TW200303238A - Molecular sieve compositions, catalysts 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 selected from Group 3 of the Periodic Table of Elements, the Lanthanide series of elements and the Actinide series of elements.

Description

r200303238 (1) 对照 Contrast of related applications of invention description This case is part of consecutive US application No. 10/2 15, 511 filed on August 9, 2002, and US application No. 60/3 applied at the same time 60,963 (Attorney Docket 2002B010) and US application serial number 60/3 60963 (Attorney Docket 2002B 05 7), 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 synthesis of the composition and the catalyst, and the use of the composition and the catalyst in a conversion method for preparing an olefin. [Prior art] Olefins are prepared in a conventional manner from a petroleum feed by a catalyst or a steam cracking method. These cracking methods, particularly steam cracking, produce light olefins, such as ethylene and / or propylene, from various hydrocarbon feeds. Ethylene and propylene are important petrochemical commodities for various processes 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 a number of techniques applied to the preparation of oxygenates, which include reactions of fermentation or synthesis gas derived from natural gas, petroleum liquids or coal-containing carbon materials, recycled plastic, local waste or any other organic material. Generally, the synthesis gas synthesis involves the combustion reaction of natural gas (mostly -6-(2) (2) 200303238 is methane) with an oxygen source to generate 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 light olefins, 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 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, US 5,3 67,100 describes the conversion of methanol to olefins using zeolite (ZSM-5); US 4,062,905 discusses the use of crystalline aluminosilicate zeolites such as zeolite T, ZK5, erionite, and chabazite (Chabazite) to convert methanol or other oxygenates to ethylene and propylene; US 4,079,095 describes the use of ZSM-34 to convert methanol to hydrocarbon products such as ethylene and propylene; and US 4,3 1 0,4 40 describes the use of crystalline phosphoric acid Aluminum salts, usually labeled aipo4, make light olefins from alcohols. (3) (3) 200303238 Some of the most useful molecular sieves for converting methanol to olefins are silicoaluminophosphate molecular sieves. The enoaluminophosphate (SAP 0) molecular sieve includes a three-dimensional microporous crystalline skeleton structure sharing [Si04], [Al〇4], and [P04] corners of a tetrahedral unit. SAPO synthesis is described in US 4,44 0,871, which is fully incorporated herein by reference. SAP O 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. The synthesis of SAPO molecular sieves, its formulation into SAPO catalysts, and its use for converting hydrocarbon feeds to olefins, especially the feed is methanol, are disclosed in US 4,499,327, 4,677,242, 4,677,243, 4,8 73,3 90 > 5,095 , 1 63, 5,7 1 4,662 and 6,1 66,282, 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 sieve catalyst composition having better conversion, improved hydrocarbon selectivity, and longer life is desired. US 4,465,8 89 describes a catalyst composition comprising a rhenium, chromium or titanium metal oxide silicate molecular sieve 'which is used to convert methanol, dimethyl ether or a mixture thereof to a hydrocarbon rich in isoC4 compounds product. US 6,1 80,82 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' Example -8- (4) (4) 200303238 such as hafnium oxide, Titanium oxide, yttrium oxide, montmorillonite or kaolin. US 5,4 1 7,949 is a method of using molecular sieves and metal oxide adhesives to convert the toxic nitrogen oxides present in the oxygen-containing effluent to nitrogen and water. The preferred adhesive is titanium dioxide, and the molecular sieve is aluminum silicate. salt. EP-A-3 1298 1 discloses a method for cracking a vanadium-containing hydrocarbon feed stream using a catalyst composition on a silica-containing carrier material, the composition comprising a zeolite embedded in an inorganic refractory matrix material and at least one beryllium, Oxides of magnesium, calcium, scandium, barium or lanthanum. Φ

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 grinding the catalyst with MgO, CaO, BaO or Cs2〇 BaO is the best. # WO 98/293 70 discloses 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, radiation elements, scandium yttrium, group 4 metals, group 5 metals, or Mixture of metals. SUMMARY OF THE INVENTION In one aspect, the present invention resides in a catalyst composition containing a molecular sieve and an oxide of at least one metal selected from Group 3 of the periodic table, lanthanides and actinides, wherein the Carbon dioxide intake: -9- (5) (5) 200303238 at 100 ° C is at least 0.03 mg / m2 metal oxide, and typically at least 0.04 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 oxide includes one or more selected from the group consisting of calcium oxide, barium oxide, lanthanum oxide, yttrium 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 the group consisting of [sio4], [aio4], and [P04] units. In another aspect, the invention resides in a molecular sieve composition comprising a Group 3 metal oxide and / or a lanthanide or actinide oxide, a binder, a matrix material, and a silicoaluminophosphate molecular sieve. In another aspect, the present invention resides in a method for preparing a catalyst composition, the method comprising combining first particles containing a molecular sieve with at least one metal selected from Group 3, lanthanide and actinide in the periodic table. The second particles of the oxide are completely mixed, and the carbon dioxide intake of the metal oxide is at least 0.03 mg / m2 metal oxide particles at 100 ° C. In one embodiment, the molecular sieve, adhesive and matrix material are prepared into a formulated molecular sieve composition, which is then contacted with an active Group 3 metal oxide and / or an active oxide of a lanthanide or actinide, Mix, combine, spray dry or more. In another aspect, the invention resides in a method for preparing a catalyst composition. (6) (6) 200303238 The method includes: (i) synthesizing a molecular sieve from a reaction mixture, the mixture including at least one sample agent and a source of silicon and a source of phosphorus And at least two of aluminum sources; and (ii) recovering the molecular sieve synthesized in (i); (iii) forming a group selected from Group 3 of the periodic table by precipitating from a solution containing the metal ion source Hydration precursors of metal oxides of lanthanides and actinides; (iv) recovery of hydrated precursors formed in (iii); (v) hydration precursors recovered in calcination (iv) to Form a calcined Group 4 metal oxide whose carbon dioxide uptake is at least 0.03 mg / m2 metal oxide at 100 ° C; and (vi) completely mixed with (i) The recovered molecular sieve and the calcined metal oxide prepared in (v). In another aspect, the present invention relates to a method for preparing an olefin, which is performed by switching a feed, such as an oxygenate, in the presence of any of the above molecular sieve compositions and / or molecular sieves or formulated molecular sieve catalyst compositions, suitably Alcohols, such as methanol. In another aspect, the invention is an integrated process for preparing one or more olefins, the integrated process comprising: (a) passing a hydrocarbon feed through a synthesis gas generation zone to produce a synthesis gas stream; (b) passing the synthesis gas stream to Contacting the catalyst to form an oxygen-containing feed; and (c) converting the oxygen-containing feed to the one or more olefins in the presence of a molecular sieve catalyst composition comprising a molecular sieve and at least one selected from the elements (7) ( 7) 200303238 An oxide of a metal of Group 3 or lanthanum or actinide in the periodic table. In one embodiment, the catalyst composition has a lifetime increase index (LEI) greater than 1, such as greater than 1.5. LEI is defined herein as the ratio of the lifetime of the catalyst composition to the lifetime of the same catalyst composition without active metal oxides. [Embodiment] Detailed description of the embodiment Introduction Lu This invention relates to a molecular sieve catalyst composition and its use for converting a hydrocarbon feed, especially an oxidized feed, to an olefin. It has been found that mixed molecular sieves with IUPAC form from Group 3 of the Periodic Table of the Elements (using the IUPAC format described in CRC Handbook of Chemistry and Physics, 7 8th Edition, CRC Press, Boca Raton, Florida [1 997]) and / or An active metal oxide of a series element to obtain a catalyst composition having an increased olefin yield and / or a longer lifespan when used for a conversion feed such as an oxygenate, more specifically methanol, to an 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 ethyl aldehyde. Molecular sieves Molecular officials have been classified by the Structure Commission of the International Zeolite Association based on the IUPAC Commission on Zeolite Nomenclature. According to this classification, the structure type zeolite and zeolite molecular sieve have been confirmed and assigned to 3 words -12- (8) 200303238 parent and described in Atlas of Zeolite Framework Types, 5th edition, Elsevier, London, England (200 1), which is incorporated herein by reference. Crystal molecular sieves all have a three-dimensional, four-connected 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 al., Introduction to Zeolite Science and Practice, Second Completely Revised and Expanded Edition, Volumene 137, pages 1-67, Elsevier Science, BV, Amsterdam, Netherlands (2001). Non-limiting examples of molecular sieves Small holes Molecular sieves, 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 sieve, AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON and their substituted forms: and macroporous molecular sieves, EMT, FAU and their substituted forms. Other molecular sieves include ANA, BEA, CFI, CLO, DON, GIS, LTL, M E R, M OR, M W W and SO D. Non-limiting examples of better molecular decorations, 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 of -13- (9) (9) 200303238, the molecular sieve of the present invention has an AEI topology or a CHA topology, or a combination thereof, and is most preferably a CHA topology. Small, intermediate, and large-pore molecular sieves are available in 4-ring to 12-ring or larger structures. 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, molecular sieves, preferably silicoaluminophosphate molecular sieves, have 8-rings and an average pore size of less than about 5A, such as in a range from 3A to about 5A, such as from 3 A to 4.5A, and particularly From 3.5A to about 4.2A. Molecular sieves have a molecular structure that shares 1, preferably 2 or more, corner [T04] tetrahedral units, more preferably 2 or more [Si04], [Al〇4], and / or [p〇4] Tetrahedral elements, and most preferably [si〇4], [aio4] and / or [P04] tetrahedral elements. 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 (MeAPO where Me is Mg, Mη, Zn or Co), US 4,440,87 1 (SAPO), EP-A-0 1 59624 (ELAPSO where El is As, Be, B, Cr, Co, Ga, Ge, F e, Li, Mg, Mη, Ti Or Zn), US 4,5 54,1 43 (FeAPO), US 4,822,478, 4,683,2 1 7, 4,744,885 (FeAPSO), EP-A-0 1 5 897 5 and US 4,93 5,2 1 6

(ZnAPSO), EP-A-0161489 (CoAPSO), EP-A-0158976 (ELAPO where EL is Co, Fe, Mg, Mn, Ti or Zn), US 4,3 10,440 (A1P04), EP-A 0158350 (SENAPO), US 4,973,460 (LiAPSO), US 4,789,535 (LiAPO), US 4,992,250 (GeAPSO), US 4,888,167 (GeAPO), US 5,057,295 (BAPSO), US 4,73 8,83 7 (CrAPSO), US (10 ) 200303238 4,75 9,9 1 9 and 4,851,106 (CrAPO), US 4,758,4 1 9,4,8 82,03 8, 5,43 4,326 and 5,47 8,78 7 (MgAPSO), US 4,5 54.1 43 (FeAPO), US 4,894,2 1 3 (AsAPSO), US 4,913,888 (AsAPO), US 4,686,092 '4, 8 4 6, 9 5 6 and 4, 7 9 3, 8 3 3

(MnAPSO), US 5,3 4 5,0 1 1 and 6, 1 5 6,9 3 1 (Μη AP O), US 4,73 7,3 5 3 (BeAPSO), US 4,940,570 (BeAPO), US

4,80 1,3 09 '4,684,6 1 7 and 4,880,520 (TiAPSO), US

4.5 00,65 1, 4,551, 23 6 and 4,605, 492 (TiAPO), US 4.824.5 54, 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, 4,801,3 64, 4,8 53, 53,197, 4,9 17,876, 4,952,3 84, 4 ,, 95 6,164, 4,956,165, 4,973,785, 5,241,093, 5,493,066, and 5,675,05 0, all of which are incorporated herein by reference.

Other molecular stores include those described in R. Szostal, Handbook of Molecular Sieves, Van No strand Reinhold, New York, New York (1992), which is incorporated herein by reference. More preferred molecular sieves include aluminum phosphate (A1PO) molecular sieves and silicon aluminum phosphate (SAPO) molecular sieves and substituted, preferably metal-substituted, A1PO and SAPO molecular sieves. The best molecular sieves are SAPO molecular sieves and metal-substituted SAPO molecular sieves. 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, thorium,鐯, 钹, 钐, 铕, 铽, 镝, 鈥, bait, watch, mirror, and distillate; -15- (11) (11) 200303238 and Tong or Biao, Wusu Group 4 to 12 of the periodic table Transition metals, or a mixture of any of these metal species. In a preferred embodiment, the 'metal system is selected from the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn, and Zr, and mixtures thereof. In another preferred embodiment, the metal atoms discussed above are inserted into the framework 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 the example, molecular sieves, as described in the above-mentioned US patent case, are 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 the ratio of R relative to Molars per mole (MxAlyPz) 02, and from 0 to 1, preferably 0 to 0.5, and most preferably 0 to 0.3; X, y, and z represent Al, P, and Mo's fraction of M, in which μ is a metal, which is selected from Groups 1, 2, 3, 4, 5, 6, 7, 8, 9, 9, 10, η, 12, 13, 14 in the periodic table of elements And the lanthanide series, preferably, the M series is selected from one of si, Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn, and Zr. In one embodiment, m is greater than or equal to 02, and x, y, and z are greater than or equal to 0.01. In another embodiment, m is greater than 0; [to about 1, X is greater than 0 to about 0.25, y ranges from 0.4 to 0.5, and z ranges from 0.25 to 0.5, more preferably , M is from 0.5 to 0.7, X is from 0.001 to 0.2, y is from 0.4 to 0.5, and z is from 0.3 to 0.5. -16-(12) 200303238

Non-limiting examples of SAPO and A1PO molecular sieves used in this article include SAPO-5, SAPO-8, SAPO-1 1, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34 , SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (US 6,162,415), SAPO-47, SAPO-56, A1PO-5, A1PO-11 , A1PO-1 8, A1PO-3 1, A1PO-34, A1PO-36, A1PO-37, A1PO-46 and one or a combination of metal-containing molecular sieves. Particularly useful molecular sieves are one or a combination of SAP0-18, SAP0-34, SAPO-35, SAPO-44, SAPO-56, A1P0-1 8 and A1PO-34 and their metal-containing derivatives, such as One or a combination of SAPO-18, SAPO-34, A1PO-34 and A1P0-1 8 and their metal-containing derivatives, and in particular, SAPO-34 and A1P0-18 and their metal-containing derivatives One or a combination.

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 No. 09 / 924,016, filed August 7, 2001, and WO 98/15496, published April 16, 1998, both of which are incorporated herein by reference. For example, SAPO-18, A1P0-18, 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. It was measured using the DIFFaX method described in Application Serial No. 09 / 924,0 1 6. -17- (13) (13) 200303238 Synthesis of molecular sieves The synthesis of molecular sieves is described in most of the materials 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, a combination of sand, aluminum, and phosphorus sources is optionally combined with one or more template 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, available from Degussa Inc., New York, New York, organic silicon compounds, such as tetraalkane Based orthosilicates (such as tetramethylorthosilicate (TMOS) 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, Acetic 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 aluminum trichloride, or any combination thereof . A convenient source of aluminum is pseudo bauxite, especially when making silicoaluminophosphate molecular sieves. Non-limiting examples of phosphorus sources, which may also include aluminum-containing phosphorus compositions' including phosphoric acid, organic phosphates, such as triethyl phosphate, and crystalline or non-crystalline phosphate salts, such as A1P 0 4, A phosphate salt, or a combination thereof. A convenient source of phosphorus is phosphoric acid, especially when making silicoaluminophosphates. Prototype agents are usually compounds containing Group 15 elements in the periodic table, especially -18- (14) (14) 200303238 nitrogen, phosphorus, arsenic and antimony. Typical model agents also include at least one alkyl or aryl group, such as an alkyl or aryl group having 1 to 10 carbon atoms, such as 1 to 8 carbon atoms. The preferred template is usually a nitrogen-containing compound ' such as an amine, a quaternary ammonium compound, and combinations thereof. Suitable quaternary ammonium compounds are of the general formula IUN +, where R is hydrogen or a hydrocarbon group or a substituted hydrocarbon group, preferably an alkyl or aryl group having from 1 to 10 carbon atoms. Non-limiting examples of model agents include tetraalkylammonium compounds and salts thereof, 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, Choline, N, N'-dimethylpiperazine, 1,4-diazabicyclo (2,2,2) octane, > 1 ',: ^',! ^, ≫ ^ tetramethyl (1,6) Hexanediamine, 1 ^ methyldiethanolamine, ~ methyl-ethanolamine, N-methylpiperidine, 3-methyl-piperidine, N-methylcyclohexylamine, 3-methylformamidine Pyridine, 4-methyl-pyridine, quinone ring, N, N, -dimethyl-I, 4-diazabicyclo (2,2,2) octane ion, di-n-butylamine, neopentyl Methylamine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, pyrrolidine and 2-imidazolidone. The pH range of synthetic mixtures containing a minimum amount of silicon-, aluminum- and / or phosphorus composition and template is usually from 2 to 10, such as from 4 to 9, such as from 5 to 80, and generally the synthetic mixture described above is Sealed in a container, preferably under self-pressure, 'heated to a temperature ranging from about 80 t: to about 250 ° C, such as from about 100 ° C to about 250 ° C, such as from about! 25 ° C to about 2 2 5 ° C, for example from about (15) (15) 200303238 1 50 ° C to about 180 ° C. In one embodiment, the synthesis of molecular sieves is assisted by seeds from another molecular sieve or phase, molecular sieve of the same structural type. The time to form a crystalline product 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 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, usually in the form of a slurry, it can be recovered by any standard technique known in the art, such as by centrifugation or filtration. The recovered crystalline product can then be rinsed, for example with water, and then dried, for example in air. A crystallization method includes preparing an aqueous reaction mixture containing an excess amount of template agent, subjecting the mixture to crystallization under hydrothermal conditions, establishing a balance between molecular sieve formation and dissolution, and thereafter removing some excess sample agent and / or organic base, To inhibit the dissolution of molecular sieves. References, such as US 5,296,208, which is incorporated herein by reference. 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 6,005,155 (using a salt-free modifier), US 5,47 5,182 ( Acid extraction), US 5,962,762 (transition metal treatment), US 5,925,586 and 6, 1 5 3,5 52 (phosphorus modification),

US 5,925,800 (supported by stone), US 5,93 2,5 1 2 (fluorinated), US 6,046,3 73 (electromagnetic wave treatment or modification), US 6,051,746 (multi-core aromatic modifier), US 6,2 2 5, 2 5 4 (Heating sample), PCT WO 0 1/3 63 29 (Synthesis of surfactants) published on March 25, 2001 (16) (16) 200303238, April 2001 PCT WO 01/25151 (phased acid addition) published on December 12, PCT WO 0 1/60746 (silicone oil) published on August 23, 2001, and U.S. patent application filed on August 15, 2001 Serial No. 09/929949 (Cooled Molecular Sieve), US Patent Application Serial No. 09 / 615,526 (including metal impregnation of copper) filed on July 13, 2000, US Patent Application Serial No. 09 / 672,469 (conductive, filed on 928) Microfilter), and US Patent No. 09/75 4 8 1 2 (freeze-dried molecular sieve) filed on January 4, 2001, all 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), but S 'low S i for SAPO synthesis / A1 is better than 値. In one embodiment, the Si / A1 ratio 分子 of the molecular decoration is less than 0.65, such as less than 0.40, such as less than 0.32, and in particular less than 0.20: In another embodiment, the Si / Al ratio 分子 of the molecular sieve ranges from about 0.6 5 to about 0.10, such as from about 0.4 to about 0.10, such as from about 0.32 to about 0.10, and especially from about 0.32 to about 0.15. Group 3 metal oxides and lanthanum or steel-based oxides The metal oxides used herein are oxides of group 3 metals and lanthanum and actinide metals, and their carbon dioxide intake is at least -21 at 10CTC- (17) (17) 200303238 0.03 mg / m2 metal oxide, such as at least 0.04 mg / m2 metal oxide. Although the upper limit of carbon dioxide uptake by metal oxides is not critical, in general, 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 2 metal oxide. Typically, the carbon dioxide uptake of the metal oxides used herein is between 0.05 and 1 mg / m2 metal oxide. When molecular sieves are used in combination, the active metal oxide is favorable for catalyst conversion methods, especially the conversion of oxygenates to olefins. To measure the carbon dioxide uptake of metal oxides, the following steps are used. Samples of metal oxides are dehydrated to a constant weight by heating in a flowing air to about 200 ° C to 500 ° C to obtain a "dry weight". The temperature of the sample was then reduced to 100 ° C, and carbon dioxide passed through the sample, either continuously or pulsed, again until a constant weight was obtained. The increase in sample weight, calculated as the dry weight of the sample and expressed as mg / mg sample, is the amount of carbon dioxide adsorbed. In the samples described below, the adsorption of carbon dioxide 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 100 ° C, the desired adsorption temperature under flowing ammonia. The sample was equilibrated at 100 ° C and flowing helium. The sample was given 20 individual pulses (about 12 seconds / pulse) of a gas mixture containing 10% by weight of carbon dioxide and the remainder ammonia. After each pulse of adsorbed gas, the metal oxide sample was flushed with flowing ammonia for 3 minutes. The increase in sample weight is calculated as the weight of the adsorbent after treatment at 500 ° C and expressed in mg / mg adsorbent (18) (18) 200303238, which is the amount of carbon dioxide adsorbed. The surface area of the sample was measured in accordance with the Brunauer, Emmett, and Teller (BET) method disclosed in ASTM D 3663 to provide carbon dioxide uptake. The preferred Group 3 metal oxides in mg carbon dioxide / m2 metal oxides include scandium, yttrium, and Oxides of lanthanum, preferred oxides of lanthanum or actinide series metals include rhenium, osmium, rhenium, osmium, osmium, osmium, osmium, osmium, rhenium, bait, surface, mirror, osmium, and osmium. The most preferred active metal oxides are erbium oxide, lanthanum oxide, yttrium oxide, ytterbium oxide, erbium oxide, ammonium oxide, and mixtures thereof, especially a mixture of lanthanum oxide and ytterbium oxide. In one embodiment, a useful metal oxide is The oxides of these Group 3 metals and / or lanthanum and actinide metals, when mixed with the molecular sieve in the catalyst composition, effectively extend the service life of the catalyst composition. The quantification of the life of the catalyst composition is measured by the Life Increasing Index (LEI) defined by the following formula: LEI The life of a catalyst mixed with active metal oxides is the life of the catalyst or catalyst composition. Measured in the same method and under the same conditions, and for the cumulative amount of processing feed per gram of catalyst composition, until the feed conversion via the catalyst composition drops below some definite 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 (19) (19) 200303238 oxides of the present invention are these Group 3 metal oxides, including lanthanum and actinide oxides. When used in combination with molecular sieves, they provide molecular sieve with LEI greater than 1. MEDIA COMPOSITION. 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 including an active Group 3 metal oxide and / or a lanthanum or actinide active oxide including a mixed molecular sieve, and the LEI thereof ranges from more than 1 to 50, for example, from about 1.5 to about 20. 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, For example, greater than 2. In one embodiment, when mixed with the molecular sieve in the catalyst composition, the active Group 3 metal oxide and / or the lanthanum or actinide-based active oxide increase the conversion of the catalyst composition into The active metal oxides used in this article for various olefin lifetimes can be prepared using a variety of methods. Preferably, the active metal oxide is prepared from a precursor of an active metal oxide, such as a metal salt, such as a halide, nitrate, sulfate or acetate. 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 3 metal oxides, such as yttrium n-propanol. In one embodiment, Group 3 metal oxides or lanthanum or actinide oxides include at least 80 ° C, The conditions are preferably at least 100 ° C, treated with hydrothermal fluids. Hydrothermal treatment can occur in sealed containers and under atmospheric pressure -24- (20) (20) 200303238. However, a preferred mode of processing involves the use of open containers under reflux conditions. Group 3 metal oxides or lanthanum or actinide oxides are agitated in a liquid medium, such as by refluxing the liquid and / or agitating, to promote effective interaction of the hydrated oxide with the liquid medium. The contact time of the hydrated oxide with the liquid medium is desirably at least 1 hour, such as at least 8 hours. The pH of the liquid medium for this treatment is about 6 or more, such as 8 or more. Non-limiting examples of suitable liquid media include water, hydroxide solutions (including hydroxides of NH4 +, Na +, K +, Mg2 +, and Ca2 +), carbonate and bicarbonate solutions (including NH4 +, Na +, K + , Carbonates and bicarbonates of Mg2 + and Ca2 +), pyridine and its derivatives, and alkyl / hydroxyamines. In another embodiment, an active Group 3 metal oxide or an active oxide of lanthanum or actinide is sufficient to produce a solid oxide by making a liquid solution, such as an aqueous solution containing a source of metal ions (such as a metal salt), a solid oxide. Precipitates of hydrated precursors of the substance are prepared, for example, by adding a precipitating agent to the solution. 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 ammonium hydroxide. The temperature is usually below about 200 ° C, for example, in the range from about 0 °: to about 2000 ° C, during which the liquid medium is maintained at this temperature. The special temperature range for precipitation is from about 20 ° C to about 100 ° C. The gel obtained is preferably at 80 ° C, preferably at least 100t, and is hydrated. Hydration treatment typically occurs in a container and at atmospheric pressure. In one embodiment, the gel is hydrated for up to 10 days, such as up to 5 days, such as up to 3 days. The hydrated precursor of the metal oxide is then recovered, for example, by filtration or centrifugation through (21) (21) 200303238, and washing and drying. The obtained material can then be calcined, for example, under 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 900 ° C, and particularly from about 65 ° C C to about 800 ° C, forming a solid oxide material. The calcination time is typically as high as 48 hours, such as for 0.5 to 24 hours, such as for about 1.0 to 10 hours. In one embodiment, the calcination is at about 70 (TC implementation takes about 1 to about 3 hours. 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 Group 3 metal oxides, and / or the above-mentioned lanthanum or actinide One or more oxides of the element, optionally with an adhesive and / or matrix material different from the active metal oxide. Typically, in the catalyst composition, the weight ratio of the molecular sieve to the active metal oxide ranges from 5% by weight To 80% by weight, for example from 10% to 60% by weight, particularly from 20% to 5,000% by weight, and more particularly from 30% to 4,000% by weight. There are various adhesives for forming contacts Vehicle composition. Non-limiting examples of adhesives include various Type of hydrated alumina, silica and / or other inorganic oxide sols, the adhesive can be used alone or in combination. A preferred sol containing alumina is basic aluminum chloride. Inorganic oxide sols like glue make synthetic Molecular sieves adhere to other substances, such as substrates, especially after heat treatment. By heating, the inorganic oxide sol, which preferably has a low viscosity, is converted into an inorganic oxide adhesive component. For example, after heat treatment The alumina sol will be converted into an alumina adhesive. Basic aluminum chloride (alumina-based sol containing chlorine counterions) -26- (22) (22) 200303238 has the general formula AUO ^ OHKClj ^ xdO) , Where m is 1 to 20, η is 1 to 8, 0 is 5 to 40, ρ is 2 to 15, and X is 0 to 30. In one embodiment, the adhesive is A11304 (0H) 24C17M2 (H20) , Which is described in GM Wolterman, et. Al. 5 Stud. Surf. Sci. And Catal.? 76, pages 105-144 (1993), which is incorporated herein by reference. In another embodiment, one or more adhesives Agents and one or more other non-limiting examples of oxidizing substances such as oxygen Aluminum hydroxide (aluminum oxyhydroxide), γ-alumina, bauxite, gibbsite, and transitional alumina, such as α-alumina, β-alumina, γ-alumina, δ-alumina, ε -Alumina, 1 <: alumina and p-alumina, aluminum trihydroxide, such as gibbsite, bayerite, nordstrandite, doyelite 'and mixtures thereof Phase mixing. 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 Nalco Chemical Co., Naperville, Illinois, and Nyacol AL20DWo catalyst commercially available from Nyacol nano Technologies, Inc., Ashland, Massachusetts. The composition includes a matrix material, which is preferably different from the metal oxide and any adhesive. The matrix material typically effectively reduces the total catalyst cost, 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 -27- (23) (23) 200303238 Abrasion resistance. Non-limiting examples of matrix materials include one or more non-reactive metal oxides including barium oxide, quartz, silica or sol, and mixtures thereof, such as silica-magnesia, silica-oxide, 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 bentonite 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 with a low content of iron 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 ο particle size distribution is less than 1 μm. The catalyst composition includes an adhesive or a matrix substance, and the catalyst composition typically includes from about 1% to about 80% by weight, such as from about 5% to about 60% by weight, and particularly from about 5% to about 60% by weight. Molecular weight of 50% by weight, calculated as total weight of catalyst composition. The catalyst composition includes an adhesive and a matrix substance, and the weight ratio of the adhesive to the matrix -28- (24) (24) 200303238 is typically from 1:15 to 1: 5, for example, from 1:10 to 1 ·· 4, and especially 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 matrix Calculation of the total weight of the substance. It has been found that a high molecular sieve content and a low matrix material content increase the performance of the sieve catalyst composition, while a low molecular sieve content and a high matrix material content improve the abrasion resistance of the composition. 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 3 g / cco Method for preparing the catalyst composition In the preparation of the catalyst composition, the molecular sieve is first formed, and then the active group 3 metal oxide, or the active oxide of lanthanum or actinide, is preferably substantially dried. , After being dried or calcined, completely mixed. 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 and generally not preferred. The catalyst composition includes a matrix and / or an adhesive, and the molecular sieve and the matrix and / -29- (25) (25) 200303238 or an adhesive are suitably firstly formulated as a catalyst precursor, and then the active metal oxidation and the formulated first质 混。 Quality mixed. 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, 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, the matrix material, and the optional adhesive may be mixed in the same or different liquids, and may 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 as a slurry, together 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 slurry of the molecular sieve composition, the adhesive and the matrix material is mixed or honed to obtain a sufficiently uniform slurry of the secondary particles of the molecular sieve catalyst composition, which is then fed to the molecular sieve Media composition -30-(26) (26) 200303238 forming unit. 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 m-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, a slurry of the uterine curtain composition and the matrix material and an optional adhesive is scooped into a spray drying container with a drying gas, and its average inlet temperature ranges from 20CTC to about _ 5 5 0 ° C, and outlet temperature range from 100 ° C to about 225 ° 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 suitably from about 65 μm to about 90 μm. Other methods for forming molecular sieve catalyst compositions are described in U.S. Patent Application Serial No. 09 / 617,714, filed July 17, 2000 (spray-dried using recovered molecular sieve catalyst compositions), which is incorporated This article is for reference. # Once the molecular sieve catalyst composition is formed in a substantially dry or dried state, in order to further harden and / or activate the formed catalyst composition, a heat treatment such as calcination is usually performed at a high temperature. Typical calcination temperatures range from about 400 ° C to about 15500 ° C, such as from about 50 ° C to about 800 ° C, such as from about 55 ° C to about 700 ° C. A typical calcination environment is air (Which may include a small amount of water vapor), nitrogen, helium, flue gas (oxygen-depleted combustion products), or any combination thereof. In a preferred embodiment, the catalyst composition is under nitrogen at a temperature from about -31 -(27) (27) 200303238 60 Heat at 0 ° C to about 700 ° C. 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. Method using molecular sieve catalyst composition The above-mentioned catalyst composition is used in various methods including cracking, such as a naphtha feed Cracking into light olefins (US 6,3 00,5 3 7) or larger molecular weight (MW) hydrocarbons into smaller MW hydrocarbons; hydrogen cracking, such as hydrogen cracking of heavy petroleum and / or ring feeds; isomerization Reaction, such as the isomerization of aromatics (such as xylene); polymerization, such as the polymerization of one or more olefins Products; reforming; hydrogenation; dehydrogenation; dehydration, such as dewaxing of hydrocarbons to remove linear paraffins; absorption, such as absorption of alkyl aromatic compounds to separate its isomers; alkylation For example, aromatic hydrocarbons (such as benzene and alkyl benzene) are optionally alkylated with propylene to produce cumene, or long-chain olefins; alkyl transfer, such as a combination of aromatic and polyalkyl aromatic hydrocarbons Radical transfer; dealkylation; hydrodecyclization; disproportionation, such as the disproportionation of toluene to produce benzene and para-xylene; oligomerization, such as oligomerization of linear and branched olefins; Hydrocyclization. Preferred methods include a method for converting naphtha into a highly aromatic mixture; a method for converting light olefins into gasoline, distillates and lubricants; a method for converting oxygenates to olefins ; Method for converting light paraffins into olefins and / or aromatics; Method for converting unsaturated hydrocarbons (ethylene and / or acetylene) into aldehydes for conversion into alcohols, acids and esters. -32- (28) ( 28) 200303238 The best method of the present invention is For converting a feed to one or more olefins. 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 carbon atoms' For example, from 1 to 10 carbon atoms, and particularly from 1 to 4 carbon atoms. Non-limiting examples of aliphatic compounds include alcohols, such as methanol and ethanol, alkyl mercaptans, such as methyl mercaptan and ethyl sulfur Alcohols, thioethers, such as dimethylsulfide, alkylamines, such as methylamine, alkyl ethers, such as dimethyl ether, diethyl ether, and methyl ether, alkyl halides, such as methyl chloride and ethyl chloride, alkyl ketones, Examples include dimethyl ketone, formaldehyde, and various acids such as acetic acid. In a preferred embodiment of the present invention, the feed includes one or more oxygenates, and more specifically, one or more organic compounds containing at least one oxygen atom. Compound. 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 that serve as a feed for the process of the present invention include lower straight and branched chain aliphatic alcohols and their unsaturated counterparts. Non-limiting examples of oxygenates include methanol, ethanol, n-propanol, isopropanol, methyl ether, dimethyl ether, diethyl ether, diisopropyl ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid, and Its mixture. In a preferred embodiment, the feed is selected from one or more of methanol, ethanol, dimethyl ether, diethyl ether, or a combination thereof, more preferably methanol and dimethyl ether, and most preferably methanol. The various feeds discussed above, especially feeds containing oxygenates, (33) (29) 200303238, more particularly feeds containing alcohols, are mainly converted to one or more olefins. 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 Ethylene and / or propylene.

The catalyst composition of the present invention is particularly used in a method commonly referred to as a gas-to-olefin (GTO) conversion method or a methanol-to-olefin (MTO) conversion method. In this method, the oxygenated feed, preferably a methanol-containing feed, is converted into one or more hydrocarbons in the presence of a molecular sieve catalyst composition, preferably and advantageously ethylene and / or propylene. /

Using the catalyst composition of the present invention to switch the feed, preferably a feed containing one or more oxygenates, the content of olefins produced is greater than 50 weight based on the total weight of the hydrocarbons produced. / 〇, typically greater than 60% by weight, such as greater than 70% by weight, and preferably greater than 80% by weight. In addition, the content of ethylene and / or propylene produced is greater than 40% by weight, typically greater than 50% by weight, such as greater than 65% by weight, and preferably based on the total weight of the hydrocarbon products produced. More than 78% by weight. Typically, the content of ethylene produced is greater than 20% by weight, such as greater than 30% by weight, such as greater than 40% by weight, based on the total weight of the hydrocarbon products produced. In addition, the content of propylene produced is typically greater than 20% by weight, such as greater than 25% by weight, such as greater than 30% by weight, and preferably greater than 35% by weight, based on the total weight of the hydrocarbon products produced. It was found that compared with similar catalyst compositions without active metal oxide components under the same conversion conditions, the catalyst composition of the present invention was used to convert a feed containing methanol and dimethyl ether to ethylene and propylene to produce ethane and propane Is reduced to -34- (30) (30) 200303238 is 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 that are generally non-beta-responsive 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, M, nitrogen, carbon monoxide, carbon dioxide, water, paraffinic hydrocarbons that are substantially non-reactive (especially alkanes such as methane, ethyl and propane), and substantially non-reactive Aromatic compounds, and mixtures thereof. The best diluents are water and nitrogen, with water being particularly preferred. Diluents, such as water, can be used in liquid or vapor form or combinations thereof. The diluent can be added directly to the feed to the reactor, or directly into the reactor, or added with the molecular sieve catalyst composition. The method of the present invention can be carried out over a wide temperature range, such as from about 200 ° C to about 100 ° C, such as from about 250 ° C to about 80 ° C, including from About 2 5 0 ° C to about 7 5 0 ° C, suitably from about 3 0 0 ° C to about 6 5 0 ° C, typical

Type from about 350 ° C to about 600 ° C, and particularly from about 350 ° C to about 5500 ° C. Similarly, the method of the present invention can be carried out over a wide range of pressures' This pressure range includes autogenous pressure. Typically, the partial pressure of the feed (excluding any diluent therein) used in the process ranges from about 0.1 kPaa to about 5 Mpaa, such as from about 5 kPaa to about IMpaa, and suitably from about 20 kPaa to about 500 kPaa ° 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, typically ranging from -35- (31) (31) 200303238 to about lhr-1 to About 50,000 hr-l, such as from about 2 hr-l to about 3,000 hr-l, such as from about 5 hr-l to about 1500 hr-l, and suitably from about iohr-hr to about 10,000 hr-1. In one embodiment, the WHSV 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 carried out in a fluidized bed, and the surface gas velocity (SGV) of the feed is at least 0.1 lm / sec, such as greater than 0.5 m / sec, such as greater than lm / sec, such as greater than 2 m / sec, suitably greater than 3 m / sec, and typically greater than 4 m / seC, the feed includes diluents and reaction products within the reactor system, particularly in the riser reactor. Reference is made to U.S. Patent Application Serial No. 09 / 708,753, filed November 8, 2000, which is incorporated herein by reference. The method of the present invention is suitably implemented as a fixed bed method, or more typically as a fluidized bed method (including a turbulent bed method), such as a continuous fluidized bed method, and particularly a continuous high-speed fluidized bed method. The 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 reaction Devices and the like. Suitable reactor types are described in, for example, US 4,076,796, US 6,287,522 (dual riser) and Fluidization Engineering, D. Kunii and 0 · Levenspiel, Robert E. Krieger Published Company, New York, New York 1 977, all of which are described below. This article is incorporated by reference. The preferred reactor type is a riser reactor, which is usually described in Riser Reactor, Fluidization and Fluid- (32) (32) 200303238

Particle System, pages 48 to 59, FA Zenz and DF Othmo, Reinhold Publishing Corporation, New York, 1 960, and US 6,1 66,282 (fast fluidized bed reactor), and U.S. patents filed on May 4, 2000 Application No. 09/5 64,6 1 3, all of which are incorporated herein by reference. In a practical embodiment, the method is implemented by a fluidized bed method or a high-speed fluidized bed using a reactor system, a regeneration system, and a recovery system. In this method, the reactor system suitably comprises a fluidized bed reactor system having a first reaction zone in one or more riser reactors and a second reaction in at least one separation vessel The zone 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 oxygenates, 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 Rising tube reactor. In one embodiment, the 'molecular sieve catalyst composition or its coking plate is brought into contact with a liquid and / or a gas before being introduced into the riser reactor. The liquid is preferably water or methanol, and the gas is, for example, inert. Gas, such as nitrogen. In one embodiment, the amount 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% to about 75% by weight. / 〇, more typically from about 5% to about 65% by weight, 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 ratios of -37- (33) (33) 200303238 same or different feeds with the same or different diluents. The feed to the reactor system is preferably partially or completely converted to a gaseous effluent in the first reaction zone, which effluent enters the separation vessel with the coked catalyst composition. 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 hydrocarbons in the separation container. Although the cyclone is better, the gravity effect in the separation container can also be applied 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, covers, elbows, and the like. In one embodiment, the separation vessel includes a stripping area typically in a 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 is brought into contact with a regeneration medium, preferably a gas containing oxygen, under conventional regeneration conditions of temperature, pressure, and residence time. Non-limiting examples of suitable regeneration media include one or more of oxygen, 03 'S03, N2 0, NO, N0 2, N2 05, air, air diluted with nitrogen or carbon dioxide, oxygen, and water (US 6,245,703), 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 range of less than 0.5% by weight (34) (34) 200303238 degrees to input to the regeneration system Calculation of the total weight of the scorched molecular sieve catalyst composition. For example, the regeneration temperature may range from about 20 CTC to about 1,500 ° C, such as from about 300 ° C to about 1,000 t, such as from about 450 ° C to about 750 ° C, and Conveniently from about 5 50 ° C to about 700 ° C. The regeneration pressure may range from about 15 psia (103 kPaa) to about 500 psia (3448 kPaa), such as from about 20 psia (138 kPaa) to about 250 psia (1 724 kPaa), including from about 25 psia (172 kPaa) to about 150 psia (1 03 4 kPaa), and Conveniently from about 30 psia (207 kPaa) to about 60 psia (414 kPaa). The residence time of the catalyst composition in the regenerator can range from about 1 minute to several hours, such as from about 1 minute to 100 minutes, and the volume of oxygen during regeneration can range from about 0.01 mole% to about 5 mol%, calculated as the total volume of the gas. The combustion of coke in the regeneration step is an exothermic reaction, and in one embodiment, the temperature in the regeneration system is controlled by various techniques in the field, which include batch, continuous or partial continuous mode, or a combination thereof. The cooled gas is fed into the regenerator container. The preferred technique includes removing the regenerated catalyst composition from the re-spring system and passing the regenerated catalyst composition through a catalyst cooler to form a cooled regenerated catalyst composition. In one embodiment, the catalyst cooler is a heat exchanger, which is located inside or outside the regeneration system. Other methods of operating a regeneration system are described in US 6,290,916 (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 -39-(35) (35) 200303238 to the 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 the flow of catalyst composition are described in Michael Louge, Experimental Techniques, Circulating Fluidized Beds, Grace, Avi d an and Knowlton, eds ·, Blackie, 1 9 9 7 (336-337), which are incorporated herein as 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% by weight to about 15% by weight, such as from about 0.1% by weight to about 10% by weight, such as from about 0.2% by weight. % By weight to about 5% by weight, and expediently from about 0.3% to about 2% by weight, based on molecular weight. The gas effluent is removed from the separation vessel and passed through a recovery system. Various known recovery systems, techniques and procedures are used to separate and purify olefins from gaseous effluents. Recovery systems usually include various separations, fractionation and / or distillation columns, columns, separators or units, reaction systems, such as the production of ethylbenzene (US 5,476,97 8) and other derivatization methods, such as aldehydes (36) (36 ) 200303238, and the manufacture of esters (US 5,675,04 1), and other combined equipment, such as various condensing pipes, heat exchangers, refrigeration systems or cooling units, compressors, separation drums or pots, pumps and the like One or more or a combination thereof. Non-limiting examples of these towers, tubing columns, separators, or units used alone or in combination include one or more methane distillers (preferably high-temperature A-house deaerators), B-house distillers, C-house Deaerator, decontamination tower (usually appreciative decontamination tower and / or quench tower), absorber, adsorber, membrane, ethylene (C2) separator, propylene (C3) separator, butene (C4) Separator and various recovery systems for the priority recovery of olefins (preferably light olefins such as ethylene, propylene and / or butene) are described in US 5,960,643 (second ethylene-rich stream), US 5,019,143, 5,452,5 8 1 and 5,082,48 1 (membrane separation), US 5,672,197 (dependent on pressure adsorbent), US 6,069,288 (hydrogen removal), US 5,90 4,88 0 (in a single step, the recovered Methanol is converted to hydrogen and carbon dioxide), US 5,927,063 (recovered methanol is converted to a gas turbine power plant) and US 6,121,504 (direct product quenching), US 6,121,503 (none Ultra-rectified high-purity olefins) and US 6,293,998 (pressure conversion adsorption), which are all incorporated herein as reference. 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, 1996 pages 249-271 and 894-899, which are incorporated into This article is for reference. Purification systems are also described in, for example, US 6,271,428 (purification of a diolefin stream), US 6,293,999 (separation of propylene from propane), and October 20-41-(37) (37) 200303238 U.S. Patent Application Serial No. 09 / 689,363 (washing streams using hydrated catalysts), all of which are incorporated herein by reference. Generally, most recovery systems are accompanied by the production, production, or accumulation of additional products, 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 burned hydrocarbons having 2 or 3 carbon atoms, minor amounts of hydrocarbons, especially hydrocarbons having 4 or more carbon atoms, are also produced. The content of + hydrocarbons is usually less than 20% by weight, such as less than 10% by weight ', such as less than 5% by weight, and particularly less than 2% by weight, 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 C 4 + impurities into useful products. Non-limiting examples of this reaction system are described in US 5,95 5,640 (conversion of 4 carbon atoms to but-1-ene), US 4,774,375 (isobutane and but-2-ene are converted to alkylated gasoline) , US 6, (H9,017 (dimerization of n-butane (38) (38) 200303238), US 4,287,3 69 and 5,763,678 (carbon dioxide carbonylation or aldehyde formation of higher olefins to produce carbonyl compounds), US 4,542,252 (multi-stage adiabatic method), US 5,63 4,3 54 (olefin-hydrogen recovery) and Cosyns, J. et. Al ·, Process for Upgrading C3, C4 and C5 Olefinic Streams, Pet · & Coal, Vol 37, No. 4 (1 995) (dimerized or oligomeric propylene, butene, and pentene), all of which are incorporated herein by reference. The preferred light olefins prepared by any of the above methods are high A pure primary olefin product, the product comprising olefins having a single carbon number 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% by weight, Calculated based on the total weight of olefins. In a practical embodiment, the method of the present invention forms part of an integrated method. The integration method is used to prepare light olefins from a hydrocarbon feed, preferably a gaseous hydrocarbon feed, especially methane and / or ethane. In the first step of the method, the gaseous feed is preferably mixed with a water stream, A synthesis gas stream is prepared through the synthesis gas generation zone, typically including carbon dioxide, carbon monoxide, and hydrogen. Synthesis gas products are known, and typical synthesis gas temperatures range from about 700 ° C to about 1 200 ° C, and the synthesis Gas pressures range from about 2 MPa to about 100 MP a. Syngas streams are made from natural gas, petroleum liquids, and carbonaceous materials such as coal, recycled plastic, municipal waste, or any other organic material. Preferably, the The holding gas stream is prepared via a recombined stream of natural gas. In the next step of the method, the synthetic gas stream is contacted with a heterogeneous catalyst, typically a copper-based catalyst, to produce an oxygenate-containing substance. i'ili 'is suspended and mixed with water. In a' constant embodiment 'the step of contacting is at a temperature of -43- (39) (39) 200303238 ranging from about 150 ° C to about 450 ° C and pressure ranging from about 5MPa to about 10 0 to be implemented at MPa The oxygenate-containing stream or crude methanol typically includes alcohol products and various other components, such as ethers, especially dimethyl ether, ketones, aldehydes, dissolved gases, such as Hydrogen, methane, carbon oxides, and nitrogen, and fuel oil. In a preferred embodiment, a stream containing oxygenates, crude methanol, is obtained by a known purification method, distillation, separation, and fractionation to obtain a purified product. Oxygenate streams, such as commercial grade A and AA methanol. An oxygenate-containing stream or a purified oxygenate-containing stream, optionally 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-0933345, 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 types of poly-combustion. (Reference, for example, US Patent Application Serial No. 09 / 615,376, 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. 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 the presence of a polymerization catalyst system (40) (40) 200303238 polymerizing one or more olefins in a polymerization reactor to prepare one or more polymerization products, wherein the one or more olefins It has been prepared by using the above molecular sieve catalyst composition to convert alcohols, particularly 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 prepared by the polymerization method include hetero-row polypropylene, co-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. In the examples, LEI is defined as the ratio of the lifetime of the active metal oxide molecular sieve catalyst composition to the lifetime of the same molecular sieve without metal oxide defined as LEI. To determine LEI, life is defined as the cumulative content of converted oxygenates (preferably converted to one or more hydrocarbon-burning species) / g molecular sieve 'until the conversion rate drops to about 0% of its initial value. If the actual -45- (41) (41) 200303238 conversion does not drop to 10% of its initial value at the end of the test, the life is calculated by a linear extrapolation method that calculates the conversion reduction ratio using the last 2 data of the experiment. 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 "C2 = / C3 =" ratio 値 is the ratio of ethylene to propylene weighted selectivity 値. "C3 purity" is calculated by dividing propylene selectivity by the sum of propylene and propane selectivity. The selectivity to methane, ethylene, ethane, propylene, propane, C4, s and C5 + 's is the average weighted selectivity. C5 + 's consists only of C55s, C6's, and C7's. The sum of the selective radon in the table is not equal to 100% because it is coke corrected and it is known. Example A Preparation of molecular sieves Silicoaluminophosphate molecular sieves, SAP0-34, known as MSA, crystallize in the presence of tetraethylammonium hydroxide (R1) and dipropylamine (R2), which serve as organic structure directing agents or model agents. A mixture having the following mole ratio: 2Si2 / Al2O3 / P205 / 0.9R1 / 1.5R2 / 50H2O was prepared by mixing Condea Pural SB with deionized water to form a hair preparation. Phosphoric acid (85%) was added to the slurry. These adducts are stirred to form a homogeneous mixture. The homogeneous mixture was added to Ludox -46- (42) (42) 200303238 AS40 (40% SiO2), then R1 was added and mixed to form a homogeneous mixture. This homogeneous mixture was added to R2. This homogeneous mixture was then stirred and heated in a stainless steel pressure cooker to 170 t for 40 hours to crystallize. 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 the binder and matrix material and dried by spraying to form particles. 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 in a furnace. Vapor methanol is fed to Micro flow reactor. The reactor was maintained at a temperature of 475 ° C and a pressure of 25 ° to 8 ° (172.41 ^ & §). The flow rate of methanol is the flow rate that causes the weight of methanol / g molecular sieve, also known as the weight space-time velocity (WHS V), to be 100 h-l. 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, a physical state mixture of the MSA molecular sieve and the active metal oxide of Example A was used. The loaded total catalyst composition was maintained at 50 mg, and when the content of molecular sieves 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 h-l. Content calculation example 1 -47- (43) (43) 200303238

La (N03) 3.xH2O (Aldrich Chemical Company) samples were calcined in air at 700 ° C for 3 hours to produce lanthanum oxide. Example 2 50 g of La (NO3) 3.xH2O (Aldrich Chemical Company) was dissolved in 500 ml of distilled water with stirring. The pH 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 (100 ° C) for 72 hours. The formed product was recovered by filtration, washed with excess water, and dried overnight at 85 ° C. Part of this catalyst was burned in flowing air to 600 ° C for 3 hours to prepare lanthanum oxide (La203). Example 3 50 g of Y (N03) 3.6H20 was stirred and dissolved in 500 ml of distilled water. The pH was adjusted to about 9 by adding concentrated ammonium hydroxide. 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. Part of this catalyst was burned to 600 ° C for 3 hours in flowing air to prepare yttrium oxide (Y203). Example 4

A sample of Sc (NO3) 3.xH2O (Aldrich Chemical Company) was calcined in air at 700 ° C for 3 hours to produce scandium oxide (Sc203). Example 5 -48- (44) (44) 200303238 50 grams of Ce (N03) 3.6H20 was stirred and dissolved in 500 ml of distilled water. The pH was adjusted to about 8 by adding concentrated ammonium hydroxide. 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, washed with excess water, and dried overnight at 85 ° C. Part of this catalyst was burned to 600 ° C for 3 hours in flowing air to prepare thorium oxide (Ce203). Example 6 # 50 g of Pr (N03) 3.6H20 was stirred and dissolved in 500 ml of distilled water. The pH was adjusted to about 8 by adding concentrated ammonium hydroxide. 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, washed with excess water, and dried overnight at 85 ° C. Part of this catalyst was burned to 600 ° C for 3 hours in flowing air to prepare thorium oxide (Pr203). Example 7 50 g of Nd (N03) 3.6H20 was stirred and dissolved in 500 ml of distilled water. The pH was adjusted to about 9 by adding concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in an air flow box (100 ° C) for 7 2 hours. The formed product was recovered by filtration, washed with excess water, and dried overnight at 8 5 t. Part of this catalyst was partially burned to 60 in flowing air (TC for 3 hours to prepare hafnium oxide (Nd203). Example 8 39 g of Ce (N03) 3.6H20 and 7.0 g of La ( N03) 3 · 6H20 -49- (45) (45) 200303238 was stirred and dissolved in 500 ml of distilled water. Another solution containing 20 g of concentrated ammonium hydroxide and 500 ml of distilled water was prepared. The two solutions were sprayed with a nozzle mixer to Mixing at a rate of 50 m 1 / mi η. The p 的 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 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 this catalyst was partially burned in flowing air to 700 ° C for 3 hours to prepare Mixed metal oxide containing 5% by weight of lanthanum, calculated based on the final weight of the mixed metal oxide. Example 9 9 g of Ce (N03) 3 · 6H20 and 30.0 g of La (N03) 3 · 6H20 were stirred and dissolved in 5 00 ml of distilled water. Prepare another solution containing 20 g of concentrated ammonium hydroxide and 500 ml of distilled water. Use these two solutions. The mouth mixer is mixed at a rate of 50 ml / miη. The pH of the final mixture is adjusted to about 9 by adding concentrated ammonium hydroxide. This slurry is then placed in a polypropylene bottle and placed in an air flow box (100 ° C) 72 Hours. The formed product was recovered by filtration, washed with excess water, and dried overnight at 85 ° C. Part of this catalyst was partially burned to 700 ° C in flowing air for 3 hours. Preparation of mixed metal oxides containing 5% by weight of rhenium, calculated based on the final weight of the mixed metal oxide. Example 1 〇 Carbon dioxide intake of the oxides of Examples 1 to 9 -50 Under ambient pressure -50- (46) 200303238 Measurements were performed using a Mettler TGA / SDTA 851 thermogravimetric analysis system. Metal oxide samples were dehydrated in flowing air at approximately 500 ° C for 1 hour, and $ 彳 彡 was measured for carbon dioxide uptake at 100 ° C. The surface area is measured in accordance with the Brunauer, Emmett, and Teller (BET) method, and provides carbon dioxide uptake 値, expressed as mg carbon dioxide / m2 metal oxide, as shown in Table 1. Example Catalyst surface area for dry adsorption C 0 2 Into the weight (Mg) C0 (mg) (m2 / g) (mfi / m2) 1 22 0.1846 40 0.210 2 3 1 0.6487 3 8 0.551 3 24 0.3 296 80 0.172 4 20 0.0490 33 0.074 5 143 0.7714 57 0.095 6 50 0.3 136 24 0.26 1 7 4 1 0.6491 18 0.880 8 130 0.8407 5 1 0.127 9 42 1.2542 46 0.649

Comparative Example 1 1 In this Comparative Example 11 (Cex. 11), the molecular sieve catalyst composition prepared in Example A was used in the method of Example B. 5 Omg of the molecular sieve catalyst composition without active metal oxide was used. Be tested. The test results are shown in Tables 2 and 3 of -51-(47) (47) 200303238. Example 1 2 In this example, the molecular catalyst catalyst composition prepared in Example A was tested in the method of Example B using 40 mg of the molecular catalyst catalyst composition. The molecular catalyst catalyst composition has 10 mg of La203 This La203 was prepared by the nitration decomposition in Example 1. The components are mixed and then diluted with sand to form a reactor bed. The test results are shown in Tables 2 and 3, indicating that La203, the addition of active Group 3 metal oxides increased the life by 149%. The selectivity to ethane was reduced by 3 6%, and the selectivity to propane was reduced by 32%, suggesting a significant reduction in the hydrogen shift reaction. Example 1 3 In this example, the molecular sieve catalyst composition prepared in Example A was tested using the 40 mg molecular sieve catalyst composition in the method of Example B. The molecular sieve catalyst composition had 10 mg of La203, and It was prepared by the precipitation in Example 2. The components are mixed and then diluted with sand to form a reactor bed. The test results are shown in Tables 2 and 3, which indicate that the La203 produced by the precipitation effect, the addition of active Group 3 metal oxides increased the life span by 34%. A 55% reduction in selectivity to ethane and a 44% reduction in selectivity to propane suggest a significant reduction in the hydrogen shift reaction. Example 14 The molecular residue catalyst group -52- (48) (48) 200303238 prepared in Example 14 in the forced Example 14 was used in the method of Example B using a 40 mg molecular sieve catalyst composition Tested, the molecular sieve catalyst composition has 10 mg of Y203 obtained in Example 3. The components are mixed and then diluted with sand to form a reactor bed. The test results are shown in Tables 2 and 3, which shows that Υ203, the addition of active Group 3 metal oxides increased the lifetime by 1,090%. A 45% reduction in selectivity to ethane and a 28% reduction in selectivity to propane suggest a significant reduction in the hydrogen shift reaction. Example 15 · In this Example 15, the molecular sieve catalyst composition prepared in Example A was tested using the 40 mg molecular sieve catalyst composition in the method of Example B. The molecular sieve catalyst composition has a 10 mg implementation. SC 2 03 obtained in Example 4. The components are mixed and then diluted with sand to form a reactor bed. The test results are shown in Tables 2 and 3, indicating that Sc203, the addition of active Group 3 metal oxides increased the lifetime by 167%. A 27% reduction in selectivity to ethane and a 21% reduction in selectivity to propane suggest a significant reduction in the hydrogen shift reaction. Example 16 In this Example 16, the molecular sieve catalyst composition prepared in Example A was tested in the method of Example B using 40 mg of the molecular sieve catalyst composition, and the molecular sieve catalyst composition had 1 0 mg of C e 203 obtained in Example 5. The components are mixed and then diluted with sand to form a reactor bed. The test results are shown in Tables 2 and 3, indicating that the addition of Ce203 'active lanthanum metal oxide increases the life of 63 0%. A 50% reduction in selectivity to ethane and a 34% reduction in selectivity to propane suggest a significant reduction in the hydrogen shift reaction. -53- (49) (49) 200303238 Example 17 In this Example 17, the molecular sieve catalyst composition prepared in Example A was tested using the 40 mg molecular sieve catalyst composition in the method of Example B. The molecular sieve catalyst composition has 10 mg of Pr203 prepared in Example 6. The components are mixed and then diluted with sand to form a reactor bed. The test results are shown in Tables 2 and 3, indicating that the addition of active lanthanum metal oxide increases the life of 640% by Pr203. A 51% reduction in selectivity to ethane and a 38% reduction in selectivity to propane suggest a significant reduction in the hydrogen shift reaction. Example 18 In this Example 18, the molecular sieve catalyst composition prepared in Example A was tested in the method of Example B using 40 mg of the molecular sieve catalyst composition. The molecular sieve catalyst composition had 10 rng. Nd203 obtained in Example 7. The components are mixed and then diluted with sand to form a reactor bed. The test results are shown in Tables 2 and 3, showing that Nd203, the addition of active lanthanum metal oxides increased the life span by 3 40%. A 49% reduction in selectivity to ethane and a 34% reduction in selectivity to propane suggest a significant reduction in the hydrogen shift reaction. Example 19 In this Example 19, the molecular sieve catalyst composition prepared in Example A was tested in the method of Example B using 40 mg of the molecular sieve catalyst composition. The molecular sieve catalyst composition has 1 0 mg of the mixed metal oxide prepared in Example 8. The components are mixed and then diluted with sand ’to form an inverse -54- (50) 4 (50) 4200303238 reactor bed. The test results are shown in Tables 2 and 3, showing that La0x / Ce203, the addition of active lanthanum metal oxide modified by Group 3 oxides increased the life expectancy by 45%. A 47% reduction in selectivity to ethane and a 37% reduction in selectivity to propane suggest a significant reduction in the hydrogen shift reaction. Example 20 In this Example 20, the molecular sieve catalyst composition prepared in Example A was tested in the method of Example B using 40 mg of the molecular sieve catalyst composition, and the molecular sieve catalyst composition had 10 mg of the example. 9 The mixed metal oxide prepared. The ingredients are mixed and then diluted with sand to form a reactor bed. The test results are shown in Tables 2 and 3 ', indicating that 5% Ce0x / La203, the addition of active Group 3 metal oxides modified with lanthanide oxides increased the lifespan by 260%. A 56% reduction in selectivity to ethane and a 45% reduction in selectivity to propane suggest a significant reduction in the hydrogen shift reaction.

-55- (51) i 200303238 (51) i

cslm C3 purity (%) 1-H rH VD On 96.9 96.0 95.5 CO MD ON 96.6 96.3 96.4 ON MD On au 0.90 oq 0.74 0.76 t H oq 0.69 0.72 rH 0.73 rH Bu major olefins (%) 72.99 73.84 73.78 73.68 1 1 73.74 70.51 72.37 72.57 70.64 70.52 Life increase index (LEI) p 3 CTS CO inch · inch · VO Ό cn reactor bed composition 100% MSA 80% MSA / 20% La2 03 3 80% MSA / 20% La 2 0 3 80 % MSA / 20% Y2〇3 80% MSA / 20% Sc2〇3 80% MSA / 20% Ce2 03 i 80% MSA / 20% Pr2 033 80% MSA / 20% Nd2 033 80% MSA / 20 % La〇x / Ce2〇3 80% MSA / 20% Ce〇x / La2〇3 Example Comparative Example 11 Oj cn 2 OO On -56- (52) 200303238 t CO rH uo rH to uo &gt; 〇CO oo vd VO MD v〇csi ON oo T—Η VO ON CO l〇rH ON 5 i〇rH (N CO wS cn rH vrj VO oo yr 9 ζ) Η vq rH ^ -H rH v〇S rH CO l〇rH r—H II 〇6 CO ON S l〇cn οά CO oq rH o (N MD r—H 2 oi 〇Ί oj 〇VO CO rH u 〇〇o CO 〇〇ίο o as cn O cn guide O rH c5 荠 c5 u un CO cn t—H CO oo 1—H CO oo CO CO as oo oo CN oo rH Οί s vo τ—H as CSI u S 〇jr—H oo CO H ON CO r- H v〇! &Lt; S o5 ι—Η sr—H s c4 CO chase S | 〇r &lt; ro (N &lt; GO g r- ^ rs &lt; ί ro &lt; s 1 00 s 沴 ro Oi 1 oo s 〇〇 <N 00 Cheng 1 CO s Cheng s 2 1 00 rs CD o ►3 | OQ m CNJ c3 CO s § U τ—Η r—Η 镒 λλ m tn v〇oo On -57- (53 ) (53) 200303238 When the present invention is described and illustrated through a specific embodiment, those skilled in the art will understand that the present invention is suitable for variations and need not be described here. For example, it is expected that a mixed-flow, fixed-bed or fluid-bed approach will be used, especially in different reaction zones in a single or multiple reactor system. It is also contemplated that the molecular sieve compositions described herein serve as absorbents, adsorbents, gas separation agents, detergents, water purifying agents, and for various uses, such as agriculture and horticulture. It is within the scope of the present invention to add one or more active Group 3 metal oxides to the synthetic mixture to prepare the aforementioned molecular sieves. Likewise, it is expected that one or more molecular sieves are used for the catalyst composition. For this reason, for the purpose of determining the true scope of the invention, only the scope of the appended patent application is referred to. -58-

Claims (1)

(1) (1) 200303238 Patent application scope 1. A catalyst composition comprising a molecular sieve and at least one oxide selected from Group 3 metal, lanthanide and actinide of the periodic table, wherein the metal The intake of carbon dioxide by oxides is at least 0.03 mg / m2 metal oxides at 100 ° C. 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 0.04 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 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 less 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 material different from the metal oxide. 6. For example, the catalyst composition of the scope of application for patent includes adhesive and matrix material, which are different from each other and different from the metal oxide. 7. For example, the catalyst composition according to item 6 of the application, wherein the adhesive is alumina sol and the matrix substance is clay. 8. The catalyst composition according to item 1 of the application, wherein the metal oxide is selected from the group consisting of lanthanum oxide, yttrium oxide, thorium oxide, thorium oxide, thorium oxide, neodymium oxide, thorium oxide, thorium oxide, and mixtures thereof. 9. The catalyst composition according to item 1 of the scope of patent application, wherein the metal -59- (2) (2) 200303238 oxide is yttrium oxide. 10. The catalyst composition according to item 1 of the scope of patent application, wherein the molecular sieve includes a framework containing at least two tetrahedral units, the unit being selected from [Si04], [Al〇4] and [p〇4] units . 11. The catalyst composition according to item 10 of the patent application scope, wherein the molecular sieve comprises silicoaluminophosphate. 12. The catalyst composition according to claim 10, wherein the molecular sieve includes a molecular structure of CHA structure type. 1 3 · The catalyst composition according to item 12 of the patent application scope, wherein the molecular sieve additionally includes molecular sieve of AEI structure type. 1 4. The catalyst composition according to the scope of the patent application, wherein the weight ratio of the molecular sieve to the metal oxide ranges from 5% to 800%. 15 • A molecular sieve catalyst composition comprising a Group 3 metal oxide and / or a lanthanide or actinide oxide, an adhesive, a matrix substance, and a silicoaluminophosphate molecular sieve. 16. A method for preparing a catalyst composition, the method comprising: first particles containing a molecular sieve; and first particles containing at least one oxide selected from Group 3 metals, lanthanides and steel elements in the periodic table. The two particles are completely mixed, wherein the carbon dioxide intake of the metal oxide is at least 0.03 mg / m2 metal oxide particles at 100 ° C. 17. The method of claim 16 in which at least one of the first and second particles also includes at least one of an adhesive and a matrix substance. 18. The method of claim 16 in which the first particle -60- (3) (3) 200303238 comprises a silicoaluminophosphate molecular sieve and / or an aluminophosphate molecular sieve. 19. The method according to item 17 of the scope of patent application, wherein the first particles include sand aluminophosphate molecular sieves, an adhesive containing oxidized sol, and a matrix material containing clay. 20 · The method according to item 16 of the patent application, wherein the metal oxide is lanthanum oxide, yttrium oxide, hafnium oxide, or a mixture thereof. 21. A method of preparing a catalyst composition, the method comprising: (i) synthesizing a molecular sieve from a reaction mixture, the mixture including at least one model 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 an oxide selected from Group 3 metals, lanthanides and actinides in the periodic table by precipitating from a solution containing the metal ion source (Iv) recovery of the hydrated precursor formed in (iii); (v) calcination of the hydrated precursor recovered in (iv) to form a calcined metal oxide, the metal oxide Intake of carbon dioxide: at least 0.003 mg / m2 metal oxide at 100 ° C; and (vi) completely mixing the molecular sieve recovered in (i) and the calcined product prepared in (v) Metal oxide. 22. The method of claim 21, wherein the molecular sieve and / or the metal oxide are mixed with the adhesive and / or the matrix material before step (vi). 23. The method of claim 21, The weight ratio of the molecular sieve to the calcined metal oxide ranges from 30% to 400%. -61-(4) (4) 200303238 24. The method according to item 21 of the patent application, wherein the molecular sieve is spray-dried before (vi) with the matrix substance and the adhesive. 25. The method of claim 24, wherein the molecular sieve is silicoaluminophosphate, the adhesive is alumina sol, and the matrix substance is clay. 26. The method of claim 21, wherein the metal oxide is selected from the group consisting of lanthanum oxide, oxide oxide, hafnium oxide, hafnium oxide, hafnium oxide, ammonium oxide, and mixtures thereof. 2 7. The method according to item 21 of the patent application range, wherein the precipitation is carried out at a pH greater than 7. 28. The method according to item 21 of the patent application, wherein (iii) also includes hydrothermally treating the precipitate at a temperature of at least 80 ° C for up to 10 days. 29. The method according to item 21 of the patent application range, wherein (v) is performed in a temperature range from about 400 ° to about 900 ° C. 30. A method for converting a feed into one or more olefins in the presence of a catalyst composition comprising a molecular sieve and at least one metal selected from Group 3 metals, lanthanides and thallium in the periodic table An oxide of a series element, in which the carbon dioxide intake of the metal oxide is at least 0.03 mg / m2 metal oxide at 100 ° C. 31. The method of claim 30, wherein the carbon dioxide intake of the metal oxide is at least 0.04 mg / m2 metal oxide at 100 ° C. 3 2 · The method according to item 30 of the scope of patent application, wherein the carbon dioxide intake of the metal oxide is less than 10 mg / m 2 at 100 ° C-62- (5) ( 5) 200303238 3 3. The method according to item 32 of the scope of patent application, wherein the carbon dioxide intake of the metal oxide is less than 5 mg / m2 metal oxide at 100 ° C. 4. If the patent is applied for The method of item 30 also includes at least one adhesive and matrix substance different from the metal oxide. 35. The method of claim 30, wherein the metal oxide is selected from the group consisting of lanthanum oxide, yttrium oxide, scandium oxide, scandium oxide, scandium oxide, ammonium oxide, scandium oxide, scandium oxide, and mixtures thereof. 36. The method of claim 30, wherein the metal oxide is yttrium oxide. 37. The method of claim 30 in the scope of patent application also includes an adhesive and a matrix substance, which are different from each other and different from the metal oxide. 38. The method according to item 37 of the scope of patent application, wherein the adhesive is an alumina sol. 39. The method according to item 37 of the scope of patent application, wherein the matrix is clay 〇 4 〇. The method according to item 30 of the scope of patent application, wherein the catalyst composition has a Lifetime Increase Index (LEI) greater than! . 41. The method of claim 30, wherein the molecular sieve is synthesized from a reaction mixture including at least two of a silicon source, a phosphorus source, and an aluminum source. 42. The method of claim 30, wherein the molecular sieve is aluminophosphate. 43. The method of claim 30, wherein the feed comprises methanol and / or dimethyl ether. -63- (6) (6) 200303238 44. A method for converting a feedstock into one or more olefins in the presence of a catalyst composition, which is applied by a method such as the 16th in the scope of patent application Prepared. 45. A method for converting a feedstock into one or more olefins in the presence of a catalyst composition, which is prepared by a method such as the item 21 of the scope of patent application. 46 · A method for preparing one or more olefins, the method comprising: (a) introducing a feed containing at least one oxygenate into a reactor system in the presence of a catalyst composition, the composition comprising a molecular sieve, an adhesive, Matrix material and at least one Group 3 element and / or lanthanide or actinide oxide; (b) discharge from the reactor system an effluent stream containing one or more hydrocarbons; and (c) allow the effluent stream Through a recovery system; and (d) recovering at least the one or more olefins. 47. The method of claim 46, wherein the adhesive is an alumina oxide sol. 48. The method according to item 46 of the patent application scope, wherein the matrix substance is clay. 49. The method according to item 46 of the patent application scope, wherein the molecular sieve is an aluminophosphate molecular sieve and / or an aluminophosphate molecular sieve. 50. The method of claim 46, wherein the metal oxide is lanthanum oxide or yttrium oxide or a mixture thereof. 51. The method according to item 46 of the scope of patent application, wherein the carbon dioxide intake of the metal oxide -64- (7) (7) 200303238 is at least 0.003 mg / m2 metal oxide at 1000 hours. 5 2 · The method according to item 46 of the patent application, wherein the feed comprises methanol and / or dimethyl ether. 53. The method of claim 46, wherein the LEI of the catalyst composition is greater than the LEI of the same catalyst composition without active metal oxides. 5 4. The method according to item 46 of the patent application scope, wherein the LEI of the sieve catalyst composition is greater than 1.5. 55. An integrated method for preparing one or more olefins, the integrated method includes: (d) passing a hydrocarbon feed through a synthesis gas generation area to generate a synthesis gas stream; (e) contacting the synthesis gas stream with a catalyst to form a Oxygen feed; and (0) convert the oxygen-containing feed to the one or more olefins in the presence of a molecular sieve catalyst composition comprising a molecular sieve and at least one selected from Group 3 or lanthanum or actinide in the periodic table of elements An oxide of an elemental metal. 5 6 · The integrated method as described in claim 55, wherein the method further includes (d) polymerizing the hydrocarbon burner or hydrocarbons to a polyolefin in the presence of a polymerization catalyst. 5 7 · If the integration method of the scope of patent application No. 55, the oxygen-containing feed includes methanol, olefins include ethylene and propylene. 5 8 · If the integration method of the scope of patent application No. 55, where the molecule is decorated with aluminophosphate molecular sieve -65- 200303238 Lu, (1), the designated representative figure in this case is ... Figure _ (2), the component representative symbols of this representative figure are simply explained: None 柒 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: None -4-