US 4,738,837 AGrant
Chromium-Aluminum-Phosphorus-Silicon-Oxide Molecular Sieve Compositions
Issue Date:1988-04-19
•71 Claims
•3 Drawing Sheets
Abstract
Molecular sieve compositions having three-dimensional microporous framework structures of CrO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 ; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is also disclosed.
Metadata
Assignee
- Union Carbide Corporation
Inventors
- Edith M. Flanigen
- Brent M. T. Lok
- Robert L. Patton
- Stephen T. Wilson
Application Information
Application Number:US 8521743
Filing Date:1986-04-15
Priority Date:1984-04-13
Art Unit:113
Classifications
IPC:
C01B 2545B01J 2714
Field of Search:
423502306;328 M;329;305214;208
Patent Drawings (3 sheets)
Description
FIELD OF THE INVENTION
The instant invention relates to a novel class of crystalline microporous molecular sieves and to the method of their preparation. The invention relates to novel chromium-aluminum-phosphorus-silicon-oxide molecular sieves containing framework tetrahedral oxide units of chromium, aluminum, phosphorus and silicon. These compositions may be prepared hydrothermally from gels containing reactive compounds of chromium, aluminum, phosphorus and silicon capable of forming framework tetrahedral oxides, and preferably at least one organic templating agent which functions in part to determine the course of the crystallization mechanism and the structure of the crystalline product.
BACKGROUND OF THE INVENTION
Molecular sieves of the crystalline aluminosilicate zeolite type are well known in the art and now comprise over 150 species of both naturally occurring and synthetic compositions. In general the crystalline zeolites are formed from corner-sharing AlO.sub.2 and SiO.sub.2 tetrahedra and are characterized by having pore openings of uniform dimensions, having a significant ion-exchange capacity and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without displacing any atoms which make up the permanent crystal structure.
Other crystalline microporous compositions which are not zeolitic, i.e. do not contain AlO.sub.2 tetrahedra as essential framework constituents, but which exhibit the ion-exchange and/or adsorption characteristics of the zeolites are also known. Metal organosilicates which are said to possess ion-exchange properties, have uniform pores and are capable of reversibly adsorbing molecules having molecular diameters of about 6 .ANG. or less, are reported in U.S. Pat. No. 3,941,871 issued Mar. 2, 1976 to Dwyer et al. A pure silica polymorph, silicalite, having molecular sieving properties and a neutral framework containing neither cations nor cation sites is disclosed in U.S. Pat. No. 4,061,724 issued Dec. 6, 1977 to R. W. Grose et al.
A recently reported class of microporous compositions and the first framework oxide molecular sieves synthesized without silica, are the crystalline aluminophosphate compositions disclosed in U.S. Pat. No. 4,310,440 issued Jan. 12, 1982 to Wilson et al. These materials are formed from AlO.sub.2 and PO.sub.2 tetrahedra and have electrovalently neutral frameworks as in the case of silica polymorphs. Unlike the silica molecular sieve, silicalite, which is hydrophobic due to the absence of extra-structural cations, the aluminophosphate molecular sieves are moderately hydrophilic, apparently due to the difference in electronegativity between aluminum and phosphorus. Their intracrystalline pore volumes and pore diameters are comparable to those known for zeolites and silica molecular sieves.
In U.S. Pat. No. 4,440,871, there is described a novel class of silicon-substituted aluminophosphates which are both microporous and crystalline. The materials have a three dimensional crystal framework of PO.sub.2.sup.+, AlO.sub.2.sup.- and SiO.sub.2 tetrahedral units and, exclusive of any alkali metal or calcium which may optionally be present, an as-synthesized empirical chemical composition on an anhydrous basis of:
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Si.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3, the maximum value in each case depending upon the molecular dimensions of the templating agent and the available void volume of the pore system of the particular silicoaluminophosphate species involved; and "x", "y", and "z" represent the mole fractions of silicon, aluminum and phosphorus, respectively, present as tetrahedral oxides. The minimum value for each of "x", "y", and "z" is 0.01 and preferably 0.02. The maximum value for "x" is 0.98; for "y" is 0.60; and for "z" is 0.52. These silicoaluminophosphates exhibit several physical and chemical properties which are characteristic of aluminosilicate zeolites and aluminophosphates.
In U.S. Pat. No. 4,500,651, there is described a novel class of titanium-containing molecular sieves whose chemical composition in the as-synthesized and anhydrous form is represented by the unit empirical formula:
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Ti.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of between zero and about 5.0; and "x", "y" and "z" represent the mole fractions of titanium, aluminum and phosphorus, respectively, present as tetrahedral oxides.
In U.S. Pat. No. 4,567,029, there is described a novel class of crystalline metal aluminophosphates having three-dimensional microporous framework structures of MO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (M.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; "M" represents at least one metal of the group magnesium, manganese, zinc and cobalt; "x", "y", and "z" represent the mole fractions of the metal "M", aluminum and phosphorus, respectively, present as tetrahedral oxides.
In U.S. Pat. No. 4,544,143, there is described a novel class of crystalline ferroaluminophosphates having a three-dimensional microporous framework structure of FeO.sub.2, AlO.sub.2 and PO.sub.2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (Fe.sub.x Al.sub.y P.sub.z)O.sub.2 and has a value of from zero to 0.3; and "x", "y" and "z" represent the mole fractions of the iron, aluminum and phosphorus, respectively, present as tetrahedral oxides.
The instant invention relates to new molecular sieve compositions comprising framework tetrahedral units of CrO.sub.2.sup.n, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2, where "n" is -1, 0 or +1.
DESCRIPTION OF THE FIGURES
FIG. 1 is a ternary diagram wherein parameters relating to the instant compositions are set forth as mole fractions.
FIG. 2 is a ternary diagram wherein parameters relating to preferred compositions are set forth as mole fractions.
FIG. 3 is a ternary diagram wherein parameters relating to the reaction mixtures employed in the preparation of the compositions of this invention are set forth as mole fractions.
SUMMARY OF THE INVENTION
The instant invention relates to a new class of chromium-aluminum-phosphorus-silicon-oxide molecular sieves having a crystal framework structure of CrO.sub.2.sup.n, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units, where "n" is -1, 0 or +1. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use of adsorbents and catalysts. The members of this novel class of compositions have crystal framework structures of CrO.sub.2.sup.n, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units, where "n" has a value of -1, 0 or +1, and have an empirical chemical composition on an anhydrous basis expressed by the formula:
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. These molecular sieve compositions comprise crystalline molecular sieves having a three-dimensional microporous framework structure of CrO.sub.2.sup.n, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units, where "n" has a value of -1, 0 or +1.
The instant molecular sieve compositions are characterized in several ways as distinct from heretofore known molecular sieves, including the aforementioned ternary compositions. The instant molecular sieves are characterized by the enhanced thermal stability of certain species and by the existence of species heretofore unknown for binary and ternary molecular sieves.
The molecular sieves of the instant invention will be generally referred to by the acronym "CAPSO" to designate the framework of CrO.sub.2.sup.n, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units, where "n" has a value of -1, 0 or +1. Actual class members will be identified by denominating the various structural species which make up the CAPSO class by assigning a number and, accordingly, are identified as "CAPSO-i" wherein "i" is an integer. This designation is an arbitrary one and is not intended to denote structural relationship to another material(s) which may also be characterized by a numbering system.
DETAILED DESCRIPTION OF THE INVENTION
The instant invention relates to a new class of chromium-aluminum-phosphorus-silicon-oxide molecular sieves comprising a crystal framework structure of CrO.sub.2.sup.n, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral oxide units, where "n" has a value of -1, 0 or +1. These new molecular sieves exhibit ion-exchange, adsorption and catalytic properties and, accordingly, find wide use as adsorbents and catalysts.
The CAPSO molecular sieves of the instant invention comprise a framework structure of CrO.sub.2.sup.n, AlO.sub.2.sup.-, PO.sub.2.sup.+ and SiO.sub.2 tetrahedral units, where "n" has a value of -1, 0 or +1, having an empirical chemical composition on an anhydrous basis expressed by the formula:
wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3, but is preferably not greater than about 0.15; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides. The mole fractions "w", "x", "y" and "z" are generally defined as being within the pentagonal compositional area defined by points A, B, C, D and E of the ternary diagram of FIG. 1. Points A, B, C, D and E of FIG. 1 have the following values for "w", "x", "y", and "z":
In a preferred subclass of the CAPSO molecular sieves the values of "w", "x", "y" and "z" in the above formula are within the hexagonal compositional area defined by the points a, b, c, d, e and f of the ternary diagram which is FIG. 2 of the drawings, said points a, b, c, d, e and f representing the following values for "w", "x", "y" and "z":
An especially preferred subclass of the CAPSO molecular sieves are those in which the values of "x" and "y" in the above formula are each within the range of about 0.4 to 0.5, and (z+w) is in the range of 0.02 to 0.15.
The CAPSOs of this invention are useful as adsorbents, catalysts, ion-exchangers, and the like in much the same fashion as aluminosilicates have been employed heretofore, although their chemical and physical properties are not necessarily similar to those observed for aluminosilicates.
CAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of chromium, aluminum, phosphorus and silicon, preferably an organic templating, i.e., structure-directing agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene and heated, preferably under autogenous pressure, at a temperature between 50.degree. C. and 250.degree. C., and preferably between 100.degree. C. and 200.degree. C., until crystals of the CAPSO product are obtained, usually for a period of from several hours to several weeks. Effective crystallization times of from about 2 hours to about 30 days are generally employed with from about 4 hours to about 20 days, and preferably about 1 to about 10 days, being typically employed. The product is recovered by any convenient method such as centrifugation or filtration.
In synthesizing the CAPSO compositions of the instant invention, it is preferred to employ a reaction mixture composition expressed in terms of the molar ratios as follows:
wherein "R" is an organic templating agent; "a" is the amount of organic templating agent "R" and has a value of from zero to about 6 and is preferably an effective amount within the range of greater than zero (0) to about 6, and desirably not greater than 0.5; "b" has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably not greater than about 20; and "r", "s", "t" and "u" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01. In a preferred embodiment the reaction mixture is selected such that the mole fractions "r", "s", "t" and "u" are generally defined as being within the pentagonal compositional area defined by points F, G, H, I and J of the ternary diagram of FIG. 3. Points F, G, H, I and J of FIG. 3 have the following values for "r", "s", "t" and "u":
Especially preferred reaction mixtures are those containing from about 0.3 to 0.5 total moles of chromium and silicon, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorus.
In the foregoing expression of the reaction composition, the reactants are normalized with respect to the total of "r", "s", "t" and "u" such that (r+s+t+u)=1.00 mole, whereas in the examples the reaction mixtures are expressed in terms of molar oxide ratios normalized to the moles of Al.sub.2 O.sub.3 and/or P.sub.2 O.sub.5. This latter form is readily converted to the former form by routine calculations by dividing the number of moles of each component (including the template and water) by the total number of moles of chromium, aluminum, phosphorus and silicon which results in normalized mole fractions based on total moles of the aforementioned components.
In forming reaction mixtures from which the instant molecular sieves are formed the organic templating agent can be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates. In general these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony, preferably nitrogen or phosphorus and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred compounds for use as templating agents are the amines, quanternary phosphonium and quaternary ammonium compounds, the latter two being represented generally by the formula R.sub.4 X.sup.+ wherein "X" is phosphorus or nitrogen and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C.sub.14 H.sub.32 N.sub.2)(OH).sub.2 ].sub.x wherein "x" has a value of at least 2 are also suitably employed. The mono-, di- and tri-amines are advantageously utilized, either alone or in combination with a quaternary ammonium compound or other templating compound. Mixtures of two or more templating agents can either produce mixtures of the desired CAPSOs or the more strongly directing templating species may control the course of the reaction with the other templating species serving primarily to establish the pH conditions of the reaction gel. Representative templating agents include tetramethylammonium; tetraethylammonium; tetrapropylammonium; and tetrabutylammonium ions; tetrapentylammonium ions; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N'-dimethylpiperazine; 1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,2) octane ion; di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Not every templating agent will direct the formation of every species of CAPSO, i.e., a single templating agent can, with proper manipulation of the reaction conditions, direct the formation of several CAPSO compositions, and a given CAPSO composition can be produced using several different templating agents.
The reactive phosphorus source is preferably phosphoric acid, but organic phosphates such as triethyl phosphate have been found satisfactory, and so also have crystalline or amorphous aluminophosphates such as the AlPO.sub.4 composition of U.S. Pat. No. 4,310,440. Organo-phosphorus compounds, such as tetrabutylphosphonium bromide, do not, apparently, serve as reactive sources of phosphorus, but these compounds do function as templating agents. Conventional phosphorus salts, such as sodium metaphosphate, may be used, at least in part, as the phosphorus source, but are not preferred.
Almost any reactive silicon source may be employed such that SiO.sub.2 tetrahedral units are formed in situ. The reactive silicon source may be silica in the form of a silica sol, may be a fumed silica or may be other conventional sources of silica used in zeolite synthesis such as reactive solid amorphous precipitated silicas, silica gel, alkoxides of silicon, tetraalkyl orthosilicates (for example, tetraethyl orthosilicate), silicic acid, alkali metal silicates and the like.
The preferred aluminum source is either an aluminum alkoxide, such as aluminum isopropoxide, or pseudoboehmite. The crystalline or amorphous aluminophosphates which are a suitable source of phosphorus are, of course, also suitable sources of aluminum. Other sources of aluminum used in zeolite synthesis, such as gibbsite, sodium aluminate and aluminum trichloride, can be employed but are not preferred.
The reactive source of chromium can be introduced into the reaction system in any form which permits the formation in situ of a reactive form of chromium, i.e., reactive to form the framework tetrahedral oxide unit of chromium. Compounds of chromium which may be employed include oxides, alkoxides, hydroxides, chlorides, bromides, iodides, sulfates, nitrates, carboxylates (e.g., acetates) and the like. Especially preferred sources of chromium are chromium acetate and chromium acetate hydroxide.
While not essential to the synthesis of CAPSO compositions, stirring or other moderate agitation of the reaction mixture and/or seeding the reaction mixture with seed crystals of either the CAPSO species to be produced or a topologically similar aluminophosphate, aluminosilicate or molecular sieve composition, facilitates the crystallization procedure.
After crystallization the CAPSO product may be isolated and advantageously washed with water and dried in air. The as-synthesized CAPSO generally contains within its internal pore system at least one form of the templating agent employed in its formation. Most commonly the organic moiety derived from an organic template is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction system. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular CAPSO species. As a general rule the templating agent, and hence the occluded organic species, is too large to move freely through the pore system of the CAPSO product and must be removed by calcining the CAPSO at temperatures of 200.degree. C. to 700.degree. C., and preferably 350.degree. C. to 600.degree. C., to thermally degrade the organic species. In a few instances the pores of the CAPSO product are sufficiently large to permit transport of the templating agent, particularly if the latter is a small molecule, and accordingly complete or partial removal thereof can be accomplished by conventional desorption procedures such as are carried out in the case of zeolites. It will be understood that the term "as-synthesized" as used herein does not include the condition of the CAPSO phase wherein the organic moiety occupying the intracrystalline pore system as a result of the hydrothermal crystalline process has been reduced by post-synthesis treatment such that the value of "m" in the composition formula:
has a value of less than 0.02. The other symbols of the formula are as defined hereinabove. In those preparations in which an alkoxide is employed as the source of chromium, aluminum, phosphorus and/or silicon, the corresponding alcohol is necessarily present in the reaction mixture since it is a hydrolysis product of the alkoxide. It has not been determined whether this alcohol participates in the synthesis process as a templating agent. For the purposes of this application, however, this alcohol is arbitratrily omitted from the class of templating agents, even if it is present in the as-synthesized CAPSO material.
Since the present CAPSO compositions are formed from CrO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units which, respectively, have a net charge of "n", -1, +1 and 0, where "n" has a value of -1, 0 or +1, the matter of cation exchangeability is considerably more complicated than in the case of zeolitic molecular sieves in which, ideally, there is a stoichiometric relationship between AlO.sub.2.sup.- tetrahedra and charge-balancing cations. In the instant compositions, an AlO.sub.2.sup.- tetrahedron can be balanced electrically either by association with a PO.sub.2.sup.+ tetrahedron or a simple cation such as an alkali metal cation, a proton (H.sup.+), a cation of chromium present in the reaction mixture, or an organic cation derived from the templating agent. Similarly, a CrO.sub.2.sup.n tetrahedron, where "n" is -1 or +1, can be balanced electrically by association with PO.sub.2.sup.+ tetrahedra, a cation or anion of chromium present in the reaction mixture, a simple cation or anion such as an alkali metal cation, a proton (H.sup.+), organic cations or anions derived from the templating agent, or other divalent or polyvalent metal cations or anions introduced from an extraneous source. It has also been postulated that non-adjacent AlO.sub.2.sup.- and PO.sub.2.sup.+ tetrahedral pairs can be balanced by Na.sup.+ and OH-- respectively [Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, DC (1971)].
The CAPSO compositions of the present invention may exhibit cation-exchange capacity when analyzed using ion-exchange techniques heretofore employed with zeolitic aluminosilicates and have pore diameters which are inherent in the lattice structure of each secies and which are at least about 3 .ANG. in diameter. Ion exchange of CAPSO compositions is ordinarily possible only after the organic moiety present as a result of synthesis has been removed from the pore system. Dehydration to remove water present in the as-synthesized CAPSO compositions can usually be accomplished, to some degree at least, in the usual manner without removal of the organic moiety, but the absence of the organic species greatly facilitates adsorption and desorption procedures. The CAPSO materials will have various degrees of hydrothermal and thermal stability, some being quite remarkable in this regard, and will function as molecular sieve adsorbents and hydrocarbon conversion catalysts or catalyst bases.
In preparing the CAPSO composition it is preferred to use a stainless steel reaction vessel lined with an inert plastic material, e.g., polytetrafluoroethylene, to avoid contamination of the reaction mixture. In general, the final reaction mixture from which each CAPSO composition is crystallized is prepared by forming mixtures of less than all of the reagents and thereafter incorporating into these mixtures additional reagents either singly or in the form of other intermediate mixtures of two or more reagents. In some instances the reagents admixed retain their identity in the intermediate mixture and in other cases some or all of the reagents are involved in chemical reactions to produce new reagents. The term "mixture" is applied in both cases. Further, it is preferred that the intermediate mixtures as well as the final reaction mixtures be stirred until substantially homogeneous.
X-ray patterns of reaction products are obtained by X-ray analysis, using standard X-ray powder diffraction techniques. The radiation source is a high-intensity, copper target, X-ray tube operated at 50 Kv and 40 ma. The diffraction pattern from the copper K-alpha radiation and graphite monochromator is suitably recorded by an X-ray spectrometer scintillation counter, pulse height analyzer and strip chart recorder. Flat compressed powder samples are scanned at 2.degree. (2 theta) per minute, using a two second time constant. Interplanar spacings (d) in Angstrom units are obtained from the position of the diffraction peaks expressed as 20.theta. where .theta. is the Bragg angle as observed on the strip chart. Intensities were determined from the heights of diffraction peaks after subtracting background, "I.sub.o " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.
Alternatively, the X-ray patterns are obtained from the copper K-alpha radiation by use of computer based techniques using Siemens type K-805 X-ray sources and Siemens D-500 X-ray powder diffractometers available from Siemens Corporation, Cherry Hill, N.J., with appropriate computer interface.
As will be understood by those skilled in the art, the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination, can impose an uncertainty of about .+-.0.4.degree. (denotes plus or minus 0.4) on each reported value of 2 theta. This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 theta values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art. In some of the X-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations vs, s, m, w and vw which represent very strong, strong, medium, weak and very weak, respectively.
In certain instances hereinafter in the illustrative examples, the purity of a synthesized product may be assessed with reference to its X-ray powder diffraction pattern. Thus, for example, if a sample is stated to be pure, it is intended only that the X-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.
The molecular sieves of the instant invention may be characterized by their X-ray powder diffraction patterns and such may have one of the X-ray patterns set forth in the following Tables A through W, wherein said X-ray patterns are for the as-synthesized form unless otherwise noted. In most cases, the pattern of the corresponding calcined form will also fall within the relevant table. However, in some cases the removal of the occluded templating agent which occurs during calcination will be accompanied by sufficient relaxation of the lattice to shift some of the lines slightly outside the ranges specified in the relevant table. In a small number of cases, calcination appears to cause more substantial distortion in the crystal lattice, and hence, more significant changes in the X-ray powder diffraction pattern.
The exact nature of the CAPSO molecular sieves is not entirely understood at present, although all are believed to contain CrO.sub.2 tetrahedra in the three-dimensional microporous crystal framework structure. The low level of chromium present in some of the instant molecular sieves makes it difficult to ascertain the exact nature of the interactions among chromium, aluminum, phosphorus and silicon. As a result, although it is believed that CrO.sub.2 tetrahedra are substituted isomorphously for AlO.sub.2 or PO.sub.2 tetrahedra, it is appropriate to characterize certain CAPSO compositions by reference to their chemical compositions in terms of the molar ratios of oxides, as has been done in some of the examples below.
The following examples are provided to further illustrate the invention and are not intended to be limiting thereof:
EXAMPLE 1
(Preparation of CAPSO-5)
(a) CAPSO-5 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
where "TPA" denotes tripropylamine and "q" denotes the oxidation state of chromium.
The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time to produce CAPSO-5 product. Solids are recovered by filtration, washed with water and dried in air at room temperature.
The CAPSO-5 product's chemical analysis shows the CAPSO-5 product contains chromium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
The X-ray powder diffraction pattern of a CAPSO-5 product is characterized by the following data:
(b) The X-ray powder diffraction pattern for a calcined CAPSO-5 is also characterized by the X-ray pattern of part (a).
(c) When the calcined CAPSO-5 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350.degree. C. in a vacuum. The following data are used in the adsorption studies:
The pore diameter of CAPSO-5 is greater than about 6.2 .ANG..
EXAMPLE 2
(Preparation of CAPSO-11)
(a) A solution was formed by combining 23.1 grams of 85 wt. percent orthophosphoric acid (H.sub.3 PO.sub.4) with 40.3 grams of water. This solution was added to 35.8 grams of aluminum isopropoxide (Al(OC.sub.3 H.sub.7).sub.3), and to the resultant mixture were added 12.1 grams of an aqueous silica sol containing 30.1 wt. percent SiO.sub.2, and the resultant mixture stirred until homogeneous. A second solution was prepared by dissolving 2.1 grams of chromium acetate hydroxide (Cr.sub.3 (OH).sub.2 (CH.sub.3 COO).sub.7) in 38.0 grams of water, and this second solution was added to the homogeneous mixture. Finally, there were added to the mixture 10.1 grams of di-n-propylamine (DPA), and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:
This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 150.degree. C. under autogenous pressure for 168 hours. The solid reaction product (which was determined by the analyses described below to be mainly CAPSO-11) was recovered by centrifugation, washed with water and dried in air at ambient temperature.
A sample of this solid reaction product was analyzed and the following chemical analysis obtained:
The above chemical analysis corresponds to a product composition in molar oxide ratios of:
which corresponds to an empirical chemical formula, on an anhydrous basis, of:
so that the product contained chromium, aluminum, silicon and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
Scanning electron microscopy of the solid product showed the dominant morphology to be aggregates of submicron particles which appeared to be CAPSO-11 crystallites. Electron microprobe spot analysis of these aggregates indicated the following approximate composition:
thus indicating that the product contained chromium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
The X-ray powder diffraction pattern of the major product, as synthesized, was characterized by the data in the following Table BA:
A portion of the solid reaction product was calcined in air at 500.degree. C. for 1.5 hours. The X-ray powder diffraction pattern of the product, as calcined, was characterized by the data in the following Table BB:
(b) A sample of the calcined CAPSO-11 produced above was utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus. Before being used in the adsorption tests, the sample was activated at 350.degree. C. in a vacuum overnight. The following data were generated in the adsorption studies:
From the above data, the pore size of the calcined product was determined to be greater that about 4.3 .ANG., as shown by the adsorption of n-hexane (kinetic diameter of 4.3 .ANG.), but less than or about 6.2 .ANG., as shown by the pressure dependent adsorption of neopentane (kinetic diameter of 6.2 .ANG.).
The as-synthesized specimen of CAPSO-11 prepared above, and other as-synthesized specimens of CAPSO-11 prepared in a similar manner, all had similar X-ray powder diffraction patterns. The following general Table BC summarizes the X-ray powder diffraction lines which were obtained from the various as-synthesized specimens of CAPSO-11; the least intense lines were not obtained from every specimen.
EXAMPLE 3
(Preparation of CAPSO-17)
(a) CAPSO-17 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
where "QN" denotes quinuclidine and "q" denotes the oxidation state of chromium.
The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time to produce CAPSO-17 product. Solids are then recovered by filtration, washed with water and dried in air at room temperature.
The CAPSO-17 product's chemical analysis shows the CAPSO-17 product contains chromium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
The X-ray powder diffraction pattern of a CAPSO-17 product is characterized by the following data:
(b) The X-ray powder diffraction pattern for a calcined CAPSO-17 is also characterized by the X-ray pattern of part (a).
(c) When the calcined CAPSO-17 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350.degree. C. in a vacuum. The following data are used in the adsorption studies:
The pore diameter of CAPSO-17 is about 4.3 .ANG..
EXAMPLE 4
(Preparation of CAPSO-31)
(a) CAPSO-31 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
where "DPA" denotes di-n-propylamine and "q" denotes the oxidation state of chromium.
The reaction mixture is seeded with crystals of AlPO.sub.4 --(U.S. Pat. No. 4,310,440) and digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time to produce CAPSO-31 product. Solids are then recovered by filtration, washed with water and dried in air at room temperature.
The CAPSO-31 product's chemical analysis shows the CAPSO-31 product contains chromium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
The X-ray powder diffraction pattern of a CAPSO-31 product is characterized by the following data:
(b) The X-ray powder diffraction pattern for a calcined CAPSO-31 is also characterized by the X-ray pattern of part (a).
(c) When the calcined CAPSO-31 of part (b) is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350.degree. C. in a vacuum. The following data are used in the adsorption studies:
The pore diameter of CAPSO-31 is greater than about 6.2 .ANG..
EXAMPLE 5
(Preparation of CAPSO-34)
An initial mixture was formed by adding 35.8 grams of water to 35.9 grams of aluminum isopropoxide (Al(OC.sub.3 H.sub.7).sub.3), and to the resultant mixture were added 12.2 grams of an aqueous silica sol containing 30.1 wt. percent SiO.sub.2, and the resultant mixture was stirred until homogeneous. A second solution was prepared by dissolving 4.9 grams of chromium acetate (Cr(CH.sub.3 COO).sub.3) in 20.6 grams of water and then adding 23.2 grams of 85 wt. percent orthophosphoric acid, and this second solution was added to the homogeneous mixture. Finally, there were added to the mixture 36.5 grams of 40 wt. percent aqueous tetraethylammonium hydroxide (TEAOH), and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:
An aliquot of this final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 150.degree. C. under autogenous pressure for 168 hours. The solid reaction product (which was determined by the analyses described below to be mainly CAPSO-34) was recovered by filtration, washed with water and dried in air at ambient temperature.
A sample of this solid reaction product was analyzed and the following chemical analysis obtained:
The above chemical analysis corresponds to a product composition in molar oxide ratios of:
which corresponds to an empirical chemical formula, on an anhydrous basis, of:
so that the product contained chromium, aluminum, silicon and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
Scanning electron microscopy of the solid product showed numerous crystals having the morphology expected for CAPSO-34. Electron microprobe spot analysis of these crystals indicated the following approximate composition:
thus indicating that the product contained chromium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
On X-ray analysis, the solid reaction product was found to be a mixture of two crystalline components. The X-ray powder diffraction pattern of the major component, CAPSO-34, as synthesized, was characterized by the data in the following Table LA:
A further aliquot of the reaction mixture prepared above was digested in the same manner as previously described, except that the digestion was conducted at 200.degree. C. for 48 hours, and the solid reaction product was recovered in the same manner as previously described. The X-ray powder diffraction pattern of this solid reaction product showed it to be similar to the reaction product described above with two crystalline components, one of which was CAPSO-34 having an X-ray powder diffraction pattern essentially identical to that set forth in Table LA above.
The specimens of CAPSO-34 prepared above, and other specimens of CAPSO-34 prepared in a similar manner, all had similar X-ray powder diffraction patterns. The following general Table LB summarizes the X-ray powder diffraction lines which were obtained from the various specimens of CAPSO-34; the least intense lines were not obtained from every specimen.
EXAMPLE 6
(Preparation of CAPSO-44)
(a) CAPSO-44 is prepared from a reaction mixture having a composition, expressed in terms of the molar oxide ratios of the components of the reaction mixture, of:
where "CHA" denotes cyclohexylamine and "q" denotes the oxidation state of chromium.
The reaction mixture is digested by placing the reaction mixture in a sealed stainless steel pressure vessel and heating it at an effective temperature and for an effective time to produce CAPSO-44 product. Solids are then recovered by filtration, washed with water and dried in air at room temperature.
The CAPSO-44 product's chemical analysis shows the CAPSO-44 product contains chromium, aluminum, phosphorus and silicon in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
The X-ray powder diffraction pattern of a CAPSO-44 product is characterized by the following data:
(b) When the calcined CAPSO-44 is utilized in adsorption capacity studies using a standard McBain-Bakr gravimetric adsorption apparatus the measurements are made on a sample after activation at 350.degree. C. in a vacuum. The following data are used in the adsorption studies:
The pore diameter of CAPSO-44 is about 4.3 .ANG..
EXAMPLE 7
(Preparation of CAPSO-16)
A solution was formed by combining 23.1 grams of 85 wt. percent orthophosphoric acid (H.sub.3 PO.sub.4) with 30.0 grams of water. This solution was added to 35.7 grams of aluminum isopropoxide (Al(OC.sub.3 H.sub.7).sub.3), and to the resultant mixture were added 12.1 grams of an aqueous silica sol containing 30.1 wt. percent SiO.sub.2, and the resultant mixture stirred until homogeneous. A second solution was prepared by dissolving 2.1 grams of chromium acetate hydroxide (Cr.sub.3 (OH).sub.2 (CH.sub.3 COO).sub.7) in 30.0 grams of water, and this second solution was added to the homogeneous mixture. Finally, there were added to the mixture a solution of 11.2 grams of quinuclidine (QN) in 18.4 grams of water, and the resultant mixture was stirred until homogeneous. The composition of the final reaction mixture thus produced, expressed in terms of the molar oxide ratios of the components of the reaction mixture, was:
This final reaction mixture was digested by sealing it in a stainless steel pressure vessel lined with polytetrafluoroethylene and heating it in an oven at 200.degree. C. under autogenous pressure for 168 hours. The solid reaction product (which was determined by the analyses described below to be mainly CAPSO-16) was recovered by centrifugation, washed with water and dried in air at ambient temperature.
A sample of this solid reaction product was analyzed and the following chemical analysis obtained:
The above chemical analysis corresponds to a product composition in molar oxide ratios of:
which corresponds to an empirical chemical formula, on an anhydrous basis, of:
so that the product contained chromium, aluminum, silicon and phosphorus in amounts within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1.
Scanning electron microscopy of the solid product showed the dominant morphology to be aggregates of submicron particles which appeared to be CAPSO-16 crystallites. Electron microprobe spot analysis of these aggregates confirmed the presence of chromium, aluminum, phosphorus and silicon in amounts consistent with the above chemical analysis.
The X-ray powder diffraction pattern of the major product, as synthesized, was characterized by the data in the following Table DA:
A portion of the solid reaction product was calcined in air at 600.degree. C. for 1.5 hours. The X-ray powder diffraction pattern of the product, as calcined, was essentially identical to that set forth in Table DA above.
The specimens of CAPSO-16 prepared above, and other specimens of CAPSO-16 prepared in a similar manner, all had similar X-ray powder diffraction patterns. The following general Table DB summarizes the X-ray powder diffraction lines which were obtained from the various specimens of CAPSO-16; the least intense lines were not obtained from every specimen.
PROCESS APPLICATIONS
The CAPSO compositions of the present invention are, in general, hydrophilic and adsorb water preferentially over common hydrocarbon molecules such as paraffins, olefins and aromatic species, e.g., benzene, xylenes and cumene. Thus the present molecular sieve compositions as a class are useful as desiccants in such adsorption separation/purification processes as natural gas drying, cracked gas drying. Water is also preferentially adsorbed over the so-called permanent gases such as carbon dioxide, nitrogen, oxygen and hydrogen. These CAPSOs are therefore suitably employed in the drying of reformer hydrogen streams and in the drying of oxygen, nitrogen or air prior to liquifaction.
The present CAPSO compositions also exhibit novel surface selectivity characteristics which render them useful as catalyst or catalyst bases in a number of hydrocarbon conversion and oxidative combustion reactions. They can be impregnated or otherwise loaded with catalytically active metals by methods well known in the art (for example ion exchange) and used, for example, in fabricating catalyst compositions having silica or alumina bases. Of the general class, those species having pores larger than about 4A are preferred for catalytic applications.
Among the hydrocarbon conversion reactions catalyzed by CAPSO compositions are cracking, hydrocracking, alkylation for both the aromatic and isoparaffin types, isomerization including xylene isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydrodecyclization and dehydrocyclization.
Using CAPSO catalyst compositions which contain a hydrogenation promoter such as platinum or palladium, heavy petroleum residual stocks, cyclic stocks and other hydrocrackable charge stocks, can be hydrocracked at temperatures in the range of 400.degree. F. to 825.degree. F. (204.degree. C. to 441.degree. C.) using molar ratios of hydrogen to hydrocarbon in the range of between 2 and 80, pressures between 10 and 3500 p.s.i.g. (0.171 to 24.23 MPa.), and a liquid hourly space velocity (LHSV) of from 0.1 to 20, preferably 1.0 to 10.
The CAPSO catalyst compositions employed in hydrocracking are also suitable for use in reforming processes in which the hydrocarbon feedstocks contact the catalyst at temperatures of from about 700.degree. F. to 1000.degree. F. (371.degree. C. to 538` C.), hydrogen pressures of from 100 to 500 p.s.i.g. (0.791 to 3.448 MPa.), LHSV values in the range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in the range of 1 to 20, preferably between 4 and 12.
These same catalysts, i.e. those containing hydrogenation promoters, are also useful in hydroisomerization processes in which feedstocks such as normal paraffins are converted to saturated branched chain isomers. Hydroisomerization is carried out at a temperature of from about 200.degree. F. to 600.degree. F. (93.degree. C. to 316.degree. C.), preferably 300.degree. F. to 550.degree. F. (149.degree. C. to 288.degree. C.) with an LHSV value of from about 0.2 to 1.0. Hydrogen (H) is supplied to the reactor in admixture with the hydrocarbon (Hc) feedstock in molar proportions (H/Hc) of between 1 and 5.
At somewhat higher temperatures, i.e. from about 650.degree. F. to 1000.degree. F. (343.degree. C. to 538.degree. C.), preferably 850.degree. F. to 950.degree. F. (454.degree. C. to 510.degree. C.) and usually at somewhat lower pressures within the range of about 15 to 50 p.s.i.g. (205 to 446 KPa.), the same catalyst compositions are used to hydroisomerize normal paraffins. Preferably the paraffin feedstock comprises normal paraffins having a carbon number range of C.sub.7 -C.sub.20. Contact times between the feedstock and the catalyst is generally relatively short to avoid undesirable side reactions such as olefin polymerization and paraffin cracking. LHSV values in the range of 0.1 to 10, preferably 1.0 to 6.0 are suitable.
The unique crystal structure of the present CAPSO catalysts and their availability in a form totally void of alkali metal content favor their use in the conversion of alkylaromatic compounds, particularly the catalytic disproportionation of toluene, ethylene, trimethyl benzenes, tetramethyl benzenes and the like. In the disproportionation process, isomerization and transalkylation can also occur. Group VIII noble metal adjuvants alone or in conjunction with Group VI-B metals such as tungsten, moybdenum and chromium are preferably included in the catalyst composition in amounts of from about 3 to 15 weight-% of the overall composition. Extraneous hydrogen can, but need not, be present in the reaction zone which is maintained at a temperature of from about 400.degree. to 750.degree. F. (204.degree. to 399.degree. C.), pressures in the range of 100 to 2000 p.s.i.g. (0.791 to 13.89 MPa.) and LHSV values in the range of 0.1 to 15.
Catalytic cracking processes are preferably carried out with CAPSO compositions using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc., with gasoline being the principal desired product. Temperature conditions of 850.degree. to 1100.degree. F. (454.degree. to 593.degree. C.), LHSV values of 0.5 to 10 and pressure conditions of from about 0 to 50 p.s.i.g. (101 to 446 KPa.) are suitable.
Dehydrocyclization reactions employing paraffinic hydrocarbon feedstocks, preferably normal paraffins having more than 6 carbon atoms, to form benzene, xylenes, toluene and the like are carried out using essentially the same reaction conditions as for catalytic cracking. For these reactions it is preferred to use the CAPSO catalyst in conjunction with a Group VIII non-noble metal cation such as cobalt and nickel.
In catalytic dealkylation wherein it is desired to cleave paraffinic side chains from aromatic nuclei without substantially hydrogenating the ring structure, relatively high temperatures in the range of about 800.degree.-1000.degree. F. (427.degree.-538.degree. C.) are employed at moderate hydrogen pressures of about 300-1000 p.s.i.g. (2.17-6.895 MPa.), other conditions being similar to those described above for catalytic hydrocracking. Preferred catalysts are of the same type described above in connection with catalytic dehydrocyclization. Particularly desirable dealkylation reactions contemplated herein include the conversion of methylnaphthalene to naphthalene and toluene and/or xylenes to benzene.
In catalytic hydrofining, the primary objective is to promote the selective hydrodecomposition of organic sulfur and/or nitrogen compounds in the feed, without substantially affecting hydrocarbon molecules therein. For this purpose it is preferred to employ the same general conditions described above for catalytic hydrocracking, and catalysts of the same general nature described in connection with dehydrocyclization operations. Feedstocks include gasoline fractions, kerosenes, jet fuel fractions, diesel fractions, light and heavy gas oils, deasphalted crude oil residua and the like. Any of these may contain up to about 5 weight-percent of sulfur and up to about 3 weight-percent of nitrogen.
Similar conditions can be employed to effect hydrofining, i.e., denitrogenation and desulfurization, of hydrocarbon feeds containing substantial proportions of organonitrogen and organosulfur compounds. It is generally recognized that the presence of substantial amounts of such constituents markedly inhibits the activity of hydrocracking catalysts. Consequently, it is necessary to operate at more extreme conditions when it is desired to obtain the same degree of hydrocracking conversion per pass on a relatively nitrogeneous feed than with a feed containing less organonitrogen compounds. Consequently, the conditions under which denitrogenation, desulfurization and/or hydrocracking can be most expeditiously accomplished in any given situation are necessarily determined in view of the characteristics of the feedstocks, in particular the concentration of organonitrogen compounds in the feedstock. As a result of the effect of organonitrogen compounds on the hydrocracking activity of these compositions it is not at all unlikely that the conditions most suitable for denitrogenation of a given feedstock having a relatively high organonitrogen content with minimal hydrocracking, e.g., less than 20 volume percent of fresh feed per pass, might be the same as those preferred for hydrocracking another feedstock having a lower concentration of hydrocracking inhibiting constituents e.g., organonitrogen compounds. Consequently, it has become the practice in this art to establish the conditions under which a certain feed is to be contacted on the basis of preliminary screening tests with the specific catalyst and feedstock.
Isomerization reactions are carried out under conditions similar to those described above for reforming, using somewhat more acidic catalysts. Olefins are preferably isomerized at temperatures of 500.degree.-900.degree. F. (260.degree.-482.degree. C.), while paraffins, naphthenes and alkyl aromatics are isomerized at temperatures of 700.degree.-1000.degree. F. (371.degree.-538.degree. C.). Particularly desirable isomerization reactions contemplated herein include the conversion of n-heptene and/or n-octane to isoheptanes, iso-octanes, butane to iso-butane, methylcyclopentane to cyclohexane, meta-xylene and/or ortho-xylene to paraxylene, 1-butene to 2-butene and/or isobutene, n-hexane to isohexene, cyclohexene to methylcyclopentene etc. The preferred form of the catalyst is a combination of the CAPSO with polyvalent metal compounds (such as sulfides) of metals of Group II-A, Group II-B and rare earth metals. For alkylation and dealkylation processes the CAPSO compositions havng pores of at least 5 .ANG. are preferred. When employed for dealkylation of alkyl aromatics, the temperature is usually at least 350.degree. F. (177.degree. C.) and ranges up to a temperature at which substantial cracking of the feedstock or conversion products occurs, generally up to about 700.degree. F. (371.degree. C.). The temperature is preferably at least 450.degree. F. (232.degree. C.) and not greater than the critical temperature of the compound undergoing dealkylation. Pressure conditions are applied to retain at least the aromatic feed in the liquid state. For alkylation the temperature can be as low as 250.degree. F. (121.degree. C.) but is preferably at least 350.degree. F. (177.degree. C.). In the alkylation of benzene, toluene and xylene, the preferred alkylating agents are olefins such as ethylene and propylene.
The following example is provided to further illustrate the use of the CAPSOs of the invention in one of the processes discussed above, but is not intended to be limitative of the possible uses of the CAPSOs.
EXAMPLE 8
(Cracking tests on CAPSO-11)
The n-butane cracking activity of the calcined CAPSO-11 prepared in Example 2 above was tested in a bench-scale apparatus, in which the reactor was a cylindrical quartz tube 254 mm. in length and 10.3 mm. in internal diameter. This reactor was loaded with the calcined CAPSO-11, which was in the form of particles having sizes of 20-40 U.S. mesh. The mixture was then activated in situ by heating from ambient temperature to 500.degree. C. under helium, and then holding the sample at 500.degree. C. in air for 1 hour; the weight of the activated mixture in the reactor was 1.61 grams.
A feedstock comprising a helium/n-butane mixture containing 2 mole percent of n-butane was then passed through the reactor at a rate of 50 mL/min. The reactor effluent was analyzed after 10 minutes of on-stream operation using conventional gas chromatography techniques. The resultant data showed a pseudo-first-order rate constant (k.sub.A) of 2.2.
Claims
We claim:
1. Crystalline molecular sieves comprising three-dimensional microporous framework structures of CrO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of set forth in one of the following Tables A to H and J to W: ______________________________________ (CAPSO-5) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-7.7 12.28-11.48 m-vs 19.4-19.9 4.58-4.46 w-m 20.85-21.3 4.26-4.17 w-vs 22.1-22.6 4.02-3.93 m-vs 25.6-26.1 3.480-3.414 vw-m ______________________________________ ______________________________________ (CAPSO-11) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.8-8.2 11.19-10.85 m-s 9.0-9.8 9.83-9.03 vw-vs 12.8-13.6 6.92-6.51 vw-m 19.9-20.5 4.46-4.33 m-s 20.8-21.8 4.27-4.08 m-vs 22.0-22.4 4.04-3.94 m-vs 22.4-23.1 3.94-3.85 vw-vs (doublet) 23.1-23.5 3.85-3.79 w-vs ______________________________________ ______________________________________ (CAPSO-14) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.6-8.9 10.3-9.93 vs 13.0 6.81 w 21.9-22.2 4.06-4.00 w 25.4 3.51 w 27.5 3.24 w 29.7 3.01 w ______________________________________ ______________________________________ (CAPSO-16) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 11.3-11.6 7.83-7.63 w-vs 18.55-18.9 4.78-4.70 vw-m 21.85-22.3 4.07-3.98 m-vs 22.8-23.3 3.900-3.818 w-m 26.4-27.3 3.370-3.267 w-m 29.6-30.0 3.018-2.978 w-m ______________________________________ ______________________________________ (CAPSO-17) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.70-7.75 11.5-11.4 vs 13.4 6.61 s-vs 15.5-15.55 5.72-5.70 s 19.65-19.7 4.52-4.51 w-s 20.5-20.6 4.33-4.31 vs 31.8-32.0 2.812-2.797 w-s ______________________________________ ______________________________________ (CAPSO-18) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.6-9.65 9.21-9.16 vs 15.5-15.55 5.72-5.70 m 16.9-17.1 5.25-5.19 m 20.15-20.25 4.41-4.39 m 20.95-21.05 4.24-4.22 m 31.8-32.5 2.814-2.755 m ______________________________________ ______________________________________ (CAPSO-20) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.8-14.2 6.42-6.23 m-vs 19.6-20.15 6.53-4.41 m 24.1-24.8 3.695-3.603 m-vs 27.9-28.6 3.198-3.121 w 31.3-32.05 2.861-2.791 w 34.35-35.0 2.610-2.601 w-m ______________________________________ ______________________________________ (CAPSO-31) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.4-9.5 10.53-9.31 w-s 20.2-20.4 4.40-4.35 m 22.0-22.1 4.040-4.022 m 22.5-22.7 3.952-3.92 vs 31.6-31.8 2.831-2.814 w-m ______________________________________ ______________________________________ (CAPSO-33) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.25-9.55 9.56-9.26 w-m 12.5-12.9 7.08-6.86 vs 16.9-17.3 5.25-5.13 w-m 20.45-20.9 4.34-4.25 w-m 23.85-24.25 3.73-3.67 w-m 26.05-26.35 3.42-3.38 w-m 27.3-27.6 3.27-3.23 vs ______________________________________ *as-synthesized form ______________________________________ (CAPSO-33) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.15-13.4 6.73-6.61 vs 18.05-18.35 4.91-4.83 m 18.4-18.6 4.82-4.77 m 26.55-26.7 3.36-3.34 m 32.0-32.1 2.80-2.79 m ______________________________________ *calcined form ______________________________________ (CAPSO-34) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 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 24.8-25.4 3.59-3.507 vw-m 30.0-30.9 2.979-2.894 vw-m ______________________________________ ______________________________________ (CAPSO-35) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 10.6-11.1 8.35-7.97 vw-vs 13.1-13.7 6.76-6.46 vw-vs 17.0-17.6 5.22-5.04 w-s 20.6-21.25 4.31-4.18 vw-m 21.6-22.3 4.11-3.99 m-vs 28.1-28.8 3.175-3.100 vw-m ______________________________________ ______________________________________ (CAPSO-36) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.45-8.0 11.14-11.05 vs 8.1-8.3 10.91-10.65 w-m 16.3-16.6 5.44-5.34 w-m 18.9-19.4 4.70-4.57 w-m 20.7-21.0 4.29-4.23 w-m ______________________________________ ______________________________________ (CAPSO-37) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 6.1-6.3 14.49-14.03 vs 15.5-15.7 5.72-5.64 w-m 18.5-18.8 4.80-4.72 w-m 23.5-23.7 3.79-3.75 w-m 26.9-27.1 3.31-3.29 w-m ______________________________________ ______________________________________ (CAPSO-39) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m 13.1-13.5 6.76-6.56 m 17.8-18.4 4.98-4.82 w-m 20.8-21.3 4.27-4.17 m-vs 22.2-22.85 4.00-3.892 m-vs 26.4-27.05 3.376-3.296 w-m ______________________________________ ______________________________________ (CAPSO-40) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.5-7.7 11.79-11.48 vw-m 8.0-8.1 11.05-10.94 s-vs 12.4-12.5 7.14-7.08 w-vs 13.6-13.8 6.51-6.42 m-s 14.0-14.1 6.33-6.28 w-m 27.8-28.0 3.209-3.187 w-m ______________________________________ ______________________________________ (CAPSO-41) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 m 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.44 w-m ______________________________________ ______________________________________ (CAPSO-42) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.15-7.4 12.36-11.95 m-vs 12.5-12.7 7.08-6.97 m-s 21.75-21.9 4.09-4.06 m-s 24.1-24.25 3.69-3.67 vs 27.25-27.4 3.273-3.255 s 30.05-30.25 2.974-2.955 m-s ______________________________________ ______________________________________ (CAPSO-43) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 12.3-12.95 7.20-6.83 m-vs 16.8-17.45 5.28-5.09 vw-w 21.45-21.85 4.145-4.071 m-vs 27.1-27.85 3.291-3.232 w-vs 32.4-33.2 2.763-2.699 vw-m ______________________________________ ______________________________________ (CAPSO-44) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m-vs 15.9-16.3 5.57-5.44 vw-m 20.5-21.0 4.33-4.23 m-vs 24.3-25.1 3.66-3.548 w-m 30.5-31.1 2.931-2.876 vw-m ______________________________________ ______________________________________ (CAPSO-46) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-8.1 12.28-10.92 vs 12.9-13.6 6.86-6.51 vw 21.2-22.2 4.19-4.501 vw-m 22.5-23.45 3.95-3.793 vw-m 26.6-27.9 3.351-3.198 vw-m ______________________________________ ______________________________________ (CAPSO-47) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.6 9.41-9.21 vs 12.8-13.1 6.92-6.76 vw-m 16.0-16.3 5.54-5.44 vw-m 20.5-21.0 4.31-4.23 m-vs 24.6-25.3 3.613-3.526 vw-m 30.6-31.1 2.921-2.876 vw-m ______________________________________
2. Crystalline molecular sieves according to claim 1 wherein the mole fractions of chromium, aluminum, phosphorus and silicon present as tetrahedral oxides are within the hexagonal compositional area defined by points a, b, c, d, e and f of FIG. 2.
3. Crystalline molecular sieves according to claim 2 wherein the mole fractions of aluminum and phosphorus are each in the range of about 0.4 to about 0.5 and the mole fractions of chromium and silicon together total about 0.02 to about 0.15.
7. The crystalline molecular sieves of claim 5 wherein the X-ray powder diffraction pattern set forth in Table B contains at least the d-spacings set forth in one of the following Tables BA and BB: ______________________________________ (CAPSO-11) Relative Intensity 2.theta. d(.ANG.) 100 .times. I/I.sub.o ______________________________________ 8.1 10.88 24 9.5 9.34 37 13.2 6.70 12 15.7 5.64 23 16.3 5.44 4 19.0 4.66 4 20.5 4.34 29 21.1 4.22 100 22.2 4.01 37 22.6 3.94 38 22.8 3.91 37 23.2 3.83 46 24.8 3.59 6 26.4 3.38 12 26.6 3.34 12 28.4 3.15 3 28.7 3.11 10 29.1 3.07 4 29.6 3.02 5 31.6 2.834 7 32.9 2.719 11 34.2 2.618 7 36.6 2.458 3 37.6 2.391 7 37.9 2.374 9 39.4 2.284 2 42.9 2.110 5 44.8 2.024 3 45.1 2.012 4 48.8 1.865 2 50.8 1.800 3 54.8 1.675 3 ______________________________________ ______________________________________ (CAPSO-11) Relative Intensity 2.theta. d(.ANG.) 100 .times. I/I.sub.o ______________________________________ 8.0 10.97 19 9.8 9.01 41 11.8 7.52 4 12.8 6.91 21 13.6 6.48 5 14.6 6.04 5 16.1 5.50 54 19.5 4.55 11 19.9 4.46 21 20.8 4.28 5 21.9 4.06 100 22.2 4.00 38 22.5 3.95 42 23.5 3.78 47 24.0 3.70 13 24.3 3.66 8 25.8 3.45 15 26.8 3.33 9 27.3 3.26 10 27.7 3.22 13 28.5 3.13 5 29.8 3.00 24 30.5 2.934 11 31.8 2.811 4 32.7 2.740 18 34.1 2.632 7 35.6 2.524 8 35.8 2.510 7 37.3 2.409 6 38.8 2.318 11 41.1 2.196 6 49.2 1.851 6 49.7 1.835 6 55.9 1.644 5 ______________________________________
10. The crystalline molecular sieves of claim 9 wherein the X-ray powder diffraction pattern set forth in Table D contains at least the d-spacings set forth in the following Table DA: ______________________________________ (CAPSO-16) Relative Intensity 2.theta. d(.ANG.) 100 .times. I/I.sub.o ______________________________________ 11.4 7.72 67 18.8 4.72 57 22.0 4.03 100 23.0 3.86 9 26.7 3.34 22 29.1 3.07 10 29.9 2.991 25 32.8 2.730 4 34.8 2.579 4 38.0 2.365 9 39.9 2.258 4 40.1 2.248 3 44.4 2.039 3 48.6 1.874 6 52.5 1.744 2 54.8 1.674 2. ______________________________________
18. The crystalline molecular sieves of claim 17 wherein the X-ray powder diffraction pattern set forth in Table L contains at least the d-spacings set forth in the following Table LA: ______________________________________ (CAPSO-34) Relative Intensity 2.theta. d(.ANG.) 100 .times. I/I.sub.o ______________________________________ 9.5 9.26 100 12.9 6.86 6 14.1 6.27 8 16.0 5.52 38 18.0 4.91 9 20.6 4.31 58 22.5 3.95 3 23.2 3.84 3 25.3 3.52 11 26.0 3.43 14 27.6 3.23 2 28.4 3.14 2 29.6 3.02 3 30.6 2.922 17 31.3 2.856 13 32.4 2.762 2 34.3 2.614 4 36.4 2.467 2 39.7 2.272 2 43.5 2.082 3 47.9 1.899 2 49.1 1.856 4 51.2 1.786 3 53.2 1.721 2. ______________________________________
30. Process for preparing crystalline molecular sieves of having three-dimensional microporous framework structures of CrO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to H and J to W: ______________________________________ (CAPSO-5) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-7.7 12.28-11.48 m-vs 19.4-19.9 4.58-4.46 w-m 20.85-21.3 4.26-4.17 w-vs 22.1-22.6 4.02-3.93 m-vs 25.6-26.1 3.480-3.414 vw-m ______________________________________ ______________________________________ (CAPSO-11) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.8-8.2 11.19-10.85 m-s 9.0-9.8 9.83-9.03 vw-vs 12.8-13.6 6.92-6.51 vw-m 19.9-20.5 4.46-4.33 m-s 20.8-21.8 4.27-4.08 m-vs 22.0-22.4 4.04-3.94 m-vs 22.4-23.1 3.94-3.85 vw-vs (doublet) 23.1-23.5 3.85-3.79 w-vs ______________________________________ ______________________________________ (CAPSO-14) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.6-8.9 10.3-9.93 vs 13.0 6.81 w 21.9-22.2 4.06-4.00 w 25.4 3.51 w 27.5 3.24 w 29.7 3.01 w ______________________________________ ______________________________________ (CAPSO-16) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 11.3-11.6 7.83-7.63 w-vs 18.55-18.9 4.78-4.70 vw-m 21.85-22.3 4.07-3.98 m-vs 22.8-23.3 3.900-3.818 w-m 26.4-27.3 3.370-3.267 w-m 29.6-30.0 3.018-2.978 w-m ______________________________________ ______________________________________ (CAPSO-17) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.70-7.75 11.5-11.4 vs 13.4 6.61 s-vs 15.5-15.55 5.72-5.70 s 19.65-19.7 4.52-4.51 w-s 20.5-20.6 4.33-4.31 vs 31.8-32.0 2.812-2.797 w-s ______________________________________ ______________________________________ (CAPSO-18) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.6-9.65 9.21-9.16 vs 15.5-15.55 5.72-5.70 m 16.9-17.1 5.25-5.19 m 20.15-20.25 4.41-4.39 m 20.95-21.05 4.24-4.22 m 31.8-32.5 2.814-2.755 m ______________________________________ ______________________________________ (CAPSO-20) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.8-14.2 6.42-6.23 m-vs 19.6-20.15 6.53-4.41 m 24.1-24.8 3.695-3.603 m-vs 27.9-28.6 3.198-3.121 w 31.3-32.05 2.861-2.791 w 34.35-35.0 2.610-2.601 w-m ______________________________________ ______________________________________ (CAPSO-31) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.4-9.5 10.53-9.31 w-s 20.2-20.4 4.40-4.35 m 22.0-22.1 4.040-4.022 m 22.5-22.7 3.952-3.92 vs 31.6-31.8 2.831-2.814 w-m ______________________________________ ______________________________________ (CAPSO-33) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.25-9.55 9.56-9.26 w-m 12.5-12.9 7.08-6.86 vs 16.9-17.3 5.25-5.13 w-m 20.45-20.9 4.34-4.25 w-m 23.85-24.25 3.73-3.67 w-m 26.05-26.35 3.42-3.38 w-m 27.3-27.6 3.27-3.23 vs ______________________________________ *as-synthesized form ______________________________________ (CAPSO-33) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.15-13.4 6.73-6.61 vs 18.05-18.35 4.91-4.83 m 18.4-18.6 4.82-4.77 m 26.55-26.7 3.36-3.34 m 32.0-32.1 2.80-2.79 m ______________________________________ *calcined form ______________________________________ (CAPSO-34) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 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 24.8-25.4 3.59-3.507 vw-m 30.0-30.9 2.979-2.894 vw-m ______________________________________ ______________________________________ (CAPSO-35) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 10.6-11.1 8.35-7.97 vw-vs 13.1-13.7 6.76-6.46 vw-vs 17.0-17.6 5.22-5.04 w-s 20.6-21.25 4.31-4.18 vw-m 21.6-22.3 4.11-3.99 m-vs 28.1-28.8 3.175-3.100 vw-m ______________________________________ ______________________________________ (CAPSO-36) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.45-8.0 11.14-11.05 vs 8.1-8.3 10.91-10.65 w-m 16.3-16.6 5.44-5.34 w-m 18.9-19.4 4.70-4.57 w-m 20.7-21.0 4.29-4.23 w-m ______________________________________ ______________________________________ (CAPSO-37) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 6.1-6.3 14.49-14.03 vs 15.5-15.7 5.72-5.64 w-m 18.5-18.8 4.80-4.72 w-m 23.5-23.7 3.79-3.75 w-m 26.9-27.1 3.31-3.29 w-m ______________________________________ ______________________________________ (CAPSO-39) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m 13.1-13.5 6.76-6.56 m 17.8-18.4 4.98-4.82 w-m 20.8-21.3 4.27-4.17 m-vs 22.2-22.85 4.00-3.892 m-vs 26.4-27.05 3.376-3.296 w-m ______________________________________ ______________________________________ (CAPSO-40) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.5-7.7 11.79-11.48 vw-m 8.0-8.1 11.05-10.94 s-vs 12.4-12.5 7.14-7.08 w-vs 13.6-13.8 6.51-6.42 m-s 14.0-14.1 6.33-6.28 w-m 27.8-28.0 3.209-3.187 w-m ______________________________________ ______________________________________ (CAPSO-41) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 m 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.44 w-m ______________________________________ ______________________________________ (CAPSO-42) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.15-7.4 12.36-11.95 m-vs 12.5-12.7 7.08-6.97 m-s 21.75-21.9 4.09-4.06 m-s 24.1-24.25 3.69-3.67 vs 27.25-27.4 3.273-3.255 s 30.05-30.25 2.974-2.955 m-s ______________________________________ ______________________________________ (CAPSO-43) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 12.3-12.95 7.20-6.83 m-vs 16.8-17.45 5.28-5.09 vw-w 21.45-21.85 4.145-4.071 m-vs 27.1-27.85 3.291-3.232 w-vs 32.4-33.2 2.763-2.699 vw-m ______________________________________ ______________________________________ (CAPSO-44) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m-vs 15.9-16.3 5.57-5.44 vw-m 20.5-21.0 4.33-4.23 m-vs 24.3-25.1 3.66-3.548 w-m 30.5-31.1 2.931-2.876 vw-m ______________________________________ ______________________________________ (CAPSO-46) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-8.1 12.28-10.92 vs 12.9-13.6 6.86-6.51 vw 21.2-22.2 4.19-4.501 vw-m 22.5-23.45 3.95-3.793 vw-m 26.6-27.9 3.351-3.198 vw-m ______________________________________ ______________________________________ (CAPSO-47) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.6 9.41-9.21 vs 12.8-13.1 6.92-6.76 vw- m 16.0-16.3 5.54-5.44 vw- m 20.5-21.0 4.31-4.23 - vs 24.6-25.3 3.613-3.526 vw- m 30.6-31.1 2.921-2.876 vw- m ______________________________________ the process comprising providing a reaction mixture composition at an effective temperature and for an effective time sufficient to produce said molecular sieves, said reaction mixture composition being expressed in terms of molar oxide ratios as follows: wherein "R" is an organic templating agent; "a" is the amount of "R" and is an effective amount greater than zero to about 6; "b" has a value of from zero to about 500; and "r", "s", "t" and "u" represent the mole fractions, respectively, of chromium, aluminum, phosphorus and silicon in the (Cr.sub.r Al.sub.s P.sub.t Si.sub.u)O.sub.2 constituent, and each has a value of at least 0.01.
31. Process according to claim 30 wherein "r", "s", "t" and "u" are within the area defined by points F, G, H, I and J of FIG. 3.
32. Process according to claim 30 wherein "a" is not greater than about 0.5.
33. Process according to claim 30 wherein "b" is from about 2 to about 500.
34. Process according to claim 33 wherein "b" is from about 2 to about 300.
35. Process according to claim 34 wherein "b" is not greater than about 20.
36. Process according to claim 30 wherein the reaction mixture composition contains from about 0.3 to about 0.5 total moles of chromium and silicon per mole of phosphorus.
37. Process according to claim 30 wherein the reaction mixture composition contains from about 0.75 to about 1.25 moles of aluminum per mole of phosphorus.
38. Process according to claim 30 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.
39. Process according to claim 30 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group consisting of pseudo-boehmite and aluminum alkoxides.
40. Process according to claim 39 wherein the aluminum alkoxide is aluminum isopropoxide.
41. Process according to claim 30 wherein the silicon source is silica.
42. Process according to claim 30 wherein the silicon source is a tetraalkyl orthosilicate.
43. Process according to claim 30 wherein the source of chromium is selected from the group consisting of oxides, hydroxides, alkoxides, chlorides, bromides, iodides, sulfates, nitrates, carboxylates and mixtures thereof.
44. Process according to claim 43 wherein the source of chromium is chromium acetate or chromium acetate hydroxide.
45. Process according to claim 30 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula: wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
46. Process according to claim 30 wherein the organic templating agent is an amine.
47. Process according to claim 30 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion; tetraethylammonium ion; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diaziabicyclo-(2,2,2)octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammonium ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt wherein x is a value of a least 2.
48. Molecular sieve prepared by calcining, at a temperature sufficiently high to remove at least some of any organic templating agent present in the intracrystalline pore system, a crystalline molecular sieve having three-dimensional microporous framework structures of CrO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1, said crystalline molecular sieves having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of set forth in one of the following Tables A to H and J to W: ______________________________________ (CAPSO-5) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-7.7 12.28-11.48 m-vs 19.4-19.9 4.58-4.46 w-m 20.85-21.3 4.26-4.17 w-vs 22.1-22.6 4.02-3.93 m-vs 25.6-26.1 3.480-3.414 vw-m ______________________________________ ______________________________________ (CAPSO-11) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.8-8.2 11.19-10.85 m-s 9.0-9.8 9.83-9.03 vw-vs 12.8-13.6 6.92-6.51 vw-m 19.9-20.5 4.46-4.33 m-s 20.8-21.8 4.27-4.08 m-vs 22.0-22.4 4.04-3.94 m-vs 22.4-23.1 3.94-3.85 vw-vs (doublet) 23.1-23.5 3.85-3.79 w-vs ______________________________________ ______________________________________ (CAPSO-14) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.6-8.9 10.3-9.93 vs 13.0 6.81 w 21.9-22.2 4.06-4.00 w 25.4 3.51 w 27.5 3.24 w 29.7 3.01 w ______________________________________ ______________________________________ (CAPSO-16) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 11.3-11.6 7.83-7.63 w-vs 18.55-18.9 4.78-4.70 vw-m 21.85-22.3 4.07-3.98 m-vs 22.8-23.3 3.900-3.818 w-m 26.4-27.3 3.370-3.267 w-m 29.6-30.0 3.018-2.978 w-m ______________________________________ ______________________________________ (CAPSO-17) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.70-7.75 11.5-11.4 vs 13.4 6.61 s-vs 15.5-15.55 5.72-5.70 s 19.65-19.7 4.52-4.51 w-s 20.5-20.6 4.33-4.31 vs 31.8-32.0 2.812-2.797 w-s ______________________________________ ______________________________________ (CAPSO-18) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.6-9.65 9.21-9.16 vs 15.5-15.55 5.72-5.70 m 16.9-17.1 5.25-5.19 m 20.15-20.25 4.41-4.39 m 20.95-21.05 4.24-4.22 m 31.8-32.5 2.814-2.755 m ______________________________________ ______________________________________ (CAPSO-20) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.8-14.2 6.42-6.23 m-vs 19.6-20.15 6.53-4.41 m 24.1-24.8 3.695-3.603 m-vs 27.9-28.6 3.198-3.121 w 31.3-32.05 2.861-2.791 w 34.35-35.0 2.610-2.601 w-m ______________________________________ ______________________________________ (CAPSO-31) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 8.4-9.5 10.53-9.31 w-s 20.2-20.4 4.40-4.35 m 22.0-22.1 4.040-4.022 m 22.5-22.7 3.952-3.92 vs 31.6-31.8 2.831-2.814 w-m ______________________________________ ______________________________________ (CAPSO-33) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.25-9.55 9.56-9.26 w-m 12.5-12.9 7.08-6.86 vs 16.9-17.3 5.25-5.13 w-m 20.45-20.9 4.34-4.25 w-m 23.85-24.25 3.73-3.67 w-m 26.05-26.35 3.42-3.38 w-m 27.3-27.6 3.27-3.23 vs ______________________________________ *as-synthesized form ______________________________________ (CAPSO-33) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.15-13.4 6.73-6.61 vs 18.05-18.35 4.91-4.83 m 18.4-18.6 4.82-4.77 m 26.55-26.7 3.36-3.34 m 32.0-32.1 2.80-2.79 m ______________________________________ *calcined form ______________________________________ (CAPSO-34) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 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 24.8-25.4 3.59-3.507 vw-m 30.0-30.9 2.979-2.894 vw-m ______________________________________ ______________________________________ (CAPSO-35) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 10.6-11.1 8.35-7.97 vw-vs 13.1-13.7 6.76-6.46 vw-vs 17.0-17.6 5.22-5.04 w-s 20.6-21.25 4.31-4.18 vw-m 21.6-22.3 4.11-3.99 m-vs 28.1-28.8 3.175-3.100 vw-m ______________________________________ ______________________________________ (CAPSO-36) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.45-8.0 11.14-11.05 vs 8.1-8.3 10.91-10.65 w-m 16.3-16.6 5.44-5.34 w-m 18.9-19.4 4.70-4.57 w-m 20.7-21.0 4.29-4.23 w-m ______________________________________ ______________________________________ (CAPSO-37) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 6.1-6.3 14.49-14.03 vs 15.5-15.7 5.72-5.64 w-m 18.5-18.8 4.80-4.72 w-m 23.5-23.7 3.79-3.75 w-m 26.9-27.1 3.31-3.29 w-m ______________________________________ ______________________________________ (CAPSO-39) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m 13.1-13.5 6.76-6.56 m 17.8-18.4 4.98-4.82 w-m 20.8-21.3 4.27-4.17 m-vs 22.2-22.85 4.00-3.892 m-vs 26.4-27.05 3.376-3.296 w-m ______________________________________ ______________________________________ (CAPSO-40) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.5-7.7 11.79-11.48 vw-m 8.0-8.1 11.05-10.94 s-vs 12.4-12.5 7.14-7.08 w-vs 13.6-13.8 6.51-6.42 m-s 14.0-14.1 6.33-6.28 w-m 27.8-28.0 3.209-3.187 w-m ______________________________________ ______________________________________ (CAPSO-41) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 13.6-13.8 6.51-6.42 w-m 20.5-20.6 4.33-4.31 w-m 21.1-21.3 4.21-4.17 vs 22.1-22.3 4.02-3.99 m-s 22.8-23.0 3.90-3.86 m 23.1-23.4 3.82-3.80 w-m 25.5-25.9 3.493-3.44 w-m ______________________________________ ______________________________________ (CAPSO-42) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.15-7.4 12.36-11.95 m-vs 12.5-12.7 7.08-6.97 m-s 21.75-21.9 4.09-4.06 m-s 24.1-24.25 3.69-3.67 vs 27.25-27.4 3.273-3.255 s 30.05-30.25 2.974-2.955 m-s ______________________________________ ______________________________________ (CAPSO-43) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 12.3-12.95 7.20-6.83 m-vs 16.8-17.45 5.28-5.09 vw-w 21.45-21.85 4.145-4.071 m-vs 27.1-27.85 3.291-3.232 w-vs 32.4-33.2 2.763-2.699 vw-m ______________________________________ ______________________________________ (CAPSO-44) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.2-9.6 9.61-9.21 m-vs 15.9-16.3 5.57-5.44 vw-m 20.5-21.0 4.33-4.23 m-vs 24.3-25.1 3.66-3.548 w-m 30.5-31.1 2.931-2.876 vw-m ______________________________________ ______________________________________ (CAPSO-46) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 7.2-8.1 12.28-10.92 vs 12.9-13.6 6.86-6.51 vw 21.2-22.2 4.19-4.501 vw-m 22.5-23.45 3.95-3.793 vw-m 26.6-27.9 3.351-3.198 vw-m ______________________________________ ______________________________________ (CAPSO-47) 2.theta. d(.ANG.) Relative Intensity ______________________________________ 9.4-9.6 9.41-9.21 vs 12.8-13.1 6.92-6.76 vw-m 16.0-16.3 5.54-5.44 vw-m 20.5-21.0 4.31-4.23 m-vs 24.6-25.3 3.613-3.526 vw-m 30.6-31.1 2.921-2.876 vw-m ______________________________________
49. Crystalline molecular sieves comprising three-dimensional microporous framework structures of CrO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1.
50. Crystalline molecular sieves according to claim 49 wherein the mole fractions of chromium, aluminum, phosphorus and silicon present as tetrahedral oxides are within the hexagonal compositional area defined by points a, b, c, d, e and f of FIG. 2.
51. Crystalline molecular sieves according to claim 50 wherein the mole fractions of aluminum and phosphorus are each in the range of about 0.4 to about 0.5 and the mole fractions of chromium and silicon together total about 0.02 to about 0.15.
53. Process for preparing crystalline molecular sieves having three-dimensional microporous framework structures of CrO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1, wherein the process comprises providing a reaction mixture composition at an effective temperature and for an effective time sufficient to produce said molecular sieves, said reaction mixture composition being expressed in terms of molar oxide ratios as follows: wherein "R" is an organic templating agent; "a" is the amount of "R" and is an effective amount greater than zero to about 6; "b" has a value of from zero to about 500; and "r", "s", "t" and "u" represent the mole fractions, respectively, of chromium, aluminum, phosphorus and silicon in the (Cr.sub.r Al.sub.s P.sub.t Si.sub.u)O.sub.2 constituent, and each has a value of at least 0.01.
54. Process according to claim 53 wherein "r", "s", "t" and "u" are within the area defined by points F, G, H, I and J of FIG. 3.
55. Process according to claim 53 wherein "a" is not greater than about 0.5.
56. Process according to claim 53 wherein "b" is from about 2 to about 500.
57. Process according to claim 56 wherein "b" is from about 2 to about 300.
58. Process according to claim 57 wherein "b" is not greater than about 20.
59. Process according to claim 53 wherein the reaction mixture composition contains from about 0.3 to about 0.5 total moles of chromium and silicon per mole of phosphorus.
60. Process according to claim 53 wherein the reaction mixture contains from about 0.75 to about 1.25 moles of aluminum per mole of phosphorus.
61. Process according to claim 53 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid.
62. Process according to claim 53 wherein the source of phosphorus in the reaction mixture is orthophosphoric acid and the source of aluminum is at least one compound selected from the group consisting of pesudo-boehmite and aluminum alkoxides.
63. Process according to claim 62 wherein the aluminum alkoxide is aluminum isopropoxide.
64. Process according to claim 53 wherein the silicon source is silica.
65. Process according to claim 53 wherein the silica source is a tetraalkyl orthosilicate.
66. Process according to claim 53 wherein the source of chromium is selected from the group consisting of oxides, hydroxides, alkoxides, chlorides, bromides, iodides, sulfates, nitrates, carboxylates and mixtures thereof.
67. Process according to claim 66 wherein the source of chromium is chromium acetate or chromium hydroxide.
68. Process according to claim 53 wherein the organic templating agent is a quaternary ammonium or quaternary phosphonium compound having the formula: wherein X is nitrogen or phosphorus and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
69. Process according to claim 67 wherein the organic templating agent is an amine.
70. Process according to claim 67 wherein the templating agent is selected from the group consisting of tetrapropylammonium ion; tetraethylammonium ion; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methyl pyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N-dimethylpiperazine; 1,4-diaziabicyclo-(2,2,2)octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine; 4-methylpridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; tetramethylammonium ion; tetrabutylammonium ion; tetrapentylammonium ion; di-n-butylamine; neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine; ethylenediamine; pyrrolidine; 2-imidazolidone; di-n-propylamine; and a polymeric quaternary ammonium salt wherein x has a value of at least 2.
71. Molecular sieves prepared by calcining, at a temperature sufficiently high to remove at least some of any organic templating agent present in the intracrystalline pore system, a crystalline molecular sieves having three-dimensional microporous framework structures of CrO.sub.2, AlO.sub.2, PO.sub.2 and SiO.sub.2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (Cr.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 and has a value of zero to about 0.3; and "w", "x", "y" and "z" represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D, and E of FIG. 1.
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