Molecular sieve catalyst composition, its making and use in conversion processes

专利摘要:
The present invention relates to a molecular sieve catalyst composition, a method for preparing or forming the molecular sieve catalyst composition, and a conversion method using the catalyst composition. In particular, the present invention relates to the preparation of molecular sieve catalyst compositions by combining molecular sieves, binders and matrix materials to form a slurry having a pH above or below the isoelectric point of the molecular sieve. The catalyst composition has improved abrasion resistance and is useful in the conversion process for producing olefins, preferably ethylene and / or propylene from a feedstock, preferably an oxygenate containing feedstock.
公开号:KR20040012973A
申请号:KR10-2003-7016896
申请日:2002-06-24
公开日:2004-02-11
发明作者:창윤-펑；보근스티븐엔；마르텡뤽알.엠.；솔드스튜어트엘；클렘케네스알；봄-가트너조셉이
申请人:엑손모빌 케미칼 패턴츠 인코포레이티드；
IPC主号:

专利说明:

Molecular sieve catalyst composition, preparation method thereof and use in conversion process {MOLECULAR SIEVE CATALYST COMPOSITION, ITS MAKING AND USE IN CONVERSION PROCESSES}
[2] Olefins are traditionally produced from petroleum feedstocks by catalyst or steam cracking processes. The cracking process, in particular steam cracking, produces light olefins such as ethylene and / or propylene from various hydrocarbon feedstocks. Ethylene and propylene are Chuo petrochemicals useful in a variety of processes for making plastics and other chemical compounds.
[3] In the petrochemical industry, it is known that oxygenates, in particular alcohols, can be converted to light olefins. There are a number of techniques available for the production of oxygenates, including fermentation or reaction of synthetic gases derived from natural gas, petroleum liquids, carbonaceous materials including coal, recycled plastics, municipal waste or any other organic material. In general, the production of syngas involves the combustion reaction of natural gas, which is mostly methane, and an oxygen source to produce hydrogen, carbon monoxide and / or carbon dioxide. Syngas production processes are well known and include conventional steam reforming, autothermal reforming, or combinations thereof.
[4] Methanol, which is a preferred alcohol for the production of light olefins, is typically synthesized from the catalytic reaction of hydrogen, carbon monoxide and / or carbon dioxide in the presence of a heterogeneous catalyst in a methanol reactor. For example, in one synthesis process methanol is produced using a copper / zinc oxide catalyst in a water cooled turbulent methanol reactor. Preferred methanol conversion processes are generally referred to as methanol-to-olefin (s) processes, in which methanol is mainly converted to ethylene and / or propylene in the presence of molecular sieves.
[5] Molecular sieves are porous solids with pores of various sizes, such as zeolite or zeolitic molecular sieves, carbon and oxides. The most commercially available molecular sieves for the petroleum and petrochemical industries are known as zeolites and are, for example, aluminosilicate molecular sieves. Zeolites generally have one-, two- or three-dimensional crystalline porous structures with uniformly sized pores of molecular dimensions that selectively adsorb molecules that can enter the pores and exclude molecules that are too large.
[6] There are many different types of molecular sieves that are well known for converting feedstocks, particularly oxygenated feedstocks, to one or more olefins. For example, US Pat. No. 5,367,100 describes the conversion of methanol to olefins using the well-known zeolite ZSM-5; US Pat. No. 4,062,905 discusses the conversion of methanol and other oxygenates to ethylene and propylene using crystalline aluminosilicate zeolites such as zeolite T, ZK5, erionite and chabazite; US Patent No. 4,079,095 describes the conversion of methanol to hydrocarbon products such as ethylene and propylene using ZSM-34; US Pat. No. 4,310,440 describes the preparation of light olefins from alcohols using crystalline aluminophosphates, often designated ALPO ₄ .
[7] One of the most useful molecular sieves for converting methanol to olefins is silicoaluminophosphate molecular sieves. Silicoaluminophosphate (SAPO) molecular sieves contain three-dimensional microporous crystalline skeletal structures of [SiO ₂ ], [AlO ₂ ] and [PO ₂ ] edge covalent tetrahedral units. SAPO synthesis is described in US Pat. No. 4,440,871, which is incorporated herein by reference in its entirety. SAPOs are generally synthesized by hydrothermal crystallization of a reaction mixture of a silicon-, aluminum- and phosphorus-source with at least one template. Synthesis of SAPO molecular sieves, blending thereof into SAPO catalysts, and their use to convert hydrocarbon feedstocks to olefins, especially when the feedstock is methanol, are described in U.S. Pat.Nos. 4,499,327, 4,677,242, which are incorporated herein by reference in their entirety. 4,677,243, 4,873,390, 5,095,163, 5,174,662 and 6,166,282.
[8] Typically, molecular sieves are formed from molecular sieve catalyst compositions to improve durability in commercial conversion processes. The collision with the catalyst composition particles themselves, the reactor walls, and other reactor systems in a commercial process causes the particles to break down into small particles called fines. Physical destruction of the molecular sieve catalyst composition particles is known as attrition. The fines often leave the reactor in the effluent stream and cause problems in the regeneration system. Catalyst compositions with higher resistance to abrasion produce less fines, requiring less catalyst composition for conversion and reducing operating costs due to longer lifetimes.
[9] Molecular sieve catalyst compositions are formed by combining molecular sieve and matrix material, usually in the presence of a binder. The purpose of the binder is to fix the matrix material, often clay, to the molecular sieve. The use of binders and matrix materials in the formation of molecular sieve catalyst compositions is well known for a variety of commercial processes. It is also known that the manner in which the molecular sieve catalyst composition is prepared or blended affects the catalyst composition wear.
[10] Examples of methods for preparing the catalyst composition include: US Pat. No. 5,126,298 combines two different clay particles in separate slurries with a zeolite slurry and a phosphorus source, and incorporates a mixture of slurries having a pH of less than 3 Discussing a process for producing a cracking catalyst having high abrasion resistance by spray drying; US Pat. Nos. 4,987,110 and 5,298,153 relate to catalyst cracking processes using spray dried abrasion resistant catalysts containing more than 25% by weight molecular sieve dispersed in a clay matrix with a synthetic silica-alumina component; US Pat. Nos. 5,194,412 and 5,286,369 disclose the formation of catalytic catalytic cracking catalysts of molecular sieves and crystalline aluminum phosphate binders having a surface area of less than 20 m ² / g and a total pore volume of less than 0.1 cc / g; US Pat. No. 4,542,118 relates to the formation of particulate inorganic oxide composites of aluminum chlorhydrol and zeolites which react with ammonia to form cohesive binders; U. S. Patent No. 6,153, 552 claims a method for preparing a catalyst by drying a slurry of SAPO molecular sieve, inorganic oxide sol, and external phosphorus source; US Patent No. 5,110,776 illustrates the formation of zeolites containing catalytic catalysts by modifying the zeolites with a phosphate containing solution; US Patent No. 5,348,643 relates to spray drying a zeolite slurry having a clay and phosphorus source at a pH of less than 3; US patent application Ser. No. 09 / 891,674, filed June 25, 2001, discusses how to remove halogens by steaming molecular sieves; US 5,248,647 illustrates spray drying of SAPO-34 molecular sieves admixed with kaolin and silica sol; U. S. Patent No. 5,346, 875 discloses a process for the preparation of catalytic cracking catalysts by matching the isoelectric point of each component of the framework structure to the pH of the inorganic oxide sol; Meier, et al, Aggregation and Peptization Behavior of Zeolite Crystals in Sols and Suspensions , Ind. Eng. Chem. Vol. 40, pages 2573-2579, 2001 discuss zeolite aggregation at or near isoelectric points; PCT Publication WO 99/21651 describes the preparation of a catalyst by drying a mixture of alumina sol and SAPO molecular sieves; PCT Publication WO 02/05950 describes the preparation of catalyst compositions of molecular sieves containing abrasive particles with fresh molecular sieves; WO 02/05952 discloses crystalline metal-aluminophosphate molecular sieves, and matrix materials of inorganic oxide binders and fillers, wherein the molecular sieves are present in an amount of less than 40% by weight based on the weight of the catalyst and are binder to molecular sieves. The weight ratio of is close to one.
[11] While the molecular sieve catalyst composition is useful for hydrocarbon conversion processes, it would be desirable to have an improved molecular sieve catalyst composition with better abrasion resistance and commercially desirable operability and cost advantages.
[12] Summary of the Invention
[13] The present invention provides a process for preparing or blending molecular sieve catalyst compositions and their use in the conversion process for converting the feedstock into at least one olefin.
[14] In one embodiment, the present invention is directed to a process for preparing a molecular sieve catalyst composition by combining, contacting, mixing, etc., molecular sieves, binders, and matrix materials in a slurry, wherein the slurries are independently or in combination And pH above or below the isoelectric point (IEP) of the binder and / or matrix material. In a preferred embodiment, the slurry has a pH about 0.3 higher or lower than the IEP of the molecular sieve. In a preferred embodiment, the molecular sieve is synthesized from two or more combinations of a crowd consisting of a silicon source, a phosphorus source and an aluminum source, optionally in the presence of a template, and more preferably the molecular sieve is silicoaluminophosphate or aluminophosphate. And most preferably silicoaluminophosphate.
[15] In one embodiment, the present invention is directed to a method of blending molecular sieve catalyst compositions, the method comprising: (a) introducing a molecular sieve to form a slurry; (b) introducing a binder into the slurry; (c) introducing the matrix material into the slurry; And (d) spray drying the slurry to produce a formulated molecular sieve catalyst composition, wherein the pH of the slurry is higher or lower than the IEP of the molecular sieve. In other embodiments, the pH of the slurry is at least 0.3 away above or below the isoelectric point of the molecular sieve. In other embodiments, the molecular sieve catalyst composition has a wear rate index (ARI) of less than 2% by weight per hour, preferably less than 1% by weight per hour, most preferably less than 0.5% by weight per hour. Preferably the molecular sieve is silicoaluminophosphate, aluminophosphate and / or carbazite structured molecular sieve.
[16] In another embodiment, the present invention relates to a process for preparing olefins in the presence of any of the above molecular sieve catalyst compositions. In particular, the process comprises a feedstock, preferably a feedstock containing an oxygenate, more preferably a feedstock containing an alcohol, and most preferably a feedstock containing methanol, of the at least one molecular sieve catalyst composition. Preparing olefins in a process for conversion in the presence.
[1] The present invention relates to a molecular sieve catalyst composition, a method for preparing or forming the molecular sieve catalyst composition, and a conversion process using the catalyst composition.
[17] Introduction
[18] The present invention relates to molecular sieve catalyst compositions, methods for their preparation and their use in converting hydrocarbon feedstocks into one or more olefins. Molecular sieve catalyst compositions are prepared or formed from a combination of molecular sieves, binders, and, optionally, most preferably, matrix materials. It is generally known in the art that for solid / liquid dispersions particle agglomeration is prevented by overcoming the van der Waals attraction potential between the solid or particle surface. Stabilization of the dispersion by electrostatic repulsion is described in EJW Verwey, et al., Theory of the Stabilization of Lyophobic Colloids , Elsevier, Amsterdam, 1948. The oxide surface is either negatively or positively charged depending on the pH of the oxide in the aqueous medium (Th. F. Tadros, Solid / Liquid Dispersions, Academic Press, London, page 5, 1987, which is incorporated herein by reference in its entirety). ] Reference). The isoelectric point (IEP) is the state in which the surface of the particles in the medium is uncharged, which corresponds to the pH value for a particular material, for example, a molecular sieve catalyst composition in water (for the whole here) See, J. Lyklema, Structure of the Solid / Liquid Interface and Electrical Double Layer, in Solid / Liquid Dispersions (Edited by Th.F. Tadors) , Academic Press, London, pages 63-90, 1987. ). Surprisingly, it has been found that by preparing the molecular sieve catalyst composition below or above the IEP of the molecular sieve, a catalyst composition with improved abrasion resistance is formed. The pH at the IEP of a given surface is also an important consideration in selecting the binder, the weight ratio of binder to molecular sieve, and the total solid particle content in the solid / liquid dispersion. Thus, in addition to IEP, it has been found that the weight ratio of binder to molecular sieve is also important for preparing abrasion resistant catalyst compositions.
[19] Molecular sieves and their catalysts
[20] Molecular sieves have a variety of chemical and physical backbones, features. Molecular sieves have been well categorized by the Structural Committee of the International Zeolite Association in accordance with the IUPAC Committee's rules for zeolite nomenclature. The skeletal form describes the abstraction of the connectivity of the tetrahedral coordinating atoms, the topological substructure, and the specific properties of these materials that make up the backbone. Skeletal zeolites and zeolitic molecular sieves with established structures are designated by a three-letter code and described in Atlas of Zeolite Framework Types , 5th edition, Elsevier, London, England (2001), which is hereby incorporated by reference in its entirety. It is.
[21] Non-limiting examples of such molecular sieves include 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, THO, and substituted forms thereof; Mesoporous molecular sieves AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON, and substituted forms thereof; And large pore molecular sieves, EMT, FAU, and substituted forms thereof. Other molecular sieves include ANA, BEA, CFI, CLO, DON, GIS, LTL, MER, MOR, MWW and SOD. Non-limiting examples of preferred molecular sieves, particularly for converting oxygenate containing feedstocks to olefins, include AEL, AFY, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW , TAM and TON. In a preferred embodiment, the molecular sieves of the invention have an AEI topology or a CHA topology, or a combination thereof, most preferably a CHA topology.
[22] Molecular Sieve Molecules all have an edge covalent TO ₄ (T is a tetrahedral coordinated cation) tetrahedral three-dimensional skeletal structure. The molecular sieve is typically described by the size of the ring defining pores, where the size is based on the number of T atoms in the ring. Other skeletal features include the arrangement of the rings that form the cage, and the dimensions of the channel, if present, and the space between the cages. See van Bekkum, et al., Introduction to Zeolite Science and Practice, Second Completely Revised and Expanded Edition , Volume 137, pages 1-67, Elsevier Science, BV, Amsterdam, Netherlands (2001).
[23] Small, medium and large pore molecular sieves have a 4-ring to 12-ring or larger skeletal form. In a preferred embodiment, the zeolitic molecular sieve has an 8-, 10- or 12-ring structure or more structure and an average pore size in the range of about 3 mm 3 to 15 mm 3. In the most preferred embodiment, the molecular sieves of the invention, preferably silicoaluminophosphate molecular sieves, are 8-rings and less than about 5 mm 3, preferably from 3 mm to about 5 mm 3, more preferably from 3 mm to about 4.5 mm 3, most preferably Has an average pore size of 3.5 kPa to about 4.2 kPa.
[24] Molecular sieves, in particular zeolitic and zeolitic molecular sieves, are preferably at least two corner-covalent [TO ₄ ] tetrahedral units, more preferably at least two [SiO ₄ ], [AlO ₄ ] and / or [PO ₄ ] tetrahedral units, most preferably [SiO ₄ ], [AlO ₄ ] and [PO ₄ ] tetrahedral units. These silicon, aluminum, and phosphorus based molecular sieves and metal containing silicon, aluminum and phosphorus based molecular sieves are described, for example, in US Pat. No. 4,567,029 (MeAPO where Me is Mg, Mn, Zn, or Co), US 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), United States Patent Nos. 4,554,143 (FeAPO), US Pat. Nos. 4,822,478, 4,683,217, 4,744,885 (FeAPSO), EP-A-0 158 975 and US 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), US Pat. No. 4,310,440 (AlPO ₄ ), EP-A-0 158 350 (SENAPSO), U.S. Patent 4,973,460 (LiAPSO), U.S. Patent 4,789,535 (LiAPO), U.S. Patent 4,992,250 (GeAPSO), U.S. Patent 4,888,167 (GeAPO), U.S. Patent 5,057,295 (BAPSO), U.S.A. Patent 4,738,837 (CrAPSO), US Patent 4,759,919, and 4, 851,106 (CrAPO), US Pat. Nos. 4,758,419, 4,882,038, 5,434,326 and 5,478,787 (MgAPSO), US Pat. No. 4,554,143 (FeAPO), US Pat. No. 4,894,213 (AsAPSO), US Pat. No. 4,913,888 (AsAPO), US Pat. Nos. 4,686,092, 4,846,956 and 4,793,833 (MnAPSO), US Pat. Nos. 5,345,011 and 6,156,931 (MnAPO), US Pat. No. 4,737,353 (BeAPSO), US Pat. No. 4,940,570 (BeAPO) ), US Pat. Nos. 4,801,309, 4,684,617 and 4,880,520 (TiAPSO), US Pat. Nos. 4,500,651, 4,551,236 and 4,605,492 (TiAPO), US Pat. Nos. 4,824,554, 4,744,970 (CoAPSO), US Patent 4,735,806 (GaAPSO) EP-A-0 293 937 (QAPSO, where Q is a framework oxide unit [QO ₂ ]), and US 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, No. 5,241,093, No. 5,493,066 and No. 5.67505 million have been described in detail in numerous publications including the call, all of which are hereby incorporated herein by reference in full. Other molecular sieves are described in R. R. Szostak , Handbook of Molecular Sieves , Van Nostrand Reinhold, New York, New York (1992).
[25] More preferred silicon, aluminum and / or phosphorus containing molecular sieves, and aluminum, phosphorus, and optionally silicon containing molecular sieves are aluminophosphate (ALPO) molecular sieves and silicoaluminophosphate (SAPO) molecular sieves, and substituted And, preferably, metal substituted ALPO and SAPO molecular sieves. Most preferred molecular sieves are SAPO molecular sieves, and metal substituted SAPO molecular sieves. In one embodiment, the metal is an alkali metal of Group IA of the Periodic Table of Elements, an alkaline earth metal of Group IIA of the Periodic Table of Elements, lanthanides: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, Rare earth metals of group IIIB including ytterbium and lutetium; And scandium or yttrium of the Periodic Table of Elements, transition metals of Groups IVB, VB, VIB, VIIB, VIIIB, and IB of the Periodic Table of the Elements, or any mixture of these metal species. In one preferred embodiment, the metal is selected from the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr, and mixtures thereof. In other embodiments, the metal atoms discussed above are inserted into the backbone of the molecular sieve through tetrahedral units, such as [MeO ₂ ], and carry a net charge depending on the valence state of the metal substituents. For example, in one embodiment, when the metal substituent has a valence state of +2, +3, +4, +5 or +6, the net charge of the tetrahedral unit is -2 to +2.
[26] In one embodiment, molecular sieves as described in many of the above U.S. patents are represented by the following empirical formula on anhydrous basis:
[27] mR: (M _x Al _y P _z ) O ₂
[28] Wherein R represents at least one template, preferably an organic template; m represents the number of moles of R per 1 mole of (M _x Al _y P _z ) O ₂ and has a value of 0 to 1, preferably 0 to 0.5, most preferably 0 to 0.3; x, y and z represent the mole fractions of Al, P and M as tetrahedral oxides, where M is selected from one of IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIB groups and lanthanides of the Periodic Table of the Elements Metal, preferably M is selected from the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr. In one embodiment, m is at least 0.2 and x, y and z are at least 0.01. In other embodiments, m is 0.1 to 1, x is 0 to about 0.25, y is 0.4 to 0.5, z is 0.25 to 0.5, more preferably m is 0.15 to 0.7, x is 0.01 to 0.2, y is 0.4-0.5, z is 0.3-0.5.
[29] Non-limiting examples of SAPO and ALPO molecular sieves of the present invention are 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 (US Pat. No. 6,162,415), SAPO-47, SAPO-56, ALPO-5, ALPO-11, One or a combination of ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37, ALPO-46, and metal containing molecular sieves thereof. More preferred molecular sieves are one or a combination of SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, even more preferably SAPO-18, SAPO-34, One or a combination of ALPO-34 and ALPO-18, and metal-containing molecular sieves thereof, most preferably SAPO-34 and ALPO-18, and one or a combination of metal-containing molecular sieves thereof.
[30] In one embodiment, the molecular sieve is an intergrowth material having two or more separate phases of crystalline structure in one molecular sieve composition. In particular, intergrowth molecular sieves are described in US patent application Ser. No. 09 / 924,016, filed Aug. 7, 2001 and PCT WO 98/15496, published Apr. 16, 1998, both of which are incorporated herein by reference. Is cited in its entirety. For example, SAPO-18, ALPO-18 and RUW-18 have an AEI framework, and SAPO-34 have a CHA framework. In other embodiments, the molecular sieve comprises an intergrown phase of one or more of AEI and CHA frameworks.
[31] Molecular Sieve Synthesis
[32] The synthesis of molecular sieves is described in many of the references discussed above. In general, molecular sieves are synthesized by hydrothermal crystallization of one or more aluminum sources, phosphorus sources, silicon sources, template agents, and metal containing compounds. Typically, the combination of a source of silicon, aluminum and phosphorus, optionally with one or more template and / or one or more metal containing compounds, is a sealed pressure vessel optionally lined with an inert plastic such as polytetrafluoroethylene. It is disposed at and heated to the formation of crystalline material at the crystallization pressure and temperature and then recovered by filtration, centrifugation and / or decantation.
[33] In a preferred embodiment, the molecular sieve is synthesized by forming a reaction product of a silicon source, an aluminum source, a phosphorus source, an organic template, preferably a nitrogen containing organic template. In this particularly preferred embodiment silicoaluminophosphate is synthesized which is then isolated by filtration, centrifugation and / or decantation.
[34] Non-limiting examples of silicon sources include silicates, fumed silicas, such as Aerosil-200, tetraalkyl orthosilicates, such as those available from Degussa Inc., New York, NY. Silicon compounds such as tetramethyl orthosilicate (TMOS) and tetraethylorthosilicate (TEOS), colloidal silica or an aqueous suspension thereof, for example E.I., Wilmington, Delaware. Ludox-HS-40 sol, silicic acid, alkali-metal silicate, or any combination thereof, available from E.I. du Pont de Nemours. The preferred source of silicon is silica sol.
[35] Non-limiting examples of aluminum sources include aluminum-containing compositions such as aluminum alkoxides such as aluminum isopropoxide, aluminum phosphate, aluminum hydroxide, sodium aluminate, pseudo-boehmite, gib Sites and aluminum trichloride, or any combination thereof. A preferred source of aluminum is pseudo-boehmite, particularly when producing silicoaluminophosphate molecular sieves.
[36] Non-limiting examples of phosphorus sources that may also include aluminum-containing phosphorus compositions include phosphorus-containing, inorganic or organic compositions such as phosphoric acid, organic phosphates such as triethyl phosphate, and crystalline or amorphous aluminophosphates such as ALPO ₄ , Phosphorus salts, or combinations thereof. A preferred source of phosphorus is phosphoric acid, especially when producing silicoaluminophosphates.
[37] The template is generally a compound containing elements of group VA of the Periodic Table of the Elements, in particular nitrogen, phosphorus, arsenic and antimony, more preferably nitrogen or phosphorus, most preferably nitrogen. Typical template agents of group VA of the Periodic Table of the Elements also contain one or more alkyl or aryl groups, preferably alkyl or aryl groups having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Preferred template are nitrogen-containing compounds such as amines and quaternary ammonium compounds.
[38] Quaternary ammonium compounds are, in one embodiment, represented by the formula R ₄ N ⁺ , where each R is hydrogen or a hydrocarbyl or substituted hydrocarbyl group, preferably an alkyl or aryl group having 1 to 10 carbon atoms . In one embodiment, the template comprises a combination of at least one quaternary ammonium compound and at least one mono-, di- or tri-amine.
[39] Non-limiting examples of template agents include tetraalkyl ammonium compounds comprising salts thereof, such as tetramethyl ammonium compounds comprising salts thereof, tetraethyl ammonium compounds comprising salts thereof, tetrapropyl ammonium including salts thereof, and salts thereof Tetrabutylammonium, cyclohexylamine, morpholine, di-n-propylamine (DPA), tripropylamine, triethylamine (TEA), triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine , N, N-dimethylbenzylamine, N, N-diethylethanolamine, dicyclohexylamine, N, N-dimethylethanolamine, choline, N, N'-dimethylpiperazine, 1,4-diazabicyclo ( 2,2,2) octane, N ', N', N, N-tetramethyl (1,6) hexanediamine, N-methyldiethanolamine, N-methyl-ethanolamine, N-methylpiperidine, 3 -Methyl-piperidine, N-methylcyclohexylamine, 3-methylpyridine, 4-methyl-pyridine, quinuclidin, N, N'-dimethyl-1,4-di Azabicyclo (2,2,2) octane ions; Di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, pyrrolidine, and 2-imidazolidone.
[40] Preferred templates or templates are tetraethylammonium compounds such as tetraethyl ammonium hydroxide (TEAOH), tetraethyl ammonium phosphate, tetraethyl ammonium fluoride, tetraethyl ammonium bromide, tetraethyl ammonium chloride and tetraethyl ammonium acetate. The most preferred template is tetraethyl ammonium hydroxide and its salts, especially when producing silicoaluminophosphate molecular sieves. In one embodiment, a combination of two or more of these template agents is used with one or more silicon-, aluminum- and phosphorus-sources.
[41] At a minimum, the synthetic mixture containing silicon-, aluminum- and / or phosphorus compositions, and template agents should have a pH of 2 to 10, preferably 4 to 9 and most preferably 5 to 8. Generally, the synthesis mixture is sealed in a vessel and is heated to a temperature of about 80 ° C to about 250 ° C, more preferably about 150 ° C to about 180 ° C, preferably under autogenous pressure. The time required to form the crystalline product typically ranges from immediate to several weeks, the duration of which generally depends on the temperature. The higher the temperature, the shorter the duration. Typically, the crystalline molecular sieve product is usually formed in a slurry and recovered by standard techniques well known in the art, such as centrifugation or filtration. In one embodiment the isolated or separated crystalline product is typically washed one to several times using a liquid such as water. The washed crystalline product is then optionally dried in air, preferably.
[42] In one preferred embodiment, when the template is used for the synthesis of the molecular sieve, the template is substantially, preferably completely removed after crystallization by a number of known techniques, for example by heat treatment such as calcination. . Calcination involves contacting the molecular sieve containing the template with a gas of any desired concentration, preferably an oxygen containing gas, at an elevated temperature sufficient to partially or completely degrade and oxidize the template.
[43] Molecular sieves have a high silicon (Si) to aluminum (Al) ratio or a low silicon to aluminum ratio, but a low Si / Al ratio is preferred for SAPO synthesis. In one embodiment, the molecular sieve has a Si / Al ratio of less than 0.65, preferably less than 0.40, more preferably less than 0.32 and most preferably less than 0.20. In other embodiments the molecular sieve has a Si / Al ratio of about 0.65 to about 0.10, preferably about 0.40 to about 0.10, more preferably about 0.32 to about 0.10, more preferably about 0.32 to about 0.15.
[44] Process for preparing molecular sieve catalyst composition
[45] Once the molecular sieve is synthesized, the molecular sieve is then formulated into the molecular sieve catalyst composition, particularly for commercial use, as required by the particular conversion process. The synthesized molecular sieve is prepared or blended into the molecular sieve catalyst composition by combining the synthesized molecular sieve with a binder and optionally but preferably a matrix material to form a molecular sieve catalyst composition or blended molecular sieve catalyst composition. This blended molecular sieve catalyst composition is formed into particles of useful shapes and sizes by known techniques such as spray drying, pelletization, extrusion and the like.
[46] The pH in the IEP for various materials including metal oxides is described in J. Lyklema, Structure of the Solid / Liquid Interface and Electrical Double Layer, in Solid / Liquid Dispersions , Academic Press, London, pages 63-90, 1987 and J.-E. Otterstedt and DA Brandreth, Small Particles Technology , page 258, Plenum, New York, 1998.
[47] In one embodiment, the molecular sieve, preferably the silicoaluminophosphate molecular sieve, more preferably the SAPO-34 molecular sieve is 3 to 7, preferably 4 to 6, more in its IEP (measured as an aqueous slurry). Preferably it has a pH of 4.5 to 5.5. In other embodiments, the binder, preferably the alumina sol, has a pH of greater than about 9, preferably greater than 10, in its IEP. In another embodiment, the matrix material, preferably clay, has a pH of less than about 2 in its IEP.
[48] In other embodiments, the slurry comprising the molecular sieve and at least one binder or matrix material has a higher or lower, preferably lower pH than the IEP of the molecular sieve and at least one binder or matrix material. In one embodiment, the pH of the slurry is 2 to 7, preferably 2.3 to 6.2; The IEP of the molecular sieve is 2.5 to less than 7, preferably about 3.5 to 6.5; The IEP of the binder is higher than 10; The IEP of the matrix material is less than two. In a particularly preferred embodiment, the IEP of the molecular sieve is 4.5 to 5.5.
[49] In another embodiment, the binder, preferably alumina sol, more preferably aluminum chlorohydrate, is positively charged and / or is at a pH of greater than 2 and less than 10. In yet further embodiments, the matrix material, clay is negatively charged and / or has a pH of less than 2 in its IEP. In other embodiments, the binder and matrix composition, preferably 20 to 60% by weight binder and 40 to 80% by weight matrix material, based on the total weight of the binder and matrix material, have a pH of about 9.8 in their IEP.
[50] In one preferred embodiment, the slurry has a pH of at least 0.3 higher or lower than the IEP of the molecular sieve and / or the IEP of the binder and / or the matrix material, and preferably the slurry is at least 0.5 higher or lower, preferably lower have a pH, more preferably the slurry has at least one high or low, preferably a low pH, most preferably the slurry has a pH at least 1.5 high or low, preferably at least two low. Preferably, the pH of the slurry is different from the IEP of the molecular sieve, binder and matrix material.
[51] In one embodiment, the weight ratio of binder to molecular sieve is about 0.1 to 0.5, preferably less than 0.1 to 0.5, more preferably 0.11 to 0.48, even more preferably 0.12 to about 0.45, even more preferably less than 0.13 to 0.45. And most preferably from 0.15 to about 0.4.
[52] In other embodiments, the molecular sieve catalyst composition or blended molecular sieve catalyst composition is greater than about 70%, preferably greater than about 75%, of the micropore surface area (MSA) of the molecular sieve itself, measured in m ² / g-molecular sieve units. , More preferably greater than 80%, even more preferably greater than 85%, most preferably greater than about 90%. The MSA of the molecular sieve catalyst composition is the total MSA of the composition divided by the fraction of molecular sieve contained in the molecular sieve catalyst composition.
[53] In other embodiments, the amount of solids present in the blend of molecular sieve catalyst compositions, for example, in the slurry of molecular sieve and binder (optionally including the matrix material) used in the spray drying process, is important. It is also preferred that the synthesized molecular sieve contains a certain amount of liquid medium, preferably water, without being calcined before being used in the slurry. If the solids content of the slurry is too low or too high, the abrasion resistance of the molecular sieve catalyst composition is reduced. In a preferred embodiment the molecular sieve catalyst composition is prepared by preparing a molecular sieve, a binder, and optionally but preferably a slurry containing the matrix material. The preferred solids content of the slurry is about 20% to about 50% molecular sieve, preferably about 30% to about 48% molecular sieve, more preferably about 40% to about 48% molecular sieve, binder From about 5% to about 20%, preferably from about 8% to about 15%, and from about 30% to about 80%, preferably from about 40% to about 60%, by weight of the matrix material. .
[54] There are many different binders useful for forming molecular sieve catalyst compositions. Non-limiting examples of binders useful alone or in combination include various types of hydrated alumina, silica, and / or other inorganic oxide sol. One preferred alumina containing sol is aluminum chlorhydrate. The inorganic oxide sol serves as a pool to bond the synthesized molecular sieve and other materials such as the matrix, in particular after heat treatment. Upon heating, the inorganic oxide sol, which preferably has a low viscosity, is converted into an inorganic oxide matrix component. For example, the alumina sol is converted to an aluminum oxide matrix after heat treatment.
[55] Aluminum chlor-hydrate, hydrochloride pair hydroxy containing ion lock misfire aluminum-base sol is the general formula _{Al m O n (OH) o} Cl p · x (H 2 O) ( wherein, m is from 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 described in GM Wolterman, et al., Stud. Surf. Sci. and Catal., 76, pages 105-144 (1993). Al ₁₃ O ₄ (OH) ₂₄ Cl ₇ .12 (H ₂ O). In another embodiment, the one or more binders are selected from aluminum oxyhydroxide, γ-alumina, boehmite, diaspore, and α-alumina, β-alumina, γ-alumina, δ-alumina, ε-alumina, κ- Alumina, and combinations with one or more other non-limiting examples of alumina materials such as transitional alumina, such as ρ-alumina, aluminum trihydroxides such as gibbsite, bayerite, nordstrandite, douelite, and mixtures thereof do.
[56] In other embodiments, the binder is an alumina sol that mainly comprises aluminum oxide and optionally comprises some silicon. In another embodiment, the binder is gelled alumina prepared by treating an alumina hydrate, such as pseudoboehmite, with an acid, preferably a halogen-free acid, to prepare a sol or aluminum ion solution. Non-limiting examples of commercially available colloidal alumina sol include Nalco 8676, available from Nalco Chemical Co., Naperville, Ill., And Niacol Nano Technologies Inn, Ashland, Massachusetts. Nyacol AL20DW, available from Nyacol Naco Technologies, Inc.
[57] The aforementioned molecular sieves are combined with one or more matrix materials in preferred embodiments. The matrix material typically acts as a heat sink to lower the overall catalyst cost, for example to help block heat from the catalyst composition during regeneration, to densify the catalyst composition, to resist crush strength and abrasion resistance It is effective in increasing the same catalyst strength and controlling the conversion rate in certain processes.
[58] Non-limiting examples of matrix materials include rare earth metals, titania, zirconia, magnesia, toria, beryllia, quartz, nonfunctional, metal oxides, or mixtures thereof, such as silica-magnesia, silica-zirconia , Silica-titania, silica-alumina and silica-alumina-toria. In one embodiment, the matrix material is natural clay, such as from the class of montmorillonite and kaolin. Such natural clays include saventonite and kaolin, for example known as Dixie, McNamee, Georgia and Florida clays. Non-limiting examples of other matrix materials include halosite, kaolinite, dickite, nacrite, or anoxite. In one embodiment, the matrix material, preferably any clay, is treated by known reforming processes such as calcination and / or acid treatment and / or chemical treatment.
[59] In one preferred embodiment, the matrix material is a clay or clay-like composition, preferably a clay or clay-like 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 solids content slurry, has a low fresh surface area and easily packs together due to its platelet structure. The preferred average particle size of the matrix material, most preferably kaolin, is from about 0.05 μm to about 0.6 μm and has a D ₉₀ particle size distribution of less than about 1 μm.
[60] In one embodiment, the binder, molecular sieve, and matrix material are combined in the presence of a liquid to form a catalyst composition, wherein the amount of binder is about 2% by weight based on the total weight of the binder, molecular sieve, and matrix material except liquid To about 30% by weight, preferably about 5% to about 20% by weight, more preferably about 7% to about 15% by weight.
[61] Combining the molecular sieve, binder, and optionally the matrix material in a liquid to form a slurry requires mixing, preferably vigorous mixing, to produce a substantially homogeneous mixture. Non-limiting examples of suitable liquids include one or a combination of water, alcohols, ketones, aldehydes, and / or esters. The most preferred liquid is water. In one embodiment, the slurry is high sheared for a time sufficient to produce the desired slurry texture, sub-particle size, and / or sub-particle size distribution. Suitable means for milling the slurry include colloid mills, in-line mixes, and the like.
[62] Slurry preparation comprising the molecular sieve, binder and matrix material is carried out by mixing the molecular sieve, binder and optionally the matrix material at a temperature of about -10 ° C to about 80 ° C. In one embodiment, depending on the particle size of the molecular sieve and binder, the particle size reduction step is performed before or after mixing. Impingement mills (micronizers available from Sturtevant, Boston) for various powders, or dry or wet mills such as Eiger mills (Grayslake, Ill.) Mills available from Eiger Machinery, In., USA. Jar rolling mills for both dry and wet milling (Paul O. Abbey, Little Falls, NJ) Use a variety of devices including, but not limited to, Paul O. Abbe, Inc., or use a high-shear mix (Silverson Machines, Inc., East Long Meadows, Massachusetts). There are many ways to achieve particle size reduction by using. Particle size distribution in the slurry is measured using, for example, a microtrack laser scattering particle size analyzer S3000 available from MicroTrac, Clearwater, Florida. In order to ensure the quality of the slurry for spray drying forming the catalyst composition of the present invention, the measurement of pH, surface area, solids content, bulk density, and viscosity is also preferably, respectively, for example Cole Palmer pH. Meters, Solids Measurements available from Micrometrics Instrument Corporation, Norcross, GA, Micrometrics Gemini 9375, CEM Corporation, Matthews, NC It is monitored using a CEM MAS 700 microwave muffle furnace for Brookfield and a Brookfield LV-DVE viscometer for viscosity. Zeta potential measurements are performed on a Matec 9800 electrokinetic device, available from Mattec Applied Science, Northboro, Massachusetts. Particle size is only one factor in the effect of the slurry in the formation of the catalyst composition of the present invention. In addition, the order in which each individual component is added, namely molecular sieve, binder, matrix material, and other components, is also important. The order of addition is most important if the surfaces of the different particles have opposite charges, negative and positive, or different charge densities, regardless of whether the different particles are particles of molecular sieve, binder or matrix material. As a general rule, after size reduction is complete, the last step, if necessary, is the addition and mixing of counter charged particles. In one preferred embodiment, it is best to add molecular sieves, binders or matrix materials with higher charge densities per mass to components with lower charge densities per mass.
[63] The molecular sieves, binders, and matrix materials are in the same or different liquids and are combined in any order, together, simultaneously, sequentially, or in combinations thereof. In a preferred embodiment, the same liquid, preferably water is used. Molecular sieves, matrix materials, and binders are added to the liquid as a solid or as a slurry, together or separately. If solids are added together, it is preferred to add a limited and / or controlled amount of liquid.
[64] In one embodiment, a slurry of molecular sieve, binder, and matrix material is mixed or milled to achieve a sufficiently uniform slurry of sub-particles of the molecular sieve catalyst composition, which is then fed into the forming unit to prepare the molecular sieve catalyst composition. . In a preferred embodiment, the forming unit is a spray dryer. Typically, the forming unit is maintained at a temperature sufficient to dry most of the liquid from the slurry and the resulting molecular sieve catalyst particles. The resulting catalyst composition, when formed in this way, preferably has the form of microspheres.
[65] When a spray dryer is used as the forming unit, typically the slurry of molecular sieve, binder and matrix material is spray dried with the drying gas at an average inlet temperature of 100 ° C. to 550 ° C. and a combined outlet temperature of 50 ° C. to about 225 ° C. Are supplied simultaneously. In one embodiment, the average diameter of the spray dried formed catalyst composition is from about 10 μm to about 300 μm, preferably from about 30 μm to about 250 μm, more preferably from about 40 μm to about 150 μm, most preferably About 50 μm to about 120 μm.
[66] During spray drying, the slurry enters the drying chamber through a nozzle that dispenses the slurry into small droplets similar to aerosol sprays. Atomization is accomplished by passing the slurry through a single nozzle or multiple nozzles to lower the pressure to 100 psig to 2000 psig (690 kPag to 13790 kPag). In other embodiments, the slurry is subjected to a pressure drop of 1 psig to 150 psig (6.9 kPag to 1034 kPag) through a single nozzle or multiple nozzles with atomizing fluid such as air, steam, associated gas, or any other suitable gas. It is supplied at the same time.
[67] In another embodiment, the aforementioned slurry is directed to the periphery of a spinning wheel that dispenses the slurry into small droplets, the size of the droplets being in terms of slurry viscosity, surface tension, flow rate, pressure, and temperature of the slurry, shape and dimension of the nozzle, Or by a number of factors including the spinning speed of the wheel. The droplets are then dried in an air stream of forward or reverse flow through the spray dryer to form a substantially dried or dried molecular sieve catalyst composition.
[68] In general, the size of the microspheres is controlled to some extent by the solids content of the slurry. However, control of the size of the catalyst composition and its spherical properties is also controllable by varying slurry feed properties and spray conditions.
[69] Other methods for the formation of molecular sieve catalyst compositions are described in US patent application Ser. No. 09 / 617,714, spray drying using a regenerated molecular sieve catalyst composition, filed July 17, 2000, incorporated herein by reference. .
[70] In other embodiments, the blended molecular sieve catalyst composition comprises from about 1% to about 99% by weight, preferably from about 10% to about 90% by weight, more preferably based on the total weight of the molecular sieve catalyst composition Is about 10% to about 80%, even more preferably about 20% to about 70%, most preferably about 20% to about 60% by weight.
[71] Once the molecular sieve catalyst composition is formed in a substantially dry or dried state, heat treatments, such as calcination, are typically carried out at elevated temperatures in order to further cure and / or activate the formed catalyst composition. Typical calcination environments are air that typically contains small amounts of water vapor. Typical calcination temperatures are from about 400 ° C. to about 1,000 ° C., preferably from about 500 ° C. to about 800 ° C., most preferably from about 550 ° C. to about 700 ° C., preferably air, nitrogen, helium, associated gas (oxygen Poor combustion products), or any combination thereof. In one embodiment, calcination of the blended molecular sieve catalyst composition is performed in any number of known apparatus, including rotary calciners, fluid bed calciners, batch ovens, and the like. The calcination time typically depends on the degree of cure and the temperature range of the molecular sieve catalyst composition and is about 1 minute to about 10 hours, preferably 15 minutes to about 5 hours.
[72] In one embodiment, the abrasion resistance of the molecular sieve catalyst composition is measured using an abrasion rate index (ARI) measured in weight percent of the abraded catalyst composition per hour. S.A., which is incorporated herein by reference in its entirety. Weeks and P. Dumbill, in Oil & Gas Journal, pages 38 to 40, 1987. ARI is measured by adding 6.0 g of catalyst composition having a particle size in the range of about 53 microns to about 125 microns to a hardened steel wear cup. About 23,700 cc / min of nitrogen gas was bubbled through the water-containing bubbler to wet the nitrogen. Wet nitrogen passes through the attrition cup and exits the attrition device through the porous fibrous thimble. Flowing nitrogen removes finer particles and larger particles are retained in the cup. The porous fibrous thimble separates the fine catalyst particles from the nitrogen exiting the thimble. The fine particles retained in the thimble are representative of the catalyst composition milled by wear. Nitrogen flow through the wear cup is maintained for 1 hour. The fines collected in the thimble are removed from the unit. After that install a new thimble. The catalyst remaining in the attrition unit is worn for an additional 3 hours at the same gas flow and moisture levels. Collect the fines collected in the thimble. After the first hour a collection of fine catalyst particles separated by thimble is weighed. The amount of fine particles expressed in grams per hour divided by the original amount of catalyst charged into the wear cup is the ARI in weight percent per hour (wt% / hour). ARI is the formula ARI = C / (B + C) / D × 100%, where B is the weight of the catalyst composition remaining in the cup after the abrasion test, C is the weight of the fine catalyst particles collected after the first time, and D Is expressed as the duration (in hours) of the processing after the first time attrition treatment.
[73] In one embodiment, the molecular sieve catalyst composition or blended molecular sieve catalyst composition is less than 15% w / h, preferably less than 10% w / h, more preferably less than 5% w / h, even more preferably 2% Have an ARI of less than% / hour, most preferably less than 1% by weight / hour. In one embodiment, the molecular sieve catalyst composition or blended molecular sieve catalyst composition is less than 0.1% w / h to less than 5% w / h, more preferably about 0.2% w / h to less than 3% w / h, most preferably Has an ARI of about 0.2% by weight to less than 2% by weight / hour.
[74] Process Using Molecular Sieve Catalyst Composition
[75] The molecular sieve catalyst compositions described above can be for example cracked of naphtha feed to light olefins (US Pat. No. 6,300,537) or cracking higher molecular weight (MW) hydrocarbons to lower MW hydrocarbons; Hydrocracking, for example of heavy petroleum and / or cyclic feedstocks; Preparation of polymer products, for example by isomerization of aromatics such as xylenes, for example by the polymerization of one or more olefins; Reforming; Hydrogenation; Dehydrogenation; Dewaxing, for example for the removal of straight chain paraffins of hydrocarbons; Absorption for, for example, isomer separation of alkyl aromatic compounds; Alkylation of aromatic hydrocarbons such as, for example, benzene and alkyl benzene, optionally with propylene or with long chain olefins for the production of cumene; Transalkylation of combinations of aromatic and polyalkylaromatic hydrocarbons, for example; Dealkylation; Hydrogenated ring opening; Disproportionation of toluene, for example to prepare benzene and paraxylene; Oligomerization of, for example, straight and branched olefins; And dehydrogenation ring opening.
[76] Preferred processes include naphtha to a high aromatic mixture; Light olefins to gasoline, distillate and lubricants; Oxygenates to olefins; Light paraffins to olefins and / or aromatics; And a conversion process of an aldehyde of an unsaturated hydrocarbon (ethylene and / or acetylene) for conversion to alcohol, acid and ester. The most preferred process of the present invention is a process involving the conversion of a feedstock comprising at least one oxygenate to at least one olefin.
[77] The molecular sieve catalyst compositions described above are particularly useful for the conversion process of different feedstocks. Typically, the feedstock contains one or more aliphatic-containing compounds, including alcohols, amines, carbonyl compounds such as aldehydes, ketones and carboxylic acids, ethers, halides, mercaptans, sulfides, and the like, and mixtures thereof. Aliphatic residues of aliphatic-containing compounds typically range from 1 to about 50 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms, most preferably from 1 to 4 carbon atoms. It contains.
[78] 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, alkyl-amines such as methyl amine, dimethyl ether, di Alkyl-ethers such as ethyl ether and methylethyl ether, alkyl-halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehyde, and various acids such as acetic acid.
[79] In a preferred embodiment of the process of the invention, the feedstock is at least one oxygenate, more specifically at least one organic compound containing at least one oxygen atom. In the most preferred embodiment of the process of the invention, the oxygenate in the feedstock is at least one alcohol, preferably an aliphatic alcohol, wherein the aliphatic residue of the alcohol has 1 to 20, preferably 1 to 10, most Preferably it is 1-4. Alcohols useful as feedstock in the process of the present invention are lower straight and branched chain aliphatic alcohols and their unsaturated counterparts.
[80] Non-limiting examples of oxygenates include methanol, ethanol, n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid, and mixtures thereof do. In the most preferred embodiment, the feedstock is selected from one or more of methanol, ethanol, dimethyl ether, diethyl ether or combinations thereof, more preferably methanol and dimethyl ether, most preferably methanol.
[81] The various feedstocks discussed above, in particular those containing oxygenates, more particularly those containing alcohols, are mainly converted to at least one olefin. The carbon number of the olefin or olefin monomer produced from the feedstock is typically from 2 to 30, preferably from 2 to 8, more preferably from 2 to 6, even more preferably from 2 to 4, most preferably ethylene And / or propylene. Non-limiting examples of olefin monomers include ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 and decene-1, preferably ethylene, propylene, butene-1, Pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 and isomers thereof. Other olefin monomers include unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins.
[82] In the most preferred embodiment, the feedstock, preferably the feedstock of at least one oxygenate, is converted to olefins having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms in the presence of the molecular sieve catalyst composition of the present invention. Most preferably, the olefins, alone or in combination, are converted from a feedstock containing an oxygenate, preferably an alcohol, most preferably methanol, to ethylene and / or propylene, which is the preferred olefin.
[83] There are many processes used to convert feedstocks to olefins, which include various cracking processes such as steam cracking, thermal regeneration cracking, fluidized bed cracking, fluid catalytic cracking, deep catalyst cracking, and visbreaking. . The most preferred process is generally referred to as gas-to-olefin (GTO) or alternatively methanol-to-olefin (MTO). In the MTO process, typically an oxygenated feedstock, most preferably a methanol containing feedstock, is in the presence of its molecular sieve catalyst composition with one or more olefins, preferably and mainly, ethylene and / or propylene, often referred to as light olefins. Is switched.
[84] In one embodiment of the process for the conversion of a feedstock, preferably a feedstock containing at least one oxygenate, the amount of olefins produced, based on the total weight of hydrocarbons produced, is greater than 50% by weight, preferably More than 60% by weight, more preferably more than 70% by weight, most preferably more than 75% by weight. In another embodiment of the process for the conversion of one or more oxygenates to one or more olefins, the amount of ethylene and / or propylene produced, based on the total weight of hydrocarbons produced, is greater than 65% by weight, preferably 70 Greater than 70% by weight, more preferably greater than 75% by weight, most preferably greater than 78% by weight.
[85] In another embodiment of the process for the conversion of one or more oxygenates to one or more olefins, the amount, in weight percent units of ethylene produced, based on the total weight of the resulting hydrocarbon product, is greater than 30 weight percent, more preferably. Preferably greater than 35% by weight, most preferably greater than 40% by weight. In another embodiment of the process for the conversion of one or more oxygenates to one or more olefins, the amount in units of weight percent of the resulting propylene, based on the total weight of the resulting hydrocarbon product, is greater than 20 weight percent, preferably Preferably greater than 25% by weight, more preferably greater than 30% by weight, most preferably greater than 35% by weight.
[86] In one embodiment, the feedstock is typically used to reduce the concentration of the feedstock and contains one or more diluents which are generally unreactive to the feedstock or molecular sieve catalyst composition. Non-limiting examples of diluents include helium, argon, nitrogen, 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. Most preferred diluents are water and nitrogen, with water being particularly preferred.
[87] Diluent, water, is used in liquid or vapor form, or a combination thereof. Diluents are added directly to the feedstock entering the reactor, directly to the reactor, or together with the molecular sieve catalyst composition. In one embodiment, the amount of diluent in the feedstock is about 1 to about 99 mole percent, preferably about 1 to 80 mole percent, more preferably about 5 to about 50 mole percent, based on the total moles of the feedstock and the diluent. And most preferably about 5 to about 25 mole percent.
[88] In one embodiment, other hydrocarbons are added directly or indirectly to the feedstock, which is olefins, paraffins, aromatics (see for example US Pat. No. 4,677,242, addition of aromatics) or mixtures thereof, preferably propylene, butylene , Pentylene, and other hydrocarbons having 4 or more carbon atoms, or mixtures thereof.
[89] The conversion of the feedstock, in particular the feedstock containing at least one oxygenate, in the presence of the molecular sieve catalyst composition of the present invention is carried out in a reaction process in a reactor, wherein the process is a fixed bed process, a fluidized bed process (turbulent bed) Process), preferably a continuous fluidized bed process, most preferably a continuous high speed fluidized bed process.
[90] The reaction process can take place in a variety of reactors, such as hybrid reactors, circulating fluidized bed reactors, riser reactors, etc., having dense or fixed bed reaction zones and / or rapid fluidized bed reaction zones coupled together. Suitable conventional reactor types are described, for example, in US Pat. No. 4,076,796, US Pat. No. 6,287,522 (dual riser), and Fluidization Engineering , D. Kunii and O. Levenspiel, Robert, all of which are hereby incorporated by reference in their entirety. E. Krieger Publishing Company, New York, New York 1977. Preferred reactor types are described in Riser Reactor , Fluidization and Fluid-Particle Systems , pages 48 to 59, FA Zenz and DF Othmo, Reinhold Publishing Corporation, New York, 1960, and US Pat. No. 6,166,282. (Quick-fluidized bed reactor), and a riser reactor generally described in US patent application Ser. No. 09 / 564,613, filed May 4, 2000.
[91] In a preferred embodiment, the fluidized bed process or the high speed fluidized bed process comprises a reactor system, a regeneration system and a recovery system.
[92] The reactor system is preferably a fluid bed reactor system having a first reaction zone in at least one riser reactor and a second reaction zone in at least one disengaging vessel (preferably including at least one cyclone). In an embodiment, the one or more riser reactors and the exit vessel are contained within a single reactor vessel. A fresh feedstock, preferably a feedstock containing at least one oxygenate, is optionally fed with one or more diluents into one or more riser reactors, where a molecular sieve catalyst composition or coke modified variant thereof is introduced. In one embodiment, the molecular sieve catalyst composition or coke modified variant thereof is contacted with a liquid or gas, or a combination thereof, before being introduced into the riser reactor, preferably the liquid is water or methanol, and the gas is nitrogen, such as Inert gas.
[93] In one embodiment, the amount of fresh feedstock fed individually or together with the steam feedstock is from 0.1% to about 85% by weight, preferably based on the total weight of the feedstock including any diluent contained therein. Preferably from about 1% to about 75%, more preferably from about 5% to about 65% by weight. The liquid and vapor feedstocks preferably contain the same or different proportions of the same or different feedstocks with the same or different diluents.
[94] The feedstock entering the reactor system is preferably partially or completely converted to a gaseous effluent in the first reactor zone, and the effluent enters the leaving vessel together with the coked molecular sieve catalyst composition. In a preferred embodiment, the cyclones in the leaving vessel are designed to separate the molecular sieve catalyst composition, preferably the coked molecular sieve catalyst composition, from the gaseous effluent containing one or more olefins in the leaving zone. Cyclones are preferred, but the gravitational effect in the leaving vessel will also separate the catalyst composition from the gaseous effluent. Other methods of separating the catalyst composition from the gaseous effluent include the use of plates, caps, elbows, and the like.
[95] In one embodiment of the release system, the release system includes a release vessel, typically the bottom of the release vessel is a stripping zone. In the stripping zone, the coke-coated molecular sieve catalyst composition is contacted with a gas, preferably one or a combination of inert gases such as steam, methane, carbon dioxide, carbon monoxide, hydrogen, or argon, preferably steam, so that Recovered from the coked molecular sieve catalyst composition, after which the molecular sieve catalyst composition is introduced into a regeneration system. In another embodiment, the stripping zone is in a vessel separate from the vessel leaving the gas on the volume basis of the volume for the coked molecular sieve catalyst composition of the gas 1hr ^-1 to time gas surface rate of about 20,000hr ^-1 (gas hourly superficial velocity (GHSV), preferably passed over the coked molecular sieve catalyst composition at elevated temperatures of 250 ° C to about 750 ° C, preferably about 350 ° C to 650 ° C.
[96] In the conversion process, in particular the conversion temperature used in the reactor system is from about 200 ° C to about 1000 ° C, preferably from about 250 ° C to about 800 ° C, more preferably from about 250 ° C to about 750 ° C, even more preferably about 300 ° C. ° C to about 650 ° C, even more preferably from about 350 ° C to about 600 ° C, most preferably from about 350 ° C to about 550 ° C.
[97] The conversion pressure used in the conversion process, in particular in the reactor system, varies over a wide range, including autogenous pressure. The conversion pressure is based on the partial pressure of the feedstock, excluding any diluent. Typically the conversion pressure used in the process is in the range of about 0.1 kPaa to about 5 MPaa, preferably about 5 kPaa to about 1 MPaa, most preferably about 20 kPaa to about 500 kPaa.
[98] In particular in the process of converting a feedstock containing at least one oxygenate in the reaction zone in the presence of a molecular sieve catalyst composition, the weight hourly space velocity (WHSV) is determined in the molecular sieve catalyst composition in the reaction zone. It is defined as the total weight of the feedstock excluding the diluent to the hourly reaction zone per weight of molecular sieve. The WHSV is maintained at a level sufficient to keep the catalyst composition fluidized in the reactor.
[99] Typically, WHSV from about 1hr ^-1 to about 5000hr ^-1, preferably from about 2hr ^-1 to about 3000hr ^-1, more preferably from about 5hr ^-1 to about 1500hr ^-1, and most preferably about 10hr ^-1 To about 1000 hr ⁻¹ . In one preferred embodiment, the WHSV is greater than 20 ^{hr −1} , and preferably the WHSV for conversion of the feedstock containing methanol and dimethyl ether is from about 20 ^{hr −1} to about 300 hr ⁻¹ .
[100] The surface gas velocity (SGV) of the feedstock comprising the diluent and reaction product in the reactor system is preferably sufficient to fluidize the molecular sieve catalyst composition in the reaction zone of the reactor. In the process, in particular in the reactor system, more particularly in the riser reactor, the SGV is at least 0.1 m / sec, preferably greater than 0.5 m / sec, more preferably greater than 1 m / sec, even more preferably greater than 2 m / sec. , Even more preferably more than 3 m / sec, most preferably more than 4 m / sec. See, eg, US patent application Ser. No. 09 / 708,753, filed November 8, 2000, incorporated herein by reference.
[101] In one preferred embodiment of the process for converting oxygenates to olefins using a silicoaluminophosphate molecular sieve catalyst composition, the process comprises a temperature corrected normalized methane selectivity (Temperature of at least 20hr ⁻¹ and less than 0.016, preferably less than 0.01 It works with Corrected Normalized Methane Selectivity (TCNMS). See, eg, US Patent Application No. 5,952,538, which is incorporated herein by reference in its entirety. Min. In another embodiment of the step of using a molecular sieve catalyst composition to convert oxygenates such as methanol to one or more olefins, at a temperature of from about 550 to about 350 ℃ ℃ WHSV is 0.01hr ^-1 to about 100hr ^-1, silica Molar ratio of Me ₂ O ₃ (where Me is an element of Group IIIA or Group VIII of the Periodic Table of Elements) is from 300 to 2500. See, eg, EP-0 642 485 B1, which is incorporated herein by reference in its entirety. Another process for converting an oxygenate, such as methanol, to one or more olefins using a molecular sieve catalyst composition is disclosed in PCT WO 01/23500 (average catalyst feed of 1.0 or higher, published April 5, 2001, incorporated herein by reference). Propane reduction in raw material exposure).
[102] The coked molecular sieve catalyst composition is withdrawn from the leaving vessel, preferably by one or more cyclones, and introduced into the regeneration system. The regeneration system comprises a regenerator, wherein the coked catalyst composition is contacted with a regeneration medium, preferably an oxygen containing gas, under the temperature, pressure and residence time of the general regeneration conditions. Non-limiting examples of regeneration media include oxygen, O ₃ , SO ₃ , N ₂ O, NO, NO ₂ , N ₂ O ₅ , air, nitrogen or carbon dioxide, air diluted with oxygen and water (US Pat. No. 6,245,703), carbon monoxide And / or one or more of hydrogen. Regeneration conditions are conditions under which coke can be combusted from the cotsified catalyst composition, preferably to a level of less than 0.5% by weight, based on the total weight of the coked molecular sieve catalyst composition entering the regeneration system. The coked molecular sieve catalyst composition withdrawn from the regenerator forms a regenerated molecular sieve catalyst composition.
[103] The regeneration temperature is in the range of about 200 ° C to about 1500 ° C, preferably about 300 ° C to about 1000 ° C, more preferably about 450 ° C to about 750 ° C, most preferably about 550 ° C to 700 ° C. The regeneration pressure is about 15 psia (103 kPaa) to about 500 psia (3448 kPaa), preferably about 20 psia (138 kPaa) to about 250 psia (1724 kPaa), more preferably about 25 psia (172 kPaa) to about 150 psia (1034 kPaa), most preferably about 30 psia (207 kPaa) to about 60 psia (414 kPaa). The preferred residence time of the molecular sieve catalyst composition in the regenerator is from about 1 minute to several hours, most preferably from about 1 minute to 100 minutes, and the preferred volume of oxygen in the gas is from about 0.01 mole percent to about total volume of the gas. It is the range of 5 mol%.
[104] In one embodiment, a regeneration accelerator, typically a metal containing compound, such as platinum, palladium, and the like, is added directly or indirectly to the regenerator, for example with the coked catalyst composition. In another embodiment, fresh molecular sieve catalyst composition is also added to a regenerator containing a regeneration medium of oxygen and water, as described in US Pat. No. 6,245,703, which is incorporated herein by reference in its entirety. In another embodiment, some of the coke-laden molecular sieve catalyst composition from the regenerator is returned directly to one or more riser reactors, or indirectly, pre-contacted with the feedstock, or the regenerated molecular sieve catalyst composition or as described below. Return by contact with the cooled regenerated molecular sieve catalyst composition.
[105] The combustion of coke is an exothermic reaction, and in one embodiment, the temperature in the regeneration system is controlled by various techniques in the art, including supplying cooled gas to the regeneration vessel, which is batch, continuous, or semi- It is operated in continuous mode, or a combination thereof. Preferred techniques include withdrawing the regenerated molecular sieve catalyst composition from the regeneration system and passing the regenerated molecular sieve catalyst composition through a catalyst cooler to form a cooled regenerated molecular sieve catalyst composition. The catalytic cooler is in one embodiment a heat exchanger located inside or outside the regeneration system. In one embodiment, the cooler regenerated molecular sieve catalyst composition is returned to the regenerator in a continuous cycle, or alternatively (see US patent application Ser. No. 09 / 587,766, dated June 6, 2000) in the cooled regenerated molecular sieve catalyst composition. Some are returned to the regeneration vessel in a continuous cycle, and some of the cooled molecular sieve catalyst composition is returned directly or indirectly to the riser reactor, or of the regenerated molecular sieve catalyst composition or the cooled regenerated molecular sieve catalyst composition Some contact with by-products in the gaseous effluent (PCT WO 00/49106, published August 24, 2000, which is incorporated herein by reference in its entirety). In another embodiment, a recycled molecular sieve catalyst composition in contact with an alcohol, preferably ethanol, 1-propanol, 1-butanol or mixtures thereof, filed February 16, 2001, which is incorporated herein by reference in its entirety. It is introduced into the reactor system as described in US patent application Ser. No. 09 / 785,122. Another method of operating the regeneration system is disclosed in US Pat. No. 6,290,916 (humidity control), which is incorporated herein by reference in its entirety.
[106] The recycled molecular sieve catalyst composition withdrawn from the regeneration system, preferably from the catalyst cooler, is combined with fresh molecular sieve catalyst composition and / or recycled molecular sieve catalyst composition and / or feedstock and / or fresh gas or liquid, and riser Sent back to the reactor. In another embodiment, the regenerated molecular sieve catalyst composition withdrawn from the regeneration system is preferably returned directly to the riser reactor after passing through the catalyst cooler. In one embodiment, the carrier, such as inert gas, feedstock vapor, steam, etc., is semi-continuous or continuous to facilitate introduction of the recycled molecular sieve catalyst composition into the reactor system, preferably into one or more riser reactors. do.
[107] By controlling the flow of the regenerated molecular sieve catalyst composition or the cooled regenerated molecular sieve 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. Many of which control the flow of molecular sieve catalyst compositions, described in Michael Louge, Experimental Techniques , Circulating Fluidized Beds , Grace, Avidan and Knowlton, eds., Blackie, 1997 (336-337), incorporated herein by reference. There is a technique. The coke level on the molecular sieve catalyst composition is determined by withdrawing the molecular sieve catalyst composition from the conversion process at one point in the process and measuring its carbon content. Typical levels of coke on the molecular sieve catalyst composition after regeneration are from 0.01 wt% to about 15 wt%, preferably from about 0.1 wt% to about 10 wt%, based on the total weight of the molecular sieve, not the total weight of the molecular sieve catalyst composition. More preferably about 0.2% to about 5%, most preferably about 0.3% to about 2% by weight.
[108] In one preferred embodiment, the mixture of fresh molecular sieve catalyst composition and regenerated molecular sieve catalyst composition and / or cooled regenerated molecular sieve catalyst composition is based on the total weight of the mixture of molecular sieve catalyst composition to produce coke or carbonaceous deposits. About 1 to 50% by weight, preferably about 2 to 30% by weight, more preferably about 2 to about 20% by weight, most preferably about 2 to about 10% by weight. See, eg, US Pat. No. 6,023,005, which is incorporated herein by reference in its entirety.
[109] The gaseous effluent is withdrawn from the leaving system and passed through the recovery system. There are many known recovery systems, techniques and sequences useful for separating and purifying olefins from gaseous effluents. Recovery systems generally comprise a variety of separation, fractionation and / or distillation columns, columns, splitters, or trains, reaction systems such as ethylbenzene production (US Pat. No. 5,476,978) and other derivative processes such as aldehydes, ketones and esters. (US Pat. No. 5,675,041), and other related equipment, such as one or more or a combination of various condensers, heat exchangers, refrigeration systems or cold trains, compressors, knock-out drums or pots, pumps, and the like. Contains water. Non-limiting examples of such towers, columns, splitters or trains used alone or in combination are demethane groups, preferably high temperature demethane groups, deethane groups, depropane groups, preferably wet depropane groups, corrosive washing. One or more of wash towers, absorbers, adsorbers, membranes, ethylene (C2) splitters, propylene (C3) splitters, butene (C4) splitters, and the like, often referred to as tower and / or quench towers.
[110] A variety of recovery systems useful for recovering primarily olefins, preferably prime or light olefins, such as ethylene, propylene and / or butenes are disclosed in U.S. Patent No. 5,960,643 (secondary enriched ethylene stream, which is incorporated herein by reference in its entirety. ), US Pat. Nos. 5,019,143, 5,452,581 and 5,082,481 (membrane separation), US Pat. No. 5,672,197 (pressure dependent adsorbent), US Pat. In one step with hydrogen and carbon dioxide, US Pat. No. 5,927,063 (recovered methanol to gas turbine power plant), and US Pat. No. 6,121,504 (direct product quenching), US Pat. No. 6,121,503 (high purity olefin without fractionation) And US Pat. No. 6,293,998 (pressure swing adsorption).
[111] In general, most recovery systems involve the generation, generation or accumulation of additional products, by-products and / or contaminants with the desired base product. Preferred base products, light olefins such as ethylene and propylene are typically purified for use in derivative preparation processes such as polymerization processes. Thus, in the most preferred embodiment of the recovery system, the recovery system also includes a purification system. For example, light olefins, in particular produced in the MTO process, pass through a purification system to remove low levels of byproducts or contaminants. Non-limiting examples of contaminants and by-products generally include polar compounds such as water, alcohols, carboxylic acids, ethers, carbon dioxide, sulfur compounds such as hydrogen sulfide, carbonyl sulfides and mercaptans, ammonia and other nitrogen compounds, arsenic, phosphine and chlorides. Include. Other contaminants or by-products include hydrogen and hydrocarbons such as acetylene, methyl acetylene, propadiene, butadiene and butyne.
[112] Other recovery systems, including, for example, purification systems for the purification of olefins, are described in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition , Volume 9, John Wiley & Sons, 1996, pages 249-271. and 894-899. Purification systems are also described, for example, in US Pat. No. 6,271,428 (purification of diolefin hydrocarbon streams), US Pat. No. 6,293,999 (propylene separation from propane), and US application filed Oct. 20, 2000. Patent application 09 / 689,363 (purge stream using a hydration catalyst).
[113] Typically, when one or more oxygenates are converted to olefins of 2 to 3 carbon atoms, an amount of hydrocarbons, in particular olefins, especially olefins of 4 or more carbon atoms, and other byproducts are formed or produced. The recovery system of the present invention includes a reaction system for converting the product contained from the effluent gas withdrawn from the reactor or for converting the product produced as a result of the recovery system used.
[114] In one embodiment, the effluent gas withdrawn from the reactor to produce one or more hydrocarbon-containing stream, in particular having 3 or more carbon atoms (C ₃ ⁺⁾ hydrocarbon-containing stream through a recovery system. In this embodiment, the C ₃ ⁺ hydrocarbon containing stream passes through the first fractionation zone to produce a crude C ₃ hydrocarbon and C ₄ ⁺ hydrocarbon containing stream, and the C ₄ ⁺ hydrocarbon containing stream passes through the second fractionation zone to yield crude C To produce a stream containing ₄ hydrocarbons and a C ₅ ⁺ hydrocarbon. Hydrocarbons having 4 or more carbon atoms include butenes such as butene-1 and butene-2, butadiene, saturated butane, and isobutane.
[115] The effluent gas removed from the conversion process, in particular the MTO process, typically has a small amount of hydrocarbons having at least 4 carbon atoms. The amount of hydrocarbons having at least 4 carbon atoms is typically less than 20% by weight, preferably less than 10% by weight, more preferably less than 5% by weight, most preferably based on the total weight of the effluent gas withdrawn from the MTO process Is an amount of less than 2% by weight. Particularly in the case of the conversion of oxygenates to olefins using molecular sieve catalyst compositions, the resulting effluent gas typically contains large amounts of ethylene and / or propylene and small amounts of products having at least 4 carbon atoms and other by-products except water.
[116] Known reaction systems suitable as part of the recovery system take predominantly low cost products and convert them into expensive products. For example, the C ₄ hydrocarbons butene-1 and butene-2 are used to prepare alcohols with 8 to 13 carbon atoms and other specialized compounds, isobutylene is used to prepare gasoline additives, methyl-t-butylether, Butadiene is converted to butene-1 and butene-2 in the selective hydrogenation unit, butane is useful as a fuel. Non-limiting examples of reaction systems are described in US Pat. No. 5,955,640, which is incorporated herein by reference in its entirety. Conversion to butene-1), US Pat. No. 4,774,375 (isobutane and butene-2 oligomerized with alkylate gasoline), US Pat. No. 6,049,017 (dimerization of n-butylene), US Pat. Nos. 4,287,369 and 5 5,763,678 (carbonyl compounds prepared by carbonylation or hydroformylation with carbon dioxide and hydrogen of higher olefins), US Pat. No. 4,542,252 (multistage adiabatic process), US Pat. No. 5,634,354 (olefin-water Number of times), and the method disclosed in [Cosyns, J. et al., Process for Upgrading C3, C4 and C5 Olefinic Streams, Pet. & Coal, Vol. 37, No. 4 (1995)] (dimerization or oligomerization of propylene, butylene and pentylene).
[117] Preferred light olefins prepared by any of the processes described above, preferably by the conversion process, comprise a single carbon number olefin of greater than 80%, preferably greater than 90%, more preferably 95% by weight based on the total weight of the olefins. High purity base olefin products containing greater than% most preferably at least about 99% by weight. In one embodiment, the high purity base olefins are prepared at a rate of more than 5 kg / day, preferably 10 kg / day, more preferably 20 kg / day and most preferably 50 kg / day in the process of the present invention. In another embodiment, the high purity ethylene and / or high purity propylene is produced by the process of the present invention at a rate of 4,500 kg / day, preferably 100,000 kg / day, more preferably 500,000 kg / day, even more preferably 1,000,000 kg / Day, even more preferably 1,500,000 kg / day, and even more preferably 2,000,000 kg / day, most preferably 2,500,000 kg / day.
[118] Other conversion processes, in particular the conversion of oxygenates to one or more olefins in the presence of a molecular sieve catalyst composition, in particular where the molecular sieve is synthesized from a silicon-, phosphorus-, and alumina-source, are all eg US Pat. No. 6,121,503 (manufacturing plastics with olefin products having paraffin to olefin weight ratios of 0.05 or less), US Pat. No. 6,187,983 (electromagnetic energy to the reaction system), April 15, 1999 Published PCT WO 99/18055 (heavy hydrocarbons in effluent gas fed to other reactors), PCT WO 01/60770 published August 23, 2001 and US patent filed July 28, 2000 Application 09 / 627,634 (high pressure), US Patent Application No. 09 / 507,838 filed on February 22, 2000, staged feedstock injection, and US Patent Application Filed on February 16, 2001 09 / 785,409 (Acetone Simultaneous Supply) Includes those described.
[119] In one embodiment, an integrated process is indicated for preparing light olefins from a hydrocarbon feedstock, preferably a hydrocarbon gas feedstock, more preferably methane and / or ethane. The first step in the process is to pass the gaseous feedstock, preferably in combination with the water stream, into the syngas production zone to produce a synthesis gas (syngas) stream. Syngas production is well known and typical syngas temperatures are from about 700 ° C. to about 1200 ° C. and the new gas pressure is from about 2 MPa to about 100 MPa. The syngas stream is made from natural gas, petroleum liquids, and carbonaceous materials such as coal, recycled plastics, municipal waste or any other organic material, and preferably the syngas stream is produced through steam reforming of natural gas. In general, heterogeneous catalysts, typically copper-based catalysts, are contacted with a synthesis gas stream, typically carbon dioxide and carbon monoxide and hydrogen, to produce alcohols, preferably methanol, often with water. In one embodiment, the synthesis gas stream passes through a carbon dioxide conversion zone at a synthesis temperature of about 150 ° C. to about 450 ° C. and a synthesis pressure of about 5 MPa to about 10 MPa to produce an oxygenate containing stream.
[120] The oxygenate containing stream, or crude methanol, typically contains an alcohol product and various other components such as ethers, in particular dimethyl ether, ketones, aldehydes, dissolved gases such as hydrogen, methane, carbon dioxide and nitrogen, and fusel oils. In a preferred embodiment, the oxygenate containing stream, crude methanol is subjected to a known purification process, distillation, separation and fractionation to produce a purified oxygenate containing stream such as commercial Class A and AA methanol. The oxygenate containing stream or the purified oxygenate containing stream is optionally in contact with one or more diluents in contact with one or more of the molecular sieve catalyst compositions described above in any of the aforementioned processes, in particular light olefins, ethylene and / or the like. Or propylene. Non-limiting examples of such integrated processes are described in EP-B-0 933 345, which is incorporated herein by reference in its entirety. In another more fully integrated process, optionally with the integrated process described above, in one embodiment, the resulting olefins are directed to one or more polymerization processes to produce various polyolefins. (See, eg, US patent application Ser. No. 09 / 615,376, filed Jul. 13, 2000, which is incorporated herein by reference in its entirety).
[121] Polymerization processes include solution, gas phase, slurry phase, and high pressure processes, or combinations thereof. Especially preferred are gas phase or slurry phase polymerizations of at least one olefin in which at least one is ethylene or propylene. The polymerization process uses a polymerization catalyst which may comprise one or a combination of the aforementioned molecular sieve catalysts, but preferred polymerization catalysts are Ziegler-Natta, Phillips type, metallocene, metallo Sen type and advanced polymerization catalysts, and mixtures thereof. Polymers produced by the above-described polymerization process include linear low density polyethylene, elastomers, plastomers, high density polyethylene, low density polyethylene, polypropylene and polypropylene copolymers. Propylene-based polymers prepared by the polymerization process include atactic polypropylene, isotactic polypropylene, syndiotactic polypropylene, and propylene random, block or impact copolymers.
[122] In a preferred embodiment, the integrated process comprises polymerizing at least one olefin in a polymerization reactor in the presence of a polymerization catalyst system to produce at least one polymer product, wherein the at least one olefin uses a molecular sieve catalyst composition. Prepared by converting alcohols, in particular methanol. Preferred polymerization processes are gas phase polymerization processes, the at least one olefin is ethylene or propylene, 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 a combination thereof, Most preferably the activator is alumoxane.
[123] In addition to polyolefins, numerous other olefin derived products are formed from olefins recovered in the processes described above, in particular in the conversion process, more particularly in the GTO process or the MTO process. These are aldehydes, alcohols, acetic acid, linear alpha olefins, vinyl acetate, ethylene dichloride and vinyl chloride, ethylbenzene, ethylene oxide, cumene, isopropyl alcohol, acrolein, allyl chloride, propylene oxide, acrylic acid, ethylene-propylene rubber, and acrylic Ronitrile, and trimers and dimers of ethylene, propylene or butylene.
[124] In order to provide a better understanding of the present invention including representative advantages, the following examples are provided. The components of the mixture used in the blending catalyst generally contain volatile components, including but not limited to water, and, in the case of molecular sieves, organic templates. It is commonly practiced to describe the amount or fraction of such ingredients as being "calcination criteria". Calcination involves heating the material at an elevated temperature sufficient to dry and remove the volatile content contained in the presence of air (650 ° C. for at least one hour). “Calcination Criteria” is defined for the purposes of the present invention as the amount or fraction of each component remaining after being mathematically reduced in view of the weight loss expected to occur when the component is calcined. The term LOI (Loss-On-Ignition) is used herein interchangeably with fragment loss during calcination, “calcination criteria”. Thus, a 10 g component containing 25% of volatiles is described as "7.5 g on a calcination basis" with a LOI of 2.5 g. The synthesis of SAPO-34 molecular sieves is well known and the SAPO-34 used in the examples below was determined to have an MSA of about 550 m ² / g-molecular sieve.
[125] MSA is measured using Micromeritics Gemini 2375 manufactured by Micromeritics Instrument Corporation, Norcross, GA. Samples in amounts of 0.15 g to 0.6 g are loaded into the sample cell and degassed for at least 2 hours at 300 ° C. During the analysis, the discharge time is 1.0 minutes, free space is not used, and a sample density of 1.0 g / cc is used. 13 adsorption data points were collected with adsorption targets:
[126]
[127] The correction factor used for the t-plot is 0.975. Desorption points were not collected. Other analysis parameters include analysis mode: equilibration; Equilibration time: 5 seconds; Scan Speed: Includes 10 seconds. T-plot from 0.00000 to 0.90000 is ASTM certified form of Harkins and Jura equations (HJ model) [t (p) = (13.99 / (0.034-log (p / p ₀ ))) ^0.5 Configured using]. It is reported in Cape and Kiwi, J. Cape and CL Kibby, J. that conventional BET surface areas of microporous materials can be quantitatively decomposed into outer area and micropore volume, as expressed in the formula below. Colloids and Interface Science, 138, 516-520 (1990)]: S _micro = S _tot -S _ext = ν _m / d _j where ν _m is the micropore volume and S _micro is S _tot and The micropore area calculated from S _ext , S _tot is given by the usual BET method, S _ext is the external area taken from the t-plot, and d _j is the nonphysical value whose value depends on the pressure used in the experiment. The proportional factor d _j is quantitatively determined by the pressure used for the BET pits.
[128] For the purposes of this patent application and the appended claims, the “solid content” is measured by weighing slurry samples, calcining slurry samples preferably at 550 ° C. to 750 ° C., and reweighing the calcined samples. ; The solids content is equal to the calcined sample weight divided by the weight of the slurry sample and multiplied by 100.
[129] Example 1
[130] The slurry was mixed by mixing 45.8 kg of SAPO-34 molecular sieve containing mold (46.6% Loss of Burning (LOI)) with 25.1 kg of deionized water under vigorous stirring conditions at 60-300 rpm for 2 hours using a turbo-blade mixer. And the solids are totally destroyed. The mixture was subjected to a high shear mixing step for two passes, which depended on size reduction, using a Silverson high-shear in-line mixer. The particle size analysis of the single pass high shear treated slurry is given in Table 1.
[131] Example 2
[132] 13.4 kg of aluminum chlorohydrate (available from Reheis, Berkeley Heights, NJ) (LOI: 51.6%) is obtained for 0.2 to 12 hours at 60 to 300 rpm using a turbo-blade mixer or when a translucent sol is obtained. A slurry of aluminum chlorohydrate was prepared by adding to 12.5 kg of deionized water. The aluminum chlorohydrate sol was then added to the slurry of Example 1 using a feed pump and mixed for 0.2 to 5 hours followed by the addition of kaolin clay (ASP grade available from Angelhard Corporation, Macon, GA). It was. 35.1 kg of kaolin clay (LOI: 13.9%) and 4.2 kg of additional deionized water were added to the mixture of SAPO-34 molecular sieve and aluminum chlorohydrate. The resulting mixture was mixed for 2 hours at 60-300 rpm using a turbo-blade mixer and then passed through a high shear inline mixer twice. This slurry was aged with constant mixing at 60-300 rpm for 15 hours using a turbo-blade mixer in a feed tank at 40 ° C. Particle size analysis of the aged slurry is shown in Table 1.
[133]
[134] Example 3
[135] The IEP of the material used in the formulation of the catalyst composition was determined from the measurement of zeta-potential using a Matek ESA 9800 Electrokinetic Apparatus, available from Martec Applied Sciences, Northboro, Massachusetts. Zeta-potential is calculated from the measurement of ultrasonic signals generated by bending doubles of colloidal particles in the high frequency ac field. The ultrasonic signals are converted to zeta-potential values to obtain particle size, particle density, and volume fraction of suspended solids.
[136] Example 4
[137] Particle size dependence as a function of pH of very dilute slurry (less than 1% by weight) of colloidal silicalite with an average particle size of 60 to 70 nm was determined using Zeta Sizer 3000 (Malvern Instrument as above). Determined by. At pH away from the IEP, the silicalite particles were in the form of individual particles. However, the individual particles aggregated to 1.45 μm when the pH was adjusted near the IEP (25-30 times larger than the primary particle size).
[138]
[139] Example 5
[140] The slurry was prepared as in Examples 1 and 2, but the weight ratio of molecular sieve to aluminum chlorohydrate and kaolin clay was 40 / 10.6 / 49.4, using a slurry of SAPO-34 molecular sieve (B) to make the total solid content 44.5%. Was maintained. Viscosity, pH, and particle size measurements of this Example 5 are given in Table 2.
[141] Example 6
[142] As in Examples 1 and 2, however, a slurry was prepared using SAPO-34 molecular sieve (C) to bring the weight ratio of molecular sieve to aluminum chlorohydrate and kaolin clay to 40 / 10.6 / 49.4 with a total solids content of 44.8%. Maintained. The viscosity, pH, and particle size measurements of this Example 6 are given in Table 2.
[143] Example 7
[144] The slurry was prepared using the same composition and procedure as in Example 6 and the pH was raised from 3.7 to 4.2 using diluted aqueous ammonia solution. The viscosity, pH, and particle size measurements of this Example 7 are given in Table 2.
[145] Example 8
[146] As in Examples 1 and 2, however, a slurry was prepared using SAPO-34 molecular sieve (D) to maintain a total solids content of 46.9% while maintaining the weight ratio of molecular sieve to aluminum chlorohydrate and kaolin clay at 40 / 10.6 / 49.4. I was. The viscosity, pH, and particle size measurements of this Example 8 are given in Table 2.
[147] Example 9
[148] Zeta-potential measurement after calcining at 550 ° C. for 5 hours in air of SAPO-34 molecular sieve (A) used in Example 2. It has been found that the presence of the template in SAPO-34 results in a substantially lower IEP pH than SAPO-34 without the template.
[149] Example 10
[150] The slurry prepared in Example 5 was spray dried using a laboratory-scale spray dryer (Yamato DL-41, available from Yamato Scientific America, Inc., Orangeburg, NY). The slurry feed rate was 40-50 g / min, the inlet temperature was 350 ° C., the product temperature was 80-85 ° C. and the atomization pressure was 1 bar. The spray dried product was calcined at 650 ° C. This catalyst composition of this Example 10 had an ARI of 0.33.
[151] Comparative Example 11
[152] In contrast to the present invention, typical commercial FCC catalysts such as W.R. The Grace Ultima 447 catalyst has an ARI of 7.94.
[153] Comparative Example 12
[154] A slurry was prepared in the same manner as in Example 8, and the pH thereof was raised to 4.5 to 4.6 using a diluted ammonia solution (5 to 15% by weight). It precipitated and solidified when the pH of the mixture reached about 4.6. The target pH value approached the IEP of the SAPO-34 molecular sieve of Example 9, thus destabilizing the slurry. The resulting material could not be spray dried.
[155] Example 13
[156] The slurry prepared in Example 6 was spray dried using a laboratory-scale spray dryer (Yamato DL-41). The slurry feed rate was 40-50 g / min, the inlet temperature was 350 ° C., the product temperature was 80-85 ° C., and the atomization pressure was 1 bar. The spray dried catalyst composition was calcined at 650 ° C. for 1 hour. This blended molecular sieve catalyst composition had an ARI of 0.32.
[157] Example 14
[158] The slurry prepared in Example 7 was spray dried using a laboratory-scale spray dryer (Yamato DL-41). The slurry feed rate was 40-50 g / min, the inlet temperature was 350 ° C., the product temperature was 80-85 ° C., and the atomization pressure was 1 bar. The spray dried catalyst composition was calcined at 650 ° C. for 1 hour. This blended molecular sieve catalyst composition had an ARI of 0.41.
[159] Example 15
[160] The slurry prepared in Example 8 was spray dried using a laboratory-scale spray dryer (Yamato DL-41). The slurry feed rate was 40-50 g / min, the inlet temperature was 350 ° C., the product temperature was 80-85 ° C., and the atomization pressure was 1 bar. The spray dried catalyst composition was calcined at 650 ° C. for 1 hour. This blended molecular sieve catalyst composition had an ARI of 0.29.
[161] While the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will recognize that the invention provides modifications that are not necessarily illustrated herein. For example, molecular sieve catalyst compositions can be used for the inter-conversion of olefins, the conversion of oxygenates to gasoline, maleic anhydride, phthalic anhydride and acrylonitrile blends, vapor phase methanol synthesis, and various Fischer Tropsch It is considered useful for the reaction. It is also contemplated that plug flow, fixed bed or fluidized bed processes are used in combination, in particular in different reaction zones in single or multiple reactor systems. It is also contemplated that the molecular sieve catalyst compositions described herein are useful for absorbents, adsorbents, gas separators, detergents, water purifiers, and various other applications such as agriculture and horticulture. It is also contemplated that the molecular sieve catalyst composition comprises one or more other molecular sieves in combination. For this reason, reference should only be made to the appended claims for purposes of determining the true scope of the invention.

权利要求:
Claims (25)
[1" claim-type="Currently amended] Combining the molecular sieve, the binder, the liquid medium, and optionally the matrix material, to form a slurry having a pH higher or lower than the isoelectric point (IEP) of the molecular sieve.
[2" claim-type="Currently amended] The method of claim 1,
A method of making a molecular sieve catalyst composition, wherein the molecular sieve is synthesized from two or more combinations selected from the group consisting of a silicon source, a phosphorus source and an aluminum source, optionally in the presence of a template.
[3" claim-type="Currently amended] The method according to claim 1 or 2,
A method of making a molecular sieve catalyst composition wherein the slurry has a pH of 2.3 to 6.5.
[4" claim-type="Currently amended] The method according to any one of claims 1 to 3,
A method of making a molecular sieve catalyst composition further comprising spray drying the slurry.
[5" claim-type="Currently amended] The method according to any one of claims 1 to 4,
A process for preparing a molecular sieve catalyst composition wherein the pH of the slurry is at least 0.3 higher or lower than the IEP of the molecular sieve.
[6" claim-type="Currently amended] The method according to any one of claims 1 to 5,
A method of making a molecular sieve catalyst composition wherein the binder has an IEP of greater than 9 and the matrix material has an IEP of less than about 2.
[7" claim-type="Currently amended] The method according to any one of claims 1 to 6,
A method of making a molecular sieve catalyst composition wherein the molecular sieve catalyst composition has an ARI of less than 2% by weight / hour after calcination.
[8" claim-type="Currently amended] The method according to any one of claims 1 to 7,
A method of making a molecular sieve catalyst composition wherein the pH of the slurry is lower than the IEP of the molecular sieve or the pH of the slurry is lower than the IEP of the molecular sieve and the IEP of the binder.
[9" claim-type="Currently amended] The method according to any one of claims 1 to 8,
A process for preparing a molecular sieve catalyst composition wherein the IEP of the molecular sieve is about 3-7.
[10" claim-type="Currently amended] The method according to any one of claims 1 to 9,
(a) introducing molecular sieves into the liquid medium to form a slurry; (b) adding a binder to the slurry; (c) A method for producing a molecular sieve catalyst composition, in which the molecular sieve, the binder and the matrix material are combined in the order of adding the matrix material to the slurry.
[11" claim-type="Currently amended] The method according to any one of claims 1 to 10,
A method of making a molecular sieve catalyst composition, wherein both of the molecular sieve and the binder have a positive charge at the pH of the slurry.
[12" claim-type="Currently amended] The method according to any one of claims 1 to 11,
A process for preparing a molecular sieve catalyst composition wherein the matrix material has a negative charge at the pH of the slurry.
[13" claim-type="Currently amended] The method according to any one of claims 1 to 12,
Each of the slurry components consisting of molecular sieves, binders and matrix materials have a charge density and molecular sieves introduced to each other such that slurry components with the highest charge density per unit mass are added to the slurry components with lower charge density per unit mass. Process for the preparation of the catalyst composition.
[14" claim-type="Currently amended] The method according to any one of claims 1 to 13,
A process for preparing a molecular sieve catalyst composition wherein the pH of the slurry is lower than the IEP of the molecular sieve.
[15" claim-type="Currently amended] The method according to any one of claims 1 to 14,
The molecular sieve is a silicoaluminophosphate or aluminophosphate molecular sieve, preferably SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, metal containing forms thereof And one or combination of these intergrowth forms.
[16" claim-type="Currently amended] The method according to any one of claims 1 to 15,
A process for preparing a molecular sieve catalyst composition wherein the binder is an alumina sol, preferably aluminum chlorohydrate.
[17" claim-type="Currently amended] The method according to any one of claims 1 to 16,
A process for preparing a molecular sieve catalyst composition wherein the matrix is clay.
[18" claim-type="Currently amended] The method according to any one of claims 1 to 17,
A process for preparing a molecular sieve catalyst composition wherein the liquid medium is water.
[19" claim-type="Currently amended] 19. A process for converting a feedstock into at least one olefin in the presence of a blended molecular sieve catalyst obtained according to the method of any one of claims 1-18.
[20" claim-type="Currently amended] The method of claim 19,
Wherein the feedstock comprises at least one oxygenate.
[21" claim-type="Currently amended] The method of claim 19 or 20,
Conversion of the feedstock to at least one olefin is carried out in a reactor system, further comprising withdrawing the effluent stream from the reactor system and passing the effluent gas through a recovery system to recover at least one olefin. .
[22" claim-type="Currently amended] The method according to any one of claims 19 to 21,
Introducing the molecular sieve catalyst composition into the regeneration system to form a regenerated molecular sieve catalyst composition and introducing the regenerated molecular sieve catalyst composition into the reaction system.
[23" claim-type="Currently amended] The method according to any one of claims 19 to 22,
Wherein the feedstock comprises methanol, the olefin comprises ethylene and propylene, and the molecular sieve is silicoaluminophosphate.
[24" claim-type="Currently amended] As a method of converting a feedstock into at least one olefin,
(i) producing the feedstock by passing one or more hydrocarbons through a syngas production zone to produce a synthesis gas stream;
(ii) contacting the synthesis gas stream obtained in step (i) with a catalyst to form a feedstock comprising at least one oxygenate;
(iii) converting the feedstock comprising at least one oxygenate obtained in step (ii) into at least one olefin according to the method of any of claims 19-22.
[25" claim-type="Currently amended] The method according to any one of claims 19 to 24,
(iv) polymerizing the at least one olefin in the presence of a polymerization catalyst to produce a polyolefin.

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同族专利:

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公开号 | 公开日

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ZA200309671B|2005-02-23|

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DE60222559D1|2007-10-31|

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BR0210670A|2004-10-13|

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DE60218673D1|2007-04-19|

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KR100886532B1|2009-03-02|

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CN1239262C|2006-02-01|

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AT373517T|2007-10-15|

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EP1412084B1|2007-09-19|

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WO2003000412A1|2003-01-03|

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CN1535177A|2004-10-06|

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JP4781627B2|2011-09-28|

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EP1401573B1|2007-03-07|

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NO20035656D0|2003-12-17|

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NO20035656L|2004-02-20|

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EP1401573A1|2004-03-31|

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EP1412084A1|2004-04-28|

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WO2003000413B1|2003-03-06|

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JP2004537398A|2004-12-16|

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CA2451667C|2012-03-27|

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AU2002350150B2|2008-02-07|

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CA2451667A1|2003-01-03|

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AT355904T|2007-03-15|

---

WO2003000413A1|2003-01-03|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-06-25|Priority to US09/891,674

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2001-06-25|Priority to US09/891,674

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2002-01-17|Priority to US10/052,058

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2002-01-17|Priority to US10/052,058

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2002-03-20|Priority to US60/365,981

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2002-03-20|Priority to US60/365,902

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2002-03-20|Priority to US36598102P

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2002-03-20|Priority to US36590202P

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2002-06-24|Application filed by 엑손모빌 케미칼 패턴츠 인코포레이티드

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2002-06-24|Priority to PCT/US2002/019869

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2004-02-11|Publication of KR20040012973A

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2007-12-07|First worldwide family litigation filed

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2009-03-02|Application granted

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2009-03-02|Publication of KR100886532B1

优先权:

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申请号 | 申请日 | 专利标题

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US09/891,674|US6440894B1|2001-06-25|2001-06-25|Methods of removing halogen from non-zeolitic molecular sieve catalysts|

---

US09/891,674|2001-06-25|

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US10/052,058|US6710008B2|2002-01-17|2002-01-17|Method of making molecular sieve catalyst|

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US10/052,058|2002-01-17|

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US36598102P| true| 2002-03-20|2002-03-20|

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US36590202P| true| 2002-03-20|2002-03-20|

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US60/365,981|2002-03-20|

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US60/365,902|2002-03-20|

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PCT/US2002/019869|WO2003000412A1|2001-06-25|2002-06-24|Molecular sieve catalyst composition, its making and use in conversion processes|