Abstract: New catalysts for photo-assisted (i.e. promoted by light) oxidation-reduction (redox) reactions are disclosed. These catalysts consist of colloidal particles of a semiconductor, containing on their surface a reduction catalyst and an oxidation catalyst. In a first class of catalysts, the semiconductor has a difference of energy between valence band and conduction band such as to allow the hole-electron separation by absorption of visible light. This semiconductor is selected, in the case of the photo-decomposition of water, from the group consisting of TiO.sub.2 doped with Mn, Cr, or Cr and Nb; CdS doped with In or Ga; SrTiO.sub.3 doped with Cr or Mn; gallium phosphide; and cadmium sulphoselenide. In the case of the other photo-decomposition reactions, the semiconductor is selected from the group consisting of the above-mentioned compounds and CdS.

Abstract: The invention is directed to inorganic phosphate aerogels and the method of preparing such inorganic phosphate aerogels which are characterized by high surface areas and high pore volume. The preparation comprises reacting an inorganic alkoxide or metal salt with a phosphate to form a gelled or colloidal material which is further treated with a fluid at or above its critical temperature and pressure to extract the solvent which is then dried to remove surface water.

Abstract: An amorphous chromium (III) phosphate catalyst is used in alkylating aromatics and in the dehydration of alcohols to ethers.

Abstract: A new catalyst system for the conversion of short-chain aliphatic alcohols to hydrocarbons having the formula[ML.sub.q ].sub.b.sup.m+ [N].sub.d.sup.n+ [X.sup.p+ Y.sub.a Z.sub.(12-a) O.sub.40 ].sup.-(8-p)wherein:[ML] is an organometallic compound where M is at least one metal selected from Group IIIA, IVA, VA, IB, IIB, IVB, VB, VIA, Fe, Co, and Ni; and L is an organic ligand,N is a positively charged species including a positively charged organic ligand,X is at least one element selected from P, Si, As, Ti, Zr, B, Co, Cu or Sn,Y and Z are independently selected from W, Mo, or V,m+n=8-pq=1-6O<a.ltoreq.12O.ltoreq.d<3b=1 to 3.

Abstract: A catalyst for use in the mild hydrocracking (MHC) of heavy vacuum gas oils to produce middle distillates and a method for the preparation of the catalyst and a process for treating the heavy vacuum gas oils with the catalyst. The catalyst comprises molybdenum, nickel and phosphorus supported on gamma alumina. The catalyst of the invention possesses a P/Mo+Ni ratio between 0.7 and 1.1, which endows it with a high capacity for hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydroconversion of the fraction which can be distilled at 370.degree. C.+ to middle distillates, when the catalyst is used under MHC conditions, that is, T=variable, P=750 psig, LHSV=0.70 m.sup.3 /m.sup.3 h and the ratio H.sub.2 /VGO=300 Nm.sup.3 /m.sup.3. The new catalyst can operate for more than 26 months, maintaining a consistent conversion of 20% and achieving the sulfur and nitrogen requirements in the product obtained.

Abstract: Ethylene polymer is particularly suitable for the production of tough film is produced under slurry conditions using a fluorided aluminophosphate support and a reaction temperature within the range of 93.degree. to 107.degree. C. in the presence of hydrogen and a small amount of trialkyl boron cocatalyst wherein said aluminophosphate has a phosphorous to aluminum ratio within the very narrow range of 0.15 to 0.4 and wherein said aluminophosphate carrying chromium catalyst is being activated at a temperature within the range of 482.degree. to 704.degree. C. The resulting film is not only substantially superior to film made from the best of the readily available commercial resins but is also better than film made from polymers using a similar catalyst system without the specific combination of parameters of this invention.

Abstract: Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory oxide support containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one methylating agent under conditions suitable for the methylating agent compounds to promote the activity of tungsten and molybdenum oxides for the disproportionation reaction.

Abstract: A process for producing an antimony-containing oxide catalyst supported on silica for use in a fluidized bed reaction is described, by the steps of preparing a slurry containing an antimony compound, a polyvalent metal compound, and silica sol as the essential ingredients, heat treating the slurry at a pH of 7 or less and at a temperature of 40.degree. C. or higher, and thereafter spray-drying the slurry and calcining the dried particles, wherein said silica sol has a multi-peak particle size distribution profile that is derived by using a mixture of silica sol A in an amount corresponding to form 10 to 90 wt % of the total silica in the catalyst and silica sol B in an amount corresponding to 90 to 10 wt % of the total silica in the catalyst, with silica sols A and B having different average particle sizes, provided that the relations 3<da<100 and 0.1<da/db<0.9 are satisfied by da (m.mu.), the average particle size of silica sol A, and db (m.mu.), the average particle size of silica sol B.

Abstract: A catalyst composition is prepared by dissolving a suitable oxygen containing compound of a Group VIB metal (preferably Mo), a suitable compound of a Group VIII metal (preferably Ni) and phosphorous acid in water, mixing this solution with an alumina containing support material, and calcining this mixture. This catalyst composition is used primarily for hydrotreating of hydrocarbon feed stream, which contain nitrogen and sulfur impurities, particularly heavy cycle oils.

Abstract: Olefins are converted into other olefins having different numbers of carbon atoms by contact with a catalyst comprising an inorganic refractory material containing at least one of tungsten oxide and molybdenum oxide and a promoting amount of at least one treating agent selected from chlorinated silicon compounds, thionyl chloride, and sulfuryl chloride under conditions suitable for the treating agent to promote the activity of tungsten and molybdenum oxides for the disproportionation reaction.

Abstract: Vanadium phosphorus mixed oxide containing catalysts are prepared by sequentially forming an alpha-VOPO.sub.4 catalyst precursor in aqueous media, and thereafter partially reducing a portion of the vanadium to a valence state of +4 in an organic liquid reducing media, in the absence of corrosive reducing agents. The catalysts exhibit excellent activity for the production of maleic anhydride from 4 carbon atom hydrocarbons such as n-butane.

Abstract: An amorphous chromium (III) phosphate catalyst is used in alkylating aromatics and in the dehydration of alcohols to ethers.

Abstract: A catalyst for production of methacrylic acid, said catalyst being molded in a ring-like shape having an outside diameter of 3.0 to 10.0 mm, an inside diameter 0.1 to 0.7 times the outside diameter and a length 0.5 to 2.0 times the outside diameter, said catalyst comprising a catalytically active material having the composition represented by the following general formulaMo.sub.a P.sub.b A.sub.c B.sub.d C.sub.e D.sub.f O.sub.

Abstract: A catalyst support based on aluminum polyphosphate or polyphosphoric acid-impregnated alumina is provided by two alternative techniques. In the first embodiment, an aluminum polyphosphate composition is heated in a dry atmosphere and thereafter impregnated with a zerovalent chromium component under anhydrous conditions. The resulting catalyst is active for olefin polymerization. In the second embodiment, alumina is impregnated with a polyphosphoric acid composition. This resulting polyphosphoric acid impregnated alumina can be used as a support for zerovalent chromium or can be impregnated with a chromium component and oxidized to give an active hexavalent chromium species. The resulting catalysts are advantageous because of their unusual sensitivity to hydrogen thus allowing great leeway in molecular weight control.

Abstract: Aluminum phosphate having reduced fines is produced by gelling said aluminum phosphate in the presence of an acrylamide polymer. The resulting support is of primary utility as a base for a chromium olefin polymerization catalyst but is also suitable as a support for titanium catalysts such as TiCl.sub.3, TiCl.sub.4 /MgCl.sub.2 and other conventional catalysts typically associated with polymerization of propylene.

Abstract: A method is disclosed for preparing a supported hydrogenation metal catalyst containing one each of Mo or W and of Co and/or Ni incorporated into a suitable support. An aqueous impregnating solution containing the desired quantity of catalytically active metals and having a pH in the range of about 0.7-2.7 is prepared containing (1) at least one each of a soluble compound of molybdenum or tungsten and a compound of cobalt and/or nickel; (2) a solubilizing amount of about 0.2-1.0 mole of phosphorous per mole Mo or W; and (3) about 2-6% w basis support, of a suitable soluble amine compound, such as amine alcohols, polyamines and amine acids. A suitable support, e.g., alumina, silica or silica-alumina, is then impregnated with the metals-containing solution. After impregnation the support is dried and calcined. This preparation method significantly increases the hydrodenitrification activity of the resulting catalyst in a hydrocarbon hydroconversion process.

Abstract: A catalyst having heteropoly-acid structure and the general formula:Mo.sub.a V.sub.b P.sub.c Cu.sub.d As.sub.e X.sub.f O.sub.gwherein, X represents one or more elements selected from the group consisting of tin, lead, cerium, cobalt, iron, zirconium, thorium, tungsten, germanium, nickel, rhenium, bismuth, antimony, chromium, boron, magnesium, silver, aluminum, zinc and titanium and a, b, c, d, e, f and g represent the atomic ratio of the elements where,a is 10,b is a number of 3 or less than 3 excluding 0,c is a number of 0.5 to 6,d is a number of 3 or less than 3 excluding 0,e is a number of 3 or less than 3 excluding 0,f is a number of 0 to 3,g is a number determined depending on the valency and atomic ratio of other elements.There is also provided a process for producing methacrylic acid by oxidizing methacrolein with molecular oxygen or molecular oxygen-containing gas in the presence of the catalyst defined above.

Abstract: A process is provided for the preparation of attrition resistant, microspheroidal fluid bed catalysts comprising the mixed oxides of vanadium and phosphorus in which a vanadium phosphorus mixed oxided catalyst precursor is densified, comminuted, formed into fluidizable particles and calcined under fluidization-type conditions. The present invention further provides the attrition resistant fluidizable catalysts prepared by the inventive process, and further provides a process for utilizing such attrition resistant catalysts in the production of maleic anhydride in the vapor phase by the oxidation of 4 carbon atom hydrocarbons.

Abstract: A novel synthetic procedure is disclosed for producing heteropolyacid catalysts having the general formula H.sub.3+x PV.sub.x W.sub.3-x Mo.sub.9 O.sub.40 where 0<x<3. The synthesis of these catalysts requires the formation of a defect structure wherein three of the twelve transition metals which surround the phosphorus hetero atom are missing. Three metal atoms of two other transition metals are then added to the cluster in a separate step by mixing Na.sub.3 H.sub.6 PMo.sub.9 O.sub.34 with the oxides of such transition metals in the presence of hydrochloric acid. A preferred catalyst having the formula H.sub.3.5 PV.sub.0.5 W.sub.2.5 Mo.sub.9 O.sub.40 is also described.

Abstract: An oxidation catalyst composition produced by comprising mixing at least one crystalline composite oxide, as the first component, selected from the group consisting of (i) a crystalline composite oxide containing vanadium and phosphorus and showing the characteristic X-ray diffraction peaks as identified in the following Table A and (ii) a crystalline composite oxide containing vanadium and phosphorus and showing the characteristic X-ray diffraction peaks as identified in the following Table B, an aqueous solution, as the second component, containing vanadium and phosphorus, and silica sol, as the third component, to form an aqueous slurry, spray-drying the slurry, and calcining the solid particles thereby obtained:TABLE A ______________________________________ X-ray diffraction peaks (Anticathode: Cu--K.sub..alpha.) 2.theta. (.+-.0.2.degree.) ______________________________________ 15.7.degree. 19.6.degree. 24.2.degree. 27.1.degree. 28.8.degree. 30.4.degree.

Abstract: A new active stable catalyst for use in the removal of sulphur, nitrogen, contaminating metals, asphaltenes and Conradson carbon from heavy crudes and residues and, in particular, a method for the preparation of the catalyst and a process for the treatment of heavy crudes and residues with the catalyst. The catalyst comprises a hydrogenation component selected from Group VIB of the Periodic Table, a hydrogenation component selected from Group VIII of the Periodic Table and a phosphorus oxide component as active components all supported on an alumina carrier. The catalyst is made up of a dispersion of the above metals on the surface of the alumina carrier such that, when the catalyst is sulphided under specific conditions, catalytic activities such as hydrodesulphurization (HDS), hydrodenitrogenation (HDN) and hydrodemetallization (HDM) and the conversion of asphaltenes and Conradson carbon are improved.

Abstract: A process is provided for activating fluidizable catalysts containing the mixed oxides of vanadium and phosphorus useful for the production of maleic anhydride from 4-carbon atom hydrocarbons and oxygen by subjecting the catalyst to fluidization conditions and contacting the fluidized catalyst with oxygen at a temperature at least 20.degree. C. greater than the temperature required to produce about 85 percent conversion of hydrocarbon. A process is also provided for adding make-up fluid bed catalyst to an equilibrated catalyst by introducing a calcined and unequilibrated make-up catalyst into the fluid bed vessel containing equilibrated catalyst, subjecting the mixture to fluidization conditions and contacting the fluidized catalyst mixture with oxygen at a temperature at least 20.degree. C. greater than the temperature required to produce about 85 percent conversion of the hydrocarbon. The catalysts so activated and a process for producing maleic anhydride from 4-carbon atom hydrocarbons is also provided.

Abstract: A process for the manufacture of a phosphorus-vanadium and phosphorus-vanadium-co-metal catalysts suitable for use in the manufacture of maleic anhydride from butane which process comprises reacting at a temperature of about 0.degree. C. to about 200.degree. C. a vanadium compound in an organic ether solvent having about 2 to about 10 carbon atoms with a phosphoryl halide in the presence of water or an aliphatic alcohol having from about 1 to about 8 carbon atoms, eliminating the solvent and activating the catalyst by the addition of butane or other hydrocarbon feedstock and a phosphorus compound at a temperature of about 300.degree. C. to about 500.degree. C. The catalysts are useful for the manufacture of maleic anhydride from butane feedstock.

Abstract: Promoted antimony phosphate oxide complexes are excellent catalysts for the ammoxidation of methanol to HCN especially at high methanol throughputs.

Abstract: A process for the manufacture of a phosphorus-vanadium oxide and a phosphorus-vanadium-co-metal catalyst suitable for the oxidation of butane to maleic anhydride is disclosed. The catalyst is prepared by reacting, in an aqueous medium, a vanadium compound, inorganic acid and, if used, a metal oxide. Ortho-phosphoric acid is then added to form a soluble vanadium-phosphorus or a vanadium-phosphorus-metal catalyst. The acidified water is removed and aliphatic alcohols and either aromatic acids or aromatic anhydrides, or a mixture of these, are added and the alcohols are removed. The solid phosphorus-vanadium, or phosphorus-vanadium-metal oxide is recovered under vacuum.

Abstract: A paraffin or mixture of paraffins having from 2 to 5 carbon atoms is oxidatively dehydrogenated in the presence of a cobalt based catalyst composition which has been calcined in the absence of oxygen. The catalyst composition comprises cobalt; phosphorus; at least one promoter selected from the group consisting of zinc, titanium, zirconium, niobium, indium, lead and bismuth; at least one alkali metal and oxygen. The catalyst composition may also contain sulfur and/or a halogen. If the feed to the oxidative dehydrogenation process contains paraffins having more than two carbon atoms, some cracking of such paraffins will also occur at the conditions at which the oxidative dehydrogenation process is carried out.

Abstract: A catalyst system suitable for olefin polymerization comprising a mixed phosphate base made up of 75-99 mole percent aluminum phosphate and 1 to 25 mole percent of a phosphate of at least one other metal selected from gallium, yttrium, zirconium, lanthanum, neodymium and thorium in conjunction with an organoboron cocatalyst. The resulting catalyst system is capable of giving ethylene polymer having relatively low melt index and at the same time exhibits great sensitivity to molecular weight control agents so as to enable the production of a broad spectrum of polymers so far as melt index is concerned from a single catalyst system.

Abstract: A process is provided for the preparation of coated iron phosphorus oxide containing catalysts useful in the oxydehydrogenation of saturated carboxylic acids, wherein the catalysts are prepared by partially wetting a carrier or support in an aqueous silica solution/suspension, contacting the partially wet carrier with a powder of the iron phosphorus oxide catalyst, drying and calcining.

Abstract: A process for producing an oxalate diester is provided. The oxalate diester is produced by reacting an aliphatic alcohol, carbon monoxide and molecular oxygen at an elevated temperature and under pressure in the presence of a catalyst comprising (1) metallic palladium or a palladium compound, (2) a heteropoly-acid and (3) at least one nitrogen compound selected from the group consisting of nitric acid, nitrogen oxides and esters of nitrous acid.

Abstract: A process for preparing an oxidation catalyst composition comprises mixing at least one crystalline composite oxide, as the first component, selected from the group consisting of (i) a crystalline composite oxide containing vanadium and phosphorus and showing the characteristic X-ray diffraction peaks as identified in the following Table A and (ii) a crystalline composite oxide containing vanadium and phosphorus and showing the characteristic X-ray diffraction peaks as identified in the following Table B, an aqueous solution, as the second component, containing vanadium and phosphorus, and silica sol, as the third component, to form an aqueous slurry, spray-drying the slurry, and calcining the solid particles thereby obtained:TABLE A ______________________________________ X-ray diffraction peaks (Anticathode: Cu--K.sub..alpha.) 2.theta. (.+-.0.2.degree.) ______________________________________ 15.7.degree. 19.6.degree. 24.2.degree. 27.1.degree. 28.8.degree. 30.4.degree.

Abstract: A process for improving the operating characteristics of a phosphorous-, molybdenum-, and oxygen-containing catalyst used for the production of an unsaturated carboxylic acid by gas phase catalytic oxidation of a corresponding unsaturated aldehyde, comprising the step of calcinating the catalyst at a temperature of 300.degree.-500.degree. C. while a gas containing 0.05-3 vol. % of ammonia and/or steam is passed over the catalyst.

Abstract: Hydrocarbon conversion catalyst comprising an active metallic component comprising at least one metal having hydrocarbon conversion activity and at least one oxygenated phosphorus component, and a support component comprising at least one porous refractory inorganic oxide matrix component and at least one crystalline molecular sieve zeolite component.

Abstract: A catalyst support is prepared from a composite comprising alumina and one or more oxides of phosphorus by forming the composite into a shaped support material having at least 0.8 cc/gm of its pore volume in pores having diameters of 0 nm (0 .ANG.) to 120 nm (1,200 .ANG.) and at least 0.1 cc/gm of its pore volume in pores having diameters of 120 nm (1,200 .ANG.) to 5,000 nm (50,000 .ANG.) and heating said shaped support material in the presence of steam at sufficient elevated temperature, steam pressure, and time period to increase the average pore diameter of said shaped support in the absence of any appreciable reduction in pore volume.A catalyst is prepared by impregnating the steam-treated support with at least one hydrogenating metal.The catalyst can be used suitably in hydrocarbon conversion processes, such as a process for the hydrodemetallization of a hydrocarbon stream containing asphaltenes and a substantial amount of metals.

Abstract: Compositions conforming to the formula A.sub.x.sup.++ B.sub.y.sup.+++ (OH).sub.2x+3y-nz D.sub.z.sup.n-.tH.sub.2 O wherein A is a divalent metal, B is a trivalent metal, D is a polyanion, x, y, z and t are numbers greater than zero and n is a whole number preferably from 1 to 10 and the ratio of x:y is equal to or greater than 0.5 and less than or equal to 10 and a method for preparing said compositions are described.

Abstract: A process for preparing an antimony-containing metal oxide catalyst, comprising the steps of calcining at about 500.degree. to 1,000.degree. C. a metal oxide composition containing, as essential elements, antimony and at least one element selected from the group consisting of iron, cobalt, nickel, manganese, uranium, tin and copper, impregnating the calcined oxide composition with a tellurium-containing solution, drying the impregnated composition, and calcining the dried composition at about 400.degree. to 850.degree. C., wherein the tellurium-containing impregnating solution is a homogeneous, stable solution containing tellurium and at least one element selected from the group consisting of molybdenum and tungsten.Thus process is also useful for the modification of existing metal oxide catalyst of low performance and the reactivation of existing deteriorated metal oxide catalyst.

Abstract: In accordance with one embodiment of this invention, a zerovalent chromium compound is introduced onto an activated phosphate-containing support and utilized in conjunction with an organometal cocatalyst, such as a trialkylborane. In accordance with another embodiment of this invention, a phosphate-containing xerogel is formed by removing water from an aluminum phosphate-containing hydrogen by means of azeotropic distillation or washing with a volatile, water miscible organic compound, activated and thereafter zerovalent chromium is incorporated therewith. In other embodiments of this invention, a phosphate-containing support is formed by forming aluminum phosphate from an aluminum alkoxide or from a melt, or by phosphating silica or alumina, or by forming an aluminum phosphate/silica combination. A support thus formed is activated and a zerovalent chromium compound added.

Abstract: The present invention relates to a method for the preparation of phosphomolybdic acid based catalysts by forming a solution of hydrated phosphomolybdic acid in a substantially anhydrous alkyl alcohol, adding a base to the solution, evaporating the solution to yield a catalyst powder and thereafter drying and calcining the powder to form the active catalysts. A second method for preparation is also provided and includes the steps of forming a solution of hydrated phosphomolybdic acid in a substantially anhydrous alkyl alcohol, evaporating the solution to form a concentrate, impregnating a catalyst support material with the concentrate, contacting the impregnated support with ammonia gas in an amount sufficient to form an insoluble precipitate of ammonium alkyl phosphomolybdic acid within the pore structure of said support material and thereafter drying and calcining said impregnated support material so as to form a coated catalyst.

Abstract: Aluminum orthophosphate is prepared by combining a source of phosphate ions with an aluminum salt to form a concentrated mass, combining with sufficient neutralizing agent to partially neutralize, and aging until gellation occurs. The resulting aluminum phosphate is particularly suited for use as a base for a chromium olefin polymerization catalyst.

Abstract: A heteropolyacid type catalyst capable of producing methacrylic acid from methacrolein and molecular oxygen at an extremely high yield for a long time at a relatively low temperature for a short contacting time under a vapor phase is provided. This catalyst is prepared by:(a) mixing molybdophosphoric acid and compounds containing the other constituent elements of the catalyst with each other in the presence of water;(b) concentrating or drying the resultant solution or slurry;(c) adjusting the water content of the resultant concentrated or dried mixture to 5% to 20% by weight; and(d) heat treating the mixture at a temperature of 100.degree. C. to 300.degree. C.

Abstract: A heterogeneous process for preparing a vanadium-phosphorus-oxygen containing catalyst for use in the preparation of carboxylic anhydrides is disclosed. This process employs an activation procedure in an air-hydrocarbon atmosphere.

Abstract: A catalyst for the oxidation of hydrocarbons comprising a phosphorus and vanadium mixed oxide wherein the catalyst prepared by using an organic medium can be recycled according to our process thus conserving up to ninety percent of the vanadium used in the preparation of the catalyst. The mixed oxide can also be promoted by a transitional element of the IV and V period of the periodic table. These catalysts are particularly useful for the oxidation of C.sub.4 hydrocarbons to maleic anhydride.

Abstract: Metals contained in a hydrocarbon containing feed stream are removed by contacting the hydrocarbon containing feed stream under suitable demetallization conditions with hydrogen and a catalyst composition comprising zirconium phosphate and chromium phosphate. The life and activity of the catalyst composition may be increased by introducing a decomposable metal compound selected from the group consisting of the metals of Group V-B, Group VI-B, Group VII-B and Group VIII of the Periodic Table into the hydrocarbon containing feed stream prior to contacting the hydrocarbon containing feed stream with the catalyst composition.

Abstract: A process is provided for the preparation of iron phosphorous mixed oxide catalysts which are highly active at moderate temperatures by introducing iron and phosphorus containing compounds and promoter element containing compounds, if any, into a substantially organic liquid medium, heating, separating the resulting precursor, drying and calcining. The catalysts are useful for the dehydrogenation or oxydehydrogenation of organic compounds such as aldehydes or carboxylic acids.

Abstract: A catalyst comprising essentially zirconium phosphate and at least one of chromium and thorium.

Abstract: An element selected from Groups IA, IB, IIB, IIIA and IIIB is incorporated into an iron bismuth molybdate oxide complex catalyst by impregnation.

Abstract: There is disclosed a catalytic composition represented by the formula:(Mo).sub.a (W).sub.b (Bi).sub.c (Pb).sub.d (Sb).sub.e (A).sub.f (B).sub.g (C).sub.h (P).sub.m (O).sub.nin which A is iron and/or chromium, B is cerium and/or magnesium and C is potassium and/or lithium; and a, b, c, d, e, f, g, h, m and n stand for the numbers of atoms for molybdenum, tungsten, bismuth, lead, antimony, A, B, C, phosphorus and oxygen elements respectively, wherein, given that a+b=12,0.ltoreq.b.ltoreq.7, 0.4.ltoreq.c.ltoreq.7, 2.ltoreq.d.ltoreq.12,0.1/22.ltoreq.e/a.ltoreq.25/22, 0.05/22.ltoreq.f/a.ltoreq.3/22,0.ltoreq.g/a.ltoreq.2/22, 0.ltoreq.h/a.ltoreq.3/22,0.ltoreq.m/a.ltoreq.7/22, andn is the numbers of oxygen necessary to satisfy the valences of atoms for the individual constituent elements other than oxygen.