TW200303237A - Molecular sieve compositions, catalyst thereof, their making and use in conversion processes - Google Patents

Abstract

The invention relates to a catalyst composition, a method of making the same and its use in the conversion of a feedstock, preferably an oxygenated feedstock, into one or more olefin(s), preferably ethylene and/or propylene The catalyst composition comprises a molecular sieve and at least one oxide of a metal from Group 4, optionally in combination with at least one metal from Groups 2 and 3, of the Periodic Table of Elements.

Description

200303237 (1) (ii) Comparison of related applications of invention description This case claims 35 USC 120 for US provisional application serial number 6 0/3 6 0,96 3 (filed on February 28, 2002) and US provisional application serial number 60 / 3 66,012 (filed on March 20, 2002) priority, and US application serial number 60 / 374,697 (Attorney Docket 2002B05 7) and US application serial number i〇 / 2i 5,511 (Attorney Docket 2〇02B) 106) Related, the entire contents of these applications are incorporated herein by reference. [Technical field to which the invention belongs] The present invention relates to a molecular sieve composition and a catalyst containing the same, the composition of the composition and the catalyst, and the composition Use of catalysts and catalysts in conversion processes for the preparation of olefins. [Prior art] Fine hydrocarbons are prepared by conventional methods from petroleum feedstocks by catalyst or black gas cracking methods. These cracking methods, especially steam cracking, produce light olefins' such as ethylene and / or propylene from various hydrocarbon feeds. Ethylene and propane are important petrochemical commodities for various methods used to make plastics and other chemical compounds. The conversion of oxygenates, especially alcohols, to light olefins has been well known in the petrochemical industry for some time. There are many techniques used to prepare oxygenates, which include reactions of fermentation or synthesis gas derived from natural gas, -6-(2) 00303237 petroleum liquid or coal-containing carbon materials, recycled plastics, local Waste or any other organic substance. Generally, synthesis gas production involves the combustion reaction of natural gas (mostly methane) with an oxygen source to form hydrogen, carbon monoxide, and / or carbon dioxide. Other known synthesis gas preparation methods include conventional steam reforming, autothermal reforming, or a combination thereof. Methanol, the preferred alcohol for the production of lightly combusted hydrocarbons, is typically prepared in a methanol reactor and in the presence of a heterogeneous catalyst by a catalytic reaction of hydrogen, carbon monoxide and / or carbon dioxide. For example, in a synthetic method, methanol is prepared in a water-cooled tubular methanol reactor using a copper / zinc oxide catalyst. A preferred method of converting a methanol-containing feed to one or more olefins (mainly ethylene and / or propylene) comprises contacting the feed with a molecular sieve catalyst composition. Molecular sieves are porous solids with pores of different sizes, such as zeolites or zeolite-type molecular sieves, carbon and oxides. The most commonly used molecular sieves in the petroleum and petrochemical industries are zeolites, such as aluminum silicate molecular sieves. Zeolites usually have a 1-, 2-, or 3-dimensional crystalline pore structure with a molecular size of pores of uniform sentence size, which selectively adsorb molecules that can enter the pores, and exclude molecules that are too large. Various types of molecular sieves are known for converting feeds, particularly feeds including oxygenates, to one or more olefins. For example, u S 5,3 6,7,0 0 describes the use of zeolite (ZSM-5) to convert methanol to olefins; US 4,0 6,2,90 5 discusses the use of crystalline aluminosilicate zeolites, such as zeolite T, ZK 5, erionite (1 *! 〇1 ^ 6) and samarium zeolite (〇1 ^ 6 & 2 ^) to convert methanol or other oxygenates to ethylene and propylene; US 4,0 7 9,09 5 description ZSM-34 was used to convert methanol to (3) (3) 200303237 for hydrocarbon products 'such as ethylene and propylene; and u S 4,3 1 ο, 4 4 0 describes the use of crystalline phosphonic acid salt' is usually not labeled as A1P 0 4. Preparation of lightly burned hydrocarbons from alcohols. Some of the most useful molecular sieves for conversion of methanol to olefins are silicoaluminophosphate molecular trims. The flaming phosphate (SAPO) molecular sieve includes a three-dimensional microporous crystalline skeleton structure that shares [Si〇4], [Al〇4], and [P〇4] corners of a tetrahedral unit. SAPO synthesis is described in US 4,440,871, which is fully incorporated herein by reference. SAPO molecular sieves are usually synthesized by hot-water crystallization of a reaction mixture of silicon-, aluminum-, and phosphorus sources, and at least one template agent. Synthesis of S AP 0 molecular sieves, its deployment as S ΑΡ Ο catalyst, and its use to convert hydrocarbon feedstocks to olefins, especially the feedstock is methanol, disclosed in US 4,49 9,3 2 7, 4,677,242, 4,677,243 , 4,8 73,3 90, 5,0 9 5,163, 5,7 1 4,6 6 2 and 6, 1 6 6,2 8 2, all of which are fully incorporated herein by reference. Molecular sieves are typically formulated with molecular sieve catalyst compositions to improve their durability in industrial conversion methods. These molecular sieve catalyst compositions are obtained by mixing a molecular sieve and a matrix substance usually in the presence of an adhesive. The purpose of the adhesive is to bind the matrix material (usually clay) with the molecular sieve. Although it is known to use adhesives and matrix materials to form molecular sieve catalyst compositions for conversion of oxygenates to olefins, these adhesives and matrix materials are typically only suitable to provide the desired physical properties to the catalyst composition. Therefore, an improved molecular coating catalyst composition having a better conversion rate, improved hydrocarbon selectivity, and longer lifetime is desired. US 4,4 6 5,8 8 9 describes a catalyst composition comprising a molecular sieve filled with hafnium, zirconium or titanium metal oxide silicate, which is used to make methanol, dimethyl ether-8- (4) ( 4) 200303237 or a mixture thereof is converted into a hydrocarbon product rich in iso-C4 compounds. US 6,18 0,8 2 8 discusses the use of modified molecular sieves to prepare methylamine from methanol and ammonia, such as silicoaluminophosphate molecular sieves mixed with one or more modifiers such as chromium oxide, titanium oxide, yttrium oxide, montmorillonite Or kaolin. US 5,41 7,949 is a method for converting toxic nitrogen oxides present in oxygen-containing effluent to nitrogen and water using molecular sieves and metal oxide adhesives. The preferred adhesive is titanium dioxide and the molecular sieve is aluminum silicate. . EP-A-3 1 298 1 discloses a method for cracking a vanadium-containing smoke feed stream using a catalyst composition on a silica-containing carrier material, the composition comprising a zeolite and at least one beryllium embedded in an inorganic refractory matrix material , Magnesium, calcium, scandium, barium or lanthanum oxides.

Kang and Inui, Effects of decrease in number of acid sites located on the external surface of Ni-SAPO-34 crystalline catalyst by the mechanochemical method, Catalyst Letters 53, pages 171-176 (1998) revealed that the use of Ni-SAPO-34 In the conversion of methanol to ethylene, the shape selectivity can be increased, and the formation of coke can be slowed. The Ni-SAPO-34 is made by honing the catalyst with MgO, CaO, BaO, or Cs20 on microsphere nonporous silica. B a 0 is the best. W 0 9 8/2 9 3 7 0 reveals the conversion of oxygenates to olefins through a small pore non-zeolitic molecular sieve, the molecular sieve comprising a member selected from the group consisting of lanthanides, actinides, samarium, yttrium, a Group 4 metal, a Group 5 Group metals or mixtures thereof. [Summary of the Invention] -9-(5) 200303237 It is stated that the present invention resides in a catalyst composition containing a molecular sieve and at least one oxide selected from the Group 4 metal of the periodic table, wherein the metal oxide The intake of carbon dioxide is at least 0.0 3 mg / m2 metal oxide at loo r, and typically at least 035 mg / m2 metal oxide. The catalyst composition also includes at least one adhesive and matrix material different from the metal oxide. • The catalyst composition also includes oxides of metals selected from Groups 2 and 3 of the periodic table. In an embodiment, the Group 4 metal oxide includes chromium oxide, and the Group 2 and / or Group 3 metal oxides include one or more selected from the group consisting of oxidation loss, barium oxide, lanthanum oxide, oxidized oxide, and hafnium oxide. Oxide. Molecular sieves desirably include a framework containing at least two tetrahedral units, such as silicoaluminophosphates, the unit being selected from [Si04], [AlO4], and [P04] units. In another aspect, the present invention resides in a molecular sieve composition comprising a lively and swollen Group 4 metal oxide and a Group 2 and / or Group 3 metal oxide, an adhesive, a matrix substance, and a silicoaluminophosphate molecular sieve . In another aspect, the present invention resides in a method for preparing a catalyst composition, the method comprising completely mixing a first particle containing a molecular sieve and a second particle containing a Group 4 metal oxide. Carbon dioxide intake: at least 0.03mg / m2 metal oxide particles at 100 ° C. In one embodiment, molecular sieves, adhesives and matrix substances are prepared as -10- (6) 200303237 once formulated molecular sieve composition The composition is then optionally contacted with a live Group 4 metal oxide, such as a live chromium metal oxide and / or a live donor metal oxide, in the presence of a Group 2 and / or Group 3 metal oxide. , Mixing, combining, spray drying. In another aspect, the invention resides in a method for preparing a catalyst composition, the method comprising: (i) synthesizing a molecular sieve from a reaction mixture, the mixture including at least one template agent and at least two of a silicon source, a phosphorus source, and an aluminum source ; And (ii) recovering the molecular sieve synthesized in (i); (iii) forming a group 4 metal oxide hydrated precursor by precipitating from a solution containing a source of a group 4 metal ion; (iv) ) Recovering the hydrated precursor formed in (iii); (v) calcining the hydrated precursor recovered in (iv) to form a Group 4 metal oxide which is subjected to calcination; Charge at least 0.03 mg / m2 metal oxide at 100 ° C; and (vi) completely mix (the molecular sieve recovered in 0 and the calcined metal oxide prepared in (v). In In another aspect, the present invention relates to a method for preparing an olefin, which is carried out by converting a feed, such as an oxygenate, suitably an alcohol, in the presence of any of the above molecular sieve compositions, or molecular sieves, or a formulated molecular sieve catalyst composition Class, such as methanol. In a viewpoint, the present invention relates to a method for converting a feedstock into one or more olefins in the presence of a molecular sieve catalyst composition, which composition includes a molecular sieve, an adhesive, a matrix material, and gold-11-which is different from the adhesive and the matrix material. (7) 200303237 is a mixture of oxides. In one embodiment, the lifetime increase index (L EI) of the catalyst composition is greater than 1 ', such as greater than 1.5. LEI is defined herein as The life ratio of the same catalyst composition of active metal oxides is 値.

Detailed description of the examples

The present invention relates to a molecular sieve catalyst composition and its use for converting hydrocarbon feeds, especially oxidized feeds, to olefins. It has been found that mixing molecular sieves with one or more active metal oxides results in a catalyst composition having increased olefin yield and / or longer lifespan when used to switch feeds, such as oxygenates, and more specifically methanol, to Olefin. In addition, the resulting catalyst composition tends to be more selective for propylene, and tends to produce smaller amounts of unwanted ethane and propane and other unwanted compounds such as aldehydes and ketones', especially acetic acid.

Preferred active metal oxides are those compounds having a Group 4 metal from the Periodic Table of the Elements (e.g., Cr and G), as described in the CRC Handbook of Chemistry and Physics, 78th Edition, CRC

Press, Boca Raton, Florida (1 997) IUPAC format. In some cases, it has been found that improved results are obtained when the catalyst composition also includes an oxide of at least one metal selected from Group 2 and / or Group 3 of the periodic table. Molecular sieves -12- (8) 200303237 Molecular sieves have been classified by the Structure Commission of the International Zeolite Association based on the IUPAC Commission on Zeolite Nomenclature. Based on this classification, structural zeolites and zeolite molecular sieves whose structures have been identified, are assigned to three letters and are described in Atlas of Zeolite Framework Types, 5th edition, Elsevier, London, England (2001), which is incorporated herein. Reference.

Crystal molecular sieves all have a three-dimensional, four-linked skeleton structure with a shared angle [T04] tetrahedron, where T is a cation coordinated by any tetrahedron. Molecular sieves are typically described in terms of ring sizes that define pores, where size is calculated as the number of T atoms in the ring. Other architectural features include the arrangement of the rings that form the cage, and, when present, the size of the aisle, and the space between the cages. See van Bekkum, et a 1., Introduction to Zeolite Science and Practice, Second Completely Revised and Expanded Edition, Volumne 137, pages 1-67, Elsevier Science, BV, Amsterdam, Netherlands (200 1). Non-limiting examples of molecular sieves Small pore molecular sieve, 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 their substituted forms; intermediate hole molecular shop, AF Ο, AEL, EU Ο, Η EU, FER, MEL, MFI, MTW, MTT, TON and their substituted forms; and large holes Molecular sieves, EMT, FAU and their substituted forms. Other molecular sieves include ANA, BEA, CFI, CLO, DON, GIS, LTL, -13- (9) (9) 200303237 MER, MOR, MWW and SOD. Non-limiting examples of preferred molecular sieves, especially for conversion of feeds including oxygenates to olefins 'including AEL' AFY, AEI, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM, and TON ° In a preferred embodiment, the molecular sieve of the present invention has AEI topology or CHA topology, or a combination thereof, and most preferably is CHA topology. Small, middle, and large-pore molecular sieves are available in a range from heart rings to 12-rings or larger. In a preferred embodiment, the zeolite molecular sieve has an 8-, 10-, or 12-ring structure, and the average pore size ranges from about 3A to 15A. In a more preferred embodiment, the molecular slab, preferably a sarcosine molecular salt ornament, has '8-rings and an average pore size of less than about 5 A', such as in a range from 3 A to about 5 people, such as from 3 people. To 4.5 people, and especially from 3.5A to about 4.2A. The molecular store has a molecular structure that shares 1, preferably 2 or more, corner [T04] tetrahedral units, more preferably 2 or more [Si04], [Α1〇4], and / or [P04] tetrahedrons Body unit, and most preferably [Si04], [Α104] and / or [Ρ04] tetrahedron unit. These silicon, aluminum and phosphorus-based molecular sieves and their metal-containing derivatives have been described in detail in several publications including, for example, US 4,4567,029 (Me ΑΡΟ where Me is Mg, Mη, Zη Or Co), US 4,440,87 1 (S AP Ο), EP-A-0 1 5 9 6 2 4 (ELAPSO where El is A s, B e, B, C r, C o, G a, G e , F e, Li, M g, M η, Ti or Zn), US 4,5 5 4,1 4 3 (FeAPO), US 4,8 22,4 7 8 ^ 4,6 8 3,2 1 7, 4,744, 8 8 5 (FeAPSO), EP-A-0 1 5 89 7 5 and US 4, 9 3 5, 2 1 6 (ZnAPSO), EP-A-0 1 6 1 4 89 (CoAPSO) , EP-A-0 1 5 89 76 (ELAPO where EL is Co, Fe, Mg, Mn, Ti or Zn) (10) 200303237 (10)

, US 4,3 1 0,440 (AlP〇4), EP-A-0 1 5 83 5 0 (SENAPO), US 4,973,460 (LiAPSO), US 4,78 9,5 3 5 (Li APO), US 4, 9 92,25 0 (GeAPSO), US 4,888, 167 (GeAPO) > US 5,057,295 (BAPSO), US 4,7 3 8,8 3 7 (CrAPSO), US 4,759,919 and 4,851,106 (CrAPO), US 4 , 75 8,4 1 9 \ 4,8 8 2,03 8, 5,43 4,3 26 and 5,4 7 8,78 7 (MgAPSO), US 4,554.143 (FeAPO), US 4,894,213 (AsAPSO), US 4,913,888 (AsAPO), US 4,6 8 6,092, 4,8 46,9 5 6 and 4,793,833 (MnAPSO), US 5,3 4 5,0 1 1 and 6, 1 5 6,93 l (MnAPO), US 4,73 7,3 5 3 (BeAPSO), US 4,940,5 70 (BeAPO), US 4,8 0 1,3 09, 4,684,6 1 7 and 4,8 8 0,520 (TiAPSO), US 4,500,651 '4 , 5 5 1,23 6 and 4,60 5 > 492 (Ti APO), US 4,8 24,5 5 4, 4,744,970 (CoAPSO), US 4,73 5,8 06 (GaAPSO), EP-A -0293 93 7 (QAPSO where Q is a framework oxide unit [Q〇2]), and US 4,567,029, 4,686,093, 4,781,814, 4,793,984, 4,801,364, 4,853,197, 4,917,876, 4,952,384, 4,9 5 6, 1 64 '4,9 56,165, 4,9 7 3,7 8 5, 5,24 1,0 93 '

5,493,066 and 5,675,050, all of which are incorporated herein by reference. Other molecular sieves include those described in R. Szostal, Handbook of Molecular Sieves, Van Nostrand Reinhold, New York, New York (199.2), which is incorporated herein by reference. More preferred molecular sieves include aluminum phosphate (A1P 0) molecular sieves and silicon aluminum phosphate (SAPO) molecular sieves and substituted, preferably metal substituted, A1PO and S AP0 molecular sieves. The best molecular sieves are sAP 0 molecular sieves, and S AP 0 molecular sieves substituted with metal -15- (11) (11) 200303237. In one embodiment, the metal is a Group 1 alkali metal in the periodic table, a group 2 alkaline earth metal in the periodic table, and a group 3 rare earth metal in the periodic table. The rare earth metal includes lanthanides: lanthanum, thallium,鐯, hinge, 钐, 铕, 釓, 钺, 钺, 镝, bait, watch, mirror, and distillate; and 铳 or yttrium, transition metals of groups 4 to 12 of the periodic table, or a mixture of any of these metal types . In a preferred embodiment, the metal system is selected from the group consisting of C0, Cr, Cu, Fe, Ga, Ge, Mg, Mη, Ni, Sη, Ti, Zη, and Zr, and mixtures thereof. . In another preferred embodiment, the metal atoms discussed above are inserted into the structure of the molecular sieve through a tetrahedral unit, such as [Me02], and have a net charge depending on the valence state of the metal substituent. 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 between -2 and +2. In one embodiment, the molecular sieve, as described in the aforementioned US patent case, is expressed in an anhydrous experimental formula: mR: (MxAlyPz) 〇 2 where R represents at least one template agent, preferably an organic template agent; m is R with respect to the number of moles per mole (MxAlyPz) 02, and from 0 to 1, preferably from 0 to 0.5, and most preferably from 0 to 0.3; x'y and Z represent acting as tetrahedral oxides Mo's fractions of Al, P, and M ', where M is a metal selected from the group consisting of elements in the periodic table], 2, 3, 4, 5, 6, 7, 8, 9, 10, -16- (12) 200303237 1 Groups 1, 1, 2, 1, 3, 1 and lanthanides, preferably, M is selected from Si, Co, Cr, Cu, Fe, Ga, Ge, Mg , M η, Ni, S η, T i, Z η, and Zr. In one embodiment, m is greater than or equal to 0.2, and x, y, and z are greater than or equal to 0.01. In another embodiment, m is greater than 0.1 to about 1, X is greater than 0 to about 0.25, y ranges from 0.4 to 0.5, and ζ ranges from 0.25 to 0.5, and more preferably, m ranges from 0.15 to 0.7, X from 0.01 to 0.2, 乂 from 0.4 to 0.5, and ζ from 0.3 to 0.5.

Non-limiting examples of S APO and A1PO molecular sieves used in this article include SAPO-5, SAPO-8, SAPO-11, SAP 0-16, SAP 0-17, S APO-1 8, SAPO-20, SAPO-31 , SAPO-34, S APO-3 5, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (US 6, 1 62, 4 1 5), S APO-47 , S APO-56, A1P0-5, A1P0-11, A1P0-1 8, A1P0-3 1, A1PO-34, A1P0-3 6, A1PO-37, A1PO-46 and one of metal-containing molecular sieves Or combination. Particularly useful molecular sieves are SAP 0-18, SAP 0-34,

S APO-3 5 'SAPO-44, SAPO-56, A1P0-18 and A1PO-34 and one or a combination of metal-containing derivatives thereof, such as SAPO-18, SAPO-34, A1PO-34 and A1P0 One or a combination of -18 and a metal-containing derivative thereof, and in particular, one or a combination of SAPO-34 and A1P0-18 and a metal-containing derivative thereof. In one embodiment, the molecular sieve is a substance having two or more distinct crystal phases in a molecular sieve composition. In particular, inter-growth molecular sieves are described in U.S. Patent Application Serial Nos. 0 9/9 2 4, 0 1 6 and 19 1 98 published on August 7, 2001. 0 9 8/1 5 4 9 6 -17- (13) 200303237, both of which are incorporated herein by reference. For example, SAPO-18, A1PO-18, and RUW-18 have AEI architecture, and SAPO-34 has CHA architecture. Therefore, the molecular sieves used in this article include at least one AEI and CHA structure with interactive growth phases, especially the ratio of CHA structure to AEI structure is greater than 1: 1, which is based on the US patent filed on August 7, 2001. The D IF F a X method described in application number 09/9 2 4, 0 16 was used for measurement. Molecular sieves Beta molecular sieves are synthesized in most of the sources discussed above. Generally, molecular sieves are synthesized from one or more aluminum sources, phosphorus sources, silicon sources, and template agents, such as nitrogen-containing organic compounds. Typically, the combination of silicon, aluminum, and phosphorus sources is optionally combined with one or more model agents and placed in a sealed pressure bottle and heated under crystallization pressure and temperature. The pressure bottle is optionally made of an inert plastic, such as polytetrafluoroethylene When lining, until the crystalline material is formed, it is then recovered by filtration, centrifuge and decantation. Non-limiting examples of silicon sources include silicates, fumed silicas, such as Aerosil-200 and CAB-O-SIL M-5, commercially available from Degussa Inc., New York, New York, organic silicon compounds such as tetraalkane Based orthosilicates (such as tetramethylorthosilicate (TM0S) and tetraethylorthosilicate (TEOS)), colloidal silica or aqueous suspensions thereof, such as those available from EI du Pont de Nemours, Wilmington, Delaware's Ludox HS-40 Sol, oxalic acid or any combination thereof. Non-limiting examples of aluminum sources include aluminum alkoxides, such as aluminum isopropoxide, aluminum phosphate, aluminum hydroxide, sodium aluminate, pseudo bauxite, gibbsite, and tri-18- (14) 200303237 chloride Ming 'or any combination thereof. A convenient source of aluminum is pseudo-alumina, especially when preparing smelters and acid salt molecular sieves. A non-limiting example of a source of phosphorus, which may also include an aluminum-containing phosphorus composition 'including phosphoric acid, organic phosphates, such as triethyl phosphate, and crystalline or non-crystalline aluminum phosphates, such as AlP04, A phosphate salt, or a combination thereof. A convenient source of phosphorus is phosphoric acid, especially when making silicoaluminophosphates.

Prototypes are usually compounds containing Group 15 elements from the periodic table, especially nitrogen, phosphorus, arsenic and antimony. A typical model agent also includes at least one radical or square radical, such as a radical or aryl 'having 1 to 8 carbon atoms, such as 1 to 8 carbon atoms. Preferred model agents are usually nitrogenated alpha compounds, such as amines, quaternary compounds, and combinations thereof. Suitable quaternary ammonium compounds are of the general formula R4N +, where R is hydrogen or a hydrocarbon group or a substituted hydrocarbon group, preferably an alkyl or aryl group having 1 to 10 carbon atoms.

Non-limiting examples of model agents include tetraalkylammonium compounds and their salts, such as methylammonium compounds, tetraethylammonium compounds, tetrapropylammonium compounds, and tetrabutylammonium compounds, cyclohexylamine, morpholine, Di-n-propylamine (DPA), tetrapropylamine, triethylamine (TEA), triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine, N, N-dimethylbenzylamine, bile Base, N, N'-dimethylpiperazine, 4_diazabicyclo (2,2,2) octane, less hydrazine, 1 tetramethyl (1,6) hexanediamine, ~ Methyldiethanolamine, 1methyl-ethanolamine, N-methylpiperidine, 3-methyl-warmidine, methylcyclohexylamine, 3-methylpyridine, 4-methyl-〇thiopyridine, quinidine Ring, n, n, _dimethyldiazabicyclo (2,2,2) octane ion, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, tert-butyl Amines, ethylenediamines, pyrrolidines and 2-19-19 (15) 200303237 imidazolidone. The pH of a synthetic mixture containing a minimum amount of silicon-, aluminum- and / or phosphorus composition and template is typically in the range of 2 to 0, such as from 4 to 9, such as from 5 to 8. Generally the 'synthetic mixture described above is sealed in a container, preferably under autoclave', to a temperature ranging from about 8 ° C to about 25 ° C, such as from about 1000 ° C to about 250 ° C 'For example from about 1 2 5 ° C to about 2 5 5 ° C, for example from about 150 ° C to about 180 ° C. _ In one embodiment, the synthesis of the molecular sieve is by Or the same structural type of molecular sieve seeds to help. The time to form crystalline products usually depends on the temperature, and may vary from immediate to several weeks. Typically, the crystallization time is from about 30 minutes to about 2 weeks, such as from From about 45 minutes to about 240 hours, such as from about 1 hour to about 120 hours. Hydrothermal crystallization can be performed with or without shaking or agitation. Once the crystalline molecular sieve product is formed, it is usually a slurry, which can be It is recovered by any standard technique known in the art, such as by centrifugation or filtration. The recovered crystalline product can then be rinsed, such as with water, and then dried, such as in air. A crystallization method includes preparing a sample containing excess Aqueous reaction mixtures of the agents, subjecting the mixture to crystallization under hydrothermal conditions, establishing a balance between the formation and dissolution of molecular sieves, and then removing some excess sample agents and / or organic bases to inhibit the dissolution of the molecular sieves. See, for example US 5, 2 9 6, 2 0 8 which is incorporated herein by reference. -20- (16) 200303237

Other methods of synthesizing or improving molecular sieves are described in US 5,8 79,65 5 (controlling the ratio of sample agent to phosphorus), US 6,00 5,155 (using a salt-free modifier), US 5,47 5,182 (acid extraction), US 5,962,7'62 (treated with transition metal), US 5,9 2 5,5 8 6 and 6, 1 5 3,5 5 2 (phosphorus modification), US 5,925,800 (after Stone support), US 5,932,512 (fluorine treatment), US 6,046,3 73 (electromagnetic wave treatment or improvement), US 6,051,74 6 (multi-core aromatic modifier), US 6,22 5,2 5 4 (heating model agent) , PCT WO 0 1/3 63 29 (Synthesis of Surfactant) published on March 25, 2001, PCT WO 01/25 15 1 (Stepwise acid addition) published on April 12, 2001 , PCT WO 01/60746 (silicone oil) published on August 23, 2001, US patent case number 09/929949 (cooled molecular sieve) filed on August 15, 2001, and US patent case number filed on July 13, 2000 09 / 615,526 (including metal impregnation of copper), US Patent Serial No. 09/6 72,4 69 (conducting microfilter) filed on September 28, 2000, and those filed on January 4, 2001 U.S. Patent No. 12 09/7548 (freeze-dried molecular sieves), Merger of which are incorporated herein by reference. Templates are used in the synthesis of molecular sieves, and any template remaining in the product can be removed after crystallization by several known techniques, such as calcination. Calcining involves contacting a molecular sieve containing a sample agent with a gas, preferably a gas containing oxygen, at any desired concentration and at a temperature high enough to partially or completely remove the sample agent. Aluminum silicate and silicon aluminophosphate molecular sieves have a high ratio of silicon (Si) to aluminum (A1) or a low ratio of silicon (Si) to aluminum (A1). However, for SAPO synthesis, it has a low S i / A1 is better than 値. In a consistent embodiment, the S i / AI ratio 分子 of the molecular store -21-(17) (17) 200303237 is less than 0.6 5, such as less than 0.4 0, such as less than 0.3 2, and especially less than 0.2. In one embodiment, the Si / Al ratio of the molecular sieve ranges from about 0.65 to about 0.10, such as from about 0.40 to about 0.10, such as from about 0.32 to about 0.10, and especially from About 0.32 to about 0.15. Active metal oxides The active metals used herein are metal oxides other than typical binders and / or matrix materials which, when combined with molecular sieves, facilitate catalytic conversion methods. Preferred active metal oxides are those Group 4 metal oxides, such as chromium and / or given metal oxides, either alone or in combination with Group 2 (such as magnesium, calcium, scandium and barium) and / Or Group 3 metal (including lanthanide and actinide) oxides (such as yttrium, scandium and lanthanum). The most preferred active Group 4 metal oxide is an active chromium metal oxide, either alone or in combination with calcium oxide, barium oxide, lanthanum oxide, and / or yttrium oxide. Generally, the oxides of silicon, aluminum, and mixtures thereof are poor. In one embodiment, the active metal oxides are metal oxides different from typical adhesives and / or matrix materials. When mixed with the molecular sieve in the catalyst composition, it effectively extends the Service life. The quantification of the extended catalyst life is measured by the Life Increasing Index (LEI) defined by the following formula: r% _ The life of the mixed active metal oxide catalyst. The life of the catalyst is the life of the catalyst or catalyst composition. In the same method and under the same conditions of -22-200303237 (18), the cumulative amount of processing feed / per gram of catalyst composition is reduced until after the conversion of the feed from the catalyst composition is reduced to less than some A clear level, such as 10%. The inactive metal oxide will have no effect on the life of the catalyst composition or will shorten the life of the catalyst composition, and therefore the LEI will be less than or equal to one. Therefore, the active metal oxides of the present invention are metal oxides different from typical adhesives and / or matrix materials. When used in combination with molecular sieves, they provide molecular sieve catalyst compositions with LEIs greater than 1. Obviously, the LEI of the molecular sieve catalyst composition not mixed with the active metal oxide will be equal to one. It was found that the catalyst composition can be prepared by an active metal oxide including a mixed molecular sieve, and its LEI ranges from more than 1 to 20, for example, from about 1.5 to about 10. Typically, the catalyst composition of the present invention exhibits a LEI 値 greater than 1.1, such as ranging from about 1.2 to 15 and, more particularly, greater than 1.3, such as greater than 1.5, such as greater than 1. 7, such as greater than 2. In one embodiment, the active metal oxide, when mixed with a molecular sieve in a catalyst composition, increases the life of the catalyst composition in the conversion of a methanol-containing feed to one or more olefins. In particular, the carbon dioxide uptake of the metal oxides used herein is at least 0.03 mg / m2 metal oxide at 100 t, such as at least 0.35 mg / m2 metal oxide. The upper limit of carbon dioxide uptake by metal oxides is not critical. Generally, the carbon dioxide of metal oxides used herein will be less than 10 mg / m2 metal oxides at 100 ° C, such as less than 5 mg / m2 metal oxide. Typically, the carbon dioxide uptake of metal oxides used herein is 0.04 to 0.2 mg / m2 metal oxide. -23- (19) 200303237 To measure the carbon dioxide uptake of metal oxides, the following procedure is used. Samples of metal oxides are dehydrated to a constant weight by heating in flowing air to about 200 ° C to 500 ° C to obtain a "dry weight,". The temperature of the sample is then reduced to 100 ° C. Carbon dioxide passes through the sample, whether continuous or pulsed, again until a constant weight is obtained. The increase in sample weight is calculated as the dry weight of the sample and expressed in mg / mg sample as the amount of carbon dioxide adsorbed.

In the samples described below, carbon dioxide adsorption was measured under ambient pressure using a Mettler TGA / SDTA 851 thermogravimetric analysis system. The metal oxide sample was dehydrated in flowing air at about 500 ° C for 1 hour. The temperature of the sample was then lowered to 10 ° C under flowing ammonia gas. The sample reached equilibrium at the desired adsorption temperature and flowing helium gas. The sample was given a gas containing 10% by weight of carbon dioxide and the remaining helium gas. 20 individual pulses of the mixture (approximately 12 seconds / pulse). After each pulse of the adsorbed gas, the metal oxide sample was rinsed with flowing gas for 3 minutes. The weight of the sample was increased to absorb the adsorbent after processing at 500 ° C Calculated by weight and expressed in mg / mg adsorbent, is the amount of carbon dioxide adsorbed. The surface area of the sample is measured in accordance with the Brunauer, Emmett, and Teller (BET) method disclosed in ASTM D 3663. Metal oxide meter. In one embodiment, the BET surface area of the active metal oxide is greater than 10 m2 / g, such as greater than 10 m2 / g to about 300 m2 / g. In another embodiment, the active metal oxide The BET surface area of the oxide is greater than 20 μm 2 / g, for example from 20 m 2 / g to 250 m 2 / g. In another embodiment, the active metal oxide-24- (20) (20) 200303237 BET surface area greater than 25 m2 / g, for example 25 m2 / g to 200 m2 / g. In a preferred embodiment, the active metal oxide includes having a BET surface area greater than 20 m2 / g, such as greater than 25 m2 / g, and particularly gij greater than 30 m2 / g. Zirconium oxide. The active metal oxides used herein can be prepared using various methods. Preferably, the active metal oxide is derived from a precursor of an active metal oxide, such as a metal salt, such as a halide, nitrate, Sulfates or acetates are prepared. Other suitable sources of metal oxides include compounds that form metal oxides during calcination, such as chlorine oxides and nitrates. Alkoxides also include suitable sources of Group 4 metal oxidation, Examples include chromium n-propoxide. A preferred source of Group 4 metal oxides is hydrated zirconia. This representation of hydration, hydrated chromium oxide, is intended to imply a covalent attachment to other chromium via a bridging oxygen atom containing chromium atoms Atoms and other materials including hydroxyl groups that can be used. In one embodiment, the hydrated oxide cone is hydrothermally treated under conditions including a temperature of at least 80 ° C 'preferably at least 100 ° C. Hydrothermal treatment typically occurs in sealed containers and at pressures greater than atmospheric pressure. However, a preferred mode of treatment involves the use of open containers under reflux conditions. Hydrated Group 4 metal oxides are agitated in a liquid medium, such as by Refluxing the liquid and / or stirring to promote effective interaction between the hydrated oxide and the liquid medium. The contact time of the hydrated oxide with the liquid medium is suitably at least 1 hour, such as at least 8 hours. The pH of the liquid medium for the treatment is approximately 6 or greater, such as 8 or greater. Non-limiting examples of suitable liquid media include water, hydroxide solutions (including NH4 +, Na +, K +, Mg2 +, and Ca2 + hydroxides (21) 200303237), carbonate and bicarbonate solutions (including NH4 +, (Na +, K +, Mg2 +, and Ca2 + carbonates and bicarbonates), pyridine and its derivatives, and alkyl / hydroxylamines. In another embodiment, the active metal oxide is, for example, by subjecting a liquid solution (eg, an aqueous solution) containing a Group 4 metal ion source to a precipitation sufficient to produce a hydrated precursor of a solid oxide material, such as, The precipitant is added to the solution under the conditions. Conveniently, the precipitation is carried out at a pH greater than 7. For example, the precipitating agent may be a base such as sodium hydroxide or sodium hydroxide. When a mixture of a Group 4 metal oxide and a Group 2 and / or 3 metal oxide is to be prepared, a first liquid solution containing a source of a Group 4 metal ion may be mixed with a group 2 and / or 3 metal ion The second liquid solution of the source is mixed. Mixing of the two solutions can occur under conditions sufficient to produce a co-precipitate of the mixed oxide species, which is a solid from a liquid medium. Alternatively, the Group 4 metal ion source and the Group 2 and / or 3 metal ion source may be combined into a single solution. This solution may then be subjected to conditions sufficient to produce a hydrated precursor of the solid mixed oxide material, e.g., the addition of a precipitating agent to the solution. The temperature is usually below about 200 ° C, for example, in the range from about 0. (: To about 2000 ° C 'during precipitation: the liquid medium is maintained at this temperature. A special temperature range for precipitation is from about 20 ° C to about 100 ° C. The obtained gel is preferably after Hydration treatment is performed at 80 ° C, preferably at least 100 ° C. Hydration treatment typically occurs in a container and at atmospheric pressure. In one embodiment, the gel is hydrated for up to 10 days, For example, up to 5 days, such as up to 3 -26- (22) (22) 200303237 days. The hydrated precursors of the metal oxides are then recovered, for example, by filtration or centrifugation, and rinsed and dried. The resulting material can then be Is calcined, for example, in an oxidizing atmosphere, and at a temperature of at least 40 ° C, such as at least 50 ° C, such as from about 600 ° C to about 90 ° C, and particularly from about 650 ° C to about 800 ° C 'forms an active metal oxide or an active mixed metal oxide. The calcination time is typically as high as 48 hours, such as lasting from 0.5 to 24 hours, such as lasting from about 1.0 to 10 hours. In one embodiment, forging Firing is performed at about 70 for about 1 to about 3 hours. In one embodiment, the Group 4 metal is oxidized And Group 2 and / or Group 3 metal oxides are prepared separately and then contacted together to form a mixed metal oxide and then contacted with a molecular sieve. For example, a Group 4 metal oxide can be introduced into Group 2 and / or The Group 3 metal oxide is contacted with the molecular sieve before, or the Group 2 and / or Group 3 metal oxide may be contacted with the molecular sieve before the introduction of the Group 4 metal oxide. The catalyst composition includes a Group 4 metal oxide And Group 3 metal oxides, the molar ratios of Group 4 metal oxides to Group 3 metal oxides can range from 1000: 1 to 1 ·· 1, such as from about 5 0 0: 1 To 2: 1, such as from about 100. 1 to about 3.1. For example, from about 75: 1 to about 5: 1, calculated as the total moles of Group 4 and Group 3 metal oxides. In addition, the catalyst composition may include a Group 3 metal from 1 to 25 wt%, such as from 1 to 20 wt%, such as from 1 to 15 wt%, based on the total weight of the mixed metal oxide, In particular, the Group 3 metal oxide is a lanthanum or samarium metal oxide, and the Group 4 metal oxide is a chromium metal oxide -27- 200303237 (23) The catalyst composition includes a Group 4 metal oxide and a Group 2 metal oxide, and the molar ratio of the Group 4 metal oxide to the Group 2 metal oxide may range from 1 〇 〇〇 ·· 1 to 1 ·· 2, such as from about 500: 1 to 2: 3, such as from about 100: 1 to about 1: 1, such as from about 50: 1 to about 2: 1, Calculated based on the total moles of Group 4 and Group 2 metal oxides. In addition, the catalyst composition may include from 1 to 25% by weight, such as from 1 to 20% by weight, such as from 1 to 15% by weight. % 'Group 2 metal is calculated based on the total weight of the mixed metal oxide, in particular,' Group 2 metal oxide is calcium oxide, and Group 4 metal oxide is pin metal oxide. Catalyst composition The catalyst composition of the present invention includes any one of the aforementioned molecular sieves, and one or more of the above-mentioned active metal oxides, optionally with an adhesive and / or matrix material different from the active metal oxides. Typically, in the catalyst composition, the weight ratio of the molecular sieve to the active metal oxide ranges from 5 wt% to 800 wt%, such as from 10 wt% to 600 wt%, especially from 20 wt% There are various adhesives for forming the catalyst composition to 500 wt%, and more specifically from 300 wt% to 400 wt%. Non-limiting examples of adhesives include various types of hydrated alumina, silica, and / or other inorganic oxide sols, which can be used alone or in combination. A preferred sol containing aluminum oxide is basic aluminum chloride. Inorganic oxide sols, like glue, bind synthetic molecular sieves to other substances, such as substrates, especially after heat treatment. By heating, the inorganic oxide sol, preferably -28- (24) 200303237, having low viscosity 'is converted into an inorganic oxide adhesive component. For example, the 'alumina sol will be converted into an alumina adhesive after heat treatment.

Basic aluminum chloride (sol containing aluminum hydroxide based on chloride counterions) has the general formula AlmOjOH ^ Clp · χ (Η20), where m is 1 to 20, η is 1 to 8, and 0 is 5 to 40. ρ is 2 to 15, and X is 0 to 30. In one embodiment, the adhesive is A11304 (0H) 24C17 · 12 (Η20), which is described in GM · Wolterman, et. Al., Stud. Surf. Sci. And C at al ·, 76, pages 105- 144 (1993), which is incorporated herein by reference. In another embodiment, one or more adhesives and one or more other non-limiting examples of alumina materials, such as aluminum ο X yhydr * ο X ide, r—alumina, alumina, Gibbsite, and transitional alumina, such as α-alumina, -alumina, r-alumina, 5-lithium, ε-oxide, / c-oxide and ρ-oxide, trihydrogen Alumina, such as gibbsite, bayerite, ηordstrandite, doye 1ite, and mixtures thereof are mixed.

In another embodiment, the adhesive is an alumina sol, which advantageously includes alumina, optionally silica. In another embodiment, the adhesive is a peptized alumina, which is prepared by treating an alumina hydrate (such as pseudo-alumina) with an acid, preferably a halogen-free acid, to prepare a sol or aluminum ion solution And made it. Non-limiting examples of commercially available colloidal alumina sols include Nalco 8676 commercially available from Na 1 c 0C hemica 1 C 0 ·, Napervi 11 e, Illi η 0is, and Nyacol nano Technologies, Inc., Ashland, Massachussetts, Nyacol AL20DW. The catalyst composition includes a matrix material, which is preferably different from -29- (25) (25) 200303237 metal oxide and any adhesive. The matrix material is typically effective in reducing the total cost of the catalyst and acts as a heat sink to assist the catalyst composition, such as shielding heat during regeneration, hardening the catalyst composition, and increasing catalyst strength, such as crush strength and abrasion resistance. Non-limiting examples of matrix materials include one or more non-reactive metal oxides. The non-reactive metal oxides include barium oxide, quartz, silica or sols, and mixtures thereof such as silica-magnesia, silica-chromia, Silica-titanium oxide, silica-alumina and silica-alumina-hafnium oxide. In one embodiment, the matrix material is natural clay, such as those from the montmorillonite and kaolin families. These natural clays include secondary bentonite clays and such well-known kaolin clays as Dixie, McNamee, Georgia, and Florida clays. Non-limiting examples of other matrix materials include halositte, kaolin, dickite, nacrite, or vermiculite. The matrix material, such as clay, may be subjected to known improvements such as calcination and / or acid treatment and / or chemical treatment. In a preferred embodiment, the matrix material is a clay or clay type composition ', especially a clay or clay type composition having a low content of rhenium or titanium dioxide, and most preferably, the matrix material is kaolin. Kaolin has been found to form a pumpable, high solids slurry, has a low fresh surface area, and is easily compressed together due to its flat structure. The preferred average particle size of the matrix material (most preferably kaolin) is from about 0.1 μm to about 0.6 μm, and the D 9 particle size distribution is less than 1 μm. The catalyst composition includes an adhesive or matrix substance, and the catalyst composition typically includes from about 1% to about 80% by weight, such as from about 5% to (26) (26) 200303237 and about 60% by weight, and In particular, molecular sieves from about 5% to 50% by weight are calculated based on the total weight of the catalyst composition. The catalyst composition includes an adhesive and a matrix substance, and the weight ratio of the adhesive to the matrix substance is typically from 1:15 to 1: 5, such as from 1:10 to 1: 4, and particularly from 1: 6 to 1: 5. The content of the adhesive is typically from about 2% to about 30% by weight, such as from about 5% to about 20% by weight, and particularly from about 7% to about 15% by weight, with the adhesive, molecular sieve, and Calculation of total weight of matrix material. It has been found that high molecular sieve content and low matrix material content increase the performance of the sieve catalyst composition, whereas low molecular sieve content and high matrix material content improve the abrasion resistance of the composition. The typical density of the catalyst composition ranges from 0.5 g / cc to 5 g / cc, such as from 0.6 g / cc to 5 g / cc, such as from 0.7 g / cc to 4 g / cc, especially from 0.8 g / cc. To 3g / cc. Method for preparing a catalyst composition In the preparation of a catalyst composition, a molecular sieve is first formed, and then is completely mixed with an active metal oxide, preferably in a substantially dry, dried or calcined state. Optimally, the molecular sieve and the active metal oxide are completely mixed in their calcined state. Without being bound by any particular theory, it is believed that the intimate mixing of the molecular sieve and one or more active metal oxides improves the conversion method using the molecular sieve composition and catalyst composition of the present invention. Intimate mixing can be achieved by any method known in the art, such as mixing in the form of a mixing honer, drum mixer, ribbon / pulp blender, kneader, or the like '. Chemical reactions between molecular sieves and metal oxides are unnecessary -31-(27) 200303237 and are usually not preferred. The catalyst composition includes a matrix and / or an adhesive. The molecular sieve and the matrix and / or the adhesive are suitably formulated as a catalyst precursor, and then the active metal is mixed with the formulated precursor. The active metal oxide can be added as unsupported particles or as a mixture with a carrier such as an adhesive or matrix. The resulting catalyst composition can then be formed into particles of useful shape and size by known techniques, such as spray drying, curing, extrusion, and the like. In one embodiment, the molecular sieve composition and the matrix material are optionally mixed with an adhesive to form a slurry with a liquid, followed by mixing, and preferably vigorously mixing, to produce a substantially homogeneous mixture containing the molecular sieve composition. Non-limiting examples of suitable liquids include one or a combination of water, alcohol + ketone, aldehyde and / or ester. The best liquid is water. In one embodiment, the slurry is honed by the colloid for a period of time sufficient to produce the desired slurry structure, secondary particle size, and / or secondary particle size distribution. The molecular sieve composition, matrix material, and optional adhesive can be mixed in the same β or different liquids, and can be mixed in any order, together, simultaneously, continuously, or a combination thereof. In a preferred embodiment, the same liquid is used, preferably water. The molecular sieve composition, matrix material, and optional adhesive are mixed in a liquid in a solid, substantially dry or dried form, or in a slurry manner, or individually. If the solids are added together as a dry or substantially dry solid, it is preferred to add a limited and / or controlled amount of liquid. In one embodiment, the -32- (28) 200303237 of the molecular sieve composition, adhesive and matrix material is mixed or honed to obtain a sufficiently uniform slurry of the molecular sieve catalyst composition secondary particles. It is fed to a formation unit that generates a 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 remove most of the liquid from the slurry and from the resulting molecular sieve catalyst composition. When the catalyst composition is formed in this manner, the obtained catalyst composition is in the form of fine particles. When a spray dryer is used as the forming unit, typically, the slurry of the molecular slab composition and the matrix material and an optional adhesive is fed into a spray drying container with a drying gas, and its average inlet temperature ranges from 200 ° C to about 5 5 0 ° C, and outlet temperature range from 100 ° C to about 22 5 ° C. In one embodiment, the average diameter of the catalyst composition formed by spray drying is from about 40 μm to about 300 μm, such as from about 50 μm to about 250 μm, such as from About 50 μm to about 200 μm 'and expediently from about 65 μm to about 90 μm. Other methods for forming molecular trim catalyst compositions are described in U.S. Patent Application Serial No. 09 / 017,7 丨 4, filed July 17, 2000 (spray drying using recovered molecular sieve catalyst composition), It is incorporated herein by reference. Once the molecular sieve catalyst composition is formed in a substantially dry or dried state, the catalyst composition formed for further hardening and / or activation is usually heat-treated at a high temperature, such as calcination. Typical calcination temperatures range from about 400 ° C to about 1,000 ° C, such as from about 500 ° C to about 800 ° C, such as from about 5 50 ° C to about 700 ° C. A typical calcination environment is air (which may include small amounts of water vapor), nitrogen, helium, flue gas (oxygen-depleted combustion products -33- (29) 200303237), or any combination thereof. In a preferred embodiment, the catalyst composition is heated under nitrogen at a temperature from about 600 ° C to about 70 CTC. Heating is continued for a period of time, typically from 30 minutes to 15 hours, such as from 1 hour to about 10 hours, such as from about 1 hour to about 5 hours, and especially from about 2 hours to about 4 hours using molecular sieves. Method of medium composition Φ The above catalyst composition is used in various methods, which include cracking, such as cracking of naphtha feed into light olefins (US 6,3 00,5 3 7) or larger molecular weight ( MW) hydrocarbons to smaller MW hydrocarbons; hydrogen cracking, such as the cracking of heavy petroleum and / or cyclic feeds; isomerization, such as the isomerization of aromatics (such as xylene); polymerization, such as Polymerization of one or more olefins to produce a polymer product; reforming; hydrogenation; dehydrogenation; dewaxing, such as dehydration of hydrocarbons to remove linear alkanes; absorption, such as absorption of alkyl aromatics to isolate them Isomers; alkylation, for example, aromatic φ hydrocarbons (such as benzene and alkylbenzene) are freely alkylated with propylene to produce cumene, or long-chain olefins; alkyl transfers, such as aromatic and Combined alkyl transfer of polyalkyl aromatic hydrocarbons; dealkylation Radical dehydrocyclization; disproportionation such as toluene disproportionation to produce benzene and para-xylene; oligomerization 'such as oligomerization of linear and branched olefins; and dehydrocyclization The best methods include a method of converting naphtha into a highly aromatic mixture; a method of converting light olefins into gasoline, distillates and lubricating oil; and a method of converting -34- (30) (30) 200303237 oxygenates into Olefins; conversion of light paraffins;): Greek and / or aromatic methods; conversion of unsaturated hydrocarbons (ethylene and / or acetylene) into aldehydes for conversion to alcohols, acids and esters . The preferred method of the present invention relates to a method for converting a feed to one or more hydrocarbons. Typically, the feed comprises one or more aliphatic-containing compounds, the aliphatic portion comprising from 1 to 50 carbon atoms, such as from 1 to 20 atoms, such as from 1 to 10 carbon atoms, and particularly Ground from 1 to 4 carbon atoms. Non-limiting examples of aliphatic-containing compounds include alcohols, such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, thioethers such as dimethylsulfide, alkylamines such as methylamine 'alkyl ether For example, dimethyl ether, diethyl ether and methyl ether, alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehyde, and various acids such as acetic acid. In a preferred embodiment of the present invention, the feed comprises one or more oxygenates 'more specifically' one or more organic compounds containing at least one oxygen atom. In a preferred embodiment of the present invention, the oxygenate in the feed is one or more alcohols, preferably aliphatic alcohols, and the aliphatic portion of the alcohols has from 1 to 20 carbon atoms, preferably From 1 to 10 carbon atoms, and preferably from 1 to 4 carbon atoms. Alcohols used as a feed for the process of the present invention include lower linear and branched aliphatic alcohols and their unsaturated analogs (counterpart). Non-limiting examples of oxygenates include methanol, ethanol, n-propyl Alcohols, isopropanol, methyl ether, dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, monomethyl ketone, acetic acid, and mixtures thereof. -35- (31) (31) 200303237 In a preferred embodiment, the 'feeding is selected from the group consisting of ~ or more of methanol, ethanol, monomethyl @ 迷, monoethyl ether or a combination thereof, and more preferably methanol and dimethyl ether , And most preferably methanol. The various feeds discussed above, especially feeds containing oxygenates, and more particularly feeds containing alcohols, are primarily converted to one or more hydrocarbon-burning species. The olefins produced from the feed typically have from 2 to 30 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, more preferably from 2 to 4 carbon atoms, and most Preferably, it is ethylene and / or propylene. The catalyst composition of the present invention is particularly used for a method generally called a gas conversion to an olefin (GTO) or a method for converting methanol to an olefin (MT0). In this method, the oxygenated feed is preferably a feed containing methanol, which is converted into one or more hydrocarbon-burning hydrocarbons in the presence of a molecular sieve catalyst composition, preferably and advantageously ethane and / or propylene. ;: Greek. Use of the catalyst composition of the present invention to switch feeds, preferably feeds containing one or more oxygenates 'content of olefins produced, calculated based on total weight of hydrocarbons produced' More than 50% by weight, typically more than 60% by weight, such as more than 70% by weight, and preferably more than 50% by weight. In addition, the content of ethane and / or propylene produced is based on the hydrocarbons produced The total weight of the product is even more than 'greater than 40% by weight, typically greater than 50% by weight, such as greater than 65% by weight' and preferably greater than 78% by weight. The total weight of the produced hydrocarbon products is greater than 20% by weight, such as greater than 30% by weight, such as greater than 40% by weight. In addition, the content of the propionate produced is based on the total amount of the produced hydrocarbon products. Recalculation 'is typically greater than 20% by weight, such as greater than 25% by weight, for example Such as Da-36- (32) 200303237 at 30% by weight, preferably more than 35% by weight. It was found that the catalyst of the present invention was used in comparison with similar catalyst compositions without active metal oxide components under the same conversion conditions The composition converts a feed containing methanol and dimethyl ether into ethylene and propylene, and the ethane and propane produced are reduced to greater than 10%, such as greater than 20%, such as greater than 30%, and particularly in a range from about 30% to 40%. In addition to the oxygenate component, such as methanol, the feed may include one or more diluents, which are generally non-reactive to the feed or molecular sieve catalyst composition, and are typically Used to reduce the concentration of the feed. Non-limiting examples of diluents include ammonia, gas, nitrogen, carbon monoxide, carbon dioxide, water, paraffinic hydrocarbons (especially alkanes such as methane, ethane, and propane that are substantially non-reactive) ), Aromatic compounds that are substantially non-reactive, and mixtures thereof. The best diluent is water and nitrogen, with water being particularly preferred. The diluent, such as water, can be in liquid or vapor form or a combination thereof. Use. Thinner can be straight The feed added to the input reactor is either directly added to the reactor or added together with the molecular sieve catalyst composition. The method of the present invention can be implemented in a wide temperature range, for example, ranging from about 2000 ° C to about 1000 ° C, such as from about 250 ° C to about 800 ° c, including from about 250 ° C to about 750 ° C 'conveniently from about 300 ° C to about 650 ° C, typically from about 350 ° C to about 600 ° C, and particularly from about 350 ° to about 550 ° C. Likewise, the method of the present invention can be Implemented over a wide range of pressures. This pressure range includes autogenous pressures. Typically, the partial pressure range of the feed used in the process (excluding any diluent therein) ranges from about 0.1 kPaa to about -37. -(33) (33) 200303237 5Mpaa, for example from about 5 kP aa to about i Mpaa, and expediently from about 20 kPaa to about 500 kPaa. The weight space-time velocity (WHS V) is defined as the total weight of the feed excluding any diluent / hour / weight of the molecular sieve in the catalyst composition, and typically ranges from about 111 to about 5000111-1, For example from about 2111 * -1 to about 3 00 011 bl, for example from about 5 hr-l to about 1 500 hr-l, and suitably from about 10 hr-l to about 1,000 hr-l. In one embodiment, the WHS V is greater than 20 hr-1, and ranges from about 20 hr-1 to about 300 hr-1, where the feed includes methanol and / or dimethyl ether. The method is in a fluidized bed In the implementation, the surface gas velocity (SGV) of the feed is at least 0.1 / sec, such as greater than 0.05 rn / sec, such as greater than 1 lm / sec, such as greater than 2 m / sec, suitably greater than 3 m / sec, and typically greater than 4m / Sec 'This feed includes the diluent and reaction products in the reactor system, especially in the riser reactor. Reference is made to U.S. Patent Application Serial No. 09 / 708,753, filed on 8th, 2000, which is incorporated herein by reference. The method of the present invention is suitably implemented in a fixed bed method, or more typically in a fluidized bed method (including a turbulent moving bed method), such as a continuous fluidized bed method, and particularly a continuous high-speed fluidized bed method. The ghai method can occur in various catalytic reactors, such as a hybrid reactor, which has a tight or fixed bed reaction zone and / or a fast fluidized bed reaction zone connected together, a circulating fluidized bed reactor, a riser Reactors and the like. Suitable reactor types are described in, for example, US 4,0 76,7 9 6, US 6,2 8 7,5 2 2 (dual riser) and (34) (34) 200303237

Fluidization Engineering, D. Kunii and O. Levenspiel, Robert E. Krieger Published Company, New York, New York 1 977, all of which are incorporated herein by reference. The preferred reactor type is a riser reactor. The riser reactor is usually described at a scale of 5 € 1'11 to (: 1〇1 *,? 111 丨 (1 丨 2 & 1: 丨 011 & 11). (1? 11 ^ 〇1-Particle System, pages 48 to 59, FA Zenz and DF Othmo, Reinhold Publishing Corporation, New York, I 960, and US 6, 166,282 (Rapid Fluidized Bed Reactor), and May 2000 U.S. Patent Application Serial No. 09/5 64,6 1 3, filed on March 4, which is incorporated herein by reference. In a practical embodiment, the method uses a fluidized bed method or a high-speed fluidized bed using a reactor System, regeneration system, and recovery system. In this method, the reactor system desirably includes a fluidized bed reactor system having a first reaction zone within one or more riser reactors, And the second reaction zone within at least one separation vessel typically includes one or more cyclones. In one embodiment, one or more riser reactors and separation vessels are contained within a single reaction vessel. Fresh Feed, preferably containing one or more Oxygen, optionally one or more diluents, is fed to the one or more riser reactors, and the molecular sieve catalyst composition or its coking plate is introduced into the riser reactor. In one embodiment, the molecular sieve Before the catalyst composition or its coking plate is introduced into the riser reactor, it is in contact with a liquid and / or a gas, the liquid is preferably water or methanol, and the gas is, for example, an inert gas such as nitrogen. (35) (35) 200303237 In one embodiment, the content of fresh feed that enters the reactor system in a liquid and / or vapor manner ranges from about 0.1% to about 85% by weight, such as from about 1% by weight % To about 75 wt.%, More typically from about 5 wt.% To about 65 wt.%, Based on the total weight of the feed containing any diluent therein. The liquid and vapor feeds may be of the same composition Or may include various proportions of the same or different feeds, the feeds having the same or different diluents. The feed to the reactor system is partially or completely preferably converted to a gaseous effluent in the first reaction zone. , The effluent with the coking catalyst The product enters a separation container. In a preferred embodiment, a cyclone is provided in the separation container to separate the coked catalyst composition from the gas effluent containing one or more olefins in the separation container. Although the cyclone A separator is preferred, and the gravity effect in the separation container can also be used to separate the catalyst composition from the gas effluent. Other methods of separating the catalyst composition from the gas effluent include the use of plates, hoods, and elbows And the like. In one embodiment, the separation vessel includes a stripping area typically in the downstream portion of the separation vessel. In the stripping area, the coked catalyst composition is in contact with a gas, preferably one of a stream, methane, carbon dioxide, carbon monoxide, a light or inert gas (such as argon), or a combination thereof, preferably a gas. To remove the adsorbed hydrocarbons from the coked catalyst composition, which is then introduced into the regeneration system. The scorched catalyst composition is removed from the separation container and is introduced into the regeneration system. The regeneration system includes a regenerator. In the regenerator, the coked catalyst composition regenerates with conventional regeneration conditions of temperature, pressure and residence time. (36) 200303237, preferably an oxygen-containing gas , Contact. Non-limiting examples of suitable regeneration media include one or more of oxygen, 03, S03, N20, NO, N02, N205, air, air diluted with nitrogen or carbon dioxide, oxygen, and water (US 6,24 5,7 〇3), carbon monoxide and / or hydrogen. Suitable regeneration conditions are those who have the ability to burn coke from the coking catalyst composition, and preferably burn the coke to a level of less than 0.5% by weight to enter the coking molecular sieve into the regeneration system. Calculation of the total weight of the media composition. For example, the regeneration temperature may range from about 2000 to about 500. 〇, such as from about 300 ° C to about 100 ° C, such as from about 4 50 ° C to about 750 ° C, and suitably from about 5 50 ° C to about 700 ° C. The regeneration pressure may range from about 15 psia (103 kPaa) to about 50 psia (3 4 48kPaa), such as from about 20 psia (138 kPaa) to about 250 psia (1724 kPaa), including from About 25? 84 (1721 ^ &) to about 150? 5 (& 031 ^ & &), and expediently from about 30psia (207kPaa) to about 60psia (414kPaa). The residence time of the catalyst composition in the regenerator can range from about 1 minute to several hours, for example, from about 1 minute to 100 minutes, and the volume of oxygen during regeneration can range from about 0.01 1 mole%. To about 5 moles. / 〇, calculated based on the total volume of the gas. In the regeneration step, the combustion of coke is an exothermic reaction, and in one embodiment, the temperature in the regeneration system is controlled by various technologies in the field, which include batch, continuous or partial continuous mode or a combination thereof, The cooled gas is fed into a regenerator container. The preferred technique includes removing the regenerated catalyst composition from the regeneration system, and passing the regenerated catalyst composition through a catalyst cooler to form a cooled regenerated catalyst composition. In one embodiment of -41-(37) 200303237, the catalyst cooler is a heat exchanger, and the heat exchanger is located inside or outside the regeneration system. Other methods of operating the regeneration system are described in US 6,29,9 1 6 (moisture control), which is incorporated herein by reference. Regenerated catalyst composition removed from the regeneration system, preferably from the catalyst cooler, and fresh molecular sieve catalyst composition and / or recycled molecular sieve catalyst composition and / or feed and / or fresh gas or liquid phase Mix and return to riser reactor. In one embodiment, the regeneration catalyst composition removed from the regeneration system is returned to the riser reactor directly, preferably after passing through the catalyst cooler. The carrier may be used in a partially continuous or continuous manner, such as inert gas, feed vapor, gas, and the like, to help introduce the regeneration catalyst composition into the reactor system, preferably to one or more riser reactors. By controlling the regeneration catalyst composition from the regeneration system or the cooled regeneration catalyst composition to flow to the reactor system, the optimal level of coke on the molecular sieve catalyst composition input to the reactor is maintained. Various techniques for controlling catalyst composition flow are described in Michael Louge, Experimental Techniques, Circulating Fluidized Beds, Grace, Avidan and Knowlton, Eds., Blackie, 1997 (336-337), which is incorporated herein by reference. The degree of coke on the catalyst composition was measured by removing the catalyst composition from the conversion method and measuring its carbon content. After regeneration, the typical degree of coke on the molecular sieve catalyst composition ranges from 0.01% to about 15% by weight, such as from about 0.1% by weight to about 10% by weight, such as from about Q. · 2% by weight to about 5% by weight, and suitably from about 0.33% by weight to -42- (2003) 200303237, about 2% by weight, calculated as the molecular sieve weight. The gas effluent is removed from the separation vessel and passed through a recovery system. A variety of known recovery systems, techniques and procedures are used to separate and purify olefins from gaseous effluents; (: Hydrocarbons. Recovery systems typically include various separations, separation and / or distillation columns, columns, separations Machine or unit, reaction system, such as the production of ethylbenzene (US 5,476,97 8) and other derivatization methods, such as the production of aldehydes, ketones and esters (US 5,6 7 5, (H1), and other combined equipment, such as One or more or a combination of various condenser tubes, heat exchangers, refrigeration systems or cooling units, compressors, separation drums or pans, pumps, and the like. These towers, tubes, separators, or Non-limiting examples of the unit include one or more methane distillers (preferably high-temperature Jiayuan weavers), ethane distillers, propane distillers, scrubbing towers (usually alkaline, raw scrubbing) And / or quenching tower), absorber, adsorber, membrane, Ecan (C2) separator, propylene (C3) separator, butene (C4) separator and the like. Light olefins, such as ethylene, propylene and / or Various recovery systems for ene) are described in US 5,960,6 4 3 (second ethylene-rich stream), US 5,019,143, 5,452,581 and 5,082,481 (membrane separation), US 5,6 72,197 (dependent Pressure adsorbent), US 6,06 9,28 8 (hydrogen removal), US 5,904,8 80 (in a single step, the recovered methanol is converted to hydrogen and carbon dioxide), US 5,92 7,063 (recovered methanol Converted into gas turbine power plant) and US 6,1 2 1,5 0 4 (direct product quenching), US 6,1 2 1,5 0 3 (highly purified olefins without ultra-rectification), and U S 6, 2 9 3, 9 9 8 (pressure conversion adsorption), all of which are incorporated herein by reference. -43- (39) 200303237 Other recovery systems containing purification systems (such as the purification of olefins) are described in Kirk- Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 9, John Wiley & Sons, 199 6 pages 249-271 and 894-899, which are incorporated herein by reference. Purification systems are also described in, for example, US 6, 2 7 1 , 4 2 8 (purification of diene stream), US 6,293,999 (propylene separated from propane), and October 2, 2000 U.S. Patent Application Serial No. 0 9/6 8 9, 3 6 3 (washing stream using hydration catalyst), which are all incorporated herein by reference. Often, 'with most recovery systems are additional products, Preparation, production or accumulation of by-products and / or contaminants and preferred main products. The preferred main products, light olefins, such as ethylene and propylene, are typically purified for use in derivative manufacturing processes, such as polymerization processes. Therefore, in the preferred embodiment of the recovery system, the recovery system also includes a purification system. For example, light olefins, particularly those produced by the MTO process, pass through a purification system that removes low levels of by-products or contaminants. Non-limiting examples of pollutants and by-products typically include polar compounds such as water, alcohols, carboxylic acids, ethers, carbon oxides, sulfur compounds such as hydrogen sulfide, carbonyl sulfide and thiols, ammonia and other nitrogen Compounds, rhenium, phosphine and chloride. Other pollutants or by-products include hydrogen and hydrocarbons, such as acetylene, methylacetylene, propadiene, butadiene, and butyne. Typically, in converting one or more oxygenates to olefins having 2 or 3 carbon atoms, minor amounts of hydrocarbons, especially olefins having 4 or more carbon atoms, are also produced. The content of C4 + hydrocarbons is usually less than 20 weight. /. For example, less than 10% by weight, for example, less than 5% by weight. /. , And especially less than 2% by weight, -44-(40) 200303237 Calculated as the total weight of the effluent gas removed from the method, excluding water. Typically, the recovery system may therefore include one or more reaction systems to convert CO impurities into useful products. Non-limiting examples of this reaction system are described in US 5,9 5 5 6 4 0 (conversion of 4 carbon atom products to butane- 丨 -ene), us 4,774,3 7 5 (isobutane and butane-2- Ignition is converted into chemical gasoline), u S 6,0 4 9, 0 1 7 (Ning Ding; (: Greek dimerization), US 4,28 7,3 69 and 5,76 3,67 8 ( Carbonyl carbonylation or aldolization of higher olefins to produce carbonyl compounds), US 4,5 4 2,2 5 2 (multistage adiabatic process), US 5,63 4,3 5 4 (olefin-hydrogen recovery) and Cosyns, j. et. al., Process for Upgrading C3? C4 and C5 Olefinic

Streams, Pet. &Amp; Coal, Vol. 37, No. 4 (1 995) (dimerized or oligomeric propylene, butene and pentene), all of which are incorporated herein by reference. A preferred light olefin prepared by any of the above methods is a high purity primary olefin product that includes a content greater than 80% by weight, such as greater than 90% by weight, such as greater than 95% by weight, such as at least about 99% Olefins of a single carbon number, based on the total weight of the olefins. In a practical embodiment, the process of the present invention forms part of an integrated process' which is used to produce light olefins from a hydrocarbon feed, preferably a gaseous hydrocarbon feed, especially methane and / or ethane. In the first step of the method, a gas feed, preferably a mixed water stream, is passed through the synthesis gas generation zone to prepare a synthesis gas stream, which typically includes carbon dioxide, carbon monoxide and hydrogen. Syngas products are known, and typical syngas temperatures range from about 700 ° C to about 12O ° C, and syngas pressures range from about 2 MPa to about 100 MPa. Syngas streams are made from natural gas, petroleum liquids (41) 200303237 and carbonaceous substances such as coal, recycled plastic, municipal waste or any other organic material. Preferably, the ' co-gas stream is prepared via a reorganized stream of natural gas. The next step in the process involves contacting a synthesis gas stream with a heterogeneous catalyst, typically a copper-based catalyst, to produce a stream containing oxygenates, usually mixed with water. In one embodiment, the step of contacting is performed at a temperature ranging from about 150 ° C to about 45 ° C and a pressure ranging from about 5MPa to about 10 MPa. φ The oxygenate-containing stream or crude methanol typically includes alcohol products and various other components, such as ethers, especially dimethyl ether, ketones, acids, dissolved gases, such as hydrogen, methane, and carbon oxidation Materials, and nitrogen, and fuel oil. In a preferred embodiment, the oxygenate-containing stream, crude methanol, is obtained by known purification methods, distillation, separation, and fractionation to obtain a purified oxygenate stream, such as commercial grade A and AA methanol. An oxygenate-containing stream or a purified oxygenate-containing stream, when combined with one or more diluents, can then be used as a feed in a process to produce light olefins such as ethylene and / or propylene. A non-limiting example of this integration method is described in EP-B-0 9 3 3 3 4 5 which is incorporated herein by reference. In another more complete integration method, which is optionally combined with the above integration method, in one embodiment, the olefins produced are directed to one or more polymerization methods for preparing various polyolefins. (Reference, for example, U.S. Patent · Application Serial No. 09/61, 5,376, filed July 13, 2000, which is incorporated herein by reference). Polymerization methods include solution, gas phase, slurry phase, and high-pressure methods, or a combination thereof -46-(42) 200303237. Particularly preferred is the gas-phase or slurry-phase polymerization of one or more olefins, at least one of which is ethylene or propylene. These polymerization methods utilize polymerization catalysts, which may include any or a combination of the molecular sieve catalysts discussed above, however, preferred polymerization catalysts are Zieg-Natta, Philips-type, metallocene , Metallocene-type and pre-polymerization catalysts, and mixtures thereof. In a preferred embodiment, the integration method includes a method of polymerizing one or more olefins in the presence of a polymerization catalyst system in a polymerization reactor to prepare one or more polymerization products, wherein the one or more olefins have been catalyzed by using the molecular sieve described above The vehicle composition is obtained by converting alcohols, especially methanol. The preferred polymerization method is a gas phase polymerization method, and at least one of the olefins is ethylene or propylene, and preferably, the polymerization catalyst system is a supported metallocene catalyst system. In this embodiment, the supported metallocene catalyst system includes a carrier, a metallocene or metallocene compound and an activator. Preferably, the activator is a non-coordinating anion or alumoxane, or a combination thereof, and Most preferably, the activator is alumoxane. The polymers prepared by the above polymerization methods include linear low density polyethylene, elastomers, plastics, high density polyethylene, low density polyethylene, polypropylene, and polypropylene copolymers. The propylene-based polymers produced by the polymerization method include hetero-row polypropylene, homo-row polypropylene, counter-row polypropylene, and propylene random, block or collision copolymers. Embodiments Examples The following examples are provided to enable the present invention, including its representative advantages, to obtain a better understanding of -47- (43) (43) 200303237. In the examples, L EI is defined as the ratio of the life of the active metal oxide molecular sieve catalyst composition to the life of the same molecular sieve without metal oxide having an LEI of 1. To determine L E1, the lifetime is defined as the cumulative content of converted oxygenates (preferably converted to one or more olefins) / g molecular sieve until the conversion rate drops to about 10% of its initial value. If the conversion does not drop to 10% of its initial value at the end of the experiment, the lifetime is calculated by linear extrapolation using the last 2 data of the experiment to calculate the conversion reduction ratio. In order to determine the LEI of the following examples, in a preferred oxygenate conversion method, methanol is converted to one or more olefins at 475 ° C, 25 psig (172 kPag), and a weight space-time velocity of 100 h-1. "Main olefin" is the sum of selectivity to ethylene and propylene. The "C 2 == / C 3 =" ratio 値 is the ratio of ethylene to propylene weighted selectivity 値. "C3 purity" is calculated by dividing the propylene selectivity by the sum of the propylene and propane selectivities. The selectivity to methane, ethylene, ethane, propylene, propane, C 4, s and C5 + 's is the average weighted selectivity. C5 +, s consists only of C5, s, C6, s and C7'S. The sum of the selectivities in the table is not equal to 100% because it is coke corrected and it is known. Example A Preparation of molecular sieve Shi Ximing Phosphate Molecular Sieve 'SAPO-34, which is called, crystallizes in the presence of tetraethylammonium hydroxide (R1) and dipropylamine (R2), which serve as the organic structure directing agent or template. A mixture having the following molar ratio: (44) (44) 200303237 2Si02 / Al203 / P205 / 0.9Rl / 1.5R2 / 50H20 is prepared by mixing C ο n d e a P u r a 1 S B with deionized water to form a slurry. Phosphoric acid (8 5%) was added to the slurry. These adducts are stirred to form a homogeneous mixture. The homogeneous mixture was forced into [[Ludox A S 40 (40% S i 0 2) '), then R 1 was added and mixed to form a homogeneous mixture. This homogeneous mixture was added to R2. This homogeneous mixture was then stirred in a stainless steel pressure cooker and heated to 170 ° C for 40 hours for crystallization. This provides a slurry of crystalline molecular sieve. The crystals were then separated from the mother liquor by filtration. The molecular sieve crystals are then mixed with an adhesive and a matrix substance, and then granulated by spray drying. Example B The conversion method uses a micro-flow reactor 'to obtain all catalytic or conversion data. The reactor consists of a stainless steel reactor (1/4 inch (0.64 cm) outside diameter) located inside the furnace.' Steam methanol is fed to the micro Flow reactor. The reactor was maintained at a temperature of 47 5 ° C and a pressure of 25 psig (172.4 kPag). The flow rate of methanol is a flow rate such that the weight of methanol / g molecular sieve is also referred to as a weight space-time velocity (WH S V) 'of 100 h-1. The product gas from the reactor is collected and analyzed using gas chromatography. The catalyst loaded in each experiment was 50 mg, and the reactor bed was diluted with quartz 'to minimize hot spots in the reactor. In particular, for the catalyst composition of the present invention, the MS A fraction of Example A -49- (45) (45) 200303237 was used as a physical state mixture of the sub-sieve and the active metal oxide. The loaded total catalyst composition was maintained at 50 mg, and when the molecular sieve content in the reactor bed was reduced by adding mixed metal oxides, the methanol flow rate was adjusted so that the WHSV of methanol was 100 hl. Calculation of the content of the internal molecular sieve. Example 1 1,000 g of Zr * OCl2.8H20 was stirred and dissolved in 3.0 liters of distilled water Φ. Another solution was prepared containing 400 g of concentrated NH40H and 3.0 liters of distilled water. Both solutions were heated to 60 ° C. The two heated solutions were mixed using a nozzle at a rate of 50 m 1 / m i η. The ρ η of the final mixture was adjusted to about 9 by adding concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in an air box (1000 ° C) for 72 hours. The formed product was recovered by filtration, washed with excess water, and dried overnight at 85 ° C. Part of the product was burned to 700 ° C in flowing air for 3 hours to prepare active chromium oxide material. ® Example 2 500 g of Zr0Cl2.8H20 and 84 g of La (N03) 3.6H20 were stirred and dissolved in 3.0 liters of distilled water. Prepare another solution containing 260 grams of concentrated NH40Η and 3.0 liters of distilled water. The two solutions were heated to 60 ° C, and then combined using a nozzle to mix at a rate of 50 ml / min to form the final mixture. The pH of the final mixture was adjusted to about 9 by adding concentrated hydroxide mirrors. This slurry was then placed in a polypropylene bottle and in an airflow box (100-50-(46) (46) 200303237 ° C) for 72 hours. The formed product was recovered by filtration, washed with excess water, and dried overnight at 85 ° C. A part of the product was partially burned in flowing air to ° C for 3 hours to prepare an active mixed metal oxide, which contained a small amount of 10% by weight of La, calculated based on the final weight of the mixed metal oxide. Example 3 50 g of Zr * 0C12.8H20 was stirred and dissolved in 300 ml of distilled water. Another solution containing 4.2 g of La (N03) 3.6H20 and 300 ml of distilled water was prepared. The two solutions are combined with stirring to form the final mixture. The pH of the final mixture, slurry, was adjusted to about 9 by adding concentrated ammonium hydroxide (28.9 g). This slurry was then placed in a polypropylene bottle and placed in an air flow box (100 ° C) for 72 hours. The formed product was recovered by filtration, washed with excess water, and dried overnight at 85 ° C. A part of the obtained product was calcined in flowing air to 700 ° C for 3 hours to produce an active mixed metal oxide, which contains 5 wt% La, based on the final weight of the mixed metal oxide . Example 4 500 g of Zr0C12.8H20 and 70 g of γ (N03) 3.5Η20 were stirred and dissolved in 3.0 liters of distilled water. Another solution containing 260 g of concentrated NH 4 O 4 and 3.0 liters of distilled water was prepared. The two solutions were heated to 60 ° C, and then mixed using a nozzle at a rate of 50 m 1 / m i η to form a final mixture. The pH of the final mixture, slurry, was adjusted to about 9 by adding concentrated ammonium hydroxide. -51-(47) (47) 200303237 This slurry was then placed in a polypropylene bottle and placed in an air flow box (100 t;) for 7 2 hours. The product formed was recovered by filtration, washed with excess water 'and dried at 85 ° C overnight. A part of the obtained product was calcined to 700 in flowing air. (: For 3 hours, an active mixed metal oxide is produced. The oxide contains 10% by weight Y (yttrium), which is calculated based on the final weight of the mixed metal oxide. Example 5 0 0 g of Zr0C12.8H20 and 56g of Ca (N03) 2.4H20 was stirred and dissolved in 3000ml of distilled water. Another solution containing 260g of NH4OH and 300m1 of distilled water was prepared. The two solutions were combined by stirring. The pH of the final mixture was added by adding concentrated hydrogen The ammonium oxide (160g) was adjusted to about 9. This slurry was then placed in a polypropylene bottle and placed in an airflow box (100 ° C) for 72 hours. The formed product was recovered by filtration, in excess. Rinse with water, and dry overnight at 85 ° C. A part of the product obtained is calcined in flowing air to 70 ° C for 3 hours to produce a lively mixed metal oxide, which contains 5% by weight of Ca (calcium), calculated based on the final weight of the mixed metal oxide. Example 6 70 g of Ti0S04 · xh2S〇4 · xH20 (x = 1) was stirred and dissolved in 400 ml of distilled water. Another 12.8 g of CeS04 was prepared And 300 ml of distilled water solution. The mixture is stirred and combined. The pH of the final mixture is adjusted to about 8 by adding concentrated ammonium hydroxide (64.3 g). This slurry is then placed in a polypropylene bottle by (48) (48) 200303237, and placed in an airflow box (100 ° C) for 72 hours. The product formed was recovered by filtration, washed with excess water, and dried overnight at 85 ° C. A portion of the product obtained was subjected to flowing air. Calcining to 70 0 ° C for 3 hours produces an active mixed metal oxide containing 5 wt% Ce, calculated based on the final weight of the mixed metal oxide. Example 7 5g of HfOCl2 · χ 20 was dissolved by stirring In 100 ml of distilled water. The pH of the final mixture was adjusted to about 9 by adding concentrated ammonium hydroxide (4.5 g). This slurry was then placed in a polypropylene bottle and placed in an air flow box (100 ° C) for 72 hours. The formed product was recovered by filtration, washed with excess water, and dried overnight at 85 ° C. A part of the product obtained was calcined in flowing air to 70 ° C lasted for 3 hours and produced a lively mixed metal oxide. Example 8 5g of Hf〇Cl2 · χΗ20 and 0.62g of La (N03) 3 · 6H20 were stirred and dissolved in 1000ml of distilled water. The pH of the final mixture was adjusted by adding concentrated ammonium hydroxide (3.5g) To about 9 ° this slurry was then placed in a polypropylene bottle 'and placed in an air flow box (100 ° C) for 72 hours. The formed product was recovered by filtration 'washed with excess water' and dried overnight at 85 ° C. A part of the obtained product was calcined in flowing air to 700 ° C for 3 hours to 'produce active 旳 mixed gold 丨 persuaded'. This oxidation (49) 200303237 contains 5 weight y〇La 'Based on the final weight of the mixed metal oxide Example 9

The carbon dioxide uptake of the oxides of Examples 1 to 8 was measured at ambient pressure using a Mettler TGA / SDTA 851 thermogravimetric analysis system. The metal oxide sample was dehydrated in flowing air at about 500 ° C for 1 hour, and then the carbon dioxide uptake was measured at 1000 ° C. The surface area of the sample was measured in accordance with the Brunauer, Emmett, and Teller (BET) method, providing carbon dioxide uptake 値, expressed as mg carbon dioxide / m2 metal oxide, as shown in Table 1.

Table 1 Example Catalyst dry weight (mg) mg of C02 surface area (m2 / g) C02 intake (mg of C02 / m2) 1 76 0.0980 29 0.045 2 115 0.7781 80 0.085 3 73 0.4243 89 0.065 4 97 0.3808 100 0.039 5 78 0.5399 85 0.081 6 43 0.1035 50 0.048 7 158 0.3704 25 0.094 8 164 0.7359 60 0.075 -54- (50) (50) 200303237 Example 1 〇 (Comparative Example) In this example, the contact The vehicle composition was composed of 40 mg of MS A from Example A and 10 mg of active osmium oxide from Example 1. The catalyst composition and the active mixed metal oxide were mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in the method of Example B are shown in Tables 2 and 3. The results show that the addition of active oxidizing pins to the catalyst bed significantly increases the life of the molecular sieve composition and reduces the content of unwanted ethane and propane.

Example 1 2 In this example, the catalyst composition is composed of 40 mg of MSA of Example A and 10 mg of active mixed metal oxide (described in Example 2) containing 10% by weight of La. . The catalyst composition and the active mixed metal oxide are mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in the method of Example B are shown in Tables 2 and 3. The data in Tables 2 and 3 show that by constituting a 20% catalyst composition loaded with an active mixed metal oxide containing 10% by weight of La, the life of the molecular sieve is doubled, as shown in its LEI 其 2. In addition, the net income was 1.7% of major olefins. In absolute terms, most of this income was due to a 2.7 6% increase in propylene and a 1.07% reduction in compensation for ethylene. The selectivity to ethane was reduced by 39% and the selectivity to propane was reduced by 37%, suggesting that the hydrogen shift reaction has been significantly reduced. Example 1 3 In this example, the catalyst composition was composed of 30 mg of -55- (51) (51) 200303237 M S A of Example A and contained 10 weight. / 0 L a composition of 20 m g of active mixed metal oxide (described in Example 2). The catalyst composition and the active mixed metal oxide are mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in the method of Example B are shown in Tables 2 and 3. The data in Tables 2 and 3 show that by constituting 40% of the catalyst composition, the composition contains 10% by weight. / 〇La, SAP 0-34 catalyst composition life increase □ 440%. The selectivity of this catalyst is similar to that shown in Example 8.

Example 1 4 In this example, the catalyst composition was composed of 40 mg of MS A of Example A and 10 mg of active mixed metal oxide (described in Example 4) containing 10% by weight of Y. The catalyst composition and the active mixed metal oxide were mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in the method of Example B are shown in Tables 2 and 3. Replacing lanthanum with yttrium has the effect of increasing L EI. However, the improvement in selectivity is not as dramatic as lanthanum, and the gain in major olefins is 1.2%, calculated in absolute terms. Example 1 5 In this example, the catalyst composition was composed of 40 mg of MSA of Example A and 10 mg of active mixed metal oxide (described in Example 3) containing 5% by weight of La. The catalyst composition and the active mixed metal oxide were mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in Example; Method B are shown in Tables 2 and 3. It will be found that the active mixed metal oxide containing 5% by weight of lanthanum oxide appears to have a stronger effect in increasing LEI than the active mixed metal oxide containing 10% by weight of La in Example 8-56- (52) 200303237. Example 16 In this example 16, the catalyst composition was composed of 30 mg of MSA of Example A and 10 mg of active mixed metal oxide (described in Example 5) containing 5% by weight of Ca. The catalyst composition and the active mixed metal oxide are mixed and then diluted with quartz to form a reactor bed. The results of this test in the reactors and conditions discussed in Example B are shown in Tables 2 and 3. The active mixed metal oxide containing 5% by weight of calcium oxide has an increase in the life of the molecular sieve composition by 2 2 3%. Example 17 (comparative example)

In this comparative example, the catalyst composition was composed of 40 mg of MSA of Example A and 10 mg of amorphous silica / alumina and an inactive mixed metal oxide. The molecular sieve catalyst composition and the inactive mixed metal oxide are mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in the method of Example B are shown in Tables 2 and 3. This comparative example: [7 shows that when the inactive mixed metal oxide is in phase 11 with Example 11 of the present invention I: d 'L EI is reduced to less than 1.0. In addition, the selectivity loss to the major olefins was 1.07%, and the production of ethane and propane was not significantly reduced. Example 18 In this example, the catalyst composition was composed of 30 mg of Example A-57- (53) (53) 200303237 MSA and 10 mg of active mixed metal oxide containing Ce and titanium dioxide (described in Example 6) Composition. The catalyst composition and the active mixed metal oxide were mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in the method of Example B are shown in Tables 2 and 3. The presence of active mixed metal oxides increases the life of the molecular sieve composition by 134%. Example 19 In this example, the catalyst composition is composed of 40 mg of MSA of Example A and 10 mg of a reactive metal oxide (described in Example 7). The catalyst composition and the active mixed metal oxide are mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in the method of Example B are shown in Tables 2 and 3. The data in Tables 2 and 3 show that by constituting a catalyst composition of 20%, the composition is loaded with active metal oxides, and the life of the molecular sieve is increased by 126%. The selectivity to ethane was reduced by 40% and the selectivity to propane was reduced by 46%, suggesting that the hydrogen shift reaction has been significantly reduced. Example 20 In this example, the catalyst composition was composed of 40 m g of M S A of Example A and 10 m g of a reactive mixed metal oxide (described in Example 8) containing 5% by weight of La. The catalyst composition and the active mixed metal oxide were mixed and then diluted with quartz to form a reactor bed. The results of testing the catalyst composition in the method of Example B are shown in Tables 2 and 3. The data in Tables 2 and 3 show that by constituting a catalyst composition of 20%, the composition is loaded with an active mixed metal oxide containing 5% by weight of La, and the life of the molecular sieve is increased by -58- (54) 200303237 1 50% . A 51% reduction in selectivity to ethane and a 51% reduction in selectivity to propane suggest that the hydrogen shift reaction has been significantly reduced. Table 2 Example reactor bed composition (wt ° / o) LEI main olefin (%) C27C3 = c3 purity (%) 10 (comparative example) 1000 / 〇MSA 1 74.65 0.92 92.7 11 80% MSA / 20% Zr. 2 2.64 74.79 0.82 96.1 12 80% MSA / 20% of 10% La / ZrO2 2.03 76.34 0.84 95.6 13 60% MSA / 40% of 10% La / ZrO2 5.41 75.50 0.85 94.6 14 80% MSA / 20% of 10% Y / ZrO2 2.79 75.81 0.85 94.9 15 80% MSA / 20% of 5% La / Zr02 4.85 75.84 0.84 94.8 16 80% MSA / 20% of 5% Ca / Zr02 3.23 73.85 0.79 96.7 17 (comparative example) 80% MSA / 20 % of Si02 / Al203 0.79 73.58 0.93 93.3 18 80% MSA / 20% of Ce / Ti02 2.34 65.65 0.87 95.1 19 80% MSA / 20% of Hf02 2.26 72.98 0.71 96.2 20 80% MSA / 20% of 5% La / HfO2 2.50 72.75 0.76 96.5

-59-(55) (55) 200303237 Table 3 Production 1 Do not choose Example reactor bed (wt%) ch4 c2 = c2 ° c3 = c3 ° C4, s C5 + 10 (comparative example) 100% MSA 1.51 35.82 0.95 38.83 3.05 14.50 2.12 11 80% MSA / 20% ZrO2 1.50 33.74 0.53 41.05 1.68 14.79 3.31 12 80% MSA / 20% of 10% La / ZrO2 1.31 34.75 0.58 41.59 1.93 14.96 2.46 13 60% MSA / 40% of 10% La / ZrO2 1.47 34.75 0.66 40.75 2.32 14.76 2.52 14 80% MSA / 20 ° / 〇of 10% Y / ZrO2 1.32 34.92 0.66 40.88 2.20 14.41 3.07 15 80% MSA / 20% of 5% La / Zr02 1.26 34.59 0.64 41.25 2.28 14.96 2.52 16 80% MSA / 20% of 5% Ca / Zr02 1.50 32.65 0.42 41.20 1.43 14.84 5.34 17 (comparative example) 80% MSA / 20% of Si02 / Al203 2.17 35.46 0.89 38.12 2.72 14.21 2.65 18 80% MSA / 20% of Ce / Ti02 6.79 30.57 0.75 35.09 1.80 12.72 3.97 19 80% MSA / 20% of HfO2 1.98 31.62 0.52 41.36 1.65 14.64 4.93 20 80% MSA / 20% of 5% La / HfO2 1.98 31.58 0.47 41.18 1.49 14.53 5.52 EXAMPLES When describing and explaining the present invention, those skilled in the art -60- (56) (56) 200303237 will understand that the present invention is suitable for variations and need not be described here. For example, it is expected that the molecular sieve compositions described herein serve as absorbents, adsorbents, gas separation agents, detergents, water purification agents, and for various uses such as agronomy and horticulture. It is within the scope of the present invention to add one or more active metal oxides to the synthesis mixture to prepare the above molecular sieves. For this reason, for the purpose of determining the true scope of the present invention, reference is only made to the scope of the attached patent application.

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Claims (1)

200303237 范围 Patent application scope 1 · A catalyst composition, including a molecular sieve and at least one oxide from a Group 4 metal of the periodic table, wherein the carbon dioxide intake of the metal oxide is at least at 100 ° C 0.03 mg / m2 metal oxide. 2. The catalyst composition according to item 1 of the patent application scope, wherein the carbon dioxide intake of the metal oxide is at least 0.035 mg / m2 metal oxide at 100 ° C. 3. The catalyst composition according to item 1 of the patent application scope, wherein the carbon dioxide intake of the metal oxide is less than 10 mg / m2 of the metal oxide at 100 ° C. 4- The catalyst composition according to item 1 of the patent application scope, wherein the carbon dioxide intake of the metal oxide is lower than 5 mg / m2 metal oxide at 100 ° C. 5. The catalyst composition according to item 1 of the patent application scope also includes at least one adhesive and matrix substance different from the metal oxide. 6. The catalyst composition according to item 1 of the patent application scope, wherein the surface area of the metal oxide is greater than 10 m 2 / g. 7 · If the catalyst composition of item 1 of the patent application scope also includes a binder and a matrix substance, which are different from each other and different from the metal oxide. 8. The catalyst composition according to item 7 of the patent application scope, wherein the adhesive is alumina sol 'and the matrix substance is clay. 9. The catalyst composition according to item 1 of the patent application scope, wherein the metal oxide is selected from chromium oxide and oxide. 10. If the catalyst composition in item 1 of the patent application diagram also includes oxides selected from Group 62 and Group 3 metals of the Periodic Table of Elements. 11. The catalyst composition according to item 10 of the application, wherein the Group 4 metal oxide includes an oxide cone, and the Group 2 and / or Group 3 metal oxide includes one or more selected from calcium oxide, oxide Barium, lanthanum oxide, yttrium oxide and hafnium oxide. 1 2 · The catalyst composition according to item 1 of the scope of patent application, wherein the molecular sieve includes a structure containing at least two tetrahedral units, the unit being selected from [Si04], [Al〇4] and [P〇4] units . φ 1 3. The catalyst composition according to item 12 of the patent application scope, wherein the molecular sieve includes silicoaluminophosphate. 14. The catalyst composition according to item 12 of the patent application scope, wherein the molecular sieve comprises a molecular sieve of CHA structure type. 15. The catalyst composition according to item 14 of the patent application scope, wherein the molecular sieve additionally includes a molecular sieve of AEI structure type. 16. The catalyst composition according to item 1 of the patent application range, wherein the weight ratio of the molecular sieve to the metal oxide ranges from 5% to 800%. β 17. A molecular sieve catalyst composition, including active Group 4 metal oxides and Group 2 and / or Group 3 metal oxides, adhesives, matrix substances, and silicoaluminophosphate molecular sieves. 18. A method for preparing a catalyst composition, the method comprising: & mixing ' the carbon dioxide of the Group 4 metal oxide with the first particles containing the molecular sieve and the second particles containing the Group 4 metal oxide Ingestion is at least 0.3 mg / 1T12 metal oxide particles at 100 ° C. 19. The method according to item 1S of the scope of patent application, wherein the surface area of the second particle -63- (3) 200303237 is greater than 10 m2 / g. 20. The method of claim 18 in the scope of patent application, wherein the surface area of the second particle is greater than 15 m2 / g. 2 1. The method of claim 18 in the scope of patent application, wherein the first particle comprises aluminophosphate molecular sieve and / or aluminophosphate molecular sieve. 2 2 · If the method of applying for the item No. 18 of the patent scope, wherein at least one of the first and second particles also includes at least one of the adhesive and the matrix material, please refer to 23 · If the method of applying for the scope of No. 18 patent application The first particles include a silicoaluminophosphate molecular sieve, a binder containing alumina sol, and a matrix substance containing clay. 24. The method of claim 18, wherein the second particle also includes a Group 2 and / or Group 3 metal oxide. 25. The method of claim 18, wherein the second particles include chromium oxide, and at least one of calcium oxide, barium oxide, lanthanum oxide, yttrium oxide, and hafnium oxide. φ 2 6. —A method for preparing a catalyst composition, the method comprising: (i) synthesizing a molecular sieve from a reaction mixture including at least one of a template agent and at least two of a silicon source, a phosphorus source, and an aluminum source; and ( ii) recovering the molecular sieve synthesized in (i); (iii) forming a hydration precursor of a Group 4 metal oxide by precipitating from a solution containing a source of a Group 4 metal ion; (iv) recovering (iii ); (V) calcined the hydrated precursor recovered in (iv) to form a Group 4 metal oxide which is subjected to calcination-64- (4) 200303237, The intake of carbon dioxide (at 100 ° C) is at least 0.03 mg / m2 of metal oxide; and (vi) the molecular sieve recovered in ⑴ and the calcined metal oxide prepared in (v) are completely mixed. 27. The method of claim 26, wherein the molecular sieve and / or the Group 4 metal oxide is mixed with an adhesive and / or a matrix substance before step (vi). 2 S. The method of claim 26, wherein the weight ratio of the molecular sieve to the calcined metal oxide ranges from 30% to 400%. 29. The method according to item 26 of the patent application, wherein the surface area of the metal oxide to be calcined is greater than 10 m2 / g. 30. The method of claim 26, wherein the molecular sieve is dry sprayed with a matrix substance and an adhesive before (vi). 31. The method of claim 30, wherein the molecular sieve is silicoaluminophosphate, the adhesive is alumina sol, and the matrix material is clay. 32. The method of claim 26, wherein the mixed metal oxide is prepared in (iii) by precipitating from at least one solution containing a precursor of a group 4 metal oxide, And at least one of a precursor of a Group 2 metal oxide and a precursor of a Group 3 metal oxide. 33. The method according to item 26 of the patent application, wherein the precipitation is carried out at a pH greater than 7. 34. The method according to item 26 of the patent application, wherein (iii) also includes hydrothermally treating the precipitate at a temperature of at least 80 ° C for 10 days. -65- (5) (5) 200303237 35. The method according to item 26 of the patent application range, wherein (v) is carried out in a temperature range from about 400 ° C to about 900 ° C. 3 6. —A method for converting a feedstock into one or more non-heavy olefins in the presence of a catalyst composition comprising a molecular sieve and a live 4th metal oxide, the carbon dioxide of the metal oxide The ingestion is at least 0.03 mg / m2 metal oxide at 10 (re). 37. The method according to item 36 of the patent application scope, wherein the carbon dioxide intake of the metal oxide is at 100 ° C At least 0.03 5 mg / m2 metal oxide. 38. The method according to item 36 of the scope of patent application, wherein the carbon monoxide intake of the metal oxide is less than 10 mg / m at 100 ° C. 2 Metal oxide. 3 9. The method according to item 36 of the patent application scope, wherein the carbon dioxide intake of the metal oxide is less than 5 mg / m2 metal oxide at 100 ° C. 40. As applied The method of item 37 of the patent also includes at least one adhesive and matrix material different from the metal oxide. 4 1 · If the method of item 37 of the patent application also includes the adhesive and matrix material 'which are mutually Different and different from the metal oxide. 4 2. If the patent application The method surrounding item 41, wherein the adhesive is an alumina sol. 43 · The method according to item 41 of the patent application, wherein the matrix is clay. 4 4 · The method according to item 36, where the contact Media composition -66- (6) (6) 200303237 The life increase index (LEI) of the substance is greater than 1. 45. For the method of item 36 of the patent application, wherein the molecular sieve is optionally selected by the presence of a sample agent The reaction mixture is synthesized, and the mixture includes at least two of a silicon source, a phosphorus source, and an aluminum source. 46. The method according to item 36 of the patent application, wherein the molecular sieve is a silicoaluminophosphate. 4 7. The method according to item 6, wherein the catalyst composition also includes active Group 2 and / or Group 3 metal oxides. 4 8. The method according to item 36 of the scope of patent application, wherein the feed includes methanol and / or dimethyl ether Ether. 4 9. A method for converting a feed to one or more olefins in the presence of a molecular sieve catalyst composition, comprising a mixture of molecular sieves, a binder, a matrix material, and a metal oxide other than a binder and a matrix material. 50 · If apply The method of claim 49, wherein the mixture of metal oxides includes Group 4 metal oxides and Group 2 and Group 7 or Group 3 metal oxides. 5 1. A method for making the feed in the presence of a catalyst composition A method for converting into one or more kinds of hydrocarbon combustion, the catalyst composition is prepared by a method such as the scope of application for patent No. 18. 5 2. A method for converting the feedstock into one or more kinds in the presence of the catalyst composition In the method of Greek hydrocarbon, the catalyst composition is prepared by a method such as the item 26 of the scope of patent application. 5 3-A method for preparing one or more olefins, the method comprising: (a) introducing a feed containing at least one oxygenate in a catalyst composition -67- (7) (7) 200303237 into the reactor System, the composition comprising a molecular sieve, an adhesive, a matrix substance, and an active Group 4 metal oxide; (b) discharging an effluent stream containing one or more olefins from the reactor system; and (c) passing the effluent stream through recovery A system; and (d) recovering at least the one or more olefins. 54. The method of claim 53 in which the adhesive is an alumina sol. 5 5. The method according to item 53 of the patent application scope, wherein the matrix substance is clay. 5 6. The method according to item 53 of the patent application scope, wherein the molecular sieve is a silicoaluminophosphate molecular sieve and / or an aluminophosphate molecular sieve. 5 7. The method according to item 53 of the scope of patent application, wherein the active Group 4 metal oxide is an active chromium metal oxide or an active metal-donor oxide or a mixture thereof. 5 8. The method according to item 53 of the scope of patent application, wherein the carbon dioxide intake of the active Group 4 metal oxide is at least 0.03 mg / m2 metal oxide at 1000 ° C. 59. The method of claim 53 in which the catalyst composition includes active Group 2 and / or Group 3 metal oxides. 60. The method of claim 53 in which the feed includes methanol and / or dimethyl ether. 61. The method according to item 53 of the patent application, wherein the surface area of the active metal oxide is greater than. -68- (8) 200303237 6 2. The method of item 53 of the patent application range, wherein the LEI of the catalyst composition is greater than the LEI of the same catalyst composition without active metal oxides. The method according to item 53, wherein the LEI of the sieve catalyst composition is greater than 1.5. 64 · An integrated method for preparing one or more olefins, the integrated method comprising: (a) passing a hydrocarbon feed through a synthesis gas generation area to generate a synthesis gas stream; (b) contacting the synthesis gas stream with a catalyst to form an oxidation Feed; and (0) convert the oxidation feed to the one or more olefins in the presence of a molecular sieve catalyst composition, the composition including molecular sieves and active metal oxides. 6 5-Integrated method as claimed in item 64 Wherein the method further comprises (d) polymerizing the one or more olefins to a polyolefin in the presence of a polymerization catalyst. 6 6. The integrated method of claim 64, wherein the oxidation feed includes methanol and the olefin includes ethylene And propylene, and the active metal oxide are active Group 4 metal oxides, and the surface area of the oxide is greater than 10 m 2 / g 〇6. The integration method of item 6 of the patent application scope, wherein the Group 4 metal is oxidized The material is active oxidation pin. 68. For example, the integrated method of the patent application No. 66, wherein the molecular sieve silicoaluminophosphate molecular sieve. -69- 200303237 Lu, (a) (b), The designated representative figure in this case is: None. The element representative symbols of this representative figure are simply explained: 柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention ...