MXPA98009940A - Catalyst conversion of hydrocarbons and its - Google Patents

Abstract

Catalysts and conversion processes are provided for converting hydrocarbons using the catalysts comprising a first phospho-molecular alumino sieve and a binder comprising a second molecular sieve alumino sieve. Exemplary conversion processes include the conversion of oxygenates to olefins, deparaffinization, reformation, dealkalization, dehydrogenation, transalkylation, alkylation and isomerization.

Description

CATALYST CONVERSION OF HYDROCARBONS AND ITS USE Field of the Invention This invention relates to aluminofosfo-molecular sieves that are linked by crystalline aluminophospho-molecular sieves and their use in hydrocarbon conversion processes. Background of the Invention The microporous, crystalline molecular sieves, both natural and synthetic, have been shown to have catalytic properties for various types of hydrocarbon conversion processes. In addition, crystalline, microporous molecular sieves have been used as adsorbents and catalyst carriers for various types of hydrocarbon conversion processes, and other applications. These molecular sieves are porous crystalline materials, ordered, having a defined crystalline structure, as determined by X-ray diffraction, within which there are a large number of smaller cavities that can be interconnected by several channels or even smaller pores. The dimensions of the channels of these pores are such that allow the adsorption of molecules with certain dimensions, while rejecting those of larger dimensions. The interstitial spaces or channels formed by the crystal lattice allow molecular sieves to be used as molecular sieves in separation processes, catalysts and catalyst supports in a wide variety of hydrocarbon conversion processes. A family of microporous, crystalline molecular sieves is that of molecular sieves containing tetrahedral units of silica framework (SiO2) and optionally alumina (A102). Another family of microporous, crystalline molecular sieves contains tetrahedral framework units of alumina (A102) and phosphorus oxide (P02). These molecular sieves are discussed in "Introduction to Zeolite Science and Practice" (H. Van Bekkem, E.M. Flanigen, J.C. Jansen, editors, 1991), which is incorporated herein by reference. Examples of such ALPO-based molecular sieves ("ABMS") include SAPO, ALPO, MeAPO, MeAPSO, ELAPO and ELAPSO. The composition of these molecular sieves is disclosed in Table I below: Table I Compositional acronyms for aterials based on ALP04 Acronym Frame Atoms T Atoms T or Me The Exemplary A1PO Al, P SAPO "Si,. Al, P MeAPO Me, Al, P Co, Fe, Mg, Mn, Zn MeAPSO Me, Al, P, Si Co, Fe, Mg, Mn, Zn E1APO The, Al, P As, B, Be, Ga, Ge, Li , Ti A1APSO El, Al, P, Si As, B, Be, Ga, Ge, Li, Ti Within a pore of the crystalline molecular sieve, hydrocarbon conversion reactions such as paraffin isomerization, skeletal isomerization of olefins or double bond , disproportionation, alkylation and transalkylation of aromatics are governed by the restrictions imposed by the channel size of the molecular sieve. Selectivity to reagents occurs when a fraction of the feedstock is too large to enter the pores to react; while product selectivity occurs when some of the products can not leave the channels or do not react later. The product distributions can also be altered by the selectivity to the transition state in which certain reactions can not occur because the transition state of the reaction is too large to form within the pores. Selectivity may also result from configuration constraints on diffusion where the dimensions of the molecule approach those of the pore system. Nonselective reactions on the surface of the molecular sieve, such as reactions like the surface acid sites of the molecular sieve, are generally not desirable since such reactions are not subject to the selective restrictions of the form imposed on those reactions that occur within the channels of the molecular sieve. molecular sieve. ABMS have been used in the past as catalysts for hydrocarbon conversion. For example, U.S. Patent 4,741,820 involves the use of a reformation process using molecular sieves of intermediate pore size such as SAPO, which are bound by amorphous material. In addition, EP-A-0 293 926 and EP-A-0 293 937 disclose hydrocarbon conversion using composite molecular sieves based on ALPO. ABMS are usually prepared by crystallization of a mixture of supersaturated synthesis. The resulting crystalline product is then dried and calcined to produce the molecular sieve powder. Although the powder has good adsorption properties, its practical applications are severely limited since it is difficult to operate fixed beds with dust. Therefore, before using the powder in commercial processes, the crystals are usually bound. The powder is typically bound to form an aggregate of the molecular sieve, such as a pill, a sphere, or an extrudate. The extrudate is usually formed by extruding ABMS in the presence of an amorphous binder and drying and calcining the resulting extrudate. The binder materials used are resistant to temperatures and other conditions, for example mechanical attrition, which occur in various hydrocarbon conversion processes. Examples of binder materials include amorphous materials such as alumina, silica, titania and various types of clays. It is generally necessary that the ABMS be resistant to mechanical attrition, ie the formation of fine particles which are small particles, for example particles having a size of less than 20 microns. Although such bonded aggregates have much better mechanical strength than the powder, when such bonded material is used in a catalytic conversion process, the catalyst performance can be reduced, for example activity, selectivity, conservation of the activity, or combinations thereof, due to the binder. For example, since the binder is typically present in an amount of up to about 50% by weight of the crystals, the binder dilutes the adsorption properties of the material. In addition, as the bound molecular sieve is prepared by extrusion or otherwise forming the molecular sieve with the binder and drying and subsequently calcining the extrudate, the amorphous binder can penetrate the molecular sieve pores, or reduce the mass transfer rate to the pores of the molecular sieve, which can reduce the effectiveness of the molecular sieve when it is used in the hydrocarbon conversion processes and other applications. Furthermore, when the bound molecular sieve is used in catalytic conversion processes, the binder can affect the chemical reactions that are taking place within the molecular sieve and can also catalyze undesirable reactions that can result in the formation of products. undesirable. SUMMARY OF THE INVENTION The present invention is directed to an ABMS catalyst linked with ABMS, which comprises first crystals of a first ABMS and a binder comprising second crystals of a second ABMS, and the use of the catalyst in hydrocarbon conversion processes. . The type of structure of the first ABMS can be the same as that of the second ABMS, or it can be different. The acidity of the second ABMS is preferably carefully controlled, for example the acidity of the second ABMS may be the same as the first ABMS crystals, or the acidity of the second ABMS crystals may be higher or lower than that of the first ABMS crystals , so that the performance of the catalyst is further improved. The catalyst of the present invention finds particular application in hydrocarbon conversion processes where the acidity of the catalyst in combination with the ABMS structure are important parameters for the selectivity of the reaction. Examples of such processes include catalytic disintegration reactions (cracking), alkylation, dealkylation, dehydrogenation, disproportionation, and transalkylation. The catalyst of the present invention can also be used in other hydrocarbon conversion processes in which carbon-containing compounds are changed to different carbon-containing compounds. Examples of such processes include hydrodisintegration, isomerization, deparaffinization, oxygenate conversion, oligomerization and reformation processes. Detailed Description of the Invention The catalyst of the present invention comprises first crystals of a first ABMS and a binder comprising second crystals of a second ABMS. Typical ABMS catalysts used in hydrocarbon conversion processes are usually bound with silica or alumina or other amorphous binders commonly used to improve the mechanical strength of ABMS. Unlike typical crystalline molecular sieve catalysts used in hydrocarbon conversion processes that are normally bound with silica or alumina, or other amorphous binders commonly used to improve their mechanical strength, the catalyst of the present invention generally does not contain significant of amorphous binders. Preferably, the catalysts contain less than 10% by weight, based on the weight of the first and second ABMS, of the non-crystalline molecular sieve binder, more preferably they contain less than 5% by weight, and most preferably the The catalyst is substantially free of non-crystalline molecular sieve binder. Preferably, the second ABMS crystals link the first ABMS crystals by adhering to the surface of the first ABMS crystals, thereby forming a matrix or bridge structure that also holds the first crystal particles together. More preferably, the second ABMS particles link the first ABMS by inter-development so as to form a partial coating or coating on the first larger ABMS crystals and, most preferably, the second ABMS crystals link the first crystals. of ABMS by inter-development to form an over-development resistant to attrition on the first crystals of ABMS. Although the invention is not intended to be limited by any theory of operation, it is believed that one of the advantages of the ABMS catalyst linked to ABMS is obtained by the fact that the second crystals of ABMS control the accessibility of acidic sites on the external surfaces of the first ABMS to the reactants. As the acid sites that exist on the outer surface of an ABMS catalyst are not selective in form, these acidic sites can adversely affect reagents entering the pores of the ABMS and products leaving the pores of the ABMS. In line with this belief, as the acidity and the type of structure of the second ABMS can be selected carefully, the second ABMS does not significantly affect negatively the reagents that come out of the pores of the first ABMS, which can occur with catalysts from ABMS conventionally bound and can beneficially affect the reagents coming out of the pores of the first ABMS. Furthermore, since the second ABMS is not amorphous but instead is a molecular sieve, hydrocarbons can have increased access to the pores of the first ABMS during the hydrocarbon conversion processes. The terms "acidity", "lower acidity" and "high acidity", as applied to zeolite, are known to those skilled in the art. The acidulated properties of zeolite are well known. However, with respect to the present invention, a distinction must be made between acid intensity and acid site density. Acid molecular sieve sites such as ABMS can be a Bronstead acid and / or a Lewis acid. The density of the acid sites and the number of acid sites are important to determine the acidity of the ABMS. The factors that directly influence the acid intensity are (i) the chemical composition of the ABMS framework, ie the relative concentration and type of tetrahedron atoms, (ii) the concentration of the extra-framework cations and the resulting extra-framework species, (iii) the local structure of ABMS, for example, the pore size and the location, within the crystal and at or near the surface of the ABMS, and (iv) the pretreatment conditions and the presence of co-adsorbed molecules. As used herein, the terms "acidity", "lower acidity" and "higher acidity" refer to the concentration of acidic sites, regardless of the intensity of such acidic sites, which can be measured by adsorption with ammonia. The term "average particle size", as used herein, means the arithmetic average of the diameter distribution of the crystals on a volume basis. First and second ABMS suitable for use in the catalyst of the present invention include large pore ABMS, intermediate pore size ABMS, and small pore size ABMS. These crystalline molecular sieves are described in "Atlas of Zeolite Structure Types", .H. Meier and D.H. Olson, editors, Buttersworth-Heineman, third edition, 1992, which is incorporated herein by reference. - Large pore ABMS generally have a pore size greater than about 7A and include, for example, ABMS with structure type VFI, AET, AFl, AFO, ATS, FAU. Examples of large pore ABMS include ALPO-8, ALPO-41, SAPO-37, ALPO-37, ALPO-5, SAPO-5, ALPO-54, and MAPO-36. Average pore size ABMS generally have a pore size of about 7 to about 5 to about 6.8 A, and include, for example, ABMS with structure type AEL, AFR, AFS, AFY, ATO, and APD. Examples of medium pore ABMS include ELAPSO-11, ELAPSO-31, ELAPSO-40, ELAPSO-41, CoAPSO-11, CoAPSO-31, FeAPSO-11, FeAPSO-31, MgAPSO-11, MgAPSO-31, MnAPSO-11 , MnAPSO-31, TiAPSO-11, ZnAPSO-11, TiAPO-11, TiAPO-31, ELAPO-11, ELAPO-31, ELAPO-40, ELAPO-41, SAPO-11, SAPO-31, SAPO-40, SAPO-41, ALPO- 31 and ALPO-11. A small pore size ABMS has a pore size of about 3 to about 5.0 Á and includes, for example, AEI, AFT, APC, ATN, ATT, ATV, AW, BIK, CAS, CHA, CHI, DAC , DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG and THO. Examples of small pore ABMS include ALPO-17, ALPO-18, ALPO-52, ALPO-22 and ALPO-25. The first ABMS will preferably have acidic activity and therefore will preferably be an ABMS having an additional metal incorporated in the lattice A1P04, such as SAPO, MeAPSO or ELAPSO. Examples of the first preferred ABMS include SAPO-34, SAPO-11, GaSAPO-11, ZnSAPO-11, SAPO-17, NiSAPO-34, SAPO-5. The type of structure of the first ABMS will depend on the particular hydrocarbon process in which the catalyst is used. For example, when the catalyst is used for dewaxing, the first ABMS is preferably SAPO-11 or SAPO-40. The average particle size of the first crystals is preferably from about 0.1 to about 15 microns. In many applications, the average particle size is preferably from about 1 to about 6 microns. The structure type of the second ABMS can be the same as or different from the first ABMS. Preferably, the second ABMS will have low acidity and more preferably will be substantially non-acidic. Preferred non-acidic ABMSs are aluminophosphates such as ALPO-17, ALPO-18, ALPO-11, ALPO-5, ALPO-41, GaALPO-11, ZnALPO-11. The pore size of the second ABMS will preferably be a pore size that does not significantly restrict access of the hydrocarbon feed stream to the pores of the first ABMS. For example, when the materials of the feed stream to be converted have a size of 5 to 6.8 A, the second ABMS will preferably be an ABMS of large pore size or an ABMS of intermediate pore size. The second ABMS is preferably present in the catalyst in an amount in the range of about 10 to about 60% by weight, based on the weight of the first ABMS, but the amount of the second ABMS present will usually depend on the hydrocarbon process in which the catalyst is used. More preferably, the amount of the second ABMS present will be from about 20 to about 50% by weight. The second ABMS crystals preferably have a smaller size than the first ABMS crystals. The second ABMS crystals preferably have an average particle size of less than 1 mire, preferably from about 0.1 to less than 0.5 micron. The second ABMS crystals, in addition to bonding to the first ABMS particles and maximizing catalyst performance, will preferably inter-develop and form an over-development that coats or partially coats the first ABMS. Preferably, the coating will be resistant to attrition. The catalysts of the present invention are preferably prepared by a three-step process. The first step involves the synthesis of the first ABMS. Processes to prepare the first ABMS are known in the art. In the next step, an ABMS bound to alumina is preferably prepared by mixing a mixture comprising the crystals of ABMS, alumina, water, and optionally an extrusion aid until a homogeneous composition develops in the form of an extrudable paste. The alumina binder used in the preparation of the ABMS aggregate bound to alumina is preferably an alumina sol. The amount of ABMS in the extrudate, upon drying, will vary from about 30 to 90% by weight, more preferably from about 40 to 90% by weight, the remainder being mainly alumina, for example about 10 to 60% by weight. alumina weight. The resulting paste can be molded, for example extruded, and cut into small filaments, for example extruded approximately 2 mm in diameter, which can be dried at 100-150 ° C for a period of 4-12 hours. Preferably, the dried extrudates are then calcined in air at a temperature of about 400 to 550 ° C for a period of about 1 to 10 hours. This calcination step also destroys the extrusion coadjuvant, if present. Optionally, the aggregate bonded to alumina can be made into small crystals that have application in fluid bed processes such as catalytic cracking. This preferably involves mixing the ABMS with an alumina-containing matrix solution so that an aqueous solution of ABMS and alumina binder can be spray-dried to result in small, fluidizable, alumina-bound aggregate crystals. The processes for preparing such aggregate particles are known to those skilled in the art. An example of such a procedure is described by Scher-zer (Octane-Enhancing Zeolitic FCC Catalysts, Julius Scherzer, Marcel Dekker, Inc., New York, 1990). The fluidizable alumina-bound aggregate particles, such as the alumina-linked extrudates described above, would then undergo the final step described below to convert the silica binder into a second ABMS. The final step in the three-step catalyst preparation process is the conversion of the alumina present in the alumina-bound catalyst into a second ABMS, which serves to bind together the residual crystals of ABMS. To prepare the catalyst, the alumina-bonded aggregate can be first aged in an appropriate aqueous solution at an elevated temperature. Next, the content of the solution and the temperature at which the aggregate is aged should be selected to convert the amorphous alumina binder into a second ABMS. The newly formed ABMS is produced as crystals. The crystals may develop in and / or adhere to the initial crystals of ABMS, and may also be produced in the form of new inter-developed crystals, which are generally much smaller than the initial crystals, for example of sub-micron size. These newly formed crystals can develop and interconnect together, thereby causing the larger crystals to be linked together. The nature of the ABMS formed in the conversion of secondary synthesis of alumina into ABMS can vary as a function of the composition of the secondary synthesis solution and the conditions of synthetic aging. The secondary synthesis solution is preferably an aqueous ionic solution containing a phosphoric acid source and a template agent sufficient to convert the alumina to the desired ABMS. The catalyst may be further subjected to ion exchange, as is known in the art, either to replace at least in part the original alkali metal present in the first ABMS with a different cation, for example an element of groups IB to VIII of the Periodic Table of the Elements, such as nickel, copper, zinc, palladium, platinum, calcium or rare earth metals, or to provide a more acidic form of the catalyst by exchange of the alkali metal with intermediate ammonium, followed by calcination of the ammonium form to provide the acid hydrogen form. The acid form can be easily prepared by ion exchange using a suitable acid reagent such as ammonium nitrate. The catalyst can then be calcined at a temperature of 400-500 ° C for a period of 10-45 hours to remove ammonia and form the hydrogen-acid form. The exchange of ions is preferably conducted after the formation of the catalysts. These include hydrogen, rare earth metals, and metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements. Examples of suitable metals include platinum, palladium, rhodium, iridium, iron, molybdenum, cobalt, tungsten, nickel, manganese, titanium, zirconium, vana-dio, hafnium, zinc, tin, lead, chromium, etc. The catalytically active metal is preferably present in an amount of about 0.05 to about 3.0% by weight, based on the weight of the first ABMS. The catalyst of the present invention can be used in the processing of hydrocarbon feedstocks. The hydrocarbon feedstocks contain carbon compounds and can be from many different sources, such as virgin oil fractions, recycle oil fractions, shale sands oil, and in general can be any carbon-containing fluid susceptible to reactions. Ceolitic catalytic Depending on the type of processing the hydrocarbon feed is going to undergo, the feed may contain metal or may be metal-free. Also, the feed may also have high or low nitrogen or sulfur impurities. The conversion of the hydrocarbon feeds can take place in any convenient way, for example in fluidized bed reactors, moving bed or fixed bed, depending on the types of process desired. The catalysts of the present invention, by themselves or in combination with one or more catalytically active substances, can be used for a variety of organic compound conversion processes, for example hydrocarbons. Examples of such hydrocarbon conversion processes include, as non-limiting examples, the following: (A) The catalytic disintegration of a naphtha feed to produce light olefins. Exemplary reaction conditions include from about 500 to about 750 ° C, pressures from sub-atmospheric to atmospheric, generally varying up to about 10 atmospheres (gauge) and residence time (volume of catalyst feed rate) of around from 10 milliseconds to around 10 seconds. (B) The catalytic disintegration of high molecular weight hydrocarbons to lower molecular weight hydrocarbons.

Exemplary reaction conditions for catalytic disintegration include temperatures of about 400 to about 700 ° C, pressures of about 0.1 to about 30 atmospheres, and space hourly rates in weight of about 0.1 to about 100 hr "1. C) The transalkylation of aromatic hydrocarbons in the presence of polyalkyl aromatic hydrocarbons Typical reaction conditions include a temperature of about 200 to about 500 ° C, a pressure of around atmospheric to about 200 atmospheres, a velocity space hourly mass of about a to about 1,000 hr "1, and a molar ratio of aromatic hydrocarbon / polyalkyl-aromatic hydrocarbon from about 1/1 to about 16/1. (D) The isomerization of aromatic components (eg, xylene) of feedstock. Exemplary reaction conditions for this include a temperature of about 230 to about 510 ° C, a pressure of about 0.5 to about 50 atmospheres, a space velocity hourly in weight of about 0.1 to about 200, and a ratio hydrogen molar / hydrocarbon from about 0 to about 100. (E) The dewaxing of hydrocarbons by selectively removing straight chain paraffins. The reaction conditions depend to a large extent on the feed used and the desired pour point. Typical reaction conditions include a temperature between about 200 and 450 ° C, a gauge pressure of up to 3,000 psi, and a space velocity hour by weight of 0.1 to 20. (F) The alkylation of aromatic hydrocarbons, for example benzene and alkylbenzenes, in the presence of an alkylating agent, for example olefins, formaldehyde, alkyl halides and alcohols having 1 to about 20 carbon atoms. Typical reaction conditions include a temperature of from about 100 to about 500 ° C, a pressure from about atmospheric to about 200 atmospheres, a space velocity by weight from about 1 to about 100 hr "1, and a molar ratio of aromatic hydrocarbon / alkylating agent from about 1/1 to about 20/1. (G) The alkylation of aromatic hydrocarbons, for example benzene, with long chain olefins, for example C14 olefin. of reaction include a temperature of about 50 to about 200 ° C, a pressure from about atmospheric to about 200 atmospheres, a space velocity hour by weight of about 2 to about 2,000 hr "1, and a molar ratio of aromatic hydrocarbon / olefin from about 1/1 to about 20/1. The product resulting from the reaction consists of long-chain alkyl aromatics which, when subsequently sulphonated, have particular application as synthetic detergents. (H) The alkylation of aromatic hydrocarbons with light olefins to provide short-chain alkyl-aromatic compounds, for example the alkylation of benzene with propylene to provide eumen. Typical reaction conditions include a temperature of from about 10 to about 200 ° C, a pressure of from about 1 to about 30 atmospheres, and a space velocity hour by weight (HSV) of aromatic hydrocarbon from 1 to about 50 hr. "1. (I) The hydrodisintegration of heavy petroleum feedstocks, cyclic materials, and other hydrodisintegration fillers The catalyst will contain an effective amount of at least one hydrogenation component of the type employed in hydrodisintegration catalysts. ) The alkylation of a reformate containing substantial quantities of benzene and toluene with fuel gas containing short chain olefins (eg, ethylene and propylene), to produce mono- and di-alkylated Typical reaction conditions include temperatures of about 100 to around 250 ° C, a pressure of about 100 to about 800 psig, an olefin WHSV of about 0.4 aa about 0.8 hr "1, a reformed WHSV of around 1 to about 2 hr'1 and, optionally, a recycle gas of about 1.5 to 2.5 vol / vol of fuel gas feed. (K) The alkylation of aromatic hydrocarbons, for example benzene, toluene, xylene and naphthalene, with long chain olefins, for example C14 olefin, to produce aromatic, alkylated base lubrication materials. Typical reaction conditions include temperatures of about 100 to about 400 ° C and pressures of about 50 to 450 psig. (L) The alkylation of phenols with olefins or equivalent alcohols to provide long chain alkyl phenols. Typical reaction conditions include temperatures of about 100 to about 250 ° C, pressures of about 1 to 300 psig, and a total WHSV of about 2 to about 10-hr-1. (M) The conversion of light paraffins into olefins and / or aromatics, as disclosed in U.S. Patent No. 5,283,563, which is incorporated herein by reference. Typical reaction conditions include temperatures of about 425 to about 760 ° C and pressures of about 10 to about 2,000 psig. (N) The conversion of light olefins in gasoline, distillates, and hydrocarbons of lubrication range. Typical reaction conditions include temperatures of about 175 to about 375 ° C and a pressure of about 100 to about 2, 000"psig. (O) Two-stage hydrodegradation to improve hydrocarbon streams having initial boiling points of more than about 200 ° C to special distillates and products with boiling range of gasoline or as feed for additional steps of processing fuels or chemical products in a first stage that uses in the first stage the catalyst comprising one or more catalytically active substances, for example a metal of group VIII, and the effluent of the first stage would be reacted in a second step using a second catalyst comprising one or more catalytically active substances, for example a metal of group VIII, as a catalyst Typical reaction conditions include temperatures of about 315 to about 455 ° C, a pressure of about 40 0 to about 2,500 psig, hydrogen circulation of about 1,000 to about 10,000 SCF / barrel and a liquid hourly space velocity (LHSV) of about 0.1 to 10. (P) A hydrodisintegration / dewaxing process in combination, in the presence of the catalyst comprising a hydrogenation component. Typical reaction conditions include temperatures of about 350 to about 400 ° C, pressures of about 1,400 to about 1,500 psig, LHSV of about 0.4 to about 0.6, and a hydrogen circulation of about 3,000 to about 5,000 SCF / barrel. (Q) The reaction of alcohols with olefins to provide mixed ethers, for example the reaction of methanol with isobutene and / or isopentene to provide the methyl-t-butyl ether (MTBE) and / or methyl t-amyl ether (TAME) . Exemplary conversion conditions include temperatures from about 20 to about 200 ° C, pressures from 2 to about 200 atmospheres, WHSV (grams of olefin per grams of zeolite hour) from about 0.1 to about 200 hr "1, and a mole ratio of alcohol to olefin feed of about 0.1 / 1 to about 5/1. (R) The disproportionation of toluene to make benzene and para-xylene Typical reaction conditions include a temperature of about 200 to about of 760 ° C, a pressure of around atmospheric to around 60 atmospheres (bars), and a WHSV of around 0.1 to about 30 hr "1. (S) The conversion of naphthas (for example, C6-C10) and similar mixtures in highly aromatic mixtures. In this way, normal and slightly branched chain hydrocarbons, preferably having a boiling range above about 40 ° C, and lower than about 200 ° C, can be converted into products having a substantial higher octane aromatics content by contacting the hydrocarbon feedstock with the zeolite at a temperature in the range of about 400 to 600 ° C, preferably 480 to 550 ° C, at pressures ranging from atmospheric to 40 bar, and LHSV ranging from 0.1 to 15. (T) The adsorption of alkyl-aromatic compounds in order to separate various isomers of the compounds. (U) The conversion of oxygenates, for example alcohols, such as methanol, or ethers, such as dimethyl ether, or mixtures thereof, into hydrocarbons including olefins and aromatics with reaction conditions including a temperature of about 275 to about 600 ° C, a pressure of about 0.5 to about 50 atmospheres, and LHSV of about 0.1 to about 100. (V) The oligomerization of straight and branched chain olefins having from about 2 to about 5 atoms carbon. The oligomers which are the products of the process are medium to heavy olefins which are useful both for fuels, ie gasoline or a physical mixture of gasoline, and for chemical products. The oligomerization process is generally carried out by contacting the olefin feedstock in a gas phase with a zeolite bound to zeolite at a temperature in the range of about 250 to about 800 ° C, an LHSV of about 0.2 to about 50, and a partial hydrocarbon pressure of around 0.1 to about 50 atmospheres. Temperatures below about 250 ° C can be used to oligomerize the feedstock when the feedstock is in the liquid phase when it contacts the catalyst. In this way, when the olefin feedstock contacts the catalyst in the liquid phase, temperatures of about 10 to about 250 ° C can be used. (W) The conversion of unsaturated C2 hydrocarbons (ethylene and / or acetylene) in aliphatic C6_12 aldehydes and conversion of said aldehydes to the corresponding C6_12 alcohols, acids or esters. (X) The isomerization of ethylbenzene in xylenes. Exemplary conversion conditions include a temperature of 600 to 800 ° F, a pressure of 50 to about 500 psig, and an LHSV of about 1 to about 10. In general, the conditions of catalytic conversion on a catalyst comprising catalyst include a temperature of about 100 to about 760 ° C, a pressure of about 0.1 to about 200 atmospheres (bars), a WHSV of about 0.08 to about 2, s00 hr "1. Conversion of hydrocarbons prefer that the second crystals of ABMS have lower acidity to reduce undesirable external reactions to the first crystals of ABMS, some processes prefer that the second crystals of ABMS have greater acidity, for example that the acidity is designed to measure so of catalyzing desirable reactions, such processes are of two types: in the first type, the acidity and the type of structure of the second ABMS are designed to equalize the acidity and the crystallographic type of the first ABMS. By doing so, the catalytically active material by weight of catalyst formed will be increased, thereby resulting in increased apparent catalyst activity. Such a catalyst would also benefit from greater adsorption, for example accessibility and reduced non-selective surface acidity. The second type of process that can benefit by custom designing the acidity of the second ABMS phase is one in which two or more reactions are taking place within the ABMS catalyst. In such a process, the acidity and / or structure type of the second phase of ABMS can be custom designed so that they are different from those of the first ABMS, but it does not have to be the case where it is essentially free of acidic sites . Such a catalyst would be comprised of two different ABMSs that can each be tailored to promote or inhibit different reactions. A process using such a catalyst would not only benefit from greater apparent activity of the catalyst, greater accessibility to the ABMS and reduced possible non-selective surface acidity with the catalyst, but would also benefit from a custom designed product. The combined processes of xylene isomerization / ethylbenzene dealkylation would benefit from this type of catalyst. An isomerization / dealkylation catalyst of ethylbenzene can be custom designed such that ethylbenzene dealkylation occurs mainly within the first ABMS crystals, and isomerization of xylenes would occur mainly within the second ABMS crystals. By designing a catalyst in this way, a balance can be reached between the two reactions that could not be achieved otherwise with a catalyst containing only one ABMS. The catalysts of the present invention have particular application in the procedures indicated below. A process where long straight chain hydrocarbons, contained in a hydrocarbon stream of high pour point and high viscosity, are isomerized to branched hydrocarbons via contact with a SAPO catalyst bound to ALPO to give a hydrocarbon fluid with reduced point of pouring and lower viscosity. The SAPO component is a molecular sieve of intermediate pore size and has an active metal for hydrogenation / dehydrogenation reactions and is acidic. The ALPO component can be of the same structure type or different, and has little or no metal component and is non-acidic. The hydrocarbon is contacted with the catalyst at 150-650 ° C in the presence of gaseous hydrogen at a pressure of 15-3,000 psig with a WHSV of 0.1-20 hr "1. A process where C2-C5 paraffins and olefins are converted into mono-nuclear aromatic compounds by contacting the paraffins with SAPO catalyst bound with ALPO at 400-700 ° C, at a pressure of 1 to 100 atmospheres, and a WHSV of 0.1 to 200 hr. "1 The SAPO component is a medium pore molecular sieve and may or may not contain a metal oxide component such as ZnO or Ga203. ALPO may or may not be of the same structural type and may contain metal oxide components such as ZnO or Ga203 A process to convert methanol to light olefins, where the methanol is contacted with SAPO bound with ALPO at 400-600 ° C , at a pressure of 1 to 100 atmospheres, sometimes in the presence of a diluent such as water vapor, with a WHSV of 0.1-100 hr "1. At least one of the ALPO or SAPO components must have a ring pore opening 8, such as SAPO-34, SAPO-17, or ALPO-17. The other component may also have a ring pore opening 8 or may be ring openings 10 or 12. Possible non-limiting combinations are SAPO-11 bound with ALPO-17 or SAPO-34 bound with ALPO-17. The catalysts of the present invention find particular application in reactions involving aromatization and / or dehydrogenation. They are particularly useful in processes for the dehydrocyclization and / or isomerization of acyclic hydrocarbons in which the hydrocarbons are contacted at a temperature of 370 to 600 ° C, preferably 430 to 500 ° C with the catalysts, preferably having the minus 90% of the cations exchangeable as alkali metal ions and incorporating at least one group VIII metal having dehydrogenation activity, so as to convert at least part of the acyclic hydrocarbons to aromatic hydrocarbons. The aliphatic hydrocarbons can be straight or branched chain acyclic hydrocarbons, and particularly paraffinic hydrocarbons such as hexane, although mixtures of hydrocarbons such as paraffin fractions containing a range of alkanes, possibly with minor amounts of other hydrocarbons, can also be used. Cycloaliphatic hydrocarbons such as methylcyclopentane can also be used. In a preferred aspect, the feed to a process for preparing aromatic hydrocarbons and particularly benzene comprises hexanes. The temperature of the catalytic reaction can be from 370 to 600 ° C, preferably 430 to 550 ° C, and pressures in excess of atmospheric, for example up to 2,000 kPa, with a greater preference of 500 to 1,000 kPa. Hydrogen is usually used in the formation of aromatic hydrocarbons, preferably with a hydrogen to feed ratio of less than 10. The following examples illustrate the invention: Example 1 I. Catalyst A - SAPO-34 bound to ALP0-5. SAPO-34 bound by means of 30% by weight of alumina was formed in SAPO-34 bound with ALPO-5, as follows: To a 300 ml autoclave, lined with Teflon, 4.18 g of 85% aqueous H3P04 were added, 10.78 g of water and 2.65 g of tripropylamine (TPA), in the order indicated. The mixture was stirred to give a homogeneous solution. Then, 10 g of dry extrudates (1/16"diameter) of SAPO-34 bound with alumina were added to the autoclave content.The extrudates were completely covered by the liquid.The molar composition of the synthesis mixture was : TPA / A1203 / P205 / H20 of 0.63 / 1.0 / 0.62 / 23.4 In the mixture, the alumina only accounts for the alumina binder in the extrudate and the P2Os account for only the 85% aqueous H3P04 .The autoclave was sealed and the mixture was heated in 2 hours at 200 ° C and maintained without agitation for 24 hours at 200 ° C. The autoclave was cooled to room temperature and the mother liquor was decanted.The extrudates were washed with deionized water until the conductivity of the filtering was less than 100 micro-Siemens The XRD analysis showed typical patterns for both SAP0-34 and ALPO-5 II Catalyst B - SAPO-34 bound with ALPO-11 SAPO-34 bound by 25% by weight was formed of alumina in SAPO-34 bound with ALPO-11, as follows e: They were added to a 100 ml autoclave, lined with Teflon, 6.36 g of 85% aqueous H3P04, 18.02 g of water and 2.82 g of dipropylamine (DPA), in the order indicated. The mixture was stirred to give a homogeneous solution. Then, 15.00 g of dry extrudates were added to the autoclave content. (1/16"diameter) of SAPO-34 bound with alumina The extrudates were completely covered by the liquid The molar composition of the synthesis mixture was: DPA / A1203 / P205 / H20 of 0.76 / 0.75 /1.0/30.9 In the mixture, the alumina only accounts for the alumina binder in the extrudate and the P205 accounts for only the 85% aqueous H3P04.The autoclave was sealed and the mixture was heated in 2 hours at 200 ° C and maintained without agitation for 22 hours at 200 ° C. The autoclave was cooled to room temperature and the mother liquor was decanted.The extrudates were washed with deionized water until the conductivity of the filtrate was less than 100 micro-Siemens. XRD showed typical patterns for both SAPO-34 and ALPO-11 III Catalyst C-SAPO-34 bound to ALPO-17 SAPO-34 bound by 25% by weight of alumina was formed in SAPO-34 bound with ALPO-5, as follows: They were added to a 300 ml autoclave, lined with Teflon, 6.35 g of 25% aqueous H3P04, 17.60 g of water and 2.77 g of cyclohexylamine, in the order indicated. The mixture was stirred to give a homogeneous solution. Then, 15.02 g of dry extrudates (1/16"diameter) of SAPO-34 bonded with alumina were added to the autoclave.The extrudates were completely covered by the liquid.The molar composition of the synthesis mixture was: 1.00 R2O5 / l .01R / 1.00Al2O3 / 39H2O In the mixture, the alumina accounts only for the alumina binder in the extrudate and the P205 accounts for only the 25% aqueous H3P04.The autoclave was sealed and the mixture was heated to 2%. hours at 200 ° C and maintained without agitation for 48 hours at 200 ° C. The autoclave was cooled to room temperature, a small sample of extrudate was removed, and then the mixture was heated to 200 ° C in two hours and maintained at 200 ° C. 200 ° C for another 48 hours The extrudates were allowed to cool and were washed four times with 800 ml of water The conductivity of the last wash water was less than 26 μS / cm The extrudates were then dried at 120 ° C The XRD analysis showed t patterns peaks for both SAPO-34 and ALPO-5. Example 2 Catalysts A, B and C were subjected to tests for use in the conversion of oxygenates to olefins. The tests were carried out using the following procedure: 5.0 cc (approximately 2.7 g) of each catalyst were mixed with 15 cc of quartz beads and loaded in a 316 stainless steel tubular reactor, 3/4"external diameter, which was heated by electric furnaces in three zones The first zone acted as a pre-heating zone, vaporizing the feed The temperature of the central zone of the furnace was adjusted to 450 ° C and the pressure was maintained at one atmosphere The reactor was purged, first with nitrogen at a flow rate of 50 cc / minute, for 30 minutes.The feed had a 4: 1 molar ratio of water to methanol and was pumped into the reactor at a rate calibrated to give a speed of flow around WHSV of 0.7 hr "1. The effluent was analyzed at predetermined intervals by in-line gas chromatography in an apparatus equipped with a thermal conductivity detector and a flame ionization detector. The results of these tests are shown later in Table IV: Table IV The data shows that the catalysts have good selectivity of ethylene and propylene and that, by custom designing the catalyst, the product distribution can be varied.

Claims (27)

1. CLAIMS 1. An ABMS catalyst linked to ABMS that does not contain significant amounts of amorphous binder, and comprises: (a) first crystals of a first ABMS, and (b) a binder comprising second crystals of a second ABMS.
2. 2. The catalyst of claim 1, wherein the second crystals are inter-developed and form at least a partial coating on the first crystals.
3. The catalyst defined in claim 1 or claim 2, which contains less than 5% by weight of non-molecular sieve binder based on the combined weight of the first ABMS and the second ABMS.
4. The catalyst defined in any of the preceding claims, wherein the second crystals are present in an amount of 10 to 60% by weight based on the weight of the first crystals.
5. 5. The catalyst defined in any of the preceding claims, wherein the first crystals have an average particle size greater than 0.1 microns.
6. 6. The catalyst defined in claim 5, wherein the first crystals have an average particle size of 1 to 6 microns.
7. The catalyst defined in any of the preceding claims, wherein the second crystals have a smaller average particle size than the first crystals.
8. The catalyst defined in any of the preceding claims, wherein the second crystals have an average particle size of 0.1 to 0.5 microns.
9. 9. The catalyst defined in any of the preceding claims, wherein the second ABMS has a lower acidity than the first ABMS.
10. The catalyst defined in any of claims 1 to 8, wherein the second ABMS has higher acidity than the first ABMS.
11. The catalyst defined in any of the preceding claims, wherein the first ABMS and the second ABMS are each, independently, of a structure type selected from the group consisting of VFI, AET, AFl, AFO, ATS, FAU , AEL, AFR, AFS, AFY, ATO, APD, AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG and THO.
12. 12. The catalyst defined in any of the preceding claims, wherein the first ABMS and the second ABMS have different structure types.
13. The catalyst defined in any of claims 1 to 11, wherein the first ABMS and the second ABMS have the same structure types.
14. The catalyst defined in any of the preceding claims, wherein the second ABMS is an ALPO.
15. 15. The catalyst defined in claim 14, wherein the second ABMS is ALPO-17, ALPO-18, ALPO-11, ALPO-5, ALPO-41, GaALPO-11 or ZnALPO-11.
16. 16. The catalyst defined in any of the preceding claims, wherein the first ABMS is a SAPO.
17. The catalyst defined in any of the preceding claims, wherein the first ABMS is SAPO-34, SAPO-37, SAPO-40, SAPO-5, MAPO-36, SAPO-11, GaSAPO-11, ZnSAPO-11, SAPO -17 or NiSAPO-34.
18. 18. The catalyst defined in any of claims 1 to 15, wherein the first ABMS is SAPO, MeAPO, MeAPSO, ELAPO or ELAPSO.
19. The catalyst defined in any of claims 1 to 15, wherein the first ABMS and the second ABMS are independently selected from the group consisting of ALPO-8, ALPO-41, SAPO-37, ALPO-37, SAPO-31, SAPO-40, SAPO-41, ALPO-5, SAPO-5, ALPO-54, MAPO-36, SAPO-11, ALPO-31, ALPO-11, ALPO-17, ALPO-18, ALPO-52, ALPO- 22 and ALPO-25.
20. The catalyst defined in any of claims 1 to 13, wherein the first ABMS is SAPO-34 and the second ABMS is ALPO-5, ALPO-17 or ALPO-11.
21. 21. A process for the conversion of hydrocarbons or oxygenates, comprising contacting a feed stream comprising a hydrocarbon or oxygenate under hydrocarbon or oxygenate conversion conditions with a catalyst according to any of the preceding claims.
22. 22. The process defined in claim 21, wherein the pore size of the first ABMS is larger than the pore size of the second ABMS.
23. 23. The process defined in claim 21, wherein the pore size of the first ABMS is less than the pore size of the second ABMS.
24. 24. The process defined in claim 21, 22 or 23, wherein the first ABMS and the second ABMS are independently ABMS of intermediate pore size or small pore size.
25. 25. The process defined in any of claims 21 to 24, wherein the conversion is selected from the group consisting of hydrocarbon disintegration (cracking), aromatic dealkylation, alkyl-aromatic isomerization, toluene disproportionation, hydrocarbon dehydrogenation, transalkylation of aromatics, alkylation of aromatics, reformation of hydrocarbons to aromatics, conversion of paraffins and / or olefins into aromatics, conversion of oxygenates into hydrocarbon products, disintegration (cracking) of naphthas to light olefins, and dewaxing of hydrocarbons.
26. 26. The process defined in claim 25, wherein the conversion is the conversion of oxygenates to olefins.
27. 27. The process defined in claim 25, wherein the conversion is reforming naphthas to aromatics.