Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/08—Bridged systems

Definitions

• This invention relates to processes for the production of amines. More specifically, this invention relates to processes for preparing triethylenediamine and/or one or more cyclic or acyclic amines by contacting one or more amine starting materials with one or more molecular sieves. By proper choice of catalysts and/or reaction conditions, the processes of this invention can be varied to alter their selectivity to a number of differing and useful products, including triethylenediamine and substituted triethylenediamines.
• Triethylenediamine also referred to as 1,4-diazabicyclo[2.2.2] octane or DABCO, is an item of commerce which is used as a catalyst for -OH + OCN- reactions to form the urethane linkage in polyurethanes.
• Various processes for the production of triethylenediamine are known.
• triethylenediamine may be produced by the method disclosed in WO 87/03592, published June 18, 1987.
• triethylenediamine may be produced by bringing an amine compound having a specific amino group into contact with a crystalline metal silicate catalyst wherein the molar ratio of silicon dioxide (SiO 2 ) to an oxide of a trivalent metal (M 2 O 3 :M being a trivalent metal) is 12 or more.
• European Patent Application No. 0158319 discloses a method for preparing 1,4-diazabicyclo[2.2.2]octanes by contacting acyclic or heterocyclic amines with a high-silica zeolite having a silica to alumina ratio of at least 20 to 1.
• This invention relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting two or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the two or more amine starting materials with the one or more molecular sieves being effected under conditions effective to convert at least one of the amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
• molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves
• This invention also relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more modified molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
• modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves
• This invention further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more non-zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
• This invention yet further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more molecular sieves being effected in the presence of water or steam and under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
• molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves
• this invention relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting two or more amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the two or more amine starting materials with the one or more molecular sieves being effected under conditions effective to convert at least one of the amine starting, materials into triethylenediamine and/or one or more cyclic or acyclic amines.
• molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves
• this invention also relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more modified molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
• modified molecular sieves selected from (a) modified silica molecular sieves, (b) modified non-zeolitic molecular sieves, and (c) modified zeolitic molecular sieves
• this invention further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or more amine starting materials with one or more non-zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more non-zeolitic molecular sieves being effected under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
• this invention yet further relates in part to a process for preparing triethylenediamine and/or one or more cyclic or acyclic amines, which process comprises contacting one or mo-re amine starting materials with one or more molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves, the contacting of the one or more amine starting materials with the one or more molecular sieves being effected in the presence of water or steam and under conditions effective to convert one or more amine starting materials into triethylenediamine and/or one or more cyclic or acyclic amines.
• molecular sieves selected from (a) silica molecular sieves, (b) non-zeolitic molecular sieves, and (c) zeolitic molecular sieves
• cyclic and acyclic amines include, for example, triethylenediamine, substituted triethylenediamines, pyrazine, substituted pyraz.ines, pyridine, substituted pyridines, piperidine, substituted piperidines, piperazine, substituted piperazines, aminoethylethanolamine, diethanolamine, ethylendiamine, morpholine, substituted morpholines, alkyleneamines, alkanolamines, alkylamines, polyalkylene polyamines, allylamines and the like.
• the processes of the present invention are useful for the conversion of piperazine to triethylenediamine and/or one or more of pyrazine, substituted pyrazines including methyl/ethyl substituted pyrazines, substituted piperazines including N-ethylpiperazine,
• the products prepared by the processes of the present invention may include both acyclic and cyclic amines.
• the cyclic products may include both monocyclic materials, for example substituted piperazines, pyrazines and morpholines, and products containing more than one ring.
• the products can selectively include triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO).
• DABCO 1,4-diazabicyclo[2.2.2]octane
• the products can selectively include a mixture of 2-methyl-triethylenediamine or 2-methyl-1,4-diazabicyclo[2.2.2] octane (methyl DABCO) and triethylenediamine or 1,4-diazabicyclo[2.2.2]octane (DABCO).
• methyl DABCO 2-methyl-1,4-diazabicyclo[2.2.2] octane
• DABCO 1,4-diazabicyclo[2.2.2]octane
• Multiple methyl homologues of 2-methyl-triethylenediamine may also be produced by the processes of this invention.
• the preferred catalysts for the above conversions include Silicalite, a microporous form of silica described in U.S. Patent No. 4,061,724 issued December 6, 1977 to R.W. Grose et al., and Silicalite treated with phosphoric acid or phosphoric acid equivalents such as diammonium hydrogen phosphate as described hereinbelow.
• amine and optionally non-amine starting materials can be used in the processes of this invention.
• Illustrative amine starting materials include one or more, substituted or unsubstituted, cyclic or acyclic amines such as piperazine, monoethanolamine, alkanolamines, ethylenediamine, propylenediamine, butylenediamine, alkylenediamines, isopropan ⁇ lamine, diisopropanolamine, alkylamines, substituted piperazines, N-(2-hydroxyethyl)piperazine, N-(2-aminoethyl)piperazine, diethanolamine, triethanolamine, substituted morph ⁇ lines, morpholine, diethylenetriamine, triethylenetetraamime, higher polyalkylene polyamines and the like.
• substituted or unsubstituted, cyclic or acyclic amines such as piperazine, monoethanolamine, alkanolamines, ethylenediamine, propyl
• Illustrative non-amine starting materials which may be used in combination with amine starting materials include one or more diols such as ethylene glycol, propylene glycol and the like.
• a preferred embodiment of this invention involves co-feeding piperazine and ethylenediamine to selectively produce triethylenediamine at enhanced reaction rates.
• the molar ratio of amine and non-amine starting materials used in the processes of this invention can vary over a wide range. The preferred molar ratio of amine and non-amine starting material(s) depends not only on the product ratio desired but also on reaction conditions. Since the product ratio changes with changing conversion, the preferred molar ratio for any desired product mix will change with pressure or temperature or anything else that affects the conversion.
• Suitable molecular sieves for use in this invention include, for example, the silica molecular sieves, such as Silicalite (U.S. Patent No. 4,061,724), Silicalite II (D. M. Bibby, et al.. Nature, 1979, Vol. 280, pg. 664), and fluoride Silicalite (U.S. Patent No. 4,073,865).
• silica molecular sieves such as Silicalite (U.S. Patent No. 4,061,724), Silicalite II (D. M. Bibby, et al.. Nature, 1979, Vol. 280, pg. 664), and fluoride Silicalite (U.S. Patent No. 4,073,865).
• suitable molecular sieves for use in this invention include the non-zeolitic molecular sieves having an empirical chemical composition on an anhydrous basis expressed by the formula:
• Q represents at least one element present as a framework oxide unit “QO 2 n " with charge “n” where “n” may be -3, -2, -1, 0 or +1;
• 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
• Q w Al x P y Si z (Q w Al x P y Si z )O 2 and has a value from zero to about 0.3; and "w”, "x", “y” and “z” represent the mole fractions of QO 2 n , AlPO 2 -, PO 2 + , SiO 2 , respectively, present as framework oxide units.
• Q is characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms.
• Q has a cation electronegativity between about 125 kcal/gm-atom to about 310 kcal/gm-atom and "Q" is capable of forming stable Q-O-P, Q-O-Al or Q-O-Q bonds in crystalline three dimensional oxide structures having a "Q-O" bond dissociation energy greater than about 59 kcal/gm-atom at 298°K; and said mole fractions being within the limiting compositional values or points as follows: w is equal to 0 to 98 mole percent; y is equal to 1 to 99 mole percent; x is equal to 1 to 99 mole percent; and z is equal to 0 to 98 mole percent.
• the "Q” of . the “QAPSO” molecular sieves of formula (I) may be defined as representing at least one element capable of forming a framework tetrahedral oxide and may be one of the elements arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc.
• the invention contemplates combinations of the elements as representing Q, and to the extent such combinations are present in the structure of a QAPSO they may be present- in molar fractions of the Q component in the range of 1 to 99 percent thereof. It should be noted that Formula (I) contemplates the non-existence of Q and Si.
• the operative structure is that of AlPO 4 as discussed below. Where z has a positive value, then the operative structure is that of SAPO, discussed below.
• the term QAPSO does not perforce represent that the elements Q and S (actually Si) are present.
• the operative structure is that of the ELAPSO or ELAPO or MeAPO or MeAPSO molecular sieves, as herein discussed.
• molecular sieves of the QAPSO variety will be invented in which Q will be another element or elements, then it is the intention to embrace the same as a suitable molecular sieve for the practice of this invention.
• zeolitic molecular. sieves such as chabazite, faujasite, levynite, Linde Type A, gismondine, erionite, sodalite, Linde Type X and Y, analcime, gmelinite, harmontome, mordenite, epistilbite, heulandite, stilbite, edingtonite, mesolite, natrolite, scolecite, thomsonite, brewsterite, laumontite, phillipsite, ZSM-5 (U.S. Patent No. 3,702,886), ZSM-20 (U.S. Patent No.
• zeolitic molecular sieves employable in the practice of this invention are those reviewed by Flanigen in Pure & Applied Chemistry, Vol. 52. pp. 2191-2211, 1980, including their ion exchanged forms. Zeolite ion exchange is reviewed by D. W.
• Preferred molecular sieves for use in this invention have a crystalline structure related to the pentasil type.
• Silica molecular sieves e.g., Silicalite
• zeolitic molecular sieves e.g., Z5M-5
• Preferred molecular sieves for use in this invention may have a silicon: aluminum ratio of at least about 6:1, preferably 10:1 or 20:1, and more preferably 40:1 or 60:1 or even greater.
• Aluminum may be a desired component of the molecular sieves even at very low concentrations.
• Aluminum present as framework aluminum may be more desirable than non-framework aluminum.
• the molecular sieves typically contain within their internal pore systems at least one form of the organic templating agents used in their synthesis.
• the organic moiety is present, at least in part, as a charge-balancing cation, and indeed this is generally the case with as-synthesized molecular sieves prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular species of molecular sieve.
• the templating agent and hence the occluded organic species, is too large to move freely through the pore system of the molecular sieve and must be removed by calcining the molecular sieve in air at temperatures of 200° to 700°C, preferably about 350° to about 600°C, to thermally degrade the organic species.
• the pores of the molecular sieve 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 hydrotreating or chemical treatment such as solvent extraction, which will be familiar to those skilled in the molecular sieve art.
• the organic templating agent may be removed in situ by placing the molecular sieve still containing the organic templating agent in the reactor, so that the organic templating agent is removed under reaction conditions.
• the molecular sieves used in this invention offer an inherent limitation to the transformation of amine starting materials to various amine products.
• the amine molecule In order to react within the molecular sieve catalyst, the amine molecule should have (i) a kinetic diameter which is less than the limiting aperture of the molecular sieve pore in order to enter the catalyst or (ii) a transition state during the reaction which is not larger than the molecular sieve pore or cavity in order transform in the catalyst.
• the resulting amine products should have a kinetic diameter less than the limiting aperture of the molecular sieve pore in order to exit the catalyst.
• non-zeolitic molecular sieves or "NZMS” is defined in the instant invention to include the "SAPO" molecular sieves of U.S. Patent No. 4,440,871 and U.S.. Serial No. 575,745, filed January 31, 1984, "ELAPSO” molecular sieves as disclosed in U.S. Serial No. 600,312, filed April 13, 1984, and certain "AlPO 4 ", "MeAPO”, “FeAPO”, “TAPO” and “ELAPO” molecular sieves, as hereinafter described. Crystalline “AlPO 4 " aluminophosphates are disclosed in U.S. Patent No. 4,310,440 issued January 12, 1982, and in U.S. Serial No.
• crystalline metal aluminophosphates (MeAPOs where "Me” is Mg, Mn, Co and Zn) are disclosed in U.S. Patent No. 4,567,029, issued January 28, 1986; crystalline ferroaluminophosphates (FeAPOs) are disclosed in U.S. Patent No. 4,554,143, issued November 19, 1985; titanium aluminophosphates (TAPOs) are disclosed in U.S. Patent No. 4,500,651, issued February 19, 1985; certain non-zeolitic molecular sieves (“ELAPO”) are disclosed in EPC Patent Application 85104386.9 (Publication No.
• ELAPSO MOLECULAR SIEVES "ELAPSO” molecular sieves are described in copending U.S. Serial No. 600,312, filed April 13, 1984, (EPC Publication No. 0159,624, published October 30, 1985, incorporated herein by reference) as crystalline molecular sieves having three-dimensional microporous framework structures of ELO 2 , AlPO 2 , PO 2 , SiO 2 oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (EL w Al x P y Si z )O 2 and has a value of from zero to about 0.3
• EL represents at least one element capable of forming a three dimensional oxide framework, "EL” being characterized as an element having a mean "T-O" distance in tetrahedral oxide structures between about 1.51 Angstroms and about 2.06 Angstroms, "EL” having a cation electronegativity between about 125 Kcal/g-atom to about 310 Kca ⁇ /gm-atom and "EL” being capable of forming stable M-O-P, M-O-Al or M-O-M bonds in crystalline three dimensional oxide structures having a "M-O” bond dissociation energy greater than about 59 kcal/g-atom at 298°K; and "w", "x", "y” and "z” represent the mo
• the "ELAPSO” molecular sieves are also described as crystalline molecular sieves having three-dimensional microporous framework structures of ELO 2 , AlPO 2 , SiO 2 and PO 2 tetrahedral oxide units and having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (EL w Al x P y Si z )O 2 and has a value of from zero to about 0.3
• EL represents at least one element capable of forming a framework tetrahedral oxide and is selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc
• w", "x", “y” and “z” represent the mole fractions of "EL", aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides, said mole fractions being within the limiting compositional values or points as follows:
• CoMnMgAPSO 600.182 April 13, 1984 CoMnMgAPSO 057,648(C) June 9, 1987 CoMnMgAPSO
• MgAPSO MOLECULAR SIEVES The MgAPSO molecular sieves of U.S. Serial No. 600,180, filed April 13, 1984 have three-dimensional microporous framework structures of MgO 2 -2 , AlO 2 -, PO 2 + and SiO 2 tetrahedral oxide units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (Mg w Al x P y Si z )O 2
• 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 (Mg w Al x P y Si z )O 2 and has a value from zero (0) to about 0.3
• w, "x", "y” and “z” represent the. mole fractions of magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each preferably has a value of at least 0.01.
• the mole fractions "w”, "x", “y” and “ z” are generally defined as being within the limiting compositional values or points as follows:
• MgAPSO compositions are generally synthesized by hydrothermal crystallization for an effective time at effective pressures and temperatures from a reaction mixture containing reactive sources, of magnesium, silicon, aluminum and phosphorus, an organic templating, i.e., structure-directing, agent, preferably a compound of an. element of Group VA of the Periodic Table, and may be 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°C and 250°C, and preferably between 100°C and 200°C until crystals of the MgAPSO product are obtained, usually a period of from several hours to several weeks.
• the crystallization period will be from about 2 hours to about 30 days with it typically being from about 4 hours to about 20 days for obtaining MgAPSO crystals.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture compositions expressed in terms of the molar ratios as follows:
• R is an organic templating agent
• a is the amount of organic templating agent "R” and can have a value within the range of from zero (0) to about 6 and is more preferably an effective amount greater than zero to about 6
• b has a value of from zero (0) to about 500, preferably between about
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• TBAOH tetrabutylammonium hydroxide (40 wt. % in water);
• Pr 2 NH di-n-propylamine;
• Pr 3 NH tri-n-propylamine;
• Quin Quinuclidine;
• MQuin Methyl Quinuclidine hydroxide,
• the MgAPSO compositions may be prepared by preparing reaction mixtures having a molar composition expressed as: eR: fMgO :hAl 2 O 3 : iP 2 O 5 : gSiO 2 : JH 2 O wherein e, f, g, h, i and j represent the moles of template R, magnesium (expressed as the oxide), SiO 2 , Al 2 O 3 , P 2 O 5 (H 3 PO 4 expressed as P 2 O 5 ) and H 2 O, respectively;
• reaction mixtures may be prepared by the following representative procedures, designated hereinafter as Methods A, B and C.
• the reaction mixture is prepared by mixing the ground aluminum source (alipro or CATAPAL) with the H 3 PO 4 and water on a gradual basis with occasional cooling with an ice bath . The resulting mixture is blended until a homogeneous mixture is observed.
• the aluminum source is CATAPAL
• the water and H 3 PO 4 are first mixed with the CATAPAL added thereto.
• the magnesium acetate is dissolved in a portion of the water and is then added followed by addition of the LUDOX-LS.
• the combined mixture is blended until a homogeneous mixture is observed.
• the organic templating agent is added to this mixture and blended until a homogeneous mixture is observed.
• the resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoro- ethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for an effective time. Alternatively, if the digestion temperature is 100°C the final reaction mixture is placed in a lined (polytetrafluoroethylene) screw top bottle for a time. Digestions are typically carried out under autogenous pressure. The products are removed from the reaction vessel, cooled and evaluated as set forth hereinafter.
• Method B When method B is employed the organic templating agent is di-n-propylamine.
• the aluminum source, silicon source and one-half of the water are first mixed and blended until a homogeneous mixture is observed.
• a second solution was prepared by mixing the remaining water, the H 3 PO 4 . and the magnesium acetate. This solution is then added to the above mixture.
• H 3 PO 4 solution is then added to the above mixture and blended until a homogeneous mixture is observed.
• the organic templating agent(s) is/are then added and the resulting reaction mixture digested and product recovered as in Method A.
• Method C is carried out by mixing aluminum isopropoxide, LUDOX LS and water in a blender or by mixing water and aluminum iso-propoxide in a blender followed by addition of the LUDOX LS.
• H 3 PO 4 and magnesium acetate are then added to the resulting mixture.
• the organic templating agent is then added to the resulting mixture and digested and product recovered as in Method A.
• MnAPSO MOLECULAR SIEVES As already mentioned, the MnAPSO molecular sieves are described in U.S. Patent No. 4,686,092 issued August 11, 1987 (incorporated herein by reference). CoAPSO MOLECULAR SIEVES The CoAPSO molecular sieves of U.S. Serial No. 600,174, filed April 13, 1984 have three-dimensional microporous framework structures of CoO 2 -2 , AKO 2 -, PO 2 + and SiO 2 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
• CoAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of cobalt, silicon, aluminum and phosphorus, an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and optionally an alkali 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 an effective temperature which is generally between 50°C and 250°C and preferably between 100°C and 200°C until crystals of the CoAPSO product are obtained, usually for an effective time of from several hours to several weeks.
• the effective crystallization time will be from about 2 hours to about 30 days and typically from about 4 hours to about 20 days.
• the product is recovered by any convenient method such as centrifugation or filtration.
• 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
• "b” has a value of from zero (0) to about 500, preferably between about 2 and 300
• "w", "x", "y” and “z” represent the mole fractions of cobalt, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• the reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• CoAPSO compositions may be prepared using numerous reagents.
• Reagents which may be employed to prepare CoAPSOs include:
• CoSO 4 cobalt sulfate, (CoSO 4 ⁇ 7H 2 O);
• TBAOH tetrabutylammonium hydroxide (25 wt % in methanol);
• CoAPSO compositions may be prepared by preparing reaction mixtures having a molar composition expressed as:
• e, f, h, i, g and j represent the moles of template R, cobalt (expressed as the oxide), Al 2 O 3 , P 2 O 5 (H 3 PO 4 expressed as P 2 O 5 ), SiO 2 and H 2 O, respectively.
• the reaction mixtures are prepared by forming a starting reaction mixture comprising the H 3 PO 4 and one half of the water. This mixture is stirred and the aluminum source (Alipro or CATAPAL) added. The resulting mixture is blended until a homogeneous mixture is observed. The LUDOX-LS is then added to the resulting mixture and the new mixture blended until a homogeneous mixture is observed. The cobalt source (e.g., Co(Ac) 2 , Co(SO 4 ) or mixtures thereof) is dissolved in the remaining water and combined with the first mixture. The combined mixture is blended until a homogeneous mixture is observed. The organic templating agent is added to this mixture and blended for about two to four minutes until a homogeneous mixture is observed.
• Alipro or CATAPAL aluminum source
• the resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C, 200°C or 225°C) for a time. Digestions are typically carried out at the autogenous pressure. The products are removed from the reaction vessel and cooled.
• ZnAPSO MOLECULAR SIEVES The ZnAPSO molecular sieves of U.S. Serial No. 600,170, filed April 13, 1984 comprise framework structures of ZnO 2 -2 , AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (Zn w Al x P y Si z )O 2 and has a value of zero to about 0.3
• w, "x", "y” and “ z” represent the mole fractions of zinc, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01.
• the mole fractions "w”, "x”, “y” and “z” are generally defined being within the limiting compositional values or points as follows: Mole Fraction
• ZnAPSO compositions are generally synthesized by hydrothermal crystallization at effective process conditions from a reaction mixture containing active sources of zinc, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element or 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°C and 250°C, and preferably between 100°C and 200°C until crystals of the ZnAPSO product are obtained, usually a period of from several hours to several weeks.
• the effective crystallization period is from about 2 hours to about 30 days with typical periods of from about 4 hours to about 20 days being employed to obtain ZnAPSO products.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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
• "b” has a value of from zero (0) to about 500, more preferably between about 2 and about 300
• "w", "x", “y” and “z” represent the mole fractions of zinc, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• the reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• ZnAPSO compositions are typically prepared using numerous reagents.
• Reagents which may be employed to prepare ZnAPSOs include:
• LUDOX-LS is the trade name of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
• ZnAc Zinc Acetate, Zn(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• TMAOH Tetramethylammonium hydroxide pentahydrate, (CH 3 ) 4 N0H ⁇ 5H 2 O;
• TPAOH 40 weight percent aqueous solution of tetrapropylammonium hydroxide, (C 3 H 7 ) 4 NOH;
• Pr 2 NH Di-n-propylamine,
• ZnAPSO compositions are typically prepared by forming reaction mixtures having a molar composition expressed as:
• e, f, g, h, i and j represent the moles of template R, zinc (expressed as the oxide), Al 2 O 3 , P 2 O 5 (H 3 PO 4 expressed as P 2 O 5 ), SiO 2 and H 2 O, respectively.
• the reaction mixtures are generally prepared by forming a starting reaction mixture comprising the H 3 PO 4 and a portion of the water. This mixture is stirred and the aluminum source added. The resulting mixture is blended until a homogeneous mixture is observed. The LUDOX LS is then added to the resulting mixture and the new mixture blended until a homogeneous mixture is observed. The zinc source (zinc acetate) is dissolved in the remaining water and combined with the first mixture. The combined mixture is blended until a homogeneous mixture is observed. The organic templating agent is added to this mixture and blended for about two to four minutes until a homogeneous mixture is observed.
• the resulting mixture (final reaction mixture) is placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. Digestions are typically carried out under autogenous pressure. The products are removed from the reaction vessel and cooled.
• 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 (M w Al ⁇ P y Si z )O 2 and has a value of from zero (0) to about 0.3
• M represents at least two elements selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc
• "w", "x", "y” and “z” represent the mole fractions of M, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
• M represents the combination of cobalt and manganese.
• the mole fractions "w”, "x”, “y”, and “z” are generally defined as being within the limiting compositional values or points as follows:
• QuinAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of the elements M, aluminum, phosphorus and silicon and preferably an organic templating agent, i.e., structure-directing, agent.
• the structure-directing agents are preferably a compound of an element of Group VA of the Periodic Table, and may be 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 and at typical effective temperatures between 50°C and 250°C, preferably between 100°C and 200°C, until crystals of the QuinAPSO product are obtained, usually over a period of from several hours to several weeks.
• Typical effective crystallization times are from about 2 hours to 30 days with from about 4 hours to about 20 days being generally employed to obtain QuinAPSO products.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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
• b has a value of from zero (0) to about 500, preferably between about 2 and about 300
• "w", "x", “y” and “z” represent the mole fractions of elements M, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• Reagents which may be employed to prepare QuinAPSOs include:
• LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent of Na 2 O;
• MnAc Manganese acetate, Mn(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O (for QuinAPSOs containing manganese);
• CoAc Cobalt Acetate, Co(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O (for QuinAPSOs containing cobalt);
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• QuinAPSOs may be prepared by forming a starting reaction mixture by adding H 3 PO 4 and one half of the quantity of water. To this mixture an aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture a silica (e.g., LUDOX-LS) is added and the .resulting mixture blended (about 2 minutes) until a homogeneous mixture is observed. A second mixture is prepared using manganese acetate (or a appropriate source of another element M) and one half of the remaining water.
• a third mixture is prepared using cobalt acetate (or a appropriate source of another element M) and one half of the remaining water.
• the three mixtures are admixed and the resulting mixture blended until a homogeneous mixture is observed.
• the organic templating agent is then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture is observed, i.e., about 2 to 4 minutes.
• the pH of the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at an effective temperature for an effective time. Digestions are typically carried out under autogeneous pressure.
• CoMnMgAPSO MOLECULAR SIEVES The CoMnMgAPSO senary molecular sieves of U.S. Serial No. 600,182, filed April 13, 1984, and of U.S. Serial No. 057,648 filed June 9, 1987, have three-dimensional microporous framework structures of CoO 2 -2 , MnO 2 -2 , MgO 2 -2 , AlO 2 , PO 2 and SiO 2 tetrahedral oxide units having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (Co t Mn u Mg v Al x P y Si z )O 2 and has a value of from zero (0) to about 0.3;
• t, "u”, “v”, “x”, “y” and “z” represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides and each has a value of at least 0.01.
• the mole fractions "w, "x”, “y” and “z”, where “w” is the sum of "t” + “u” + “v”, are. generally defined as being within the limiting compositional values or points as follows:
• CoMnMgAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, and preferably an organic templating agent, i.e., structure-directing agent.
• the structure-directing agents are 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°C and 250°C, and preferably between 100°C and 200°C, until crystals of the CoMnMgAPSO product are obtained, usually over a period of from several hours to several weeks. Typical crystallization times are from about 2 hours to about 30 days with from about 4 hours to about 20 days generally being employed to obtain CoMnMgAPSO products.
• the product is recovered by any convenient method such as centrifugation or filtration.
• R is an organic templating agent
• a is the amount of org'anic 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 more preferably from greater than zero to about 2
• "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300
• "t", "u”, “v”, “x”, “y”, and “z” represent the mole fractions of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z”, where "w” is the sum of "t” + “u” + “v”, are generally defined as being within the limiting compositional values or points as follows:
• CoMnMgAPSO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare CoMnMgAPSOs include:
• LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
• H 3 PO 4 aqueous solution which is 85 weight percent phosphoric acid
• MnAc Manganese acetate, Mn(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O;
• CoAc Cobalt Acetate; Co(C 2 H 3 O 2 ) 2 ⁇ 4H 2 O;
• MgAc Magnesium Acetate Mg(C 2 H 3 O 2 ) ⁇ 4H 2 O;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• CoMnMgAPSOs may be prepared by forming a starting reaction mixture by adding H 3 PO 4 and one half of the quantity of water. To this mixture an aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture a silica (e.g., LUDOX-LS) is added and the resulting mixture blended (about 2 minutes) until a homogeneous mixture is observed.
• silica e.g., LUDOX-LS
• Three additional mixtures are prepared using cobalt acetate, magnesium acetate and manganese acetate using one third of the remainder of the water for each mixture.
• the four mixtures are then admixed and the resulting mixture blended until a homogeneous mixture is observed.
• An organic templating agent is then added to the resulting mixture and the resulting mixture blended until a homogeneous mixture is observed, i.e., about 2 to 4 minutes.
• the mixture is then placed in a lined . (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature for a time. Digestions are typically carried out under autogenous pressure.
• SenAPSO MOLECULAR SIEVES The SenAPSO molecular sieves of U.S. Serial No. 600,183, filed April 13, 1984 have three-dimensional microporous framework structures of MO 2 n , AlO 2 -, PO 2 + and SiO 2 tetrahedral oxide units, where "n" is -3, -2, -1, 0 or +1, and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (M w Al ⁇ P y Si z )O 2
• 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 (M w Al x P y Si z )O 2 , and has a value of from zero to about 0.3
• M represents three elements selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc
• "n” may have the aforementioned values depending upon the oxidation state of "M”
• "w", "x", “y” and “z” represent the mole fractions of elements "M", aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
• the mole fractions "w”, “x”, “y” and “z” are generally defined as being within the limiting compositional values or points as follows, wherein “w” denotes the combined mole fractions of the three
• each element "M" has a mole fraction of at least 0.01:
• SenAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of elements "M", aluminum, phosphorus and silicon, and preferably an organic templating, i.e., structure-directing, agent.
• the structure-directing agents are 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°C and 250°C, and preferably between 100°C and 200°C, until crystals of the SenAPSO product are obtained, usually over a period of from several hours to several weeks.
• Typical crystallization times are from about 2 hours to about 30 days with from about 4 hours to about 20 days generally being employed to obtain SenAPSO products.
• the product is recovered by any convenient method such as centrifugation or filtration.
• 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 more preferably from greater than zero to about 2
• "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300
• "w", "x", “y”, and “z” represent the mole fractions of elements "M", aluminum, phosphorus and. silicon, respectively, and each has a value of at least 0.01, with the proviso that each "M” is present in a mole fraction of at least 0.01.
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “ z " are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
• the SenAPSO molecular sieves are prepared by preparative techniques, and using sources of the elements "M” similar to those described for the other APSO molecular sieves described above and below.
• the AsAPSO.molecular sieves of U.S. Serial No. 599,808, filed April 13, 1984, and U.S. Serial No. 845,484 filed March 31, 1986 have a framework structure of AsO 2 n , AIO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
• AsAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of arsenic, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
• the reaction mixture 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the AsAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 12 hours to about 10 days, have been observed.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 1.0
• "b” has a value of from zero (0) -to about 500, preferably between about 2 and about 300, most preferably not greater than about 60
• "w", "x", “y”- and “z” represent the mole fractions of arsenic, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• reaction mixtures are those containing from about 1 to about 2 total moles of silicon and arsenic, and from about 1 to about 2 moles of aluminum, per mole of phosphorus.
• AsAPSO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare AsAPSOs include:
• LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 .and 0.1 weight percent Na 2 O;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• AsAPSOs may be prepared by forming a starting reaction mixture by dissolving the arsenic (V) oxide and the H 3 PO 4 in at least part of the water. To this solution the aluminum isopropoxide or CATAPAL is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and then the silica is added and the resulting mixture blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• BAPSO MOLECULAR SIEVES The BAPSO molecular sieves of U.S. Serial No. 600,177, filed April 13, 1984, and U.S. Serial No. 845,255 filed March 28, 1986 have a framework structure of BO 2 -, AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (B w Al x P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• w, "x", "y” and “z” represent the mole fractions of the elements boron, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
• the mole fractions "w”, "x” , "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• the values of w, x, y and z are as follows:
• BAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of boron, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
• the reaction mixture 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the BAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, have been observed.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 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
• "w", "x", "y” and “z” represent the mole fractions of boron, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• the reaction mixture is selected such that the mole fractions "w”, "x”, “y” and “z” are generally defined as being within the limiting compositional values or points as follows
• reaction mixtures are those containing from about 1.0 to about 2 total moles of silicon and boron, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorus.
• Molecular sieves containing boron, aluminum, phosphorus and silicon as framework tetrahedral oxide units are prepared as follows:
• BAPSO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare BAPSOs include:
• CATAPAL Trademark of Condea Corporation for hydrated pseudoboehmite
• LUDOX-LS LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• BAPSOs may be prepared by forming a starting reaction mixture by dissolving aluminum isopropoxide in an alcohol such as isopropanol, adding the H 3 PO 4 and recovering the solid which precipitates.
• This solid is then added to water, and trialkylborate (for example trimethyl borate) added, followed by silica and the templating agent.
• This mixture is then blended until a homogeneous mixture is observed.
• the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel. and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• BeAPSO MOLECULAR SIEVES The BeAPSO molecular sieves of U.S. Serial No. 600,176, filed April 13, 1984, and U.S. Serial No. 841,752 filed March 20, 1986 have a framework structure of BeO 2 -2 , AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (Be w Al x P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• w, "x", "y” and “z” represent the mole fractions of the elements beryllium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
• the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• the values of w, x, y and z are as follows:
• BeAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of beryllium, silicon, aluminum and phosphorus, preferrably 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the BeAPSO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, have been observed, with from 1 to 10 days being preferred.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 0.5
• "b” has a value of from zero (0) to about 500, preferably between about 2 to about 300, most preferably not greater than about 20
• "w", "x", “y” and “z " represent the mole fractions of beryllium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01,
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “ z" are generally defined as being within the limiting compositional values or points as follows:
• BeAPSO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare BeAPSOs include:
• CATAPAL Trademark of Condea Corporation for hydrated pseudoboehmite
• LUDOX-LS LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• BeAPSOs may be prepared by forming a starting solution by mixing H 3 PO 4 in at least part of the water. To this solution is added beryllium sulfate (or another beryllium salt) and the resultant mixture stirred until a homogeneous solution is obtained. To this solution may be added successively the aluminum oxide, the silica and the templating agent, with the mixture being stirred . between each addition until it is homogeneous. Themixture is then placed in a lined (polytetra- fluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• CAPSO MOLECULAR SIEVES The CAPSO molecular sieves of U.S. Serial No. 599,830, filed April 13, 1984, and U.S. Serial No. 852,174 filed April 15, 1986 have a framework structure of CrO 2 n , AIO 2 -, PO 2 + and SiO 2 tetrahedral units (where "n" is -1, 0 or +1) having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 w Al x P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• w, "x” , "y” and “z” represent the mole fractions of the elements 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 limiting compositional values or points as follows:
• 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 about 0.02 to 0.15. Since the exact nature of the CAPSO molecular sieves is not clearly understood at present, although all are believed to contain CrO 2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the CAPSO molecular sieves by means of their chemical composition. This is due to the low level of chromium present in certain of the CAPSO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between chromium, aluminum, phosphorus and silicon.
• CAPSO compositions are generally synthesized by hydrothermal crystallization from- a reaction mixture containing reactive sources of chromium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
• the reaction mixture 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the CAPSO product are obtained, usually a period of from several hours to several weeks.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 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
• "w", "x", "y” and " z " represent the mole fractions of chromium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• reaction mixtures are those containing from about 0.3 to about 0.5 total moles of silicon and chromium, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorus.
• CAPSO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare CAPSOs include:
• LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• CAPSOs may be prepared by forming a starting solution by dissolving H 3 PO 4 in at least part of the water. To this solution the aluminum isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the silica, the chromium acetate or chromium acetate hydroxide and the templating agent are successively added and at each step the resulting mixture is blended until a homogeneous mixture is observed.
• the water and aluminum isopropoxide may first be mixed, and then the silica, the chromium acetate or chromium acetate hydroxide, the. phosphoric acid and the templating agent added, and .again at each step the resulting mixture is blended until a homogeneous mixture is observed.
• the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• GaAPSO MOLECULAR SIEVES The GaAPSO molecular sieves of U.S. Serial No. 599,925, filed April 13, 1984, and U.S. Serial No. 845,985 filed March 31, 1986 have a framework structure of GaO 2 -, AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (Ga w Al x P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.2
• w, "x", "y” and “z” represent the mole fractions of the elements gallium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
• the mole fractions "w”, "x”, “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• the.values of w, x, y and z are as follows:
• GaAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of gallium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
• the reaction mixture 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GaAPSO product are obtained, usually a period of from several hours to several weeks.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows: aR : (Ga w Al x P y Si z )O 2 : bH 2 O
• 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 most preferably not more than about 1.0
• "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
• "w", "x", “y” and “z” represent the mole fractions of gallium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• reaction mixtures are those containing from about 0.5 to about 1.0 total moles of silicon and gallium, and from about 0.75 about 1.25 moles of aluminum, per mole of phosphorus.
• GaAPSO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare GaAPSOs include:
• LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• GaAPSOs may be prepared by forming a starting solution by dissolving H 3 PO 4 in at least part of the water. To this solution the aluminum hydroxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture is added a second solution prepared by adding silica to a solution containing the gallium hydroxide and the templating agent and then the combined mixture is blended until a homogeneous mixture is observed.
• the templating agent may be added to the solution containing the phosphoric acid and water, and a solution of gallium sulfate in water added, followed by successive additions of silica and aluminum oxide and then the combined mixture is blended until a homogeneous mixture is observed.
• the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• GeAPSO MOLECULAR SIEVES The GeAPSO molecular sieves of U.S. Serial No. 599,971, filed April 13, 1984, and U.S. Serial No. 852,175 filed April 15, 1986 have a framework structure of GeO 2 , AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (Ge w Al ⁇ P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• w, "x", "y” and “z” represent the mole fractions of the elements geranium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
• the mole fractions "w”, "x", “y” and “z” are generally defined as being within the limited compositional values or points as follows:
• the values of w, x, y and z are as follows:
• the values of w, x, y and z are as follows:
• GeAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of geranium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
• the reaction mixture 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GeAPSO product are obtained, usually a period of from several hours to several weeks.
• Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 20 days, and preferably about 12 hours to about 7 days have been observed.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 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 desirably not greater than about 10
• "w", "x", “y” and “z” represent the mole fractions of germanium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "w”, "x” , “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• reaction mixtures are those containing from about 0.2 to about 0.3 total moles of silicon and germanium, and from about 0.75 about 1.25 moles of aluminum, per mole of phosphorus.
• GeAPSO compositions may be prepared by using numerous reagents. Reagents which may be employed to prepare GeAPSOs include:
• LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• Preparative Procedures it may be advantageous, when synthesizing the GeAPSO compositions, to first combine sources of germanium and aluminum, or of germanium, aluminum and silicon, to form a mixed germanium/aluminum or germanium/aluminum/silicon compound (this compound being typically a mixed oxide) and thereafter to combine this mixed compound with a source of phosphorus to form the final GeAPSO composition.
• Such mixed oxides may be prepared for example by hydrolyzing aqueous solutions containing germanium tetrachloride and aluminum chlorhydrol, or germanium ethoxide, tetraethylorthosilicate, and aluminum tri-sec-butoxide.
• GeAPSOs may be prepared by forming a starting solution by dissolving H 3 PO 4 in at least part of the water. To this solution the aluminum isopropoxide or CATAPAL is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture is the templating agent and then a solution containing tetraethylorthosilicate and germanium ethoxide, and the resulting mixture blended until a homogeneous mixture is observed.
• the phosphoric acid may first be mixed with the templating agent, and then a solution containing tetraethylorthosilicate and germanium ethoxide combined with the phosphoric acid/templating agent solution. Then the aluminum oxide is added and the resultant mixture blended until homogeneous.
• the phosphoric acid may first be mixed with the templating agent and water, and to the resultant solution is added the solid aluminum/ silicon/germanium mixed oxide prepared as described above. The resultant mixture is then blended until homogeneous.
• the final mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• LiAPSO MOLECULAR SIEVES The LiAPSO molecular sieves of U.S. Serial No. 599,952, filed April 13, 1984, and U.S. Serial No. 847,227 filed April 2, 1986 have a framework structure of LiO 2 -3 , AlO 2 -, PO 2 + and SiO 2 tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (Li w Al ⁇ P y Si z )O 2
• 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 (Li w Al ⁇ P y Si z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• w, "x” , "y” and “z” represent the mole fractions of the elements lithium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides.
• the mole fractions "w”, "x”, “y” and “z” are generally defined as being within the limiting compositional values or points, as follows:
• the. values of w, x, y and z are as follows:
• the value of w+z is not greater than about 0.20. Since the exact nature of the LiAPSO molecular sieves is not clearly understood at present, although all are believed to contain LiO 2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the LiAPSO molecular sieves by means of their chemical composition. This is due to the low level of lithium present in certain of the LiAPSO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between lithium, aluminum, phosphorus and silicon.
• LiO 2 tetrahedra are substituted isomorphously for AlO 2 , PO 2 or SiO 2 tetrahedra, it is appropriate to characterize certain LiAPSO compositions by reference to their chemical composition in terms of the mole ratios of oxides.
• LiAPSO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of lithium, silicon, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
• the reaction mixture 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the LiAPSO product are obtained, usually a period of from several hours to several weeks.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows :
• 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 most preferably not more than about 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 most desirably not greater than about 10
• "w", "x", “y” and “ z” represent the mole fractions of lithium, aluminum, phosphorus and silicon, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "w”, "x", “y” and “ z " are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
• LiAPSO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare LiAPSOs include:
• LUDOX-LS is the tradename of DuPont for an aqueous solution of 30 weight percent SiO 2 and 0.1 weight percent Na 2 O;
• LiAPSOs may be prepared by forming a starting reaction mixture mixing lithium phosphate and aluminum oxide, then adding the resultant mixture to the H 3 PO 4 . To the resultant mixture is added silica and the templating agent and the resulting mixture is blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• AlPO 4 aluminophosphate molecular sieves are described in U.S. Patent No. 4,310,440 (incorporated herein by reference); these AlPO 4 molecular sieves are also described in U.S. Serial No. 880,559, filed June 30, 1986.
• MeAPO MOLECULAR SIEVES MeAPO molecular sieves are crystalline microporous aluminophosphates in which the substituent metal is one of a mixture of two or more divalent metals of the group magnesium, manganese, zinc and cobalt and are disclosed in U.S. Patent No. 4,567,029 (incorporated herein by reference).
• ferroaluminophosphates are disclosed in U.S. Patent No. 4,554,143 (incorporated herein by reference).
• TAPO MOLECULAR SIEVES As already mentioned, TAPO molecular sieves are disclosed in U.S. Patent No. 4,500,561 (incorporated herein by reference).
• ELAPO MOLECULAR SIEVES "ELAPO” molecular sieves are a class of crystalline molecular sieves in which at least one element capable of forming a three-dimensional microporous framework forms crystal framework structures of AlO 2 -, PO 2 + and MO 2 n tetrahedral oxide units wherein "MO 2 n " represents at least one different element (other than Al or P) present as tetrahedral oxide units "MO 2 n " with charge "n” where "n” may be -3, -2, -1, 0 or +1.
• the members of this novel class of molecular sieve compositions have crystal framework structures of AlO 2 -, PO 2 + and MO 2 n tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (M x Al y P z )O 2
• M represents at least one element capable of forming framework tetrahedral oxides
• x, "y” and “z” represent the mole fraction of "M” , aluminum and phosphorus, respectively, present as tetrahedral oxides.
• M is at least one different (i.e., not aluminum, phosphorus or oxygen) element such that the molecular sieves contain at least one framework tetrahedral unit in addition to AIO 2 - and PO 2 + .
• M is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc, subject to certain restrictions on the combinations of elements as will appear from the discussions of individual groups of ELAPOs below.
• ELAPOs and their preparation are disclosed in European Patent Application Serial No. 85104386.9, filed April 11, 1985 (EPC Publication No. 0158976, published October 13, 1985, incorporated herein by reference) and 85104388.5, filed April 11, 1985 (EPC Publication No. 158349, published October 16, 1985, incorporated herein by reference).
• ESAPO electroactive polystyrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-styrene-S-S-S-s
• ElAPO (M comprises two different
• ELAPO ELAPO molecular sieves
• ELAPO ELAPO molecular sieves
• M element (s) "M” in a framework of AlO 2 -, PO 2 + and Mo 2 n tetrahedral oxide units.
• ELAPO element (s) "M” in a framework of AlO 2 -, PO 2 + and Mo 2 n tetrahedral oxide units.
• EL element
• MgBeAPO designates a molecular sieve comprised of AlO 2 -, PO 2 + , MgO 2 -2 and BeO 2 -2 tetrahedral units.
• each species is assigned a number and is identified as "ELAPO-i" wherein "i” is an integer.
• the given species designation is not intended to denote a similarity in structure to any other species denominated by a similar identification system.
• the ELAPO molecular sieves comprise at least one additional element capable of forming framework tetrahedral oxide units (MO 2 n ) to form crystal framework structures with AlO 2 - and PO 2 + tetrahedral oxide uni.ts wherein "M” represents at least one element capable of forming tetrahedral units "MO 2 n " where "n” is -3, -2,
• -1, 0 or +1 is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc.
• the ELAPO molecular sieves have crystalline three-dimensional microporous framework structures of AlO 2 -, PO 2 + and MO 2 n tetrahedral units and have an empirical chemical composition, on an anhydrous basis expressed by the formula: mR : (M x Al y P z )O 2 ;
• 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 (M x Al y P z )O 2 and has a value of zero to about 0.3
• M represents at least one element capable of forming framework tetrahedral oxides where "M” is at least one element selected from the group consisting of arsenic, beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc.
• the relative amounts of element (s) "M", aluminum and phosphorous are expressed by the empirical chemical formula (anhydrous):
• the ELAPO molecular sieves have crystalline three-dimensional microporous framework structures of MO 2 n , AlO 2 - and PO 2 + tetrahedral units having an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (M ⁇ Al y P z )O 2
• R represents at least one organic templating agent present in the intracrystalline pore system
• m represents a molar amount of “R” present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3
• M represents at least one different element (other than Al or P) capable of forming framework tetrahedral oxides, as hereinbefore defined
• x, "y” and “z” represent the mole fractions of "M", aluminum and phosphorous, respectively present as tetrahedral oxides
• said mole fractions "x” , “y” and “z” are within the following values for "x", “y” and “z", although as will appear hereinbelow, the limits for "x”, “y” and “z” may vary slightly with the nature of the element “M” :
• ELAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of the elements "M", aluminum and phosphorous, 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°C and 250°C, and preferably between 100°C and 200°C, until crystals of the ELAPO product are obtained, usually a period of from several hours to several weeks. Typical crystallization times are from about 2 hours to about 30 days with from about 2 hours to about 20 days being generally employed to obtain crystals of the ELAPO products.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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
• "b” has a value of from zero (0) to about 500, preferably between about 2 and 300
• M represents at least one element, as above described, capable of forming tetrahedral oxide framework units, MO 2 n , with AlO 2 - and PO 2 + tetrahedral units
• "n” has a value of -3, -2, -1, 0 or +1
• "x", "y” and “z” represent the mole fractions of "M", aluminum and phosphorous, respectively; "y” and “z” each have a value of at least 0.01 and "x” has a value of at least 0.01 with each element "M” having a mole fraction of at least 0.01.
• This latter form is readily converted to the former form by routine calculations by dividing the total number of moles of "M”, aluminum and phosphorous into the moles of each of "M", aluminum and phosphorous.
• the moles of template and water are similarly normalized by dividing by the total moles of "M", aluminum and phosphorous.
• the organic templating agent can be any of those heretofore proposed for use in the synthesis of conventional zeolite aluminosilicates.
• these compounds contain elements of Group VA of the Periodic Table of Elements, particularly nitrogen, phosphorous, arsenic and antimony, preferably nitrogen or phosphorous and most preferably nitrogen, which compounds also contain at least one alkyl or aryl group having from 1 to 8 carbon atoms.
• templating agents are the amines, quaternary phosphonium compounds and quaternary ammonium compounds, the latter two being represented generally by the formula R 4 X + wherein "X" is nitrogen or phosphorous and each R is an alkyl or aryl group containing from 1 to 8 carbon atoms.
• Polymeric quaternary ammonium salts such as [(C 14 H 32 N 2 ) (OH) 2 ] ⁇ 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 ELAPOs 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 or tetrabutylammonium ions; tetrapentylammonium ion; di-n-propylamine; tripropylamine; triethylamine; triethanolamine; piperidine; cyclohexylamine; 2-methylpyridine; N,N-dimethylbenzylamine; N,N-dimethylethanolamine; choline; N,N'-dimethyl ⁇ i ⁇ erazine; 1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine; N-methylethanolamine; N-methylpiperidine; 3-methyl ⁇ i ⁇ eridine; n-methylcyclohexylamine; 3-methyl ⁇ yridine; 4-methyl ⁇ yridine; quinuclidine; N,N'-dimethyl-1,4-diazabicyclo (2,2,
• the phosphorous source is preferably phosphoric acid, but organic phosphates such as triethyl phosphate may be satisfactory, and so also may crystalline or amorphous aluminophosphates such as the AlPO 4 composition of U.S. P. 4,310,440.
• Organophosphorous compounds such as tetrabutylphosphonium bromide, do not apparently serve as reactive sources of phosphorous, but these compounds may function as templating agents.
• Conventional phosphorous salts such as sodium metaphosphate, may be used, at least in part, as the phosphorous source, but are not preferred.
• the aluminum source is preferably either an aluminum alkoxide, such as aluminum isopropoxide, or pseudoboehmite.
• the crystalline or amorphous aluminophosphates which are a suitable source of phosphorous are, of course, also suitable sources of aluminum.
• the element (s) "M” can be introduced into the reaction system in any form which permits the formation in situ of reactive form of the element, i.e., reactive to form the framework tetrahedral oxide unit of the element.
• the organic and inorganic salts, of "M” such as oxides, alkoxides, hydroxides, halides and carboxyates, may be employed including the chlorides, bromides, iodides, nitrates, sulfates, phosphates, acetates, formates, and alkoxides, including ethoxides, propoxides and the like. Specific preferred reagents for introducing various elements "M” are discussed hereinbelow.
• the as-synthesized ELAPO generally contains within its internal pore system at least one form of the templating agent employed in its formation.
• the organic moiety is present, at least in part, as a charge-balancing cation as is generally the case with as-synthesized aluminosilicate zeolites prepared from organic-containing reaction systems. It is possible, however, that some or all of the organic moiety is an occluded molecular species in a particular ELAPO species.
• the templating agent and hence the occluded organic species, is too large to move freely through the pore system of the ELAPO product and must be removed by calcining the ELAPO at temperatures of 200°C to 700°C to thermally degrade the organic species.
• the pores of the ELAPO 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 carried out in the case of zeolites.
• the present ELAPO compositions are formed from MO 2 n , AlO 2 - and PO 2 + tetrahedral oxide units which, respectively, have a net charge of "n", (where "n" may be -3, -2, -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 stoichiometric relationship between AlO 2 - tetrahedra and charge-balancing cations.
• an AlO 2 - tetrahedron can be balanced electrically either by association with a PO 2 + tetrahedron or a simple cation such as an alkali metal cation, a proton (H + ), a cation of "M" present in the reaction mixture, or an organic cation derived from the templating agent.
• an MO 2 n tetrahedron where "n" is negative, can be balanced electrically by association with PO 2 + tetrahedra, a cation of "M” present in the reaction mixture, organic cations derived from the templating agent, a simple cation such as an alkali metal cation, or other divalent or polyvalent metal cation, a proton (H + ), or anions of cations introduced from an extraneous source. It has also been postulated that non-adjacent AlO 2 - and PO 2 + tetrahedral pairs can be balanced by Na + and OH- respectively (Flanigen and Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971).
• the AsAPO molecular sieves of U.S. Serial No. 600,166, filed April 13, 1984, and U.S. Serial No. 830,889 filed February 19, 1986 have a framework structure of AsO 2 n , AlO 2 - and PO 2 + tetrahedral units (where "n" is -1 or +1) and have an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (As x Al y P z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• x, "y” and “z” represent the mole fractions of the elements arsenic, aluminum and phosphorous, respectively, present as tetrahedral oxides.
• the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• AsAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of arsenic, aluminum and phosphorous, 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the AsAPO product are obtained, usually a period of from several hours to several weeks.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 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
• "x", "y” and “z” represent the mole fractions of arsenic, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• Especially preferred reaction mixtures are those wherein the mole fractions "x", "y” and “z” are within the limiting compositional values or points as follows:
• AsAPO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare AsAPOs include:
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• AsAPOs may be prepared by forming a starting reaction mixture by dissolving the arsenic (V) oxide and the H 3 PO 4 in at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and the resulting mixture blended until a homogeneous mixture is observed.
• the mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• BAPO MOLECULAR SIEVES The BAPO molecular sieves of U.S. Serial No. 599,812, filed April 13, 1984, U.S. Serial No. 804,248, filed December 4, 1985, and U.S. Serial No. 029,540, filed March 24, 1987, have a framework structure of BO 2 -, AlO 2 - and PO 2 + tetrahedral units and have an empirical chemcial composition on an anhydrous basis expressed by the formula:
• 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 (B x Al y P z )O 2 and has a value of zero to about 0.3
• x", "y” and “z” represent the mole fractions of the elements boron, aluminum and phosphorus, respectively, present as tetrahedral oxides.
• the more fractions "x”, “y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• the values of x, y, and z are within the limiting compositional values or points as follows:
• BAPO molecular sieves are those in which the mole fraction, "x", of boron is not greater than about 0.3.
• BAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of boron, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal .
• the reaction mixture 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the BAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 14 days, and preferably about 1 to about 7 days, have been observed.
• the product is recovered by any conveniently method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• R is an organic templating agent
• a is the amount of organic templating agent “R” and is an effective amount preferably within the range of greater than zero (0) to about 6, and most preferably not more than about 1.0
• "b” has a value of from zero (0) to about 500, ' preferably between about 2 and about 300, desirably not greater than about 20, and most desirably not greater than about 10
• "x", "y” and “z” represent the mole fractions of boron, aluminum and phosphorus, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the . mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• reaction mixtures are those containing from 0.5 to 2.0 moles of B 2 O 3 and from 0.75 to 1.25 moles of Al 2 O 3 for each mole of P 2 O 5 .
• BAPO molecular sieves The exact nature of the BAPO molecular sieves is not entirely understood at present, although all are believed to contain BO 2 , AlO 2 and PO 2 tetrahedra in the three-dimensional microporous framework structure.
• the low level of boron present in some of the instant molecular sieves makes it difficult to ascertain the exact nature of the interactions among boron, aluminum and phosphorus.
• BO 2 tetrahedra are present in the three-dimensional microporous framework structure, it is appropriate to characterize certain BAPO compositions in terms of the molar ratios of oxides.
• Molecular sieves containing boron, aluminum and phosphorus as framework tetrahedral oxide units are prepared as follows:
• BAPO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare BAPOs include:
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• Pr 3 N tri-n-propylamine, (C 3 H 7 ) 3 N;
• TMAOH tetramethylammonium hydroxide
• TPAOH tetrapropylarnmonium hydroxide
• Preparative Procedures In the preferred method of synthesizing the BAPO compositions, one first combines sources of boron, aluminum and phosphorus to form an amorphous material containing all three elements, and thereafter heats the amorphous material to produce a crystalline BAPO molecular sieve. It is not necessary that the total quantities of the reactive sources of boron, aluminum and phosphorus to be used in the final reaction mixture be present in the amorphous material, since additional quantities of the elements can be added during the later heat treatment; in particular, it has been found convenient to add additional quantities of phosphorus to the amorphous material before the heat treatment. The preliminary formation of the amorphous material assists in the incorporation of the boron into the final molecular sieve.
• BAPOs may be prepared by forming a solution of boric acid in a methanolic solution of the templating agent, then adding a hydrated aluminosphosphate and water and stirring to form a homogeneous reaction slurry. This slurry is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• BeAPO MOLECULAR SIEVES The BeAPO molecular sieves of U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984, and U.S. Serial No. 599,776, filed April 13, 1984,
• No. 835,293 filed March 3, 1986 have a framework structure of BeO 2 -2 , AlO 2 - and PO 2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (Be x Al y P z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• x, "y” and “z” represent the mole fractions of the elements beryllium, aluminum and phosphorus, respectively, present as tetrahedral oxides.
• the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows: Mole Fraction
• the values of x, y and z are within the limiting compositional values or points as follows:
• BeAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of beryllium, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
• a reaction mixture containing reactive sources of beryllium, aluminum and phosphorus, preferably an organic templating, i.e., structure-directing, agent, preferably a compound of an element of Group VA of the Periodic Table, and/or optionally an alkali or other metal.
• the reaction mixture 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 about 50°C and about 250oC, and preferably between about 100°C and about 200°C until crystals of the BeAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 4 hours to about 14 days, and preferably about 1 to about 7 days, have been observed.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 1.5
• "b” has a value of from zero (0) to about 500, preferably between about .2 and about 300, most preferably not greater than about 50
• "x", "y” and “z” represent the mole fractions of beryllium, aluminum and phosphorus, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• Especially preferred reaction mixtures are those wherein the mole fractions "x", "y” and “z” are within the limiting compositional values or points as follows:
• BeAPO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare BeAPOs include:
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• BeAPOs may be prepared by forming a starting reaction mixture by dissolving the beryllium sulfate and the H 3 PO 4 in at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent and the resulting mixture blended until a homogeneous mixture is observed. The mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• CAPO MOLECULAR SIEVES The CAPO molecular sieves, of U.S. Serial No. 599,813, filed April 13, 1984, and U.S. Serial No. 830,756 filed February 19, 1986 have a framework structure of CrO 2 n , AlO 2 - and PO 2 + tetrahedral units (where "n" is -1, 0 or +1) and have an empirical chemical composition on an anhydrous basis expressed by the formula
• CAPO molecular sieves Since the exact nature of the CAPO molecular sieves is not clearly understood at present, although all are believed to contain CrO 2 tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the CAPO molecular sieves by means of their chemical composition. This is due to the low level of chromium present in certain of the CAPO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between chromium, aluminum and phosphorous. As a result, although it is believed that CrO 2 tetrahedra are substituted isomorphously for AlO 2 or PO 2 tetrahedra, it is appropriate to. characterize certain CAPO compositions by reference to their chemical composition in terms of the mole ratios of oxides.
• CAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of chromium, aluminum and phosphoro.us, 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the CAPO product are obtained, usually a period of from several hours to several weeks.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 0.6
• 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
• x, "y” and “z” represent the mole fractions of chromium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• reaction mixtures are those containing from about 0.1 to about 0.4 moles of chromium, and from about 0.75 to about 1.25 moles of aluminum, per mole of phosphorous.
• CAPO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare CAPOs include:
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• CAPOs may be prepared by forming a starting reaction mixture by adding aluminum chlorhydrol or aluminum oxide to a solution of chromium acetate hydroxide in water, then adding successively phosphoric acid and the templating agent. Between each addition, and after formation of the final mixture, the mixture is blended until a homogeneous mixture is observed.
• the phosphoric acid may be mixed with at least part of the water, and aluminum oxide or isopropoxide mixed in.
• a solution of chromium acetate hydroxide is then added, followed by the templating agent, and the resultant mixture mixed until homogeneous.
• amorphous chromium phosphate is ground dry with aluminum oxide and the resultant dry mixture added to an aqueous solution of phosphoric acid in an ice bath. The templating agent is then added, and the final mixture mixed until homogenous.
• this mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• GaAPO MOLECULAR SIEVES The GaAPO molecular sieves of U.S. Serial No. 599,771, filed April 13, 1984, and U.S. Serial No. 830,890 filed February 19, 1986 have a framework structure of GaO 2 -, AlO 2 and PO 2 tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (Ga x Al y P z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• x, "y” and “z” represent the mole fractions of the elements gallium, aluminum and phosphorous, respectively, present as tetrahedral oxides.
• the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• the value ,of "z" in the GaAPO molecular sieves is not greater than about 0.60.
• the values of x, y and z are within the limiting compositional values or points as follows:
• the values of x, y and z are as follows:
• GaAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of gallium, aluminum and phosphorous, 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GaAPO product are obtained, usually a period of from several hours to several weeks.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows:
• 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 most preferably not more than about 1.0
• "b” has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably between about 2 and 20
• "x", "y” and “z” represent the mole fractions of gallium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• reaction mixtures are those containing from 0.2 to 0.5 mole of Ga 2 O 3 and from 0.3 to 1 mole of Al 2 O 3 for each mole of
• GaAPO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare GaAPOs include: (a) aluminum isopropoxide;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• GaAPOs may be prepared by forming a starting reaction mixture by mixing the phosphoric acid with at least part of the water. To this solution the aluminum oxide or isopropoxide is added. This mixture is then blended until a homogenous mixture is observed. To this mixture the gallium sulfate or gallium hydroxide and the templating agent are successively added and the resulting mixture blended until a homogeneous mixture is observed.
• the aluminum oxide may be mixed with a solution of the gallium sulfate or hydroxide, and then the phosphoric acid and the templating agent successively added. The resulting mixture is then blended until a homogeneous mixture is observed.
• the templating agent may be dissolved in water, the gallium hydroxide or sulfate added with stirring, a solution of the phosphoric acid added, and finally the aluminum oxide mixed in. The resulting mixture is then blended until a homogeneous mixture is observed.
• the mixture is then placed in .a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressures.
• GeAPO MOLECULAR SIEVES The GeAPO molecular sieves of U.S. Serial No. 599,807, filed April 13, 1984, and U.S. Serial No. 841,753 filed March 20, 1986 have a framework structure of GeO 2 , AIO 2 - and PO 2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula: mR : (Ge x Al y P z )O 2
• 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 (Ge ⁇ Al y P z )O 2 and has a value of zero to. about 0.3, but is preferably not greater than 0.2
• x, "y” and “z” represent the mole fractions of the elements germanium, aluminum and phosphorous, respectively, present as tetrahedral oxides.
• the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• the values of x, y and z are within the limiting compositional values or points as follows:
• An especially preferred subclass of the GeAPO molecular sieves are those in which the value of "x" is not greater than about 0.13.
• .GeAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of germanium, aluminum and phosphorous, 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C, until crystals of the GeAPO product are obtained, usually a period of from several hours to several weeks.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios as follows: aR : (Ge x Al y P z )O 2 : bH 2 O
• 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 most preferably not more than about 0.6
• b has a value of from zero (0) to about 500, preferably between about 2 and about 300, most preferably between about 10 and about 60
• "x", "y” and “z” represent the mole fractions of germanium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• reaction mixtures are those containing from 0.2 to 0.4 mole of GeO 2 and from 0.75 to 1.25 mole of Al 2 O 3 for each mole of
• GeAPO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare GeAPOs include:
• germanium tetrachloride, germanium ethoxide and germanium dioxide (d) germanium tetrachloride, germanium ethoxide and germanium dioxide;
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• germanium and aluminum may be advantageous, when synthesizing the GeAPO compositions, to first combine sources of germanium and aluminum, to form a mixed germanium/aluminum compound (this compound being typically a mixed oxide) and thereafter to combine this mixed compound with a source of phosphorous to form the final GeAPO composition.
• a mixed germanium/aluminum compound this compound being typically a mixed oxide
• Such mixed oxides may be prepared for example by hydrolyzing aqueous solutions containing germanium tetrachloride and aluminum chlorhydrol, or aluminum tri-sec-butoxide.
• GeAPOs may be prepared by forming a starting reaction mixture by mixing the phosphoric acid with at least part of the water. To this solution is added the mixed germanium/aluminum oxide prepared as described above. This mixture is then blended until a homogeneous mixture is observed. To this mixture the templating agent is added and the resulting mixture blended until a homogeneous mixture is observed.
• germanium ethoxide may be added to a solution of aluminum isopropoxide.
• the resultant solution may optionally be dried to produce a mixed oxide.
• To the mixed solution or dried oxide are added successively the phosphoric acid and the templating agent. The resulting mixture is then blended until a homogeneous mixture is observed.
• a solution is formed by dissolving the phosphoric acid in water, adding aluminum oxide or isopropoxide and mixing thoroughly.
• a solution containing the templating agent and germanium dioxide To the resultant mixture is added a solution containing the templating agent and germanium dioxide. The resulting mixture is then blended until a homogeneous mixture is observed.
• the -mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• LiAPO MOLECULAR SIEVES The LiAPO molecular sieves of U.S. Serial No. 599,811, filed April 13, 1984, and U.S. Serial No. 834,921 filed February 28, 1986 have a framework structure of LiO 2 -3 , AlO 2 - and PO 2 + tetrahedral units and have an empirical chemical composition on an anhydrous basis expressed by the formula:
• 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 (Li x Al y P z )O 2 and has a value of zero to about 0.3, but is preferably not greater than 0.15
• x, "y” and “z” represent the mole fractions of the elements lithium, aluminum and phosphorous, respectively, present as tetrahedral oxides.
• the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• the values of x, y and z are within the limiting compositional values or points as follows:
• LiAPO compositions are generally synthesized by hydrothermal crystallization from a reaction mixture containing reactive sources of lithium, aluminum and phosphorous, 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 about 50°C and about 250°C, and preferably between about 100°C and about 200°C until crystals of the LiAPO product are obtained, usually a period of from several hours to several weeks. Typical effective times of from 2 hours to about 30 days, generally from about 12 hours to about 5 days, have been observed.
• the product is recovered by any convenient method such as centrifugation or filtration.
• reaction mixture composition expressed in terms of the molar ratios a's follows:
• 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 most preferably not more than about 2
• "b” has a value of from zero (0) to about 500, preferably between 2 and 300, most preferably not greater than about 40
• "x", "y” and “z” represent the mole fractions of lithium, aluminum and phosphorous, respectively, and each has a value of at least 0.01.
• reaction mixture is selected such that the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:
• LiAPO molecular sieves Since the exact nature of the LiAPO molecular sieves is not clearly understood at present, although all are believed to contain LiO, tetrahedra in the three-dimensional microporous crystal framework structure, it is advantageous to characterize the LiAPO molecular sieves by means of their chemical composition. This is due to the low level of lithium present in certain of the LiAPO molecular sieves prepared to date which makes it difficult to ascertain the exact nature of the interaction between lithium, aluminum and phosphorous. As a result, although it is believed that LiO 2 tetrahedra are substituted isomorphously for AIO 2 or PO 2 tetrahedra, it is appropriate to characterize certain LiAPO compositions by reference to their chemical composition in terms of the mole ratios of oxides. Molecular sieves containing lithium, aluminum and phosphorous as framework tetrahedral oxide units are prepared as followed:
• LiAPO compositions may be prepared by using numerous reagents.
• Reagents which may be employed to prepare LiAPOs include:
• TEAOH 40 weight percent aqueous solution of tetraethylammonium hydroxide
• TBAOH 40 weight percent aqueous solution of tetrabutylammonium hydroxide
• LiAPOs may be prepared by forming a starting reaction mixture by suspending aluminum oxide in at least part of the water. To this mixture the templating agent is added. The resultant mixture is then blended until a homogeneous mixture is observed. To this mixture the lithium phosphate or sulfate is added and the resulting mixture blended until a homogeneous mixture is observed.
• an initial mixture may be formed by mixing aluminum oxide and lithium phosphate or sulfate.
• To the resultant mixture are added successively phosphoric acid and an aqueous solution of the templating agent, and the resulting mixture blended until a homogeneous mixture is observed.
• the phosphoric acid is mixed with at least part of the water, and the aluminum oxide is mixed in.
• the resultant mixture are added lithium sulfate and the templating agent, and the resulting mixture blended until a homogeneous mixture is observed.
• reaction mixture is then placed in a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• a lined (polytetrafluoroethylene) stainless steel pressure vessel and digested at a temperature (150°C or 200°C) for a time or placed in lined screw top bottles for digestion at 100°C. Digestions are typically carried out under autogenous pressure.
• FeTiAPO MOLECULAR SIEVES The FeTiAPO molecular sieves of U.S. Serial No. 599,824, filed April 13, 1984, and U.S. Serial No. 902,129 filed September 2, 1986 have three-dimensional microporous framework structures of FeO 2 n , TiO 2 , AlO 2 - and PO 2 + tetrahedral oxide units, where "n" is -2 or -1, and have an empirical chemical composition on an anhydrous basis expressed by the formula:
• R represents at least one organic templating agent present in the intracrystalline pore system
• M represents iron and titanium
• m represents the molar amount of "R” present per mole of (M x Al y P z )O 2 and has a value of ze.ro (0) to about 0.3
• x, "y” and ⁇ "z” represent the mole fractions of "M", aluminum and phosphorus, respectively present as tetrahedral oxides.
• the mole fractions "x", "y” and “z” are generally defined as being within the limiting compositional values or points as follows:

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