the product of part (a) above.

.~ .

8~ZO

EXAMPLES 28 - 30. Preparation of AlP04-8 A procedure similar to that in example 27 was followed except where indicated in Table B. The compo-sition of each final reaction mixture in molar oxide ratios.was:
l.O~R:Al203:p2os 4o H20 where R is indicated in Table B. In each case a product phase characterized by an X-ray powder diffraction pattern essentially the same as that in example 27 was obser~ed. Some extraneous phases were also present.

TABLE B
EXAMPLE ORGANIC DIGESTIO~ TEMP(-C) # USED (R) TIME (Hrs) 28 (n-C5H11)4NOH 24 150 29 (n-C~H9)2NH 72 150 (n-C5Hl 1)2NH * 24 150 * Small amount of acetone used to wash solid product.
The species AlP04-8 as herein referred to is a crystalline metallophosphate whose essential framework structure has a chemical composition, expressed in terms of molar ratios of oxides, is A1203 : 1.0 + 0.2 P205 and having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in TABLE 4 below:

2~ d 100 x I~Io 6:S - 6 65 16 7 - 16 4 30 _10O
21.2 - 21.3 4 51 - 4 48 46 - 82 21 8 - ~1.9 4.08 - 4.06 14 - 56 22 4 - ~2.9 3.97 - 3.88 35 - 39 All of the AlP04-8 compositions ~or which the X-ray powder diffraction data has presently been obtained have patterns that are within the generalized pattern of TABLE 5 below:

2~ d 100 x I/Io -5.3 - 5.4 16.7 - 17.4 80 -100 6.5 - 6.65 13.6 - 13.3 30 -100 9.9 - 10.1 8.9 - 8.8 15 - 20 10.75 - 10.8 8.23 - 8.19 2 - 9 14.6 - 14.8 6.07 - 5.99 4 - 17 16.1 - 16.2 5.50 - 5.47 7 - 16 18.8 - 18.9 4.72 - 4.70 2 - 12 19.7 - 19.8 4.51 - 4.48 8 - 29 20.1 - 20.2 4.42 - 4.40 9 - 12 21.2 - 21.3 4.19 - 4.17 46 - 82 21.8 - 21.9 4.08 - 4.06 14 - 56 22.4 - 22.5 3.97 - 3.9s 35 39 22.7 - 22.9 3.92 - 3.88 23.55 - 23.65 3.77 - 3.76 3 - 7 24.1 - 24.2 3.69 - 3.68 9 - 11 24.9 - 25.1 3.58 - 3.55 11 - 15 27.1 - 27.2 3.29 - 3.28 2 - 16 28.2 - 28.3 3.16 - 3.15 4 - 8 31.35 - 31.4 2.853- 2.849 4 - 6 32.9 2.722 3 - 8 34.2 - 34.3 2.622- 2.614 1 - 2 35.6 2.522 o - 3 38.0 - 38.2 2.368- 2.356 9 - 16 38.4 - 38.6 2.344- 2.332 -~ 3 - 18 43.2 - 43.3 2.094- 2.090 2 - 4 46.9 - 47.0 1.937- 1.933 1 - 2 49.4 - 49.5 1.845- 1.841 2 - 4 , ~
. , .
.

U

EXAMPLE 31. Preparation of AlPO4-9.
(a) A reaction mixture was prepared by combining 27.6 grams of 85% orthophosphoric acid (H3PO4) and 36.0 grams of water! to which was added 16.5 grams of a hydrated alu~inum oxide ( pseudo-boehmite phase, 74.2 wt.Z A1203, 25.8 wt.% H20), and stirred until homogeneous. To this mixture was added 13.5 grams of 1,4-diazabicyclo (2.2.2)octane (DABCO) dissolved in 24.0 grams of water, then 11.7 grams of water, and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
1. 0 DABCo A12o3 p2o5;4o H20 The reaction mixture was sealed in a stainless steel pressùre vessel lined wlth inert plastic and heated in an oven at 200C at autogenous pressure for 336 hours.
The solid reaction product was recovered and washed by repeated centrifugat~on with water, and dried in air at 110C. A portion of the solids was subjected to X-ray analysis and chemical analysis; Chemical analysis showed 10.6 wt.% C, 3.9 wt.Z N, 32.5 wt.% A1203, 46.5 wt.% P205, 19.0 wt.Z LOI, giving a product composition in molar oxide ratios of:
0-46 DABCO l-00 A1203 1 3 P205:0.44 H20 The above product, denominated.AlPO4-9, had an-X-ray powder diffraction pattern characterized by the following data, wherein "I" is the intensity and "d" the inter-planar spacing:

'.1 _ d 100 x I/Io 8.4 10.5 12 11.1 7.97 43 12.5 7.08 14 0 6.33 6 15 1 5.87 5 16.8 5.28 18.3 4.85 19 3 4.60 11 21 0 ' 4.23 100 21.9 4.06 30 22.3 3.99 18 22.8 3.90 3 25.4 3.51 38 25.7 3.47 79 26 5 3.36 13 27 7 3.22 2 28.5 3.13 30 6 2.92 5 31 45 2.843 10 31.8 2.814 27 32 4 2.763 < 1 33 15 2.702 12 33.7 2.660 18 34.3 2.614 S
34.8 2.578 3 35.5 2.529 4 ~6.4 2.468 37.8 2.380 4-38'455 2 3441 (lsho)*
38 9 2.315 10 41.3 2.186 2 42,15 2.144 6 42 6 2.122 4 44 55 2.034~ 3 44.65 2.029) ~ 46 5 1.953 2 48 0 1.895 3 48 4 1.881 49 75 1.833 7 50.2 1.817 9 51.9 1.762 53.65 1.708~ 4 53 8 1.704) 55 35 1.660 7 * sh-shoulder (b) The procedure and gel composition of part (a~ above were repeated except that the reaction mixture was heated for 168 hours. AlP04-9 was produced.

V

The species AlP04-9 as herein referred to is a crystall~ne ~etallophosphate whose essential frame-work structure ~as a chemical composition, expressed ~n terms of lar ratios of oxides, is A1203 : 1. 0 + 0 . 2 P205 and having a characteristic X^ray powder diffraction pattern wh~ch contains at least the.d-spacings set forth in TA8LE 6 below: _ 2~ a loo x I~Io 11.1 - 11.15 7.97 - ~.94 43 - 68 12.5 - 12.65 7.08 - 7.00 12 -100 18.25 - 18.35 ~ .86 -4.83 19 - 4~
21.0 - 21.1 4.23 - 4.21 41 -100 25.4 - 25.6 3.51 - 3.48 38 - 82 25.7 - 25.8 3.~ - 3-45 - ~9 All of the AlP04-9 compositions for which the X-ray powder t$ffraction data has presently been obtained have patterns that are within the generalized pattern of TABLE 7 below:

d 100 x I~Io .
8.4 - 8.5 10.5 - 10.4 ~1 - 22 10 8 8.19 ~sh) 11.1 - 11 15 7 97 - 7 94 12 -100 14.0 - 14.2 6.33 - 6.24 2 - 8 15.1 - 15 25 5.87 - 5;81 4 - 6 16. 8 - 16 85 5.28 - 5. 26 3 - 13 18.25 - 18.35 4. 86 - 4.83 19 - 47 21.0 - 21 1 4 23 - 4 21 41 -100 1 9 ~ ~ 05 3'5~ ~ ~'ï 33~ ~ 3~

28.2 3 22 - 3.20 o -(sh) ~r~J
(TAB~ 7 con~ ' d) 28.45 - 28.55 3.136- 3.126 16 - 36 30.3 - 30.7 2.950- 2.912 S - 21 31.45 - 31.6 2.844- 2.831 (Sh) 3~.8 - 31.85 2.814- 2.810 14 - 30 33. lS - 33.3 2.702- 2.691 S - 16 33.6 - 33.7 2.667- 2.660 12 - 18 34.0 2.637 0 - 6 34.3 - 34. S 2.614- 2.600 5 - 6 34.8 - 34.9 2.578- 2.571 0 - 3 35.5 - 35.7 2.529- 2.~15 4 - 6 36.1 - 36.4 2.488- 2.468 1 - 3 37.8 - 38.0 2.380- 2.368 2 - 7 38.35 - 38.5 2.347- 2.338 4 - 10 38.9 - 39.1 ~ 2.315- 2.304 8 - 10 41.1 - 41.3 2.196- 2.186 0 - 2 42.1 - 42.2 2.146- 2.141 3 - 6 42.6 - 42.7 2.1~2- 2.118 2 - 4 44.55 - 44.85 2.034- 2.021 1 - 3 46.3 - 46.7 1.961- 1.945 2 - 4 48.0 - 48.05 1.895- ~ 1.893 3 - 4 48.4 - 48.7 1.881- 1.870 <1 - 3 49.75 - 50.0 1.833- 1.824 0 - 14 50.2 - 50.3 1.817- 1.814 0 - 14 51.0 - Sl.l 1.791- 1.787 <1 - 2 51.7 - 51.8 1.768- 1.765 (sh) - 12 51.9 - 52.1 1.762- 1.755 7 - 11 53.65 - 54.0 1.708- 1.698 3 - 4 SS.3 - 55.5 1.661- 1.656 6 - 8 EXAMPLE 32. Preparation of ~lPO4-11.
(a) A reaction mixture was prepared by combining 46.0 grams of 85D/o orthophosphoric acid (H3PO4) and 119.2 grams of water, to which was added 27.5 grams of the same hydrated aluminum oxide as in Example 1, and stirred until homogeneous. To this mixture was added 20.3 grams of di-(n-propyl)amine(Pr2NH), and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
1. 0 Pr2NH:Al203;p2os 4o H20 .~
The reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 200~C at autogenous pressure for 24 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room - 2~ -. ~
. ~ .., zo temperature. Chemical analysis o the reaction solids showed 5.1 wt.7~ C, 1.00 wt.% N, 37.6 wt.% Al203, 51.6 wt.% P205, 10.4 wt.% LOI, giving a product composition in molar oxide ratios of:
9 Pr2NH l ~ OOAl203 0 ~ 98P205 o 48 H20 The above product, denominated AlPO4-11, had an X-ray powder diffraction pattern characterized by the following data, wherein "I" i~ the ~ntensity and "d" the inter-planar spacing:

'``~ '1 2e d lOO x I/Io .
8.15 10.85 34 9.5 9.31 49 13.3 6.66 16 15.7 ~ 5.64 30 16.35 5.42 S
19.0 4.67 6 20.55 4.32 50 21.0 4.23 100 22.2 4.00 58 22.65 3.93 75 23.25 3.83 67 24.6 3.62 10 24.8 3.59 11 26.4 3.38 13 26.7 3.34 17 28.5 (sh)* 3.13~ lS
28.7 3.11~
29.2 3.06 6 29.6 3.02 9 3~.5 2.84 10 33.0 2.71 15 34.3 2.61 11 35.8 2.51 3 36.6 2.46 6 37.6 (sh~ 2.39 ~ 14 37.9 2.37 ~
39.6 2.28 4 40.5 2.23 2 42.9 2.11 5 44.8 2.02 2 45.2 2.01 4 46.1 1.99 -6 48.1 1.89 2 49.~ 1.86 4 50.6 1.80 3 54.8 1.68 4 *sh=~houlder ~' (b) A portion of a 801~ d crystalline product exh~b~t~ng an X-ray powder dlffraction pattern essentially ~dentical t~ that sbove was calcined ~n air at about 200C for 2 hours, then at 600~ overnight. The calcined product had an X-ray powder tiffraction pattern characterized by the following data:
2e d 100 x I/~o 8.0 11.1 14 9.8 9.03 40 11.7 7.56 3 12.75 6.94 20 13.65 6.49 6 14.7. 6.03 S
16.1 5.so 54 17.55 5.05 2 l9.S (sh) 4.55 17 19.85 4.47 23 20.7 4.29 8 21.9 4.06 100 22.1 (~h) 4.02 44 22.5 ~sh) 3.95 4B
Z3.5 3.79 54 24 .0 (sh) 3.71 16 24. 2 l5h) 3.68 10 25.7 3.47 20 25.9 (sh) 3-44 25.7 3.34 13 27.3 (sh) 3.27 14 27.65 3.23 20 28.5 3.13 8 29.6 3.02 29 30.3 2.95 16 31.75 2.82 8 32.6 2.75 22 33.95 2.64 7 34.4 (sh) 2.61 5 35.5 2.53 9 37.2 2.42 8 38.2 (sh) 2.36 6 38.8 2.32 14 39.4 2.29 2 39.7 2.27 2 41.0 2.20 8 41.4 (sh) 2.18 5 43.6 2.08 3 44.6 2.03 5 45.3 2.00 6 49.21 1.85 49.6~ 1.84 8 50,4 1.81 3 52.4 1.75 53.6 1 71 5 54.6 1 68 2 (sh~shoulder3 ~ Z V 12679 EXA~LES 33 - 36. Preparat~on of AlP04-11.
A proceture 8 imilar to that in example 32 was followed except where lndicated ln Table C below. The composition of each final reaction mixture ln ~olar oxide ratios was:
1.0 R:A1203 P2s 4o H20 The solid product from each reactlon contained in each case a phase characterized hv an X-ray powder diffraction pattern essentially the same as that of the uncalc~ned product of example 32.

TABLE C
EXAMPLE R REACTION REACTION
_ #_ TIME (Hrs) 33 (i-C3H7)2NH 24 200 34 (C2H5) (n-C4Hg)NH 24 200 (n-C4~g.)2NH 48 200 3B (n-C5Hl 1)2NH 24 200 37 " 24 150 The species AlP04-11 as herein referred to is a crystalline metallophosphate whose essential framework structure has a chemical composition, expréssed in terms of ~olar ratios of oxides, is A1203 : 1.0 + 0.2 P20~
and having a characteristic X-ray powder diffraction pattern which contains at least the t-spacings set forth in TABLE 8 below:

V

2~ d 100 x I/Io 9.4 - 9.5 9.41 - 9.31 31 - 49 20.5 - ~0.6 4.33 - 4.31 34 - 53 21,0 - 21.25 4.23 - 4.19 100 22.15 - ~2.25 4.01 - 4.00 12 - 5P, 22.5 - ~2.7 3.95 - 3.92 47 - 75 23.15 - 23.5 3.84 - 3.79 10 - 68 All of the AlPO4-11 compos~tions for which the X-ray powder t~ffraction data has presently been obtained have patterns that are w~thin the generali~e~ ~attern of TABLE 9 below 2~ d 100 x I/Io 8.1 - 8.2 10.9 - 10.8 19 - 34 8.5 - 8.5 10.4 ~sh) 9.4 - 9.5 9.41 - 9.31 49 - 31 13.2 - 13.3 6.71 - 6.66 11 - 16 15.7 - 15.8 5.64 - 5.61 16 - 30 16.3 - 16.4 5,44 - 5,40 3 - 5 19.0 - 19.2 4.67 - 4.62 4 - 7 20.5 - 20.6 4.33 - 4.31 34 - 53 21.0 - 21.25 4.23 - 4.19 100 22.15 - 22.25 4.01 - 4.00 12 - 58 22.5 - 22.7 3.95 - 3.92 47 - 75 23.15 - 23.5 3.84 - 3.79 10 - 68 24.6 - 24.8 3.62 - 3.59 4 - 10 24.8 - 25.0 3.59 - 3.56 4 - 11 26.3 - 26.4 3.39 - 3.38 11 - 18 26.6 - 26.8 3.35 - 3.33 11 - 18 28.3 - 28.5 3.15 - 3.13 ~sh) 28.~ - 28.9 3.11 - 3.09 11 - lS
29.1 - 29.25 3.07 - 3.05 5 - 7 29.5 - 29.6 3.03 - 3.02 5 - 9 31.5 - 31.6 2.84 - 2.83 5 - 10 32.8 - 33.0 2.~3 - 2.~1 6 - 15 34.0 - 34.4 2.64 - 2.61 4 - 13 35.6 - 35.9 2.52 - 2.50 2 - 3 36.6 - 36.65 2.46 - 2.45 4 - 6 37.6 2.39 12 37.8 - 38.0 2.38 - 2.37 8 - lS
39.4 - 39.7 2.29 - 2.27 2 - 4 40.5 - 40.8 2.23 - 2.21 2 42.2 - 42.5 2.14 - 2.13 2 - 3 42.7 - 43.2 2.12 - 2.09 4 - 5 44.8 - 45.0 2.02 - 2.01 2 - 4 45.2 - 45.5 2.01 - 1.99 2 - 4 46.0 - 46.2 1.97 - 1.96 2 - 6 47.9 - 48.1 1.90 - 1.89 2 48.9 - 49.1 1.86 - 1.86 2 - 4 50.6 - 51.0 1.80 - 1.79 2 - 3 ~4.8 - 54.85 1.68 - 1.67 2 - 4 55.5 - 55~6 1.66 - 1.65 ~ 2 o _-EXAMPLE 37. Preparation of AlPO4-12.
A reactlon mixture was prepared by comb$n$ng 46.0 grams of 85% orthophosphoric acid (H3PO4) and 119.2 grams of water, to which was added 27.5 grams of the same hydrated aluminum oxide as in Example 1 (a pseudo-boehmite phase, 74.2 wt.% A1203, 25.8 wt.% H20), and stirred until homogeneous. To this m$xture was added 6.0 grams of ethylenediamine (C2H8N2), and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
o.5C2H8N2 Al2o3 P205 4o H20 The reaction mixture was sealed in a stainless steel pressure ~essel lined with polytetrafluoroethylene and heated in an oven at 200C at autogenous pressure for 24 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature.
Chemical analysis showed 4.3 wt.% C, 4.3 wt.% N, 35.0 wt.% A1203, 49.5 wt.%-P205, 15.4 wt.% LOI, giving a product composition in molar oxide ratios of:
Q.52c2H8N2 l-ooAl2o3 l-o2p2os 2 The crystalline AlPO4-12 phase had an X-ray powder diffraction pattern characterized by the following data, wherein "I" ~s the intensity and "d" the interplanar spacing:

2e d 100 x I/Io 6.15 14.37 2S
11.2 7.90 7 12.3 7.20 22 13.3 6.66 56 14.1 6.28 5 15.2 5.83 4 17.2 5.16 20 18.5 4.80 27 18.9 4.70 13 19.9 (sh) 4.46 20.9 4.25 100 22.3 3.99 44 23.05 3.86 31 23.85 3.73 55 25.05 3.55 35 26.5 ~ 3.36 31 26.7 ~sh)~ 3.34 27.95(sh~) 3.19 28.2 (sh~ 3.16 20 28.95 3.08 11 29.8 3.00 25 30.4 (sh)~ 2.94 30.85(sh)( 2.90 44 31.15(sh~ 2.87 32.55 2.75 7 33.0 (~h)~ 2.71 S
33.2 ~h)J 2.70 34.0 2.64 18 34.8 2.58 18 37.8 2.38 4 38.6 2.33 11 39.3 2.29 9 40.0 2.25 7 40-7 2.22 9 41.8 2.16 7 42.7 (sh) 2.12 43.6 2.08 5 44.5 2.04 5 45.6 1.99 4 46.6 1.95 7 48.15 1.89 9 48.6 1.87 5 50-0 1.82 5 51.a 1.76 7 52.7 1.74 4 54.6 1.68 9 55.5 1.66 2 (sh=shoulder) .. .. .. . .. ... . . . . . . .

1267~

EXAMPLE 38. Preparation of AlPO4-12 A reaction mixture was prepared by combining 76.8 grams of 85% orthophosphDric acid (H3PO4) and 183.7 grams of water, to which was added 45.8 ~ram~ of the same hydrated aluminum oxide as in Example 38, and stirred until homogeneous. To this mixture was added 28.7 grams of 2-lmidazolidone t(CH2NH) ~CO] dissolved in 75 grams of H20, and the mixture stirred until homo~eneous. The composition of the final reaction mixture in molar oxide ratios was:
(CH2NH)2cO A1203:P205:50 H20 The reaction mixture was placed in a stainless steel pressure vessel hav~ng an inert liner ant heated in an -oven at 200C at autogenous pressure for 169 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at 110C. Chemical analysis showed 5.2 wt.% C, 6.2 wt.% N, 33.2 wt.% A1203, 48.2 wt.% P205, 18.1 wt.% LOI, giving a product composition in lar oxide ratios of:
(CH2NH)2CO:A1203:1.04P2o5;o.g7H2o The above product was AlPO4-12 as indicated by having an X-ray powder diffraction pattern essentially identical to that in example 37.

i267 V

The ~pecies AlP04-12 as herein referret to is a crystall~ne metallophosphate whose essential framework structure has a chem~cal compoQition, expr^ssed ~n terms of molar ratios of oxides, ~9 A1203 : 1.0 + 0.2 P205 and hav~ng a characteristic X--ay powder diffractlon pattern which contains at least the d-spaclngs set forth ~n TABLE 10 below:

. d 100 x I/Io 6.15 - 6.2 14.37 - 14.26 -2; - 48 13.3 - 13.35 6.66 - 6.63 56 - 63 20.9 - 21.0 4.25 - 4.44 100 22.~ - 22.4 3.99 - 3.97 33 - 45 23.85 - 24.0 3.73 - 3.71 46 - 61 30.85 - 30.9s 2.90 - 2.89 34 - 44 All of the AlP04- 12 co~?ositions ~or which the X-rav powder diffraction data has presently been obtained ha~e patterns that are within the generalized pattern of Table 11 below:

2~ d I~Io x 100 6.15 - 6.2 14.37 - 14.26 48 - 25 11.2 - 11.3 7.90 - 7.83 15 - 7 12.3 - 12.35 7.20 - 7.17 34 - 22 13.3 - 13.35 6.66 - 6.63 63 - 56 14.1 - 14.15 6.28 - 6.26 8 - 5 15.2 5.83 4 -17.2 - 17.3 5.16 - 5.13 29 - 20 18.4 - 18.6 4.82 - 4.~7 37 - 27 18.9 4.70 16 - 13 19.9 4.46 SH
20.9 - 21.0 4.25 - 4.23 100 21.65 - 21.8~ 4.10 - 4.0~ 14 - 13 22.3 - 22.4 3.99 - 3.97 45 - 33 22.6 SH 3.93 14 23.0 - 23.05 3.87 - 3.86 31 - 9 23.85 - 24.0 3.73 - 3.71 61 - 46 25.05 - 25.2 3.55 - 3.53 35 - 25 26.5 - 26.6 3.36 - 3.35 35 - 31 26.7 - 26.8 3.34 - 3.33 SH
27.95 - 2~.0 3.19 - 3.19 6 - 5 28.2 - 28.3 3.16 - 3.15 SH
28.95 - 29.0 3.08 - 3.08 13 - 10 ~ 8Z2~ 12679 TABLE 11 (continued) 29. ~l - 30.0 3.00 - 2.98 25 - 20 30.4 2.94 SH
30.85 - 30.95 2.90 - 2. B9 44 - 34 31.1 - 31.2 2.88 - 2.87 SX
32.55 - 32.6 2.75 - 2.75 7 - 6 33.0 - 33.1 2.71 - 2.71 6 - 5 33.~ - 33.4 2.70 - 2.68 s~
34.0 - 34.1 2.64 - 2.63 18 - 17 34. a - 34.95 2.58 - 2.57 19 - 18 35.4 - 35.5 2.54 - 2.53 SH
36.2 2.48 4 -37.0 2.43 1 - 0 37.4 2.40 4 - 0 37.6 - 37.8 2.39 - 2.38 4 - 0 37.9 2.37 S~
38.3 2.35 SH
38.6 - 38.65 2.33 - 2.33 11 - 8 39.3 - 39.4 2.29 - 2.29 9 - 7 40.0 2.25 8 - 7 40.7 - 40.8 2.22 - 2.21 9 - 7 41.0 - 41.9 2.16 - 2.16 7 - 5 42.6 - 42.7 2.12 - 2.12 SH
43.6 - 43.8 2.08 - 2.07 7 - 5 44.5 - 44.7 2.04 - 2.03 5 - 3 45.6 - 45.7 1.99 - 1.99 4 - 2 46.5 - 46.6 1.95 - 1.95 7 - 2 48.0 - 48.15 1.90 - 1.89 9 - 4 48.6 - 48.7 1.87 - 1.87 5 - 4 50.0 - 50.2 1.82 - 1.82 8 - 5 51.8 1.76 8 - 7 52.7 - 5.29 1.74 - 1.73 4 - 2 54.6 1.68 9 - 8 55.5 1.66 2 3 1~ 20 EXAMPLE 39. Preparation of AlPO4-14 (a) A reaction mixtuse W8S prepared by c~mblnlng 57.7 grams of 85% orthophosphoric acid (H3PO4) and 100 gr~ms of water, to wh~ch was added 34.4 grams of a hydrated alumlnum oxide (74.2 wt.% A1203, 25.8 wt.% H20), snd stlrred until homogeneous. To this mixture was added 18.3 grams of t-butylamine (t-BuNH2) and then 49.1 grams of water, and the mixture stirred until homogeneous.
The compcsition of the final reaction mixture in lar oxide ratios was:
uNH2 A12 o3 P2o5 4o H20 The reaction mixture was sealed in a stainless steel pressure vessel havlng an lnert plastic llning and heated in an oven at 150C at autogenous presQure for 96 hours.
The solid reaction product was recovered by filtration, wa~hed with water, and dried in air at 110C. Chemical analysis inticated the product contained 7.2 wt.% C, 2,6 wt.~ N, 34.3 wt.% A1203, 47.7 wt.% P205, 17.5 wt.% LOI, giving a protuct composition in molar oxide ratios of:
2 A123 1-00 ~205:0.~1 H20 The above product had an X-ray powder diffraction pattern characterized by the following data, wherein "I"~
is the intensity and "t" the interplanar spacing:

XO

28 _d_ 100 x ~/Io 9.2 9.61 100 9.4 9.41 ~h) 11.2 ~.90 18 13.1 6.76 17 13.4 6.61 ~h) 14.8 5.9R 3 5.8 ~.61 23 8.0 4.93 12 18.8 4.72 19.2 4.62 20.9 4.25 5 21.6 4.11 10 22.2 4.00 22 22.7 3.92 36 23.4 3.80 23.7 3.75 25.2 3.54 2 26.1 3.41 20 27.1 3.29 9 27.7 3.22 2 28.5 3.13 S
29.5 3.03 12 30.2 2.96 8 30.5 2.93 (sh) 30.9 ~89 4 31.2 2. 87 (sh~
32.0 ~.80 32.4 2.76 33.2 2.70 (sh) 33.5 2.67 6 34.1 2.63 35.0 2.56 35.5 2.53 2 36.4 2.47 3 38.1 2.36 3 38.8 2.32 S
39.5 2.28 40.4 2.~3 5 40.8 ~,21 42.0 2.15 2 42.4 ~ 2 43.6 ~.08 44.0 2.Q6 3 44.~ 2.~2 3 45.9 1.98 2 46.3 1.96 2 47.8 1.90 2 48. 5 1.8~ 2 49.8 1.83 51.6 1.77 2 52.7 1.74 53.5 '.71 4 55.7 ' .65 2 ( sh-shoulder) ., . ,, ~ ., ... ., . ., ... , , ... . . . , .. , .. ., .. ~.... .

12~79 ZO

The product WBS designated AlP04-14.
~ b) A portion of the solid cry~talline product obtained above was calcined in air at bbout 550C
for 2 hours. The calcined product h~d an X-ray powder diffraction pattern characteri2ed by the following data:

2~ d 100 X ~/Io 9.0 9.83 100 9.6 9.21 (sh) ll.S 7.69 29 12.0 7.38 9 13.2 6.71 45 13.3 6.66 (sh) 13.6 6.51 32 14.3 6.19 10 14.8 5.99 5 16.0 5.54 10 16.2 5.47 (sh) 16.8 5.28 2 18.2 4.87 35 18.6 4.77 38 18.9 4.70 (sh) 19.9 4.46 5 20.7 4.29 9 20.9 4.25 9 21.6 4.11 (sh) 22.0 4.04 23 22.5 3.95 29 22.8 3.90 (sh) 23.2 3.83 7 23.s 3.79 6 24.2 3.68 3 24.8 3.59 (sh) 25.1 3.55 6 25.9 3.44 3 26.6 3.35 12 27.0 3.30 20 27.4 3.25 16 27.8 3.21 11 28.0 3.19 11 28.6 3.12 (sh) 29.2 3.06 11 29.7 3.01 20 30.4 2.94 14 ~ 2 ( cont ' d) d 100 x I/Io 31.0 2.88 9 32.3 2.77 4 33.0 2.71 6 33.9 2.64 4 34.8 2.~8 4 35.6 2.52 2 36.8 2.44 5 37.7 2.39 3 38.4 2.34 2 39.1 2.30 3 40.1 2.25 3 40.6 2.22 3 41.8 2.16 42.6 2.12 3 43.0 2.10 2 44.2 2.05 6 45.3 2.00 46.2 1.95 2 47.4 1.92 2 48.6 1.87 3 50.0 1.82 3 52.1 1.76 3 54.1 1.70 4 ~ 8 ~2~3 EXAMPLE 40. Preparstion of AlP04-14.
A reaction mixture was prepared by combining 46.1 grams of 85% orthophosphoric acid (H3P04) and 119.2 grams of water, to which was added 27.5 grams of the same hydrated aluminum oxide as ~n Example 27 and stirred until homo~eneous. To this mixture was added 11.8 grams of isopropylamine (iPrNH2), and the mixture stirred until homogeneous. The composieion of the final reaction mixture in molar oxide ratios was:
1. 0 i-PrNH2 Al203 P2o5 ;4o H20 The reaction mixture was se~led in a stainless steel pressure vessel lined with an inert plastic material (polytetrafluoroethylene) and heated in an oven at 200C at autogenous pressure for 24 hours. The solid reaction product was recovered by filtration, washed with water, and tried in air at room temperature. Chemical analysis of the product showed 6.0 wt.% C, 2.4 wt.% N, 34.8 wt.% A1203, 48.6 wt.70 P205, 16.1 wt.% LOI, giving a product composition in molar oxide ratios of:
O.49 i-PrNH2:1.00A1203:1.00P205:1.03H20 The above product was established to be AlP04-14 by virtue of having an X-ray powder diffraction pattern essentially identical to that of the uncalcined product in example 39.
The species AlP04-14 as herein referred to is a crystalline metallophosphate whose essential framework structure has a chemical composition, exp.essed in terms of molar ratios of oxides, is A1203 : 1.0 ~ 0.2 P205 ~nd having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings 8et forth in Table 12 below:

2~ d lOo x I/Io 8.9 - 9.2 9.94 - 9.61 100 ->100 11.1 - 11.2 7.97 - 7.90 18 - 28 13.05 - 13.1 6.78 - 6.76 1~ - 23 15.8 - 15.85 5.61 - 5.59 21 - 23 22.2 - 22.3 4.00 - 3.99 22 - 28 22.7 3.92 36 - 49 26.1 - 26.2 3,44 - 3.40 20 - 25 All of the AlP04-14 compositions for which the X-ray powder diffraction data has presently been obtained have patterns that are within the generalized pattern of T~BLE 12(a) below:

1~679 ~ 2 TABLE 12 (a) 2~ d 100 x I/Io 8.9 - 9.2 9.94 - 9.61 100 ->100 9.4 9.41 ~sh) 11.1 - 11.2 7.97 - 7.90 18 - 28 13.1 6.76 17 - 23 13.4 6.61 (~h)- 9 14~8 5.98 3 15.8 - 15.85 5.61 - 5.59 21 - 23 18.0 4.93 12 - 20 18.8 4. ~2 ~ - 2 19.2 4.62 20.9 4.25 5 - 10 21.6 - 21. g 4.11 - 4.06 S - 10 22.2 - 22.3 4.00 - 3.99 22 - 28 22.~ 3.92 36 - 49 23.4 3.80 23.7 - 23.85 3.75 - 3.73 1 - 2 25.2 - 25.4~ 3.54 - 3.5~ 2 - 4 26.1 - 26.2 3.41 - 3.40 20 - 25 27.1 - 27.2 3.29 - 3.28 6 - 9 27.7 3.22 2 - 4 28.5 - 28.85 3.13 - 3.09 (sh) - S
29.5 - 29.6 3.03 - 3.02 12 - 20 30.2 - 30.3 2.96 - 2.95 8 - 11 30.5 2.93 (sh) 30.9 2.89 4 - 18 31.2 - 31.3 2.87 - 2.86 (sh) 32.0 - 32.2 2.80 - 2.78 1 - 3 32.4 - 32.6 2.76 - 2.75 1 - 3 33.2 - 33.3 2.70 - 2.69 (sh)- 3 33.5 - 33.8 2.67 - 2.65 6 - 8 34.1 2.63 35.0 - 35.2 2.56 - 2.55 1 - 3 35.5 - 35.7 2.53 - 2.51 2 - 5 36.4 - 36.6 2.47 - 2.46 3 - 4 37.3 2.41 38.0 - 38.1 2.37 - 2.36 1 - 3 38.5 - 38.8 2.34 - 2.32 2 - 5 39.1 - 39.5 2.30 - 2.;'8 (sh) - 4 40.4 - 40.5 2.23 - 2.23 4 - 5 40.8 - 41.0 2.21 - 2.20 2 - 4 42.4 2.13 2 - 3 42.8 2.11 2 43.6 2.08

4~ .0 - 44.2 2.06 - 2.05 3 44.6 - 44.8 2.03 - 2.02 3 45.0 2.01 3 45.9 1.98 2 4~ .2 - 46.3 1.96 - 1.96 2 46.6 1.95 3 4~.8 - 48.0 1.90 - 1.90 2 - 3 48.5 - 48.7 1.88 - 1.87 2 - 3 49.8 - 50.0 1.83 - 1.82 1 - 2 51.6 - 52.0 1.77 - 1.76 ' 2 - 3 52.7 - 52.8 1.73 - 1.74 1 - 2 53.5 - 54.1 1.71 - 1.70 , 4 55.2 - 55.7 1.66 - 1.65 1 - 2 ( sh- ~houlder) .. , ... -- .. .. . .... . .

EXAMPLE 41. ~reparatlon of AlPO4-16.
(a) A reaction mixture was prepared by combining 57.7 grams of 85% orthophosphoric acit (H3PO4) and 69 . 6 grams of water, to which was atded 34.4 gram~ of a hydrated aluminum oxide (a pseudo-boehmite phase, 74.2 wt.7. A1203, 25.8 wt.% H20), and stirred until ho geneous.
To this mix~ure wa~ added 27.~ grams of quinuclidine (C7H1 3N) dissolvet in 50.4 ~rams of water, and then 29.1 grams of water and the mixture stirred until ho -geneous. The composition of the final reaction mixture in molar oxide ratios was:
1-C7H13N A123 P205 4o H2 The~ reaction mixture was sealed in a stainless steel pressure ~essel lined with an inert plastic material and heated in an oven at 150C at autogenous pressure or 48 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at 110C. Chemical analysis of the product indicated the presence of 7.6 wt.% C, 1.33 wt.% N, 32.4 wt.% A1203, 43.4 wt.% P205, 24.1 wt.% LOI, giving a product conposition in molar oxide ratios of:
o~28c7Hl3N l-ooAl2o3 0-96P205 2- 2 The above product had an X-ray powder diffraction pattern characterized by the following data wherein "I" is the intensity snd "d" the interplanar spacing:

... .. . . . ..... ... . .. . . . . .. . . . . . . . . .................. . . .. .. . . .
... .... ..... . . .

ZO

2e _d100 x ~/~o 11.3 7.83 62 15.5 s.72 2 17.3 5.13 2 18.7 ~ 75 21.9 4.06 100 22.9s 3.8759 (~h) 26.55 3.3s7 27 27.6 3.23 2 28.0 3.19 2 29.0 3.08 12 29.75 3.00 28 32.7 2.739 4 34.7 2.585 5 37.9 2.374 8 39.6 ~.2~6 2 44.2 2.049 2 48.5 1.8~7 6 52.4 1.746 3 54.8 1.675 3 ~he product was designated AlPO~-16.
(b) Using the same procedure and reaction mixture composition as in part (a) except that the proportion of quinuclidine was decreased by 50 percent and the mixture was heated at 200C for 24 hours, AlPO4-16 was again produced. A small amount of AlPO4-17 was also present as an impuri~y.
(c) The procedure and gel composition of part (a) were followed except that the reaction mixture was heated for 16 hours. A portion of the sollds was submitted for X-ray analysis. The above product was established to be AlP04-16 by virtue of having a powder diffraction pattern essentially ~dentical with that in part (a).

_ 47 -(d) A portion of the solid crystalline product obtained above was calcined in air from 200C to 500C
turing 1 hour and then a~ about 500C for 2 hours. The calcined product had an X-ray powder diffraction pattern es~entially identical to that in pare (c).
The species AlPO4-16 as herein referred to is a crystalline metallophosphate whose essential framework structure has a chemical composition, e:cpressed in terms of molar ratios of oxides, is A1203 : 1.0 + 0.2 P205 and having a characteristic X-ray powder diffraction pattern which contains aè least the d-spacings set forth in Table 13 below:

2~ . d 100 x I/Io 11.3 - 11.5 7.83 - 7.69 59 - 63 18.7 - 18. 85 4 . 75 - 4 . 71 4E - 54 21.9 - 22.2 4.06 - 4.00 100 26.55 - 26.75 3.36 - 3.33 23 - 27 29.75 - 29.95 3.00 - 2. 98 26 - 30 All of the AlPO4-16 compositions for which the X-ray powder diffraction data has presently been obta~ned ha~e patterns that are within the genera~ zed pattern of Table 14 below:

12~79 ~ z,~

2~ d _ 100 x I/Io 11.3 - ll.S 7.83 - 7.69 59 - 63 lS.X - 15.9 5.72 - 5.57 0 - 2 17.3 - 17.4 5.13 - S.10 0 - 2 18.7 - 18.85 4.75 - 4.71 48 - 54 21. g - 22.2 4.06 - 4.00 100 22.95 - 23.1 3.875 - 3.850 9 - 11 26.55 - 26.75 3.357 - 3.332 23 - 27 27.4 - 27.6 3.255 - 3.232 0 - 2 28.0 - 28.2 3. lB7 - 3.164 0 - 2 29.0 - 29.1 3.079 - 3.058 8 - 1~
29.75 - 29.95 3.003 - 2.9B3 26 - 30 32.~ - 32.9 2.739 - 2.~22 4 - 5 34.7 - 34.95 2.585 - 2.567 5 - 7 37.9 - 38.1 2.374 - 2.362 8 - 10 39.6 - 40.0 2.2~6 - 2.254 0 - 2 ~4.2 - 44.5 2.049 - 2.036 2 - 3 48.5 - 48.7 1.877 - 1.8~0 6 - 8 52.4 - 52.6 1.746 - 1.740 2 - 3 54.8 - 55.0 1.675 - 1.670 2 - 3 EXA~LE 42. Preparation of AlP04-17.
(a) A resction mixture was prepared by combining 56. 7 gra~s of 85% orthophosphoric acid (H3P04) and 69.6 grams of water, to which was added 34.4 grams of a hydrated aluminum oxide (a pseudo-boehmite phase, 74.2 wt.% A1203, 35.8 wt.% H20), and stirred until ho geneous.
To this mixture was added 27.8 grams of quinuclidine (C7H13N) dissolved in 50.4 grams of water, and then 29.1 grams of water, and the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxi.de ratios was:
1.0 C7H13N:Al2o3 P205 4o H20 The reaction mixture was placedin a sealed stainless steel pressure vessel lined with an inert plastic material (polytetrafluoroethylene) and heated in an oven at 200 C at autogenous pressure for 96 hours. The solid reaction product was recovered and washed by repeated centrifugation with water, and dried in air at 110C.
Chemical analysis showed 12.4 wt.% C, 2,2 wt.% N, 32.5 wt.% A1203, 45.9 wt.% P205, 21.4 w~.% LOI, giving a product composition in molar oxide ratios of:
C7H13N: 1. OOA1204; 0.99 P205:O. 87 H20 The above product, denominated AlP04-17 had an X-ray powder diffraction pattern characterized by the ~ollowing tata, wherein "I" is the intensity and "d" the interplanar spacing:

- SO -Z~O
2e ~ 100 x I/Io .65 11.55 100 9.7 9.12 41 11.35 7.79 2 ~1.9 ~.44 3 13.35 6.63 39 14.2 6.24 13 14.7 6.03 2 15.4 5.75 62 16.6 5.34 33 18.0 4.93 20 18.8 4.72 2 19.6 ~.53 67 20.5 ~.33 93 21.4 4.15 50 22.1 4.02 2 22.5 3.95 15 23.3 3.82 34 23.8 3.74 ~ 39 24.2 3.68 3 25.3 3.52 S5 26.95 3.38 35 27.4 3.26 20 28.05 3.18 S
28.7 3.11 20 30.6 2.92 17 31.2 2.87 29 31.8 2.81 68 32.4 2.76 2 33.5 2.67 18 34.0 2.64 2 34.6 2.59 2 35.15 2.55 2 35,9 2.50 7 36.4 .2.47 6 36.8 ?.44 2 37.3 2.41 2 38.0 2.37 3 39.4 - 2.29 2 39.8 2.26 7 40.4 2.23 4 41.2 2.19 3 42.2 2.14 3 42.8 2.11 43.6 2.08 9 44.45 2.04 2 45.75 1.98 5 ~6.2 1.96 46.6 1.95 4 47.8 1.90 3 48.6 1.87 2 49.25 1.85 8 49.S5 1.84 11 50.2 1;82 2 51.25 ~.78 52.0 1.76 11 53.2 1.72 53.85 1.70 5 55.45 1.66 8 .

l:t~ 20 (b) A portion of the solid crysealllne product obtainet after continuin~ the digestion of the abo~e reaction mixture to ~68 hours exhibited ~n X-ray powder diffraction pattern e~sentially identical to that above.
(c~ A portion of the product from part (b) calcined in air at about S50C for 2 hours. The calcined product h~d an X-ray powder diffraction pattern charcterized by the following data:
2~() d(A) 100 x I/Io 7.~ 11.5 ~7 9.7 9.1 46 11.6 7.63~
11.85 ~.475 13 13.45 6.58 100 14.0 6.33 21 14.2 6.24 28 ~4.8 5.99 2 15.6 5.68 16 16.8 5.28 6 18.0 5.22 3 19.2 4.62 5 19.65 4.52 12 20.5 4~33~
20.8 4.273 42 21.6 4.11 22 22.2 4.00 2 22.6 3.93 2 23.65 3.~6~ 29 23.9~ 3.723

- 5~ -22o (Table cont~nued from previow page) 29 d 100 X I/Io 24.4 3.65~ 22 24.6 3.63~
25.0 3.56 7 25.3 3.52 12 26.2 3.40 27.3 3.26 20 28.2 3.16 15 28.8 3.10 10 29.4 3.038~ 7 29.6 3.018 30.1 2.969 30.8 2.903 7 31.4 2.849 24 31.9 2.805~ lS
32.1 2.788~
33.7 2.660 11 35.2 2.550 36.1 2.488~ 7 36.35 2.471J
3g .6 2.281 2 41.3 2.186 3 42.0 2.151 2 42.7 2.118 4 43.8 2.067 44.9 2.019 46.1 1.9~3 46.6 1.953 2 47,4 1.972 3 48.0 1.895 2 49.2 1.852 2 50.2 1.817 7 51.3 1.781 7 52.8 1.734 2 54.0 1.698 55,3 1.661 2 .. ... ... .. . ..

EXAMPLE 43. Preparstion of AlPO4-17 A reaction mixture was preparet by combining 115.3 grams of 85~ orthophosphoric acid (H3PO4) and 256 grams of water, to which was added 68.7 grams of a hydrated aluminum oxide (a pseudo-boehmite phase, 74.2 wt.%
A1203, 25,8 wt.% H20), and stirred until ho geneous.
To this mixture was added 43.6 grams of neopentylamine (CSH13N) and then 44.1 grams of water, and the mixture sitrred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
1.0 C5H13N A123 P205 40 H2 The reaction mixture was placed in a stainless steel pressure vessel lined with an inert plastic material (polytetrafluoroethylene) and heated in an oven at 150C
at autogenous pressure for 168 hours. The solid reaction protuct was recovered and washed by repeated centrifugation with water, and dried in air at 110C. Chemical analysis showed 9.9 wt.% C, 2.5 wt.% N, 32.6 wt.% A1203, 44.2 wt.% P205, 21.8 wt.% LOI, giving a product composition in molar oxide ratios of:
5 13N:1.00Al203:0.97P205:1.28H20 .
The ma~or phase in the above product had an X-ray powder diffraction pattern very similar to that of the product in example 42 (a). The product was designated AlPO4-17.

22~

EXAMPLES 44 - 45. Preparation of AlP04-17.
A procedure similsr to that in example 42 was followed except where ~ndicatet in Table D. The camposition of each final reaction mixture ln mclar-oxide ratios was:
1. 0 R:A1203 P205 40 H20 where R is indicated in Table D. A portion of the ~olid product from each reaction was sub~ected to X-ray analysis and in each case a phase characterised by an X-ray powder diffraction pattern essentially the same as that of the product of exam~le 42 (a) was obser~ed.

EXA~LE R REACTION REACTION
# TIME(Hrs) TEMP. (C) 44 Cyclohexylamine 168 200 Piperidine 168 200 5he species AlP04-17 as herein referred to is a crystalline metallophosphate whose essential fra~ework structure has a chemical composition, expressed in terms of lar ratios of oxides, is A1203 : 1-0 + 0-2 P205 and having a characteristic X-ray powder diffraction pattérn which contain~ at least the d-spacings set forth in Table 15 below:

2~ d 100 x I/lo 7 . 6 - 7 . 8 11 . 6 - 11 . 33100 13.25 - 13.5 6.68 - 6.56 39 - 54 ~5 . 35 - 15. 6 5. 77 - 5. 68 26 - 62 19. 55 - 19. 75 4 . 54 - 4 . 50 14 - 67 20. 35 - 20. 65 4 . 36 - 4 . 30 45 - 93 21. 25 - 21. 5 4 . 18 - 4 . 13 20 - 50 25 . 3 - 25 . 45 3. 52 - 3. 50 12 - 55 31. ~5 - 31. 85 2 . 83 - 2 . 81 19 - ~

.. . .... .. ... . . .. ..... . ~ . .. .. . . . . . . .

22() All of the AlP04-17 compos~tions for which the X-ray powder t~ffrsction data has pre~ently been obta~net have patterns that are w~thln the generalized pattern of ~able 16 below:

2~ d 100 x ~/Io 7.6 - 7.8 11.6 - 11.33 100 9.7 - 9.9 9.12 - 8.93 15 - 41 11.35 - 11.9 7.80 - 7.44 4 - 5 13.25 - 13.5 6.68 - 6.56 39 - 54 14.2 - 14.4 6.24 - 6.15 2 - 13 15.35 - 15.6 5.7~ - 5.68 26 - 62 16.5 - 16.7 5.37 - 5.31 10 - 33 17.9 - 18.15 4.96 - 4.89 4 - 20 19.55 - 19.75 4.54 - 4.50 14 - 67 20.35 - 20.65 4.36 - 4.30 45 - 93 21.25 - 21.5 4.18 - 4.13 20 - 50 21.7 - 21.8 4.10 - 4.08 (sh) 22.5 - 22.65 3.95 - 3.93 3 - 15 23.1 - 23.45 3.85 - 3.79 17 - 34 23.7 - 23.95 3.75 - 3.72 14 - 39 24.1 - 24.2 3.69 - 3.68 ~sh) 25.3 - 25.45 3.52 - 3.50 12 - 55 26.75 - 27.0 3.33 - 3.30 14 - 35 27.35 - 27.5 3.26 - 3.24 5 - 20 27.85 - 28.2 3.20 - 3.16 2 - S
28.6 - 28.8 3.12 - 3.10 5 - 20 29.45 - 29.8 3.03 3.00 2 -30.45 - 30.7 2.94 - 2.91 4 - 17 31.0 - 31.3 2.88 - 2.86 13 - 29 31.65 - 31.85 2.83 - 2.81 19 - 68 32.3 - 32.4 2.77 - 2.76 1 - 2 33.4 - 33.6 2.68 - 2.67 18 - 8 34.0 2.64 2 34.6 2.59 2 35.15 2.55 2 35.7 - 36.0 2.51 - 2.49 4 - 7 36.3 - 36.6 2.47 - 2.45 1 - 6 36.8 2.44 2 37.3 2.41 2 3~.8 - 38.0 2.38 1 - 3 39.2 - 3S.4 2.30 2 39.65 - 39.9 2.27 - 2.26 2 - 7 40.3 - 40.5 2.24 - 2.23 1 - 4 41.0 - 41.2 2.20 - 2.19 1 - 3 41.9 - 42.2 2.16 - 2.14 1 - 3 42.8 2.11 43.6 - 43.8 2.08 - 2.07 2 - 9 44.45 2.04 2 (sh-~houlter) ~ Z~O 12~79 TABLE 16 (continued) ~5.5 - 45.8 1.99 - 1.98 1 - 5 46.2 1.97 ~6.5 - 46.7 1.95 - 1.95 1 - 4 47.35 - 47.8 1.92 - 1.90 1 - 3 48.55 - 48.8 1.88 - 1.87 1 - 2 ~9.25 1.85 8 49. ~5 - 49.7 1.84 - 1~ 83 4 - 11 50.2 - 5025 1.82 - 1.82 1 - 2 51.25 1.78 52.0 - 52.2 1.76 - 1.75 3 - 11 53.1 - 53.2 1.72 - 1.72 53.75 - 54.0 1.71 - 1.~0 1 - 5 55.2 - 55.5 1.66 - 1.66 3 - 8 ~ 2 ~ 0 ;2679 EXAMPLE 46. Preparation of AlP04-18.
A reaction mlxture was prepared by combining 46.1 grams of 85% orthophosphor~c acid (H3P04) and 53.8 grams of water, to which was added 27.5 grams of a pseuto-boehmite phase, (74.2 wt.% A1203, 25.8 wt.7. H20), ant st~rret until homogeneous. To this mixture was added an aqueous solution prepared by combining 6.5 grams of 37 wt.% HCl and 98.0 grams of 40 wt.% tetraethylammonium hydroxide (TEAOH), ant the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ra~ios was:
0-33HCl 0-67tTEA)20:A1203 P205 40 2 The reaction mixture was placet in a sealed stainless steel pressure vessel linet with an inert plastic material (polytetrafluoroethylene) and heatedin an oven at 150C
at autogenous pressure for 336 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at room temperature. Chemical analysis showed 8.9 wt.% C, 1.28 wt,% N, 33.5 wt.% Al203, 38.9 wt.%
P205, 26.4 wt.Z LOI, giving a product composition in molar oxide ratios of:
0 14 (TEA) 20 1- OOA1203 0 83P2n5 0 9 H20 The above product contained a minor amount of crystalline impurity but the ma30r phase, denominated AlP04-18, had an X-ray powd~r diffractlon pattern characterized by the following data, wherein "I" is the intensity and "d" the interplanar spacing:

~ 58 -~ ~t;~zo ~ 12679 -2e d _ 100 x I/Io 9.60 9.21 100 10.45 8.47 8 11.0 8.04 9 13.1 6.76 6 14.0 6.33 8 14.8 5.99 10 15.5 5.72 2 16.9) 5.25 61 17.03 5.22 17.9 4.96 20 19.3~ 4.60 17 19.5J 4.55 20.15 4.41 35 20.95 4.24 45 22.1 ~ 4.02 17 22.3~ 3.99 23.3 3.82 5 23.85 3.73 6 24.4 3.65 14 24.9 3.58 g 25.4 3.51 6 26.1 3.41 13 26.45~ 3.37 12 26.8 ~ 3.33 28.0 3.19 16 230 8 2:~ 20 30.75 2. gl 14 31.3 2.86 14 31.8~ 2.81 24 32.4J 2.76 33.4 2.68 6 34.5 2.60 3 35.8~ 2.51 3 36.25 2.48 38.2 2.36 2 40.2 2.24 41.7 2.17 3 42.9 2.11 5 47.8 1.90 3 48.6 1.87 2 49.6 1.84 4 51.0 1.79 4 52.0 1.~6 2 54.2 1.69 4 55.1 1.67 2 ._ .. , . _ .. .. _ _ ~_._ .. , _ .. __ .. . ....
... . . . . .. .,, . . . . .. . ~ . . . .. , .. . . . . . . . . , . _ ~ O 12679 The spec~es AlP04-18 as herein referr2t to is a cry~talline met~llophosphate whose essent~ 81 fr2mework structure has a chemlcal compositlon, expressed ln terms of molar ratios of oxltes, is A1203 : 1.0 + 0.2 P205 and ha~ing a characteristic X-ray powder tiffraction pattern which conta~ns at lea~t the d-~pacings set forth in Table 17 below:

2~ d 100 x I/~o _ .
9.60 - 9.6S 9.21 - 9. 100 15.5 - 15.55 5.72 - 5.70 27 - 34 16.9 - 17.1 S.25 - 5.19 61 - 70 17.9 4.96 .20 - 25 20.15 - 20.25 4.41 - 4.39 35 - 43 20.95 - 21.05 4.24 - 4.22 45 - 52 30.0 - 30.1 2.98 - 2.97 20 - 25 31.8 - 32.5 2.81 - 2.75 24 - 27 All of the AlP04-18 compositions for which the X-ray powder diffract~on data has presently been obtained have patterns that are within the generalized pattern of Table 18 below:

28 d 100 x I/~o 9.60 - 9.65 9.21 - 9.17 100 10.4S - 10.50 8.47 - 8.42 8 11.0 - ll.OS 8.04 - 8.01 9 - 1 13~1 - 13.2 6.76 - 6.71 6 - 7 5.5 - 15 S5 S.72 - S 70 27 - 34 17.9 4.96 20 - 25 19.35 - lg.6 4.59 - 4.53 8 - 17 20.15 - 20.25 4.41 - 4.39 35 - 43 20.95 - 21.05 4.2~ - 4.22 45 - 52 22.1 - 22.3 4.02 - 3.99 17 - 19 23.3 - 23.4 3.82 - 3.80 5 - 7 ~3.~5 - 24.0 3.73 - 3.71 6 - 8 .. .. . .. . . .. ..... . . . ............ ... . . . . .. .. . . .. . . . . .

~.ttj~ 2 ~ O 12679 TABLE 18 (contlnued) 24.4 - 24.5 3.65 - 3.63 14 24.9 - 25.0 3.58 - 3.56 9 - 11 25.4 - 25.55 3.51 - 3.49 6 - 7 26.1 - 26.2 3.41 - 3.40 13 - lS
26 45 - 26.9 3.37 - 3.31 12 28 0 - 28.2 3.19 - 3.16 16 - 1~ -30.0 - 30.1 3.98 - 3.9? 20 - 25 30.75 - 30.9 2.91 - 2.87 14 - 17 31.3 - 31.4 2.86 - 2.85 14 - 15 31.8 - 32.5 2.81 - 2.75 24 - 27 33.3 - 33.55 2.69 - 2.67 6 34.5 - 34.6 2.60 - 2.59 3 - 4 35.8 - 36.2 2.51 - 2.48 3 - 4 40.0 - 40.2 2.25 - 2.24 1 - 2 41.7 - 41.8 2.17 - 2.16 2 - 3 42.9 - 43.0 2.11 - 2.10 5 47.8 1.90 3 - 4 49.6 1.84 4 - 5 Sl.0 1.79 4 - 7 52.0 1.76 2 - 4 54.2 - 54.4 1.69 - 1.69 3 - 4 (b) A portion of the solid crystalline product obtained from a similar preparation and exhibiting an X-ray powter diffraction pattern essentially identical to that of part (a) was calcined stepwise in 100 increments from 100 to 600C, being held at each temperature for one hour before the next increment. The calcined product had an X-ray powder diffraction pattern characterized by the following tata:

~ Z2v 12679 2~ d 100 x I/Io 9.5 9.31 100 10.0 8.85 h 10.4 8.51 sh 10.6 8.35 14 11.3 7.83 4 12.95 6.83 9 13.5 6.56 8 14.5 6.11 4 16.1 5.50 11 17.0 5.22 18 17.2 5.16 17 19.1 4.65 5 19.7 4.51 7 20.0 4.44 6 20.? 4.29 12 21.3 4.17 15 21.9 4.06 5 22.5 3.95 8 22.9 3.88 9 23.9 3.72 12 24.3 3.66 ~h 24.9 3.58 3 25.2 3.53 3 25.7 3.47 ~h 26.0 3.43 8 26.3 3-39 27.1 3.29 4 27.8 3.21 7 29.1 3.07 7 30.0 2.98 8 30.4 2.94 sh 31.0 2.88 13 31.6 2.83 5 32.2 2.78 7 32.6 2.75 sh 33.0 2.71 sh 33. ~ 2.66 4 34.7 2.59 3 37.0 , 2.43 2 38.8 2.32 2 43.2 2.09 2 49.0 1.86 4 55.2 1.66 3 55.8 ~ 1.65 2 1 1~;8220 EXAMPLE 47. Preparation of AlPO4-20.
(8) A reaction m$xture was preparet by combining 23.1 grams of 85% osthophosphoric acit (H2PO4) ant 34.6 grams of water, to which was atded 13.8 grams of a hytratet aluminum oxite (a pseudo-boehmite phase, 74.2 wt.% A1203, 25.8 wt.Z H20), and stirred until homogeneous. To this mixture was atted 36.2 gsams of tetramethylammonium hytroxite pentahytrate (TMAOH- 5H20) tissolvet in 50 grams of H20 ant the mixture stirred until homogeneous. The composition of the final reaction mixture in molar oxide ratios was:
0-5 (TMA)20:A1203 P205 43 H20 The reaction mixture was sealed in a stainless steel pressure vessel linet with polytetrafluoroethylene and heatet in an oven at 150C at autogenous pressure for 71 hours. The solit reaction product was recovered by repeated centrifuga~ion and washing with water, and tried in air at room temperature. Chem~cal analysis of the product ~howed 6.0 wt.% C, 1.76 wt.% N, 32.7 wt.Z
A1203, 44.8 we.% P205, 22.8 wt.% LOI, giving a product composition in molar oxide ratios of:
( ~A)2o:l.ooAl2o3:o.98p2~5;2.l7H2o Th~ AlPO4-20 protuct con~ainet a minor amount of crystalline impurity, but the major phase hat an X-ray powder diffrac-tion pattern characterized by the following data, wherein "I" is the intensity and '!d" the interplanar spacing:

Zo J~

2e ~ loO x ~/Io 14.0 6.326 51 19.9 4.462 44 22.3 3.~86 16 24.5 3.633 100 28.2 3.164 25 31.6 2.831 18 34.~ 2.585 18 ~0.3 2.238 4 ~3.1 2.099 5 47.8 1.903 4 52.2 1.752 10 (b) A portion of the solid crystall~ne product obtained from a s~milar preparation and exhibiting an X-ray powder diffraction pattern essentially $dentical to that of part (a) was calcined in air at about 100C for 1 hour, 200C for 1 hour, 400C for 1 hour and finally at 620C for 1 hour. The calcined product had an X-ray powder diffraction pattern characterized by the followin~
data:

29 d 100 x Itlo 14.3 6.19 100 20.3 4.37 27 22.7 3.92 9 24.8 3.59 57 28.4 3.14 20 32.1 2.79 19 35.1 2.56 13 40.9 2.21 4 52.7 1.74 6 AlPO4-20 appears to be a structural analogue of the alumino-silicate sodalite.

- 6~ -~ 2 ~

EXAMPLF 48. Preparation of AlP04-20.
A reaction mixture was prepared by combining 57.6 grams of ~5% orthophosphoric acid (H3P04) and 90.5 grams of water, to which was added 37.8 grams of the sa~e hydrated aluminum oxide as ~n E~ample 47 hnd stirred until homogeneous. To this mixture was atded 36.2 grams of tetramethylammon$um hydroxide pentahydrate (TMAOH-5H20) and 2.0 grams of sodium hydroxide dissolved ~n 50 grams of H20, and the mixture stirred until ho geneous. The com~osition of the final reaction mixture in lar oxide ratios was:
O.1 Na20:0,4(TMA)20;1.lA123 P25 43 2 The reaction mixture was placed in a sealed stainless steel pressure vessel lined with an inert plastic material and heated $n an oven at 150C at autogenous pressure for 72 hours. The solid reaction product was recovered by centrifuging and washing with water, and dried in air at 110C. A portion of the solids was subjected to X-ray analysis. The AlP04-20 product had an X-ray powder diffraction pattern essentially identical to that of the uncalc$ned product in example 47 (a).

1267~

EXAMPLE 49. Preparaeion of AlPO4-20.
A reaction mixture was prepared by co~bining 92.1 grsms of 85% orthophosphoric acid (H3PO4) snd 220.9 grams of water, to which was sdded 55.0 grams of a hydrated aluminum ox~de (Catapal S8, a pseudo-boehmite phase, 74.2 wt.7. A1203, 25.8 wt.X H20), and stirred until homogeneous.
To this mixture was atded 72.5 grams of tetramethylammonium hydroxide pentahydrate (TMAOH-5 H20) dissolved in 50 grams H20 and the mixture Q~irred until homogeneous. To this mixture 13.0 grams of NaA zeollte were added and the mixture homogenized. Exclusive of the ~aA zeolite, the composition of the final reaction mixture in molar oxide ratios was:
0.5 (TMA)20;A1203 P205 50 H20 The reaction mixture was placed in a stainless steel pressure vessel having an inert plastic lining and heated in an oven at 125C at autogenous pressure for 53 hours.
The qolid reaction product was recovered by centrifuging and washing with water, and dried in air at 110C. The AlPO4-20 product had an X-ray powder diffraction pattern essentially identical to that of the product in Example 47 (a)-The species AlPO4-20 a~ herein referred to is a crystalline metallophosphate whose essential framework structure has a chemical composition, expressed in terms of mclar ratios of oxides, is Al203 : 1.0 ~ 0.2 P205 .. . . ... ". . . . . . . . ..... . . . . . .. . . .... . .

22~

and ha~ing a characteristic X-ray powder difiraction pattern which contain~ at lea~t the d-spacin~s set forth ln Tsble 19 below:

2~ d 100 x I/Io 13.9 - 14.1 6.3~ - 6.28 40 - 55 lg.8 - 20.0 4.4B - 4.44 40 - 4B
24.3 - 24.5 3.66 - 3.63 100 31.4 - 31.7 2.85 - 2.82 11 - 18 All of the AlP04-20 compositions for which the X-ray powder d~ffraction data has presently been obta~ned have patterns that are within the generalized pattern of Table 20 below:

2~ d 100 x I/Io .
13.9 - 14.1 6.37 - 6.28 40 - 55 19.8 - 20.0 4.48 - 4.44 40 - 48 22.2 - 22.4 4.00 - 3.97 5 - 16 24.3 - 24.5 3.66 - 3.63 100 28.2 - 28.3 3.16 - 3.15 12 - 25 31.4 - 31.7 2.85 - 2.82 11 - 18 34.6 - 34.8 2.59 - 2.58 15 - 18 40.2 - 40.5 2.24 - 2.23 4 - 5 42.7 - 43.1 2.12 - 2.01 5 - 8 47.5 - 47.8 1.91 - l.gO 4 - 7 51.9 - 52.2 1.76 - 1.75 10 - 11 .

2 2 ~

~XAMPLE 50. Preparation of AlP04-22.
(a) A reaction mixture was preparet by combin~ng 57.7 grams of 85% orthophosphoric acid (H3P04) and 80.4 grams of water, to which was sdded 34.4 grams of a hytrated aluminum oxide (8 pseudo-boehmite phase, ~4.2 wt.Z A1203, 25.8 wt.% H20), and stirred until homogeneous. To th~s mixture was added 110.6 grams of an aqueous solution of 68.2 wt.% N,N'-dimethyl-1,4-diazabicyclo(2,2,2)octane dihydroxide (DDO), and the mixture stirred until homogeneous.
The composition of the final reaction mixture in molar oxide ratios was:

The reaction mixture was sealed in a linet stainless steel pressure vessel ant heatet in an oven at 200C
at autogeneous pressure for 72 hours. The solit reaction product was recovered by filtration, washed with water, and dried in air at 110C. Chem~cal analysis showet 9.6 wt.% C, 2.9 wt.% N, 33.2 wt.% A1203, 47.6 wt.% P205, 19-4 wt.% LOI, giving a product composition in molar oxide ratios of:
0.31 DDO:LO A1203:1-03 P20s;0.31 H20 The above product, denominated AlP04-22, had an X-ray powter diffraction pattern characterized by the following data, wherein "I" is the intensity and "~" the interplanar spacing:

11~8~`~V

_23 d 100 x I/Io 8.55 10.34 25 9.0 9.83 2 (~h) 9.1 9.72 57 11.4 ~.76 13 0 66 871 (~h) 14.6 6.07 4 lS.6 5.68 17.3 5.13 26 18.5 4.80 100 20.65 4.30 43 21.4 4.15 1 (sh) 21. ~5 4.08 19 22.6 3.93 6 24.2 3.68 8 24.8 3.59 24 26.2 3.40 36 27.0 3.30 ~sh) 27.3 3.27 20 27.8 3.21 8 28.6 3.12 10 29.3 3.05 30 30.1 2.969 8 31.55 2.835 16 32.2 2.780 2 33.0 2.714 2 33.2 2 698 2 34.15 2 625 2 34.9 2.571 11 35.55 2.525 S
37.4 2.404 (sh) 37.6 2.392 9 39.1 2.304 39.25 2.295 39.75 2- 268 2 40.35 2.235 4 41.2 2.191 2 4~ .1 2.146 2 43.7 2.071 44.3 2.045 4 44.7 2.027 2 45.2 2.006 4 46.4 1.957 47.0 1.933 2 48.4 (~h) 1.881 4 48.7S 1.868 13 49.7 1.834 5 50.2 1,817 2 51.4 1.778 cl S3.2 1.722 3 54.0 1.698 5 54.4 1.687 2 ( shsshoulder) (b) A portion of the ~olid crystalllne product obtainet abo~e was calcined in air st about 600C for 2 hours. The calcined AlP04-22 had an X-ray powder diffract~on pattern chsracterized by the following data:
2~ _ d 100 x I/Io 8.6 10.28 Ish) 9.1S 9.65 100 12.6 7.
12.9 6.86 J 4 13.0 6.81 14.4 6.15 ~ 21 14.7 6.03 J
17.3 5.13 S0 18.5 4.80 92 20.4 4.35 64 21.55 4.12 23 22.5 3.95 11 23.9 3.72 34 24.8 3.59 18 25.9 3.44 ~ 32 26.1 3.41 J (sh) 27.3 3.27 ~ 24 27.5 3.24 J (sh) 28.4 3.14 12 29.1 3.07 31 31.2 2.867 31.4 2.84gJ 19 32.9 2.~22 4 34.55 2.596 lS
34.9 2.571 14 35.5 2.529 S
37.3 2.411 3 39.6 2.275 40.8 2.212 3 41.5 2.176 44.4 2.040 4 44.9 2.919 2 46.7 1.945 3 47.2 1.92S 2 47.8 1.903 3 48.2 1.888 3 49.0 1.859 2 52.7 1.737 2 53.4 1.7~ 4 . _ . _ " . . . . . .. ... , . . . _ . ..
... ... . ...... ... .. . . .

~ 2 ~ 0 The ~pec~es AlP04-22 as herein referret to is a crystalline metsllophosphate whose essential framework structuse has a chemical compos~tion, expre~Qet in terms of mclar ratios of oxites, ls A1203 : 1.0 + 0.2 P205 ant ha~ing a characteristic X-ray powde~ tlffraction pattern which contains at least ~he d-spacings set forth in Table 21 below:

2~ d 100 x I/Io 9.1 - 9.1S 9.72 - 9.66 5~ -100 18.45 - 18.5 4.81 - 4.80 66 -100 20.55 - 20.65 4.32 - 4.30 43 - 70 26.1 - 26.2 3.41 - 3.40 36 - 44 29.3 3.05 30 - 32 31.55 2.835 16 - 29 All of the AlPO4-22 compositions for which the X-ray powder diffraction data has presently been obtained have patterns that are within the ~eneralized pattern of Ta~le 22 below:

2~ d 100 x I/Io 8.55 10.34 15 - 25 9~0 9.83 (sh) 9.1- 9.1S 9.72- 9.66 57 -100 11.4 7.~6 0 -12.7 6.97 ~sh) 12.95 - 13.0 6.83 - 6.81 9 - 14 14.5 - 14.6 6.11 - 6.07 3 - 5 15.55 - 15.6 5.70 - 5.68 4 - 6 1~.25 - 17.~ 5.14 - 5.13 22 - 26 18.45 - 18.5 4.81 - 4.80 66 -100 20.55 - 20.65 4.32 - 4.30 43 - 70 21.65 - 21.75 4.10 - 4.09 12 - 19 22.6 3.93 6 - 7 23.6 - 23.7 3.77 - 3.75 22 23.8 - 23.85 3.74 - 3.73 18 - 23 24.2 3.68 8 - 14 24.7 - 24.8 3.60 - 3.59 10 - 24 26.1 - 26.2 3.41 - 3.40 36 - 44 , ~ 2~0 12679 TABLE 22 (continued) 27.0 3.30 (sh) 27.2 - 27.3 3.28 - 3.2~ 17 - 20 2~ 2~.8 3.22 - 3.21 8 - 23 28.6 3.12 10 - 14 29.3 3.05 . 30 - 32 30.1 2.969 6 - 8 31.55 2.835 16 - 29 32.2 2.~80 0 - 2 32.9 - 33.0 2.722 - 2. ~14 2 - 3 33.2 - 33.3 2.698 ~ 2.691 2 - 3 34.1 - 34.15 2.629 - 2.625 2 ~ 3 34.9 2.571 5 - 11 35.55 2.525 S - 8 37-4 2.404 (sh) 37.5 - 37.6 2.398 - 2.392 6 - 9 39.0 - 39.25 2.309 - 2.295 1 - 2 39.75 2.26~ 0 - 2 40.30 - 40.35 2.238 - 2.235 2 - 3 41.0 - 41.2 2.201 - 2.191 1 - 2 41.9 - 42.1 2.156 - 2.146 2 - 3 43. ~ 2.0~1 1 - 5 44.2 - 44.3 2.049 - 2.045 3 - 4 44. ~ - 44.9 2.02~ - 2.019 1 - 2 45.2 - 45.3 2.006 - 2.002 <1 - 4 46.2 - 46.4 1.965 - 1.957 ~1 - 1 46.8 - 47.0 1.941 - 1.933 ~1 - 2 48.1 - 48.4 1.892 - 1.881 (sh) - 6 48.6 - 48.75 1.873 - 1.868 13 - 19 49.6 - 49.7 1.838 - 1.834 4 - S
50.1 - 50.2 1.821 - 1.817 1 - 2 51.4 1.778 <1 53.0 - 53.2 1.728 - 1.722 2 - 3 53.8 - 54.0 1.704 - 1.698 5 - 6 54.3 - 54.4 1.689 - 1.687 2 1267g ~ lt;,~220 EXAMPL~ Sl. Preparation of AlPO4-25 The crystall~ne metallophosphate denominated AlP04-25 i8 preferably prepared by the thermally intuced structural converslon of a less stable cryatall~ne lnter-mediate which i8 ~ynthesized by hydrothermal crystalllza-tion from B reaction gel in a manner similar to that employed to obtain mo~t of the AlP04-n species of the present ~nvention. Thi~ lntermediate, identified as AlPO4-21 is readily synthesized using a considerable variety of organic templating agents which are removed from the structure during calcination to ~roduce the stable AlPO4-25.
(a) Preparation ~f AlP04-21.
A reaction mixture was prepared by combining

7.7 grams of 85% orthophosphoric acid (Y3~O4) and 25.9 grams of water, to which was added 4.6 ~rams of a pseudo-boehmite phase (74.2 wt.% A1203, 25.8 wt.% H20), and stirred until homogeneous. To this mixture was added 2.4 grams of (CH2)4:NH, (pyrrolidine), and the mixture stirred until homogeneous. The composit$on of the final reaction mixture in molar oxide ratios was:
1.0 (CH2)4:~H A123 P205 2 The reaction mixture was sealed in a sta$nless steel pressure vessel lined with polytetrafluoroethylene and heated in an oven at 150C at autogenous pressure for 150 hours. The solid reaction product was recovered by filtration, washed with water, and dried in air at 110C. Chemical analysis of the product showed 10.2 wt.-%
C, 3.2 wt.-Z N, 32.1 wt.Z A1203, 47.1 wt.% P205, 19,8 wt.%
LOI, giving a product composition in molar oxide rat$os of:

_ 7~ _ ~ 2 0 0.~7 (cH2)4NH:l 00 A1203 1~05 P205 0 83 ~2 The product was designated A1~04-21, and had an X-ray powter d1ffraction pattern characterized by the following tata, wherein ~" ls the $ntenslty and "d" the interplanar ~pacing:

10.0 1~1~5 1005l 1/1 10.5 8.425 11.3 7.830 14 11.8 ~.500 13 12.2 ~.255 36 13.2 6.707 6 14.2 6.237 36 14.6 6.067 27 lS.9 5.574 31 16.8 5.277 6 18.5 4.796 4 19.6 4.529 11 20.4 4.353 25 22.6 3.934 97 22.8 3.900 88 23.7 3.754 23 25.1 3.548 100 25.8 3.453 6 26.2 3.401 19 26.6 3.351 53 27.6 3.232 47 28.2 3.164 2~
29.0 3.079 11 31.0 2.885 8 32.0 2.797 35 32.6 2.747 23 32.9 2.722 38 34.0 2.637 15 35.2 2.550 2 35.9 2.501 6 37.2 2.417 12 37.8 2.380 3 38.8 2.321 5 40.2 2.243 7 44.4 2.040 7 47.6 1.910 8 50.8 1.797 7 S2.0 1.759 3 52.6 1.740 11 53.2 1.722 8 ~4.0 1.6g8 7 (b) A procedure similar to that in part (a) above was followed except where indicated in Table E.
A portion of the solid product from each reaction was subjected to X-ray analysis and in each case a phase characterized by an X-ray powder diffraction pattern essentially the same as that in part (a) was o~served alone or in admixture.
TABLE E

7 Ubed (R) Raaction M~xtume Composition Digestion Temp.

R A123 P25 H2 (Hrs.) (C) (b)l (CH3~3N 1 1 1 50 94 150 (b)2 (CH2)4:NH 1 1 1 50 166 150 Pyrrolidine (b)3 C6H14N2 1 1 1 50 168 200 1,4-Dinethyl PiperA7ine ~b)4 CllH26N2 1 1 1 40 168 200 3-(di-n-butylamino~-Prcpylamine ~b)S ~H18N2 1 1 1 40 168 200 N,N,N',N'-tetramethyl-1,3-propanedismine (b)6 C4HllN 1 1 1 40 336 200 N,N-dimethyl-ethano-Læmine (b)7 n-C3H ~H2 1 1 1 50 33' 20Q

n-Propylamine nb)8 C6H16N2 1 1 1 50 168 20Q

N,N,N',N'-tetramethyl-ethylenedi~mine (b)9C3H8N0 1 1 1 50 168 200 N-Methyl-ethanolamme ZXO

Preparation of AlPO4-25 (c) A portion of the AlPO4-21 crystalline product obtained in part (a) was calcined in air at about 600C for 2 hours. The calcined product had an X-ray powder diffraction pattern quite different from the starting AlPO4-21 and is a new and novel microporous aluminophosphate species denominated AlPO4-25.
The X-ray pattern of this species is characterized by the following data:

- 75a -2~0 2~ _d _ 100 x ~/Io 7.6 11 532 3 9.6 9 213 83 10.6 8 346 11.8 7 500 14 12.6 7.025 3 15.2 5.829 100 19.1 4.64~ 71 21.3 4.171 84 24.6 3.619 6 25.5 3.490 43 26.1 3.414 14 28 ~ ~ 3 121 10 31.0 2.885 23 33.2 2.698 8 35.7 2.515 7 37.4 2.404 . 8 37.9 2.374 8 43.2 2 094 3 (t) Five AlP04-21 samples crystallized in parts (b)l, (b)3, (b)5, (b)7 ant (b)9, respectively, were calcined at 500 - 600C in air and found to convert to the crystal structure characteristic of AlP04-25. It is believed all AlPO4-21 compositions can be converted to AlPO4-25 in a similar manner.
The species ~lPO4-25 as herein referred to is a crystalline metallophosphate whose essential framework structure has a chemical composition, expressed in terms of molar oxides, is A1203 : 1.0 + 0.2 P205 and having a characteristic X-ray powder diffraction pattern whlch contains at least the d-spacings set forth ln Table 23 below:

1 1 ~8 22Xv 2~ d 100 x I/Io 9.4 9.41 32 - 96 15.0 5.91, 35 - 76 18.8 - 18.9 4.72 - 4.70 35 -100 21.1 4.21 28 -100 22.5 3.95 16 - 32 25.3 3.52 14 - 37 30.8 - 30.9 2.90 - 2.89 20 - 31 Eu~PLe 52. Preparation ofA1~4-26.
A solution of 200 grams 1, 4-dibromobutane in 500cc of a 4:1 volume mixture of dimethylformamide:
methanol (DMF/MeOH) was prepared and cooled to O in an ice/water bath. To this was added a solution of 159.4 grams N,N,N',N'-tetramethyl-1,6-hexanediamine in 500 cc 4:1 DMF/MeOH. This mixture was stirred for three days, gradually warming to ambient temperature. The product mass was slurried in diethylether, filtered, washed with ether and dried in air at ambient temperature. The product was a polymeric quaternary ammonium salt, [(C14 H32N2)Br2]X:

Br~ )X
In order to obtain the hydroxide form, 200 grams of the above polymer was dissol~et in 800 grams of H20 and added dropwise over 6 hours to a stirred suspension of 131.4 grams Ag20 in 1000 grams H20. The resulting mixture was stirred overnight and filtered.
Chemical analysis of the filtrate showed 1.9 ut.% C, 0.32 wt.7. N, and 0.014 wt.% Br, corresponding to an aqueous solution containing 3.0 wt.% o~ the polymer l(C14H32N2)(OH)2]X. The concentration of the polymer in a portion of the filtrate was increased to 12.9 wt.% by re ving ~2 at reduced pressure.

X

A reaction mixture was prepared by combining101.6 grams of the above aqueous soluti~n containin 12.9 wt.% of the polymeric quaternary ammonium hydroxide with 6.9 grams of a hydrated aluminum oxide (a pseudo-boehmite phase, 74.2 wt.% A1203, 25.8 wt.Z H20) This mixture was stirred until homogeneous. To this mixture was added 11.5 grams 85 wt.~ orthophosphor;c acid and the mixture stirred until homo~eneous. The composition of the final reaction mixture in molar oxide rat~os was:
1.0 (C14H32N2)(oH)2 Al2o3 p2o5 lo5 2 The reaction mixture was placed in a sealed stainless steel pressure vessel havlng an inert liner and heated in an oven at 200C at autogenous pressure for 24 hours.
The solid reaction product was recovered by filtration, washed with water, and dried in air at 110C. The resulting AlPO4-26 produot had an X-ray powder diffraction pattern characterized by the following data, wherein "I" is the intensity and "d" the interplanar spacing:

æ d 100 x I/Io

8.35 10.59 100

9.85 B.98 4

10.2 8.67 lsh) 10.55 8.38 68

11.8 7.50 13.5 6.56 8 14.5 6.11 6 15.45 5.73 3 1~.8 5.28 10 17.~5 5.0~ 15 18.05 4.91 18 19.0 4.67 19.9 4.46 11 20.3 4.37 21.65 4.10 4 22.25 3.99 31 23.05 3.86~ 74 22.9 3.B8) 24.7 3.60 6 Z2~) TA~ ~ ~L ~ontinued .
2~ d 100 x ~/Io 25.25 3.527 10 25 . B5 3.446 2 27.2 3.2~8 10 27.~5 3.249 6 27.95 3.192 6 29.2 3.958 29.7 3.008 30.45 3.936 9 30 9 2.8938 ~ 12 31.1 2.875 J
31.6 2.83 2 32.2~ 2.?~6 8 32.7 2.~39 33.8 2.652 34.3 2.614 6 35.0 2.564 35.4 2.536 36.15 2.485 <1 36.4 2.~68 ~1 37.45 2.401 2 38.6 2.332 ~1 3~.0 2.309 c1 39.4 2.287 40.0 2.254 <1 40.5 2.22~ 2 41.3 2.186 2 42.4 2.132 2 43.1 2.099 4 44.2 2.049 ~1 45.7 1.985 <1 46.1 1.969 47.8 1.903 48.15 1.890 2 49.1 1.855 2 49.7 1.834 ~1 50.7 1.801 ~1 51.4 1.778 2 52.5 1.743 52,9 ~.731 Cl 53.7 1.707 2 S4.4 1.687 3 55.2 1.664 The species AlPo4-26 as herein referred to i~ crystalline metsllophosphate whose es~entlal framework ~tructure has chemical cornpositlon, expressed ln terms of molar ratios of oxides i~:
Al203 : l + 0-2 P205 and hsv~ng an X-ray powaer dlffraction pattern esscntlally as ~-t forth in IABL~ 24.

- 78(a) -EXAMPLE 53. Preparation of AlP04 - 28 The crystalline metallophosphate denom~nated AlP04-28 i8 preferably prepared by the thermally lnduced structural con~ersion of a less stable crystal-line intermetiate which ~ synthesized by'hydrothermal crystallization fr~m a reaction gel in a manner similar to that employed to obtain moQt of the AlP04-n species of the present invention. This intermediate, identif~et as AlP04-23 is readily synthesized using pyrrolitine aQ the templating agent which i8 removed from the structure during calcination to produce the stable AlPO4-28.
(a) Preparation of AlP04-23.
A reaction mixture was prepared by combining 23.1 gram~ of 85Z orthophosphoric acid (H3P04) and 77.6 grams of water, to which was added 13.8 grams of a hydrated aluminum oxide (a p~eudo-boehmite phase, 74.2 wt.% A1203, 25.8 wt.% H20), and stirred until homogeneou~.
To this mixture was added 7.1 grams of (CH2)4:~H (pyrrolidine), and the mixture stirred until homogeneou~. The composition of the final reactlon mixture in molar oxide ratio~ was:
1.0 (C~2)4 NH : A1203 : ~25 5 2

12~79 The reaction mixture was placed in a sealet stainless steel pressure vessel l~n~d with an inert pla~tic mat~rial and heated ~n an oven at ~00C at autogenous pre~sure for 91 hours. The 801it reaction product was recovered by flltration, washed with water,.
ant dried in air ~t 110C. Chemical anelysis ~howed 9.9 wt.% C, 31. wt.% N, 32.8 wt.Z A1203, 47.5 wt.Z P205, 19.3 wt.% LOI, giving a product corposition in molar oxide ratios of:
0.64 (CH2)4:NH:l-0oAl2o3 1-~ 24; 2 The product denominated AlP04-23 had an X-ray powder diffraction pattern characterized by ;~e following data, wherein "I" is the intensity and "d" the interplanar spacing:
2~ d _ 100 x I/Io 7-4 11.946 47 10.3 8.588 24 10.7 8.268 64 11.6 7.628 54 11.9 7 437 43 (sh)

13.4 6.607 4

14.7 6.026 4

15.0 5.906 6

16.8 5.277 6 19.0 4.671 21 20.4 4.353 28 21.3 4.171 100 23.2 3.834 65 24.0 3.~08 9 226 25 3 4301 6 (sh) 27.2 3.278 11 27.8 3.209 12 28.6 3.121 36 29.6 3.018 30 30.8 2.903 11 32.2 2.780 74 33.8 2.~52 2 34.9 2.571 7 36.2 2.481 8 37.4 2.404 4 43.3 2.090 4 48.2 1.888 8 49.~ 1.831 - 4 51,8 1.765 2 52.~ 1.734 5 - 80 _ 12~79 ~ lt;~3220 (b) Preparation of AlPO4-28.
A portlon of the AlP04-23 composition prepared ln psrt (~), supra, was calcinet ln air at about 600C
for 2 hours. The calc~net product was crystalllne but had sn X-rsy powder dlffraction pattern substantially different from the precursor material. It i8 apparent that the calcination procedure convertet the original AlPO4-23 to a new microporous aluminophosphate species of the present invention, namely AlP04-28. The X-ray powder diffraction pattern of the AlPO4-28 protuct is as follows:

_2~ d 100 x I/Io 7.9 11.191 41 9.9 8.934 7 12.2 7.255 100 13.3 ~sh) 6.657 22 lS.~ 5.644 7 18.6 4.770 47 19.2 (sh) 4.6Z3 25 ~1.0 4.230 9 21.9 4.058 30 ~23.5 3.786 7 25.4 3.507 20 26 1 3.414 13 27 0 3.302 16 29.7 3.008 13 30.9 2.894 13 32 1 2.788 11 35 4 2.536 6 36.4 2.468 2 The species AlPO4-28 as herein referred to is a crystalline metallophosphate whose esse.ntial framework structure has a chemical composition, expressed in terms of molar ratios of oxides, is A1203 : 1.0 + 0.2 P205 and having a characteristic X-ray powder diffraction pattern which conta~ns at least the d-spacings set forth in Table 2S below:

. .. ... .... . . ...
. .... ~ ,.. ....... .... ~... . .. ......... ... .. . .. . . . . . . . . . . . . .

~ lt;~ ~ 2 2~ d 100 x I~Io 7 9 11.19 41 12 2 7.26 100 18.6 4.77 47 21.9 4.06 30 25.4 3.51 20 27.0 3.30 16 EXAMPLE 54 Preparation of AlPO4~
(a) A reaction mixture was prepared by dispersing 164.8 grams of a pseudo-boehmite phase (74.2 wt.Z A1203, 25.8 wt.X H20) in 715.2 grams of water, to which was added 276.7 grams of 85% orthop~pboric scid,ant stirred until ho geneous. To this mixture was added 121.4 grams of di-(n-propyl) amine (Pr2NH), and the mixture ctirred until ho geneous. The composition of the final reaction mixture in molar oxide ratios was:
1.0 Pr2NH:Al2o3 P2s 4o H20 The reaction mixture was sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and heated in an o~en at 200C at autogeneous pressure for 46 hours. The solid reaction product was recovered by repeated centrifugation and washing with H20, and dried in air at room temperature. Chemical analysis of the reaction product showed 4.7 wt.% C, 0.85 wt.% N, 37.4 wt.% A1203, 51.6 wt.% P205, 10.3 wt.% LOI, giving a product composition expressed in molar oxide ratios of 0.18 Pr~NH:1.00 A1203:0.99 P205 0 2 The above product, teno~inated AlPO4-31, had an X-ray powder diffraction pattern characterized by the following tata, wherein "I" is the intensity and "d" the interplanar spacing:

- ~l(a) -~ABLE 26 2~ d lOo x I/Io .S 10.40 85 l3 35 6 63 12 14.8 S g9 2 ~ 455.. 8169 6 2~.0 sh 4 44 __ 24 2 sh 3'93 26 28 3 3'15 1 29.9 2.99 9 31.4 sh 2.85 31.6 2.83 14 35.2 '.~S 10 35.8 2.51 ~ 6 38.0 2.37 8 40.0 2.25 4 (b) A portion of the solit crystalline product obtained above was calcinet to a temperature of 1000C.
This calcined material hat an X-ray powder diffraction pattern essentially identical to that o~ part (a).

- 82 _ V

(a) Atsorption capacities of AlP04-5 (prepared ln Ex. 3(b) supra) were measuret using a stantard Mc8ain-Bskr grav~metric adsorptlon apparatus. Ihe followin~
data were obtainet on a sample activated st 350C:
Xinetic . Prcssure, wt.%
Diameter, A Torr emp , C Adsorbed 02 3.46 97 -183 12.6 o, 3.46 750 -183 17.0 Neopentane 6.2 102 24 5.5 (C~F,)~N(after 4 hours)10 0.073 24 1.2 ~,o 2.65 4.6 2g 4.6 ~,0 2.65 18.5 23 26.4 The pore size of the calcined product is greater than 6 and less than lOA as shown by adsorption of neopentane, kinetic diameter of 6.2A, and nil adsorption of (C4F9)3N, kinetic diameter of lOA.
(b) Adsorption capacities of AlP04-5 (prepared in Example 2(b) supra) were measured usin~ a standard McBain-Bakr gravimetric adsorption a~paratus. The following data were obtained on a sample activated at 350C:
Xinetic . Pressure, Wt.~
Diameter, A Torr Temp.,-C Adsorbed 0, 3.46 99 -183 13.3 ~, 3.46 730 -183 18.3 Cyclohexane6.0 54 24 9.5 Neopentane 6.2 102 24 4.8 H,0 2.65 4.6 24 3.9 H,0 2.65 21.0 24 29.8 ZO

The pore size of the calcined product is greater than 6.2A, as shown by adsorption of neopentane, kinetic diameter of $.2A.
(c) Adsorption capacities of AlP04-5 (prepared ~n a manner similar to that of example ~(b) ~upra) were measured using a standard Mc~ain^Baks gra~imetric adsorption apparatus. The followlng data were obtained on a sample activated at 350C:

Kinetic Diameter Pressure, Temp., C wt. %
A torr Adsorbed 0~ 3.46 105 -183 14.6 01 3.46 705 -183 21.3 Neopentane 6.2 103 25 6.5 H,o 2.65 4.6 25 6.5 H20 2.65 20.7 25 32.6 .. .. .. .. _ . . . _.. _ __ . . .. . . .. ... . ... _ .

ZO

Adsorptlon capaclties of AlPO4-28 (prepared in Example 53(b), supra) were measured us$ng a standard McBain-Bakr gravimetric adsorption apDaratus. The following tata were obta$ned on a sample acti~atet at 350C:
Xinetic . Pressure, Wt.%
Diameter,A Torr Tem~ CAdsorbed o, 3.46 103 -183 1.0 o, 3.46 761 -183 2.5 n-Hexane 4.3 28 24 0.4 Neopentane 6.2 310 24 0.5 ~,o 2.65 4.6 24 11.1 ~,o ~.65 20.0 24 21.4 The pore size of the calcined ~rotuct is >2.65A, and <3.46~ as shown by adsorption of H20, kinetic diameter or-2.65A, and nil atsorption of 2~ kinetic tiameter of 3.46A.

Adsorption capacities of AlP04-25 (prepared in Ex. 52(c),supra) were measured using a standard McBain Bakr gravimetri~ adsorption apparatus. The followin~
data were obtained on a sample activated at 350C:
Rinetic .Pressure, wt.%
Diameter,ATorr _ _mp.,^C Adsorbed o, 3.46 103 -183 4.9 O, 3.46 761 -183 5.9 n-Hexane 4.3 28 25 0.3 Neopentane 6.2 310 25 0.4 ~,o 2.65 4~6 2S 4.4 H~O 2.65 20.0 25 16.6 The pore size of the calcined product i8 ~3~4A and ~4.3A, as shown by adsorption of 2~ kinetic diameter of 3.46A, and nil adsorption of n-hexane, kinetic diameter of 4.3A.

~, ;~! `

2Z() EL~.MPT-S 5 8 Atcorption capacities of AlP04-20 (prepared as in Example 47(b) supra) were measured using a standard McBain-Bakr Rra~imetric adsorntion apparatus.
The following data were obtained on a samDle act~vated at 350C.:
Klnet~c .Pressure O ~t.%
Diameter,A ~orr TemP., C Adsorbed 0, 3.46 97 -1~3 2.7 O, 3.46 750 -183 11.5 n-Hexane 4.3 45 24 1.7 neopentane 6.2 303 24 1.5 Cyclohexane 6.0 11 24 1.3 ~.0 2.65 4.6 24 22.6 H~O 2.65 18.5 24 37.2 The pore size of the calcined product is ca. 3A, as shown by adsorption of H20, kinetic diameter of 2.65A, and low adsorption at low partial pressures of 2 kinetic diameter of 3.46A.

EXA~LE 5 9 Atsorptlon capac~ties of AlP04-17 (prepared ln Ex. 42(c) supra) uslng a standard ~cBain-Bakr gravimetric adsorpt~on apparatus. The followlng data were obtainet on a sample activated at 35~C:
X~neti~ O Pressure Wt.~
Diameter,A Torr _ _~emP.,-C_ _Adsorbed 0, 3.46 102 -183 22.2 O, 3.46 724 -183 23.1 n-Hexane 4.3 45 23 7.7 I~obutane 5.0 101 22 0.2 Neopentane 6.2 308 23 0.3 ~,0 2.65 4.6 22 24.9 ~,0 2.65 18 22 27.8 The pore,size of the calcined ~roduct is ~4.3A
ant C5. OA, as shown by atsorption of n-hexane, kinetic d$ameter of 4.3A, ant nil adsorption of isobutane, kinetic diameter of 5 . OA.

- ~8 -, .. ., . . . ... . ....... . . , , .. . . ,.. _ _ .. .. . . . . . . . ~ . . .
. . .. . ... _ . . ... . _ .. .. .... . ... .. . . . . ..

22~

Adsorption capacities of AlPO4-16 (prepared in Example 41(d) supra) were measured using 8 standard McBain-Bakr gravimetric atsorption an~aratus. The following data were obtained on a sample activated ~t 350C:
Xinetic O Pressure Diameter,A Torr _, Temp.,C Adsorbed O, 3.46 101 -183 1.2 O, 3.46 ~S~ -183 11.6 ~_gutane 4.3 768 24 2.0 Neopentane 6.2 301 25 1.4 ~2 2.65 4.624 19.0 ~,o 2.6S 20 24 36.3 The pore size of the calcined nroduct is >2.65 and ~3.46A as shown by adsorption of H20, kinetic diameter of 2.65A, and low adsorption of ~2 at low partial pressures kinetic diameter of 3.4CA.

- 8g -Adsorption capacities of AlP~4-14 (prepared in Ex.39(b) supra) using a standard McBain-Bakr gravimetric adsorption apparatus. The ollowing data were obtained on a sample activated at 350C:

~lnet~c Pressure, Wt.~

~dsorbate Diameter, ~ Torr Temp., 'C Adsorbed 0, 3.46 102 -183 15.53 0. 3.~6 ~63 -183 21.~6 n-He~ane 4.3 45 26 - 0.25 neopentAne 6.2 499 24 0.37 ~,0 2.65 ~.6 24 21.46 ~,0 2.65 21.0 24 28.66 N. 3.64 100 -196 11.28 ~, 3.64 747 -196 14.99 The pore size of the calcined product is >3.64A
and <4.3A as shown by adsorption of N2~ kinetic diameter of 3.64A, and nil adsorption of n-hexane, kinetic diameter of 4.3A.

j;~;, ` 12679 ` `
~. t~22V

Adsorption capacit~e~ of AlPO4-8 (prepared as in Example 29, supra) using a standard~McBain-Bakr gravimetric adsorption apparatus. The following data were obtained on a sample activated at 350C:
Kinetic OPressure Wt.%
Diameter, ATorrTemp.,C Adsorbed O~ 3.46 101 -183 8.9 O2 3.46 755 -183 18.6 n-Butane 4.3 768 24 5.0 Neopentane 6.2 501 24 4.5 (C4F9),N 10 0.073 25 8.2 (After 4 hours) H20 2.65 4.6 24 18.5 H20 2.65 20.0 24 31.9 The pore size of the calcined product is greater than 6.2A, as shown by adsorption of neopentane, kinetic diameter of 6.2A.

Adsorption capacities of AlPO4-31 (prepared as in Example 54(b) supra except that product was calcined to a temperature of 600C) were measured using a standard McBain-Bakr gravimetric adsorption apparatus. The following data were obtained on a sample activated at 350C:
Kinetic OPressure, Wt.%
Diameter, ATorr Temp.,C Adsorbed O1 3.46 99 -183 8.1 02 3.46 711 -183 11.5 Butane 4.3 107 24 4.0 Cyclohexane 6.0 54 24 5.3 Neopentane 6.2 109 24 3.1 H~O 2.65 4.6 24 5.3 HaO 2.65 14.0 24 13.9 The pore size is larger than 6.2A as shown by the adsorption of neopentane.

A portion of the cryst~lline A1~04-11 product of Exam~le 32(a) supra was calcined in alr from 200C
to 500C over a period of 1 hour, followed by heating at 500C for 2 hours.
Adsorption capacities were measured on this calcined product using a standard McBain-8akr gravimetric adsorption apparatus. The followin~ tata were obtained on a sample activated at 350C:
~inetic O Pressure Wt.%
Atsorbate Diameter,A Torr Temp.,-C Adsorbed 0~ 3.46 101 -183 9.22 O, 3,46 755 -183 10.7 N-butane 4.3 304 24 4.35 l~obutane 5.0 502 24 4.71 Neopentane 6.2 301 24 1.22 Cyclohexane 6.0 30 24 5.30 H20 2.6S 4.6 24 11.8 H~O . 2.65 20.0 24 16.4 The pore size of the calcined product is greater than 6.OA and less than 6.2A, as shown by adsorption of cyclohexane, kinetic di~meter of 6.0A, and nil adsorption of neopentane, kinetic diameter of 6.2A.

'V

Adsorption'capacities of AlP04-18 (prepared in Example 46(b) supra) were meaQured using a standard McBain-Bakr gravlmetric adsorplton s~aratus. The following data were obtained on a sample actl~ated at 350C:
Xinetic O Pressure, Temp. wt.~
Diameter, A torr _ C Adsorbed o~ 3.46 130 -183 23.0 2 3.46 697 -183 27.9 n-Butane 4.3 718 24 16.2 iso-Butane 5.0 101 24 0.1 H~O 2.65 4.6 24 30.3 H20 2.65 21.0 ~4 36.9 The pore size of the calcined oroduct is 4.3 and 5.OA , as shown by adsorption o~ n-butane and nil atsorption of iso-butane at low partial pressure.
Somewhat surprisingly the aluminophosphate compositions of the present invention are found to be strongly hydrophilic. All species are observed to adsorb water preferentially over common hydrocarbon molecules such as paraffins, olefins and benzenoid aromatic species, e.g., benzene, xylenes and cumene.
Thus the present aluminophosphates as a class are useful as desiccants in such adsorption separationl purification processes as natural gas trying, cracked gas drying. ~ater is also preferentially adsorbed o~er the so-called permanent gases such as carbon dioxide, nitrogen,,oxygen and h,ydrogen. These aluminoohosphates are therefore suitably employed in the drying of reformer hydro~en streams and ~n the dry$ng of oxygen, nitrogen or air prior to llquefaction. In this respect the adsorptive properties of the present all~nophosphates appears to be quite similar to those of the low sllica aluminosillcate zeolites, despite the fact that they exhibit essentially ~o ion-exchange cspacity--a quintessential property of zeolites.
The adsorpti~e properties of the present AlP04-n compositions are illustrated by the data ~et forth in Table F and Table G below.

TABLE F
Static DrYing of Moist Air at Room TemPerature % HumiditY Contact Time, SamPle Initial F al _ hours Zeolite 4A 60 21 3 Zeolite 5A 54 5 16 Silica Gel 56 18 16 AlPO4-5 55 29 4 AlPO4-8 60 21 3.5 " 61 19 18 AlP04-11 57 29 5.5 AlPO3-14 56 19 3.0 AlPO4-16 70 22 3.0 " . 56 14 72 AlPO4-17 63 24 18.5 AlPO4-20 60 17 16 AlPO4-28 56 7 17.5 AlPO4-25 56 25 18.5 AlPO4-9 51 29 23 AlPO4-18 56 19 24 AlP04-31 51 24 19 -11~;S~2ZO

To illustrate the hydrophilic character of the AlP04-n compositions ln contact with an aqueous orRanic solution, dehydrated samples of AlP04 compounds and prior known comparison ad~orbent, each weighin~ 0.5 grams were placed in 2 grams of ~ solut$on of 4 vol.-%
H20 and 96 vol.-% 2-butanone at ambient room temperature and agitated moderately for 2 hours. Thereafter the residual solution and the adsorbent were analyzed for water content. The resul~s appear below:
TABLE G
% Water Removal Adsorbent_ __ fsom Solution ~ Loadin~**
AlP04-5 55 23 AlP04-8 74 45 AlP04 11 21 23 AlP04-14 ~80 >45 AlP04-16 ~80 ~45 AlP04 17 77 41 AlP04-20 87 58 Zeolite NaY 80 37 Silica Gel 28 --Silicalite * -5 --* ~.S.P. 4,061,724 ** Percent of maximum theoretical capacity The present AlP04-n compositions exhibit novel gurface 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 cataly-tically active metals by methots well known in the art and used, for example, in fabricating catalysts compositions .. .. . . ..... ~ .. .. ... . . . . .

~ Z Z O 12679 having sil~calite or alumina bs~es. Of the general class, those species having pores larger than about 5A are preferred.
Among the hydrocarbon conversion reactions catalyzed by AlP04-n compositions are crack~ng, hytro-cracking, alkylation of both the aromatic and isoparaffin types, isomerization including xylene ~somerization, poly-merization, reforming,hydrogenation, dehydrogenation, transalkylation, dealkylation and hydration.
Using AlPO4-n catalysts compositions which contain a hytrogenation pro ter such as platinum or palladium, hea~y petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks can be hydrocracked at temperatures in the range of 400~F to 825F using molar ratios of hydrogen to hvdrocarbon in the ran~e of between 2 and 80, pressures between 10 and 3500 p.s.i.g., and a liquid hoùrly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.
The AlP04-n catalyst compositions employed in hydrocracking are also suitable 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 p.s.i.g., LHSV values in ~e 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 same cata~ysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomeriza-tion processes in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydro-isomerizat~on is carried out at a temperature of from about ._ ._ ... _._ . . _, . _, _.. _ ._ . ........... . .. .. . . . , _ . . . _ . ~_ . .. , .. , _ .,, . _ .. _ .. ... . ~, . .. .... .. . . . _ 126 7q 2;~) 200F to 600F, preferably 300F to 550F with an LHSV
value of from about 0.2 to lØ Hydrogen is ~upplied to the reactor in atmixture with the hydrocarbon feedstock ln molar proportions (H/Hc) of between 1 and 5.
At somewhat higher temperature~, l.e. from about 650F to 1000F, preferably 850F to 950F ~nd usually at somewhat lower pressures wlthin the ran~e of about 15 to 50 p.s.$.g., the same catalyst comDositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins havin,e a carbon number range of C7-C20. Contact tlme between t~e feedstock and the catalyst is generally relatively short to avoit unde-sireable side reactions such as olefin polymerization and paraffin cracklng. LHSV values ln the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.
The unique crystal structure of the present AlP04 catalysts and their total lac~ of alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionatioa of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disporportionation process isomerization and transalkylation can also oc~ ur. Group VI~I noble metal adjuvents alone or in con~unction with Group VI-B metals such as tungstèn, lybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall compos1tion.
Extraneous hydrogen can, but need not be present in the reaction zone which is maintained at a teulperature of from a~out 400 to 750F, pressures in the range of lO0 to 2000 p.s.i.g. and LHSV values in the range of û.l to 15.

- 97 _ 2~0 Catalytic cracking processes are preferably carried out with AlP04-n compositions using feedstocks such as gas oils, hea~y naphthas, dea~phalted crude oll resldua CtC. 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.
~ ehydrocyclization reactions employing pasaffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylene3, toluene and the like are carried out usin~ essent$ally the same reaction conditions as for catalytic crackin~.
For these reactions it is preferred to use the AlP04-n catalyst in conjunction wi~h a Grou~ VIII non-noble metal cation such as cobalt and nickel.
In catalytic dealkylation wherein it is desired to cleave paraffinic side chains from aromatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the range of about 800-1000F 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. Parti-cularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.
In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic ~ulfur ant/or nitrogen compounds in the feed, without 1~679 substantlally affecting hydrocarbon molecules therein.
For this purpose it i9 pre~erret to employ the aame general conditions descrlbed above for catalytic hydrocracking, and catalysts of the ssme general nature tescribed in connection with dehytrocyclization operations. Feetstocks inclute ~asoline fractions, kerosenes, ~et fuel fractlons, diesel fractlons, lightand heavy gas 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 ant desul~urization, of hydrocarbon feeds containing substantial proportions of organonitrogen ant organosulfur compounts. It i6 generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of catalysts for hytrocracking. Consequently, it is necessary to operate at re extreme conditions when it is tesired to obtain the same tegree of hydrocracking conversion per pass on a relatively nitrogenous feed than are required with a feed containing less organonitrogen compounts.
Consequently, the contitions unter which denitrogenation, desulfurization ant/or hytrocracking can be most expeti-tiously accomplished in any given situation are necessarily determined in view of the characteristics of the feetstocks in particualr the concentration of organonitrogen compounts in the feetstock. As a result of the effect of organo-nitrogen co~pounds on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most suitable for denitrogenation of a given feedstock _ 99 _ , 12679 2~V

havlng a relatively high organonitrogen content with minimal hydrocracking, e.g., le88 than 20 vol~me percent of fresh feed per pass, mlght be the same as those preferred for hydrocrack~ng another feedstock having a lower concen-tration of hydrocracking inhibiting constit~ents e.g., organonitrogen compounds. ConQequently, $t has become the practice in this art to establish the conditions under which a certain feed i~ to be contacted on the basis of preliminary screening tests with the specific catalyst and feedstock.
Isomerization reactions are carried out under conditions similar to those described above for reforming, using ~omewhat more acidic catalysts. Olefins are pre-ferably isomerized at temperatures of 50~-900F, while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700-1000F. Particularly desirable lsomerization reactions contemplated herein include the conversion of n-heptane and/or n-octane to isoheptanes, 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 ~so-hexene, cyclohexene to methylcyclopentene etc. The preferred cation form is a combination of the AlP04-n 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 AlPO4-n compositions having pores of at least 5A are preferred.
When employed for dealkylation of alkyl aromat~cs, the temperature is usually at least 350F and ranges up to a temperature at which substantial cracking of the feedstock ' 12679 or con~erslon products occurs, generally up to about 700F. Ihe temperature i8 preferably st least 450F
and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retaln at least the aromatic feed in the liquid state. For alkylation the temperature ~an be as low as 250F but is preferably at least 350F. In alkylation benzene, toluene and xylene, the preferred alkylating agent are olefins such as ethylene and propylene.

Claims (38)

WHAT IS CLAIMED IS:

1. Crystalline aluminophosphates each having a framework structure whose chemical composition expressed in terms of mole ratios of oxides is:
Al2O3 : 1.0 ? 0.2 P2O5;
each of said framework structures being microporous in which the pores are uniform and have nominal diameters within the range of about 3 to about 10 Angstroms, an intracrystalline adsorption capacity for water at 4.6 torr and 24°C of at least 3.5 weight percent, the adsorption and desorption of water being completely reversible while re-taining the same essential framework topology in both the hydrated and dehydrated state.

2. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 2.

3. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 4.

4. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction Pattern which contains at least the d-spacings set forth in Table 6.

5. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 8.

6. Crystalline aluminophosphate according to claim 1 which has.an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 10.

7. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 12.

8. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 13.

9. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 15.

10. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 17.

11. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 19.

12. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 21.

13. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 23.

14. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern essentially as set forth in Table 24.

15. Crystalline aluminophosphate according to claim l which has an X-ray powder diffraction pattern which contains at least the d-spacings set forth in Table 25.

16. Crystalline aluminophosphate according to claim 1 which has an X-ray powder diffraction pattern essentially as set forth in Table 26.

17. Process for preparing a crystalline alumino-phosphate having a framework structure whose chemical composition expressed in terms of mole ratios of oxides is:
Al2O3 : 1.0 ? 0.2 P2O5;
said framework structures being microporous in which the pores are uniform and have nominal diameters within the range of about 3 to about 10 Angstroms, an intra-crystalline adsorption capacity for water at 4.6 torr and 24°C of at least 3.5 weight percent, the adsorption and desorption of water being completely reversible while retaining the same essential framework topology in both the hydrated and dehydrated state, which com-prises forming a reaction mixture having a composition expressed in terms of mole ratios of oxides of Al2O3 : 1 ? 0.5 P2O5 : 7-100 H2O
and containing from about 0.2 to 2.0 moles of an organic templating agent per mole of Al2O3, and heating said reaction mixture at a temperature of at least 100°C until crystals of said aluminophosphate are produced.

18. Process according to claim 17 wherein the reaction mixture is heated at a temperature of from 100°C to 300°C under autogeneous pressure.

19. Process according to claim 18 wherein the reaction mixture has a composition expressed in terms of mole ratios of oxides of Al2O3 : 0.8 - 1.2 P2O5 : 25-75 H2O
and is heated at a temperature of from 125°C to 200°C.

20. Process according to claim 19 wherein the source of P2O5 is phosphoric acid, the source of Al2O3 is pseudoboehmite hydrated aluminum oxide and the reaction mixture contains per mole of Al2O3, from 0.5 to 1.5 moles of organic templating agent, from 40 to 50 moles H2O and about 1.0 mole P2O5.

21. Process according to claim 19 wherein the templating agent is selected from the group consisting of tetrapropylammonium hydroxide; tetraethylammonium hydroxide; tripropylamine; triethylamine; triethanola-mine; piperidine; cyclohexylamine; 2-methyl pyridine;
N, N-dimethylbenzylamine; N, N-diethylethanolamine;
dicyclohexylamine; N, N-dimethylethanolamine; choline;
N, N-dimethylpiperazine; 1,4- diazabicyclo (2,2,2) octane; N-methyldiethanolamine; N-methylethanolamine;

N-methylpiperidine; 3-methylpiperidine; N-methylcyclo-hexylamine; 3-methylpyridine; 4-methylpyridine; quinu-clidine; and N,N'-dimethyl-1, 4-diazabicyclo (2,2,2) octane dihydroxide.

22. Process according to claim 19 wherein the templating agent is selected from the group consisting of tetramethylammonium hydroxide; tetraethylammonium hydroxide; tetrabutylammonium hydroxide; tetrapentyl-ammonium hydroxide; di-(n-butyl)-amine; neopentylamine;
di-(n-pentyl)-amine; isopropylamine and t-butylamine.

23. Process according to claim 19 wherein the templating agent is an alkyl amine in which the alkyl moiety contains from 2 to 7 carbon atoms.

24. Process according to claim 19 wherein the templating agent is selected from the group consisting of ethylenediamine and 2-imidazolidone.

25. Process according to claim 23 wherein the alkylamine is di-(n-propyl) amine.

26. Process according to claim 19 wherein the templating agent is a polymeric quaternary ammonium salt [(C14H32N2)(OH)2]x wherein x is a value of at least 2.

27. Process for separating polar molecular species having effective molecular diameter of less than about 10 Angstroms from admixture with less polar molecular species by contacting said mixture with at least one aluminophosphate of claim 1, said aluminophosphate being at least partially dehydrated at the initiation of con-tact and have a pore diameter large enough to adsorb the more polar molecular species.

28. Process according to claim 24 wherein the more polar molecular species is water.

29. Hydrocarbon conversion process which comprises contacting said hydrocarbon under hydrocarbon converting conditions with an aluminophosphate of claim 1.

30. Process according to claim 29 wherein the hydrocarbon conversion process is cracking.

31. Process according to claim 29 wherein the hydrocarbon conversion process is hydrocracking.

32. Process according to claim 29 wherein the hydrocarbon conversion process is hydrogenation.

33. Process according to claim 29 wherein the hydrocarbon conversion process is polymerization.

34. Process according to claim 29 wherein the hydrocarbon conversion process is alkylation.

35. Process according to claim 29 wherein the hydrocarbon conversion process is reforming.

36. Process according to claim 29 wherein the hydrocarbon conversion process is hydrotreating.

37. Process according to claim 29 wherein the hydrocarbon conversion process is isomerization.

38. Process according to claim 37 wherein the isomerization is xylene isomerization.