NOVEL METHOD FOR MAKING MOLECULAR SIEVES AND NOVEL MOLECULAR SIEVE COMPOSITIONS

Abstract: This invention relates to the synthesis of large pore composite molecular sieves and the synthetic large pore composite molecular sieves so produced. The molecular sieves of the invention have the same general utilities of the comparable molecular sieves of the prior art but have been found to be superior catalysts and absorbents. This invention relates to a hydrothermal synthesis of large pore molecular sieves from nutrients, at least one of which contains an amorphous framework-structure, and which framework-structure is essentially retained in the synthetic molecular sieve. This invention stems from a discovery that the intrinsic porosity characteristics of a nutrient that possesses an amorphous cation oxide-framework can be substantially retained in the final molecular sieve containing product formed by a hydrothermal process by carefully controlling the conditions under which the hydrothermal process is conducted. For example, the invention contemplates retention of the particle size in a final molecular sieve-containing product that corresponds with that of an amorphous cation oxide-framework nutrient used in its manufacture. This invention drives the selection of process conditions to achieve one or more of macro and meso porosity ("large pore composite porosity") in the final molecular sieve product as a direct product of the hydrothermal reaction producing the molecular sieve. The invention allows the production of a molecular sieve that is in in situ incorporated in the framework morphology of a solid cation oxide-framework used in the molecular sieve's manufacture.

Description: NOVEL METHOD FOR MAKING MOLECULAR SIEVES AND NOVEL MOLECULAR SIEVE COMPOSITIONS BRIEF DESCRIPTION OF THE INVENTION A method that stems from a discovery that the intrinsic porosity characteristics of a nutrient that possesses an amorphous cation oxide-framework can be substantially retained in the final molecular sieve containing product formed by a hydrothermal process by carefully controlling the conditions under which the process is conducted. This invention drives die selection of process conditions to achieve one or more of macro and meso po- rosity in the final molecular sieve product as a direct product of die hydrothermal reaction producing the molecular sieve. The invention allows the production of a molecular sieve that is incorporated in the framework morphology of a solid cation oxide-framework used in molecular sieve's manufacture. The invention is directed to a novel solid molecular sieve composition that contains a) a preformed porous geometric framework where the pores are one or more of macro and meso pores, and b) interconnected in situ formed crystalline molecular sieve particles that (i) contain micro pores and (ii) are structural components of the framewotk. BACKGROUND TO THE INVENTION The definition of molecular sieve, according to Szostak, "Molecular Sieves, Principles Of Synthesis And Identification," 1989, Van Nostrand Reinhold, New York, N.Y., at page 3, is — "A molecular sieve framework is based on an extensive three-dimensional network of oxygen ions containing generally tetrahedral-type sites. In addition to the Si *4 and AT 3 that compositionally define the zeolite molecular sieves, other cations also can occupy these sites. These cations need not be isoelectronic with Si +4 and Al * , but must have the ability to occupy framework sites. Cations presently known to occupy these sites within molecular sieve structures are — (M +2 0-)- 2 where M is Be, Mg, Zn, Co, Fe, Mn (M +i O, l where M is Al, B, Ga, Fe, Cr (MTOJ 0 where M is Si, Ge, Mn, Ti ((M +5 0_) +1 where M is P." The term molecular sieve encompasses the variety of structures within the classification set forth in Figure 1J of Szostak, supra, page 2, which classification is incorporated by reference. Molecular sieves come in two varieties, zeolitic molecular sieves ("ZMS") and non-zeolitic molecular sieves ("NZMS"). Szostak (page 4) treats aluminosilicates generally to be ZMS provided there is at least one aluminum ion per unit cell based on the bulk composition of the sample. The remaining structures are recognized to be NZMS. According to this characterization, the ZSM-5 structure is considered a ZMS at sil- ica/alumina less than 190 and NZMS above 190. This same convention holds when ZMS's contain trace amounts of other elements in the framework ion positions. (See Szostak, page 5, who considers a crystalline structure a ZMS if the number of other cations in the framework, other than aluminum and silicon, averages less than one per unit cell, all others being a NZMS.) Zeolitic molecular sieves are typically made from a source of silica that is reacted with a source of aluminum, in d e presence of materials that insure significantly alkaline conditions, water and ~ OH. The mix of the reactants may be called die reaction's nutrients. Many of the reactions are conducted in the presence of an organic template or crystal-directing agent, which induces a specific zeolite structure that can not be formed in die absence of the organic template. Most of the organic templates are bases, and many introduce hydroxyl ions to the reaction system. The reaction involves a liquid gel phase ("soup") in which rearrangements and transitions occurs, such that a redistribution occurs between the alumina and silica nutrients, and structural molecular identities corresponding to specific zeolites or other molecular sieves are formed. It is known that zeolites are not often formed above 350°Q diough descriptions of higher temperature formation of certain molecular sieves has been mentioned in the literature (see Szostak, supra, page 52). Lower temperatures than about 100°C require extensive crystallization time. As Szostak, supra, page 54, points out — Upon mixing of the reagents on the synthesis of zeolite molecular sieves, a gel generally is observed to form, which with time begins to separate into two phases: a solid and a liquid. isually, as the crystallization progresses, the gel plus the forming crystals increases in density and begins to settle to the boαom of the crystalliza- iion vessel, as the forming zeolite crystals have a density greater dian that of the initial gel. Thus successful crystallization sometimes can be suspected if a very dense, easily settling solid phase is observed in the crystallization vessel when the crystallization is terminated. When the desired crystal structure is obtained, the molecular sieve is brought to ambient temperatures and the crystallization process is arrested. The product of die reaction is iso- lated typically as a loose powder. The crystals that are formed in the powder are so assembled in the structure as to form special micro pores and micro pore openings of a kind that distinguishes the structure. The resulting crystals are an assemblage of individual units the growth of which may be small, medium or large, depending on d e conditions employed in the traditional method. The crystals may then, in the usual case, be formed into composite structures that allow their use as, e.g., absorbents and catalysts. A number of references describe processes for making ZMS by reacting an amorphous precursor in the presence of a small amount of water to form a dense interbonded mass. The amount of water is selected to be less dian that which is used in the aforementioned traditional method but large enough to interbond die ZMS particles into dense masses. For example, Haden et al., U.S. 3,065,064, convert to a ZMS, a dehydrated kaolin clay having a Si0 2 /_ 2 0 3 mol ratio of about 2, in the presence of a "concentrated aqueous solution of NaOH." The H-Oto Nz/D mol ratio in the mixture is within the range of 4.5- 11.5 "and being present in an amount such that the Na-O/SiO- mol ratio in the mixture is about 0.5." According to Haden et al.: "... the alkali is then reacted wid the alumina and/or silica of the dehydrated aluminum silicate until substantially all of the alkali is consumed, such reaction being carried out while controlling the temperature of the mass below that at which water will be evaporated from d e mass at the pressure employed and in the absence of an aqueous liquid phase external to and in contact with the mass. The reaction product is a coherent mass of substantially homogeneous amorphous composition and is the precursor of the desired synthetic crystalline zeolite. The amorphous reaction product is dien aged without substantial dehydration d ereof, preferably at elevated temperature under autogenous pressure or greater, to crystal- lize the material into the desired substantially homogeneous polyαystalline zeolite of the empirical formula Na-0 , Al-0 3 *2SiO : , 4-5H 2 0 in the form of a hard coherent mass of essentially the same volume as the original aluminum silicate-alkali mass." According to the patentee, d e object of the process is to form the ZMS into a "compact mass or masses" which is defined as a "dense or substantially nonporous mass." The patentee states, "only such dense masses react to provide a sufficient number of structural bridges between crystals to form the zeolite in the desired form of hard crystalline aggregates occupying essentially the same volume as die unreacted mass as opposed to the finely divided or pulverulent masses inherendy formed in carrying out prior art methods for producing die synthetic crystalline zeolite A." Miller, U.S. 5,558,851, patented September 24, 1996, relates to shaped zeolite structures wherein the reactants, in making the structures, are formed into a water-wet thick paste and crystallized after forming into a shaped structure. According to Miller's process, and as practiced by Haden et al, αystallization occurs without the presence of an "external liquid phase." 1 Needless to say, Miller's process transforms the reactants into the typical hydrothermally induced liquid phase reaction. According to Miller, the zeolites in the shaped structures contain "very small crystallites." Miller's use of low amounts of alkali 1 Compare with the "in the absence of an aqueous liquid phase external to and in contact with the mass" description of Haden et al., supra. metal should be expected to generate smaller crystallites (See Szostak, supra, page 73). As is the case with Haden et al., supra, Miller interbonds the ZMS particles so as to form die dense mass structure described by Haden et al. According to Miller's example 16 (specifically at column 21, lines 1-20), a mixture of TPAOH, NaOH and water were combined widi a mixture of silica and sodium alumi- nate, and die combination was mixed for 3 hours. A paste was formed of the combination by the addition of more water. Miller then combined die technique of Haden et al., supra, by the addition of kaolin clay, and he reduced the volatiles level to 53 weight percent by continued mixing at 60°C. Miller then air-dried the mixture to form a powder of 48 weight percent volatiles. According to Miller, "[t]he molar ratio of H 2 0/Si0 2 at this point was about 2.5." It is assumed d at the powder was an aggregation of pasted particles that no longer exhibit the particulateness and porosity of the silica. Miller placed the powder into a Teflon botde and the bottle was placed "in a stainless steel pressure vessel and heated at 140°C. and autogenous pressure for two days." According to Miller, the "resulting product was washed widi water, dried overnight in a vacuum oven at 120°C, and calcined in air for three hours at 593°C." Miller states that "X-ray diffraction analysis showed die product to be nearly 100% ZSM-5. The average crystallite size by SEM was about 0.1 micron." Ramesh B. Borade and Abraham Clearfield, ("Borade and Clearfield"), 2 make a zeolite Beta in a 24 hour synthesis at 170°C. from an extremely dense system in which the weight ratio of solid, measured as sodium aluminate and silica, to liquid, measured as tetra- ethylammonium hydroxide and water, mixtures is 1:1.8. They found that the product has comparable catalytic properties to samples prepared by previous methods. According to the detail description of Borade and Clearfield, die amount of the aforementioned liquid component "is just sufficient to wet all the solid particles and in some cases (especially at Si/Al ratio < 10) the reaction mixture is in the form of small lumps." According to die authors, the process uses "a much smaller proportion of TEAOH and shorter reaction time as compared to die usually synthetic mediods." Lowering die proportion of TEAOH allows the decrease in the amount of water content. "This change increases the weight ratio 2 "Synthesis of zeolite Beta from dense system containing a minimum of template," Catalysis Letters, 26 (1994) 285-289. of solid to liquid in the systems from 1:9.1 to 1:1.8. The mole ratios of Si0 2 /TEAOH increased from 0.53 to 6 and H 2 0/Si0 2 decreased from 23 to 6.1." The procedure employed by Borade and Clearfield is as follows: "Sodium alumi- nate, TEAOH and water were mixed and stirred for about 15 minutes. Then, this solution was added to a highly reactive fumed silica and stirred widi a spatula for about 15 minutes. Initially, the mixture appears to be a dry powder. As stirring continued for about 2 hours the mixture turned into a very dense and thick solid (solid: liquid " 1: 2), which was transferred into a stainless-steel autoclave and heated at 443K and autogenous pressure for 24 hours. The pH of the initial reaction mixture was iri the range 13.2-13.8 and after αystalli- zation it was in the range 11.4-12.0. After synthesis samples were dried at 120°C and dieii calcined at 540°C for about 15 hours," According to die audiors, n [T]he marked reduction in the use of TEAOH in the present method (2.5 versus 10-28 moles of TEAOH with reference to 1 mole of Al 2 0 3 ), shorter crystallization time (24 hours versus 4-10 days) and increased productivity (per batch) should lead to a lower synthesis cost of zeolite Beta. The product obtained also has comparable catalytic properties at least with reference to the cracking of hexane." The methods of Haden et al., U.S. 3,065,064, Miller, US. 5,558,851, and Borade and Clearfield, take a common approach to making ZMS, by reducing die amount of gelation of SiO : . This is accomplished by the use of smaller amounts of water dian has been used in the traditional process for making ZMS. As a result, Borade and Clearfield produce a very dense and diick solid, Miller produces a paste diat forms a dense and diick solid, and Haden et al. produce a dense or substantially nonporous mass. In effect, these authors have developed a process that depends on surface gelation of the silica particles .for ZMS formation. Surface gelation occurs at the particle interior and exterior surfaces. It allows the particles to become glued to each other by interfacial wetting of one viscid exterior surface by anodier. It also affects the interior pores by filling or collapsing pores thereby reducing the particle's pore volume. Surface gelation allows Haden et al. and Miller to make shaped ZMS structures. However, such surface gelation as pointed out by Haden et al. results in a relatively nonporous structure, meaning that the macro and meso pores 3 of the silica are eliminated by the gelation and bonding that occur in their processes. It is well known that molecular sieves are made from cation-oxide containing materials, such as silica and alumina, which prior to hydrothermal conversion contain macro and meso pores and a geometric framework that surrounds and forms such pores. In the thermal conversion of these porous materials, the framework is degraded and the framework becomes part of a viscid (gelatinous) soup, no longer capable of providing d e macro and meso pore network The typical product of the typical hydrothermal conversion is a powdery precipitate. Haden et al., U.S. 3,065,064, Miller, U.S. 5,558,851, and Borade and Clearfield, operate a "non-soup" hydrothermal process designed to create an amount of surface gelation that essentially eliminates the porosity inherent in the precursor cation-oxide containing framework materials in order to form a paste and achieve increased density. There is described in die heterogeneous catalyst art a number of processes for forming a catalyst. One method is characterized as an impregnation of the catalyst support wid liquid reagents that deposit in the pores of the support. It is commonly known as an impregnation process. The amount of liquid reagent deposited on d e support leaves an apparent incipient wet film. Those ingredients invariably reaα on the surface of the support to form the catalys The support is not changed by virtue of such treatment, and re- tains its original porosity. In most cases, the support is not thought to reaα with the liquid reagents. (See Stiles and Koch, Catalyst Manufacture, Second Edition, 1995, published by Marcel Dekker, Inc., New York, N.Y. 10016.) There is no process known in the art that causes conversion of conventional molecular sieve forming nutrients diat retains macro and meso porosity charaαeristics of a geometric framework cation-oxide containing nutrient. It would be desirable to produce As used herein, "macro pores" means above 500 angstroms (over 50 nanometers); "meso pores" means 20 to 500 angstroms (2-50 nanometers); and "micro pores" means less than 20 angstroms (under 2 nanometers). Also, in the terms describing the invention of this application, the terms "large pore" and "large pores," encompass structures that contain macro and/or meso pores. molecular sieves that possess a framework morphology charaαeπstic of at least one of cation oxide containing nutrients in the reaction. It would be desirable to have a reaαion of the typical nutrients in the formation of a molecular sieve that retains the framework morphology charaαeristic of at least one cation oxide containing nutrients in the reaction. THE INVENTION This invention relates to the synthesis of large pore composite molecular sieves and to the synthetic large pore (as defined herein) composite molecular sieves so produced. The molecular sieves of the invention have the same general utilities of the comparable molecular sieves of the prior art. However, the large pore composite molecular sieves of the invention have been found to be superior catalysts and absorbents to the composition- ally and structurally comparable molecular sieves of the prior art. This superiority is seen to result from the large pore composite feature of the composite molecular sieves obtained by the process of the invention. This invention relates to a hydrothermal synthesis of composite molecular sieves from nutrients, at least one of which contains an amorphous framework-structure, and which framework-structure is essentially retained in the synthetic molecular sieve. This invention stems from a discovery diat the intrinsic porosity charaαeristics of a nutrient that possesses an amorphous cation oxide-framework can be substantially rαained in the final molecular sieve containing produα formed by a hydrotiiermal process by carefully control- ling the conditions under which d e hydrotiiermal process is conduαed. For example, the invention contemplates retention of die particle size in a final molecular sieve-containing produα diat corresponds with that of an amorphous cation oxide-framework nutrient used in its manufacture. The invention further contemplates hydrothermal impregnation of an amorphous cation oxide-framework having an average particle size of about 0J microns to about 5 millimαers with aqueous containing nutrients to produce a molecular sieve- containing structure therefrom that has essentially die same average particle size. This invention drives the selection of process conditions to achieve one or more of macro and meso porosity ("large pore composite porosity") in the final molecular sieve produα as a direα produα of the hydrothermal reaction producing the molecular sieve. The invention allows the production of a molecular sieve diat is in situ incorporated in the framework morphology of a solid cation oxide-framework used in the molecular sieve's manufacture. This invention relates to the hydrotiiermal treatment of nutrients used in the manufacture of molecular sieves where at least one of the nutrients possesses geometric frame- works that contains one or more of macro and meso porosity (the "framework porosity") within it. According to this invention, hydrotiiermal conditions are seleαed to preserve at least 25 volume percent of the framework porosity, preferably 50 volume percent of the framework porosity, while at the same time effecting reaction of the nutrients such that a molecular sieve is formed within the boundaries of the framework-structures. The process of this invention effeαs intermolecular reactions of the nutrients such that a molecular sieve of the type desired is formed while at the same time substantially preserving the geometric framework-structure or morphology of at least one of the nutrients possessing said geometric framework. The process of this invention uses a nutrient with a porous framework-structure. The process of this invention effeαs at least partial reaction and transfor- mation of the framework nutrient widiout destroying die porous nature of the framework. In another aspeα of this invention, die process of the invention involves the incremental reaction of impregnated nutrients within a cation oxide geometric framework that is suitable for forming a molecular sieve therein. The added nutrients reaα with the cation oxide geomαric framework in such a way that it allows one to produce a crystalline molecular sieve within such framework. In this embodiment, die framework-structure is impregnated by die incipient wetness mαhod widi the additional nutrients, in one or more steps to produce a uniform distribution widiin the structure. It is believed d at the added nutrients reaα within the framework-structure in such a way that they mαer the rate at which solubilization occurs during die induction period to molecular sieve growth and or during die molecular sieve crystallization process. This allows for an ordered reaction of the added nutrients with the framework-structure nutrient, and diis insures and promotes high yields of molecular sieve in the framework-structure while retaining the large composite pores provided by the cation oxide geometric framework. The original framework-structure is amorphous, and the final framework-structure after crystallization contains a substantial crystalline content, typically at least 15 weight percent, preferably at least 25 weight percent, more preferably at least 40 weight percent and most preferably at least 50 weight percent, basis weight of the molecular sieve. The final framework-structure may contain from 75 to 100 weight percent crystalline molecular sieves, basis weight of the molecular sieve. This invention relates to a "dry" process for the making of a molecular sieve by impregnating a solid cation oxide-framework-structure with other nutrients suitable for a hydrodiermal reaction between the other nutrients and die solid cation oxide-framework- structure, to form an impregnated paste-free composition. Then the impregnated paste- free composition is subjeαed to conditions of temperature and pressure to effeα a hy- drothermal reaction and convert die nutrients of the reaction into a crystalline molecular sieve that possesses the morphologic charaαeristics of the solid cation oxide-framework- structure. The mαhod of diis invention for making a molecular sieve comprises a) crystallizing at an elevated temperature, i) a solid amorphous cation oxide-containing framework material possessing framework porosity and physical boundaries , ii) optionally in the presence of a pore forming material (template), iii) in the absence of an amount of free water (as contrasted with bound water) that is sufficient to cause substantial surface gelation, and b) transforming the solid macro and meso pore-containing amorphous cation oxide-containing framework material into a solid molecular sieve-containing produα having the physical boundaries and morphology of the solid pore-containing amorphous cation oxide-containing framework material and a framework porosity similar to the framework porosity of the amorphous cation oxide-containing framework material. Specifically, the invention relates to a method for making a molecular sieve, such as a zeolite, by crystallizing into a molecular sieve, solid shaped amorphous silica framework materials ("solid material") possessing a level of framework porosity, by heating the solid materials in the presence of (a) an aluminum containing component residing widiin the pores of the solid material and (b) a small quantity of water that contains, as needed, a micro pore forming component, sufficient to crystallize the silica and transform a significant portion of the solid material into a molecular sieve, 1. without significantly changing the shape of the solid materials and 2. wid out causing substantial surface gelation of the solid materials that causes interbonding of the solid materials to occur. The invention is direαed to a novel solid molecular sieve composition that contains ii) a preformed large pore geometric framework-structure, and iii) crystalline molecular sieve particles diat contain micro pores therein occupying structural components of the framework-structure. DETAILED DESCRIPTION OF THE INVENTION In the description of the invention, the effects of "surface gelation" distinguish d e prior art from this invention. In the case of the prior art, surface gelation of the cation ox- ide-framework causes loss of large pore composite porosity in the resulting molecular sieve containing structures and diat affects their performance capability. In the praαice of this invention, impregnation of a large pore cation oxide keeps surface gelation to a minimum and there is rriiriimal loss of large pore composite porosity of the cation oxide-framework. As a result, the molecular sieves of the invention are more active catalysts and better ab- sorbents than comparable molecular sieve containing structures. The invention relates to novel molecular sieve containing structures and processes for making the structures. The molecular sieves of the invention cover die wide variety of synthetic ZMS's and NZMS's known in the art, each embodied widiin a framework- structure possessing framework meso and/or macro, i.e., large pore composite porosity. The process of the invention mαers the interreactions of the molecular sieve nutrients, at least one of which is amorphous framework-structure, and through such metering, one can control surface gelation, cation transitions, molecular sieve crystal size, and structural integ- rity within such framework-structure. For example, the process of die invention limits the amount of liquid in the hydrothermal reaction such that there is very little to no surface gelation visible to the naked eye. In other words, the reaction appears to be "dry" because the liquid provided to the reaction wets the interior voids of die amorphous framework nutrient. It is believed that the chemical reactions occurring within the amorphous frame- work-structure predominantly occur within d e pores of the amorphous framework- structure. However, the nature of these reactions is such that the porosity of the amorphous framework-structure is essentially retained. If the amount of liquid, in any such case, were to destroy die interior voids of die framework-structure during hydrotiiermal re- aαion, tiien the amount of liquid is probably too great for the objectives of this invention, and should be reduced in order to preserve such porosity and framework-structure. It is believed diat the conversion of a amorphous cation oxide-framework-structure to a molecular sieve containing structure is a phase transition involving either a solid-solid transformation (see R. Szostak, supra, page 190) or a viscid gel surface reaction that creates nuclei crystals which grow to the molecular sieve crystals. The reaction is believed to ad- vance from die interior voids of die particle by a phase transition of the surface of d e particle structure and subsequendy proceeds to consume the particle tiiroughout the structure as crystallization progresses substantially uniformly therein. This "dry" process for d e making a molecular sieve involves impregnating a solid cation oxide-framework-structure with other nutrients such as water and a micro pore forming agent (e.g., an organic templating agent and/or a mαal (e.g., an alkali or alkaline earth mαal base)) widiout forming a paste and widiout destroying the structure of the cation-oxide framewor The impregnation is suitable for a paste-free hydrotiiermal reaction between the other nutrients and the solid cation oxide-framework-structure. The impregnated paste-free composition is subjeαed to conditions of temperature and pressure to ef- feα a surface hydrothermal reaction and convert the nutrients of the reaαion into a crys- talline molecular sieve that possesses the morphologic charaαeristics of the solid cation oxide-framework-structure. The "dry" reaction between the molecular sieve nutrients occurs at the interior surfaces of die amorphous framework-providing nutrient. Consequendy, die amorphous framework-providing nutrient is maintained dry thereby preserving the structural integrity of the framework-structure of one of the ingredients. A dry reaction, as used herein, means that the amount of surface gel formation is insufficient to cause destruαion of framework porosity of a framework precursor, such as particles of silica, alumina, alumino- silicate, titanium oxide, zirconium oxide, gallium oxide, arsenic oxide, germanium oxide, metal phosphate, and the like. For example, if the amorphous framework-providing nutrient were a free-flowing particle, it would remain free flowing after impregnation by the other nutrients used in the hydrodiermal reaction and before the hydrodiermal reaαion. However, it is contemplated according to die invention diat individual framework- structures may be interbonded prior to the hydrodiermal reaction and in many such cases, the interbonding creates macro pores within the interbonded structure. For example, porous framework material can be subjeαed to die hydrodiermal conditions of reaction and can undergo subde surface gelation to structural points on the exterior of the framework. Such surface gelation causes bonding widi adjacent framework-structures, and die interbonding typically creates additional porosity, typically maαo pores in the aggregated structure. This bonding results in clustering and aggregations of the molecular sieve containing framework-structures. Thus the amorphous framework-structure that one may use in making the molecular sieves of the invention may be particulate structures, and any bonded amorphous framework-structure that contains porosity within which the dry process can be conduαed. The invention can be carried out with small, medium and large size porous particles and any porous macrostructure of such particles, including monolithic and joined monolithic structures. Such an interbonded structure may then be subjeαed to hydrothermal conditions of reaαion in the presence of the correα nutrients to cause the formation of molecular sieve crystals therein without destroying the porosity and shape of the structure. A significant embodiment of diis invention involves the process of making small crystalline molecular sieve particles that are of a size amenable to extrusion and odier molding processes into catalyst structures. According to this process, cation oxide particles such as silica, alumina, aluminosilicate, titanium oxide, zirconium oxide, gallium oxide, ar- senic oxide, germanium oxide, metal phosphate, and die like, are comminuted to a smaller size porous particle than the ultimate molecular sieve composite particle size. These smaller particles are composited by conventional means to larger uniform large pore- containing particles, e.g., having a mean average particle size of about 5mm, suitable for making catalysts. Then the composited particles are subjeαed to hydrodiermal reaction conditions according to the invention to make a molecular sieve-containing produα diat is ideal for catalysts in reactions that molecular sieves are conventionally employed. The seleαion of process conditions in the practice of this invention is dependent upon die proportion of nutrients, especially the amount of liquid in the nutrient mixture and the absorptive properties of the amorphous cation oxide-framework-structure. For example, the amount of water should be insufficient to cause pore elimination and full densification of the framework-structure. The amount of water should be insufficient to cause the formation of a paste from the nutrients. The absorptive properties should be sufficient to assure a dry reaction, as defined above. In most instances, the amorphous framework-structure is subjeαed to conditions sufficient to either maintain a low bound water content in the structure or to sufficiently dry the amorphous framework-structure to achieve a low bound water content. This is achieved by calcining the amorphous framework-structure at a temperature and for a period of time to remove excess bound water from the framework-structure. Typically, calcination is effeαed at a temperature, at normal conditions, of at least 150°C to about 1000° or higher, until the desired water content is achieved. Lower temperatures result in longer calcination times and higher temperatures result in shorter calcination times. The desired bound water content of the amorphous framework-structure is dependent on die amount of molecular sieve crystal development one desires in the final produα and die amount of water that it is desirable to add in the process. The more water that one desires to add to the amorphous framework-structure the less bound water one will tolerate in the amorphous framework-structure. There is no clear limit on the amount of water that is tolerated in the amorphous framework-structure and is useable in the hydrothermal process other than the limitation that die amount should be such as to provide for a dry reaction, as defined above. For example, die amount of water that can be used to effeα the dry reaαion might, in the presence of different nutrients, cause the formation of a paste or a soup because of the amount of water that is provided by the nutrients. Generally, the water content of the nutrients is not mentioned or adequately controlled by the prior art. In addition, the hydrothermal reaction should be earned out in a sealed reaction vessel, typically at autogenous pressure, at moderate temperatures, such as from about 25°C to about 500°C, preferably from about 75°C to about 350°C and more preferably from about 100°C to about 250°C. The reaction has been most effectively carried out at temperatures of about 150°G Contrary to the conventional "soup" hydrodiermal reaction, the process of the invention does not generate a liquid or paste phase that is separable from the solid crystal phase. Any liquid or paste phase is to be avoided in carrying the impregnation process of the invention. After die hydrodiermal reaction has been carried out, typically within 2 to 130 hours, the solid reaction produα containing the framework- structure of a framework nutrient of the reaction may be used as such, or calcined to generate desired properties in the final produα. That calcination may range from about 150°C to about 1000°C, preferably from about 300°C to about 700°C, and most preferably, from 400°C to about 650°C. The resulting molecular sieve may then be used without any further processing, such as water washing and filtering. However, water washing and filtration may be employed if the cleanliness of the produα diαates that such treatments are desirable. The framework precursor to the framework-structure of the molecular sieve of the invention, may be any one of a variety of cation oxide containing nutrients used in making molecular sieves. It may be a silica, an alumina, a titanium oxide, a zirconium oxide, a gallium oxide, an arsenic oxide, a germanium oxide, a mαal phosphate, and the like. Such framework-structure, as pointed out above, may be small to large particles; aggregates of particles, fused particles, extruded particles, molded particles, sheets of bonded particles, monolidiic fused particles, and the like, provided there is a porous framework inherent in such structures. A preferred amorphous framework-structure nutrient for use in the process of die invention is silica, typically containing a low water content. Most desirably, the silica is a synthetic material. Any process may be used to form such silica so long as the silica contains large pores, as defined herein. For example, the silica may be formed by predpitation from a solution, by fuming silica forming materials, and die like processes. A very desirable framework-structure is silica, typically a pure silica (i.e., it does not contain any other cation oxide component), that has been reaαed with a solvent soluble aluminum source incorporated by impregnation up to indpient wetness of the silica, without destroying die amorphous framework-structure of the silica, allows on heating the formation of an alumi- num silicate therefrom. It is believed diat such ingestion of altiminum into the silica framework, aids in the subsequent dry hydrodiermal processing of nutrients to form the molecular sieves of the invention. Suitable solvent soluble altiminum sources indude alkali metal (e.g., Li, Na, K, Rb, ) and alkaline earth mαal (e.g., Be, Mg, Ca, Sr, Ba) salts of aluminum hydroxides and aluminas, aluminum salts of inorganic and organic acids, such as aluminum nitrate, aluminum sulfate, aluminum chloride, altiminum phosphate, aluminum monoacαate, aluminum diacetate, altiminum triacetate, aluminum monodtrate, aluminum didtrate, umiπum triάtrate, and mono, di, and tri alkyi (e.g., -C,) esters of aluminum hydroxide. The reaction is typically carried out by forming a solvent solution or liquid dispersion of the solvent soluble aluminum source and mixing it with die silica framework-structure up to indpient wαness of the silica framework-structure, followed by heating suffidendy to effeα transformation of die aluminum by reaαion with die silica surface and/ or reaction with the silica bulk itself. The reaction conditions are essentially the same conditions as the hydrothermal reaction used in forming the molecular sieve except that a micropore-forming agent is not present in the reaction. The solvent used in the reaction is typically water, though organic solvents such as alcohols, organic adds, polyols, and the like, may be employed instead. The amount of solvent soluble aluminum incorporated into the amorphous framework-structure is dependent on die amount of aluminum desired in the molecular sieve structure of the invention. Generally, the impregnation up to indpient et- ness of the silica with the aluminum source in the solvent takes up to about 1 to 2 hours. After the Al incorporation reaction has been carried out, typically within 2 to 130 hours, the solid reaction produα containing the framework-structure of a framework nutrient of the reaction may be used as such, or calcined to generate desired properties in the final produα. That calcination may range from about 150°C to about 1000°C, preferably from about 300°C to about 700°C, and most preferably, from 400°C to about 650°C. The resulting molecular sieve may dien be used widiout any further processing, such as water washing and filtering. Templates for the hydrodiermal reaction may be any of those known in the art for controlling molecular sieve micro porosity, and influencing the reaction to die desired mo- lecular sieve crystals. The template is generally charaαerized as an ion or neutral spe es which upon its addition to the reaction mixture, crystallization is induced of a spedfic zeolite structure that could not be formed in the absence of the agent. Inorganic cations aα- ing as counterions also are dominant in dαeπnining which zeolite structure is obtained. It is known that the cations can influence crystal morphology, crystallinity, and yield. (See Szostak, supra, page 73) It has been shown that such inorganic cations can influence crystal size. Suitable inorganic cations are die alkali mαals (Li, Na, K, Rb, Cs), the alkaline earth mαals (Be, Mg, Ca, Sr, Ba), the transition metals (Ti, Zr, Hf, V, Nb, Ra, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, As, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg) , and the like. In general the templating agent may be an organic compound diat contain elements of Group VA of the periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony, preferably N or P and most preferably N. The compounds also contain at least one alkylene, alkyl or aryl group having from 1 to 8 carbon atoms. Particularly preferred nitrogen-containing compounds for use as templating agents are the amines and quaternary ammonium compounds, the latter being represented generally by the formula R 4 N wherein each R is an alkyl or aryl group containing from 1 to 8 carbon atoms. Polymeric quaternary ammonium salts such as [(C, 4 H 32 N 2 )(OH) 2 j x wherein "x" has a value of at least 2 are also suitably employed. Both mono-, di- and triamines are advantageously utilized, either alone or in combination widi a quaternary ammonium compound or odier templating compound. Mixtures of two or more templating agents can either produce mixtures of the desired molecular sieve or the more strongly directing templating species may control the course of the reaction with die odier templating spedes serving primarily to establish the pH conditions of the reaction gel. Illustrative organic templating cations are the following: tetramethylamonium ("TMA"), tetraethylammonium ("TEA"), tetra-n- propylammonium ("TPA"), tetra-isopropylammonium, tetrabutylammonium ions, di-n- propylamine, di-n-butyiamine, tri-n-propylamine, triethyiamine, tnl-αitylamine, triethanola- mine, quinuclidine ("Q"), methyl quinudidine hydroxide, cydohexylamiiie, neopentyla- mines, N.N-dimethylberizylamine, N-N-dimethyiedianolamine, di-n-pentylamine, isopro- pylamine, t-butylamine, αhylenediamine; hexamethylenediamine, pyrrolidine; and 2- imidazolidone, piperidine, 2-medτylpyridine, N. -dimethylpiperazine, N- mediyldiethanolamine, N-methylethanolamine, N-methylpiperidine, 3-methylpiperidine, N- methylcydohexylamine, 3-methylpyridine, 4-medrylpyridine, diethylpiperidinium ("DEPP"), trimethylberizylammonium ("TMBA"), tetramethylphosphonium ("TMP"), 5- azoniaspiro(4,4)nonane or bispyrrolidinium ("BP"), (2-hydroxyethyl)trimethylammoniιιm ("choline"), l,4-dimethyl-l,4-diazoniabicydo (2,2,2) oαane ("DDO"), 1,4- diazoniabicydo(2,2,2)oαane ("DO" or "OABCO"), NJST-dimethyl-l,4-diazabicydo (2,2,2) octane ion. It is well understood by the art that every templating agent will direα die formation of every spedes of molecular sieve, i.e., a single templating agent can, with proper manipulation of the reaction conditions, direα the formation of several molecular sieve compositions, and a" given molecular sieve composition can be produced using several dif- ferent templating agents. The variety of molecular sieve covered by diis invention indudes all of the synthetic molecular sieves. The invention embraces all molecular sieves that can be made by chemical synthesis. This includes such ZMS as die faujasite (Types X and Y), mordenite, cancrinite, gmelinite, Type L, mazzite, offretite, omega, ZSM-12, beta, ZSM-5 and silicalite, ZSM-11, dachiardite, epistilbite, ferrierite, laumontite, stilbite, ZSM-23, thαa-1 and ZSM- 22, Eu-1 and ZSM-50, ZSM-48 and Eu-2, Type A and ZK-5, bikitaite, brewsterite, chaba- zite, TMA-E and AB, edingtonite, erionite, gismondine, heulandite, levyne, merlinoite, na- trolite, phillipsite, paulingite, rho, thomsonite, yugawaralite, and the like. It also indudes the variety of NZMS's that have been discovered such as the aluminophosphate molecular sieves, whose acronyms are set forth in the following table: Cauons -\cro__vm Cauons Acronym Al,P AlPO< Me, Al, P, Si MeAPSO Fe, Al, P, Si FAPSOA Si, Al, P SAPO Mg,Al,P,Sι MAPSO Mn,Al,P,Si CoAPSO Me,Al,P eAPO Co,Al,P,Si CoAPSO Fe,Al,P FAPO Zn,Al,P,Si ZAPSO g,Al,P MAPO Mn,Al,P MnAPO Other Elanσ-v Co,Al,P CoAPO E1.-A1.P E1APO Zn,Al,P ZAPO El,Al,P,Si E1APSO See Szostak, supra, page 211 A listing of such NZMS can be found in U.S. Patent No.4,440,871, to Lok α al, and U.S. Patent No.4,791,083, to Pellα et al., and such listing, and dtanons of patents and applications where the manufacture of such NZMS can be found, are incorporated herein by reference. A vaπety of non-aluminosilicate molecular sieves are charaαerized by Szostak, supra, at table 4J (page 209), which is reported below for convenience, and such non-aluminosilicate molecular sieves are incorporated herein by reference. Some metallosilicate molecular sieves reported in the patent literature and their known zeolite structure t e: * Agency ot industrial Science and Technology. ** Center for industrial Research of Quebec. Szostak, supra, pages 51 to 132 indusive, which is incorporated herein by reference, describes in great detail the hydrodiermal process for making ZMS, and at pages 205 to 281 indusive, which is also incorporated herein by reference, describes in great detail die hydrodiermal processes for making the various NZMS's. The process of this invention, which makes new ZMS and NZMS structures, draws upon tiiose descriptions developed in the prior art, but distinguishes from die prior art in the manner by which the hydrodiermal process is carried out. The fundamental difference from die prior art is that the process of this invention limits the hydrodiermal reaction conditions within the cation oxide amorphous framework-structure so that the process is dry, as charaαerized above. This means that die various conditions used in the prior art can be employed in the practice of this invention with die modification that die reaction be controlled to operate as a dry rea ion. This also means that the rate at which water is incorporated in making the molecular sieve is controlled to asstire that dry conditions prevail. In some cases, water is incrementally fed widi or widiout odier nutrients to the amorphous framework-structure, and/or water widi or without odier nutrients is provided to die amorphous framework-structure, to a state of incipient wetness, .and after digestion, more water is similarly added. In this way the degree of conversion of the amorphous framework-structure to molecular sieve is readily control- lable. Surprisingly, such procedures result in faster reactions and quicker conversion of amorphous framework-structures to molecular sieve. In some reactions, a limited amount of routine experimentation such as reordering addition of nutrients and temperature condition for crystal growth will be necessary to make a seleαed ZMS or NZMS. However, such experimentation will not be undue making the objectives of diis invention inoperative with respeα to any molecular sieve structure already known in the art. In addition, die process of diis invention creates the potential for the development of novel molecular sieves. In die following examples, the conversion levels of the products were measured by x-ray powder diffraction pattern ("XRD"). The crystallinity of the produα was compared to the crystallinity of a reference sample by calculating the ratio of die peak areas (A): αys- tallinity-A -ample /A --- ( m!n<:e . For zeolite beta, the ratio of the peak areas at 20= 22.4° was used. The reference H-beta sample was obtained from UOP. For ZSM-5 and silicalite-1 the crystallinity was calculated by the ratio between the sum of the peaks between 20=23° and 25°. The reference Na-ZSM-5 sample was obtained from UOP. For zeolite Y the crystallinity was calculated by the ratio of the peaks areas at 23.6, 26.9 and 31.3°. The reference NaY sample was obtained from Akzo. All samples were washed widi an excess of water on a filter, and dried in air at 120°C before measurement of the X-ray spectrum- Example 1 Conversion to zeolite beta Davison * Sylopol * 948 silica gel 50 μ spheres (486 grams) were fully impregnated to die indpient wetness point by an aqueous Al(N0 3 ) 3 solution (made widi 202 grams of Al( 0 3 ) 3 -9H 2 0 (Merck) dissolved in 800 grams of water), over a one-hour period, then dried in air at 120°C to a constant weight. After drying, d e dried impregnated silica spheres were caldned at 500°C for 2 hours, resulting in a 5.35 weight % Al,0 3 content and a Si/Al ratio of 15. These spheres (1J0 grams) were mixed with 1J0 grams of an aqueous 35 w ght % tαraαhylammonium hydroxide (Aldrich) solution and 0.57 gram of an aqueous 3.68 weight % NaN0 3 solution, corresponding to a molar oxide ratio of: 13.3 SiO : : 0.44 Al,0 3 : 1 TEA 2 0: 0.1 Na.0: 55 H 2 0 The mixture was placed in a 35 ml autodave with a 4 ml Teflon * insert and heated at 155°C for 44 hours. The product, which contained crystallite dusters of approximately 250 nm and large pores between these dusters, consisted of 50 μm partides with a framework-structure, as determined by scanning eleαroπ microscopic analysis, similar to die original Davison * Sylopol * 948 silica gel 50 μm spheres. The crystallinity of the zeolite b a produα was 78%. Example 2 Conversion to zeolite beta Shell * (S 980 A 3.0) 3.0 mm silica spheres (3.09 grams) were fully impregnated to indpient wetness by a mixture of 1.25 grams of Al(N0 3 ) 3 -9H 2 0 dissolved in 6.00 grams of water to obtain a Si/Al ratio of 15 in die impregnated prσduα. The impregnated produα was air dried at 120°C to a constant weight. Two grams of these impregnated spheres were additionally impregnated widi an aqueous 35 weight % tetraαhylammonium hydroxide solution and 1.04 grams of an aqueous 3.68 weight % NaN0 solution, giving a molar oxide ratio of — 13.3 SiO,: 0.43 Al,0 3 : 1 TEA 2 Q 0.1 Na 2 0: 55 H 2 0 The mixture was placed in a 30 ml stainless steel autodave with a 25 ml Teflon * insert. After heating for 44 hours at 155°C, the produα possessed 82% zeolite beta crystals and the morphology of the Shell 3.0 mm silica spheres. Example 3 Conversion to zeolite beta Davison * Sylopol * 948 silica gel 50 μm spheres were air-milled to a partide size of 3.-5 μm. Then 3J0 grams of the milled partides were fully impregnated to indpient wetness by a mixture of 1.25 grams of A1(N0 3 ) 3 and 10.0 grams of water to result in a Si/Al ratio of 15, and dien dried in air at 120°C to a constant wdght. Two and one-half grams of the milled and impregnated partides were impregnated wid 2.50 grams of an 35 weight % aqueous tetraethylammonium hydroxide solution and 1.25 grams of an 3.68 weight % aqueous NaN0 3 solution, resulting in a molar oxide ratio of 13.2 SiO 2 :0.44 Al 2 O 3 :1.00 TEA,Q0J Na,Q55 H,0 The mixture was placed in a 35 ml stainless steel autodave with a 10 ml Teflon insert. After 46 hours at 155°C, the powder had been converted to 47 weight % zeolite beta. After ultrasonic treatment for 3 hours, the individual partide size of 3-5 μm was regained. The average crystallite size, according to TEM analysis (transmission deαron microscopy), was 75-100 nm. The individual crystallites had a more ordered stacking than the reference zeolite beta powder. Example 4 Conversion to zeolite beta As described in Example 1 above, 3J0 grams of Davison * Sylopol" 948 silica gel 50 μm spheres were fully impregnated to indpient wetness by a solution made from 1.26 grams of Al(N0 3 ) 3 -9H 2 0 and 8.60 grams of water, dried in air at 120°C and calcined at 400°C for 3 hours, cooled to room temperature and calcined at 800°C for 3 hours, resulting in 5.35 w ght % Al 2 0 3 content (Si/Al ratio is 15). Two and one-half grams (2.50 grams) of these spheres were impregnated with 2.50 grams of an aqueous 35 weight % tetraethylammonium hydroxide solution and 1.25 grams of an aqueous 3.68 weight % NaN0 3 solution. The molar oxide ratio was: 13.2 SiO,: 0.44 Al 2 0 3 : 1.00 TEA 2 Q 0.10 Na-Q 55 H 2 0 The mixture was placed in a 35 ml stainless steel autodave with a 10 ml Teflon insert. After 44 hours at 160°C, the spheres were converted to 94 wdght % zeolite beta. According to SEM analysis, the original size and shape of the spheres were not affeαed by the hydrodiermal processing. Large pores were present in the converted spheres and crystallite dusters of 0.20-0.25 μm were formed. Typical features observed by TEM are cr y stallite sizes of 50-100 mm and a more ordered stacking of crystallites than in the reference zeolite beta powder. Example 5 Conversion to zeolite beta As described in Example 1 above, Davison Sylopol * 948 silica gel 50 μm spheres were impregnated with an aqueous Al(N0 3 ) 3 -9H 2 0 .olu- tion, dried in air at 120°C and calcined at 400°C for 3 hours, cooled to room temperature, resulting in 5.35 weight % Al 2 0 3 content (SiΛ l ratio is 15). Two and one-half grams (2.50 grams) of these spheres were impregnated with 1.65 grams of an aqueous 35 weight % tetraediylammonium hydroxide solution and 1.25 grams of an aqueous 3.68 wdght % NaN0 3 solution. The molar oxide ratio was: 20.1 Si0 2 : 0.66 Al 2 0,:l TEA 2 0: 0.14 N- O: 64.5 H 2 0 The mixture was placed in a 35 ml stainless steel autodave with a 10 ml Teflon * insert. After 120 hours at 160°C the zeolite beta crystallinity of the produα was 32.4%, as measured by XRD versus the reference sample, while maintaining according to light microscopy the sphere morphology of the Davison * Sylopol * 948 silica gel 50 μm spheres. Example 6 Conversion to ZSM-5 As described in Example 1 above, 3J0 grams of Davison * Sylopol * 948 silica gel 50 μm spheres were impregnated widi a mixture of 0.63 gram Al(N0 3 ) 3 -9H 2 0 and 11.5 grams of water to obtain a Si/Al ratio of 30„ and dried in air at 120°C to a constant weight. Two and one-half grams (2.50 grams) of these spheres were impregnated with 1.25 grams of an aqueous 35 wdght % tetrapropylammonium hy- droxide solution and 1.25 grams of an aqueous 3.68 wdght % NaN0 3 solution, giving a molar oxide ratio of: . 33.6 Si0 2 : 0.56 Al 2 0 3 : 1 TPA 2 Q 0.22 N-uQ 108 H 2 0 The mixture was placed in a 35 ml stainless steel autodave with a 10 ml Teflon insert. After 25 hours at 158°C the ZSM-5 crystallinity of the produα was 25.1% as meas- ured by XRD versus the reference sample. The partide shape and size of the parent amorphous framework-structure spheres were retained in the produα. Large pores were formed in the produα spheres upon conversion to ZSM-5. According to SEM analysis, the produα spheres contained cubic crystals sized between 0.5 μm and 1.5 μm. Example 7 Conversion to ZSM-5 Shell * (S 980 A 3.0) 3.0 mm silica spheres (6.20 grams) were fully impregnated to indpient wetness by a mixture of 1.26 grams of Al(N0 3 ) 3 -9H 2 0 dissolved in 12.08 grams of water to obtain a Si/Al ratio of 30 in the impregnated produα. The impregnated produα was air dried at 120°C to a constant weight. Two and one-half grams (2.50 g) of these spheres were impregnated wid 1.25 g of an aqueous 40 weight % tαrapropylammonium hydroxide solution and 0.55 g of an aqueous 3.68 weight % NaN0 3 solution, corresponding to the following molar oxide ratio: 33.6 SiO : : 0.56 Al 2 0 3 : 1 TPA 2 0 : 0.1 Na 2 0 : 60 H 2 0 The mixture was placed in a 35 ml stainless sted autodave with 10 ml Teflon insert. After 18 hours at 155°C the S 980 spheres were partially converted to ZSM-5 (10% cr y stallinity), while rαaining the original S 980 sphere morphology. Example 8 Conversion to Silicalite-1 In this example, 1J0 g of Davison * Sylopol * 948 silica gel 50 μm spheres were fully impregnated to indpient wetness by mixing with 0.55 g of an aqueous 40 weight % tαrapropylammonium hydroxide solution and 0.55 g of an aqueous 3.68 weight % NaN0 3 solution, giving the following molar oxide ratio: 33.7 SiO,:1.00 TPA 2 O:0.22 NajO.92.4 H 2 0 The mixture was placed in a 35 ml stainless steel autodave with 4 ml Teflon insert. After 23 h at 165°C the impregnated spheres were partially converted to silicalite-1 (crystallinity 11%). By light microscopy it was observed that d e partide size and shape of the precursor material was maintained. Example 9 Conversion to zeolite Y In this example, 495 grams of Davison * Sylopol ® 948 silica gel 50 μm spheres were fully impregnated to indpient wetness by a mixture of 294 grams of Al(Nθ 3 ) 3 and 770 grams of water, dried in air at 120°C to a constant wdght, and calcined in at 500°C for 2 hours. The resulting .Al 2 0 3 content was 7.50 wt %. Ten grams of these spheres were impregnated wid 24.30 grams of a mixture of 13.44 grams of Al(N0 3 ) 3 -9H 2 0 and 35.3 of water to obtain a Si/Al ratio of 4.75, dried in air at 120°C to a constant wdght and calcined at 300°C for 6 hours. Finally the spheres were fully impregnated with 24.44 grams of the above mentioned A1(N0 3 ) 3 solution to obtain a Si/Al ratio of 3, dried in air at 120°C to a constant weight and calcined at 300°C for 6 hours. Two grams of these spheres were impregnated with 3.50 g of an aqueous 20% NaOH solution. The resulting molar oxide ratio was: 2.94 SiOj:0.49 Al 2 O 3 :1.00 Na.O.17.8 H 2 0 The impregnated spheres were heated at 100°C in a 50 ml polypropylene botde. After 16 hours, the crystallinity of the produα was 102% zeolite Y in the form of crystallite dusters of 1.5-2.0 μm in size. By TEM it was found diat these crystallite dusters consisted of or- dered 50- 100 nm crystals. According to SEM analysis, die produα's shape and size was that of the parent partides widi large pores within the sphere structure. Example 10 Conversion to zeolite Y Davison * Sylopol" 948 silica gel 50 μm spheres (486 grams) were fully impregnated to indpient wetness with an aqueous Al(N0 3 ) 3 solution (made with 202 grams of Al(N0 3 ) 3 -9H 2 0 dissolved in 800 grams of water), then dried in air at 120°C to a constant weight. .Aiter drying, die dried impregnated silica spheres were calcined at 500°C for 2 hours, resulting in a 5.35 weight % Al 2 0 3 content and a Si/Al ratio of 15. The spheres were jet milled to a partide size of 3-5 μm. Of these partides 10.03 grams were fully impregnated to indpient wetness by 25.42 grams of a mixture of 15.84 grams of Al(N0 3 ) 3 -9H,0 and 35.0 g of water to obtain a Si/Al ratio of 5.0, dried in air at 120°C to a constant weight, and calcined at 300°C for 6 hours. The partides were then impregnated with 25.42 grams of the above-mentioned Al(N0 3 ) 3 solution to obtain a Si/Al ratio of 3, dried in air at 120°C to a constant weight, and calcined at 300°C for 6 hours. Of these partides, 2.00 grams were fully impregnated to indpient wetness by 4.00 grams of an aqueous 20% NaOH solution. The resulting molar oxide ratio was: 2.58 SiO 2 :0.43 Al 2 O,:1.00 Na-Ql7.8 H 2 0 The mixture was heated at 100°C in a 100 ml polypropylene botde. After 22 hours the crystallinity of the produα was 86% zeolite Y. After ultrasonic treatment for 3 hours, particle size measurements indicated a typical partide size equal to that of the parent material.

Claims: CLAIMS: 1. A synthetic large pore composite porosity molecular sieve that possesses a cation oxide-framework containing large pores composite porosity wherein the cation ox- ide-framework-struαure is essentially that of a cation oxide containing nutrient used in making the molecular sieve and preserves at least 25 volume percent of die nutrient's cation oxide-framework porosity. 2. A process for making a large pore molecular sieve having a framewoik- structure containing large pore composite porosity which comprises impregnating an amorphous cation oxide-framework-structure under controlled hydrodiermal conditions widi nutrients suitable for forming a synthetic molecular sieve and preserving at least 25 volume percent of the amorphous framework-structure. 3. The synthetic large pore composite porosity molecular sieve of daim 1 wherein the framework-structure contains molecular sieve crystals therein. 4. The process of claim 2 wherein the amorphous cation oxide-framework has an average partide size of about 0J microns to about 5 millimαers and is impregnated with aqueous containing nutrients to produce a molecular deve-containing structure therefrom that has essentially the same average partide size. 5. This process of daim 4 wherein hydrodiermal conditions are seleαed to preserve at least 50 volume percent of the framework porosity while at the same time ef- fecting reaction of the nutrients such that a molecular sieve is formed within the boundaries of die framework-structure. 6. The process of daim 2 wherein the controlled hydrothermal conditions involves the incremental reaction of impregnated nutrients within a cation oxide geometric framework that is suitable for forming a molecular sieve therein. 7. The process of daim 6 wherein the nutrients reaα with d e cation oxide- framework to produce a crystalline molecular sieve within such framework. 8. The process of daim 7 wherein the framework-structure is impregnated in one or more steps with reactive nutrients. 9. The process of daim 7 wherein the added nutrients reaα within the framework-structure to mαer the rate of the solubilization of the added nutrients and die framework nutrient during the transformation to crystalline molecular sieve structure. 10. The process of daim 9 wherein the molecular sieve structure is a zeolite. 11. The synthαic large pore composite porosity molecular sieve of daim 1 wherein cation oxide of the nutrient is amorphous and die framework-structure of the molecular sieve contains a substantial microporous crystalline content. 12. The synthetic large pore composite porosity molecular sieve of daim 11 wherein crystalline content is at least 15 wdght percent of the weight of the synthetic large pore composite porosity molecular sieve. 13. The synthetic large pore composite porosity molecular sieve of daim 12 wherein crystalline content is at least 25 wdght percent of the wdght of the synthetic large pore composite porosity molecular sieve. 14. The synthetic large pore composite porosity molecular sieve of daim 13 wherein crystalline content is at least 40 weight percent of the weight of the synthetic large pore composite porosity molecular sieve. 15. The synthetic large pore composite porosity molecular sieve of daim 14 wherein crystalline content is at least 50 wdght percent of the wdght of the synthetic large pore composite porosity molecular sieve. 16. The synthetic large pore composite porosity molecular sieve of claim 15 wherein crystalline content is from 75 to 100 wdght percent of the weight of the synthetic large pore composite porosity molecular sieve. 17. The synthetic large pore composite porosity molecular sieve of daim 1 wherein the molecular sieve is one of a ZMS and a NZMS. 18. The synthetic large pore composite porosity molecular sieve of daim 17 wherein the molecular sieve is ZMS. 19. The synthαic large pore composite porosity molecular sieve of claim 17 wherein the molecular sieve is NZMS. 20. The synthetic large pore composite porosity molecular sieve of daim 18 wherein the ZMS is zeolite beta. 21. The synthetic large pore composite porosity molecular sieve of daim 18 wherein die ZMS is zeolite Y. 22. The synthetic large pore composite porosity molecular sieve of daim 18 wherein the ZMS is ZSM-5. 23. The synthetic large pore composite porosity molecular sieve of claim 19 wherein die molecular sieve is silicalite-1. 24. A dry process for die making of a molecular sieve which comprises im- pregnating a solid cation oxide-framework-structure with other nutrients suitable for a hydrothermal reaction between the other nutrients and die solid cation oxide-framework- structure, to form an impregnated paste-free composition, and d en subjecting the impregnated paste-free composition to conditions of temperature and pressure to effeα a hydrothermal reaction and convert the nutrients of the reaction into a crystalline molecular sieve that possesses the morphologic charaαeristics of the solid cation oxide-framework- structure. 25. A method for making a molecular sieve which comprises a) crystallizing at an elevated temperature, i) a solid amorphous cation oxide-containing framework material possessing framework porosity and physical boundaries , ii) optionally in the presence of a pore forming material (template), iii) in the absence of an amount of free water that is suffident to cause substantial surface gelation, and b) transforming d e solid macro and meso pore-containing amorphous cation ox- ide-containing framework material into a solid molecular sieve-containing produα having the physical boundaries and morphology of the solid pore-containing amorphous cation oxide-containing framework material and a framework porosity similar to the framework porosity of the amorphous cation oxide-containing framework material. 26 A mαhod for making a zeolitic molecular sieve by i) crystallizing into a molecular sieve, solid shaped amorphous silica frame- work materials possessing a level of framework porosity, (1) by heating the solid materials in the presence of (a) an aluminum containing component residing within the pores of the solid material and (b) a small quantity of water that contains, as needed, a micro pore forming component, suffident to crystallize the silica and transform a significant portion of the solid material into a molecular sieve, • 1. without significantly changing the shape of the solid materials and 2. widiout causing substantial surface gelation of die solid materials that causes interbonding of the solid materials to occur. 27 A process for making a molecular sieve containing structures possessing framework large pore composite porosity which involves the hydrod ermally reacting molecular sieve nutrients, at least one of which is amorphous framework-structure, and controlling surface gelation, cation transitions, molecular sieve crystal size, and structural integ- rity widiin such framework-structure by limiting the amount of liquid in the hydrodiermal reaction such that there is very l rie to no surface gelation visible to the naked eye. 28. A dry process for making a molecular sieve containing structure possessing framewoik large pore composite porosity which involves hydrodiermally reacting molecular sieve nutrients, at least one of which is amorphous framework-structure, and controlling surface gelation, cation transitions, molecular sieve crystal size, and structural integrity within such framework-structure by limiting the amount of liquid in the hydrothermal reaction such that there is very little to no surface gelation visible to the naked eye. 29. The process of daim 28 wherein the reaction appears to be dry because the liquid provided to the reaction was the interior voids of the amorphous framework nutrient. 30. The process of daim 29 wherein the reaction occurring within die amor- phous framework-structure predominantly occurs within die pores of the amorphous framework-structure. 31. The process of daim 30 wherein the reaction is such diat the interior pores of the amorphous framework-structure are essentially retained. 32. A dry process for making a molecular sieve which involves impregnating an amorphous solid cation oxide-framework-structure with other nutrients induding water and a micro pore forming agent to form a paste-free hydrodiermal reaction mixture between the other nutrients and die solid cation oxide-framework-structure, placing the reaction mixture under conditions of temperature and pressure to effeα a hydrodiermal reaction at the interior surface of the amorphous solid cation oxide-framework-structure to convert die nutrients of the reaction into a crystalline molecular sieve that possesses the morphologic charaαeristics of the amorphous solid cation oxide-framework-structure. 33. The dry process of daim 32 wherein the reaction between the molecular sieve nutrients occurs at the interior surfaces of the amorphous solid cation oxide- framework-providing nutrient. 34. The dry process of daim 32 wherein amorphous cation oxide-framework- providing nutrient is maintained dry diereby preserving the structural integrity of the framework-structure of one of the nutrients. 35. The dry process of daim 32 wherein there is formed a surface gel within the framework-structure, and the amount of surface gel formation is insuffident to cause destruction of framework porosity of the framework. 36. The dry process of claim 32 wherein the amorphous framework-structure comprises parades of one or more of silica, alumina, aluminosilicare, titanium oxide, zirconium oxide, gallium oxide, arsenic oxide, germanium oxide, and mαal phosphate. 37. The dry process of claim 32 wherein the framework-structure is interbonded prior to the hydrotiiermal reaction. 38. The dry process of claim 32 wherein cation oxide partides from the group consisting of silica, alumina, aluminosilicate, titanium oxide, zirconium oxide, gallium ox- ide, arsenic oxide, germanium oxide, and mαal phosphate are cornminuted to a smaller size porous partide than the ultimate molecular sieve composite partide size and such smaller partides are composited to larger uniform large pore-containing partides, after which such composited particles, as the amorphous solid cation oxide-framework-structure, are subjeαed to hydrothermal reaαion conditions. 39. The dry process of daim 32 wherein the amorphous solid cation oxide- framework-structure is subjeαed to conditions sufficient to either maintain a low bound water content in the structure or to suffidendy dry the amorphous framework-structure to achieve a low bound water content. 40. The dry process of claim 39 wherein the amorphous solid cation oxide- framework-structure is calcined at a temperature and for a period of time to remove excess bound water from die framework-structure. 41. The dry process of daim 40 wherein calcination is effeαed at a temperature, at normal conditions, of at least 250°C to about 800°C until the desired water content is achieved. 42. The dry process of daim 32 wherein the hydrothermal reaction is carried out in a sealed reaction vessel at autogenous pressure and at moderate temperature. 43. The dry process of daim 42 wherein the moderate temperature is from about 25°C to about 500°C 44. The dry process of claim 43 wherein the moderate temperature is from about 75°C to about 350°C. 45. The dry process of claim 44 wherein the moderate temperature is from about 100°C to about 250°G 46. The dry process of daim 45 wherein the moderate temperature is about 150°C. 47. The dry process of daim 32 wherein a template is provided in the hy- drodieπnal reaction.

Inventors: CHANG YUN-FEN, MURRELL LAWRENCE L, OVERBEEK RUDOLF A, VAN DER PUIL NELLEKE, YEH CHUEN Y, CHANG, YUN-FEN, MURRELL, LAWRENCE, L., OVERBEEK, RUDOLF, A., VAN DER PUIL, NELLEKE, YEH, CHUEN, Y.
Applicants: ABB LUMMUS GLOBAL INC, ABB LUMMUS GLOBAL INC.
Application year: 1998
Main classification: C01B37
IPC codes: C01B37, C01B39