JPH0676204B2 - Manufacturing method of molecular sieve - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a molecular sieve. More specifically, the present invention relates to a method of making non-zeolitic molecular sieves from alumina or silica-alumina bodies.

PRIOR ART AND ITS PROBLEMS Crystalline aluminosilicate zeolite type molecular sieves are well known in the art and currently consist of more than 150 types, including both naturally occurring and synthetic compositions. In general, crystalline zeolite is a corner-sharing Al
Formed from O ₂ and SiO ₂ tetrahedra, with uniformly sized pores and outstanding ion exchange capacity, and dispersed throughout the internal voids of the crystal without replacing any atoms that make up the framework crystal structure. It is characterized in that the adsorbed phase thus formed can be desorbed reversibly.

Early zeolite synthesis operations produced extremely fine materials, often smaller than a few microns in size. Powders with such small particle sizes are difficult to use in many industrial processes. Moreover, the small dimensions can also create a dust hazard for those who handle the material. Larger particles with an average particle size of 10 microns or more are preferred for many applications. However, in order for such large particle zeolites to be useful in all processes in which zeolites are used industrially, large particle zeolites have ion exchange properties, adsorption capacities and selectivities, thermal stability of finely divided crystalline zeolites and The catalyst volume must be retained. In addition, the large zeolite particles should also exhibit high wear resistance and crush strength.

Larger zeolite bodies with dimensions above about 5 microns can be made by agglomerating small crystals, but a typical agglomeration process is with a suitable binder such as clay,
Processing conditions are required to ensure the reproducibility and properties of silica or alumina gels, or inorganic or organic adhesives and agglomerates.
Because such processing conditions are often complex and difficult to control, and binder materials, which are relatively inert materials with relatively no adsorption capacity, can be diluted and otherwise used. This approach is not optimal because it tends to reduce and / or modify the adsorptive and catalytic properties of zeolites.

Thus, processes have been developed to produce zeolites with relatively large particle sizes in the range of tens of microns to millimeters or more. Many such processes include precursors that contain certain reactive or non-reactive kaolin type clays and can be converted by chemical means into zeolite bodies that retain the shape of the preformed body. Starting with material or preform.

Early preformed type products were costly multiple synthesis steps, eg 1) mixing the synthesized zeolite with kaolin clay, burning the composite to make it reactive and then further reacting by caustic treatment. Requires the synthesis of additional zeolite from the clay component, or 2) combining the synthetic zeolite with silica sol, gelling, and further treating the composite material with sodium aluminate at high pH to form the additional zeolite. (See West German Patent 1,165,562 to Bayer), a nasty process using sodium aluminate gel and a water-immiscible hydrocarbon liquid was also adopted (US patent assigned to Engelhard Corporation). See No. 3,094,383).

U.S. Pat. No. 2,992,068 describes a process for making zeolite A bodies from preformed bodies containing calcined kaolin clay, caustic and optionally added silica or alumina.

U.S. Pat. No. 3,065,054 describes a process for making zeolite bodies from preformed bodies containing uncalcined kaolin clay, caustic and a porosity inducing agent.

U.S. Pat.No. 3,119,659 discloses a method for making a zeolite body from a preform containing either calcined or uncalcined kaolin clay, or both, caustic and optionally added silica or alumina. Is described.

The preform may also contain added zeolite powder.

U.S. Pat.No. 3,119,660 describes a process for making zeolite bodies from preforms containing either calcined or uncalcined kaolin clay or both and optionally added silica or alumina. . The preform may also contain included zeolite powder and diluent.

U.S. Pat. Nos. 3,367,886 and 3,367,887 describe methods for making zeolite bodies from preforms containing zeolite powder, calcined and uncalcined kaolin clay, and sodium hydroxide.

U.S. Patent 3,370,917 No. Na ₂ clay and sodium hydroxide calcined kaolin type O: describes a process for producing a zeolite Z-12 bodies from preformed bodies containing at SiO ₂ molar ratio of about 0.13.

U.S. Pat. C.) for producing them by cooking them in oil.

U.S. Pat. It has been described.

U.S. Pat. No. 3,909,076 describes the preparation of zeolite bodies from preforms containing particles of both zeolite X and meta-kaolin clay. Particles have an average size of about 0.1
To about 50 microns, preferably 0.5 to 10 microns.

US Pat. Nos. 4,424,144 and 4,058,856 generally describe the preparation of zeolite bodies from preforms containing zeolite powder, meta-kaolin and sodium hydroxide.

However, zeolite bodies made by these and similar methods often exhibit unexpectedly poor crush strength and / or adsorptivity. In addition, the wet strength of the preforms made by the prior art methods is usually very low, and the preforms to be converted to zeolites, during aging and digestion, especially if stirring from any is used, Often decays. In addition, zeolite formation rates are usually slow, and many of the examples in the prior art require reaction times of 3 days or longer.

Some of the microporous compositions that have recently been referred to as "non-zeolitic molecular sieves" (which term is defined in more detail hereinbelow) that are not zeolitic and henceforth as aggregates. The class has been reported. These non-zeolitic molecular sieves are 1982
US Pat. No. 4,310, issued to Wilson et al. On January 12, 2014,
No. 440, which includes the crystalline aluminophosphate composition. These materials are formed from AlO ₂ and PO ₂ tetrahedra and have a charge-neutral framework as in the case of the silica polymorph. Unlike silica molecular sieves, which are hydrophobic due to the absence of extra-structured cations, aluminophosphate molecular sieves are moderately hydrophilic due to the apparent electronegativity difference between alumina and phosphorus. Is. Their intra-crystal pore volume and pore diameter are comparable to those known for zeolites and silica molecular sieves.

U.S. Pat. No. 4,440,871 describes a new class of silicon-substituted aluminophosphate non-zeolitic molecular sieves that are both microporous and crystalline. These materials have a three-dimensional crystal framework of PO ₂ ⁺ , AlO ₂ ⁻ and SiO ₂ tetrahedral units and, with the exception of optionally present alkali metals or calcium, have the formula mR: (Si _x Al _y P _z ) O ₂ [wherein “R” is at least 1 present in the intracrystalline pore system]
Indicates an organic templating agent; "m" is (Si _x Al _y P _z ) O ₂
Represents the moles of "R" present per mole of
Has a value of 3, the maximum in each case depending on the molecular size of the template agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; "x",
"Y" and "z" each represent the molar fraction of silicon, aluminum and phosphorus present as tetrahedral oxides]. "X",
The minimum value of each of "y" and "z" is 0.01, preferably 0.
02. The maximum value for "x" is 0.98, for "y" is 0.60 and for "z" is 0.52. These silicoaluminophosphates exhibit some physical and chemical properties that are characteristic of both aluminosilicate zeolites and aluminophosphates.

U.S. Patent 4,500,651 Pat, a titanium-containing non-zeolitic molecular sieves of a new class, their as-synthesized at and chemical composition of the following units empirical formula in the anhydrous state: mR: (Ti _x Al _y P _z ) O ₂ [wherein “R” represents at least one organic templating agent present in the intracrystalline pore system; “m” is (Ti _x Al _y P _z ).
Indicates the moles of "R" present per mole of O ₂ and
Has a value of about 5.0; "x", "y" and "z" respectively represent the mole fractions of titanium, aluminum and phosphorus present as tetrahedral oxides].

U.S. Patent 4,567,029 Pat, MO _2, have a three-dimensional microporous framework structure of AlO ₂ and PO ₂ tetrahedral units and the following formula on an anhydrous _{basis: mR: (M x Al y} P z) O ₂ [wherein “R” represents at least one organic templating agent present in the intracrystalline pore system; “m” is (M _x Al _y P _z ) O 2
₂ moles of "R" present per mole of ₂ and 0 to
Has a value of 0.3; "M" represents at least one metal from the group consisting of magnesium, manganese, zinc, cobalt; "x", "y" and "z" are each tetrahedral oxides A new class of crystalline metal aluminophosphate non-zeolitic molecular sieves is described having an experimental chemical composition represented by the metal "M" present, indicating the mole fractions of aluminum and phosphorus.

U.S. Patent 4,544,143 Pat, FeO _2, have a three-dimensional microporous framework structure of AlO ₂ and PO ₂ tetrahedral units and the following formula on an anhydrous _{basis: mR: (Fe x Al y} P z) O ₂ [wherein “R” is at least 1 present in the intracrystalline pore system]
Indicates an organic templating agent; "m" is (Fe _x Al _y P _z ) O ₂
Represents the moles of "R" present per mole of
A value of 3; "x", "y" and "z" represent the mole fractions of iron, aluminum and phosphorus, respectively, present as tetrahedral oxides] Of crystalline ferroaluminophosphate non-zeolitic molecular sieves are described.

Other aluminophosphates and silicoaluminophosphate non-zeolitic molecular sieves are described in a number of co-pending patent applications, which are described in more detail below.

The above-mentioned patents and patent applications describe a substantially homogeneous liquid containing the necessary sources of aluminium, phosphorus, silicon (in the case of silicoaluminophosphates) and other elements, if any, required for non-zeolitic molecular sieves. A method for preparing hydrothermally crystallized non-zeolitic molecular sieves from a reaction mixture is described. The reaction mixture preferably also contains an organic templating agent, ie a structure directing agent, preferably a compound of the elements of group VA of the Periodic Table and / or optionally an alkali metal or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene, preferably under autogenous pressure at 50 ° C to 250 ° C, preferably 100 ° C to 200 ° C. Heating at temperature is usually for several hours to several weeks until crystals of the non-zeolitic molecular sieve product are obtained. It is common to employ an effective crystallization time of about 2 hours to about 30 days. Non-zeolitic molecular sieves are recovered by any convenient method such as centrifugation or filtration.

Although these hydrothermal crystallization methods are effective in producing non-zeolitic molecular sieves in high yield, it is likely that the crystallization of non-zeolitic molecular sieves is substantially uniform and has a relatively high viscosity liquid or Since it is carried out from a semi-gel, it has the disadvantage that the average particle size of the non-zeolitic molecular sieve produced is very small, typically in the submicron range.
This problem of small particle size of the product is especially noted in US Pat.
440,871 SAPO molecular sieves, especially SAPO-34. Such a small average particle size means that
The non-zeolitic molecular sieves are difficult to over or centrifuge, and thus difficult to separate purely from the reaction mixture that forms the molecular sieves. Moreover, the small average particle size of the non-zeolitic molecular sieves has the same problems as the small average particle size zeolites discussed above (ie difficulty in use in some industrial applications, risk of dust). , Difficult to bind without reducing and / or modifying adsorptive and catalytic properties, lack of reproducibility of properties after binding).

From the above, the non-zeolitic molecular sieve, it is possible to produce a non-zeolitic molecular sieve having a substantially larger average particle size than the non-zeolitic molecular sieve produced by the hydrothermal crystallization process described above. There is a demand for a manufacturing method.

Therefore, the present invention is a method for producing a crystalline non-zeolitic molecular sieve in a preformed body of alumina or silica-alumina, in which a reactive source of phosphorus pentoxide and an organic template agent are provided. A method is provided that comprises contacting a liquid reaction mixture that contains and contacting at a time and temperature such that the body reacts with the liquid reaction mixture to form non-zeolitic molecular sieve crystals in the body. In this way, if the non-zeolitic molecular sieve is intended to contain silica, a reactive source of silica, which can be silica itself, can be placed in the body and / or in the liquid reaction mixture. Similarly, if the non-zeolitic molecular sieve is intended to contain one or more elements different from alumina, silicon and phosphorus, the reactive source of these elements may be silica or a silica-alumina body and / or It can be placed in a liquid reaction mixture.

DETAILED DESCRIPTION OF THE INVENTION The term "non-zeolitic molecular sieve" or "NZ-MS" as used herein is defined to mean the following: U.S. Pat. Nos. 4,310,440;
0,871 (and related U.S. Application No. 575,745, filed January 31, 1984); 4,500,651; 4,554,143;
No. 4,567,029 claimed molecular sieves; US Application No. 880,559 filed June 30, 1986, AlPO ₄ -41 molecular sieves; April 13, 1984 The "ELAPSO" molecular sieve as disclosed in filed U.S. application No. 600,312 and the "ELAPO" molecular sieve as described later in this Paraguf, certain non-zeolitic molecular sieves ("ELAPO") are EPC patents. Application 85104386.9 (1985 10
No. 0158976) and No. 85104388 published on March 13.
No. 5 (Publication No. 0158349, published October 16, 1985), and the ELAPSO molecular sieve is 1984.
Co-pending U.S. Application No. 600,312, filed April 13, 2013 (EPC Publication No. 0159624, published October 30, 1985).

More specifically, "Non-zeolitic molecular sieve"
The term includes all molecular sieves claimed in the following patent application [(A) after the application number in the table below indicates that the application has been abandoned and ( CIP) indicates that the application is a continuation of the application immediately above, and (C) after the application number indicates that it is a continuation of the application immediately above]: The aforementioned applications and patents are used herein. Mentioned above
The nomenclature used herein to describe the elements of NZ-MS is consistent with that used in the aforementioned applications or patents. Certain elements within a class are generally "n" species (where "n" is an integer), eg
Called SAPO-11, MeAPO-11, ELAPSO-31.

The non-zeolitic molecular sieves that can be produced by the method of the present invention may include aluminum, phosphorus and (in the case of silicoaluminophosphate) silicon in addition to one or more other elements. Due to such a large number of aluminophosphates and silicoaluminophosphates having different crystal structures, a description of how to prepare these non-zeolitic molecular sieves according to the method of the present invention is given first, followed by the non-zeolitic molecular sieves. The chemical properties will be explained.

Process of the Invention As already mentioned, in the process of the invention, the alumina or silica-alumina body (optionally the reactivity of the desired one or more other elements in the non-zeolitic molecular sieve) Source) and a reactive source of phosphorus pentoxide and an organic templating agent (and, optionally, a reactive source of one or more other elements desired in the non-zeolitic molecular sieve). The liquid reaction mixture containing it is contacted, whereby the body reacts with the liquid reaction mixture and forms non-zeolitic molecular sieve crystals in the alumina or silica-alumina body. In this method, alumina or silica-alumina in the body reacts with phosphorus in a liquid reaction mixture to form a non-zeolitic molecular sieve aluminophosphate or silicoaluminophosphate framework structure in an alumina or silica-alumina preform. Cause

One or more elements (unlike aluminum, phosphorus, silicon and oxygen) that can be incorporated into this framework
If present in the body or in the liquid reaction mixture, these elements will normally enter the framework of the aluminophosphate or silicoaluminophosphate, but the amount of such element that enters the framework is the abundance of the element, its use. It is a matter of course that it depends on the reactivity of the form of the element, and the ease with which the element joins the framework. If such elements are desired in the non-zeolitic molecular sieve product, it is desirable to include them in the liquid reaction mixture.

In the process of the invention, the solid body contains alumina (and optionally silica), while the liquid reaction mixture contains a phosphorus pentoxide source. However, silica can be added to the liquid reaction mixture either in addition to or in place of the silica in the solid body, while the solid body adds it to the phosphorus pentoxide source present in the liquid reaction mixture. Can be included.
Optimal partitioning of silica between the solid body and the solution can depend on a number of factors, including the exact silica source used, other components of the reaction mixture, etc., but it is usually convenient to incorporate silica into the solid body. Is.

Alumina or silica in the body used in the method of the present invention
Alumina is preferably amorphous or poorly crystalline. The presence of strongly crystalline alumina or silica-alumina may tend to prevent or even prevent the formation of the desired crystalline form of the non-zeolitic molecular sieve. is there. To ensure that the alumina or silica-alumina is in the amorphous or poorly crystalline form, it is desirable to calcine the alumina or silica-alumina prior to use in the method of the present invention. Firing in this manner not only ensures that the alumina or silica-alumina is in an amorphous or poorly crystalline form, but also that the reactivity and accessibility of the alumina or silica-alumina is high. And thus promote the reaction of the alumina or silica-alumina with the liquid reaction mixture and also improve the integrity of the solid body. The optimum calcination temperature for the alumina or silica-alumina used in the process of the present invention is slightly lower than that typically used in producing zeolites from clay preforms by the prior art processes described above. The preferred firing temperature for alumina or silica-alumina is about
A range of 250 ° to about 750 ° C is common, but the optimum calcination temperature will depend on the particular alumina or silica-alumina employed.

The alumina or silica-alumina bodies used in the method of the present invention may have various physical forms. The body can be in the form of small particles. However, in order to facilitate the separation of the non-zeolitic molecular sieve from the liquid reaction mixture after completion of the reaction and to make the non-zeolitic molecular sieve in the form of large particles, relative to the alumina or silica-alumina body. It is highly preferred to have a relatively large body, typically having a minimum dimension of at least about 0.5 mm. (Effective filtering and washing of solid particles can be achieved by using spray dried alumina or silica-alumina bodies in the method of the present invention, as discussed in more detail below, much smaller particles,
For example, it can be performed on particles having a diameter of about 60 micrometers. The body may be shaped into many shapes such as spheres, microspheres, pellets, beads, tablets, cylinders, discs, granules, cubes or blocks. Suitable shaping techniques for forming such bodies are conventional and include extrusion, spray drying, prilling, molding, casting, slip-casting, tableting, briquetting and beading processes such as tumbling, drum rolling, Includes Nauta mixing and disk molding. Preferred methods are extrusion, spray drying, prilling and beading processes, extrusion being a particularly preferred technique.

If the body is intended to be extruded or similar techniques, the first step in shaping it is to form a suspension or paste of alumina (and optionally other ingredients) in a liquid dispersion medium. Is normal. Various techniques may be used to form such suspensions or pastes, such as suspensions or pastes that hydrolyze aluminum alkoxides or deaggregate alumina into acids. The residual acid can then be substantially neutralized to form. Alternatively, it may be sufficient to simply mix the alumina and any other ingredients, preferably first by grinding or crushing the ingredients into a finely divided form, then mixing with water with appropriate agitation. The amount of water added should be such as to allow shaping of the shaped body from the resulting paste. For most modeling methods, the solids content is about 50% to about 65% of the mixture.
It becomes the range of. The water content typically ranges from about 35 to about 45% by weight of the mixture, preferably from about 38 to about 42% by weight.

Body size can be varied not only by the die or other shaping tool used, but also by adjusting the composition of the mixture to be shaped and the shaping method. If the particle shape is approximately spherical or cylindrical, typical body dimensions range from about 0.4 to about 7 mm in diameter. If the body is shaped by several spray-drying and prilling techniques, smaller bodies are often produced, often as small as about 50 to about 90 microns in average diameter.

The body, once shaped, is ready to be fired. However, prior to this step, the body should be heated to a temperature of approximately 50 °
It may be dried at about 150 ° C. for about 0.5 to 36 hours. But,
Because of the time and expense involved, it is common to fire immediately after shaping. Drying and / or calcination serves to remove at least a portion of the liquid dispersion medium added to the alumina or silica-alumina prior to extruding or otherwise shaping the body.

The alumina or the alumina in the silica-alumina body can be in any form that is reactive enough to react with the liquid reaction mixture, including most of the forms of alumina used in the zeolite synthesis process described above. It can be used in the method of the present invention. Preferred alumina forms include boehmite and pseudoboehmite.

If the body is intended to contain silica, almost any source of reactive silicon such as in situ formation of SiO ₂ tetrahedral units may be used. The silicon source can be silica in the form of a silica sol, can be fumed silica, or other conventional silica source used in zeolite synthesis,
For example, reactive solid amorphous precipitated silica, silica sol, silicon alkoxide, tetraalkyl orthosilicate (for example, tetraethyl orthosilicate), silicic acid,
It can be an alkali metal silicate or the like. Preferred silica sources are colloidal silica and silica sols.
Also, if the body is intended to contain silica, an aluminosilicate clay such as kaolin may be used as the source of both silica and alumina, but if the calcination temperature used is inadequate, silica from such clay may be used. It should be noted that there are some cases where the use of aluminosilicate clays can be disadvantageous as they are not readily available for joining non-zeolitic molecular sieves.

If the alumina or silica-alumina body is to contain one or more elements other than aluminum, silicon and oxygen for joining the non-zeolitic molecular sieve, the other elements are those elements discussed below. It can be in the form of a compound. However, other elements should not be present in a manner that significantly interferes with the formation of the alumina or silica-alumina bodies.

The liquid reaction mixture used in the method of the present invention comprises a reactive source of phosphorus. The reactive phosphorus source is preferably orthophosphoric acid or a salt thereof, and the liquid reaction mixture preferably comprises an aqueous solution of orthophosphoric acid or a salt thereof. Organic phosphates such as triethyl phosphate can also be used. Organophosphorus compounds, such as tetrabutylphosphonium bromide, for example, apparently do not act as reactive sources of phosphorus, but they do act as template agents. Conventional phosphorus salts such as sodium metaphosphate may be used as the phosphorus source at least in part, but are not preferred.

The liquid reaction mixture used in the method of the present invention also contains an organic templating agent. The organic templating agent can be any of the conventional zeolite aluminosilicates or those previously proposed for use in the synthesis of NZMS. In general, these compounds contain elements of Group VA of the Periodic Table of the Elements, especially nitrogen, phosphorus, arsenic and antimony, preferably nitrogen or phosphorus, particularly preferably nitrogen, these compounds also containing 1 to 8 carbons. Contains at least one alkyl or aryl group having atoms. Particularly suitable compounds for use as template agents are amines, quaternary phosphonium compounds and quaternary ammonium compounds, the latter two of which are generally of the formula R ₄
X ⁺ (where “X” is nitrogen or phosphorus, and each R
Is an alkyl or aryl group containing 1 to 8 carbon atoms]. Polymeric quaternary ammonium salts such as, for example, [(C ₁₄ H ₃₂ N ₂ ) (OH) ₂ ] _x, where "x" has a value of at least 2 are also suitable. Advantageously, mono-, di- and tri-amines are used alone or in combination with quaternary ammonium compounds or other templating compounds. A mixture of two or more templating agents can produce the desired mixture of non-zeolitic molecular sieves, or a more directing templating species is one that predominantly establishes the pH conditions of the reaction gel. The process of reaction with other working template species can be controlled. Typical templating agents are tetramethylammonium; tetraethylammonium; tetrapropylammonium and tetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2
-Methylpyridine; N, N-dimethylbenzylamine; N, N-
Diethylethanolamine; Dicyclohexylamine;
N, N-dimethylethanolamine; choline; N, N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2) octane; N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine; 3- Methylpiperidine; N
-Methylcyclohexylamine; 3-methylpyridine; 4-
Methyl pyridine; quinuclidine; N, N'-dimethyl-1,4
-Diazabicyclo (2,2,2) octane ion; di-n-
Butylamine; neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine and 2-imidazolidone. Not necessarily all template agents dominate the formation of non-zeolitic molecular sieves of all species, and a single template agent can be used to prepare several non-zeolitic molecular sieve compositions by appropriate adjustment of reaction conditions. The non-zeolitic molecular sieve composition that governs production and can be produced using several different templating agents.

If the liquid reaction mixture is to contain a silica source, the silica source may be any of those silica sources already mentioned for use in the silica-alumina body, provided that the silica source and the liquid reaction Dissolved in the mixture and /
Alternatively, the condition is that they can be dispersed. The preferred silica source for use in the liquid reaction mixture is silica sol.

If the liquid reaction mixture is intended to contain a source of one or more elements different from phosphorus, silicon and oxygen for joining the non-zeolitic molecular sieve, other elements may be added to the desired elements in the liquid reaction mixture. May be introduced in any form that allows in situ formation of the reactive form of, i.e., the reactive form that forms the skeleton tetrahedral oxide units of the elements present in the non-zeolitic molecular sieve. Compounds of elements that can be used are oxides, alkoxides,
Includes hydroxides, chlorides, bromides, iodides, sulfates, nitrates, carboxylates (eg acetates), and the like. Particularly preferred sources of various elements are discussed in the description of various non-zeolitic molecular sieves set forth below.

Similarly, if the solid body is intended to contain a phosphorus source,
The phosphorus source can be any of those phosphorus sources already mentioned for use in the liquid reaction mixture provided that the phosphorus source can be incorporated into the solid body without interfering with the process of the invention. As a condition. The person skilled in the art is also aware of other sources of slightly soluble phosphorus that can be used in solid form.

The proportions of the various components in the liquid reaction mixture and the ratio of these components present in the solid body to alumina (and optionally silica and other elements) depend, among other things, on the rate at which the process of the present invention proceeds, the formation. Affects the yield and composition of non-zeolitic molecular sieves. Generally, the proportions of the various components of the reaction mixture (including the body) used in the process of the present invention will vary depending on the hydrothermal crystallization described in the above mentioned patents and pending patent applications describing non-zeolitic molecular sieves. Similar to the proportions used in the process, but in the case of components present in the solid body, especially if the solid body is formed from clay, the reaction or conversion of such components may be incomplete. You may have to take it into consideration. From this, when synthesizing the non-zeolitic molecular sieve by the method of the present invention, it is preferable to use a liquid reaction mixture containing about 6 mol or less, preferably about 2 mol or less, of the organic template agent per 1 mol of phosphorus. Preferably, the liquid reaction mixture contains no more than 500 moles of water per mole of phosphorus, desirably no more than about 100 moles, and most desirably no more than about 50 moles. When the liquid reaction mixture contains silica, the liquid reaction mixture preferably contains from about 0.1 to about 0.5 moles of silicon per mole of phosphorus.

The proportions of the elements different from phosphorus, silicon and oxygen, which are intended to be added to the non-zeolitic molecular sieve in the liquid reaction mixture, are determined by the proportion of the desired element in the non-zeolitic molecular sieve to be produced and the non-zeolitic element. It will depend on both the ease of entering the crystalline framework of the system molecular sieve. General guidance on the proper proportions of the individual components to be included in the liquid reaction mixture is given below in the description of the various non-zeolitic molecular sieves.

The weight ratio of the body to the liquid reaction mixture is preferably adjusted so that the body contains from about 0.75 to about 1.25 moles of aluminum per mole of phosphorus in the liquid reaction mixture.

In those cases where alkoxide is used as the desired aluminum, phosphorus, silicon or other elemental limit in non-zeolitic molecular sieves, the corresponding alcohol is always present in the reaction mixture as it is the hydrolysis product of the alkoxide. . It has not been determined whether this alcohol participates in the synthetic process as a template agent. However, for this application, the alcohol is optionally omitted from the class of templating agents, even if the alcohol is present, for example, in the as-synthesized non-zeolitic molecular sieve.

The liquid reaction mixtures used in the process of the present invention are formed by forming a mixture of less than all reagents followed by addition of additional reagents to these mixtures alone or in the form of other intermediate mixtures of two or more reagents. It is usually made by joining. In some cases, the admixed reagents retain their predisposition in the intermediate mixture, while in others, some or all of the reagents are entrained in the chemical reaction to yield new reagents. The term "mixture" applies in both cases. Moreover, it is preferred to stir the intermediate mixture, as well as the final reaction mixture, until substantially homogeneous.

In the process of the present invention, the reaction mixture is generally charged to a sealed vessel, preferably a sealed vessel to avoid contamination of the reaction mixture lined with an inert plastic material such as tetrafluoroethylene, preferably under autogenous pressure, at about 10 ° C. 100 °
Heating is usually carried out for a few hours to a few weeks at temperatures of ~ 300 ° C, preferably about 150 ° -250 ° C, until crystals of the non-zeolitic molecular sieve product are obtained. Effective crystallization times are from about 2 hours to about 30 days, typically about 24 to about 240 hours, preferably about 48 to about 144 hours.

Although not essential for the synthesis of the non-zeolitic molecular sieve composition, the non-zeolitic molecular sieve or topologically similar aluminophosphate is prepared by stirring or otherwise moderately stirring the reaction mixture and / or producing a reaction mixture. Seeding the aluminosilicate or molecular sieve composition facilitates the crystallization procedure. The product is recovered by any convenient method such as centrifugation or filtration.

The present invention provides a non-zeolitic molecular sieve product,
It may be produced in a form having a significantly larger average particle size than the non-zeolitic molecular sieve produced by the hydrothermal crystallization synthesis method of the non-zeolitic molecular sieve described in the related patents and copending applications mentioned above. That is one significant advantage of the method of the present invention. Optimally, the non-zeolitic molecular sieve is produced as a single solid body having substantially the same size and shape as the alumina or silica-alumina body used in the synthesis.
For example, non-zeolitic molecular sieves are still produced by the hydrothermal crystallization process described above, even though this optimal result is not usually obtained and some fracturing of alumina or silica-alumina may occur. Made with a significantly larger average particle size than Whereas these hydrothermal crystallization processes typically produce particles of non-zeolitic molecular sieves having a mean particle size in the submicron range, the process of the present invention is generally at least about 10 microns, preferably Produces a product having an average particle size of about 20 to about 40 microns or greater.

After crystallization, the non-zeolitic molecular sieve product can be isolated and advantageously washed with water and dried in air. As-synthesized non-zeolitic molecular sieves generally contain within their internal pore system at least one form of the templating agent used for their formation. The organic components most commonly derived from organic templates are
It is present, at least in part, as a charge-harmonizing cation generally similar to that of as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. However, it is possible for some or all of the organic components to become occluded molecular species in certain non-zeolitic molecular sieve species. Generally the templating agent, and thus the occluded organic species, is too large to move freely through the pore system of the non-zeolitic molecular sieve product, and the non-zeolitic molecular sieve is 200 ° C to 700 ° C, preferably 350 ° C.
These organic species must be removed by pyrolysis by firing at a temperature of ° to 600 ° C. In some examples, the pores of the non-zeolitic molecular sieve product are large enough to allow migration of the template agent, especially if the template agent is a small molecule.
Its complete or partial removal can thus be achieved by conventional desorption means, such as is done with zeolites. As used herein, the term "as-synthesized" means that the organic components present in the intracrystalline pore system have been reduced by post-synthesis processing to reduce the organic components that occupy the intracrystalline pore system as a result of the synthetic process. It will be appreciated that the template does not include a state of the non-zeolitic molecular sieve phase which is less than 0.02 moles per 2 grams of oxygen present in the system.

The non-zeolitic molecular sieve composition produced by the method of the present invention exhibits cation exchange capacity when analyzed using the ion exchange technique conventionally used in the case of zeolitic aluminosilicates, and has a lattice structure of each species. And have a pore diameter that is at least about 3Å. Ion exchange of non-zeolitic molecular sieve compositions is usually only possible after the organic components present as a result of the synthesis have been removed from the pore system.
Dehydration, excluding the water present in the as-synthesized non-zeolitic molecular sieve composition, can usually be accomplished to the extent that at least some of the usual organic components have been removed, although organic species are present. Otherwise, it greatly facilitates the adsorption and desorption procedures. Non-zeolitic molecular sieve materials have varying degrees of hydrothermal and thermal stability, some of which are quite noticeable in this regard, in that they function as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases. Become.

As is well known to those skilled in the art of using molecular sieves as catalysts, the molecular sieve catalytic activity obviously depends on the ability of the reactants and products to diffuse into the pores of the molecular sieve. The reaction rate of is often strongly influenced by the pore size of the molecular sieve. The pore size of the non-zeolitic molecular sieve produced by the method of the present invention varies over a wide range, and based on the size of the pores, the non-zeolitic molecular sieve can be classified into small, medium and large pore materials. . The small pore material, when fired, has less than about 2% adsorption of isobutane due to the weight of the non-zeolitic molecular sieves at a partial pressure of 300 torr and a temperature of 20 ° C. The medium-pore material is
In the fired state, at a partial pressure of 500 torr and a temperature of 20 ° C,
At least about 2% isobutane, preferably at least about 4% by weight of the non-zeolitic molecular sieve.
At an adsorption and partial pressure of 2.6 torr and a temperature of 22 ° C., the adsorption of triethylamine is less than 5% due to the weight of the non-zeolitic molecular sieve. The macroporous material is one that adsorbs at least about 2% isobutane and at least 5% triethylamine by weight of the non-zeolitic molecular sieve in the calcined state at a partial pressure of 2.6 torr and a temperature of 22 ° C. Adsorption of at least about 2% by weight of non-zeolitic molecular sieves of isobutane at a partial pressure of 500 torr and a temperature of 20 ° C corresponds to a minimum pore size of approximately 5Å, a partial pressure of 2.6 torr and a temperature of 22
Adsorbing less than 5% by weight of non-zeolitic molecular sieves of triethylamine at ° C corresponds to a maximum pore size of approximately 7Å.

In most of the catalytic processes employing NZMS made by the method of the present invention, medium and large pore non-zeolitic molecular sieves are fine enough to adequately diffuse all the molecular species involved in the reaction. Medium and macroporous materials are preferred as they have pores. Thus, in a preferred embodiment of the method of the present invention, the NZMS produced is a medium or large pore material. Medium and large pore NZMS include, but are not limited to, ELAPSO-5, ELAPSO-11, ELAPSO-31, ELAPSO-36, ELAPSO-.
37, ELAPSO-40, ELAPSO-41, SAPO-5, SAPO-11, SAPO-3
1, SAPO-36, SAPO-37, SAPO-40, SAPO-41, CoAPSO-5, C
o APSO-11, CoAPSO-31, CoAPSO-36, CoAPSO-37, CoAPSO-
40, CoAPSO-41, FeAPSO-5, FeAPSO-11, FeAPSO-31, FeA
PSO-36, FeAPSO-37, FeAPSO-40, FeAPSO-41, MgAPSO-
5, MgAPSO-11, MgAPSO-31, MgAPSO-36, MgAPSO-37, MgA
PSO-40, MgAPSO-41, MnAPSO-5, MnAPSO-11, MnAPSO-3
1, MnAPSO-36, MnAPSO-37, MnAPSO-40, MnAPSO-41, TiA
PSO-5, TiAPSO-11, TiAPSO-31, TiAPSO-36, TiAPSO-3
7, TiAPSO-40, TiAPSO-41, ZnAPSO-5, ZnAPSO-11, ZnAP
SO-31, ZnAPSO-36, ZnAPSO-37, ZnAPSO-40, ZnAPSO-4
1, CoMnAPSO-5, CoMnAPSO-11, CoMnAPSO-36, CoMnAPSO-
37, CoMnAPSO-40, CoMnAPSO-41, CoMnMgAPSO-5, CoMnMg
APSO-11, CoMnMgAPSO-31, CoMnMgAPSO-36, CoMnMgAPSO-
37, CoMnMgAPSO-40, CoMnMgAPSO-41, AsAPSO-5, AsAPSO
-11, AsAPSO-31, AsAPSO-36, AsAPSO-37, AsAPSO-40, A
sAPSO-41, BAPSO-5, BAPSO-11, BAPSO-31, BAPSO-36, B
APSO-37, BAPSO-40, BAPSO-41, BeAPSO-5, BeAPSO-11,
BeAPSO-31, BeAPSO-36, BeAPSO-37, BeAPSO-40, BeAPSO
-41, CAPSO-5, CAPSO-11, CAPSO-31, CAPSO-36, CAPSO-
37, CAPSO-40, CAPSO-41, GaAPSO-5, GaAPSO-11, GaAPS
O-31, GaAPSO-36, GaAPSO-37, GaAPSO-40, GaAPSO-41,
GeAPSO-5, GeAPSO-11, GeAPSO-31, GeAPSO-36, GeAPSO-
37, GeAPSO-40, GeAPSO-41, LiAPSO-5, LiAPSO-11, LiA
PSO-31, LiAPSO-36, LiAPSO-37, LiAPSO-40, LiAPSO-4
1, MeAPO-5, MeAPO-11, MeAPO-31, MeAPO-36, MeAPO-3
7, MeAPO-40, MeAPO-41, TiAPO-5, TiAPO-11, TiAPO-3
1, TiAPO-36, TiAPO-37, TiAPO-40, TiAPO-41, FCAPO-
5, FCAPO-11, FCAPO-31, FCAPO-36, FCAPO-37, FCAPO-4
0, FCAPO-41, AsAPO-5, AsAPO-11, AsAPO-31, AsAPO-3
6, AsAPO-37, AsAPO-40, AsAPO-41, BAPO-5, BAPO-11,
BAPO-31, BAPO-36, BAPO-37, BAPO-40, BAPO-41, BeAPO
-5, BeAPO-11, BeAPO-31, BeAPO-36, BeAPO-37, BeAPO-
40, BeAPO-41, CAPO-5, CAPO-11, CAPO-31, CAPO-36, C
APO-37, CAPO-40, CAPO-41, GaAPO-5, GaAPO-11, GaAPO
-31, GaAPO-36, GaAPO-37, GaAPO-40, GaAPO-41, GeAPO
-5, GeAPO-11, GeAPO-31, GeAPO-36, GeAPO-37, GeAPO-
40, GeAPO-41, LiAPO-5, LiAPO-11, LiAPO-31, LiAPO-3
6, LiAPO-37, LiAPO-40, LiAPO-41, and MAPO-5, MAPO-
11, a mixed element APO that can be designated as MAPO-31, MAPO-36, MAPO-37, MAPO-40, MAPO-41, and mixtures thereof.

The above characterization of the NZMS used in the present invention is based on the post synthesis treatment, such as calcination or chemical treatment, excluding a substantial portion of the template "R" present as a result of the synthesis.
It is related to the adsorption characteristic display performed for. While certain NZMSs are characterized herein with respect to adsorption of isobutane in the calcined state, the present invention is not calcined or modified which can be characterized by adsorption in such calcined state.
Be sure to synthesize NZMS. This is because when using non-calcined NZMS in various catalytic processes under effective process conditions, the NZMS will be calcined or hydrothermally treated in situ, which will have the characteristic adsorption of isobutane. . Thus, NZMS can be converted in situ to a form with the above adsorption properties. For example, as-synthesized MgAPO-11 or MgAPSO-11 does not exhibit the above adsorption properties of isobutane due to the presence of the template agent "R" present as a result of the synthesis, but MgAPO-11 and MgAPSO-11 The calcined form will have the above isobutane adsorption properties. Thus, in the present application, referring to NZMS having specific adsorption properties in the calcined or anhydrous form means that the NZMS has been subjected to in situ calcination hydrothermal treatment and / or other treatments, such as ion exchange in suitable ions. It is not intended in this case to exclude its use in the as-synthesized form that results in such adsorption properties.

Non-zeolitic molecular sieves can be characterized by their X-ray powder diffractogram, as described in the above-mentioned patents and applications describing non-zeolitic molecular sieves. That is, each non-zeolitic molecular sieve, such as SAPO-1
Various crystal forms such as 1, SAPO-34, SAPO-41, etc. can be identified and distinguished from each other by X-ray powder diffractogram.
Some of the non-zeolitic molecular sieves made in the examples below are characterized in this way, and the method for obtaining their X-ray powder diffractograms is described below.

An X-ray diagram of the reaction product is obtained by X-ray analysis using standard X-ray powder diffractometry techniques. The irradiation source is a copper target 50
It is a high-intensity X-ray tube operated at Kv and 40ma. Copper K-α
The radiation and diffractograms from the graphite monochromator are recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. A flat compressed powder sample is scanned at 2 ° (2θ) per minute with a time constant of 2 seconds. The interplanar distance (d) in Angstroms is obtained from the position of the diffraction peak, expressed as 2θ (where θ is the Bragg angle observed on the strip chart). The intensity is obtained from the height or area of the diffraction peak after the background is subtracted. "I ₀ " is the intensity of the strongest line or peak and "I" is the intensity of each of the other peaks. Alternatively, the X-ray diagram is a computer using copper K-α irradiation with a Siemens type K-805 X-ray source and a Siemens D-500 X-ray powder diffractometer available from Siemens Corporation of Cherry Hill, NJ. It can be obtained by using the base technique.

As will be appreciated by those skilled in the art, the measurement of the parameter 2 [Theta] is subject to both human and mechanical error, which, combined, can give an uncertainty of about ± 0.4 [deg.] For each recorded value of 2 [Theta]. Of course, this uncertainty is also calculated from the 2θ value d
-Represented by the recorded value of the interval. This inaccuracy is common throughout the field and does not preclude distinguishing non-zeolitic molecular sieves from each other and from prior art compositions.

In some cases in the examples hereinbelow, the purity of the synthesized non-zeolitic molecular sieve product can be evaluated by reference to its X-ray powder diffractogram.
That is, for example, if a sample is said to be pure, the X-ray pattern of the sample is meant only to be free of lines due to crystalline impurities and not to the absence of amorphous material.

In the examples below, when the non-zeolitic molecular sieves made by the method of the present invention were characterized by their X-ray powder diffractogram, these X-ray diagrams were synthesized unless otherwise specified. It is about the form as it is. In most cases, the corresponding fired form figure will also be included in the relevant table. However, in some cases, the removal of occluded template agent that occurs during calcination is accompanied by a looseness of the lattice that shifts some of the lines slightly outside the ranges specified in the relevant table. Will be seen. In a few cases, calcination can cause more significant crystal lattice distortions and thus more significant changes in the X-ray powder diffractogram.

The non-zeolitic molecular sieve produced by the method of the present invention is modified by synthesizing and (if necessary) calcining and then attaching or impregnating the non-zeolitic molecular sieve with a cation, anion or salt. Thus, as described in the above-mentioned patents and applications describing non-zeolitic molecular sieves, non-zeolitic molecular sieves may have improved catalytic efficacy in various processes in which they are useful. Techniques that can be used to deposit or impregnate non-zeolitic molecular sieves are generally known in the art. Such a procedure comprises: (1) depositing one or more modifier solvents or solubilizers on the non-zeolitic molecular sieve in the desired weight of the modifier into the non-zeolitic molecular sieve. Can be impregnated with a solution containing such an amount and / or (2) replacing the non-zeolitic molecular sieve with a solution containing a modifier. The impregnation or deposition of the modifier is usually performed by heating the non-zeolitic molecular sieve at a high temperature and applying the modifier to the inner surface and / or the outer surface of the non-zeolitic molecular sieve. Can be completely evaporated, or by exchanging the cations present in the non-zeolitic molecular sieve with cations which impart the desired properties. Alternatively, the modifier can be formed on the non-zeolitic molecular sieve by heating the non-zeolitic molecular sieve from an emulsion or slurry containing the modifier. The impregnation or exchange procedure is usually the preferred technique because it uses and introduces the modifier more effectively than other procedures such as the coating procedure, since the coating procedure is usually a non-zeolitic molecular sieve. This is because it is impossible to substantially introduce the modifier into the inner surface. In addition, coated materials are more commonly susceptible to modifier loss due to wear.

Suitable modifiers include alkali metals, alkaline earth metals, transition metals and their salts, including inorganic and organic salts, such as nitrates, halides, hydroxides, sulfates, carboxylates. It is believed that other modifiers commonly used in the art can also be used in the non-zeolitic molecular sieves.

Blended with non-zeolitic molecular sieves
Alternatively, or under certain process conditions, certain properties that are advantageous, such as improved heat resistance or other materials that may provide improved catalyst life by minimizing coking, or simply under the process conditions used. It may be applied subsequently to other substances which are only inert. Such materials include synthetic or naturally occurring materials, as well as inorganic materials such as clay, silica, alumina, crystalline aluminosilicate zeolites,
It can include metal oxides and mixtures thereof. In addition, the non-zeolitic molecular sieves include silica, alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-berrillia, silica-titania, and ternary compositions, such as silica-, which are present as binders. Alumina-Thia, Silica-
It can be formed of materials such as alumina-zirconia and clay. The relative proportions of the above mentioned substances and non-zeolitic molecular sieves can vary widely, the content of non-zeolitic molecular sieves being about 1 to about 1% of the composite material.
It is in the range of about 99% by weight.

The above general description of the process of the invention may be applied to use in the synthesis of all non-zeolitic molecular sieves mentioned in the patents and patents mentioned above which describe non-zeolitic molecular sieves. . The more detailed description below details preferred variants of the process of the invention for synthesizing certain preferred non-zeolitic molecular sieves.

A preferred group of non-zeolitic molecular sieves made by the method of the present invention is the aluminophosphate (Al) disclosed in the claims of U.S. Pat. No. 4,310,440.
PO _4), in particular AlPO ₄ -5. Preferred organic templating agents for synthesizing AlPO ₄ are tetraethylammonium hydroxide, tetrapropylammonium hydroxide, diethylethanolamine, tripropylamine. A particularly preferred organic templating agent for this synthesis is a mixture of tetraethylammonium hydroxide and tripropylamine and the liquid reaction mixture is from about 0.1 to about 0.4 moles of phosphorus.
It contains moles of tetraethylammonium hydroxide and about 0.5 to about 2 moles of tripropylamine. In this synthesis, the alumina body and the liquid reaction mixture are heated to a temperature of about 100 ° to about 2 °.
The contact is preferably in the range of 00 ° C for a period of about 12 to about 72 hours.

A preferred second group of non-zeolitic molecular sieves made by the method of the present invention are the silicoaluminophosphates (SAPO), preferably SAPO-5, SAPO-11, SAPO described in the claims of US Pat. No. 4,440,871. -34,
SAPO-41, most preferably SAPO-34. Preferred organic templating agents for synthesizing SAPO are tetraethylammonium hydroxide, diethanolamine, di-n-propylamine. A particularly preferred organic templating agent for this synthesis is a mixture of diethanolamine and di-n-propylamine and the liquid reaction mixture comprises from about 0.5 to about 2 moles diethanolamine and about 0.1 to about 1 mole of phosphorus.
It contains about 0.5 mol of di-n-propylamine. In this synthesis, it is desirable to calcine the alumina or silica-alumina body at a temperature of about 250 ° to about 450 ° C prior to contacting with the liquid reaction mixture. Also, in this synthesis, the alumina or silica-alumina body and the liquid reaction mixture are heated to about
Contacting in the range of 150 ° to about 250 ° C. for a period of about 48 to about 144 hours is desirable.

Some of the examples below also illustrate the synthesis of certain GeAPO and GeAPSO non-zeolitic molecular sieves, respectively, which are claimed in the aforementioned co-pending applications 841,758 and 852,175, respectively.

The following examples are provided to further illustrate the method of the invention and are not intended to limit the invention.

Examples The following examples show AlPO ₄ -5, SAPO-5, SAP according to the method of the invention.
O-11, SAPO-34, SAPO-41, CoAPSO-34, GeAPO-5, GeAPO-
17 illustrates synthesizing 17 and GeAPSO-34. A table of proper X-rays for ALPO ₄ -5 appears in US Pat. No. 4,310,440, column 8, table 2. SAPO-5, SAPO-11, SAPO-34 and SAPO-4
The specific X-ray table for each is US Pat. No. 4,440,871,
Table I (column 20), Table III (column 27), Table XI (column 44) and Table XXV
(Column 69) The intrinsic X-ray tables for the remaining species made in these examples are: CoAPSO-34 2θ d (Å) Relative Intensity 9.4-9.8 9.41 -9.03 s-vs 12.86-13.06 6.86 -6.76 w 14.08- 14.30 6.28 −6.19 w−m 15.90−16.20 5.57 −5.47 vw−m 20.60−20.83 4.31 −4.26 w−vs 30.50−30.80 2.931−2.903 w−m GeAPO-5 2θ d (Å) Relative strength 7.3−7.65 12.1 −11.56 m-vs 19.5 -19.95 4.55 -4.46 m-s 20.9 -21.3 4.25 -4.17 m-vs 22.2 -22.6 4.00 -3.93 w-vs 25.7 -26.15 3.47 -3.40 w-m GeAPO-17 2θ d (Å) Relative strength 7.7 −7.75 11.5 −11.4 vs 13.4 6.61 s−vs 15.5−15.55 5.75−5.70 s 20.5−20.6 4.33−4.31 vs 31.8−32.00 2.812−2.797 w−s GeAPO-34 2θ d (Å) Relative strength 9.3−9.8 9.51−9.03 m-vs 12.6 -13.2 7.03 -6.71 w-m 15.8 -16.3 5.61 -5.44 vw-m 20.25-21.2 4.39 -4.19 w-vs 24.8 -55.4 3.59 -3.507 vw-m 30.0 -30.9 2.979 -2.894 vw- Examples 1-12 These examples useful alumina and silica in the method of the present invention - illustrates that forming an alumina body.

Example 1 395.4 grams of aluminum isopropoxide (containing 25.8 wt% Al ₂ O ₃ ) was placed in the mixing bowl of a Hobart mixer and sufficient water was added to make an extrudable paste, the mixture being substantially Mix until a uniform paste is formed. The paste was extruded using a home kitchen meat grinder attachment equipped with a 1/8 inch (approximately 3 mm) die, which molded 1/8 inch diameter extruded alumina precursor cylinders. These extrusion cylinders were air dried for several days and then heated to 350 ° C. in air for 2.5 hours. The water content of the produced alumina body was smaller than 1% by weight.

Example 2 400 grams of hydrated aluminum oxide in the form of a boehmite phase containing 75.1% by weight Al ₂ P ₃ and 24.9% by weight H ₂ O in a mixing bowl of a Hobart mixer with a solution of 2.1% by weight nitric acid 287.0.
Deaggregated in grams. The deflocculated alumina thus prepared was mixed for 20 minutes and 120 grams of 2.0 wt% ammonium hydroxide solution was added. The resulting paste was extruded as in Example 1 above and the extrusion cylinder
Oven dry at 0 ° C for 5 hours, then 2.5 at 350 ° C in air.
Heated for hours. The water content of the formed alumina body is 1% by weight.
Was smaller.

Example 3 Al ₂ O ₃ were placed 69.0% by weight and H ₂ O31.0 wt% in the form of a hydrated aluminum oxide about 2 pounds pseudoboehmite phase containing (about 900 grams) to the mixing bowl of a boric Bad mixer, sufficient Add water to make an extrudable paste,
The mixture was mixed until a substantially uniform paste was formed. The resulting paste was extruded as in Example 1 above and the extruded cylinder was oven dried at 100 ° C. for 16 hours. The oven dried cylinder was divided into 3 parts which were then heated in air at the following temperatures for 2.5 hours: A-350 ° C. B-400 ° C. C-500 ° C. Example 4 Al ₂ O ₃ 69.0 wt% and H ₂ O 31 240 grams of hydrated aluminum oxide in the form of a pseudoboehmite phase containing 0.0% by weight and 76.2 grams of colloidal silica containing 94.5% by weight of SiO ₂ are mixed to give an oxide molar ratio of 0.74 SiO ₂ : 1.0Al ₂ This resulted in an alumina / silica mixture with O ₃ . This alumina / silica mixture was dry blended in the mixing bowl of a Hobart mixer for approximately 10 minutes. Sufficient water was added to the blended mixture to make an extrudable paste and the mixture was mixed for an additional 20 minutes until a substantially homogeneous paste was formed. The resulting paste was extruded as in Example 1 above and the extruded cylinder was oven dried at 100 ° C. for 16 hours. The oven dried cylinder was divided into 3 parts which were then heated in air at the following temperatures for 2.5 hours.

A-350 ° C. B-400 ° C. C-500 ° C. Example 5 240 grams of hydrated aluminum oxide in the form of pseudoboehmite phase containing 69.0% by weight Al ₂ O ₃ and 1.0% by weight H ₂ O and SiO ₂ 30 % Silica and 240 grams of silica sol containing 70% by weight of H ₂ O were placed in a mixing bowl of a Hobart mixer to yield an alumina / silica mixture having an oxide molar ratio of 0.74 SiO ₂ : 1.0Al ₂ O ₃ . The alumina / silica mixture was dry blended for approximately 10 minutes. Sufficient water was added to the blended mixture to make an extrudable paste and the mixture was mixed for an additional 20 minutes until a substantially homogeneous paste was formed. The resulting paste was extruded as in Example 1 above and the extruded cylinder was oven dried at 100 ° C. for 16 hours. The oven dried cylinder was divided into 3 parts which were then heated in air at the following temperatures for 2.5 hours: A-350 ° C. B-400 ° C. C-500 ° C. Example 6 Al ₂ O ₃ 69.0 wt% and H ₂ O 31 240 grams of hydrated aluminum oxide in the form of a pseudo-boehmite phase containing 0.0% by weight and 81.36 grams of colloidal silica containing 88.5% by weight of SiO ₂ are approximately 10 in a mixing bowl of a Hobart mixer.
Dry blend for minutes and oxide molar ratio 0.74 SiO ₂ : 1.0Al ₂ O
_This resulted in an alumina / silica mixture with ₃ . Sufficient water is added to the blended mixture to make an extrudable paste, and the mixture is further mixed until a substantially homogeneous paste is formed.
Mix for 20 minutes. The resulting paste was extruded as in Example 1 above and the extruded cylinder was oven dried at 100 ° C. for 16 hours. Divide the oven-dried cylinder into three parts, which are then placed in air at 2.5
Heated for: A-350 ° C. B-400 ° C. C-500 ° C. Example 7 11 lbs of hydrated aluminum oxide in the form of pseudoboehmite phase containing 69.0 wt% Al ₂ O ₃ and 1.0 wt% H ₂ O ₃ ( Approximately 4.9 kilograms) was blended with approximately 5 liters of water in a muller for 30 minutes until a substantially uniform paste was formed. 1/8 inch (approx. 3 mm) of generated paste
Extrusion was performed using a 5 inch (127 mm) barrel extruder with a die and the extruded cylinder was oven dried at 100 ° C for 16 hours and then heated in air at 350 ° C for 2.5 hours. The water content of the produced alumina body was smaller than 1% by weight.

Example Muller 8 and Al ₂ O ₃ 69.0 wt% and H ₂ O31.0 wt% in the form of a hydrated aluminum oxide pseudoboehmite phase containing 1,693 g, the colloidal silica 577 g containing SiO ₂ 88.5 wt% Dry blending for approximately 45 minutes to yield an alumina / silica mixture having an oxide molar ratio of 0.74SiO ₂ : 1.0Al ₂ O ₃ . Sufficient water was added to the blended mixture to make an extrudable paste and the mixture was milled for an additional 45 minutes until a substantially homogeneous paste was formed. The resulting paste was extruded as in Example 7 above, the extruded cylinder was oven dried at 100 ° C. for 16 hours and then heated in air at 350 ° C. for 2.5 hours. The water content of the formed alumina / silica body was less than 1% by weight.

Containing a hydrated aluminum oxide 2196 g in the form of a pseudoboehmite phase, Al ₂ O ₃ 45.95 wt% and SiO ₂ 54.05 wt% containing Example 9 Al ₂ O ₃ 69.0 wt% and H ₂ O31.0 wt% Then
This was dry blended in a muller for approximately 45 minutes with 74.45 grams of meta-kaolin clay having an oxide molar ratio of ₂ SiO ₂ : Al ₂ O ₃ . Sufficient water was added to the blended mixture to make an extrudable paste and the mixture was milled for an additional 45 minutes until a substantially homogeneous paste was formed.
The resulting paste was extruded as in Example 7 above,
Oven extruded cylinder at 100 ° C for 16 hours,
It was then heated in air at 350 ° C. for 2.5 hours. The water content of the formed alumina / silica body was less than 1% by weight.

Example 10 551.68 grams of kaolin clay having an oxide molar ratio of 2SiO ₂ : Al ₂ O ₃ : 2H ₂ O, 29.94 grams of attapulgite clay and 5.00 grams of burn-out mixture were dried in a Hobart mixer for approximately 30 minutes. Blended. Sufficient water was added to the blended mixture to make an extrudable paste and the mixture was mixed for an additional 30 minutes until a substantially homogeneous paste was formed. The resulting paste was extruded as in Example 1 above and the extruded cylinder was
It was oven dried at 100 ° C for 24 hours and then heated at 650 ° C for 1.5 hours with an air purge.

Example 11 Al ₂ O ₃ 69.0 wt% and H ₂ O31.0% by weight hydrated aluminum oxide 4585 g in the form of a pseudoboehmite phase containing colloidal silica 1207 g of distilled water containing SiO ₂ 88.5 wt% 7.5 liters were milled in a vibrating media mill for 15 minutes to produce a slurry. Separately, sodium silicate solution containing 8.9% by weight Na ₂ O and 28.7% by weight SiO ₂ 9.00
10.5 kg of a 10 wt% sulfuric acid solution and 1 kg of water
Mixing with 12.5 liters gave silica gel containing approximately 8.0% by weight of SiO ₂ . 11.43 grams of this silica gel and the slurry formed above were mixed until a substantially uniform mixture was formed. The resulting mixture is bowed (Bo
wen) In the spray dryer, the inlet temperature is approximately 1200 ° F (approximately 649
C.) and an outlet temperature of approximately 300.degree. F. (approximately 149.degree. C.) to produce a spray dried material having an average particle size of 60-70 microns. The spray dried material was washed extensively with distilled water and then treated with a 20 wt% ammonium hydroxide solution for ammonium ion exchange.

A sample of the ion-exchanged material was analyzed to obtain the following chemical analysis: Component wt% Al ₂ O ₃ 44.1 SiO ₂ 31.2 LOI ^* 24.7 * LOI indicates loss on ignition.

The above chemical analysis is consistent with the product composition below in oxide molar ratio.

1.00Al ₂ O ₃ : 1.21SiO ₂ : 3.2H ₂ O Example 12 3250 grams of hydrated aluminum oxide in the form of pseudoboehmite phase containing 69.0% by weight Al ₂ O ₃ and 1.0% by weight H ₂ O and distilled 8 liters of water were stirred together and then milled in a vibrating media mill for 15 minutes to produce a slurry. After this milling, 1880 grams of an aqueous solution of aluminum hydroxychloride containing 23.4 wt% Al ₂ O ₃ was added and the resulting mixture was mixed until a substantially homogeneous mixture was obtained. The resulting mixture was spray dried as in Example 11 above. A sample of the spray dried material produced was analyzed to obtain the following chemical analysis: Component wt% Al ₂ O ₃ 80.8 Cl 2.9 Moisture 18.3 Examples 13-22 These examples show the synthesis of AlPO ₄ -5 by the process of the invention. Indicates.

Example 13 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 19.2
The gram was combined to form a solution. To this solution was added 10.2 grams of the alumina extrudate made in Example 1 above and the mixture was stirred. To the resulting mixture, 36.8 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) was added to 30.
A solution dissolved in 5 grams was added and the resulting mixture was briefly stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.0TEAOH: 1.0Al ₂ O ₃ : 1.0P ₂ O ₅ : 40H ₂ O This final reaction mixture was sealed in a polytetrafluoroethylene lined stainless steel pressure vessel and digested by heating in an oven at 150 ° C. under autogenous pressure for 16 hours. The solid in the reaction mixture was collected by filtration, then washed well and dried in air at 100 ° C.

Crush a sample of the dried solid reaction product and
Equilibrated at 50% and X-ray powder diffraction analysis was performed. This analysis was carried out on AlPO ₄ -5 with an X-ray powder diffractogram characterized by the data in Table I below, with the main crystalline phase of the product (which contained only minor amounts of crystalline impurities) as-synthesized. Table I 2θ d (Å) Relative strength 100 × I / I ₀ 7.5 11.8 100 13.0 6.83 10 15.0 5.90 20 19.9 4.46 44 21.1 4.216 42 22.5 3.945 55 26.1 3.409 20 29.2 3.061 14 30.3 2.954 12 34.8 2.577 9 37.9 2.377 8 Example 14 Example 13 was repeated except that the alumina extrudate used was that made in Example 2 above. A crystalline product was made and the main phase of this product was AlPO ₄ -5, which has essentially the same X-ray powder diffractogram as listed in Table I above.

Example 15 Example 13 was repeated except that the alumina extrudate used was from Part A made in Example 3 above. Make a crystalline product,
The main phase of this product was AlPO ₄ -5, which has essentially the same X-ray powder diffractogram as listed in Table I above.

Example 16 85 wt% orthophosphoric acid (H ₃ PO ₄ ) 11.55 grams and water 9.59
The gram was combined to form a solution. To this solution was added 10.2 grams of the alumina extrudate made in Example 1 above and the extrudate was immersed in the orthophosphoric acid solution for 24 hours at room temperature and ambient conditions. To the resulting mixture, 85 wt% of orthophosphoric acid (H ₃ PO ₄₎ a combination of 11.6 grams of water 19.2 g of the second solution formed by adding, the mixture was stirred briefly. To the resulting mixture was added a third solution formed by combining 36.8 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) and 27.3 grams of water and the resulting mixture was briefly stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.0TEAOH: 1.0Al ₂ O ₃ : 1.0P ₂ O ₅ : 40H ₂ O The final reaction mixture was sealed in a polytetrafluoroethylene lined stainless steel pressure vessel and cooked in an oven at 150 ° C. under autogenous pressure for 16 hours. The solid in the reaction mixture was collected by filtration, washed thoroughly with water and dried in air at 100 ° C.

Crush a sample of the dried solid reaction product and
Equilibrated at 50% and X-ray powder diffraction analysis was performed. This analysis showed the product AlPO ₄ (pure did not) in the main crystal phase having essentially the same X-ray powder diffraction pattern as that listed in Table I -
It was shown to be 5.

Example 17 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 19.2
The gram was combined to form a solution. To this solution was added 10.2 grams of alumina extrudate from Part A made in Example 3 above and the mixture was stirred. 40% by weight in the resulting mixture
Aqueous tetrapropylammonium hydroxide (TPAOH) 51.
A solution of 0 grams in 27.3 grams of water was added and the resulting mixture was briefly stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.0TPAOH: 1.0Al ₂ O ₃ : 1.0P ₂ O ₅ , 40H ₂ O The final reaction mixture was sealed in a polytetrafluoroethylene lined stainless steel pressure vessel and cooked in an oven at 150 ° C. under autogenous pressure for 16 hours. The solid in the reaction mixture was collected by filtration, washed thoroughly with water and dried in air at 100 ° C.

Crush a sample of the dried solid reaction product and
Equilibrated at 50% and X-ray powder diffraction analysis was performed. This analysis showed that the main crystalline phase of the product (which was not pure) was AlPO ₄ -5 with as-synthesized, essentially the same X-ray powder diffractogram as listed in Table I above. Indicated.

Example 18 Example 17 was repeated except that a solution of tetrapropylammonium hydroxide was used instead of a solution of 11.7 grams of diethyl ethanolamine in 49.3 grams of water. The molar ratio of template agent to other components of the reaction mixture was unchanged. A crystalline product was made, the main phase of this product (not pure) was AlPO ₄ -5 which has essentially the same X-ray powder diffractogram as listed in Table I above.

Example 19 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 19.2
The gram was combined to form a solution. To this solution was added 12.0 grams of Alina extrudate from Part A made in Example 3 above and the mixture was stirred. To the resulting mixture was added a solution of 14.3 grams of tripropylamine (Pr ₃ N) in 47.5 grams of water and the resulting mixture was briefly stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.0Pr ₃ N: 1.0Al ₂ O ₃ : 1.0P ₂ O ₅ : 4H ₂ O This final reaction mixture was digested by sealing in a polytetrafluoroethylene lined stainless steel pressure vessel and heating in a furnace at 150 ° C. under autogenous pressure for 24 hours. The solid in the reaction mixture was collected by filtration, washed thoroughly with water and dried in air at 100 ° C.

A sample of the dried solid reaction product was sieved to -200
US mesh (equal to or less than 74 microns)
Fractions and +200 US mesh (greater than 74 microns) fractions were produced. X-ray powder diffraction analysis was performed on the -200 mesh fraction. This analysis showed that the main crystalline phase of the -200 mesh fraction (which was not pure) was AlPO ₄ -5 with essentially the same X-ray powder diffractogram as listed in Table I above.

Example 20 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 36.0
Grams were combined to form a solution. To this solution was added 10.2 grams of alumina extrudate from Part A made in Example 3 above and the mixture was stirred. 40% by weight in the resulting mixture
9.2 grams of aqueous tetraethylammonium hydroxide (TEAOH) was added and the resulting mixture was stirred. To the resulting mixture was added 14.3 grams of tripropylamine (Pr ₃ N),
The resulting mixture was stirred until homogeneous. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 0.25 TEAOH: 1.0Pr ₃ N: 1.0Al ₂ O ₃ : 1.0P ₂ O ₅ : 40H ₂ O The final mixture was cooked, dried and fractionated as in Example 19 above. X-ray powder diffraction analysis was performed on this product. This analysis showed that the main crystalline phase of the product, until synthesized, was AlPO ₄ -5, which had essentially the same X-ray powder diffractogram as listed in Table I above.

A sample of the product was calcined in air at 600 ° C for 3 hours. The X-ray powder diffractogram of the calcined sample was essentially the same as the as-synthesized sample as listed in Table I above.

The calcined samples were used in an adsorption study using a standard McBain-Baker gravimetric adsorption device. The samples were activated by heating in vacuum at 350 ° C. for 16 hours before being used for adsorption tests. The following data were generated in the adsorption study: From the above data, the pore size of the calcined product was determined to be greater than about 6.2Å, as indicated by the adsorption of neopentane (kinetic diameter 6.2Å).

Example 21 Example 20 was repeated except that the alumina extrudate used was the 40-60 US mesh fraction from Part A made in Example 3 above. A crystalline product was made and the main phase of this product was Table I above.
AlPO having essentially the same X-ray powder diffractogram as listed in 1.
₄ was -5.

Example 22 85 wt.% Orthophosphoric acid (H ₃ PO ₄₎ 82.0 grams of 40 wt% aqueous oxidized tetraethylammonium (TEAOH) 32.
A solution was formed by combining 4 grams with 89.1 grams of tripropylamine (Pr ₃ N) and 198.2 grams of water. To this solution was added 43.7 grams of spray dried alumina prepared in Example 12 above and the resulting mixture was stirred until homogeneous.
The composition of the final reaction mixture thus prepared was as follows, expressed by the molar oxide ratio of the components of the reaction mixture: 0.25 TEAOH: 1.75Pr ₃ N: 1.0Al ₂ O ₃ : 1.0P ₂ O ₅ : 50H ₂ O This final reaction mixture was cooked, washed and dried as in Example 19 above, except that the cooking was carried out for 4 hours with continuous stirring. The product was submitted for X-ray powder diffraction analysis. This analysis showed that the predominant crystalline phase of the product was AlPO ₄ -5, which has essentially the same X-ray powder diffractogram as listed in Table I above.

Examples 23-25 These examples show the synthesis of SAPO-5 by the method of the invention.

Example 23 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 72.0
The gram was combined to form a solution. To the resulting mixture was added 12.0 grams of silica sol containing 30% by weight SiO ₂ and 70% by weight H ₂ O and the resulting mixture was stirred until homogeneous. To the resulting mixture was added 9.2 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) and the resulting mixture was stirred until homogeneous. Next, 28.6 grams of tripropylamine (Pr ₃ N) was added to the resulting mixture and the resulting mixture was stirred until homogeneous. Finally, 10.2 grams of the alumina extrudate from Part A made in Example 3 above was added to the resulting mixture and the mixture was stirred.
The composition of the reaction mixture thus prepared was expressed as follows, expressed by the molar oxide ratio of the components of the reaction mixture: 0.25 TEAOH: 2.0Pr ₃ N: 1.0Al ₂ O ₃ : 0.6SiO ₂ : 1.0 P ₂ O ₅ : 50H ₂ O The final reaction mixture was sealed by heating in a polytetrafluoroethylene-lined stainless steel pressure vessel and heated in a furnace at 200 ° C. under autogenous pressure for 48 hours. The solid in the reaction mixture was collected by filtration, washed thoroughly with water and dried in air at 100 ° C.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis shows that the crystalline product remains as-synthesized,
It has been shown to be SAPO-5 with an X-ray powder diffractogram characterized by the data in Table II below: Table II 2θ d (Å) Relative Intensity 100 × I / I ₀ 7.4 11.9 100 12.9 6.9 10 14.9 5.95 20 19.8 4.49 46 21.1 4.22 46 22.4 3.966 76 26.0 3.430 24 29.1 3.073 14 30.1 2.971 13 33.7 2.660 5 34.6 2.592 11 37.8 2.383 10 47.8 1.904 4 A sample of the product was calcined in air at 600 ° C. for 3 hours. The X-ray powder diffractogram of the calcined sample was essentially the same as the as-synthesized sample as listed in Table II above.

A sample of the product was analyzed to obtain the following chemical analysis: Component wt% Carbon 5.3 Nitrogen 0.66 Al ₂ O ₃ 40.9 SiO ₂ 2.5 P ₂ O ₅ 43.2 The above chemical analysis is on a calcined basis (ie water. And on the basis of no templating agent), corresponding to a product composition of the following molar oxide ratios: 1.0 Al ₂ O ₃ : 0.10SiO ₂ : 0.76P ₂ O ₅ calcined samples in a standard McBane-Baker gravimetric adsorption device Was used for adsorption studies. Samples were heated and activated in vacuum at 400 ° C. for 16 hours before being used for adsorption tests. The following data were generated in the adsorption study: From the above data, the pore size of the calcined product was determined to be greater than about 6.2Å as shown by adsorbing neopentane (dynamic diameter 6.2Å).

20-40 U.S. of the activated calcined product used for the adsorption test.
N-butane decomposition activity of the mesh fraction, the length of the reactor
It was tested on a bench scale device which is a cylindrical quartz tube of 254 mm and an inner diameter of 10.3 mm. The reactor was charged with 1.65 grams of the calcined fraction. Rate feed containing helium / n-butane mixture containing 2 mol% n-butane
It was passed through the reactor at a temperature of 500 ° C. at 50 mL / min. The reactor effluent was analyzed 10 minutes after on-stream operation using conventional gas chromatography techniques. The data obtained showed a pseudo first-order rate constant (k _A ) of 0.83.

Example 24 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 79.2
The gram was combined to form a solution. To the resulting solution was added 9.2 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) and the resulting mixture was stirred until homogeneous. To the resulting mixture was added 28.6 grams of tripropylamine (Pr ₃ N) and the resulting mixture was stirred until homogeneous. Finally, to the resulting mixture was added 13.8 grams of the alumina / silica extrudate from Part A made in Example 5 above and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 0.25 TEAOH: 2.0Pr ₃ N: 0.94Al ₂ O ₃ : 0.70SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O This final reaction mixture was digested, crystallized, washed, dried and fractionated as in Example 23 above. An X-ray powder diffraction analysis was performed on a sample of the product. This analysis indicates that the main crystalline phase of the product is essentially the same as that listed in Table II above.
It was shown to be SAPO-5 with a line powder diffractogram.

A sample of the as-synthesized product was analyzed to obtain the following chemical analysis: Component wt% Carbon 5.7 Nitrogen 0.72 Al ₂ O ₃ 31.7 SiO ₂ 15.5 P ₂ O ₅ 40.4 The above chemical analysis was on a calcined basis. The product composition of the following oxide molar ratios (ie, on the basis of no water and no templating agent) corresponds to: 1.0Al ₂ O ₃ : 0.83SiO ₂ : 0.92P ₂ O ₅ Example 25 Alumina / Silica Extrusion Used Example 24 was repeated except that the article was from Part A made in Example 6 above. A crystalline product was made and the main phase of this product was SAPO-5 with essentially the same X-ray powder diffractogram as listed in Table II above.

A sample of the product was analyzed to obtain the following chemical analysis: Component wt% Carbon 5.6 Nitrogen 0.89 Al ₂ O ₃ 31.9 SiO ₂ 13.6 P ₂ O ₅ 41.4 The above chemical analysis is on a calcined basis (ie water. And on the basis of no template agent), corresponding to a product composition of the following oxide molar ratios: 1.0Al ₂ O ₃ : 0.72SiO ₂ : 0.93P ₂ O ₅ Examples 26-41 These examples are the methods of the invention. Shows the synthesis of SAPO-34 by.

Example 26 85 wt.% Orthophosphoric acid (H ₃ PO ₄₎ 23.1 grams of water 19.2
The gram was combined to form a solution. To the resulting solution was added the alumina extrudate 10.2 from Part A prepared in Example 3 above.
Grams were added and the mixture was stirred. Si in the resulting mixture
Silica sol containing 30% by weight of O ₂ and 70% by weight of H ₂ O 12.0
Grams were added and the resulting mixture was briefly stirred. Finally, a solution of 73.5 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) in 14.84 grams of water was added to the resulting mixture, and the resulting mixture was briefly stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0TEAOH: 1.0Al ₂ O ₃ : 0.6SiO ₂ : 1.0P ₂ O _5: 50H ₂ O was cooked by heating for 120 hours under autogenous pressure in the final reaction mixture 200 ° C. in sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and furnace a. The granular powder present in the reaction mixture at the end of this digestion was recovered by filtration, washed thoroughly with water and dried in air at 100 ° C.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis shows the product as-synthesized and has an X-ray powder diffractogram characterized by the data in Table III below.
It was APO-34: Table III 2θ d (Å) Relative intensity 100 × I / I ₀ 9.5 9.3 100 12.8 6.9 12 14.1 6.28 12 16.0 5.549 39 18.0 4.92 17 23.1 3.852 31 25.3 3.526 17 25.8 3.448 13 29.6 3.023 3 30.5 2.927 22 31.3 2.860 15 43.3 2.085 3 49.0 1.858 4 A sample of the solid product was calcined in air at 500 ° C. for 2 hours. The X-ray powder diffractogram of the calcined sample was homogenously the same as the as-synthesized sample as listed in Table III above.

Example 27 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 19.2
The gram was combined to form a solution. A second solution was made by dissolving 73.5 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) in 23.2 grams of water and mixing the two solutions until homogeneous. Alumina / silica extrudate 1 from Part A prepared in Example 14 above was added to the resulting mixed solution.
3.8 grams were added and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0TEAOH: 0.94Al ₂ O ₃ : 0.76SiO ₂ : 1.0P ₂ O _5: 50H ₂ O was cooked by heating for 96 hours under autogenous pressure in the final reaction mixture 200 ° C. in a sealed and a furnace lined stainless steel pressure vessel with polytetrafluoroethylene. At the end of this digestion, the granular powder present in the reaction mixture was recovered by filtration, washed thoroughly with water and dried in air.
It was dried at 100 ° C.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis showed that the product, as-synthesized, was SAPO-34 with essentially the same X-ray powder diffractogram as listed in Table III above.

Example 28 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 42.4
The gram was combined to form a solution. To the resulting solution, 73.5 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) was added and the resulting solution was stirred until homogeneous. To the resulting mixture was added 13.8 grams of the alumina / silica extrudate from Part B made in Example 14 above,
The mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0TEAOH: 0.94Al ₂ O ₃ : 0.70SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O The final reaction mixture was sealed in a polytetrafluoroethylene lined stainless steel pressure vessel and cooked in a furnace at 150 ° C. under autogenous pressure for 120 hours. At the end of this digestion, the granular powder present in the reaction mixture was recovered by filtration, washed thoroughly with water and dried in air.
It was dried at 100 ° C.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis showed that the product was SAPO-34 with essentially the same X-ray powder diffractogram as listed in Table III above.

Example 29 Example 28 was repeated except that the alumina / silica extrudate used was from Part C made in Example 4 above. A solid product was made which was found to be SAPO-34 upon X-ray analysis having essentially the same X-ray powder diffractogram as listed in Table III above.

Example 30 85 wt% orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 42.4
The gram was combined to form a solution. To the resulting solution, 73.5 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) was added and the resulting solution was stirred until homogeneous. To the resulting solution was added 13.8 grams of the alumina / silica extrudate from Part A made in Example 5 above and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0TEAOH: 0.94Al ₂ O ₃ : 0.70SiO ₂ : 1.0P ₂ O _5: 50H ₂ O was cooked by heating for 120 hours under autogenous pressure in the final reaction mixture 200 ° C. in sealed in a stainless steel pressure vessel lined with polytetrafluoroethylene and furnace a. At the end of this digestion, the granular powder present in the reaction mixture was recovered by filtration, washed thoroughly with water and dried in air.
It was dried at 100 ° C.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis showed that the product was SAPO-34 with essentially the same X-ray powder diffractogram as listed in Table III above.

A sample of the product was calcined in air at 600 ° C. for 3 hours and an adsorption study using a standard McBain-Baker gravimetric adsorption apparatus was used. Samples were heated and activated in vacuum at 420 ° C. for 16 hours before being used for adsorption tests. The following data were generated in the adsorption study: From the above data, the pore size of the calcined product is n-
Greater than about 4.3Å was sought, as indicated by the adsorption of hexane (kinetic diameter 4.3Å).

The n-butane decomposition activity of the activated calcined product was determined to be 1.83 grams except that the weight of the sample charged to the reactor was 1.83 grams.
Tested as in Example 23 above. The data obtained showed a pseudo first-order rate constant (k _A ) of 7.58.

Example 31 Example 30 was repeated except that the alumina / silica extrudate used was from Part B made in Example 5 above. A solid product was made which was found to be SAPO-34 upon X-ray analysis having essentially the same X-ray powder diffractogram as listed in Table III above.

Example 32 Example 30 was repeated except that the alumina / silica extrudate used was from Part C made in Example 5 above. A solid product was made which was found to be SAPO-34 upon X-ray analysis having essentially the same X-ray powder diffractogram as listed in Table III above.

Example 33 Example 30 was repeated except that the alumina / silica extrudate used was from Part A made in Example 6 above. A solid product was made which was found to be SAPO-34 upon X-ray analysis having essentially the same X-ray powder diffractogram as listed in Table III above.

A sample of the product was calcined in air at 600 ° C. for 3 hours and used for adsorption studies using a standard McBain-Baker gravimetric adsorption device. The samples were activated by heating in vacuum at 425 ° C for 16 hours before being used for adsorption tests. The adsorption study yielded the following data: From the above data, the pore size of the calcined product is n-
Greater than about 4.3Å was sought, as indicated by the adsorption of hexane (kinetic diameter 4.3Å).

The n-butane decomposing activity of the activated calcined product was the same except that the weight of the sample charged to the reactor was 1.41 grams.
Tested as in Example 23 above. The data obtained showed a pseudo first-order rate constant (k _A ) of 4.62.

Example 34 Example 30 was repeated except that the alumina / silica extrudate used was from Part B made in Example 6 above. A solid product was made which was found to be SAPO-34 upon X-ray analysis having essentially the same X-ray powder diffractogram as listed in Table III above.

A sample of the product was analyzed to obtain the following chemical analysis: Component wt% Carbon 10.7 Nitrogen 1.5 Al ₂ O ₃ 30.1 SiO ₂ 12.8 P ₂ O ₅ 36.0 The above chemical analysis is on a calcined basis (ie water. And on the basis of no template agent), corresponding to a product composition with the following molar oxide ratios: 1.0Al ₂ O ₃ : 0.72SiO ₂ : 0.86P ₂ O ₅ Example 36 85 wt% orthophosphoric acid (H ₃ PO ₄ ) 23.1 grams and water 45.0
The gram was combined to form a solution and stirred. To the resulting solution was added 12.0 grams of silica sol containing 30% by weight SiO ₂ and 70% by weight H ₂ O and the resulting mixture was briefly stirred. To the resulting mixture was added 55.1 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) and the resulting mixture was briefly stirred. Next, 7.2 grams of tripropylamine (Pr ₃ N) was added to the resulting mixture and the resulting mixture was stirred until homogeneous. Finally, to the resulting mixture was added 10.1 grams of the alumina extrudate made in Example 7 above and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.5TEAOH: 0.5Pr ₃ N: 1.0Al ₂ O ₃ : 0 .. 6SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O This final reaction mixture was digested, washed and dried as in Example 28 above. A solid product was made which, upon X-ray analysis, was found to be SAPO-34 having essentially the same X-ray powder diffractogram as listed in Table III above.

A sample of the product was analyzed to obtain the following chemical analysis: Component wt% Carbon 9.3 Nitrogen 1.3 Al ₂ O ₃ 31.4 SiO ₂ 16.5 P ₂ O ₅ 32.7 The above chemical analysis was performed on a calcined basis (water and template). Corresponding to a product composition having the following oxide molar ratios (on the basis of no agent): 1.00Al ₂ O ₃ : 0.90SiO ₂ : 0.75P ₂ O ₅ Example 37 85 wt% orthophosphoric acid (H ₃ PO ₄ ) 23.1 grams and water 56.0
The gram was combined to form a solution and stirred. To the resulting solution was added 12.0 grams of silica sol containing 30 wt% SiO ₂ and 70 wt% H ₂ O and the resulting mixture was briefly stirred. Diethanolamine (DE
A) 21.02 grams were added and the resulting mixture was briefly stirred. Next, dipropylamine (Pr ₂ N
H) 10.2 grams was added and stirred until the resulting mixture was homogeneous. Finally, 10.2 grams of the alumina extrudate from Part A made in Example 3 above was added to the resulting mixture and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows:

1.0DEA: 2.0Pr ₂ NH: 1.0Al ₂ O ₃ : 0.6SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O This final reaction mixture was digested, washed and dried as in Example 28 above. A solid product was made which was found to be SAPO-34 upon X-ray analysis having essentially the same X-ray powder diffractogram as listed in Table III above. X-ray analysis showed a SAPO-34 content of over 91% with unreacted alumina as the main impurity.

By comparing both the crystallinity of the sample, the oxygen adsorption and the X-ray diffraction of the sample with that of a highly crystalline sample of SAPO-34 made by the hydrothermal crystallization process described in the above-mentioned US Pat. No. 4,440,871. 100% crystallinity of the sample tested and made by hydrothermal crystallization process
And Oxygen adsorption tests were performed on samples calcined and activated as in Example 23 above, using a standard Mike Bain-Baker gravimetric adsorber. X-ray diffraction comparisons were performed using as-synthesized samples equilibrated to humidity and comparing the sum of the areas under the five most intense peaks in the X-ray powder diffractogram.

Oxygen adsorption data shows 102% crystallinity of the reference material, X
The line diffraction data showed a crystallinity of 91% of the reference material.

The n-butane decomposition activity of the activated calcined product was determined as in Example 23 above.
Tested in the same way. The data obtained showed a pseudo first-order rate constant (k _A ) of 3.92.

Example 38 85 wt% orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 56.0
The gram was combined to form a solution and stirred. To the resulting solution was added 12.0 grams of silica sol containing 30 wt% SiO ₂ and 70 wt% H ₂ O and the resulting mixture was briefly stirred. Diethanolamine (DE
A) 10.5 grams was added and the resulting mixture was briefly stirred. Next, dipropylamine (Pr ₂ N
H) 20.4 grams was added and stirred until the resulting mixture was homogeneous. Finally, 10.2 grams of the alumina extrudate from Part A made in Example 3 above was added to the resulting mixture and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.0DEA: 2.0Pr ₂ NH: 1.0Al ₂ O ₃ : 0.6SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O This final mixture was cooked, washed and dried as in Example 28 above. A solid product was made which was found to be SAPO-34 upon X-ray analysis having essentially the same X-ray powder diffractogram as listed in Table III above. X-ray analysis showed a SAPO-34 content of over 97% with unreacted alumina as the main impurity.

Compare the crystallinity of the sample to that of a highly crystalline sample of SAPO-34 made by the hydrothermal crystallization process described in US Pat. No. 4,440,871 which described both oxygen adsorption and X-ray diffraction of the sample. The crystallinity of samples made by the hydrothermal crystallization process tested by 100
%. The comparison was done as described in Example 37 above.

Oxygen adsorption data show 106% crystallinity of the reference material, X
The line diffraction data showed a crystallinity of 98% of the reference material.

The n-butane decomposition activity of the activated calcined product was determined as in Example 23 above.
Tested in the same way. The data obtained showed a pseudo first-order rate constant (k _A ) of 1.71.

A sample of the product was analyzed to obtain the following chemical analysis: Component wt% Carbon 9.6 Nitrogen 2.3 Al ₂ O ₃ 31.1 SiO ₂ 10.6 P ₂ O ₅ 37.7 The above chemical analysis is based on calcined standards (water and template). Corresponding to a product composition having the following oxide molar ratios (on the basis of no agent): 1.00Al ₂ O ₃ : 0.58SiO ₂ : 0.87P ₂ O ₅ Example 39 85 wt% orthophosphoric acid (H ₃ PO ₄ ) 23.1 grams and water 64.4
The gram was combined to form a solution and stirred briefly.
To the resulting solution was added 20.4 grams of dipropylamine (Pr ₂ NH) and the resulting mixture was stirred vigorously until the dipropylamine dissolved. Finally, to the resulting solution was added 13.8 grams of the alumina / silica extrudate made in Example 8 above,
The mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0Pr ₂ NH: 0.94Al ₂ O ₃ : 0.70SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O The final reaction mixture was digested, washed and dried as in Example 28 above. X-ray powder diffraction analysis was performed on a sample of the dried crystalline reaction product. This analysis showed that the product, as-synthesized, is SAPO-34 with an X-ray powder diffractogram characterized by the data in Table IV below: Example 40 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 42.4
The gram was combined to form a solution and stirred. To the resulting solution was added 73.5 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) and the resulting mixture was stirred. Finally, in the resulting solution, Part A prepared in Example 9 above
23.4 grams of meta-kaolin extrudate from was added and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0TEAOH: 1.0Al ₂ O ₃ : 0.6SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O This final reaction mixture was digested, crystallized, washed and dried as in Example 28 above, except that the digestion was carried out at 200 ° C for 96 hours. X-ray powder diffraction analysis was performed on a sample of the dried crystalline reaction product. This analysis shows that the product is SA
It was shown to be PO-34.

Example 41 85 wt.% Orthophosphoric acid (H ₃ PO ₄₎ 32.8 grams of water 92.0
The gram was combined to form a solution. To the resulting solution was added 26.2 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) and the resulting mixture was stirred until homogeneous. To the resulting mixture was added 28.8 grams of di-n-propylamine (Pr ₂ NH) and the resulting mixture was stirred until homogeneous. Finally, the resulting mixture was spray-dried with the alumina / silica 2 prepared in Example 11 above.
0.3 grams was added and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 0.5TEAOH: 2.0Pr ₂ NH: 1.0Al ₂ O ₃ : 1.2SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O The final reaction mixture was cooked by heating in a sealed stainless steel pressure vessel at 175 ° C. under autogenous pressure for 72 hours. The solid in the reaction mixture was collected by filtration, washed thoroughly with water and dried in air at 100 ° C. The product was submitted for X-ray powder diffraction analysis. This analysis shows that the main crystalline phase of the product is essentially the same as that listed in Table III above.
It was shown to be SAPO-34 with a line powder diffractogram.

A sample of the product was analyzed to obtain the following chemical analysis: Component wt% Carbon 10.2 Nitrogen 1.7 Al ₂ O ₃ 26.6 SiO ₂ 21.5 P ₂ O ₅ 34.5 The above chemical analysis is on a calcined basis (ie water. And on the basis of no templating agent), corresponding to a product with the following oxide molar ratio: 1.0Al ₂ O ₃ : 0.69SiO ₂ : 0.91P ₂ O ₅ A sample of the product is calcined in air at 600 ° C. for 3 hours. did. The n-butane degrading activity of the calcined product was the above example except that the weight of the sample charged to the reactor was 1.51 grams.
Tested as in 23. The data obtained showed a pseudo first-order rate constant (k _A ) of 4.88.

Examples 42-43 These examples show the synthesis of SAPO-41 by the method of the invention.

Example 42 85% by weight of orthophosphoric acid (H ₃ PO ₄ ) 23.1 g and water 56.0
The gram was combined to form a solution and stirred. To the resulting solution was added 12.0 grams of silica sol containing 30 wt% SiO ₂ and 70 wt% H ₂ O and the resulting mixture was briefly stirred. Dipropylamine (Pr ₂ NH) 2 was added to the resulting mixture.
0.4 grams was added and the resulting mixture was stirred until homogeneous. Finally, 10.2 grams of the alumina extrudate made in Example 7 above was added to the resulting mixture and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0Pr ₂ NH: 1.0Al ₂ O ₃ : 0.6SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O The final reaction mixture was digested, crystallized, washed and dried as in Example 28 above. X-ray powder diffraction analysis was performed on a sample of the dried crystalline reaction product. This analysis showed that the predominant crystalline phase of the product (which was not pure) was SAPO-41 with the as-synthesized X-ray powder diffractogram characterized by the data in Table V below.

A sample of the as-synthesized product was analyzed to obtain the following chemical analysis: Component wt% Carbon 5.0 Nitrogen 0.86 Al ₂ O ₃ 38.8 SiO ₂ 0.23 P ₂ O ₅ 50.4 The above chemical analysis was on a calcined basis. The product composition of the following oxide molar ratios (ie, on the basis of water and no template) is matched: 1.00 Al ₂ O ₃ : 0.01SiO ₂ : 0.93P ₂ O ₅ A sample of the product in air at 600 Calcination was carried out for 2 hours. The X-ray powder diffractogram of the calcined sample was essentially the same as that of the as-synthesized sample as listed in Table V above.

The calcined sample was used for adsorption studies using a standard McBain-Baker gravimetric adsorption device. Samples were activated by heating in vacuum at 350 ° C for 16 hours before being used for adsorption tests. The following data were generated in the adsorption study: The n-butane decomposition activity of the activated calcined product was the same except that the weight of the sample charged in the reactor was 2.00 grams.
Tested as in Example 23 above. The data obtained showed a pseudo first-order rate constant (k _A ) of 1.19.

Example 43 85 wt.% Orthophosphoric acid (H ₃ PO ₄₎ 23.1 grams of water 64.4
The gram was combined to form a solution and stirred. 2.6 grams of diethanolamine (DEA) was added to the resulting solution,
The resulting mixture was briefly stirred. To the resulting mixture was added 20.4 grams of dipropylamine (Pr ₂ NH) and the resulting mixture was stirred until homogeneous. Finally, to the resulting mixture was added 13.8 grams of the meta-kaolin containing alumina extrudate made in Example 9 above and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0DEA: 1.0Pr ₂ NH: 1.0Al ₂ O ₃ : 0.6SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O The final reaction mixture was cooked as in Example 28 above,
Crystallized, washed and dried. X-ray powder diffraction analysis was performed on a sample of the dried crystalline reaction product. This analysis showed that the predominant crystalline phase of the product (which was not pure) was SAPO-41, as-synthesized, with essentially the same X-ray powder diffractogram as listed in Table V above. .

Examples 44-45 These examples demonstrate the synthesis of SAPO-11 by the method of the invention.

Example 44 85 wt% orthophosphoric acid (H ₃ PO ₄ ) 23.1 grams and water 64.4
The gram was combined to form a solution and stirred. To the resulting solution was added 21.0 grams of diethanolamine (DEA) and the resulting mixture was briefly stirred. To the resulting mixture was added 2.6 grams of dipropylamine (Pr ₂ NH) and the resulting mixture was stirred until homogeneous. Finally, to the resulting mixture was added 13.8 grams of the meta-kaolin containing alumina extrudate made in Example 9 above and the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 0.25DEA: 2.0Pr ₂ NH: 1.32Al ₂ O ₃ : 0.05SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O The final reaction mixture was digested, crystallized, washed and dried as in Example 28 above. X-ray powder diffraction analysis was performed on a sample of the dried crystalline reaction product. This analysis showed that the main crystalline phase of the product (which was not pure) was SAPO-11 with an as-synthesized X-ray powder diffractogram characterized by the data in Table VI below.

A sample of the product was calcined in air at 600 ° C for 3 hours. The X-ray powder diffractogram of the calcined sample was essentially the same as that of the as-synthesized sample listed in Table VI above.

The calcined samples were used for adsorption studies using a standard McBain-Baker gravimetric adsorption device. Samples were heated and activated in vacuum at 390 ° C. for 16 hours before being used for adsorption tests. The following data were generated in the adsorption study: From the above data, the pore size of the calcined product was determined to be greater than about 6.0Å, as indicated by adsorbing cyclohexane (kinetic diameter 6.0Å).

Example 45 Example 44 was repeated except that the amount of dipropylamine used was increased to 5.2 grams. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 2.0DEA: 0.5Pr ₂ NH: 1.32Al ₂ O ₃ : 0.05SiO ₂ : 1.0P ₂ O ₅ : 50H ₂ O The final reaction mixture was digested, washed and dried as in Example 28 above. X-ray powder diffraction analysis was performed on a sample of the dried crystalline reaction product. This analysis showed that the predominant crystalline phase of the product (which was not pure) was SAPO-11, as-synthesized, with essentially the same X-ray powder diffractogram as listed in Table VI above. .

The as-synthesized product was analyzed to obtain the following chemical analysis: Component wt% Carbon 5.4 Nitrogen 1.55 Al ₂ O ₃ 37.3 SiO ₂ 0.9 P ₂ O ₅ 50.0 The above chemical analysis is on a calcined basis (ie , Water and no template agent), corresponding to a product composition with the following oxide molar ratios: 1.00Al ₂ O ₃ : 0.04SiO ₂ : 0.96P ₂ O ₅ Example 46 This example is according to the method of the present invention. 3 shows the synthesis of CoAPSO-34.

41.5 g of 85 wt% orthophosphoric acid (H ₃ PO ₄ ) and water 49.14
The gram was combined to form a solution. To the resulting solution was added 21.6 grams of the alumina extrudate from Part A made in Example 3 above and the mixture was stirred. In the resulting mixture, SiO ₂
24.0 grams of silica sol containing 30% by weight and 70% by weight H ₂ O were added and the resulting mixture was briefly stirred. next,
Cobalt (II) acetate tetrahydrate [(Co
(CH ₃ CO ₂₎ and the ₂ · 4H ₂ O] 9.96 grams stirred briefly mixture produced by adding a solution prepared by dissolving in water 20.0 g. Finally, a solution of 73.5 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) in 27.4 grams of water was added to the resulting mixture, and the resulting mixture was briefly stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.0TEAOH: 0.9Al ₂ O ₃ : 0.6SiO ₂ : 0.2CoO: 0.9 P ₂ O ₅ : 50H ₂ O The final reaction mixture was sealed in a polypropylene jar and cooked in an oven at 100 ° C. under autogenous pressure for 120 hours. The solids present in the reaction mixture at the end of this digestion were collected by filtration, washed thoroughly with water and dried in air at 100 ° C.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis shows the product as-synthesized and has an X-ray powder diffractogram characterized by the data in Table VII below.
It was shown to be APSO-34.

Table VII 2θ d (Å) Relative strength 100 × I / I ₀ 9.5 9.28 100 12.9 6.89 16 14.1 6.28 13 16.0 5.53 43 18.0 4.93 15 20.6 4.31 71 25.2 3.53 20 25.4 3.51 8 25.9 3.44 13 30.6 2.93 26 31.2 2.86 19 Composite Another sample of the raw product was analyzed to obtain the following chemical analysis: Component wt% Carbon 5.0 Nitrogen 0.61 CoO 2.3 Al ₂ O ₃ 45.1 SiO ₂ 3.0 P ₂ O ₅ 27.4 The above chemical analysis was calcined. On a basis (ie, without water and templating agent), the product composition is matched with the following molar oxide ratio: 1.00Al ₂ O ₃ : 0.07CoO: 0.11SiO ₂ : 0.44P ₂ O ₅ Example 47− 51 These examples refer to application No. 84 mentioned above by the method of the invention.
Various GeAPOs described in 1,753 and 599,971
And Ge APSO molecular sieve synthesis such as Ge
Presented with the preparation of precursors useful in the synthesis of APO and GeAPSO molecular sieves.

Example 47 (Preparation of Al ₂ O ₃ / GeO ₂ Precursor) 100 grams of 99.9% pure germanium tetrachloride (GeCl ₄ ) and aluminum chlorohydrol (Al ₂ Cl (OH) ₅ .2H ₂ O) 676
Mixed with gram. The composition of this mixture was expressed in terms of the molar ratio of the oxide components as follows: 0.3GeO ₂ : 1.0Al ₂ O ₃ until the volume of the mixture formed was obtained using a rotary evaporator until a thick gel was obtained. Decrease, dilute the gel with water and slowly add concentrated ammonium hydroxide until the pH reaches approximately 8.0 to precipitate a solid mixture of oxides.

To remove all traces of the liquid phase, the oxide mixture was washed twice by centrifugation, passed and washed with dilute ammonium hydroxide solution at pH around 8 to eliminate chloride ions. The solid oxide mixture thus produced was dried at room temperature for several hours and finally at 100 ° C.

A sample of this solid oxide mixture was analyzed to obtain the following chemical analysis: Ingredient wt% Al ₂ O ₃ 51.3 GeO ₂ 15.4 Cl 3.3 LOI ^* 32.0 ^* LOI indicates loss on ignition.

The above chemical analysis, on a chloride free basis, is in agreement with the product composition at the following oxide molar ratios: 0.29GeO ₂ : 1.0Al ₂ O ₃ : 3.5H ₂ O of the solid oxide mixture thus prepared. Part of it was allowed to stand at 350 ° C for 3 hours. A sample of this calcined solid oxide mixture was analyzed to obtain the following chemical analysis: Component wt% Al ₂ O ₃ 60.0 GeO ₂ 17.9 Cl 2.8 LOI ^* 20.5 ^* LOI indicates loss on ignition.

The above chemical analysis, on a chloride free basis, is consistent with the product composition at the following oxide molar ratios: 0.29GeO ₂ : 1.0Al ₂ O ₃ : 1.9H ₂ O Example 48 (Al ₂ O ₃ / SiO ₂ Preparation of / GeO ₂ precursor) Germanium ethoxide (Ge (OC ₂ H ₅ ) ₄ ) 12.6 g was mixed with tetraethyl orthosilicate 10.4 g, and then aluminum tri-sec-butoxide (Al (OC
₄ H _{9) 3)} was mixed 98.5 grams. Water in the resulting mixture 14.
4 grams were added and the resulting mixture was blended using a mechanical mixer. An additional 40.0 grams of water was added to ensure complete hydrolysis of the alkoxide and the resulting mixture was dried at 100 ° C for several hours. Water on dry solids 20.
0 gram was added and the resulting slurry was dried at 100 ° C. overnight.

A sample of the resulting solid oxide mixture was analyzed to obtain the following chemical analysis: Component wt% Al ₂ O ₃ 41.2 GeO ₂ 10.2 Cl 8.8 LOI ^* 38.2 ^* LOI indicates loss on ignition.

The above chemical analysis corresponds to the following product composition in oxide molar ratio: 0.24GeO ₂ : 1.00Al ₂ O ₃ : 0.36SiO ₂ : 5.25H ₂ O Example 49 (Preparation of GeAPO-5) 85% by weight 23.1 g of orthophosphoric acid (H ₃ PO ₄ ) and water 33.7
The gram was combined to form a solution. To this solution was added 16.1 grams of the alumina extrudate made in Example 47 above and the mixture was stirred. To the resulting mixture was added 36.8 grams of 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) and the resulting mixture was stirred until homogeneous. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.0TEAOH: 0.3GeO ₂ : 1.0Al ₂ O ₃ : 1.0P ₂ O ₅ : 30.0H ₂ O The final reaction mixture was digested by sealing in a polytetrafluoroethylene lined stainless steel pressure vessel and heating in a furnace at 200 ° C. under autogenous pressure for 72 hours. The solids in the reaction mixture were collected by centrifugation, washed thoroughly with water, air at room temperature, then 100%.
Dry overnight at ° C.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis has an X-ray powder diffractogram characterized by the data of Table VIII below, with the product as-synthesized.
It was GeAPO-5: Table VIII 2θ d (Å) Relative strength 100 × I / I ₀ 7.5 11.81 100 13.0 6.82 8 15.0 5.91 19 19.9 4.47 38 21.1 4.21 30 22.5 3.95 50 26.1 3.50 15 29.2 3.06 8 30.2 2.96 10 34.8 2.58 8 37.9 2.38 6 Scanning electron microscopy of the solid product showed a large number of crystals with morphology consistent with that expected for GeAPO-5. EDAX (Electron Dispersion Analysis by X-ray) microprobe analysis of one of the clean crystals showed the following approximate weight composition (normalized to P ₂ O ₅ + Al ₂ O ₃ + GeO ₂ = 100): A sample of P ₂ O ₅ 49 Al ₂ O ₃ 48 GeO ₂ 3 product was analyzed to obtain the following chemical analysis: Ingredient wt% Carbon 6.3 Nitrogen 0.92 GeO ₂ 2.7 Al ₂ O ₃ 35.9 P ₂ O ₅ 50.3 Above Chemical analysis of is consistent with the following product composition in molar oxide ratio: 0.19TEAOH: 1.0Al ₂ O ₃ : 0.07GeO ₂ : 1.01P ₂ O ₅ A sample of the product was calcined in air at 600 ° C. for 3 hours. did. The calcined sample was used for adsorption studies using a standard McBain-Baker gravimetric adsorption device. Samples were activated by heating in vacuum at 350 ° C. for 16 hours before being used for adsorption tests. The following data were generated in the adsorption study: From the above data, the pore size of the calcined product was determined to be greater than about 6.2Å as shown by adsorbing neopentane (dynamic diameter 6.2Å).

Example 50 (GeAPO-17 Preparation of) 85% by weight of Oritorin acid (H ₃ PO ₄₎ 23.1 grams of water 42.5
The gram was combined to form a solution. To this solution was added 16.1 grams of the alumina extrudate made in Example 47 above and the mixture was stirred. To the resulting mixture was slowly added 9.9 grams of cyclohexylamine (CHA) and the resulting mixture was blended until homogeneous. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 1.23CHA: 0.29GeO ₂ : 1.00Al ₂ O ₃ : 1.24P ₂ O ₅ : 30.0H ₂ O The final reaction mixture was digested by sealing in a polytetrafluoroethylene lined stainless steel pressure vessel and heating in a furnace at 200 ° C. under autogenous pressure for 72 hours. The solids in the reaction mixture were collected by centrifugation and dried in air at room temperature and then 100 ° C. overnight.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis showed that the main crystalline phase of the product was as-synthesized, GeAPO-17 with an X-ray powder diffractogram characterized by the data in Table IX below: Table IX 2θ d (Å) Relative intensity 100 × I / I ₀ 7.7 11.42 100 9.8 9.10 40 13.4 6.608 55 14.6 6.050 15 15.5 5.727 30 20.5 4.332 65 23.3 3.822 15 23.8 3.733 15 26.9 3.312 20 31.2 2.866 20 31.8 2.814 20 49.7 1.835 15 Scanning electron for solid product Microscopy showed a large number of crystals with morphology consistent with that expected for GeAPO-17. EDAX microprobe analysis of one of the clean crystals showed the following approximate weight composition (normalized to P ₂ O ₅ + Al ₂ O ₃ + GeO ₂ = 100): P ₂ O ₅ 48 Al ₂ O A sample of ₃ 48 GeO ₂ 4 product was analyzed to obtain the following chemical analysis: Component wt% Carbon 9.3 Nitrogen 1.7 GeO ₂ 6.1 Al ₂ O ₃ 31.9 P ₂ O ₅ 43.7 The above chemical analysis was based on molar oxide. The ratio corresponds to the following product composition: 0.41CHA: 1.00Al ₂ O ₃ : 0.19GeO ₂ : 0.98P ₂ O ₅ A sample of the product was calcined in air at 600 ° C. for 3 hours. The calcined sample was used for adsorption studies using a standard McBain-Baker gravimetric adsorption device. Samples were activated by heating in vacuum at 350 ° C. for 16 hours before being used for adsorption tests. The following data were generated in the adsorption study: Forming a solution example 51 (GeAPSO-34 Preparation) 85 wt% of orthophosphoric acid (H ₃ PO ₄₎ 9.3 grams of water 15.2 g and 40 wt% aqueous tetraethylammonium hydroxide (TEAOH) and 7.4 grams together did.
To this solution was added 6.5 grams of the alumina extrudate made in Example 47 above and the mixture was stirred. To the resulting mixture was added 8.2 grams of dipropylamine (DPA) and the resulting mixture was stirred until homogeneous. Finally, the generated tetraethylorthosilicate mixture _{(Si (OC 2 H 5)} 4) was added 2.5 grams of the mixture was stirred. The composition of the final reaction mixture thus prepared, expressed by the molar oxide ratio of the components of the reaction mixture, was as follows: 0.63TEAOH: 2.48DPA: 0.29GeO ₂ : 1.00Al ₂ O ₃ : 1.23 P ₂ O ₅ : 0.37
SiO ₂ : 43H ₂ O: 1.5C ₂ H ₅ OH The final reaction mixture was sealed in a polytetrafluoroethylene lined stainless steel pressure vessel and heated in a furnace at 200 ° C. under autogenous pressure for 72 hours. Cooked The solids in the reaction mixture were collected by centrifugation, washed with water, dried at room temperature and then 100 ° C. overnight.

X-ray powder diffraction analysis was performed on a sample of the dried solid reaction product. This analysis showed that the main crystalline phase of the product was as-synthesized and was GeASO-34 with an X-ray powder diffractogram characterized by the data in Table X below: Table X 2θ d (Å) Relative intensity 100 × I / I ₀ 9.5 9.28 100 12.9 6.89 15 14.1 6.28 15 16.0 5.53 46 18.0 4.92 26 20.6 4.31 83 25.3 3.58 28 25.9 3.45 16 30.6 2.93 30 31.3 2.86 21 Non-zeolitic molecular sieve The term "non-zeolitic molecular sieve" or "NZMS" is used herein to refer to the "SAPO", "ELAPSO", "AlP" described in the patents and applications mentioned above for non-zeolitic molecular sieves.
O ₄ "," MeAPO "(" Me "is at least one of Mg, Mn, Co and Zn)," FeAPO "," TAPO "and" E
Used to mean "LAPO" molecular sieve.

In the following discussion of NZMS, the NZMS mole fraction is defined as the compositional value plotted in the phase diagram in each patent, published application or co-pending application that has a source for the non-zeolitic molecular sieve.

Silicoaluminophosphate Molecular Sieves Today, the preferred NZMS are the silicoaluminophosphate molecular sieves described in U.S. Pat. No. 4,440,871 and U.S. Patent Application No. 575,745, filed January 31, 1984. The use of such molecular sieves in reforming catalysts or as components in conventionally used reforming / dehydrocyclization catalysts results in improved catalysts and improved selectivity to iso-products. And give improved activity in the reforming / dehydrocyclization reaction.

The silicoaluminophosphate molecular sieves of U.S. Pat. No. 4,440,871 and above-mentioned Application No. 575,745 have pores that are uniform and have a nominal diameter of greater than about 3 angstroms, and must be as-synthesized and anhydrous. The experimental chemical composition is as follows: mR: (Si _x Al _y P _z ) O ₂ [where “R” is at least 1 present in the intracrystalline pore system]
Indicates an organic templating agent; "m" is (Si _x Al _y P _z ) O ₂
Represents the moles of "R" present per mole of, and 0.
Has a value of 02 to 0.3; "x", "y" and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides, which mole fractions are described in the above U.S. Pat. No. 4,440,871. Points A, B of the three-component diagram of FIG.
C, D and E within the pentagonal composition region, preferably within the pentagonal composition region defined by points a, b, c, d and e of FIG. 6 of this patent]. It is disclosed as a porous crystalline silicoaluminophosphate. The SAPO molecular sieves of U.S. Pat. No. 4,440,871 and above-mentioned Application No. 575,745 also contain PO ₂
⁺ , AlO ₂ ^- and SiO ₂ tetrahedral units have a three-dimensional microporous crystal framework structure, and their essential experimental chemical composition is represented by the formula: mR: (Si _x Al _y P _z ) O ₂ [ Where "R" is at least 1 present in the intracrystalline pore system
Indicates an organic templating agent; "m" is (Si _x Al _y P _z ) O ₂
Represents the moles of "R" present per mole of
It has a value of 0.3; "x", "y" and "z" respectively represent the mole fractions of silicon, aluminum and phosphorus present in the oxide component, which mole fractions are shown in FIG. Is within the composition region bounded by points A, B, C, D and E in the three-component diagram of], which is described as silicoaluminophosphate,
The silicoaluminophosphate is at least US Pat.
440,871 Tables I, III, V, VII, IX, XIII, XVII, XXI,
1. Have a characteristic X-ray powder diffractogram containing the d-spacings listed below in either one of XXIII or XXV. Further, the as-synthesized crystalline silicoaluminophosphates of U.S. Pat.No. 4,440,871 can be calcined at temperatures high enough to remove at least some of the organic templating agent present in the intracrystalline pore system as a result of the synthesis. .
The silicoaluminophosphate of U.S. Pat. No. 4,440,871 is generally referred to in that patent as "SAPO", or a group, or "SAPO".
-n ", where" n "is manufactured by US Patent 4,
An integer that represents a particular SAPO as reported in 440,871. The method of making SAPO is disclosed in US Pat. No. 4,440,871, which is incorporated herein by reference.

Medium Pore (MP) -SAPO is SAPO-11, SAPO-31, SAPO-40 and SAPO
Including -41.

ELAPSO Molecular Sieve "ELAPSO" molecular sieve is co-pending US Application No. 600,312 filed April 13, 1984, EPC Publication No. 0,159,624, published October 30, 1985, incorporated herein by reference) Has a three-dimensional microporous framework structure of ELO ₂ , AlO ₂ , PO ₂ , and SiO ₂ oxide units and has the formula on an anhydrous basis; mR: (EL _w Al _x P _y Si _z ) O ₂ [formula Where “R” is at least 1 present in the intracrystalline pore system
Indicates an organic templating agent; "m" is (EL _w Al _x P _y S
i _z ) O ₂ indicates the molar amount of “R” present per mole of O ₂ and has a value of 0 to about 0.3; “EL” is at least one element capable of forming a three-dimensional oxide framework. Shown, `` EL '' is about 1.
The average "T- in the tetrahedral oxide structure of 51 to about 2.06Å
Characterized as an element with an "O" spacing, an "EL" of about 12
It has a cation electronegativity of 5 to about 310 Kcal / g-atoms, and "EL" is larger than about 59 Kcal / g-atoms at 298 ° K.
-O "Stable M-O-P, M-O-Al or M-O in crystalline three-dimensional oxide structure with bond dissociation energy
-M bond can be formed; "w", "x",
"Y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as framework oxides, which mole fractions are within the limiting composition values or points below. enter: Here, “p” is the element “E in the (EL _w Al _x P _y Si _z ) O ₂ component.
L is an integer corresponding to the number of L]], and is described as a crystalline molecular sieve having an experimental chemical composition.

The "ELAPSO" molecular sieve is also made up of ELO ₂ , AlO ₂ and Si.
It has a three-dimensional microporous framework structure of O ₂ and PO ₂ tetrahedral oxide units and has a formula on an anhydrous basis; mR: (EL _w Al _x P _y Si _z ) O ₂ [wherein “R” is a crystal At least 1 present in the inner pore system
Indicates an organic templating agent; "m" is (EL _w Al _x P _y S
i _z ) O ₂ indicates the molar amount of “R” present per mole of O ₂ and has a value of 0 to about 0.3; “EL” is at least one element capable of forming a framework tetrahedral oxide. Shown is selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc; "w", "x",
"Y" and "z" represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, which mole fractions are within the limiting composition values or points as follows: : (Where "p" is as defined above)].

A number of co-pending and commonly assigned applications and several issued patents describing ELAPSO non-zeolitic molecular sieves have already been listed above, and are not repeated here but for each individual ELAPSO The group will now be described in more detail.

TiAPSO Molecular Sieves US Pat. No. 600,179 (now US Pat. No. 4,684,617) filed April 13, 1984 and TiAPSO molecular sieves of US patent application 49,274 filed May 13, 1987 have the following formula: mR: (Ti _w Al _x P _y Si _z ) O ₂ [where “R” is at least 1 present in the intracrystalline pore system.
Represents an organic templating agent of a species; "m" represents the molar amount of R present per mole of (Ti _w Al _x P _y Si _z ) O ₂ and has a value from 0 to about 0.3;
"W", "x", "y" and "z" represent the respective mole fractions of titanium, aluminum, phosphorus and silicon present as tetrahedral oxides, and each is at least
Having a value of 0.01], TiO ₂ , Al having an experimental chemical composition of anhydrous standard represented by
It has a three-dimensional microporous framework structure of O ₂ , PO ₂ and SiO ₂ tetrahedral oxide units. The molar fractions "w", "x", "y" and "z" are usually defined as being within the range of limiting composition values or points as follows: In a subclass of TiAPSO molecular sieves, the values of the above formula, "w", "x", "y" and "z" are within the rectangular composition region defined by points a, b, c and d, And these points a, b, c and d are “w”,
The following values are represented for "x", "y" and "z".

In synthesizing the TiAPSO composition, the following formula: aR: (Ti _w Al _x P _y Si _z ) O ₂ : bH ₂ O [where “R” is an organic template agent; An amount of "R" having a value of 0 to about 6, preferably an effective amount in the range of greater than 0 to about 6; "b" is 0 to about 500, preferably about 2 About 300
Has a value of; w, "x", "y" and "z" represent the respective mole fractions of titanium, aluminum, phosphorus and silicon, and each has a value of at least 0.01] Preference is given to using the reaction mixture composition expressed as a ratio.

In one embodiment, the reaction mixture has a molar fraction "w",
"X", "y" and "z" are usually chosen to be defined as being within a range of limiting composition values or points as follows; Regarding the above-mentioned indication of reaction composition, the reactant is "w",
For the sum of “x”, “y” and “z”, (w + x +
It is standardized to be y + z) = 1.00 mol.

Manufacturing Reagents TiAPSO compositions are typically manufactured using multiple reactants. Representative reagents and US patents that can be used
Abbreviations used for the reagents in 600,179 are as follows: (a) Alipro: aluminum isopropoxide (b) LUDOX-LS: LUDOX-LS is 30 wt% SiO ₂ and 0.1 wt% Na ₂ O. It is a trade name of DuPont for aqueous solutions of.

(C) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution (d) Tiipro: titanium isopropoxide (e) TEAOH: 40 wt% tetraethylammonium hydroxide aqueous solution (f) Pr ₂ NH: di-n-propylamine , (C ₃ H ₇ ) ₂ NH (g) Pr ₃ NH: tri-n-propylamine, (C ₃ H ₇ ) ₃ N (h) Quin: quinuclidine (C ₇ H ₁₃ N) (i) MQuin: water Methyl quinuclidine oxide (C ₇ H ₁₃ NCH ₃ OH) (j) C-hex: cyclohexylamine MgAPSO molecular sieves USA 600,180 filed April 13, 1984 MgA
PSO molecular sieve ^{_{MgO 2 -2, AlO 2 -,}} PO 2 + and SiO ₂
It has a three-dimensional microporous skeleton structure of tetrahedral oxide units and is of anhydrous formula: mR: (Mg _w Al _x P _y Si _z ) O ₂ [wherein “R” is an intracrystalline pore system Exists in at least 1
Indicates an organic templating agent; "m" is (Mg _w Al _x P _y S
i _z ) O ₂ indicates the molar amount of “R” present per mole and has a value of 0 to about 0.3, where “w”, “x”, “y” and “z” are tetrahedral oxidations. The respective molar fractions of magnesium, aluminum, phosphorus and silicon present in the product, each preferably having a value of at least 0.01]. The mole fractions "w", "x", "y" and "z" are usually defined to be within the limiting composition values or points as follows: In a preferred subclass of MgAPSO molecular sieves,
The values "w", "x", "y" and "z" of the above formula are within the limiting composition values or points as follows: In synthesizing the MgAPSO composition, a molar ratio of the formula: aR: (Mg _w Al _x P _y Si _z ) O ₂ : bH ₂ O [wherein “R” is an organic template agent; The amount of agent "R" can have a value in the range of 0 to about 6, more preferably an effective amount of greater than 0 to about 6; "b" has a value of 0 to about 500. And preferably about 2 to about 300; "w", "x",
"Y" and "z" each represent a molar fraction of magnesium, aluminum, phosphorus and silicon and each has a value of at least 0.01].

In one embodiment, the reaction mixture has a molar fraction "w",
The "x", "y" and "z" are usually chosen to be defined as being within the limiting composition values or points as follows: In the above description of the reaction composition, the reactant is "w",
For the sum of "x", "y" and "z" (w + x + y +
z) = 1.00 mol is standardized.

Manufacturing Reagents MgAPSO compositions are manufactured using multiple reagents. MgAPSO ₃
Representative reagents that can be used to prepare the following include: (a) Alipro: aluminum isopropoxide; (b) CATAPAL: Condea's trademark for hydrated pseudoboehmite; (c ) LUDOX-LS: SiO ₂ 30 wt% and Na ₂ O 0.1 wt% aqueous solution of DuPont's trade name; (d) Mg (Ac) ₂ : magnesium acetate tetrahydrate, Mg (C ₂ H ₃ O ₂ ) ・ 4H ₂ O; (e) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution; (f) TBAOH: tetrabutylammonium hydroxide (40 wt% in water); (g) Pr ₂ NH: di- n- propylamine; (h) Pr ₃ N: tri -n- propylamine; (i) Quin: quinuclidine; (j) MQuin: methyl quinuclidine hydroxide (17.9% in water); (k) C-hex : Cyclohexylamine; (l) TEAOH: tetraethylammonium hydroxide (40% by weight in water); (m) DEEA: diethyl ether _{Noruamin; (n) i-Pr 2} NH: di - isopropylamine; (o) TEABr: tetraethylammonium bromide; (p) TPAOH: tetrapropylammonium hydroxide (40 wt% in water).

MnAPSO Molecular Sieve US Application No. 600,175 filed April 13, 1984 (currently US Pat. No. 4,686,092 issued April 11, 1987)
The MnAPSO molecular sieves _{^{No.) MnO 2 -2, AlO 2 -}} , PO 2
^It has a tetrahedral unit skeleton structure of ⁺ and SiO ₂ and has the formula: mR: (Mn _w Al _x P _y Si _z ) O ₂ [wherein “R” is present in the intracrystalline pore system] At least 1
Indicates an organic templating agent; "m" is (Mn _w Al _x P _y S
i _z ) O ₂ is the molar amount of “R” present per mole,
And has a value from 0 to about 0.3; "w", "x", "y" and "z" indicate the respective mole fractions of manganese, aluminum, phosphorus and silicon present as tetrahedral oxides. ] Has an experimental chemical composition represented by: The mole fractions "w", "x", "y" and "z" are usually defined to be within the limiting composition values or points as follows: The values for "w", "x", "y" and "z" can be as follows: Upon synthesizing MnAPSO compositions, wherein the molar ratio _{of: aR: (Mn w Al x} P y Si z) O 2: bH 2 O [ wherein "R" is an organic templating agent; "a" is an organic template An amount of agent "R" having a value from 0 to about 6 and more preferably an effective amount ranging from greater than 0 to about 6; "b" having a value from 0 to about 500; Preferably about 2 to about 300; "w", "x", "y" and "z" each represent the mole fraction of manganese, aluminum, phosphorus and silicon, and each has a value of at least 0.01. ] It is preferable to use a reaction mixture composition represented by

In one embodiment, the reaction mixture has a mole fraction "w",
"X", "y" and "z" are usually defined to be within the limiting composition values or points as follows: In the above description of the reaction composition, the reactant is "w",
For the sum of "x", "y" and "z" (w + x + y +
z) = 1.00 mol is standardized.

Manufacturing Reagents MnAPSO compositions can be manufactured using a number of reagents. Typical reagents which may be used to manufacture the MnAPSO ₃ include the following: (a) Alipro: aluminum isopropoxide; (b) CATAPAL: Trademark of Condea Corporation for hydrated pseudoboehmite; (c) LUDOX-LS: DuPont trade name for an aqueous solution of 30 wt% SiO ₂ and 0.1 wt% Na ₂ O; (d) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution; (e) MnAc: manganese acetate _{, Mn (C 2 H 3 O} 2) 2 · 4H 2 O; (f) TEAOH: an aqueous solution of 40 wt% of tetraethylammonium hydroxide; (g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide; (h ) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH; (i) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (j) Quin: quinuclidine _{, (C 7 H 13 N)} ; (k) MQuin: methyl quinuclidine hydroxide _{(C 7 H 13 NCH 3 OH} ); (l) C-hex: cyclohexylamine; ( ) TMAOH: tetramethylammonium hydroxide; (n) TPAOH: tetrapropylammonium hydroxide; (o) DEEA: 2- diethylaminoethanol.

CoAPSO Molecular Sieve CoA of US Application No. 600,174 filed April 13, 1984
PSO molecular sieves _{^{CoO 2 -, AlO 2 -,}} PO 2 + and SiO ₂
Which has a three-dimensional microporous framework structure of a tetrahedral unit of
The anhydride based on having the following empirical formula: mR: the _{(Co w Al x P y Si} z) O 2 [ wherein "R" is the intracrystalline pore system in our least one organic templating agent Existing in, "m" is 1 mol
Represents the molar amount of "R" present per (Co _w Al _x P _y Si _z ) O ₂ and has a value of 0 to about 0.3, where "w", "x", "y" and "z" are Represents the molar fractions of those present as tetrahedral oxides of cobalt, aluminum, phosphorus, silicon, respectively, with the molar fractions "w", "x", "y" and "z" each being at least 0.01, and usually Defined as within the limiting composition values or points as follows: In a preferred subclass of CoAPSO molecular sieves,
The values "w", "x", "y" and "z" in the above formula are within the limiting composition values or points as follows: Upon synthesizing a CoAPSO composition, wherein the molar ratio _{of: aR: (Co w Al x} P y Si z) O 2: bH in ₂ O [wherein "R" is an organic templating agent, "a" is an organic The amount of template agent "R" has a value of 0 to about 6 and is preferably an effective amount in the range of greater than 0 to about 6; "b" has a value of 0 to about 500. , Preferably about 2-300; "w", "x", "y" and "z".
Each represents a molar fraction of cobalt, aluminum, phosphorus and silicon and each has a value of at least 0.01]. In a preferred embodiment, the reaction mixture is defined such that the mole fractions "w", "x", "y" and "z" are usually within the limiting composition values or points as described below. Choose: In the above expression of the reaction composition, the reactants are "w", "x",
“Y” and “z” are standardized so that (w + x + y + z) = 1.00 mol.

Manufacturing Reagents CoAPSO compositions can be prepared using various reagents. Reagents that can be used to prepare CoAPSO include: (a) Alipro: aluminum isopropoxide; (b) CATAPAL: Trademark of Condea Corporation for pseudoboehmite; (c) LUDOX-LS: Dupont trademark of about 30 wt% of SiO ₂ and 0.1 wt% of Na ₂ O aqueous solution; (d) Co (Ac) 2 cobalt _{acetate, Co (C 2 H 3 O} 2) 2 · 4H 2 O; ( e) CoSO _4: cobalt _{sulfate, CoSO4 · 7H 2 O; (} f) H 3 PO 4: 85 aqueous solution wt% phosphoric acid; (g) TBAOH: tetrabutylammonium hydroxide (25 wt% in methanol); (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH; (i) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (j) Quin: quinuclidine, _{C 7 H 13 N; (k} ) MQuin: methyl hydroxide quinuclidine _{C 7 H 13 NCH 3 OH;} (l) C-hex: cyclohexylamine; (m) TEAOH: hydroxide Te Raethylammonium (40% by weight in water); (n) DEEA: Diethanolamine; (o) TPAOH: Tetrapropylammonium hydroxide (40% by weight in water) (p) TMAOH: Tetramethylammonium hydroxide (40% by weight in water) ZnAPSO Molecular sieve ZnA of US Application No. 600,170 filed April 13, 1984
The PSO molecular sieve has the formula: mR: (Zn _w Al _x P _y Si _z ) O ₂ [wherein “R” is at least 1 present in the intracrystalline pore system] on an anhydrous basis.
Represents an organic templating agent; "m" is (Zn _w Al _x P _y S
i _z ) O ₂ indicates the number of moles of “R” present per mole of O ₂ and has a value from 0 to about 0.3; “w”, “x”, “y” and “z” are each a tetrahedron. ZnO ₂ ^-2 , AlO ₂ having the experimental chemical composition represented by the molar fractions of zinc, aluminum, phosphorus and silicon present as oxides and each having a value of at least 0.01]
^- , Including a tetrahedral unit frame structure of PO ₂ ⁺ and SiO ₂ . The mole fractions "w", "x", "y" and "z" are usually defined as falling within the limiting composition values or points as follows: In a preferred subclass of ZnAPSO molecular sieves, the values "w", "x", "y" and "z" in the above formula fall within the limiting composition values or points as follows: In synthesizing the ZnAPSO composition, the molar ratio is as follows: aR: (Zn _w Al _x P _y Si _z ) O ₂ : bH ₂ O [wherein “R” is an organic template agent and “a” is an organic template agent]. The amount of template agent "R" has a value of 0 to about 6 and is preferably an effective amount in the range of greater than 0 to about 6; "b" has a value of 0 to about 500. And more preferably about 2 to about 300; "w", "x", "y",
And "z" respectively represent the mole fractions of zinc, aluminum, phosphorus and silicon and each has a value of at least 0.01]. In a preferred embodiment, the reaction mixture is defined such that the mole fractions "w", "x", "y" and "z" are usually within the limiting composition values or points as set forth below. Choose: In the above description of the reaction composition, the reactant is "w",
For the sum of "x", "y" and "z" (w + x + y
+ Z) = 1.00 mol is standardized.

Preparation Reagents ZnAPSO compositions are typically prepared using multiple reagents. Reagents that can be used to make ZnAPSO include: (a) Alipro: aluminum isopropoxide; (b) LUDOX-LS: LUDOX-LS is 30 wt% SiO ₂ and 0.1 wt% Na ₂ O. % Is the DuPont trade name for aqueous solutions; (c) CATAPAL: Condea trademark for hydrated pseudoboehmite; (d) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution; (e) ZnAc: zinc _{acetate, Zn (C 2 H 3 O} 2) 2 · 4H 2 O; (f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; (g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide ; (h) TMAOH: tetramethylammonium pentahydrate _{hydroxide, (CH 3) 4 NOH ·} 5H 2 O; (i) TPAOH: tetrapropylammonium _{hydroxide, (C 3 H 7) 4} NOH 40 wt% solution; (j) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH; (k) Pr 3 N: tri n- _{propylamine, (C 3 H 7) 3} N; (l) Quin: _{quinuclidine, (C 7 H 13 N)} ; (m) C-hex: cyclohexylamine; (n) DEEA: diethylethanolamine, (C ₂ H ₅ ) ₂ NC ₂ H ₅ OH.

FeAPSO molecular sieves, 1984 April 13, U.S. Application No. 600,173 filed on (now U.S. Pat. No. 4,683,217) FeAPSO molecular sieves of, FeO ₂ ^-2 (and / or ^{_{FeO 2 -), AlO 2 -}} , PO ₂ ⁺ and Si
It has a three-dimensional microporous crystal skeleton structure of tetrahedral oxide units of O ₂ and has a unit empirical formula on an anhydrous basis: mR: (Fe _w Al _x P _y Si _z ) O ₂ (1) [wherein "R" is at least 1 present in the intracrystalline pore system
Indicates an organic templating agent; "m" is (Fe _w Al _x P _y S
i _z ) indicates the molar amount of "R" present per mole of O ₂ and has a value of 0 to about 0.3; the maximum value of "m" in each case is related to the molecular size of the template agent and Depends on the available void volume of the pore system of the particular molecular sieve;
“W”, “x”, “y” and “z” represent the mole fractions of iron, aluminum, phosphorus and silicon, respectively, which are present as tetrahedral oxides, and the mole fractions are the limiting composition values below. Or try to fall within the dots: Having a molecular sieve having

"W", "x", "y" and "z" can be as follows: Preparation Reagents A number of reagents can be used to make the FeAPSO composition. Reagents that can be used to produce FeAPSO include the following: (a) Alipro: aluminum _{isopropoxide; Al (OCH (CH 3)} 2) 3 (b) LUDOX-LS: LUDOX-LS is SiO ₂ Trademark of DuPont for an aqueous solution of 30% by weight and 0.1% by weight Na ₂ O; (c) about 75% by weight of CATAPAL: Al ₂ O ₃ (pseudoboehmite phase) and about 25% by weight of water. (D) Fe (Ac) ₂ : iron (II) acetate; (e) FeSO ₄ : iron (II) sulfate hexahydrate; (f) H ₃ PO ₄ : 85 Wt% phosphoric acid aqueous solution; (g) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (h) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide; (i) Pr ₂ NH: di-n-propyl _{amine, (C 3 H 7) 2} NH; (j) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (k) Quin: _{quinuclidine, (C 7 H 13 N)} ; l) MQuin: Methyl quinuclidine _{hydroxide, (C 7 H 13 NCH 3} OH); (m) TMAOH: tetramethylammonium hydroxide pentahydrate: (n) C-hex: cyclohexylamine; 5 component molecular sieves The QuinAPSO 5 component molecular sieves of US patent applications Nos. 600,168 and 600,181 (both filed on April 13, 1984) are three-dimensional microporous frameworks of MO ₂ , AlO ₂ , PO ₂ and SiO ₂ tetrahedral units. has the structure and wherein an anhydrous _{basis: mR: (M w Al x} P y Si z) O 2 [ wherein "R" is at least 1 present the intracrystalline pore system
Represents an organic templating agent; "m" is (M _w Al _x P _y Si _z ).
Indicates the molar amount of "R" present per mole of O ₂ and is 0
Has a value of about 0.3; "M" is arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron,
Represents at least two elements selected from the group consisting of lithium, magnesium, manganese, titanium, vanadium and zinc; "w", "x", "y" and "z" are elements present as tetrahedral oxides, respectively. Shows the molar fractions of M, aluminum, phosphorus and silicon which are]. Preferably M represents a combination of cobalt and manganese. The mole fractions "w", "x", "y" and "z" are generally defined as being within the range of limiting composition values or points as follows: It is preferred that the mole fractions w, x, y and z fall within the limiting composition values or points as follows: In synthesizing the QuinAPSO composition, a molar ratio of the formula: aR: (M _w Al _x P _y Si _z ) O ₂ : bH ₂ O [wherein “R” is an organic template agent and “a” is an organic template agent]. The amount of template agent "R" has a value of 0 to about 6 and is preferably an effective amount in the range of greater than 0 to about 6; "b" has a value of 0 to about 500. , More preferably about 2 to about 300; "w", "x", "y",
And "z" each represent the mole fraction of each element of "M", aluminum, phosphorus and silicon, and each is at least
Having a value of 0.01] is preferred.

In a preferred embodiment, the reaction mixture is defined such that the mole fractions "w", "x", "y" and "z" are generally within the limiting composition values or points as set forth below. Choose to: In the above description of the reaction composition, the reactant is "w",
For the sum of "x", "y" and "z" (w + x + y +
z) = 1.00 mol is standardized. QuinAPSO
The composition was prepared using a number of reagents. Suitable sources of the various elements M are the same as those used in the preparation of various APO and APSO molecular sieves containing the same elements, as described in detail above and below.

Reagents that can be employed to prepare QuinAPSO include: (a) Alipro: aluminum isopropoxide (b) LUDOX-LS: LUDOX-LS is 30 wt% SiO ₂ and 0.1.
Trade name of DuPont for an aqueous solution of wt% Na ₂ O.

_{(C) H 3 PO 4:} 85 wt% phosphoric acid aqueous solution (d) MnAc: (For QuinAPSO containing manganese) manganese _{acetate, Mn (C 2 H 3 O} 2) 2 · 4H 2 O (e) CoAc: cobalt _{acetate, Co (C 2 H 3 O} 2) 2 · 4H 2 O ( for QuinAPSO containing cobalt) (f) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide (g) Pr ₂ NH: di -n - _{propylamine, (C 3 H 7) 2} NH; CoMnMgAPSO molecular sieves April 1984 filed on the 13th U.S. application No. 600,182 and 1
CoMnM of US Application No. 57,648 filed on June 9, 987
gAPSO six-component molecular sieves are CoC ₂ ^-2 , MnO ₂ ^-2 , MgO
_{It has} a three-dimensional microporous framework structure of tetrahedral oxide units of ₂ ^-2 , AlO ₂ , PO ₂ and SiO ₂ , and has the following formula on an anhydrous basis: mR: (Co _t Mn _u Mg _v Al _x P _y Si _z ) O ₂ [wherein “R” is at least 1 present in the intracrystalline pore system]
Represents an organic template agent; "m" is (Co _t Mn _u Mg _v Al
_x P _y Si _z ) O ₂ indicates the molar amount of “R” present per mole and has a value of 0 to about 0.3; “t”, “u”, “v”,
"X", "y" and "z" each represent the molar fraction of cobalt, manganese, magnesium, aluminum, phosphorus and silicon present as tetrahedral oxides and each has a value of at least 0.01] Has an experimental chemical composition. Molar fraction "t",
"U", "v", "x", "y" and "z" are usually defined to be within the limiting composition values or points as follows: In a preferred subclass of CoMnMgAPSO molecular sieves, the values of "w", "x", "y" and "z" in the above formula are within the limiting composition values or points as follows: In synthesizing the CoMnMgAPSO composition, it is preferable to use a reaction mixture composition represented by the following formula in terms of molar ratio: aR: (Co _t Mn _u Mg _v Al _x P _y Si _z ) O ₂ : bH ₂ O [formula Wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R", having a value of 0 to about 6 and preferably greater than 0 and up to about 6, more preferably 0. An effective amount in the range of greater than to about 2;
"B" has a value of 0 to about 500, preferably about 2 to about 300.
And "t", "u", "v", "x", "y", and "z" each represent the mole fraction of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, each at least Has a value of 0.01].

In a preferred embodiment, the reaction mixture has a molar fraction "w",
“X”, “y” and “z” (where “W” is “t” +
"U" + "v") is usually defined as falling within the limiting composition values or points as follows: In the above description of the reaction composition, the reactant is "t",
The sum of “u”, “v”, “x”, “y” and “z” is normalized so that (t + u + v + x + y + z) = 1.00 mol.

Manufacturing Reagents CoMnMgAPSO compositions can be made using many reagents. Reagents that can be used to produce CoMnMgAPSO ₃ include: (a) Alipro: aluminum isopropoxide; (b) LUDOX-LS: LUDOX-LS is 30% by weight SiO ₂ and 0.1% by weight. It is a DuPont trade name for an aqueous solution with Na ₂ O; (c) H ₃ PO ₄ : 85% by weight phosphoric acid aqueous solution; (d) MnAc: manganese acetate, Mn (C ₂ H ₃ O ₂ ) ₂ · _{4H 2 O; (e) CoAc} : cobalt _{acetate, Co (C 2 H 3 O} 2) 2 · 4H 2 O; (f) MgAc: magnesium _{acetate, Mg (C 2 H 3 O} 2) 2 · 4H 2 O; (g) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH.

SenAPSO Molecular Sieve US Application No. 600,183, filed April 13, 1984, SenAP
SO molecular sieves are MO ₂ ⁿ , AlO ₂ ⁻ , PO ₂ ⁺ and SiO ₂ tetrahedral oxide units (where “n” is −3, −2, −1,
0 or +1) and has an experimental chemical composition represented by the following formula on an anhydrous basis: mR: (M _w Al _x P _y Si _z ) O ₂ [wherein , "R" is at least 1 present in the intracrystalline pore system
Represents an organic templating agent; "m" is (M _w Al _x P _y Si
_z ) represents the molar amount of "R" present per mole of O ₂ and has a value of 0 to about 0.3; "M" is arsenic, beryllium,
Boron, chromium, cobalt, gallium, germanium,
Represents three elements selected from the group consisting of iron, lithium, magnesium, manganese, titanium, vanadium and zinc; "n" can have the values mentioned above depending on the oxidation state of "M"; , "X", "y" and "z" represent the respective mole fractions of the element "M", which is present as a tetrahedral oxide, aluminum, phosphorus and silicon].

The molar fractions "w", "x", "y" and "z" are generally defined as falling within the range of limiting composition values or points as described below. Here, “w” indicates the total mole fraction of the three elements “M”, and is “w” − “w ₁ ” + “w ₂ ” + “W ₃ ”, and each element “M” is at least 0.01. Having a mole fraction of: Preferred subclasses of SenAPSO molecular sieves include "w", "x", "y" and "z" in the above formula.
The value of is within the range of restricted composition values or points as follows: Is hitting the synthesizing ScnAPSO composition, following represented by a molar ratio _{of: aR: (M w Al x} P y Si z) O 2: bH in ₂ O [wherein "R" is an organic templating agent: "A" is the amount of the organic templating agent "R" and has a value of 0 to about 6 and preferably ranges from greater than zero (0) up to about 6, more preferably greater than 0 to about 2. Is an effective amount within; "b" is from 0 to about 500, preferably from about 2 to about 300.
Has a value of; and "w", "x", "y", and "z" each represent a mole fraction of "M", aluminum, phosphorus and silicon, and each has a value of at least 0.01. , Provided that each "M" is present in a mole fraction of at least 0.01].

In a preferred embodiment, the reaction mixture has a molar fraction "w",
The "x", "y" and "z" are generally selected to define that they fall within a range of defined composition values or points as follows: In the above reaction mixture representation, the reactants are (w + x + y
+ Z) = 1.00 mol so that "w", "x", "y"
And the sum of “z”. SenAPSO molecular sieves are prepared using the same "M" element source as described for the other APSO molecular sieves above and below.

AsAPSO molecular sieves AsAPSO molecular sieve U.S. Patent Application No. 599,808 (1984 April 13 filed) and the No. 845,484 (March 31, 1986 filed) _{^{is, AsO 2 n, AlO 2 -}} , PO 2 + and It has a SiO ₂ tetrahedral skeleton structure and the following experimental chemical composition on an anhydrous basis: mR: (As _w Al _x P _y Si _z ) O ₂ [where “R” is the intracrystalline pore system Exists at least 1
Represents an organic templating agent; "m" is (As _w Al _x P _y S
i _z ) O ₂ represents the molar amount of “R” present per mole of
Has a value from 0 to about 0.3, preferably 0.15 or less;
"W", "x", "y", and "z" represent the mole fractions of arsenic, aluminum, phosphorus, and silicon that are present as tetrahedral oxides, respectively. Generally, these mole fractions are defined as "x", "y", "z" being within the region of the limiting composition value or point as follows: In a preferred subclass of AsAPSO molecular sieves, the w, x, y and z values are as follows: In a particularly preferred subclass of AsAPSO, w, x, y
And the values of z are as follows: To synthesize the AsAPSO composition, it is preferred to use the following reaction mixture composition expressed in molar ratios.

aR: (As _w Al _x P _y Si _z ) O ₂ : bH ₂ O [where “R” is an organic template; “a”
Is an amount of organic templating agent, having a value of 0 to about 6, preferably an effective amount of greater than 0 and about 6 or less, most preferably about 1.0 or less; "b" is 0 to about 500, preferably Is a value of about 2 to 300, most preferably about 60 or less;
“W”, “x”, “y”, “z” represent the mole fractions of arsenic, aluminum, phosphorus and silicon, respectively and each has a value of at least 0.01.

In one embodiment, the reaction mixture has a mole fraction "w",
The "x", "y" and "z" are generally chosen to be defined as being within the limiting composition values or points as follows: A particularly preferred reaction mixture contains about 1-2 moles of silicon and arsenic and about 1-2 moles of aluminum (per mole of phosphorus).

In the above expression of the reaction composition, the reactant is "w",
W + x + y + for the sum of “x”, “y” and “z”
It is standardized so that z = 1.00 mol.

Manufacturing Reagents AsAPSO compositions can be manufactured using a variety of reagents. AsAPSO
Reagents that can be used to make the include:

(A) Alipro: Aluminum isopropoxide (b) CATAPAL: Hydrated pseudoboehmite commercially available from Condea Corporation (c) LUDOX-LS: 30 wt% SiO ₂ commercially available from DuPont-
Na ₂ O 0.1 wt% aqueous solution (d) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution (e) As ₂ O ₅ : arsenic oxide (V) (f) TEAOH: tetraethylammonium hydroxide
40 wt% aqueous solution (g) TBAOH: tetrabutylammonium hydroxide
40 wt% aqueous solution (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH (i) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N (j ) Quin: quinuclidine C ₇ H ₁₃ N (k) M Quin: methyl quinuclidine hydroxide C ₇ H ₁₃ NCH ₃ OH (l) C-hex: cyclohexylamine (m) TMAOH: tetramethylammonium hydroxide (n) TPAOH : Tetrapropylammonium hydroxide (o) DEEA: 2-diethylaminoethanol (p) tetraalkylorthosilicate (eg, tetramethylorthosilicate).

BAPSO molecular sieves BAPSO molecular sieve U.S. Patent Application No. 600,177 (Apr. 13, 1984 filed) and the No. 845,255 (March 28, 1986 filed) _{^{is, BO 2 -, AlO 2 -}} , PO 2 + and It has a framework structure of SiO ₂ tetrahedral units and has the following experimental chemical composition on an anhydrous basis: mR: (B _w Al _x P _y Si _z ) O ₂ where “R” is in the intracrystalline pore system. Represents at least one template agent present in the formula; "m" is (B _w Al _x P _y Si _z ).
Present per mole of O ₂ represents the molar amount of "R", 0
Has a value of about 0.3, preferably less than or equal to 0.15;
"W", "x", "y", and "z" represent the mole fractions of boron, aluminum, phosphorus, and silicon present as tetrahedral oxides, respectively. Generally, these mole fractions "x", "y", "z" and "w" are defined as being within the range of limiting composition values or points as follows: In preferred subclasses of BAPSO compositions, w, x,
The y and z values are as follows: In a particularly preferred subclass of BAPSO molecular sieves, the values of w, x, y and z are as follows: To synthesize the BAPSO compositions, expressed in terms of mole ratio is preferably used for the next reaction mixture _{composition: aR: (B w Al x} P y Si z) O 2: bH 2 O where "R" Is an organic templating agent; “a” is the amount of organic templating agent, having a value from 0 to about 6;
Preferably an effective amount greater than 0 and up to about 6; most preferably up to about 0.5; "b" is from 0 to about 500, preferably about 2-300, most preferably up to about 20; "w",
"X", "y", "z" represent the respective mole fractions of boron, aluminum, phosphorus and silicon, each having a value of at least 0.01.

In one example, the reaction mixture has a molar fraction "w",
The "x", "y", and "z" are generally chosen to be defined as being within a range of limiting composition values or points as follows: A particularly preferred reaction mixture is about 1.0 to 2 per mole phosphorus.
It contains moles of silicon and boron, and about 0.75-1.25 moles of aluminum.

In the above expression of the reaction composition, the reactant is "w",
W + x + y + for the sum of “x”, “y” and “z”
It is standardized so that z = 1.00 mol.

Manufacturing Reagents BAPSO compositions can be manufactured using a variety of reagents. Reagents that can be used to make BAPSO include:

(A) Alipro: Aluminum isopropoxide (b) CATAPAL: Hydrated pseudoboehmite commercially available from Condea Corporation (c) LUDOX-LS: 30 wt% SiO ₂ commercially available from DuPont-
Na ₂ O 0.1 wt% aqueous solution (d) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution (e) H ₃ BO ₄ : boron and trialkylborate (f) TEAOH: tetraethylammonium hydroxide
40 wt% aqueous solution (g) TBAOH: tetrabutylammonium hydroxide
40 wt% aqueous solution (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH (i) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N (j ) Quin: quinuclidine C ₇ H ₁₃ N (k) M Quin: methyl quinuclidine hydroxide C ₇ H ₁₃ NCH ₃ OH (l) C-hex: cyclohexylamine (m) TMAOH: tetramethylammonium hydroxide (n) TPAOH : Tetrapropylammonium hydroxide (o) DEEA: 2-diethylaminoethanol (p) tetraalkylorthosilicate (eg tetraethylorthosilicate) BeAPSO Molecular Sieve US Patent Application No. 600,176 (filed April 13, 1984) and the same BeAPSO molecular sieves No. 841,752 (March 20, 1986 filed) ^{_{is, BeO 2 -2, AlO 2 -}} , have a framework structure of PO ₂ ⁺ and SiO ₂ tetrahedral units, the following empirical chemical composition on an anhydrous basis the _{a: mR: (Be w Al x} P y Si z) O 2 In this, "R" represents at least one templating agent present in the intracrystalline pore system; "m" (Be _w Al _x P _y S
i _z ) O ₂ represents the molar amount of “R” present per mole of
Has a value from 0 to about 0.3, preferably 0.15 or less;
“W”, “x”, “y”, and “z” represent the mole fractions of the elements existing as tetrahedral oxides, beryllium, aluminum, phosphorus, and silicon. Generally, these mole fractions "x,""y,""z," and "w" are defined to be within the range of limiting composition values or points as follows: In a preferred subclass of BeAPSO molecular sieves, the values of w, x, y and z are as follows: To synthesize the BeAPSO composition, it is preferred to use the following reaction mixture composition expressed in molar ratio: aR: (Be _w Al _x P _y Si _z ) O ₂ : bH ₂ O where "R" is Is an organic templating agent; “a” is the amount of organic templating agent, having a value from 0 to about 6;
Preferably an effective amount greater than 0 and up to about 6; most preferably up to about 0.5; "b" is from 0 to about 500, preferably about 2-300, most preferably up to about 20; "w",
"X", "y", "z" are beryllium, aluminum,
Represents the respective phosphorus and silicon mole fractions, each having a value of at least 0.01.

In one example, the reaction mixture has a molar fraction "w",
The "x", "y" and "z" are generally chosen to be defined as being within the range of limiting composition values or points as follows: In the above expression of the reaction composition, the reactant is "w",
For “x”, “y” and “z”, w + x + y + z =
Standardized to be 1.00 mol.

Manufacturing Reagents BeAPSO compositions can be manufactured using a variety of reagents. BeAPSO
Reagents that can be used to make the include:

(A) Alipro: Aluminum isopropoxide (b) CATAPAL: Hydrated pseudoboehmite commercially available from Condea Corporation (c) LUDOX-LS: 30 wt% SiO ₂ commercially available from DuPont-
Na ₂ O 0.1 wt% aqueous solution (d) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution (e) Beryllium sulfate, BeSO ₄ (f) TEAOH: tetraethylammonium hydroxide
40 wt% aqueous solution (g) TBAOH: tetrabutylammonium hydroxide
40 wt% aqueous solution (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH (i) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N (j ) Quin: quinuclidine C ₇ H ₁₃ N (k) M Quin: methyl quinuclidine hydroxide C ₇ H ₁₃ NCH ₃ OH (l) C-hex: cyclohexylamine (m) TMAOH: tetramethylammonium hydroxide (n) TPAOH : Tetrapropylammonium hydroxide (o) DEEA: 2-diethylaminoethanol (p) tetraalkylorthosilicate (eg tetraethylorthosilicate) CAPSO Molecular Sieve CAPSO Molecular Sieve is US Patent Application No. 599,830 (filed April 13, 1984) ) And No. 852,174 (April 1986)
Filed on Jan. 15) and has a skeleton structure of CrO ₂ ⁿ , AlO ₂ ⁻ , PO ₂ ⁺ and SiO ₂ tetrahedral units (n = −1, 0 or +1), It has an experimental chemical composition: mR: (Cr _w Al _x P _y Si _z ) O ₂ where “R” represents at least one templating agent present in the intracrystalline pore system; “m” is ( Cr _w Al _x P _y S
i _z ) O ₂ is the molar amount of “R” present per mole,
Has a value of from about 0.3, preferably less than or equal to 0.15;
"W", "x", "y", "z" represent the mole fractions of the elements chromium, aluminum, phosphorus, and silicon present as tetrahedral oxides. Molar fraction "w", "x",
"Y" and "z" are generally defined to be within the range of limiting composition values or points as follows: In a preferred subclass of CAPSO molecular sieves,
The values of w, x, y and z are as follows: In a particularly preferred subclass of CAPSO molecular sieves, the values of x and y in the above formula are each in the range of about 0.4 to 0.5 and (x + w) is in the range of about 0.02 to 0.15.

The exact composition of the CAPSO molecular sieve is not fully understood at this time, so all are believed to contain CrO ₂ tetrahedra in a three-dimensional microporous crystalline framework structure.
It is advantageous to characterize the CAPSO molecular sieve by its chemical composition. This is because the low levels of chromium present in some of the CAPSO molecular sieves made to date make it difficult to ascertain the exact nature of the chromium-aluminum-phosphorus-silicon interaction. . As a result, it appears that CrO ₂ tetrahedra can be isomorphically substituted for AlO ₂ , PO ₂ or SiO ₂ tetrahedra, but some CAPSO compositions characterize chemical composition by oxide molar ratio. Is suitable.

To synthesize the CAPSO composition, it is preferred to use the following reaction mixture composition expressed in molar ratios: aR: (Cr _w Al _x P _y Si _z ) O ₂ : bH ₂ O where "R" is Is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value from 0 to about 6, preferably an effective amount within the range of greater than 0 and up to about 6, most preferably about. 0.5 or less; "b" is 0 to about 5
00, preferably about 2 to about 300, most preferably about 20 or less; "w", "x", "y", "z" are the molar fractions of chromium, aluminum, phosphorus and silicon. Represented respectively, each having a value of at least 0.01.

In one embodiment, the reaction mixture has a mole fraction "w",
The "x", "y" and "z" are generally chosen to be defined as being within the range of limiting composition values or points as follows: A particularly preferred reaction mixture is from about 0.3 to about 1 mole of phosphorus.
It contains 0.5 moles of silicon and chromium, and about 0.75 to about 1.25 moles of aluminum.

In the above expression of the reaction composition, the reactant is "w",
W + x + y + for the sum of “x”, “y” and “z”
It is standardized so that z = 1.00 mol.

Manufacturing Reagents CAPSO compositions can be manufactured using a variety of reagents. Reagents that can be used to make CAPSO include:

(A) Alipro: Aluminum isopropoxide (b) CATAPAL: Hydrated pseudoboehmite commercially available from Condea Corporation (c) LUDOX-LS: 30 wt% SiO ₂ commercially available from DuPont-
Aqueous solution of 0.1 wt% Na ₂ O (d) H ₃ PO ₄ : 85 wt% aqueous solution of phosphoric acid (e) Chromium acetate and chromium acetate hydroxide (f) TEAOH: Tetraethylammonium hydroxide
40 wt% aqueous solution (g) TBAOH: tetrabutylammonium hydroxide
40 wt% aqueous solution (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH (i) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N (j ) Quin: quinuclidine C ₇ H ₁₃ N (k) M Quin: methyl quinuclidine hydroxide C ₇ H ₁₃ NCH ₃ OH (l) C-hex: cyclohexylamine (m) TMAOH: tetramethylammonium hydroxide (n) TPAOH : Tetrapropylammonium hydroxide (o) DEEA: 2-diethylaminoethanol (p) tetraalkylorthosilicate (eg tetraethylorthosilicate) GaAPSO Molecular Sieve US Patent Application No. 599,925 (filed on April 13, 1984) GaA described in No. 845,985 (filed on March 31, 1986)
PSO molecular ^{_{sieves, GaO 2 -, AlO 2 -}} , PO 2 + and SiO
₂ has a tetrahedral unit skeleton structure and has the following experimental chemical composition on an anhydrous basis: mR: (Ga _w Al _x P _y Si _z ) O ₂ where “R” is in the intracrystalline pore system. Represents at least one templating agent present; "m" is (Ga _w Al _x P _y S
i _z ) O ₂ represents the molar amount of “R” present per mole of
0 to about 0.3, preferably 0.2 or less;
"W", "x", "y", and "z" represent the mole fractions of the respective elements gallium, aluminum, phosphorus, and silicon present as tetrahedral oxides. Generally, these mole fractions "w", "x", "y", "z" are defined to be within the limits of compositional values or points as follows: In a preferred subclass of GaAPSO molecular sieves,
The values of w, x, y and z are as follows: In a particularly preferred subclass of GaAPSO molecular sieves, the w, x, y and z values are as follows: To synthesize a GaAPSO composition, it is preferred to use the following reaction mixture composition expressed in molar ratios: aR: (Ga _w Al _x P _y Si _z ) O ₂ : bH ₂ O where "R" is Is an organic templating agent; “a” is the amount of organic templating agent, having a value from 0 to about 6;
Preferably an effective amount of greater than 0 and up to about 6; most preferably up to about 1.0; "b" is 0 to about 500, preferably about 2 to about 300, most preferably about 20 or less;
"W", "x", "y", "z" represent the mole fractions of gallium, aluminum, phosphorus and silicon, respectively, each having a value of at least 0.01.

In one embodiment, the reaction mixture has a mole fraction "w",
The "x", "y" and "z" are generally chosen to be defined as being within the range of limiting composition values or points as follows: A particularly preferred reaction mixture is from about 0.5 to about 1 mole of phosphorus.
It contains 1.0 mole of silicon and gallium, and about 0.75 to about 1.25 moles of aluminum.

In the above expression of the reaction composition, the reactant is "w",
W + x + y + for the sum of “x”, “y” and “z”
It is standardized so that z = 1.00 mol.

Manufacturing Reagents GaAPSO compositions can be manufactured using a variety of reagents. GaAPSO
Reagents that can be used to make the include:

(A) Alipro: Aluminum isopropoxide (b) CATAPAL: Hydrated pseudoboehmite commercially available from Condea Corporation (c) LUDOX-LS: 30 wt% SiO ₂ commercially available from DuPont-
0.1% by weight Na ₂ O aqueous solution (d) H ₃ PO ₄ : 85% by weight phosphoric acid aqueous solution (e) gallium hydroxide or gallium sulfate (f) TEAOH: tetraethylammonium hydroxide
40 wt% aqueous solution (g) TBAOH: tetrabutylammonium hydroxide
40 wt% aqueous solution (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH (i) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N (j ) Quin: quinuclidine C ₇ H ₁₃ N (k) M Quin: methyl quinuclidine hydroxide C ₇ H ₁₃ NCH ₃ OH (l) C-hex: cyclohexylamine (m) TMAOH: tetramethylammonium hydroxide (n) TPAOH : Tetrapropylammonium hydroxide (o) DEEA: 2-diethylaminoethanol (p) tetraalkylorthosilicate (eg tetraethylorthosilicate) GeAPSO Molecular Sieve US Patent Application No. 599,971 (filed April 13, 1984) and the same GeA described in No. 852,175 (filed on April 15, 1986)
PSO molecular ^{_{sieves, GeO 2, AlO 2 -,}} PO 2 + and SiO ₂
It has a tetrahedral skeleton structure and has the following experimental chemical composition on an anhydrous basis: mR: (Ge _w Al _x P _y Si _z ) O ₂ where “R” is in the intracrystalline pore system. Represents at least one templating agent; "m" is (Ge _w Al _x P _y S
i _z ) O ₂ represents the molar amount of “R” present per mole of
Has a value from 0 to about 0.3, preferably 0.15 or less;
"W", "x", "y", and "z" represent the mole fractions of the elements germanium, aluminum, phosphorus, and silicon present as tetrahedral oxides, respectively. Generally, the mole fractions "w", "x", "y", and "z" are defined to be within the range of limiting composition values or points as follows: In the preferred subclass of GeAPSO molecular sieves,
The values of w, x, y and z are as follows: In a particularly preferred subclass of GeAPSO molecular sieves, the w, x, y and z values are as follows: To synthesize a GeAPSO composition, it is preferred to use the following reaction mixture composition expressed in molar ratios: aR: (Ge _w Al _x P _y Si _z ) O ₂ : bH ₂ O where "R" is Is an organic templating agent; “a” is the amount of organic templating agent, having a value from 0 to about 6;
It is preferably an effective amount of greater than 0 and up to about 6, most preferably about 0.5 or less; "b" is 0 to about 500, preferably about 2 to about 300, most preferably about 20 or less, desirably about 1
It has values less than or equal to 0: "w", "x", "y", and "z" represent the respective mole fractions of germanium, aluminum, phosphorus and silicon, each having a value of at least 0.01.

In one example, the reaction mixture has a molar fraction "w",
The "x", "y", and "z" are generally chosen to specify that they are within the range of limiting composition values or points as follows: A particularly preferred reaction mixture is about 0.2-0.3 per mole phosphorus.
It contains moles of silicon and germanium, and about 0.75-1.25 moles of aluminum.

In the above expression of the reaction composition, the reactant is "w",
For “x”, “y” and “z”, w + x + y + z =
Standardized to be 1.00 mol.

Manufacturing Reagents GeAPSO compositions can be manufactured using a variety of reagents. GeAPSO
Reagents that can be used to make the include:

(A) Alipro: Aluminum isopropoxide (b) CATAPAL: Hydrated pseudoboehmite commercially available from Condea Corporation (c) LUDOX-LS: 30 wt% SiO ₂ commercially available from DuPont-
Na ₂ O 0.1 wt% aqueous solution (d) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution (e) Germanium tetrachloride or germanium ethoxide (f) TEAOH: tetraethylammonium hydroxide
40 wt% aqueous solution (g) TBAOH: tetrabutylammonium hydroxide
40 wt% aqueous solution (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH (i) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N (j ) Quin: quinuclidine C ₇ H ₁₃ N (k) M Quin: methyl quinuclidine hydroxide C ₇ H ₁₃ NCH ₃ OH (l) C-hex: cyclohexylamine (m) TMAOH: tetramethylammonium hydroxide (n) TPAOH : Tetrapropylammonium hydroxide (o) DEEA: 2-diethylaminoethanol (p) tetraalkylorthosilicate (eg tetraethylorthosilicate) (q) aluminum chlorohydrol In some cases to synthesize GeAPSO compositions, Germanium and aluminum or germanium, aluminum and silicon sources first combined and mixed germanium / aluminum or germanium / aluminum / silicon Npaundo (This compound is typically mixed oxides in which) is formed and then is to form the GeAPSO composition of the final reacted the mixture with a phosphorus source may be advantageous. Such a mixed oxide can be prepared by hydrolyzing an aqueous solution containing, for example, germanium tetrachloride and aluminum chlorhydrol, or germanium ethoxide, tetraethyl orthosilicate, or aluminum tri-sec-butoxide.

LiAPSO Molecular Sieves US Patent Application No. 599,952 filed April 13, 1984 and US Patent Application No. 847,22 filed April 2, 1986.
LiAPSO molecular sieves No. _{^{7, LiO 2 -3, AlO 2 -}} , PO
₂ ⁺ and have a framework structure of SiO ₂ tetrahedral units, and wherein an anhydrous basis: mR: in _{(Li w Al x P y Si} z) O 2 [ wherein "R" is the intracrystalline pore system Indicates at least one templating agent present within; "m" is (Li _w Al _x P _y Si _z ) O
₂ represents the molar amount of "R" present per mole of ₂ and has a value from 0 to about 0.3, preferably 0.15 or less;
"W", "x", "y", and "z" represent the molar fractions of the elements lithium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides]. The mole fractions "w", "x", "y", and "z" are usually defined to be within the limiting composition values or points as follows: In a preferred subclass of LiAPSO molecular sieves, the w, x, y and z values are as follows: In a particularly preferred subclass of LiAPSO molecular sieves, the value of w + z is about 0.20 or less.

The exact nature of the LiAPSO molecular sieves is not clearly understood at this time, so all are believed to contain LiO ₂ tetrahedra in the three-dimensional microporous crystalline framework, but LiAP
It is advantageous to characterize SO molecular sieves by chemical composition. This is due to the low levels of lithium present in some of the LiAPSO molecular sieves made to date, making it difficult to establish the exact nature of the interaction between lithium, aluminum, phosphorus and silicon. As a result, it is conceivable to replace the AlO ₂ , PO ₂ , or SiO ₂ tetrahedron with a different type of LiO ₂ tetrahedron.
It is suitable to characterize the chemical composition of the APSO composition by the oxide molar ratio.

In synthesizing the LiAPSO composition, the molar ratio is represented by the formula: aR: (Li _w Al _x P _y Si _z ) O ₂ : bH ₂ O [wherein “R” is an organic template agent; An amount of template agent having a value of 0 to about 6 and preferably greater than 0 to about 6, most preferably about.
An effective amount of 0.5 or less; "b" has a value of 0 to about 500, preferably about 2 to about 300, most preferably about 20 or less, most desirably about 10 or less; "w", "x , "Y" and "z" each represent a mole fraction of lithium, aluminum, phosphorus and silicon, and each has a value of at least 0.01]. .

In one embodiment, the reaction mixture has a mole fraction "w",
The "x", "y" and "z" are usually chosen to be defined as being within the limiting composition values or points as follows: In the above description of the reaction composition, the reactant is "w",
For the sum of "x", "y" and "z" (w + x + y +
z) = 1.00 mol is standardized.

Manufacturing Reagents LiAPSO compositions can be manufactured using a number of reagents. Reagents that can be used to produce LiAPSO include: (a) Alipro: aluminum isopropoxide: (b) CATAPAL: Condea's trademark for hydrated pseudoboehmite; (c) LUDOX-LS: Dipon trade name for aqueous solution of SiO ₂ 30 wt% and Na ₂ O0.1 _{wt%; (d) H 3 PO} 4: 85 wt% aqueous solution of phosphoric acid; (e) lithium orthophosphate; (f) TEAOH : an aqueous solution of 40 wt% of tetraethylammonium hydroxide; (g) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide; (h) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH ; (i) Pr ₃ N: tri -n- _{propylamine, (C 3 H 7) 3} N; (j) Quin: _{quinuclidine, (C 7 H 13 N)} ; (k) MQuin: methyl hydroxide quinuclidine (C ₇ H ₁₃ NCH ₃ OH); (l) C-hex: cyclohexylamine; (m) TMAOH: tetramethyl hydroxide Ammonium; (n) TPAOH: tetrapropylammonium hydroxide; (o) DEEA: 2-diethylaminoethanol; (p) Tetraalkyl orthosilicate, for example tetraethyl orthosilicate.

Aluminophosphate Molecular Sieves Various groups of aluminophosphate non-zeolitic molecular sieves are described.

ALPO ₄ luminometer phosphate Tomo les sieve U.S. Patent 4,310,440 No. and ALPO ₄ aluminophosphate Tomo les sieve of U.S. application Ser. No. 880,559 filed June 30, 1986, the chemical composition expressed by the molar ratios of oxides the following: Al ₂ O _3: 0.8-1.2P are disclosed as microporous crystalline aluminophosphates having an essential crystalline framework structure is ₂ O _5. The pores of the skeleton are uniform and have a nominal diameter of 3-10 Angstroms in each species. Aluminophosphate is 4.6
At least the adsorption capacity of water at 24 ° C
3.5% by weight, the water adsorption is completely reversible, retaining the same essential framework topology in both hydrated and dehydrated states. The term "essential framework topology" refers to the species Al-
It means the spatial arrangement of O and P—O bond linkages.
The unchanged structure of the framework indicates the absence of disruption of these main bond linkages.

In the as-synthesized form, the structure-directing agent is usually a
Add in an amount that does not exceed the mole per mole of ₂ O ₃ . The structure directing agent is essentially completely absent of ion-exchange properties of the as-synthesized composition, and is also contained internally in the as-synthesized form of at least one species of the total population. This structure directing agent does not appear to be easily removed by washing or calcination to become an essential component of the aluminophosphate, as evidenced by the complete absence of certain organic molecules. Evidence that the structure-directing agent is a critical component is found in some of the examples of Patent 4,310,440, in which the same reaction mixture that yields other ALPO ₄ products but without the presence of the template agent is used. AL instead of the previously known aluminophosphate
This gives rise to the PO ₄ , 1.1-1.3H ₂ O, ALPO ₄ -tridymite, ALPO ₄ -quartz and ALPO ₄ -cristobalite phases.

ALPO ₄ aluminophosphate contains the following according to the molar ratio of the oxides: Al ₂ O ₃ : 0.5-1.5P ₂ O ₅ : 7-100H ₂ O, and about 0.2-2.0 mol per mol of Al ₂ O ₃ It can be prepared by forming a reaction mixture containing a templating agent.

MeAPO Molecular Sieve MeAPO Molecular Sieve is a crystalline microporous aluminophosphate where the substituted metal is one of a mixture of two or more divalent metals from the group consisting of magnesium, manganese, zinc and cobalt and US Pat. 4,567,02
No. 9 is disclosed. The elements of this novel group of compositions are M
O ₂ ^-2 , AlO ₂ ^- and PO ₂ ⁺ having a three-dimensional microporous crystal framework structure of tetrahedral unit, the formula on an anhydrous basis: mR: (M _x Al _y P _z ) O ₂ [wherein "R" is at least 1 present in the intracrystalline pore system
Represents a template agent of some species, where "m" is 1 of (M _x Al _y P _z ) O ₂ .
Indicates the moles of "R" present per mole, and is from 0 to 0.3
And the maximum in each case depends on the molecular size of the template agent and the available void volume in the pore system of the particular metal aluminophosphate involved, "x",
“Y” and “z” are the metal “M” (ie magnesium, manganese,
Zinc and cobalt), aluminum and phosphorus mole fractions, the mole fractions representing the following values for "x", "y" and "z": It has the essential experimental chemical composition of. When combining, the minimum value of "m" in the above equation is 0.02. In a preferred subclass of metal aluminophosphates of the invention, the values of "x", "y" and "z" in the above formula are "x",
The following values are shown for "y" and "z": The as-synthesized composition can withstand calcination in air at 350 ° C. for extended periods of time, ie for at least 2 hours and does not become amorphous. The M, Al and P bone constituents are considered to exist in tetrahedral coordination with oxygen, but theoretically, a small proportion of these bone constituents is 5%.
And 6 oxygen atoms can be coordinated to exist. Moreover, not necessarily the M, Al and / or P content of any given synthesis product is all part of the framework in the above type of coordination with oxygen. Some of each component are merely occluded, or in some cases still undecided, and may or may not be structurally significant.

The term “metal aluminophosphate” is briefly referred to as “MeAP because it is a bit cumbersome when describing such a composition, because it requires repeated use over and over.
"O" is often used below. Also, in those cases where the metal "Me" in the composition is magnesium, the MAPO symbol applies to the composition. Similarly, ZAP for compositions containing zinc, manganese, and cobalt, respectively.
O, MnAPO and CoAPO apply. To identify the different structural species that make up each of the subgroups, namely MAPO, ZAPO, CoAPO and MnAPO, various numbers are assigned, for example ZA
Identify as PO-5, MAPO-11, CoAPO-11, etc.

The term "essential experimental chemical composition" is meant to include a crystalline framework and may contain an organic templating agent present in the pore system, but because it is contained in the reaction mixture,
Alternatively, it does not include alkali metals or other ions that may be present as a result of post-synthesis ion exchange. If there,
Such ions are mainly Al, which is not associated with PO ₂ ⁺ tetrahedra.
It functions as a charge-balancing ion for O ₂ ^- and / or MO ₂ ^-2 tetrahedra or as an organic ion derived from an organic templating agent.

When synthesizing a MeAPO composition, it is preferable to use a reaction mixture composition represented by the following formula as a molar ratio.

_{aR: (M x Al y P} z) O 2: bH in ₂ O [wherein "R" is an organic templating agent; "a" is large enough to constitute an effective concentration of "R" Has a value and is in the range>0-6;"b" has a value of 0-500, preferably 2-30, and "M" is a metal of the group consisting of zinc, magnesium, manganese and cobalt. Indicates;
"X", "y" and "z" (M _x Al _y P _z), respectively, in O ₂ component "M" indicates the mole fraction of aluminum and phosphorus, each having a value of at least 0.01, Points E, F,
G, H, I and J represent the following values for "x", "y" and "z]: In the above description of the reaction composition, the reactant is (M + Al +
P) = (x + y + z) = 1.00 Normalized for a total of moles.

The metals zinc, cobalt, magnesium and manganese can be introduced into the reaction system in any form capable of producing the reactive divalent ions of the respective metal in situ. Preference is given to using metal salts, oxides or hydroxides, for example cobalt oxide hexahydrate, α-cobalt iodide, cobaltous-sulfate, cobalt-acetate, cobaltous-bromide, cobalt-chloride. Monocobalt, zinc acetate, zinc bromide, zinc formate, zinc iodide, zinc sulfate heptahydrate, magnesium acetate, magnesium bromide, magnesium chloride, magnesium iodide, magnesium nitrate, magnesium sulfate, manganese acetate acetate, odor Examples include manganese iodide and manganese sulfate.

FAPO Molecular Sieve Ferroaluminophosphates are disclosed in US Pat. No. 4,554,143, which is incorporated herein by reference, AlO ₂ , Fe
It has a three-dimensional microporous crystal framework structure of O ₂ and PO ₂ tetrahedral units, and has the formula: mR: (Fe _x Al _y P _z ) O ₂ [wherein “R” is the crystal At least 1 present in the pore system
Indicates an organic templating agent; "m" is (Fe _x Al _y P _z ) O ₂
Represents the moles of "R" present per mole of
Has a value of 3, the maximum in each case depending on the molecular size of the template agent and the available void volume of the pore system of the particular ferroaluminophosphate involved; "x",
"Y" and "z" represent the respective mole fractions of iron, aluminum and phosphorus present as tetrahedral oxides,
Represents the following values for "x", "y" and "z": It has the essential experimental chemical composition of. When combining, the minimum value of "m" in the above equation is 0.02. In a preferred subclass of ferroaluminophosphates, the "x", "y" and "z" values in the above formula represent the following values for "x", "y" and "z": The iron of the FeO ₂ structural unit can be in either the ferric or ferrous state, depending mainly on the iron source in the synthetic gel. That is, the FeO ₂ tetrahedra in the structure can have a net charge of -1 or -2. Fe, Al and P
Although bone constituents appear to exist in tetrahedral coordination with oxygen (and as so referred to herein), certain small portions of these bone constituents coordinate with 5 or 6 oxygen atoms. It is theoretically possible to exist.
Moreover, not necessarily all Fe, Al and / or P content of any given synthesis product is part of the framework for coordination with oxygen of the above type. Some of each component may simply be occluded or may be in an as yet undetermined form and may or may not be structurally significant.

For convenience in describing ferroaluminophosphate, the shorthand abbreviation "FAPO" is often used in the following for convenience. To identify the various structural species that make up the general class of FAPO, each species is numbered, for example
Identify as FAPO-11, FAPO-31, etc.

The term "essential experimental chemical composition" is meant to include a crystalline framework and may contain any organic templating agent present in the pore system, but either in the reaction mixture or as a result of ion exchange after synthesis. It does not include alkali metal ions or other ions that may be present by inclusion.
If present, such ions are primarily FeO ₂ ^- and (or) AlO ₂ ^- tetrahedra associated with PO ₂ ⁺ tetrahedron or PO ₂ ⁺
It functions as a charge-balancing ion for organic ions derived from FeO ₂ ^-2 tetrahedra not related to tetrahedra or organic templating agents.

When synthesizing the FAPO compositions, it is preferable use a reaction mixture composition expressed by the following molar _{ratio: aR: (Fe x Al y} P z) O 2: bH in ₂ O [wherein "R" is an organic A template agent; "a" has a value large enough to constitute an effective concentration of "R" and is in the range>0-6;"b" is a value 0-500; preferably has a value of 2 to 80; "x", "y" and "z" indicates the (Fe _x Al _y P _z) respectively iron present O ₂ component, the mole fraction of aluminum and phosphorus, And each has a value of at least 0.01, representing the following values for "x", "y" and "z": In the above description of the reaction composition, the reactant is (Fe + Al + P)
= (X + y + z) = 1.00 Normalized for a total of moles.

Iron can be introduced into the reaction system in any form that can produce reactive ferrous or ferric ions in situ. Iron salts, oxides or hydroxides are preferably used, for example iron sulfate, iron acetate, iron nitrate and the like. Other sources such as freshly precipitated iron oxide, i.e. γ-FeOOH, are also suitable.

TAPO Molecular Sieves TAPO molecular sieves are disclosed in US Pat. No. 4,500,561, which is incorporated herein by reference, and [TiO ₂ ], [AlO
₂ ], a three-dimensional microporous crystalline framework structure of the [PO ₂ ] tetrahedral unit, which structure has an anhydrous empirical unit empirical formula: mR: (Ti _x Al _y P _z ) O ₂ [Wherein "R" is at least 1 present in the intracrystalline pore system]
Represents a class of organic templating agents; "m" is (Ti _x Al _y P _z ).
O ₂ 1 present per mole represent moles of "R", and 0
Has a value of about 5.0, the maximum in each case depending on the molecular size of the template agent and the effective void volume of the pore system of the particular titanium molecular sieve; "x", "y",
“Z” is titanium, which exists as a tetrahedral oxide,
Represents the mole fraction of aluminum, phosphorus, which has the following values for "x", "y", and "z": The parameters "x", "y", "z" are preferably within the following values for "x", "y", "z": Titanium-containing molecular sieves are hereinafter referred to simply as "TAPO" molecular sieves for reference purposes, or "TAPO" when referring to the group as a whole. This notation is provided herein for ease of reference only and is not meant to indicate a particular structure for any of the given TAPO molecular sieves. As used hereinafter, members of the TAPO class are referred to simply as TAPO.
-5, TAPO-11, etc., ie, a particular species is identified as TAPO-n (where “n” is specific to a given group of members, the preparation of which is reported herein). Is the number of). This label is arbitrary and is not intended to represent a structural relationship to another material that features a numbering system.

The term “unit empirical formula” is used herein in accordance with its ordinary meaning, “TiO ₂ ”, which is in the titanium-containing molecular sieve and forms the molecular framework of the TAPO composition,
"PO _2" means that displays the simplest formula which gives the titanium to form a "AlO _2" tetrahedral units, aluminum, the relative number of phosphorus molecules. The unit empirical formula is given by titanium, aluminum, phosphorus as shown in equation (1) above, either as a result of preparation or as a result of the presence of other impurities or substances in the bulk composition not containing the tetrahedral units described above. It is free of other compounds, cations or anions that may be present. The amount of template R is reported as part of the composition if it gives the as-synthesized unit empirical formula, and also water if not defined as anhydrous. For convenience, the coefficient “m” for the template “R”
Reports the number of moles of organic templating agent divided by the total moles of titanium, aluminum and phosphorus as a standardized value.

Unit empirical formulas for TAPO can be given on an "as-synthesized" basis, or can be provided for "post-synthesis" TAPO compositions after some post-treatment process, such as calcination. The term "as-synthesized" is used herein to refer to the TAPO composition formed as a result of hydrothermal crystallization, and the TAPO composition is post-treated to remove any volatilities present therein. It is before the removal of the sex component. The actual value of "m" for post-treated TAPO is due to several factors (specific TAPO, template, ability to remove template from TAPO, post-treatment severity, TA
(Including the intended use of the PO composition, etc.) and the value for "m" can be in the range of values as defined for the as-synthesized TAPO composition, although such post-treatment processes The value of "m" is usually smaller than the as-synthesized TAPO, except when the template is added to such treated TAPO. Baked or otherwise post-treated TAPO compositions typically have an empirical formula represented by equation (1), except that the value of "m" is typically less than about 0.02. If burned under sufficiently harsh post-treatment conditions, such as high temperature in air for a long time (more than 1 hour), the value of "m" may be zero or template R is not detected by standard analytical means anyway. .

TAPO is preferably formed from a reaction mixture having a sufficiently low mole fraction of alkali metal cations that it does not interfere with the formation of the TAPO composition. TAPO compositions are usually Ti
O _2, Al ₂ O _3, made from a reaction mixture containing reactive sources and organic templating agent of P ₂ O _5. The reaction mixture comprises a composition in terms of oxide molar ratio of the _{formula: fR 2 O: (Ti x} Al y P z) O 2: gH in ₂ O (wherein "R" is an organic templating agent; "F" is an effective amount of "R" and has a value large enough to make up the amount that forms the TAPO composition: "g" has a value of 0-500: "x", "y", "z" represents, respectively of titanium, aluminum, mole fraction of phosphorus in _{(Ti x Al y P z)} O 2 component, and each has a value of at least 0.001,
One of the following values for "x", "y", "z": If higher concentrations of alkali metal cations are present, TA
Although a PO composition is formed, such reaction mixtures are usually not preferred. A reaction mixture containing the following bulk compositions expressed in molar ratios of oxides is preferred: oR ₂ O: wM ₂ O: (Ti _x Al _y P _z ) O ₂ : nH ₂ O, where “R” is organic Is a template agent; "o" has a value large enough to constitute an effective concentration of "R",
And preferably in the range of greater than 0 to about 5.0: "M" is an alkali metal cation: "w" is 0
Has a value of .about.2.5 and "n" has a value of about 0 to about 500:
"X", "y", "z" _{(Ti x Al y P z)} O 2 represents titanium respectively in the component, aluminum, the molar fraction of phosphorus, and each has a value of at least 0.001, "x ",
Includes the following values for "y" and "z": When TAPO is synthesized by this method, the value of "m" in equation (1) is usually greater than about 0.02.

The presence of alkali metal cations is not preferred, but when the cations are present in the reaction mixture, at least a portion (eg, at least about 10% by weight) of each of the aluminum and phosphorus sources is initially added to the titanium source. It is preferred to mix in the absence of large amounts (eg, preferably less than about 20% of the total weight of aluminum and phosphorus sources). This procedure avoids adding a phosphorus source to the base reaction mixture containing a titanium source and an aluminum source (zeolitic structure [SiO ₂ ] tetrahedra to heteromorphic [PO ₂ ] tetrahedra). As in most published attempts to replace). The reaction mechanism is by no means clear at this point, the function of the template, [TiO _2] tetrahedral heterologous isomorphic [PO _2] in frame structure of crystalline product by replacing the tetrahedral [PO ₂ ] And [AlO ₂ ] tetrahedra may be advantageous for incorporation.

If an alkali metal cation is present in the reaction mixture, it may promote crystallization of certain TAPO phases,
The exact function of cations in their crystallization, when present, is
It is unknown at this time, if any. Alkaline cations present in the reaction mixture usually appear in the resulting TAPO composition as occluded (foreign) cations and / or as structural cations that balance the net negative charge at various loci in the crystal lattice. Although the unit formula for TAPO does not specifically mention the presence of alkali cations, it does not exclude alkali cations in the same sense as hydrogen cations and / or hydroxyl groups are not given in the conventional formula for zeolite-based aluminosilicates. You should understand.

Almost any reactive thiane source can be used in the present invention. Suitable sources of reactive titanium include titanium alkoxides, water soluble titanates and titanium chelates.

All TAPO molecular sieves are thought to contain [TiPO ₂ ] tetrahedra in the three-dimensional microporous crystal framework structure.
It is advantageous to characterize TAPO molecular sieves by their chemical composition, as their exact nature is not known at this time. This is the TA ever made
This is due to the low levels of titanium present in some of the PO molecular sieves, making it difficult to establish the exact nature of the interaction between titanium, aluminum and phosphorus. As a result, titanium and [TiO ₂ ] become heterogeneous and inhomogeneous [AlO ₂ ]
Or, it is thought that it replaced the [PO ₂ ] tetrahedron, but some T
It is appropriate to characterize the APO composition as follows in relation to the chemical composition of the as-synthesized and anhydrous oxide expressed as a molar ratio: vR: pTiO ₂ : qAl ₂ O ₃ : rP ₂ O ₅ (where “R” is at least 1 present in the intracrystalline pore system)
Represents an individual organic templating agent: "v" represents an effective amount of an organic templating agent forming the TAPO composition, preferably a value from 0 (inclusive) to about 3.0: "p",
“Q” and “r” represent the moles of titanium, alumina, and phosphorus pentoxide, respectively, and the moles of “p”, “q”, and “r” fall within the following values. Do: The parameters "p", "q", "r" are preferably
The following values for "p", "q", "r": To get inside.

ELAPO molecular sieves "ELAPO" molecular sieve is at least one element capable of forming a three-dimensional microporous framework is AlO ₂ ^-, PO ₂ ⁺ and MO ₂
ⁿ tetrahedral oxide unit [where “MO ₂ ⁿ ” is the charge n (n is −
Which represents at least one different element (other than Al or P) present as a tetrahedral unit “MO ₂ ⁿ ”, which may be 3, −2, −1, 0 or +1]. It is a class of crystalline molecular sieves. The elements of this new class of molecular sieve composition are:
AlO ₂ ⁻ , PO ₂ ⁺ and MO ₂ ⁿ having a tetrahedral unit crystal skeleton structure and having the following formula mR: (M _x Al _y P _z ) O ₂ [where “R” is an intracrystalline pore system. It represents at least one templating agent present; the "M" framework tetrahedral oxides; "m" is (M _x Al _y P _z) there per mole of O ₂ represents the molar amount of "R" Represents at least one element that can be formed; "x", "y" and "z" represent the respective mole fractions of "M", aluminum and phosphorus present as tetrahedral oxides; It has a reference experimental chemical composition.
"M" is at least one different element (ie, not aluminium, phosphorus or oxygen) such that the molecular sieve contains at least one skeleton tetrahedral unit in addition to AlO ₂ ⁻ and PO ₂ ⁺ . “M” is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc, and each of the following ELAPO groups As is clear from the examination of 1., certain restrictions are imposed on the combination of elements. Regarding ELAPO and their manufacturing methods, European Patent Application No. 85104386.9 filed on April 11, 1985 (EPC Publication No. 0158976 published on October 13, 1985, incorporated herein by reference) and It is disclosed in European Patent Application No. 85104388.5, filed April 11, 1985 (EPC Publication No. 158349, published October 16, 1985, incorporated herein by reference).

"ELAPO" molecular sieves further include a number of species disclosed in the above-referenced patents for non-zeolitic molecular sieves and elsewhere in the co-pending and commonly assigned application.

ELAPO molecular sieves are referred to herein as AlO ₂ ^-, PO ₂ ⁺
And the generic term "ELAPO" to denote the element "M" within the skeleton of the MO ₂ ⁿ tetrahedral oxide unit. Elements of the actual class will be identified by replacing the acronym "EL" with elements that exist as MO ₂ ⁿ tetrahedra.

For example, "MgBeAPO" _{^{is, AlO 2 -, PO 2 +}} , and MgO ₂ ^-2 and B
eO ₂ ^-2 Show molecular sieves consisting of tetrahedral units. In addition, each species is assigned a number to identify the various structural species that make up each of the subclasses,
Identify as "ELAPO-1" (where 1 is an integer). Nomenclature of a given species is not intended to represent structural similarities to other species governed by similar nomenclature systems.

ELAPO molecular sieves are skeletal tetrahedral oxide units (M
A containing at least one additional element capable of forming O ₂ ⁿ )
Form a crystalline framework structure with lO ₂ ⁻ and PO ₂ ⁺ tetrahedral oxide units [where “M” is the tetrahedral unit “MO ₂ ⁿ ”, where n is −
3, -2, -1, 0 or +1), and arsenic, beryllium, boron, cobalt, chromium, gallium, germanium,
It is at least one element selected from the group consisting of iron, lithium, magnesium, manganese, titanium and zinc].

ELAPO molecular sieves, AlO ₂ ^-, PO ₂ ⁺ and MO ₂ ⁿ has a crystalline three-dimensional microporous framework structure of tetrahedral units, and the formula _{mR: (M x Al y P} z) O 2 [ wherein in, "R" represents at least one templating agent present in the intracrystalline pore system; the molar amount of "m" are present per mole of _{(M x Al y P z)} O 2 "R" Has a value of 0 to about 0.3; "M" represents at least one element capable of forming a framework tetrahedral oxide (where "M" is arsenic, beryllium, boron, cobalt, chromium, gallium). ,germanium,
Has at least one element selected from the group consisting of iron, lithium, magnesium, manganese, titanium and zinc)].

Element "M", the relative amounts of aluminum and phosphorus, the following empirical formula _{(anhydrous) mR: (M x Al y} P z) O 2 ( "x", where "y" and "z" element M, Represents the mole fraction of aluminum and phosphorus). (If or M is representative of the two or more elements, M _1, M _2, M _3, etc.) each of "M" individual mole fractions of "x _1", "x _2", " x ₃ ”, etc. (where“ x ₁ ”,“ x ₂ ”,“ x ₃ ”, etc. are the individual mole fractions of elements M ₁ , M ₂ , M ₃ etc. for“ M ”as defined above. Can be represented by). "X ₁ ",
Values such as “x ₂ ”, “x ₃ ”, etc. are as specified for “x” below, in which case “x ₁ ” + “x ₂ ” + “x ₃ ” ...
...... is _{"x", x 1, x 2, x} 3 each, such as at least 0.01
Is.

ELAPO molecular sieve has the formula _{mR: (M x Al y P} z) of at least 1 O ₂ [wherein "R" is present in the intracrystalline pore system
It represents the type of templating agent; "m" represents the molar amount of "R" present per mole of _{(M x Al y P z)} O 2, 0~ about
Has a value of 0.3: "M" represents at least one different element (other than Al or P) capable of forming a skeletal tetrahedral oxide as defined above: "x", "y" And "z" represent the respective mole fractions of "M", aluminum and phosphorus present as tetrahedral oxides; the mole fractions "x", "y" and "z" are generally "x", "Y"
And within the following values for "z", but "x",
The limits for "y" and "z" may vary slightly depending on the nature of the element "M", as will appear later in this specification: MO with anhydrous reference experimental chemical composition represented by
₂ ^n, AlO ₂ ^-, and a crystalline three-dimensional microporous framework structure of PO ₂ ⁺ tetrahedral units.

In a preferred subclass of ELAPO of the invention, the values of "x", "y" and "z" in the above formula also typically fall within the following values for "x", "y" and "z": However, again the relevant limits may be somewhat altered by the element "M" as shown hereafter: In synthesizing the ELAPO compositions of the present invention is generally the formula _{aR: (M x Al y P} z) O 2: bH 2 O ( wherein "R" is an organic templating agent: "a" organic template The amount of agent "R", and from 0 to about 6
Is an effective amount having a value of 0, preferably greater than 0 and within the range of about 6, "b" has a value of 0 to about 500, preferably about 2 to 300, and "M" is Represents at least one element as described above which is capable of forming tetrahedral oxide framework units MO ₂ ⁿ with AlO ₂ ^- and PO ₂ ⁺ tetrahedral units:
"N" has a value of -3, -2, -1, 0 or +1:
"X", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus respectively; "y" and "z" each have a value of at least 0.01: "x" is at least 0 .
It is preferred to use a reaction mixture composition having a value of 01 and each element "M" has a molar fraction of at least 0.01). Usually, the mole fraction "x",
"Y" and "z" preferably fall within the following range of values for "x", "y" and "z": Further guidance regarding preferred reaction mixtures for forming ELAPO with various elements "M" is provided below.

In displaying the above reaction mixture, the reactants are (M +
Al + P) = (x + y + z) = 1.00 mol, standardized with respect to the sum, in other cases the reaction mixture may be expressed by the oxidation molar ratio and standardized to 1.00 mol of P ₂ O ₅ and / or Al ₂ O ₃ . The latter form is "M",
The former form can be easily converted by dividing the total number of moles of aluminum and phosphorus into "M", each mole of aluminum and phosphorus. Similarly, the moles of template and water are normalized by dividing by the total moles of "M", aluminum and phosphorus.

The element "M" can be introduced into the reaction system in any form that allows the reactive form of the element to be formed in situ, i.e., in such a reactive form as to form the skeleton tetrahedral oxide units of the element. Organic and inorganic salts such as "M" oxides, alkoxides, hydroxides, halides and carboxylates can be used, including chlorides, bromides, iodides, nitrates,
Included are sulfates, phosphates, acetates, formates, ethoxides, alkoxides including propoxide, and the like. Certain preferred reagents that introduce various elements "M" are discussed below.

AsAPO Molecular Sieves US Patent Application No. 600,166 filed April 13, 1984 and US Patent Application No. 830,88 filed February 19, 1986.
No. 9 AsAPO molecular sieves are AsO ₂ ⁿ , AlO ₂ ⁻ and PO ₂ ⁺
(Where "n" is a is -1 or +1) tetrahedral units having a framework structure of, and the following formula on an anhydrous _{basis: mR: (As x Al y} P z) O 2 [ wherein "R" Is at least 1 present in the intracrystalline pore system
Indicates the type of templating agent; "m" is 1 _{(As x Al y P z)} O 2
Indicates the molar amount of "R" present per mole and is from 0 to about 0.
Having a value of 3, preferably not more than 0.15; "x",
"Y" and "z" represent the molar fractions of the elements arsenic, aluminum and phosphorus present as tetrahedral oxides, respectively]. The mole fractions "x", "y", "z" are usually defined as falling within the limiting composition values or points as follows: As depending on whether the value of “n” is −1 or +1 (that is, whether arsenic is trivalent or pentavalent)
It is understood that there are two preferred subclasses of APO molecular sieves and that mixtures of these are placed in a given AsAPO. When "n" is -1, preferred values for x, y and z fall within the limiting composition values or points as follows: When "n" is +1, preferred values for x, y and z fall within the limiting composition values or points as follows: In a particularly preferred subclass of AsAPO molecular sieves where "n" = + 1, the values of x, y and z are as follows: Upon synthesizing AsAPO compositions, the molar ratio of as _{follows: aR: (As x Al y} P z) O 2: bH in ₂ O [wherein "R" is an organic templating agent: "a" organic The amount of template agent "R" having a value of 0 to about 6 and preferably an effective amount in the range of greater than 0 to about 6, most preferably about 0.5 or less; "b" is 0 to about 500, preferably about 2 to 300, most preferably about 20
With the following values; "x", "y" and "z" each represent the molar fraction of arsenic, aluminum and phosphorus and each has a value of at least 0.01]. Is preferred.

In one embodiment, the reaction mixture has a molar fraction "x",
Choose so that "y" and "z" are usually defined to fall within the limiting composition values or points as follows: Particularly preferred reaction mixtures are those in which the mole fractions "x", "y" and "z" fall within the limiting composition values or points as follows: In the above description of the reaction composition, the reactant is "x",
It is normalized such that (x + y + z) = 1.00 mol with respect to the sum of “y” and “z”.

Preparation Reagents AsAPO compositions can be manufactured using a number of reagents. Reagents that can be used to produce AsAPO include: (a) aluminum isopropoxide; (b) pseudoboehmite or other aluminum oxide; (c) H ₃ PO ₄ : 85 wt% phosphorus. (D) As ₂ O ₅ : Arsenic (V) oxide; (e) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (f) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide; (g) ) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH; (h) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (i) Quin: quinuclidine (C ₇ H ₁₃ N); (j) MQuin: Methyl quinuclidine hydroxide; (C ₇ H ₁₃ NCH ₃ OH); (k) C-hex: Cyclohexylamine; (l) TMAOH: Tetramethylammonium hydroxide (M) TPAOH: tetrapropylammonium hydroxide; (n) DEEA: 2-diethylaminoethane Lumpur; BAPO molecular sieves April 1984 U.S. Application No. 599,812, filed 13 days, 198
US Application Nos. 804,238 and 1987 filed December 4, 5
BAPO molecular sieves, filed March 24 year U.S. Application No. 29,540 is, BO ₂ ^-, AlO ₂ ^- has and PO ₂ ⁺ tetrahedral units of the framework structure and the formula mR :( on an anhydrous basis B _x Al _y P _z ) O ₂ [where “R” represents at least one templating agent present in the intracrystalline pore system; “m” is 1 of (B _x Al _y P _z ) O ₂ ). Represents the molar amount of "R" present per mole and has a value from 0 to about 0.3: "x", "y" and "z" are each of boron, aluminum and phosphorus present as tetrahedral oxides. Has an experimental chemical composition represented by The mole fractions "x", "y" and "z" are generally defined as being within the range of limiting composition values or points as follows: In a preferred subclass of BAPO molecular sieves,
The values of x, y and z fall within the limiting composition values or points as follows: A particularly preferred subclass of BAPO molecular sieves is
The boron mole fraction "x" is about 0.3 or less.

Upon synthesizing BAPO compositions, following by the molar ratio _{of: aR: (B x Al y} P z) O 2: bH 2 O ( wherein "R" is an organic templating agent; "a"
Is an amount of organic templating agent "R", and is preferably an effective amount in the range of greater than 0 to about 6, most preferably about 1.0 or less; "b" is 0 to about 500, preferably about 2 About 300, preferably about 20 or less, most preferably about 1
Has a value of 0 or less; "x", "y" and "z" represent the mole fractions of boron, aluminum and phosphorus, respectively,
And each has a value of at least 0.01).

In one embodiment, the reaction mixture has a molar fraction "x",
Choose so that "y" and "z" are usually defined to be within the limiting composition values or points as follows: A particularly preferred reaction mixture is B ₂ O ₃ 0.5-0.5 mol / mol P ₂ O _5.
It contains 2.0 mol and 0.75 to 1.25 mol of Al ₂ O ₃ .

In the above description of the reaction composition, the reactant is "x",
(X + y + z) = 1.00 for the sum of “y” and “z”
It is standardized to be molar.

The exact nature of the BAPO molecular sieves has not been sufficiently understood at present, all are believed to contain a three-dimensional microporous framework structure in BO _2, AlO ₂ and PO ₂ tetrahedra. The low levels of boron present in some of the present molecular sieves make it difficult to determine the exact nature of the boron-aluminum-phosphorus interaction. As a result, it is believed that the BO ₂ tetrahedra are present in the three-dimensional microporous framework structure, but some BAPO compositions are suitable to be characterized by the oxide molar ratio.

Preparation Reagents BAPO compositions can be manufactured using a number of reagents. Reagents that can be used to produce BAPO include: (a) aluminum isopropoxide; (b) pseudoboehmite or other aluminum oxide; (c) H ₃ PO ₄ : 85 wt% phosphorus. (D) Boric acid or trimethylborate; (e) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (f) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide; (g) Pr ₂ NH : di -n- _{propylamine, (C 3 H 7) 2} NH; (h) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (i) Quin: quinuclidine (C ₇ H ₁₃ N); (j) MQuin: methylquinuclidine hydroxide; (C ₇ H ₁₃ NCH ₃ OH); (k) C-hex: cyclohexylamine; (l) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: tetrapropylammonium hydroxide; (n) DEEA: 2-diethylami Ethanol; BeAPO molecular sieves, 1984 April 13 to U.S. patent application No. filed US patent application Ser. No. 599,776 and March 3, 1986 Application No. 835,29
BeAPO Molecular Sieve No. 3 is BeO ₂ ^-2 , AlO ₂ ^- and PO ₂
⁺ Four has a framework structure of tetrahedral units and formula mR an anhydrous basis: in _{(Be x Al y P z)} O 2 [ wherein "R" is at least 1 present the intracrystalline pore system
It indicates the type of templating agent; "m" is 1 _{(Be x Al y P z)} O 2
Indicates the molar amount of "R" present per mole and is from 0 to about 0.
Has a value of 3, preferably less than or equal to 0.15; "x",
"Y" and "z" respectively represent the mole fractions of beryllium, aluminum and phosphorus elements present as tetrahedral oxides]. The mole fractions "x", "y", "z" are usually defined to be within the limiting composition values or points as follows: In a preferred subclass of BeAPO molecular sieves,
The values of "x", "y" and "z" in the above formula are within the limiting composition values or points as follows: In a particularly preferred subclass of BeAPO molecular sieves, x, y and z are as follows: Upon synthesizing BeAPO compositions, the molar ratio of as _{follows: aR: (Be x Al y} P z) O 2: bH in ₂ O [wherein "R" is an organic templating agent; "a" is an organic The amount of template agent "R" has a value of 0 to about 6 and is preferably an effective amount in the range of about 6 greater than 0, most preferably about 1.5 or less; "b" is 0.
To about 500, preferably about 2 to about 300, most preferably about 50
With the following values; "x", "y" and "z" represent the mole fractions of beryllium, aluminum and phosphorus, respectively and each has a value of at least 0.01]. Is preferred.

In one embodiment, the reaction mixture has a molar fraction "x",
Choose so that "y" and "z" are usually defined to fall within the limiting composition values or points as follows: Particularly preferred reaction mixtures are those in which the mole fractions "x", "y" and "z" fall within the limiting composition values or points as follows: In the above description of the reaction composition, the reactant is "x",
It is standardized that (x + y + z) = 1.00 mol with respect to the sum of “y” and “z”.

Preparation Reagents BeAPO compositions can be manufactured using a number of reagents. Reagents that can be used to produce BeAPO include: (a) aluminum isopropoxide; (b) pseudoboehmite or other aluminum oxide; (c) H ₃ PO ₄ : 85 wt% phosphorus. (D) Beryllium sulfate; (e) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (f) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide; (g) Pr ₂ NH: di-n - _{propylamine, (C 3 H 7) 2} NH; (h) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (i) Quin: quinuclidine (C ₇ H ₁₃ N); (J) MQuin: methyl quinuclidine hydroxide; (C ₇ H ₁₃ NCH ₃ OH); (k) C-hex: cyclohexylamine; (l) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: hydroxylation Tetrapropylammonium; (n) DEEA: 2-diethylaminoethanol; CAPO Molecular Sieves US Patent Application No. 599,813 filed April 13, 1984 and US Patent Application No. 830,75 filed February 19, 1986.
No. 6 CAPO molecular sieves are CrO ₂ ⁿ , AlO ₂ ^- and PO ₂ ⁺
(Where "n" is a is -1, 0 or +1) tetrahedral units having a framework structure of, and the following formula on an anhydrous _{basis: mR: (Cr x Al y} P z) O 2 [ wherein " R "is at least 1 present in the intracrystalline pore system
Indicates a certain template agent; "m" is (Cr _x Al _y P _z ) O ₂ 1
Indicates the molar amount of "R" present per mole and is from 0 to about 0.
Having a value of 3, preferably not more than 0.15; "x",
"Y" and "z" respectively represent the molar fractions of the elements chromium, aluminum and phosphorus present as tetrahedral oxides, respectively]. "N" is-
When 1 or +1 the mole fractions "x", "y", "z"
Is usually defined as falling within the limiting composition values or points as follows: When "n" is 0, the mole fractions "x", "y" and "z" are usually defined to fall within the limiting composition values or points as follows: There are three preferred subclasses of CAPO molecular sieves, depending on whether the value of "n" is -1, 0 or +1 (ie, chromium has an oxidation number of 3, 4 or 5),
It will be appreciated that putting these mixtures into a given CAPO. When "n" is -1, preferred values for x, y and z fall within the limiting composition values or points as follows: In a particularly preferred subclass of these CAPO molecular sieves where "n" =-1, the values of x, y and z are as follows: When "n" is 0, the preferred values for x, y and z fall within the limiting composition values or points as follows: When "n" is +1, preferred values for x, y and z fall within the limiting composition values or points as follows: The exact nature of CAPO molecular sieves is not clearly understood at this time, so all are believed to contain CrO ₂ tetrahedra in the three-dimensional microporous framework structure, but CAPO molecular sieves are characterized by chemical composition. Is advantageous. This is due to the low levels of chromium present in some of the CAPO molecular sieves made to date, making it difficult to establish the exact nature of the interaction between chromium, aluminum and phosphorus. As a result, AlO ₂
Alternatively, it is conceivable to replace the PO ₂ tetrahedron with a heteromorphic CrO ₂ tetrahedron, but it is appropriate to characterize a given CAPO composition by its chemical composition expressed as the molar ratio of the oxides.

Upon synthesizing CAPO compositions, the molar ratio of as _{follows: aR: (Cr x Al y} P z) O 2: bH in ₂ O [wherein "R" is an organic templating agent; "a" is an organic The amount of template agent "R" has a value of 0 to about 6 and is preferably an effective amount in the range of greater than 0 to about 6, most preferably about 0.6 or less; "b" is 0 to about 500, preferably about 2 to about 300, most preferably about
A value of 20 or less; "x", "y" and "z" each represent a mole fraction of chromium, aluminum and phosphorus and each has a value of at least 0.01]. It is preferably used.

In one embodiment, the reaction mixture has a molar fraction "x",
Choose so that "y" and "z" are usually defined to fall within the limiting composition values or points as follows: A particularly preferred reaction mixture contains about 0.1 chromium per mole phosphorus.
It contains from 1 to about 0.4 moles and from about 0.75 to about 1.25 moles of aluminum.

In the above description of the reaction mixture, the reactant is "x",
It is normalized such that (x + y + z) = 1.00 mol with respect to the sum of “y” and “z”.

Preparation Reagents CAPO compositions can be manufactured using a number of reagents. Reagents that can be used to produce CAPO include: (a) aluminum isopropoxide or aluminum chlorohydrol; (b) pseudoboehmite or other aluminum oxide; (c) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution; (d) Chromium (III) orthophosphate, chromium acetate (II
I), chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ COO) ₇ ); (e) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (f) TBAOH: 40 wt% of tetrabutylammonium hydroxide % aqueous solution; (g) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH; (h) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; ( i) Quin: quinuclidine (C ₇ H ₁₃ N); (j) MQuin: methyl quinquelidine hydroxide; (C ₇ H ₁₃ NCH ₃ OH); (k) C-hex: cyclohexylamine; (l) TMAOH: Tetramethylammonium hydroxide; (m) TPAOH: Tetrapropylammonium hydroxide; (n) DEEA: 2-diethylaminoethanol; GaAPO Molecular Sieve US Patent Application Nos. 599,771 and 1 filed April 13, 1984.
GaAP of US Patent Application No. 830,890 filed February 19, 986
O molecular sieve has a skeleton structure of GaO ₂ ⁻ , AlO ₂ ⁻ and PO ₂ ⁺ tetrahedral units, and has the formula: mR: (Ga _x Al _y P _z ) O ₂ [wherein “R Is at least 1 present in the intracrystalline pore system
Represents a certain template agent; "m" represents the molar amount of "R" present per mole of (Ga _x Al _y P _z ) O ₂ and 0-
Is preferably less than 0.15 with a value of about 0.3; and "x", "y" and "z" represent the mole fractions of gallium, aluminum and phosphorus elements respectively present as tetrahedral oxides] Has an experimental chemical composition. The mole fractions "x", "y" and "z" are generally defined to fall within the limits of compositional values or points as follows: Generally, the value of "z" in GaAPO molecular sieves is about 0.60 or less.

In a preferred subclass of GaAPO molecular sieves,
The values of x, y and z fall within the range of defined composition values or points as follows: Particularly preferred subclasses of GaAPO molecular sieves have the following values for x, y and z: In synthesizing the GaAPO composition, aR: (Ga _x Al _y P _z ) O ₂ : bH ₂ O is represented by a molar ratio, wherein “R” is an organic template agent and “a” is An amount of organic templating agent "R" having a value of 0 to about 6 and preferably an effective amount in the range of greater than zero (0) up to about 6, most preferably about 1.0 or less. "B" has a value of 0 to about 500, preferably about 2 to about 300, most preferably about 2 to about 20; and "x",
"Y" and "z" represent the mole fractions of gallium, aluminum and phosphorus, respectively, each having a value of at least 0.01].

In one embodiment, the reaction mixture has a molar fraction "x",
The "y" and "z" are generally selected to be defined as falling within a range of defined composition values or points as follows: Especially preferred reaction mixtures are those containing P ₂ O ₅ 1 mol per 0.2 to 0.5 moles in the Ga ₂ O ₃ and the 0.3 moles of Al ₂ O _3.

In the above expression of the reaction composition, the reactants are "x", "y".
And the sum of "z" are standardized to be (x + y + z) = 1.00 mol.

Preparation Reagents GaAPO compositions can be prepared with a number of reactants. Reactants that can be used to prepare GaAPO include:

(A) Aluminum isopropoxide, (b) Pseudo-boehmite or other aluminum oxide; (c) H ₃ PO ₄ : 85% by weight phosphoric acid aqueous solution; (d) Gallium sulfate or gallium hydroxide (III) (e) TEAOH: 40 weight percent aqueous solution of tetraethylammonium hydroxide; (f) TBAOH: 40 weight percent aqueous solution of tetrabutylammonium hydroxide; (g) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH ; (h) Pr ₃ N: tri -n- _{propylamine, (C 3 H 7) 3} N; (i) Quin: quinuclidine _{(C 7 H 13 N);} (j) MQuin: methyl hydroxide quinuclidine; _{(C 7 H 13 NCH 3 OH} ); (k) C-hex: cyclohexylamine; (l) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: tetrapropylammonium hydroxide; (n) DEEA: 2- diethylamino Ethanol; GeAPO Molecular Sieve, April 13, 1984 U.S. Patent Application Nos. 599,807 and 1
GeAP of US Patent Application No. 841,753, filed March 20, 986
O molecular sieve has a skeleton structure of GeO ₂ , AlO ₂ ⁻ and PO ₂ ⁺ tetrahedral units, and has the formula: mR: (Ge _x Al _y P _z ) O ₂ [wherein “R” Is at least 1 present in the intracrystalline pore system
It represents the type of templating agent; "m" _{(Ge x Al y P z)} O 2 1
Represents the molar amount of "R" present per mole and is from 0 to
Has a value of about 0.3 but preferably not more than 0.2; and "x", "y" and "z" represent the mole fractions of germanium, aluminum and phosphorus elements respectively present as tetrahedral oxides] It has the experimental chemical composition represented. The mole fractions "x", "y" and "z" are generally defined as falling within the range of defined composition values or points as follows: In a preferred subclass of GeAPO molecular sieves,
The values of x, y and z fall within defined compositional values or points as follows: A particularly preferred subclass of GeAPO molecular sieves are those having an "x" value of about 0.13 or less.

Is hitting the synthesizing GeAPO compositions, aR expressed by the molar _{ratio: (Ge x Al y P z} ) O 2: bH in ₂ O [wherein "R" is an organic templating agent; "a" An amount of organic templating agent "R" having a value of 0 to about 6 and preferably an effective amount in the range of greater than zero (0) up to about 6, most preferably about 0.6 or less;
"B" has a value of 0 to about 500, preferably about 2 to about 300, most preferably about 10 to about 60; and "x", "y" and "z" are germanium, aluminum and phosphorus, respectively. Of the reaction mixture composition, each having a value of at least 0.01].

In one embodiment, the reaction mixture has a molar fraction "x",
The "y" and "z" are generally selected to be defined as falling within a range of defined composition values or points as follows: Especially preferred reaction mixtures are those containing P ₂ O ₅ 1 mol per 0.2 to 0.4 moles of GeO ₂ and 0.75 to 1.25 moles of Al ₂ O _3.

In the above description of the reaction composition, the reactant is "x",
(X + y + z) = 1 for the sum of “y” and “z”.
It is standardized to be 00 mol.

Preparation Reagents GeAPO compositions can be prepared using a number of reactants. The reactants can be used to prepare the GeAPO, include: (a) a aluminum isopropoxide, (b) pseudoboehmite or other aluminum _{oxide; (c) H 3 PO 4} : 85 wt% phosphoric acid aqueous solution; (d) Germanium tetrachloride, germanium ethoxide and germanium dioxide (e) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (f) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide ; (g) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH; (h) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (i) Quin: quinuclidine (C ₇ H ₁₃ N); (j) MQuin: hydroxymethyl quinuclidine; (C ₇ H ₁₃ NCH ₃ OH); (k) C-hex: cyclohexylamine; (l) TMAOH: hydroxylated Tetramethylammonium; (m) TPAOH: Hydroxyl (N) DEEA: 2-diethylaminoethanol; Manufacturing Procedure When synthesizing a GeAPO composition, first a source of germanium and aluminum are mixed to form a mixed germanium / aluminum compound (this compound is typically a mixed There are some cases in which it may be advantageous to combine the hybrid compound with a phosphorus source to form the final GeAPO composition after forming the oxide). Such a mixed oxide can be prepared, for example, by hydrolyzing an aqueous solution containing germanium tetrachloride and aluminum chlorohydrol or aluminum tri-sec-butoxide.

LiAPO Molecular Sieves US Patent Application Nos. 599,811 and 1 filed April 13, 1984
LiAP of US Patent Application No. 834,921 filed on February 28, 986
O molecular sieves, LiO ₂ ^-3, AlO ₂ ^- and PO ₂ ⁺ have a framework structure of tetrahedral units, and formula on an anhydrous _{basis: mR: (Li x Al y} P z) O 2 [ wherein " R "is at least 1 present in the intracrystalline pore system
Represents an organic templating agent; "m" is (Li _x Al _y P _z ).
Represents the molar amount of "R" present per mole of O ₂ and
Has a value from about 0.3 but preferably not more than 0.15;
And "x", "y" and "z" represent the mole fractions of the lithium, aluminum and phosphorus elements respectively present as tetrahedral oxides]. The mole fractions "x,""y," and "z" are generally defined to fall within the range of defined composition values or points as follows: In a preferred subclass of LiAPO molecular sieves,
The values of x, y and z fall within defined compositional values or points as follows: In a particularly preferred subclass of LiAPO molecular sieves, the values of x, y and z fall within the following ranges: Is hitting the synthesizing LiAPO compositions, aR expressed by the molar _{ratio: (Li x Al y P z} ) O 2: bH in ₂ O [wherein "R" is an organic templating agent; "a" An amount of an organic templating agent "R" having a value of 0 to about 6 and preferably an effective amount in the range of greater than zero (0) up to about 6, most preferably about 2 or less;
"B" is 0 to about 500, preferably about 2 to about 300, most preferably about 40 or less; and "x", "y" and "z" are the mole fractions of lithium, aluminum and phosphorus, respectively. , Each having a value of at least 0.01].

In one embodiment, the reaction mixture has a molar fraction "x",
The "y" and "z" are generally selected to be defined as falling within a range of defined composition values or points as follows: In a particularly preferred subclass of reaction mixture, "x",
The "y" and "z" values fall within a range of defined composition values or points as follows: In the above description of the reaction composition, the reactant is "x",
(X + y + z) = 1 for the sum of “y” and “z”.
It is standardized to be 00 mol.

The exact nature of LiAPO molecular sieves is not clearly understood at this time, so although it is believed that all contain LiO ₂ tetrahedra in the three-dimensional microporous crystal framework structure, LiAPO molecular sieves It is advantageous to characterize by chemical composition. This was due to the low levels of lithium present in some of the LiAPO molecular sieves manufactured to date (this makes it difficult to ascertain the exact nature of the interaction between lithium, aluminum and phosphorus). There is). As a result, it is believed that the AlO ₂ or PO ₂ tetrahedra are isomorphically substituted with LiO ₂ tetrahedra, but some LiAPO
The compositions are suitably characterized by their chemical composition by the molar ratio of the oxides.

Preparation Reagents LiAPO compositions can be prepared with a number of reactants. The reactants can be used to prepare the LiAPO, include: (a) a aluminum isopropoxide, (b) pseudoboehmite or other aluminum _{oxide; (c) H 3 PO 4} : 85 wt% phosphoric acid aqueous solution; (d) lithium sulfate or lithium orthophosphate; (e) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (f) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide; (g ) Pr ₂ NH: di -n- _{propylamine, (C 3 H 7) 2} NH; (h) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (i) Quin: quinuclidine (C ₇ H ₁₃ N); (j) MQuin: Methyl quinuclidine hydroxide; (C ₇ H ₁₃ NCH ₃ OH); (k) C-hex: Cyclohexylamine; (l) TMAOH: Tetramethylammonium hydroxide (M) TPAOH: tetrapropylammonium hydroxide; ( ) DEEA: 2-diethylaminoethanol; FeTiAPO molecular sieve April 1984 filed on the 13th U.S. Patent Application No. 599,824 and 1986 September U.S. patent application 2 days Application No. 902,12
No. 9 FeTiAPO molecular sieves have the following formula on an anhydrous basis: mR: (M _x Al _y P _z ) O ₂ [where “R” represents at least one organic templating agent present in the intracrystalline pore system. ; M represents iron and titanium; "m" represents the molar amount of "R" present per mole of _{(M x Al y P z)} O 2, has a value of 0 to about 0.3, "x ",
"Y" and "z" are tetrahedra present as oxides "M", FeO _2, TiO ₂ and PO ₂ tetrahedral oxide having the empirical chemical composition represented by the representative of the respective molar fractions of aluminum and phosphorus] It has a three-dimensional microporous framework structure for each object. The mole fractions "x", "y" and "z" are generally defined as being within the range of limiting composition values or points as follows: In a preferred subclass of FeTiAPO molecular sieves, the x, y and z values are within the limiting composition values or points as follows: In synthesizing the FeTiAPO composition has the formula _{aR: (M x Al y P} z) O 2: bH 2 O ( wherein "R" is an organic templating agent; "a"
Is an amount of the organic templating agent "R", having a value of 0 to about 6, and preferably an effective amount in the range of greater than 0 up to about 6; "b" is 0 to about 500, preferably Has a value from about 2 to about 300; "x", "y" and "z" represent the respective mole fractions of "M" (iron and titanium), aluminum and phosphorus, and each is at least 0.01.
It is preferred to use a reaction mixture composition having a molar ratio of

In one embodiment, the reaction mixture has a molar fraction "x",
Choose so that "y" and "z" are generally defined to be within the range of limiting composition values or points as follows: In the above description of the reaction composition, the reactant is "x",
(X + y + z) = 1.00 for the sum of “y” and “z”
Normalized to be molar.

Preparative Reagents FeTiAPO compositions can be manufactured using a number of reactants. The preferred iron and titanium sources for producing FeTiAPO are the same as those for producing FeAPO and TiAPO already mentioned above. Other reagents that can be used to produce FeTiAPO comprises: (a) aluminum isopropoxide, (b) pseudoboehmite or other aluminum _{oxide; (c) H 3 PO 4} : 85 wt% (D) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (e) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide; (f) Pr ₂ NH: di-n-propylamine, _{C 3 H 7) 2 NH;} (g) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (h) Quin: quinuclidine _{(C 7 H 13 N);} (i) MQuin: methyl hydroxide _{quinuclidine; (C 7 H 13 NCH 3} OH); (j) C-hex: cyclohexylamine; (k) TMAOH: tetramethylammonium hydroxide; (l) TPAOH: tetrapropylammonium hydroxide; ( m) DEEA: 2-diethylaminoethanol; XAPO molecular sea Filed on April 13, 1984 U.S. Patent Application No. 599,810 and filed on September 2, 1986 U.S. Patent Application Serial No. 902,02
No. 0 XAPO molecular sieves have the following formula on an anhydrous basis: mR: (M _x Al _y P _z ) O ₂ [where “R” represents at least one organic templating agent present in the intracrystalline pore system. "M" represents at least one element from each of the groups 1) iron and titanium and 2) cobalt, magnesium, manganese and zinc; "n" is 0, -1 or -2; There; "m" represents the molar amount of "R" present per mole of _{(M x Al y P z)} O 2, has a value of 0 to about 0.3, "x", "y" and ""z" represents the molar fraction of each of M and aluminum and phosphorus present as tetrahedral oxides] and the tertiary of MO ₂ ⁿ , AlO ₂ and PO ₂ tetrahedral acid units having the experimental chemical composition It has an original microporous framework structure. The mole fractions "x", "y" and "z" are generally defined as being within the range of limiting composition values or points as follows: In a preferred subclass of XAPO molecular sieves,
The values of x, y and z are within the range of limiting composition values or points as follows: In synthesizing the XAPO compositions, the following equation _{aR: (M x Al y P} z) O 2: bH 2 O [ wherein "R" is an organic templating agent; "a"
Is the amount of the organic templating agent "R", which has a value of 0 to about 6 and is preferably an effective amount within the range of greater than 0 up to about 6; "M" is 1) of iron and titanium. Group and 2) represents at least one element from each group of the group of cobalt, magnesium, manganese and zinc; "b" is 0
To about 500, preferably about 2 to about 300; "x",
"Y" and "z" represent "M" (iron and / or titanium, and at least one of cobalt, aluminum, manganese, and zinc), the respective mole fractions of aluminum and phosphorus, and each is It has a value of at least 0.01. However, "x" has a value of at least 0.02. ] It is preferable to use the reaction mixture composition represented by the molar ratio.

In one embodiment, the reaction mixture has a molar fraction "x",
Choose so that "y" and "z" are generally defined to be within the range of limiting composition values or points as follows: In the above expression of the reaction composition, the reactant is "x",
(X + y + z) = 1.00 for the sum of “y” and “z”
Normalized to be molar.

Preparation Reagents XAPO compositions can be manufactured using a number of reagents. The preferred source of elemental "M" for making XAPO is the same as for making other APO containing the same elements as described above and below. Other reagents that can be used to make XAPO include: (a) aluminum isopropoxide; (b) pseudoboehmite or other aluminum oxide; (c) H ₃ PO ₄ : 85% by weight. (D) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (e) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide; (f) Pr ₂ NH: di-n-propylamine, _{C 3 H 7) 2 NH;} (g) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (h) Quin: quinuclidine _{(C 7 H 13 N);} (i) MQuin: methyl hydroxide _{quinuclidine; (C 7 H 13 NCH 3} OH); (j) C-hex: cyclohexylamine; (k) TMAOH: tetramethylammonium hydroxide; (l) TPAOH: tetrapropylammonium hydroxide; ( m) DEEA: 2-diethylaminoethanol; mixed element APO molecular US Pat. No. 599,978 of the sheave 1984, April 13, with applications and 198
The mixed element APO molecular sieve of U.S. Pat. No. 846,088, filed March 3, 2006, contains MO ₂ ⁿ , AlO ₂ ^- and PO ₂ ⁺ tetrahedral units [where MO ₂ ⁿ is the charge "n" ( Where "n" may be -3, -2, -1, 0 or +1) having at least two different elements present as tetrahedral units "MO ₂ ⁿ ". Have. At least one of the elements “M” is arsenic, beryllium, boron,
It is selected from the group consisting of chromium, gallium, germanium, lithium and vanadium and the second of the elements "M" is selected from the group consisting of cobalt, iron, magnesium, manganese, titanium and zinc. Preferred is a mixture of "M" lithium and magnesium. Hybrid element molecular sieves have the formula on an anhydrous basis _{mR: (M x Al y P} z) O 2 [ wherein "R" is at least 1 present the intracrystalline pore system
Represents an organic templating agent; "m" is (Li _x Al _y P _z ).
Represents the molar amount of "R" present per mole of O ₂ and
Has a value from about 0.3 but preferably not more than 0.15;
And “x”, “y” and “z” are the mole fractions of the element “M” and aluminum and phosphorus, respectively, which exist as tetrahedral oxides (that is, “x” is the mole fraction of two or more elements “M”). Represents the sum of the fractions)]. The mole fractions "x", "y" and "z" are generally defined as falling within the range of defined composition values or points as follows: In a preferred subclass of mixed element AIO molecular sieves, the values of x, y and z fall within defined compositional values or points as follows: A particularly preferred subclass of mixed element AIO molecular sieves is such that the value of x is less than or equal to about 0.10: U.S. Patent No. 600,171 filed April 13, 1984 (currently August 11, 1987). The second group of hybrid element APO molecular sieves (FCAPO) described in issued U.S. Pat. No. 4,686,093 are MO ₂ ⁿ , AlO ₂ ^- and PO ₂ ⁺ tetrahedral units [where MO ₂ ⁿ is the charge " n "(where" n "is -3,-
2, -1, 0, or a +1 exist as tetrahedral units "MO ₂ ^+" having a good) and arsenic, beryllium, boron, chromium, at least 2 to select gallium, germanium, from the group consisting of lithium and vanadium Represents different elements). These hybrid elements molecular sieves formula on an anhydrous basis _{mR: (M x Al y P} z) O 2 [ wherein "R" is at least 1 present the intracrystalline pore system
Represents an organic templating agent; "m" is (M _x Al _y P _z ) O
₂ represents the molar amount of "R" present per mole and
Has a value of about 0.3; "x", "y" and "z" are each element "M" (ie, present as a tetrahedral oxide).
"X" is the sum of the mole fractions of two or more elements "M"), and represents the mole fractions of aluminum and phosphorus]. Molar fractions "x", "y" and "z" are generally defined as falling within the range of limiting composition values or points as follows: In a preferred subclass of mixed element AIO molecular sieves, the values of x, y and z fall within the defined compositional values or points as follows: The hitting To synthesize a hybrid element APO compositions, expressed by the molar ratio _{aR: (M x Al y P} z) O 2: bH in ₂ O [wherein "R" is an organic templating agent; "a Is the amount of organic templating agent "R" and has a value from 0 to about 6 and is preferably greater than zero (0) to about 6.
An effective amount in the range of up to about 50, most preferably about 0.5 or less; "b" is a value of 0 to about 500, preferably about 2 to about 300, most preferably about 20 or less, and most preferably about 10 or less. And “x”, “y” and “z” represent the mole fractions of “M”, aluminum and phosphorus, respectively,
"Y" and "z" each have a value of at least 0.01,
"X" has a value of at least 0.02 and each element "M"
Has a molar fraction of at least 0.01].

In one embodiment, the reaction mixture has a molar fraction "x",
The "y" and "z" are generally chosen to be defined as falling within a range of defined composition values or points as follows: Preferred reaction mixtures are those which contain no more than about 0.2 mole of metal "M" per mole of phosphorus.

In the above reaction mixture representation, the reactants are "x", "y".
And for the sum of "z" are normalized to be (x + y + z) = 1.00 mol.

The exact nature of the mixed element APO molecular sieves is not clearly understood at this time, so although it is believed that all contain MO ₂ tetrahedra in the three-dimensional microporous crystal skeleton structure, the mixed element APO molecular sieves It is advantageous to characterize the sieves by their chemical composition.
This is due to the low level of element "M" present in some of the hybrid elemental APO molecular sieves produced to date (thereby determining the exact interaction between metal "M", aluminum and phosphorus). It is difficult to confirm the nature). As a result, the AlO ₂ or PO ₂ tetrahedra are
Although it is thought that they are isomorphically substituted with O ₂ tetrahedra,
Suitably certain hybrid elemental APO compositions are characterized by their chemical composition by the molar ratio of the oxides.

Reactants Mixed element APO compositions can be prepared using a number of reactants. Reactants that can be used to prepare the mixed element APO composition include:

(A) Aluminum isopropoxide; (b) Pseudoboehmite or other aluminum oxide; (c) H ₃ PO ₄ : 85 wt% phosphoric acid aqueous solution; (d) Lithium phosphate or magnesium hydroxide or as described above. Suitable salt of other element “M” (e) TEAOH: 40 wt% aqueous solution of tetraethylammonium hydroxide; (f) TBAOH: 40 wt% aqueous solution of tetrabutylammonium hydroxide; (g) Pr ₂ NH: di- n- _{propylamine, (C 3 H 7) 2} NH; (h) Pr 3 N: tri -n- _{propylamine, (C 3 H 7) 3} N; (i) Quin: quinuclidine (C ₇ H ₁₃ N) (J) MQuin: methylquinuclidine hydroxide; (C ₇ H ₁₃ NCH ₃ OH); (k) C-hex: cyclohexylamine; (l) TMAOH: tetramethylammonium hydroxide; (m) TPAOH: water Tetrapropylammonium oxide; (n) DEEA: 2-diethylaminoethanol

 ─────────────────────────────────────────────────── ————————————————————————————————————— Inventor Edith Marie Frannigen Woodland Hills Road, White Plains, NY, USA 502

Claims (5)

[Claims] 1. A process for producing a crystalline non-zeolitic molecular sieve in a preformed body of alumina or silica-alumina, which comprises a liquid source containing a reactive source of phosphorus pentoxide and an organic templating agent. Contact the mixture,
A method comprising contacting for a time and at a temperature such that the body reacts with the liquid reaction mixture to form non-zeolitic molecular sieve crystals in the body. 2. A paste containing alumina or silica-alumina bodies, alumina or alumina and silica, and a liquid dispersion medium is prepared, the paste is extruded, and the extrudate is heated to produce at least one of the liquid dispersion mediums. The method according to claim 1, wherein the method is performed by excluding parts. 3. A method according to claim 1 wherein the alumina or silica-alumina body is in the form of particles of alumina or silica-alumina spray dried. 4. A process according to claim 1 wherein the reactive source of phosphorus pentoxide in the liquid reaction mixture comprises orthophosphoric acid or a salt thereof. 5. The liquid reaction mixture contains 0.75 to 1 mol of phosphorus.
A method according to claim 1 containing 1.25 moles of aluminum.