WO2005056184A1 - Spray drying molecular sieve catalyst - Google Patents

Abstract

This invention concerns methods of making attrition resistant molecular sieve catalyst, which incorporate the use of appropriate spray drying methods or techniques. The degree of attrition resistance is affected by a variety of spray drying control variables such as spray dryer inlet and outlet temperatures and rate of drying of catalyst slurry materials.

Description

SPRAY DRYING MOLECULAR SIEVE CATALYST

Field of the Invention

[0001] This invention relates to molecular sieve catalyst and methods of making molecular sieve catalyst. In particular, this invention relates to making attrition resistant molecular sieve catalyst, which incorporates the use of appropriate spray drying methods.

Background of the Invention

[0002] Molecular sieve catalysts are compositions made of molecular sieve particles bound together to form particles larger than the molecular sieve components. The molecular sieve catalyst particles can also include other components such as binders, fillers, like clay, and optionally other catalytically active agents such as rare earth metal oxides, transition metal oxides, or noble metal components.

[0003] Conventional methods of making molecular sieve catalyst particles include mixing together molecular sieve and binder, as well as other optional components such as matrix materials. The mixture is typically stirred in solution to form a slurry, and the slurry is dried to form molecular sieve catalyst particles. Following drying, the particles are calcined to harden, as well as activate, the catalyst particles.

[0004] U.S. Patent No. 5,098,448 (Puppe et al.) discloses a process for producing silica-bound zeolite granulates that are considered to be relatively attrition resistant. The process is carried out by adding aqueous alkali metal silicate to silica sol immediately before the silica sol is mixed with the solid zeolite. Compared with processes in which silica sol is used on its on as binder, the process is considered to produce higher granulate strength values, even in the moist state, and after drying, even greater attrition resistant values. [0005] U.S. Patent No. 6,503,863 (Fung et al.) a method of heat treating a molecular sieve composition, which results in an attrition resistant catalyst. According to the method, a catalyst composition comprising molecular sieve and a binder is heated to remove a portion of a template material within the molecular sieve, with the heating being further effective to provide a catalyst composition having a Davison Index of not greater than 30.

[0006] U.S. Patent No. 6,541,415 (Vaughn et al.) describes a molecular sieve catalyst that contains molecular sieve-containing attrition particles and virgin molecular sieve, with the attrition particles having been recycled from a catalyst manufacture process or from a reaction system. The finished catalyst can be used in a variety of catalytic reaction processes, such as making olefins from a catalytic reaction process.

[0007] In large, commercial scale reaction systems that use molecular sieve catalyst, attrition resistant catalyst is still desired to minimize loss of catalyst due to physical damage in the reaction systems. Such large scale systems will typically require at least 10 tons, and up to as much as 100 tons, and even 500 tons, of molecular sieve catalyst to operate efficiently. Given a high cost of catalyst, reduction in damage due to physical stress in the large scale systems is particularly desirable.

Summary of the Invention

[0008] This invention provides improvements to methods of making molecular sieve catalyst. The resulting products that are produced are particularly attrition resistant, and particularly suitable for use in large, commercial scale reaction systems. The methods of making the molecular sieve catalyst incorporate various spray drying methods that provide the attrition resistant catalyst. The degree of attrition resistance is affected by a variety of spray drying control variables such as spray dryer inlet and outlet temperatures and rate of drying of catalyst slurry materials.

[0009] In one embodiment, the invention provides a process of making a molecular sieve catalyst composition, which comprises drying a slurry containing molecular sieve and binder in a spray dryer at a drying rate of not greater than 0.275 kg/hr liq. per kg/hr gas, preferably not greater than 0.25 kg/hr liq. per kg/hr gas, and more preferably not greater than 0.2 kg/hr liq. per kg/hr gas. [0010] In another embodiment, there is provided a process of making a molecular sieve catalyst composition, which comprises injecting a molecular sieve slurry into a spray dryer at a spray dryer inlet temperature of not greater than 500°C, preferably not greater than 450°C, more preferably not greater than 400°C, and most preferably not greater than 300°C.

[0011] In another embodiment, the slurry is dried in the spray dryer at a temperature differential between spray dryer inlet and outlet temperatures of not greater than 350°C, preferably not greater than 250°C, more preferably not greater than 200°C, and most preferably not greater than 150°C. [0012] hi yet another embodiment, the spray dried catalyst is removed from the spray dryer at a spray dryer outlet temperature of not greater than 300°C, preferably not greater than 250°C, more preferably not greater than 200°C, and most preferably not greater than 150°C.

[0013] The spray dried molecular sieve catalyst is removed from the spray dryer for further use or processing, hi one embodiment, the spray dried molecular sieve catalyst is removed from the spray dryer and heated or calcined. Preferably, the spray dried molecular sieve catalyst is removed from the spray dryer and heated or calcined to an ARI of not greater than 1 %/hr, more preferably not greater than 0.8 %/hr, still more preferably not greater than 0.7 %/hr, and most preferably not greater than 0.5 %/hr.

[0014] Any variety of molecular sieves can be used to make the catalyst of this invention. Such molecular sieves include zeolites or non-zeolites, preferably non-zeolites. Examples of zeolites suitable for use in this invention include zeolite L, zeolite Y, zeolite X, offretite, omega, Beta, mordenite, ZSM-3, ZSM-4, ZSM-5, ZSM-18, ZSM-20, ZSM-34, ZSM-38, ZSM-48, ZK-4, ZK-5, zeolite A, zeolite T, gmelinite, chinoptilolite, chabasite and erionite. Preferred non-zeolite molecular sieves include metalloaluminophosphate molecular sieves. Particularly preferred metalloaluminophosphate molecular sieves include silicoaluminophosphate (SAPO) molecular sieves, aluminophosphate molecular sieves and metal substituted forms thereof. Non-limiting examples of SAPO and ALPO molecular sieves that may be present in the molecular sieve catalyst of the invention include molecular sieves selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO- 34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO- 36, ALPO-37, ALPO-46, metal containing molecular sieves thereof, and mixtures thereof.

Detailed Description of the Invention

L Providing a Catalyst of High Attrition Resistance

[0015] This invention provides methods relating to the manufacture of molecular sieve catalyst. The catalyst that is made according to this invention is particularly attrition resistant. A catalyst of high attrition resistance is particularly beneficial in large scale commercial units where high temperature and mechanical stress are primarily responsible for physical damage to the catalyst in the system. [0016] In particular, this invention provides methods for making attrition resistant molecular sieve catalyst using appropriate spray drying methods. The catalyst is made by forming a slurry of molecular sieve particles, with the slurry including binder, as well as optionally including matrix materials, and spray drying the slurry to form the attrition resistant molecular sieve catalyst. The spray drying is used to control the degree of attrition resistance of the final catalyst product. The degree of attrition resistance is affected by a variety of spray drying control variables. Examples of such variables include, but are not limited to, spray dryer inlet and outlet temperatures, rate of flow of slurry into the spray dryer, and rate of flow of drying gas to the spray dryer. Appropriate control of various spray drying control variables results in a catalyst that is extremely attrition resistant.

IL Types of Molecular Sieves

[0017] Any variety of molecular sieves can be used to make the catalyst of this invention. Such molecular sieves include zeolites or non-zeolites, preferably non-zeolites.

[0018] Conventional crystalline aluminosilicate zeolites having catalytic activity are desirable molecular sieves that can be used in making the catalyst of this invention. Examples of such zeolite materials are described in U.S. Pat. Nos. 3,660,274 and 3,944,482, both of which are incorporated herein by reference. Non-limiting examples of zeolites which can be employed in the practice of this invention, include both natural and synthetic zeolites. These zeolites include zeolites of the structural types included in the Atlas of Zeolite Framework Types, edited by Ch. Baerlocher, W. M. Meier, D. H. Olson, Fifth Revised edition, Elsevier, Amsterdam, 2001, the descriptions of which are incorporated herein by reference.

[0019] Zeolites typically have silica-to-alumina (SiO₂/Al₂O₃) mole ratios of at least about 2, and have uniform pore diameters from about 3 to 15 Angsfroms. They also generally contain alkali metal cations, such as sodium and/or potassium and/or alkaline earth metal cations, such as magnesium and/or calcium, h order to increase the catalytic activity of the zeolite, it may be desirable to decrease the alkali metal content of the crystalline zeolite to less than about 5 wt. %, preferably less than about 1 wt. %, and more preferably less than about 0.5 wt. %. The alkali metal content reduction, as is known in the art, may be conducted by exchange with one or more cations selected from the Groups LIB through VIII of the Periodic Table of Elements (the Periodic Table of Elements referred to herein is given in Handbook of Chemistry and Physics, published by the Chemical Rubber Publishing Company, Cleveland, Ohio, 45th Edition, 1964 or 73rd Edition, 1992), as well as with hydronium ions or basic adducts of hydronium ions, e.g., NH₄ , capable of conversion to a hydrogen cation upon calcination. Desired cations include rare earth cations, calcium, magnesium, hydrogen and mixtures thereof. Ion-exchange methods are well known in the art and are described, for example, in U.S. Pat. No. 3,140,249; U.S. Pat. No. 3,142,251 and U.S. Pat. No. 1,423,353, the teachings of which are hereby incorporated by reference.

[0020] Examples of zeolites suitable for use in this invention include large pore zeolites, medium pore zeolites, and small pore zeolites. A large pore zeolite generally has a pore size of >7 angstroms and includes zeolite types such as MAZ, MEI, FAU, EMT. Examples of large pore zeolites include zeolite L, zeolite Y, zeolite X, offretite, omega, Beta, mordenite, ZSM-3, ZSM-4, ZSM-18, and ZSM- 20. A medium pore size catalyst generally has a pore size <7 angsfroms, preferably from about 5 angsfroms to about 6.8 angsfroms; and generally the pore apertures consist of about 10 to 12, preferably about 10, membered ring structures and include MFI, MEL, MTW, EUO, MTT, HEU, FER, and TON. Examples of medium pore zeolite include ZSM-5, ZSM-34, ZSM-38, and ZSM-48. A small pore size zeolite has a pore size from about 3 angstroms to about 5.0 angstroms. Generally, the pore apertures of the structure consist of from about 8 to 10, preferably about 8, membered ring structures and include CHA, ERI, KFI, LEV, and LTA. Examples of small pore zeolite include ZK-4, ZK-5, zeolite A, zeolite T, gmelinite, chinoptilolite, chabasite and erionite. The zeolites can also comprise gallosilicates and titanosilicates.

[0021] Non-zeolite molecular sieves can also be included in the first dried molecular sieve catalyst particles used to make the catalysts of this invention. Preferred non-zeolite molecular sieves include metalloaluminophosphate molecular sieves.

[0022] The metalloaluminophosphate molecular sieve may be represented by the empirical formula, on an anhydrous basis: mR:(M_xAl_yP_z)O₂ wherein R represents at least one templating agent, preferably an organic templating agent; m is the number of moles of R per mole of (M_xAlyP_z)O₂ and m has a value from 0 to 1, preferably 0 to 0.5, and most preferably from 0 to 0.3; x, y, and z represent the mole fraction of Al, P and M as tefrahedral oxides, where M is a metal selected from one of Group IA, IIA, LB, I LB, LVB, VB, VLB, VIIB, VIILB and Lanthanide's of the Periodic Table of Elements, preferably M is selected from one of the group consisting of Si, Ge, Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn, Zr and mixtures thereof. In an embodiment, m is greater than or equal to 0.2, and x, y and z are greater than or equal to 0.01. In another embodiment, m is greater than 0.1 to about 1, x is greater than 0 to about 0.25, y is in the range of from 0.4 to 0.5, and z is in the range of from 0.25 to 0.5, more preferably m is from 0.15 to 0.7, x is from 0.01 to 0.2, y is from 0.4 to 0.5, and z is from 0.3 to 0.5.

[0023] Examples of metalloaluminophosphate molecular sieves which may be present in the molecular sieve catalysts have been described in detail in numerous publications including for example, U.S. Pat. No. 4,567,029 (MeAPO where Me is Mg, Mn, Zn, or Co), U.S. Pat. No. 4,440,871 (SAPO), European Patent Application EP-A-0 159 624 (ELAPSO where El is As, Be, B, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. Nos. 4,822,478, 4,683,217, 4,744,885 (FeAPSO), EP-A-0 158 975 and U.S. Pat. No. 4,935,216 (ZnAPSO, EP-A-0 161 489 (CoAPSO), EP-A-0 158 976 (ELAPO, where EL is Co, Fe, Mg, Mn, Ti or Zn), U.S. Pat. No. 4,310,440 (AlPO.sub.4), EP-A-0 158 350 (SENAPSO), U.S. Pat. No. 4,973,460 (LiAPSO), U.S. Pat. No. 4,789,535 (LiAPO), U.S. Pat. No. 4,992,250 (GeAPSO), U.S. Pat. No. 4,888,167 (GeAPO), U.S. Pat. No. 5,057,295 (BAPSO), U.S. Pat. No. 4,738,837 (CrAPSO), U.S. Pat. Nos. 4,759,919, and 4,851,106 (CrAPO), U.S. Pat. Nos. 4,758,419, 4,882,038, 5,434,326 and 5,478,787 (MgAPSO), U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. No. 4,894,213 (AsAPSO), U.S. Pat. No. 4,913,888 (AsAPO), U.S. Pat. Nos. 4,686,092, 4,846,956 and 4,793,833 (MnAPSO), U.S. Pat. Nos. 5,345,011 and 6,156,931 (MnAPO), U.S. Pat. No. 4,737,353 (BeAPSO), U.S. Pat. No. 4,940,570 (BeAPO), U.S. Pat. Nos. 4,801,309, 4,684,617 and 4,880,520 (TiAPSO), U.S. Pat. Nos. 4,500,651, 4,551,236 and 4,605,492 (TiAPO), U.S. Pat. Nos. 4,824,554, 4,744,970 (CoAPSO), U.S. Pat. No. 4,735,806 (GaAPSO) EP-A- 0293 937 (QAPSO, where Q is framework oxide unit [QO.sub.2]), as well as U.S. Pat. Nos. 4,567,029, 4,686,093, 4,781,814, 4,793,984, 4,801,364, 4,853,197, 4,917,876, 4,952,384, 4,956,164, 4,956,165, 4,973,785, 5,241,093, 5,493,066 and 5,675,050, all of which are herein fully incorporated by reference. [0024] Other metalloaluminophosphate molecular sieves include those described in EP-0 888 187 Bl (microporous crystalline metallophosphates, SAPO₄ (UIO-6)), U.S. Pat. No. 6,004,898 (molecular sieve and an alkaline earth metal), PCT WO 01/62382 published August 30, 2001 (integrated hydrocarbon co-catalyst), PCT WO 01/64340 published Sep. 7, 2001(thorium containing molecular sieve), and R. Szostak, Handbook of Molecular Sieves, Van Nostrand Reinhold, New York, N.Y. (1992), which are all herein fully incorporated by reference.

[0025] Most preferably, the molecular sieves are silicoaluminophosphate

(SAPO) molecular sieves, aluminophosphate molecular sieves and metal substituted forms thereof. [0026] Non-limiting examples of SAPO and ALPO molecular sieves that may be present in the molecular sieve catalyst of the invention include molecular sieves selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO- 16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37, ALPO-46, metal containing molecular sieves thereof, and mixtures thereof. The more preferred molecular sieves include molecular sieves selected from the group consisting of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 ALPO-34, metal contaimng molecular sieves thereof, and mixtures thereof; even more preferably molecular sieves selected from the group consisting of SAPO-18, SAPO-34, ALPO-34, ALPO-18, metal containing molecular sieves thereof, and mixtures thereof; and most preferably molecular sieves selected from the group consisting of SAPO-34, ALPO-18, metal containing molecular sieves thereof, and mixtures thereof.

[0027] As used herein, the term mixture is synonymous with combination and is considered a composition of matter having two or more components in varying proportions, regardless of their physical state. In particular, it encompasses physical mixtures as well as intergrowths of at least two different molecular sieve structures, such as for example those described in PCT Publication No. WO 98/15496. In an embodiment, the molecular sieve is an intergrowth material having two or more distinct phases of crystalline structures within one molecular sieve composition. In another embodiment, the molecular sieve comprises at least one intergrown phase of AEI and CHA framework-types. For example, SAPO-18, ALPO-18 and RUW-18 have an AEI framework-type, and SAPO-34 has a CHA framework-type, fri a further embodiment the molecular sieve comprises a mixture of intergrown material and non-intergrown material. III. Methods of Making Molecular Sieve and Molecular Sieve Catalyst

A. Making Molecular Sieve Crystals

[0028] Generally, molecular sieves (i.e., molecular sieve crystals) are synthesized by the hydrothermal crystallization of one or more of a source of aluminum, a source of phosphorus, a source of silicon, water and a templating agent, such as a nifrogen containing organic compound. Typically, a combination of sources of silicon and aluminum, or silicon, aluminum and phosphorus, water and one or more templating agents, is placed in a sealed pressure vessel. The vessel is optionally lined with an inert plastic such as polytefrafluoroethylene, and heated under a crystallization pressure and temperature, until a crystalline material is formed, which can then recovered by filtration, centrifugation and/or decanting. [0029] Non-limiting examples of silicon sources include silicates, fumed silica, for example, Aerosil-200 available from Degussa Inc., New York, New York, and CAB-O-SIL M-5, organosilicon compounds such as tetraalkylorthosilicates, for example, teframethylorthosilicate (TMOS) and tetraethylorthosilicate (TEOS), colloidal silicas or aqueous suspensions thereof, for example Ludox-HS-40 sol available from E.I. du Pont de Nemours, Wilmington, Delaware, silicic acid or any combination thereof. [0030] Non-limiting examples of aluminum sources include aluminum alkoxides, for example aluminum isopropoxide, aluminum phosphate, aluminum hydroxide, sodium aluminate, pseudo-boehmite, gibbsite and aluminum trichloride, or any combination thereof. A convenient source of aluminum is pseudo-boehmite, particularly when producing a silicoaluminophosphate molecular sieve.

[0031] Non-limiting examples of phosphorus sources, which may also include aluminum-containing phosphorus compositions, include phosphoric acid, organic phosphates such as triethyl phosphate, and crystalline or amorphous aluminophosphates such as AlPO₄, phosphorus salts, or combinations thereof. A convenient source of phosphorus is phosphoric acid, particularly when producing a silicoaluminophosphate.

[0032] In general, templating agents or templates include compounds that contain elements of Group 15 of the Periodic Table of Elements, particularly nitrogen, phosphorus, arsenic and antimony. Typical templates also contain at least one alkyl or aryl group, such as an alkyl or aryl group having from 1 to 10 carbon atoms, for example from 1 to 8 carbon atoms. Preferred templates are nitrogen-containing compounds, such as amines, quaternary ammonium compounds and combinations thereof. Suitable quaternary ammonium compounds are represented by the general formula P^N^1", where each R is hydrogen or a hydrocarbyl or substituted hydrocarbyl group, preferably an alkyl group or an aryl group having from 1 to 10 carbon atoms. [0033] Non-limiting examples of templates include tefraalkyl ammonium compounds including salts thereof, such as tetramethyl ammonium compounds, tefraethyl ammonium compounds, tetrapropyl ammonium compounds, and tetrabutylammonium compounds, cyclohexylamme, morpholine, di-n- propylamine (DPA), tripropylamine, triethylamine (TEA), triethanolamine, piperidine, cyclohexylamme, 2-methylpyridine, N,N-dimethylbenzylamine, N,N- diethylethanolamine, dicyclohexylamine, N,N-dimethylethanolamine, choline, N,N'-dimethylpiperazine, l,4-diazabicyclo(2,2,2)octane, N', N',N,N-tetramethyl- (l,6)hexanediamine, N-methyldiethanolamine, N-methyl-ethanolamine, N-methyl piperidine, 3-methyl-piperidine, N-methylcyclohexylamine, 3-methylpyridine, 4- methyl-pyridine, quinuclidine, N,N'-dimethyl-l,4-diazabicyclo(2,2,2) octane ion; di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butyl- amine, ethylenediamine, pyrrolidine, and 2-imidazolidone. Preferred templates are selected from the group consisting of tefraethyl ammonium salts, cyclopentylamine, aminomethyl cyclohexane, piperidine, triethylamine, cyclohexylamme, tri-ethyl hydroxyethylamine, moφholine, dipropylamine (DPA), pyridine, isopropylamine, heated degraded forms thereof, and combinations thereof.

[0034] The pH of the synthesis mixture containing at a minimum a silicon, aluminum, optionally a phosphorus composition, and a templating agent, is generally in the range of from 2 to 10, such as from 4 to 9, for example from 5 to 8.

[0035] Generally, the synthesis mixture described above is sealed in a vessel and heated, preferably under autogenous pressure, to a temperature in the range of from about 80°C to about 250°C, such as from about 100°C to about 250°C, for example from about 125°C to about 225°C, such as from about 150°C to about 180°C. [0036] In one embodiment, the synthesis of molecular sieve crystalline particles is aided by seeds from another or the same framework type molecular sieve.

[0037] The time required to form the crystalline particles is usually dependent on the temperature and can vary from immediately up to several weeks. Typically, the crystallization time is from about 30 minutes to around 2 weeks, such as from about 45 minutes to about 240 hours, for example from about 1 hour to about 120 hours. The hydrothermal crystallization may be carried out with or without agitation or stirring.

[0038] One method for crystallization involves subjecting an aqueous reaction mixture containing an excess amount of a templating agent to crystallization under hydrothermal conditions, establishing an equilibrium between molecular sieve formation and dissolution, and then, removing some of the excess templating agent and/or organic base to inhibit dissolution of the molecular sieve. See, for example, U.S. Patent No. 5,296,208, which is herein fully incorporated by reference.

[0039] Other methods for synthesizing molecular sieves or modifying molecular sieves are described in U.S. Patent No. 5,879,655 (controlling the ratio of the templating agent to phosphorus), U.S. Patent No. 6,005,155 (use of a modifier without a salt), U.S. Patent No. 5,475,182 (acid extraction), U.S. Patent No. 5,962,762 (treatment with transition metal), U.S. Patent Nos. 5,925,586 and 6,153,552 (phosphorus modified), U.S. Patent No. 5,925,800 (monolith supported), U.S. Patent No. 5,932,512 (fluorine treated), U.S. Patent No. 6,046,373 (electromagnetic wave treated or modified), U.S. Patent No. 6,051,746 (polynuclear aromatic modifier), U.S. Patent No. 6,225,254 (heating template), PCT WO 01/36329 published May 25, 2001 (surfactant synthesis), PCT WO 01/25151 published April 12, 2001 (staged acid addition), PCT WO 01/60746 published August 23, 2001 (silicon oil), U.S. Patent Application Publication No. 20020055433 published May 9, 2002 (cooling molecular sieve), U.S. Patent No. 6,448,197 (metal impregnation including copper), U.S. Patent No. 6,521,562 (conductive microfilter), and U.S. Patent Application Publication No. 20020115897 published August 22, 2002 (freeze drying the molecular sieve), which are all herein fully incorporated by reference.

[0040] Once the crystalline molecular sieve product is formed, usually in a slurry state, it may be recovered by any standard technique well known in the art, for example, by centrifugation or filtration. The recovered crystalline particle product, normally termed the "wet filter cake", may then be washed, such as with water, and then dried, such as in air, before being formulated into a catalyst composition. Alternatively, the wet filter cake may be formulated into a catalyst composition directly, that is without any drying, or after only partial drying. B. Making Formulated Molecular Sieve Catalyst

1. Components of Formulated Molecular Sieve Catalyst

[0041] Molecular sieve catalyst, which contains molecular sieve crystal product, and typically binder and matrix materials, is also referred to as a formulated catalyst. It is made by mixing together molecular sieve crystals (which includes template) and a liquid, optionally with matrix material and/or binder, to form a slurry. The slurry is then dried (i.e., liquid is removed), without completely removing the template from the molecular sieve. Since this dried molecular sieve catalyst includes template, it has not been activated, and is considered a preformed catalyst. The catalyst in this form is resistant to catalytic activity loss by contact with moisture or water. However, the preformed catalyst must be activated before use, and this invention provides appropriate methods of activating, preferably by further heat treatment, to maintain a low water content within the activated catalyst.

[0042] The liquid used to form the slurry can be any liquid conventionally used in formulating molecular sieve catalysts. Non-limiting examples of suitable liquids include water, alcohol, ketones, aldehydes, esters, or a combination thereof. Water is a preferred liquid.

[0043] Matrix materials are optionally included in the slurry used to make the formulated molecular sieve catalyst of this invention. Such materials are typically effective as thermal sinks assisting in shielding heat from the catalyst composition, for example, during regeneration. They can further act to densify the catalyst composition, increase catalyst sfrength such as crush strength and attrition resistance, and to control the rate of conversion in a particular process. Non- limiting examples of matrix materials include one or more of: rare earth metals, metal oxides including titania, zirconia, magnesia, thoria, beryllia, quartz, silica or sols, and mixtures thereof; for example, silica-magnesia, silica-zirconia, silica- titania, silica-alumina and silica-alumina-thoria.

[0044] In one embodiment, matrix materials are natural clays, such as those from the families of montmorillonite and kaolin. These natural clays include kaolins known as, for example, Dixie, McNamee, Georgia and Florida clays. Non-limiting examples of other matrix materials include: halloysite , kaolinite, dickite, nacrite, or anauxite. Optionally, the matrix material, preferably any of the clays, are calcined, acid treated, and/or chemical treated before being used as a slurry component. Under the optional calcination treatment, the matrix material will still be considered virgin material as long as the material has not been previously used in a catalyst formulation.

[0045] In a particular embodiment, the matrix material is a clay or a clay- type composition, preferably a clay or clay-type composition having a low iron or titania content, and most preferably the matrix material is kaolin. Kaolin has been found to form a pumpable, high solid content slurry; it has a low fresh surface area, and it packs together easily due to its platelet structure. [0046] Preferably, the matrix material, particularly clay, and preferably kaolin, has an average particle size of from about 0.05 μm to about 0.75 μm; more preferably from about 0.1 μm to about 0.6 μm. It is also desirable that the matrix material have a d₉₀ particle size distribution of less than about 1.5 μm, preferably less than about 1 μm.

[0047] Binders are also optionally included in the slurry used to make the formulated molecular sieve catalysts of this invention. Such materials act like glue, binding together the molecular sieve crystals and other materials, to form a formulated catalyst composition. Non-limiting examples of binders include various types of inorganic oxide sols such as hydrated aluminas, silicas, and/or other inorganic oxide sols. In one embodiment of the invention, the binder is an alumina-containing sol, preferably aluminium chlorohydrate. Upon calcining, the inorganic oxide sol, is converted into an inorganic oxide matrix component, which is particularly effective in forming an attrition resistant molecular sieve catalyst composition. For example, an alumina sol will convert to an aluminium oxide matrix following heat treatment.

[0048] Aluminium chlorohydrate, a hydroxylated aluminium based sol containing a chloride counter ion, also known as aluminium chlorohydrol, has the general formula Al_mO_n(OH)₀Cl_p.χ(H₂O) wherein m is 1 to 20, n is 1 to 8, o is 5 to 40, p is 2 to 15, and x is 0 to 30. In one embodiment, the binder is Alι₃O₄(OH)₂₄Cl₇»12(H₂O) as is described in G.M. Wolterman, et al., Stud. Surf. Sci. and Catal, 76, pages 105-144, Elsevier, Amsterdam, 1993, which is herein incorporated by reference, h another embodiment, one or more binders are present in combination with one or more other non-limiting examples of alumina materials such as aluminium oxyhydroxide, γ-alumina, boehmite and transitional aluminas such as α-alumina, /3-alumina, γ-alumina, δ-alumina, €-alumina, -alumina, and p-alumina, aluminium trihydroxide, such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.

[0049] In another embodiment, the binders are alumina sols, predominantly comprising aluminium oxide, optionally including silicon, hi yet another embodiment, the binders are peptised alumina made by treating alumina hydrates such as pseudobohemite, with an acid, preferably a non-halogen acid, to prepare sols or aluminium ion solutions. Non-limiting examples of commercially available colloidal alumina sols include Nalco 8676 available from Nalco Chemical Co., Naperville, Illinois, and Nyacol AL20DW available from the Nyacol Nano Technology Inc., Ashland, Massachusetts. [0050] If binder is not used in making the molecular sieve catalyst, the catalyst is considered a binderless catalyst. If binder is used, the amount of binder used to prepare the molecular sieve catalyst ranges from about 2% by weight to about 30% by weight, based on the total weight of the binder, the molecular sieve, and optionally included matrix material, excluding the liquid (i.e., after drying). Preferably the amount of binder used to prepare the molecular sieve catalyst ranges from about 5% by weight to about 27% by weight, more preferably from about 7% by weight to about 20% by weight, based on the total weight of the binder, the molecular sieve, and optionally included matrix material, excluding the liquid (i.e., after drying).

2. Making a Slurry with Molecular Sieve Crystals

[0051] The molecular sieve crystals are mixed with liquid, and the optional matrix material and/or binder, using conventional techniques to form a slurry. The components can be mixed in any order, and the mixture is thoroughly stirred to form the slurry. The more thorough the stirring, the better the consistency of the slurry.

[0052] The mixing of the slurry is preferably sufficient to break any aggregates or large particles into smaller, more uniform particles. In general, the more vigorous the mixing, the smaller the catalyst particles formed in the slurry.

Mixing using high-shear mixers is preferred. In general, high-shear mixers are capable of rotating at speeds of at least about 3,000 rpm laboratory scale equivalent.

[0053] Solids particle size of the slurry can be indirectly determined by measuring the viscosity of the slurry. In general, at comparable solids content and composition, the higher the viscosity, the smaller the solids particle size in the slurry. The viscosity of the slurry should not be too high, so that mixing is not effective in breaking apart large particles, or too low, so that drying will not produce acceptable particle formation.

[0054] In one embodiment, the slurry has a viscosity of from about 100 cP

(0.1 Pa/sec) to about 12,000 cP (12.0 Pa/sec), as measured using a Brookfield LV-

DVE viscometer with a No. 3 spindle at 10 rpm. Preferably, the slurry has a viscosity of from about 200 cP (0.2 Pa/sec) to about 10,000 cP (10.0 Pa/sec), and more preferably from about 350 cP (0.350 Pa/sec) to about 9,500 cP (9.5 Pa/sec), as measured using a Brookfield LV-DVE viscometer with a No. 3 spindle at 10 φm.

[0055] In another embodiment, the slurry has a solids content of from about 10 wt % to about 75 wt %, based on total weight of the slurry. Preferably the slurry has a solids content of from about 15 wt % to about 70 wt %, more preferably from about 20 wt % to about 65 wt %, based on the total weight of the slurry. The solids content can be measured using any conventional means. However, a CEM MAS 700 microwave muffle furnace is particularly preferred to give results consistent with the values recited herein. [0056] hi one embodiment, the slurry used to make the formulated molecular sieve catalyst contains binder and matrix material at a weight ratio of from 0: 1 to 1 : 1. Preferably, the slurry used to make the molecular sieve catalyst contains binder and matrix material at a weight ratio of from 1:15 to 1:2, more preferably 1:10 to 1:2, and most preferably 1:6 to 1:1. LV. Spray Drying to Increase Attrition Resistance

[0057] According to this invention, the molecular sieve containing slurry is appropriately spray dried to provide the attrition resistant molecular sieve catalyst of this invention. The slurry is spray dried within the spray dryer at a rate that provides an attrition resistant catalyst particle. Rate of drying is controlled by such variables as spray dryer inlet and outlet temperatures, temperature differential between spray dryer inlet and outlet, rate of feed of slurry to the spray dryer, rate of removal of water from the slurry spray dryer, and rate of drying gas fed to the spray dryer.

[0058] During spray drying, the slurry is passed through a nozzle distributing the slurry into small droplets, resembling an aerosol spray into a drying chamber. Atomization is achieved by forcing the slurry through a single nozzle or multiple nozzles with a pressure drop in the range of from 100 psia to 1000 psia (690 kpaa to 6895 kpaa). In another embodiment, the slurry is co-fed through a single nozzle or multiple nozzles along with an atomization fluid such as air, steam, flue gas, or any other suitable gas.

[0059] hi yet another embodiment, the slurry described above is directed to the perimeter of a spinning wheel that distributes the slurry into small droplets, the size of which is controlled by many factors including slurry viscosity, surface tension, flow rate, pressure, and temperature of the slurry, the shape and dimension of the nozzle(s), or the spinning rate of the wheel. These droplets are then dried in a co-current or counter-current flow of drying gas passing through a spray drier to form a partially, substantially or totally dried molecular sieve catalyst composition. Examples of drying gas include, but are not limited to, such gases as air, nifrogen , flue gas and steam. Air is particularly preferred. [0060] An example of a spray drying process that may be used to prepare the first dried molecular sieve catalyst composition is disclosed in U.S. Pat. No. 4,946,814, the description of which is incoφorated herein. A. Catalyst Attrition Resistance

[0061] hi this invention, attrition resistance is measured using an Attrition

Rate Index (ARI). The ARI is used over other measurement methods, since many other methods are not sufficient to measure very highly attrition resistant molecular sieve catalysts such as those made according to this invention. [0062] The ARI methodology is similar to the conventional Davison Index method. The smaller the ARI, the more resistant to attrition the catalyst. The ARI is measured by adding 6.0 ± 0.1 g of catalyst having a particles size ranging from 53 to 125 microns to a hardened steel attrition cup. Approximately 23,700 scc/min of nifrogen gas is bubbled through a water-containing bubbler to humidify the nitrogen. The wet nitrogen passes through the attrition cup, and exits the attrition apparatus through a porous fiber thimble. The flowing nitrogen removes the finer particles, with the larger particles being retained in the cup. The porous fiber thimble separates the fine catalyst particles from the nifrogen that exits through the thimble. The fine particles remaining in the thimble represent catalyst that has broken apart through attrition.

[0063] The nifrogen flow passing through the attrition cup is maintained for 1 hour. The fines collected in the thimble are removed from the unit. A new thimble is then installed. The catalyst left in the attrition unit is attrited for an additional 3 hours, under the same gas flow and moisture levels. The fines collected in the thimble are recovered. The collection of fine catalyst particles separated by the thimble after the first hour are weighed. The amount in grams of fine particles divided by the original amount of catalyst charged to the attrition cup expressed on per hour basis is the ARI, in wt %/hr. ARI = C/(B+C)/D x 100% wherein B = weight of catalyst left in the cup after the attrition test C = weight of collected fine catalyst particles after the first hour of attrition treatment D = duration of treatment in hours after the first hour attrition treatment. [0064] The calcined molecular sieve catalyst particles which are made from the method of this invention desirably have an ARI of not greater than about 1 wt %/hr, preferably not greater than about 0.8 wt %/hr, more preferably not greater than about 0.7 wt %/hr, and most preferably not greater than about 0.5 wt %/hr.

B. Agglomeration of Catalyst Particles

[0065] In one aspect, the rate of spray drying of the slurry of this invention is controlled so as to limit the amount of catalyst agglomerates. Agglomerates are essentially large particles made of more than one individual catalyst particle. [0066] In general, agglomerates are formed as a result of improperly drying the slurry. Improper drying can occur by a number of ways, including incomplete drying or the formation of localized regions within the dryer that lead to trapping or accumulation of catalyst material. Incomplete drying can lead to the accumulation of partially dried catalyst material on the wall of the spray dryer. Such partially dried material has a tendency to be sticky, since the slurry itself tends to be sticky. Thus, incomplete drying leads to the build up of catalyst material on the wall of the slurry. As the build up becomes greater, deposits tend to break off the wall as wet or partially dried lumps and become mixed with the dried catalyst material. These lumps include agglomerates of catalyst particles. [0067] Agglomerates of even two individual catalyst particles are not particularly desirable. However, agglomerates of 20 or more particles are particularly undesirable, and agglomerates of 50 or more particles are especially unacceptable. Thus, appropriately dried catalyst coming out of the spray dryer preferably has agglomerates of less than 50 particles, more preferably less than 20 particles. The number of particles in an agglomerated particle can be measured using an optical microscope with a magnification of greater than lOOx. Preferably, the number of particles in an agglomerate is measured using a scanning electron microscope. [0068] Although a limited amount of particle agglomerates can be acceptable, the size of the agglomerates should not be too large such that feed and product transport is significantly affected. Agglomerate particles having an average diameter of 100 microns or more are not particularly desirable. Particle agglomerates having an average diameter of 200 microns or more, particularly 250 microns or more, are especially undesirable. Thus, any agglomerates in the spray dried catalyst removed from the spray dryer will have an average diameter of less than 250 microns, preferably less than 200 microns, and more preferably less than 100 microns.

C. Spray Dryer Inlet and Outlet Temperatures

[0069] The degree of attrition resistance of the catalyst of this invention is also controlled in part by the inlet and outlet temperatures of the spray dryer, as well as the inlet and outlet temperature differential. In general, a lower spray dryer inlet temperature is preferred, and a lower inlet and outlet temperature differential is preferred.

[0070] According to one embodiment of the invention, the slurry containing the molecular sieve is injected into the spray dryer at a spray dryer inlet temperature of not greater than about 500°C. Preferably, the slurry containing the molecular sieve is injected into the spray dryer at a spray dryer inlet temperature of not greater than about 450°C, more preferably at a spray dryer inlet temperature of not greater than about 400°C, and most preferably at a spray dryer inlet temperature of not greater than about 300°C.

[0071] According to another embodiment of the invention, the drying of the slurry containing the molecular sieve is achieved in the spray dryer at a spray dryer outlet temperature of not greater than about 350°C. Preferably, the drying of the slurry containing the molecular sieve is achieved in the spray dryer at a spray dryer outlet temperature of not greater than about 250°C, more preferably at a spray dryer outlet temperature of not greater than about 200°C, and most preferably at a spray dryer outlet temperature of not greater than about 150°C. [0072] Desirably, the temperature differential between the spray dryer inlet and outlet is low enough to provide uniformly attrition resistant, finished catalyst product. A temperature differential that is too high will likely provide catalyst particles that are not as attrition resistant as they will likely have a relatively hard or brittle external shell, with a relatively soft core. The temperature differential should not be so low, however, that drying is incomplete, which would result in a catalyst that is insufficiently hard to be appropriately attrition resistant. [0073] hi one embodiment, the sluny is dried in the spray dryer at a spray dryer inlet and outlet temperature differential of not greater than about 350°C. Preferably, the slurry is dried in the spray dryer at a spray dryer inlet and outlet temperature differential of not greater than about 250°C, more preferably not greater than about 200°C, and most preferably not greater than about 150°C.

D. Rate of Drying Slurry to Form Spray Dried Material

[0074] The rate of drying of the sluny in the spray dryer is controlled so as to provide a uniformly dried product. An appropriately dried product will form, upon further heating such as by calcining, a highly attrition resistant catalyst composition.

[0075] The rate of drying of the sluny in the spray dryer is a function of the mass feed rates of liquid in the sluny, solids in the sluny, heating gas flowed through the spray dryer, and physical properties of the slurry such as droplet size, particle size, size distribution of the slurry particles, and solids content of the slurry. The finer the droplets, or the greater the evaporation surface area, the faster the rate of drying. The rate of drying also depends upon the changes in enthalpy for each of the stated variables, e.g., ΔHii_qujd, ΔH_soiid_S, and ΔH_gas, respectively.

[0076] According to this invention, the drying rate of the sluny is calculated as kg/hr of liquid removed from the sluny (i.e., kg/hr liq.) per kg/hr of drying gas fed to the spray dryer (kg/hr gas), hi one embodiment of the invention, the slurry is dried in the spray dryer at a drying rate of not greater than 0.275 kg/hr liq. per kg/hr gas. Preferably, the sluny is dried in the spray dryer at a drying rate of not greater than 0.25 kg/hr liq. per kg/hr gas, more preferably not greater than 0.2 kg/hr liq. per kg/hr gas.

E. Additional Drying of Spray Dried Catalyst Particles [0077] Once the sluny is appropriately dried to form the spray dried product, the spray dried product is removed from the spray dryer and further dried or heated to achieve the desired or predetermined attrition resistance (i.e., predetermined ARI). The spray dried material is, preferably, further heated to an ARI of not greater than 1 %/hr. More preferably, the spray dried molecular sieve is removed from the spray dryer and further heated to an ARI of not greater than 0.8 %/hr, still more preferably not greater than 0.7 %/hr, and most preferably not greater than 0.5 %/hr.

[0078] Further heating to form the attrition resistant catalyst of this invention is generally refened to as calcination. Conventional calcination devices can be used. Such devices include rotary calciners, fluid bed calciners, batch ovens, and the like. Calcination time is typically dependent of the desired or predetermined degree of attrition resistance of the catalyst and the calcination temperature.

[0079] Conventional calcination temperatures are effective to achieve the desired or predetermined attrition resistance. Such temperatures are generally in the range of from about 400°C to about 1,000°C, preferably from about 500°C to about 800°C, and most preferably from about 550°C to about 700°C. Preferably, the duration of calcinations ranges from about 5 minutes to about 20 hours, more preferably from about 10 minutes to about 10 hours, and most preferably from about 15 minutes to about 6 hours.

V. Type of Reaction Systems in Which Catalyst Can Be Used

[0080] The molecular sieve catalyst product made according to this invention is useful in a variety of processes including cracking of, for example, a naphtha feed to light olefin(s) (U.S. Patent No. 6,300,537) or higher molecular weight (MW) hydrocarbons to lower MW hydrocarbons; hydrocracking of, for example, heavy petroleum and/or cyclic feedstock; isomerization of, for example, aromatics such as xylene; polymerization of, for example, one or more olefin(s) to produce a polymer product; reforming; hydrogenation; dehydrogenation; dewaxing of, for example, hydrocarbons to remove straight chain paraffins; absoφtion of, for example, alkyl aromatic compounds for separating out isomers thereof; alkylation of, for example, aromatic hydrocarbons such as benzene and alkyl benzene, optionally with propylene to produce cumene or with long chain olefins; fransalkylation of, for example, a combination of aromatic and polyalkylaromatic hydrocarbons; dealkylation; hydrodecyclization; disproportionation of, for example, toluene to make benzene and paraxylene; oligomerization of, for example, straight and branched chain olefin(s); and dehydrocyclization.

[0081] Prefened processes include processes for converting naphtha to highly aromatic mixtures; converting light olefin(s) to gasoline, distillates and lubricants; converting oxygenates to olefin(s); converting light paraffins to olefins and/or aromatics; and converting unsaturated hydrocarbons (ethylene and/or acetylene) to aldehydes for conversion into alcohols, acids and esters. [0082] The most prefened process of the invention is a process directed to the conversion of a feedstock to one or more olefin(s). Typically, the feedstock contains one or more aliphatic-containing compounds such that the aliphatic moiety contains from 1 to about 50 carbon atoms, such as from 1 to 20 carbon atoms, for example from 1 to 10 carbon atoms, and particularly from 1 to 4 carbon atoms.

[0083] Non-limiting examples of aliphatic-containing compounds include alcohols such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide, alkylamines such as methylamine, alkyl ethers such as dimethyl ether, diethyl ether and methylethyl ether, alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehydes, and various acids such as acetic acid.

[0084] h a prefened embodiment of the process of the invention, the feedstock contains one or more oxygenates, more specifically, one or more organic compound(s) containing at least one oxygen atom. In the most prefened embodiment of the process of invention, the oxygenate in the feedstock is one or more alcohol(s), preferably aliphatic alcohol(s) where the aliphatic moiety of the alcohol(s) has from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms. The alcohols useful as feedstock in the process of the invention include lower straight and branched chain aliphatic alcohols and their unsaturated counteφarts. [0085] Non-limiting examples of oxygenates include methanol, ethanol, n- propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethyl ether, di- isopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid, and mixtures thereof.

[0086] hi the most prefened embodiment, the feedstock is selected from one or more of methanol, ethanol, dimethyl ether, diethyl ether or a combination thereof, more preferably methanol and dimethyl ether, and most preferably methanol.

[0087] The various feedstocks discussed above, particularly a feedstock containing an oxygenate, more particularly a feedstock containing an alcohol, is converted primarily into one or more olefm(s). The olefin(s) produced from the feedstock typically have from 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbons atoms, and most preferably are ethylene and/or propylene. [0088] The catalyst composition of the invention is particularly useful in the process that is generally refened to as the gas-to-olefins (GTO) process or, alternatively, the methanol-to-olefms (MTO) process. In this process, an oxygenated feedstock, most preferably a methanol-containing feedstock, is converted in the presence of a molecular sieve catalyst composition into one or more olefin(s), preferably and predominantly, ethylene and/or propylene. [0089] Using the catalyst composition of the invention for the conversion of a feedstock, preferably a feedstock containing one or more oxygenates, the amount of olefin(s) produced based on the total weight of hydrocarbon produced is greater than 50 weight percent, typically greater than 60 weight percent, such as greater than 70 weight percent, and preferably greater than 75 weight percent, h one embodiment, the amount of ethylene and/or propylene produced based on the total weight of hydrocarbon product produced is greater than 65 weight percent, such as greater than 70 weight percent, for example greater than 75 weight percent, and preferably greater than 78 weight percent. Typically, the amount of ethylene produced in weight percent based on the total weight of hydrocarbon product produced, is greater than 30 weight percent, such as greater than 35 weight percent, for example greater than 40 weight percent. In addition, the amount of propylene produced in weight percent based on the total weight of hydrocarbon product produced is greater than 20 weight percent, such as greater than 25 weight percent, for example greater than 30 weight percent, and preferably greater than 35 weight percent.

[0090] In addition to the oxygenate component, such as methanol, the feedstock may contains one or more diluent(s), which are generally non-reactive to the feedstock or molecular sieve catalyst composition and are typically used to reduce the concentration of the feedstock. Non-limiting examples of diluents include helium, argon, nifrogen, carbon monoxide, carbon dioxide, water, essentially non-reactive paraffins (especially alkanes such as methane, ethane, and propane), essentially non-reactive aromatic compounds, and mixtures thereof. The most prefened diluents are water and nifrogen, with water being particularly prefened.

[0091] The diluent, for example water, may be used either in a liquid or a vapor fonri, or a combination thereof. The diluent may be either added directly to the feedstock entering a reactor or added directly to the reactor, or added with the molecular sieve catalyst composition.

[0092] The present process can be conducted over a wide range of temperatures, such as in the range of from about 200°C to about 1000°C, for example from about 250°C to about 800°C, including from about 250°C to about 750 °C, conveniently from about 300°C to about 650°C, typically from about 350°C to about 600°C and particularly from about 350°C to about 550°C. [0093] Similarly, the present process can be conducted over a wide range of pressures including autogenous pressure. Typically the partial pressure of the feedstock exclusive of any diluent therein employed in the process is in the range of from about 0.1 kPaa to about 5 MPaa, such as from about 5 kPaa to about 1 MPaa , and conveniently from about 20 kPaa to about 500 kPaa. [0094] The weight hourly space velocity (WHSV), defined as the total weight of feedstock excluding any diluents per hour per weight of molecular sieve in the catalyst composition, typically ranges from about 1 hr^"1 to about 5000 hr^"1, such as from about 2 hr^"1 to about 3000 hr^"1, for example from about 5 hr^"1 to about 1500 hr^"1, and conveniently from about 10 hr^"1 to about 1000 hr^"1. In one embodiment, the WHSV is greater than 20 hr^"1 and, where feedstock contains methanol and/or dimethyl ether, is in the range of from about 20 hr^"1 to about 300 hr^"1.

[0095] Where the process is conducted in a fluidized bed, the superficial gas velocity (SGV) of the feedstock including diluent and reaction products within the reactor system, and particularly within a riser reactor(s), is at least 0.1 meter per second (m sec), such as greater than 0.5 m/sec, such as greater than 1 m sec, for example greater than 2 m/sec, conveniently greater than 3 m/sec, and typically greater than 4 m/sec. See for example U.S. Patent Application Serial No. 09/708,753 filed November 8, 2000, which is herein incoφorated by reference. [0096] The process of the invention is conveniently conducted as a fixed bed process, or more typically as a fluidized bed process (including a turbulent bed process), such as a continuous fluidized bed process, and particularly a continuous high velocity fluidized bed process.

[0097] The process can take place in a variety of catalytic reactors such as hybrid reactors that have a dense bed or fixed bed reaction zones and/or fast fluidized bed reaction zones coupled together, circulating fluidized bed reactors, riser reactors, and the like. Suitable conventional reactor types are described in for example U.S. Patent No. 4,076,796, U.S. Patent No. 6,287,522 (dual riser), and Fluidization Engineering, D. Kunii and O. Levenspiel, Robert E. Krieger Publishing Company, New York, New York 1977, which are all herein fully incoφorated by reference.

[0098] The prefened reactor types are riser reactors generally described in

Riser Reactor, Fluidization and Fluid-Particle Systems, pages 48 to 59, F.A. Zenz and D.F. Othmo, Reinhold Publishing Coφoration, New York, 1960, and U.S. Patent No. 6,166,282 (fast-fluidized bed reactor), and U.S. Patent Application Serial No. 09/564,613 filed May 4, 2000 (multiple riser reactor), which are all herein fully incoφorated by reference.

[0099] In one practical embodiment, the process is conducted as a fluidized bed process or high velocity fluidized bed process utilizing a reactor system, a regeneration system and a recovery system. [0100] In such a process the reactor system conveniently includes a fluid bed reactor system having a first reaction zone within one or more riser reactor(s) and a second reaction zone within at least one disengaging vessel, typically comprising one or more cyclones. In one embodiment, the one or more riser reactor(s) and disengaging vessel are contained within a single reactor vessel. Fresh feedstock, preferably containing one or more oxygenates, optionally with one or more diluent(s), is fed to the one or more riser reactor(s) into which a molecular sieve catalyst composition or coked version thereof is introduced. In one embodiment, prior to being introduced to the riser reactor(s), the molecular sieve catalyst composition or coked version thereof is contacted with a liquid, preferably water or methanol, and/or a gas, for example, an inert gas such as nifrogen.

[0101] In an embodiment, the amount of fresh feedstock fed as a liquid and/or a vapor to the reactor system is in the range of from 0.1 weight percent to about 85 weight percent, such as from about 1 weight percent to about 75 weight percent, more typically from about 5 weight percent to about 65 weight percent based on the total weight of the feedstock including any diluent contained therein. The liquid and vapor feedstocks may be the same composition, or may contain varying proportions of the same or different feedstocks with the same or different diluents.

[0102] The feedstock entering the reactor system is preferably converted, partially or fully, in the first reactor zone into a gaseous effluent that enters the disengaging vessel along with the coked catalyst composition. In the prefened embodiment, cyclone(s) are provided within the disengaging vessel to separate the coked catalyst composition from the gaseous effluent containing one or more olefin(s) within the disengaging vessel. Although cyclones are prefened, gravity effects within the disengaging vessel can also be used to separate the catalyst composition from the gaseous effluent. Other methods for separating the catalyst composition from the gaseous effluent include the use of plates, caps, elbows, and the like.

[0103] In one embodiment, the disengaging vessel includes a stripping zone, typically in a lower portion of the disengaging vessel. In the stripping zone the coked catalyst composition is contacted with a gas, preferably one or a combination of steam, methane, carbon dioxide, carbon monoxide, hydrogen, or an inert gas such as argon, preferably steam, to recover adsorbed hydrocarbons from the coked catalyst composition that is then introduced to the regeneration system.

[0104] The coked catalyst composition is withdrawn from the disengaging vessel and introduced to the regeneration system. The regeneration system comprises a regenerator where the coked catalyst composition is contacted with a regeneration medium, preferably a gas containing oxygen, under conventional regeneration conditions of temperature, pressure and residence time. [0105] Non-limiting examples of suitable regeneration media include one or more of oxygen, O₃, SO₃, N₂O, NO, NO₂, N₂O₅, air, air diluted with nitrogen or carbon dioxide, oxygen and water (U.S. Patent No. 6,245,703), carbon monoxide and/or hydrogen. Suitable regeneration conditions are those capable of burning coke from the coked catalyst composition, preferably to a level less than 0.5 weight percent based on the total weight of the coked molecular sieve catalyst composition entering the regeneration system. For example, the regeneration temperature may be in the range of from about 200°C to about 1500°C, such as from about 300°C to about 1000°C, for example from about 450°C to about 750°C, and conveniently from about 550°C to 700°C. The regeneration pressure may be in the range of from about 15 psia (103 kPaa) to about 500 psia (3448 kPaa), such as from about 20 psia (138 kPaa) to about 250 psia (1724 kPaa), including from about 25 psia (172kPaa) to about 150 psia (1034 kPaa), and conveniently from about 30 psia (207 kPaa) to about 60 psia (414 kPaa). [0106] The residence time of the catalyst composition in the regenerator may be in the range of from about one minute to several hours, such as from about one minute to 100 minutes, and the volume of oxygen in the regeneration gas may be in the range of from about 0.01 mole percent to about 5 mole percent based on the total volume of the gas.

[0107] The burning of coke in the regeneration step is an exothermic reaction, and in an embodiment, the temperature within the regeneration system is controlled by various techniques in the art including feeding a cooled gas to the regenerator vessel, operated either in a batch, continuous, or semi-continuous mode, or a combination thereof. A prefened technique involves withdrawing the regenerated catalyst composition from the regeneration system and passing it through a catalyst cooler to form a cooled regenerated catalyst composition. The catalyst cooler, in an embodiment, is a heat exchanger that is located either internal or external to the regeneration system. Other methods for operating a regeneration system are in disclosed U.S. Patent No. 6,290,916 (controlling moisture), which is herein fully incoφorated by reference. [0108] The regenerated catalyst composition withdrawn from the regeneration system, preferably from the catalyst cooler, is combined with a fresh molecular sieve catalyst composition and/or re-circulated molecular sieve catalyst composition and/or feedstock and/or fresh gas or liquids, and returned to the riser reactor(s). In one embodiment, the regenerated catalyst composition withdrawn from the regeneration system is returned to the riser reactor(s) directly, preferably after passing through a catalyst cooler. A carrier, such as an inert gas, feedstock vapor, steam or the like, may be used, semi-continuously or continuously, to facilitate the introduction of the regenerated catalyst composition to the reactor system, preferably to the one or more riser reactor(s).

[0109] By controlling the flow of the regenerated catalyst composition or cooled regenerated catalyst composition from the regeneration system to the reactor system, the optimum level of coke on the molecular sieve catalyst composition entering the reactor is maintained. There are many techniques for controlling the flow of a catalyst composition described in Michael Louge, Experimental Techniques, Circulating Fluidized Beds, Grace, Avidan and Knowlton, eds., Blackie, 1997 (336-337), which is herein incoφorated by reference.

[0110] Coke levels on the catalyst composition are measured by withdrawing the catalyst composition from the conversion process and determining its carbon content. Typical levels of coke on the molecular sieve catalyst composition, after regeneration, are in the range of from 0.01 weight percent to about 15 weight percent, such as from about 0.1 weight percent to about 10 weight percent, for example from about 0.2 weight percent to about 5 weight percent, and conveniently from about 0.3 weight percent to about 2 weight percent based on the weight of the molecular sieve.

[0111] The gaseous effluent is withdrawn from the disengaging system and is passed through a recovery system. There are many well known recovery systems, techniques and sequences that are useful in separating olefin(s) and purifying olefin(s) from the gaseous effluent. Recovery systems generally comprise one or more or a combination of various separation, fractionation and/or distillation towers, columns, splitters, or trains, reaction systems such as ethylbenzene manufacture (U.S. Patent No. 5,476,978) and other derivative processes such as aldehydes, ketones and ester manufacture (U.S. Patent No. 5,675,041), and other associated equipment, for example various condensers, heat exchangers, refrigeration systems or chill trains, compressors, knock-out drums or pots, pumps, and the like.

[0112] Non-limiting examples of these towers, columns, splitters or trains used alone or in combination include one or more of a demethanizer, preferably a high temperature demethanizer, a dethanizer, a depropanizer, a wash tower often refened to as a caustic wash tower and/or quench tower, absorbers, adsorbers, membranes, ethylene (C2) splitter, propylene (C3) splitter and butene (C4) splitter.

[0113] Various recovery systems useful for recovering olefin(s), such as ethylene, propylene and/or butene, are described in U.S. Patent No. 5,960,643 (secondary rich ethylene stream), U.S. Patent Nos. 5,019,143, 5,452,581 and 5,082,481 (membrane separations), U.S. Patent 5,672,197 (pressure dependent adsorbents), U.S. Patent No. 6,069,288 (hydrogen removal), U.S. Patent No. 5,904,880 (recovered methanol to hydrogen and carbon dioxide in one step), U.S. Patent No. 5,927,063 (recovered methanol to gas turbine power plant), and U.S. Patent No. 6,121,504 (direct product quench), U.S. Patent No. 6,121,503 (high purity olefins without superfractionation), and U.S. Patent No. 6,293,998 (pressure swing adsoφtion), which are all herein fully incoφorated by reference. [0114] Other recovery systems that include purification systems, for example for the purification of olefin(s), are described in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 9, John Wiley & Sons, 1996, pages 249-271 and 894-899, which is herein incoφorated by reference. Purification systems are also described in for example, U.S. Patent No. 6,271,428 (purification of a diolefin hydrocarbon sfream), U.S. Patent No. 6,293,999 (separating propylene from propane), and U.S. Patent Application No. 09/689,363 filed October 20, 2000 (purge stream using hydrating catalyst), which are herein incoφorated by reference.

[0115] Generally accompanying most recovery systems is the production, generation or accumulation of additional products, by-products and/or contaminants along with the prefened prime products. The prefened prime products, the light olefins, such as ethylene and propylene, are typically purified for use in derivative manufacturing processes such as polymerization processes. Therefore, in the most prefened embodiment of the recovery system, the recovery system also includes a purification system. For example, the light olefm(s) produced particularly in a MTO process are passed through a purification system that removes low levels of by-products or contaminants. [0116] Non-limiting examples of contaminants and by-products include generally polar compounds such as water, alcohols, carboxylic acids, ethers, carbon oxides, sulfur compounds such as hydrogen sulfide, carbonyl sulfides and mercaptans, ammonia and other nitrogen compounds, arsine, phosphine and chlorides. Other contaminants or by-products include hydrogen and hydrocarbons such as acetylene, methyl acetylene, propadiene, butadiene and butyne. [0117] Typically, in converting one or more oxygenates to olefin(s) having

2 or 3 carbon atoms, a minor amount hydrocarbons, particularly olefm(s), having 4 or more carbon atoms is also produced. The amount of C₄+ hydrocarbons is normally less than 20 weight percent, such as less than 10 weight percent, for example less than 5 weight percent, and particularly less than 2 weight percent, based on the total weight of the effluent gas withdrawn from the process, excluding water. Typically, therefore the recovery system may include one or more reaction systems for converting the C₄+ impurities to useful products. [0118] Non-limiting examples of such reaction systems are described in

U.S. Patent No. 5,955,640 (converting a four carbon product into butene-1), U.S. Patent No. 4,774,375 (isobutane and butene-2 oligomerized to an alkylate gasoline), U.S. Patent No. 6,049,017 (dimerization of n-butylene), U.S. Patent Nos. 4,287,369 and 5,763,678 (carbonylation or hydroformulation of higher olefins with carbon dioxide and hydrogen making carbonyl compounds), U.S. Patent No. 4,542,252 (multistage adiabatic process), U.S. Patent No. 5,634,354 (olefin-hydrogen recovery), and Cosyns, J. et al., Process for Upgrading C3, C4 and C5 Olefinic Streams, Pet. & Coal, Vol. 37, No. 4 (1995) (dimerizing or oligomerizing propylene, butylene and pentylene), which are all fully herein incoφorated by reference.

[0119] The prefened light olefin(s) produced by any one of the processes described above are high purity prime olefin(s) products that contain a single carbon number olefin in an amount greater than 80 percent, such as greater than 90 weight percent, such as greater than 95 weight percent, for example at least about 99 weight percent, based on the total weight of the olefin. [0120] In one practical embodiment, the process of the invention forms part of an integrated process for producing light olefin(s) from a hydrocarbon feedstock, preferably a gaseous hydrocarbon feedstock, particularly methane and/or ethane. The first step in the process is passing the gaseous feedstock, preferably in combination with a water sfream, to a syngas production zone to produce a synthesis gas (syngas) sfream, typically comprising carbon dioxide, carbon monoxide and hydrogen. Syngas production is well known, and typical syngas temperatures are in the range of from about 700°C to about 1200°C and syngas pressures are in the range of from about 2 MPa to about 100 MPa. Synthesis gas streams are produced from natural gas, petroleum liquids, and carbonaceous materials such as coal, recycled plastic, municipal waste or any other organic material. Preferably synthesis gas stream is produced via steam reforming of natural gas.

[0121] The next step in the process involves contacting the synthesis gas sfream generally with a heterogeneous catalyst, typically a copper based catalyst, to produce an oxygenate containing sfream, often in combination with water. In one embodiment, the contacting step is conducted at temperature in the range of from about 150°C to about 450°C and a pressure in the range of from about 5 MPa to about 10 MPa. [0122] This oxygenate containing sfream, or crude methanol, typically contains the alcohol product and various other components such as ethers, particularly dimethyl ether, ketones, aldehydes, dissolved gases such as hydrogen methane, carbon oxide and nifrogen, and fuel oil. The oxygenate containing stream, crude methanol, in the prefened embodiment is passed through a well known purification processes, distillation, separation and fractionation, resulting in a purified oxygenate containing stream, for example, commercial Grade A and AA methanol.

[0123] The oxygenate containing sfream or purified oxygenate containing stream, optionally with one or more diluents, can then be used as a feedstock in a process to produce light olefin(s), such as ethylene and/or propylene. Non- limiting examples of this integrated process are described in EP-B-0 933 345, which is herein fully incoφorated by reference.

[0124] In another more fully integrated process, that optionally is combined with the integrated processes described above, the olefin(s) produced are directed to, in one embodiment, one or more polymerization processes for producing various polyolefins. (See for example U.S. Patent Application Serial No. 09/615,376 filed July 13, 2000, which is herein fully incoφorated by reference.)

[0125] Polymerization processes include solution, gas phase, slurry phase and a high pressure processes, or a combination thereof. Particularly prefened is a gas phase or a sluny phase polymerization of one or more olefin(s) at least one of which is ethylene or propylene. These polymerization processes utilize a polymerization catalyst that can include any one or a combination of the molecular sieve catalysts discussed above. However, the prefened polymerization catalysts are the Ziegler-Natta, Phillips-type, metallocene, metallocene-type and advanced polymerization catalysts, and mixtures thereof. [0126] In a prefened embodiment, the integrated process comprises a process for polymerizing one or more olefin(s) in the presence of a polymerization catalyst system in a polymerization reactor to produce one or more polymer products, wherein the one or more olefin(s) have been made by converting an alcohol, particularly methanol, using a molecular sieve catalyst composition as described above. The prefened polymerization process is a gas phase polymerization process and at least one of the olefins(s) is either ethylene or propylene, and preferably the polymerization catalyst system is a supported metallocene catalyst system. In this embodiment, the supported metallocene catalyst system comprises a support, a metallocene or metallocene-type compound and an activator, preferably the activator is a non-coordinating anion or alumoxane, or combination thereof, and most preferably the activator is alumoxane.

[0127] The polymers produced by the polymerization processes described above include linear low density polyethylene, elastomers, plastomers, high density polyethylene, low density polyethylene, polypropylene and polypropylene copolymers. The propylene based polymers produced by the polymerization processes include atactic polypropylene, isotactic polypropylene, syndiotactic polypropylene, and propylene random, block or impact copolymers. VI. Examples of Manufacturing and Spray Drying Methods

A. Example 1

[0128] A slurry having a total solids content of 40 wt % SAPO molecular sieve, 10.6 wt % alumina (added as aluminum chlorohydrate) and the balance kaolin clay was prepared by first producing a slurry of SAPO sieve and water, followed by addition of a solution of aluminum cholorhydrate and water and followed finally by the addition of kaolin clay. The sluny was aged for 15 hours at 40°C, and then used as the feed to a spray dryer equipped with a wheel type atomizer. The sluny was dried at a wheel speed of 9,000 rpm, an outlet temperature of 305°F (152°C), and an inlet temperature of 550°F (288°C). The dried catalyst removed from the spray dryer and calcined at an average temperature of approximately 650°C, for a nominal residence time of 30 minutes, to an ARI of 0.4. The results are shown in Table 1.

B. Example 2

[0129] The procedure of Example 1 was repeated, except that the sluny was dried in the spray dryer at a spray dryer inlet temperature of 800°F (427°C) and an outlet temperature of 305°F (152°C). The dried catalyst removed from the spray dryer was calcined, as described in Example 1, to an ARI of 0.63. The results are shown in Table 1. C. Example 3 [0130] As a comparative example, the procedure of Example 1 was repeated, except that the slurry was dried in the spray dryer at a spray dryer intlet temperature of 940°F (504°C) and an outlet temperature of 305°F (152°C). The dried catalyst removed from the spray dryer was calcined, as described in Example 1, to an ARI of 1.02. The results are shown in Table 1.

Table 1

[0131] Having now fully described this invention, it will be appreciated by those skilled in the art that the invention can be performed within a wide range of parameters, without departing from the spirit and scope of the invention.

Claims

CLAIMS:We Claim:

1. A process of making a molecular sieve catalyst composition, comprising the steps of: a) drying a slurry containing molecular sieve and binder in a spray dryer at a drying rate of not greater than 0.275 kg/hr liq. per kg/hr gas; and b) removing spray dried molecular sieve catalyst from the spray dryer.

2. The process of claim 1 , wherein the slurry in the spray dryer is dried at a drying rate of not greater than 0.25 kg/hr liq. per kg/hr gas, preferably at a drying rate of not greater than 0.2 kg/hr liq. per kg/hr gas.

3. The process of any preceding claim, wherein the process further comprises a step of calcining the spray dried molecular sieve catalyst removed from the spray dryer to an ARI of not greater than 1 %/hr, preferably to an ARI of not greater than 0.8 %/hr, more preferably to an ARI of not greater than 0.7 %/hr, most preferable to an ARI of not greater than 0.5 %/hr.

4. The process of any preceding claim, wherein the sluny is dried in the spray dryer at a spray dryer inlet and outlet temperature differential of not greater than 350°C, preferably at a spray dryer inlet and outlet temperature differential of not greater than 250°C, more preferably at a spray dryer inlet and outlet temperature differential of not greater than 200°C, most preferably at a spray dryer inlet and outlet temperature differential of not greater than 150°C. The process of any preceding claim, wherein the slurry is injected into the spray dryer at a spray dryer inlet temperature of not greater than 500°C, preferably at a spray dryer inlet temperature of not greater than 450°C, more preferably at a spray dryer inlet temperature of not greater than 400°C, most preferably at a spray dryer inlet temperature of not greater than 300°C.

The process of any preceding claim, wherein the spray dried catalyst is removed from the spray dryer at a spray dryer outlet temperature of not greater than 300°C, preferably at a spray dryer outlet temperature of not greater than 250°C, more preferably at a spray dryer outlet temperature of not greater than 200°C, most preferably at a spray dryer outlet temperature of not greater than 150°C.

The process of any preceding claim, wherein the molecular sieve is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO- 17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO- 37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, ALPO- 5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37, ALPO- 46, metal containing molecular sieves thereof, and mixtures thereof.