TW200306890A - Molecular sieve compositions, catalyst thereof, their making and use in conversion processes - Google Patents

Abstract

The invention relates to a catalyst composition, a method of making the same and its use in the conversion of a feedstock, preferably an oxygenated feedstock, into one or more olefin(s), preferably ethylene and/or propylene. The catalyst composition comprises a molecular sieve and at least one metal oxide, such as a magnesium oxide that, when saturated with acetone and contacted with said acetone for 1 hour at 25 DEG C, converts more than 80% of the acetone.

Description

200306890 (1) (ii) Contrast of related applications of invention description This case claims priority of US provisional application serial number 60/3 74,69 7 (filed on April 22, 2002) based on 3 5 USC 1 2 0, and at the same time The U.S. application serial number 6 0/3 60,96 3 (Attorney Docket 2002B010) and the U.S. application serial number i〇 / 215,511 (Attorney Docket 2 0 0 2 B 1 0 6) are related. The entirety of these applications The contents 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 many techniques applied to the preparation of oxygenates, including the reaction of fermentation or synthesis gas derived from natural gas, petroleum liquids or coal-containing carbon materials, recycled plastics, local waste or any -6-( 2) (2) 200306890 Other organic substances. In general, the synthesis of 'syngas' involves the combustion reaction of natural gas (mostly A hospital) with an oxygen source to form hydrogen, carbon monoxide and / or carbon dioxide. Other known synthesis gas preparation methods include conventional steam reforming, autothermal reforming, or a combination thereof. Methanol, the preferred alcohol for the production of 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 5,367,100 describes the use of zeolite (ZSM-5) to convert methanol to olefins; US 4,062,905 discusses the use of crystalline aluminosilicate zeolites such as zeolite T, ZK5, erionite, and 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 10,44〇 describes the use of (3) (3 ) 200306890 Light olefins are prepared from alcohols using crystalline aluminum phosphate, usually labeled A1PO4. Some of the most useful molecular sieves for converting methanol to olefins are silicoaluminophosphate molecular sieves. The aluminophosphate (SAPO) molecular sieve includes a three-dimensional microporous crystalline skeleton structure sharing [Si〇4], [A1CU], and [P04] corners of a tetrahedral unit. SAPO synthesis is described in US 4,440,8 71, 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. The synthesis of SAPO molecular sieves, its preparation as a SAPO catalyst, and its use for the conversion of hydrocarbon feedstocks to olefins, in particular methanol, is disclosed in US 4,4 9 9,3 2 7 > 4,6 77,242 > 4,6 7 7,24 3, 4,8 7 3,3 90, 5,0 9 5,163, 5,7 1 4,662 and 6,1 66,2 82, 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 advantages of better conversion rate, improved hydrocarbon selectivity, longer lifetime, and commercial operability and cost is desired. US 4,4 65,8 89 describes a catalyst composition comprising a molecular sieve filled with hafnium, zirconium or titanium metal oxide silicates, which is used to make methanol, dimethyl ether-8- (4) (4) 200306890 or a mixture thereof is converted to a hydrocarbon product rich in iso-C4 compounds. US 6,1 80,828 discusses the use of modified molecular sieves to prepare methylamine from methanol and ammonia, such as silicoaluminophosphate molecular sieves mixed with one or more modifiers such as chromium oxide, titanium oxide, yttrium oxide, montmorillonite or kaolin. US 5,4 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 1 2 9 8 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 and refractory matrix material and At least one oxide of beryllium, magnesium, calcium, scandium, barium or lanthanum.

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) In the conversion of methanol to ethylene, the shape selectivity can be increased and the formation of coke can be slowed down. The Ni-SAPO-34 is made by grinding with MgO, CaO, BaO or Cs20 on micro_spherical nonporous silica. As the medium, B a 〇 is the best. W Ο 9 8/2 9 3 7 0 reveals the conversion of oxygenates to olefins through small-pore non-zeolitic molecular sieves, the molecular sieves being selected from the group consisting of lanthanides, actinides, samarium, yttrium, Group 4 metals, Group 5 Group metals or mixtures thereof. [Summary of the Invention] -9- (5) (5) 200306890 Description] In one aspect, the present invention resides in a catalyst composition including: (a) a metal oxide having a surface area greater than 20 m2 / g, the metal The oxide has been calcined at a temperature greater than that, and when the metal oxide is saturated with acetone and contacted with the acetone at 25 ° C for 1 hour, the metal oxide is converted to more than 80% acetone; (b) adhesive (C) a matrix substance; and (d) a molecular sieve having an average pore size of less than 5 A. Molecular sieves suitably include a framework containing at least [A104] and [P〇4] tetrahedral units, and more particularly a framework containing at least [Si〇4], [Al〇4] and [PCU] tetrahedron units, For example, silicoaluminophosphate. In one embodiment, the metal oxide includes magnesium oxide. In one aspect, the present invention resides in a catalyst composition containing a molecular sieve and at least one oxide selected from the Group 4 metal of the periodic table, wherein the carbon dioxide intake of the metal oxide is at 100 ° C At least 0 03 mg / m2 metal oxide, and typically at least 0.0035 mg / m2 metal oxide. Conveniently, the catalyst composition also includes at least one oxide from a Group 3 metal in the periodic table, such as yttrium oxide, lanthanum oxide, hafnium oxide, and mixtures thereof. In another aspect, the present invention resides in a method for preparing a catalyst composition, the method comprising physically combining a first particle containing a molecular sieve and a second particle containing at least one oxide from a Group 2 metal in the periodic table. Phase -10- (6) (6) 200306890 mixed, wherein the carbon dioxide intake of the metal oxide is at least 0 0 3 mg / m2 metal oxide particles at 100 ° C. In another aspect, the present invention resides in a method for preparing a catalyst composition, the method comprising mixing a silicoaluminophosphate molecular sieve, an adhesive, a matrix material, and at least one metal oxide, and the metal oxide is saturated with acetone And in contact with the acetone at 25 ° C for 1 hour, the metal oxide converted more than 25% of acetone. In another aspect, the invention resides in a method of preparing a catalyst composition, the method comprising (a) mixing a molecular sieve, an adhesive, and a matrix material to produce a catalyst precursor; and (b) adding a metal oxide to The catalyst precursor has been calcined in a temperature range from 200 ° C to 700 ° C. In one embodiment, the metal oxide is magnesium oxide and is physically mixed with a molecular sieve synthesized from a reaction mixture, the reaction mixture including at least one template and at least two of a silicon source, a phosphorus source, and an aluminum source. In another aspect, the present invention is a method for converting a feed to one or more olefins in the presence of a molecular sieve catalyst composition, the catalyst composition including a molecular sieve, an adhesive, a matrix material, and a metal oxide. The metal oxide was saturated with acetone and contacted with the acetone at 25 ° C for 1 hour, and the metal oxide converted more than 80% of acetone. In another aspect, the invention resides in 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 Including small pore molecular sieve, viscosity -11-(7) (7) 200306890 adhering agent, matrix substance, magnesium oxide and Group 3 metal oxide, the magnesium oxide has been in the temperature range from 2000 ° C to 60 ° C is calcined; (b) the effluent stream containing one or more olefins is discharged from the reactor system; and (c) the effluent stream is passed through a recovery system; and (d) at least the one or more olefins are recovered. [Embodiment] Detailed description of the examples · Introduction The present invention relates to a catalyst composition, its synthesis, and its use for converting hydrocarbon feeds, especially oxidation feeds, to olefins. It has been found that mixing molecular sieves with special metal oxides' results in a catalyst composition having a longer catalyst life when the catalyst composition is used to switch feeds, such as oxygenates, especially methanol, to olefins. In addition, the obtained catalyst composition tends to be more selective to propylene, and tends to generate less amounts of unwanted ethane and propane. The preferred metal oxide is a Group 2 metal oxide, and the carbon dioxide intake of the metal oxide is at least 0.3 mg / m2 metal oxide at 1000 ° C, and / or the metal oxide is Room temperature has the ability to convert more than 80% acetone. In one embodiment, the metal oxide is magnesia, and the surface area of the magnesia is greater than 20 m2 / g and is calcined at a temperature greater than 200 ° C. When an oxide from a Group 3 metal (such as scandium, lanthanum, or yttrium) in the periodic table is mixed with magnesium oxide, the Group 3 metal oxide is described in the CRC Handbook of Chemistry and Physics, 78th -12- (8) (8) 200306890

Edition, CRC Press, Boca Raton, Florida (19 9 7), this unexpected result was further increased. Molecular sieves Molecular decorations have been classified by the Structure Commission of the International Zeolite Association based on the IUPAC Commission on Zeolite Nomenclature. Based on this classification, structural zeolites and zeolite-type molecular sieves whose structures have been confirmed are assigned to three letters and described in Atlas of Zeolite Framework Types, 5th edition, Elsevier, London, England (2001), which is incorporated herein. Reference. Crystal molecular sieves all have a three-dimensional, four-linked skeleton structure with a shared angle [T04] tetrahedron, where T is a cation coordinated by any tetrahedron. Molecular sieves are typically described in terms of ring sizes that define pores, where size is calculated as the number of T atoms in the ring. Other architectural features include the arrangement of the rings that form the cage, and, when present, the size of the aisle, and the space between the cages. Refer to van Bekkum, et a 1, Introduction to Zeolite Science and Practice, Second Completely Revised and Expanded Edition, Volumne 137, pages 1-67, Elsevier Science, BV, Amsterdam, Netherlands (200 1) Non-limiting example of small pores of molecular sieves Molecular sieve, aei, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI, DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO , ROG, THO and its 200306890 0) substituted forms; intermediate hole molecular sieve, AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON and their substituted forms; and large hole molecular sieve, EMT , FAU and its replaced form. Other molecular sieves include ANA, BEA, CFI, CLO, DON, GIS, LTL, MER, MOR, MWW and SOD. Non-limiting examples of preferred molecular slabs, especially for conversion of feedstocks including oxygenates to olefins, including AEL, AFY 'AEI, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI , MOR, MTT, MWW, TAM, and TON. In a preferred embodiment, the molecular sieve of the present invention has an AEI φ topology or a CHA topology, or a combination thereof, and most preferably a CHA topology. Small, middle, and large pore molecular sieves are available in 4 -ring to 1 2 -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 3 A to 15 A. In a more preferred embodiment, the molecular sieve, preferably a sand phosphate phosphate sieve, has 8-rings and an average pore size of less than about 5 A, such as in a range from 3 A to about 5 A, such as from 3 A to 4 5 A, and especially from 3 5 A to about 4 2 A. A molecular sieve has a molecular structure that shares 1, preferably 2 or more g, and a corner [T04] tetrahedron unit, more preferably 2 or more [Si04], [Al〇4], and / or [P〇4 ] Tetrahedral units, and most preferably [Si〇4], [Al〇4] and / or [ΡΟ 4] tetrahedral units. These silicon, aluminum and phosphorus-based molecular sieves and their molecular sieves containing silicon, aluminum and phosphorus have been described in detail in several publications including, for example, US 4,45 67,029 (MeAPO where Me is Mg, Mη, Zn or C ο), US 4,4 4 0, 8 7 1 (SAPO), EP-A-0 1 5 9 6 2 4 (ELAPSO where El is As, Be, B, Cr, Co, Ga, -14- (10) (10) 200306890

Ge, Fe, Li, Mg, Mn ′ Ti or Z n), U S 4,5 5 4,14 3 (FeAPO), US 4,822,478, 4,6 83,2 1 7, 4,744,88 5

(FeAPSO), EP-A- 0 1 5 8 97 5 and US 4,93 5,2 1 6 (ZnAPSO), EP-A-0 1 6 1 4 89 (CoAPSO), EP-A-0 1 5 8 976 (ELAPO where EL is Co, Fe, Mg, Mn, Ti or Zn), US 4,3 10,440 (Α1Ρ〇4), EP-A-0158350 (SENAPO), US 4,973,460 (LiAPSO), US 4 , 78 9,53 5 (LiAPO), US 4,992,250 (GeAPSO), US 4,8 8 8,1 67 (GeAPO), US 5,057,295 (B APSO), US 4,7 3 8,8 3 7 (CrAPSO), US 4,7 5 9,9 1 9 and

4.8 5 1,1 06 (CrAPO), US 4,7 5 8,4 1 9, 4,8 82,03 8 '5,43 4,3 26 and 5,4 7 8,7 87 (MgAPSO), US 4,5 5 4 1 43 (FeAPO) 'US 4.8 94,2 1 3 (AsAPSO), US 4,9 1 3,8 8 8 (AsAPO), US 4,6 8 6,092, 4,8 46,9 5 6 and 4,7 9 3,8 3 3 (MnAPSO), US 5,3 4 5,0 1 1 and 6, 1 5 6,93 1 (MnAPO), US 4,73 7,3 5 3 (BeAPSO) US 4,940,5 70 (BeAPO), US 4,8 0 1,3 09 Λ 4,684,617 and 4,880,520 (TiAPSO), US 4,500,651 4,5 5 1,23 6 and 4,605, 492 (Ti APO), US 4,824,554 4,744,970 (CoAPSO ), US 4,735,806 (GaAPSO), EP-.A-0293937 (Q APSO where Q is a framework oxide unit [Q〇2]), and US 4,5 67,029 Λ 4,686,093, 4,781,814 Λ 4,793,984 Λ 4,8 0 1, 3 64 Λ 4,853,197, 4,917,876, 4,9 5 2,3 84 Λ 4,956,1 64,4,95 6,165, 4,973,78 5,5,24 1,093 > 5,493,066 and 5,675, 〇50, all of them This article is incorporated by reference. Other molecular stores include those described in R Szostal, Handbook of -15- (11) (11) 200306890

Molecular Sieves, Van Nostrand Reinhold, New York, New York (1992), which is incorporated herein by reference. More preferred molecular sieves include aluminum phosphate (A1P 0) molecular sieves and silicon aluminum phosphate (SAPO) molecular sieves and substituted, preferably metal substituted, A1PO and S APO molecular sieves. The best molecular sieves are SAP0 molecular sieves and metal-substituted S AP 0 molecular sieves. In an 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, sister, Thallium, ammonium, thorium, thorium, chaos, thallium, thorium, bait, watch, mirror, and distillate; and thorium or yttrium, transition metals of groups 4 to 12 in the periodic table, 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 one embodiment, the molecular sieve, as described in the above U.S. patent case, is expressed in an anhydrous experimental formula: mR (MxAlyPz) 02

Where R represents at least one templating agent, preferably an organic templating agent; m is R -16- (12) 200306890 relative to the number of moles per mole (M x A1 y P z) 〇 2 'and from 0 to 1 , Preferably 0 to 05, and most preferably 0 to 03; X, y, and ζ show the Mohr fractions of Al, P, and M serving as tetrahedral oxides, where μ is a metal, which is selected From the Periodic Table of the Elements 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and the lanthanide system ', preferably, the μ system is selected from Si, Co, Cr, Cu, Fe, Ga, Ge, Mg '] Vfn, Ni, Sn,

One of 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 0.001. In another embodiment, the claw is greater than 0 1 to about 1, X is greater than 0 to about 0 2, 5, y ranges from 0 4 to 05, and z ranges from 0 2 5 to 0 5, more preferably, m from 0 to 5 to 07, X from 001 to 02, y from 04 to 05, and z from 03 to 0 5

Non-limiting examples of SAP 0 and A1P0 molecular sieves used in this article include SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAP0-31, SAPO-34 , SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (US 6, 1 62, 4 1 5), S APO-47, S APO-56, One or a combination of A1P0-5, A1PO-11, A1PO-18, A1PO-31, A1PO-34, A1PO-36, A1PO-37, A1PO-46 and metal-containing molecular sieves. Particularly useful among these are S AP0-1 8, S APO-34, SAPO-35, S APO-44, S APO-56, A1PO-1 8 and A1PO-34 and their metal-containing derivatives Or a combination thereof, for example, one or a combination of SAPO-1 8, SAPO-34, A1PO-34, and A1P 0-1 8 and metal-containing derivatives thereof, and in particular, SAP 0-3 4 and A1P 0 One or a combination of -18 and its derivatives containing -17- (13) (13) 200306890 metal. In one embodiment, the molecular trim is a substance having two or more definite crystal phases interactively growing in a molecular composition. In particular, inter-growth molecular sieves are described in U.S. Patent Application Serial No. 09 / 924,0 1 6 filed on August 7, 2001 and WO 98/15496 published on April 16, 1998. This article is incorporated herein by reference. For example, SAP 0-18, A1PO-18, and RUW-18 have AEI architecture, and SAPO-34 has CHA architecture. Therefore, the molecular sieves used in this article include at least one interactive growth phase of AEI and CHA structure, especially the ratio of CHA structure to AEI structure is greater than 1 1, which is based on the US patent application filed on August 7, 2001. The DIFFaX method described in application serial number 09 / 924,0 1 6 was used for the measurement. In a specific example, the molecular sieve is SAPO-1 8, SAP 0-34, or an interactive growth thereof, wherein the structure of the molecular sieve is essentially composed of [si〇4], [aio4], and [P〇4] tetrahedral units, And therefore no additional architectural elements, such as nickel. Molecular Synthesis Synthesis of molecular sieves is described in most of the materials discussed above. Generally, molecular sieves are synthesized from one or more sources of aluminum, phosphorus, silicon, and stencils, such as nitrogen-containing organic compounds. Typically, silicon, aluminum, and phosphorus sources are optionally combined with one or more templating 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 by -18- (14) (14) 200306890, it is recovered by filtration, centrifuge and decantation. Non-limiting examples of silicon sources include silicates, fumed silica, such as Aerosil-200 and C AB-O-SIL M-5, available from Degussa Inc, New York, New York, organic silicon compounds, such as tetraalkyl 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 Ludox HS-40 Sol, Silicic 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 aluminum phosphates, such as aipo4, phosphorus salts , Or a combination thereof. A convenient source of phosphorus is phosphoric acid, especially when making silicoaluminophosphates. Templates are usually compounds containing elements from Group 15 of the periodic table, especially nitrogen, phosphorus, arsenic and antimony. A typical templating agent also includes at least one alkyl or aryl group, such as a halo or aryl group having 1 to 10 carbon atoms, such as 1 to 8 carbon atoms. Preferred templating agents are usually nitrogen-containing compounds such as amines, quaternary ammonium compounds, and combinations thereof. Suitable quaternary mirror compounds are of the general formula R4N + 'where R is hydrogen or a hydrocarbon group or a substituted hydrocarbon group, preferably an alkyl or aryl group having 1 to 10 carbon atoms. Non-limiting examples of template agents include tetraalkylammonium compounds and their salts-19- (15) (15) 200306890 classes, such as methylammonium compounds, tetraethylammonium compounds, tetrapropylammonium compounds, and tetrabutyl Ammonium compounds, cyclohexylamine, morpholine, di-n-propylamine (DPA), tetrapropylamine, triethylamine (TEA), triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine, N , N-dimethylbenzylamine, choline, dimethylpiperazine, ι, 4-diazabicyclo (2,2,2) octane, N ', N', N, N-tetramethyl (1,6) Hexanediamine, N-methyldiethanolamine, N-methyl-ethanolamine, N-methylpiperidine, 3-methyl-piperidine, N-methylcyclohexylamine, 3-methyl Methylpyridine, 4-methyl-D-pyridine, quinidine ring, N, N 5 -dimethyl-1, cardiac diazabicyclo (2,2,2) octane ion, di-n-butylamine, Neopentyl reference amine, di-n-pentylamine, isopropylamine, t-butylamine, ethylenediamine, pyrrolidine and 2-imidazolidone. Synthetic mixtures containing a minimum amount of silicon-, aluminum- and / or phosphorus composition and templating agent typically have a pH ranging from 2 to 10, such as from 4 to 9, such as from 5 to 8. Generally, the above-mentioned synthetic mixture is sealed in a container, preferably under self-pressure, and heated to a temperature ranging from about 8 (TC to about 250 ° C, for example, from about 100 ° C to about 250 ° C). ° C, for example from about 12 5 t to about 2 5 5 ° C, for example from about g 15 0 ° C to about 180 ° C. In one embodiment, the synthesis of the molecular sieve is by means of Molecular sieves or molecular sieves of the same architecture 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', for example from about 4 5 minutes to about 240 hours, such as from about 丨 hour to about 120 hours. Hydrothermal crystallization can be performed with or without shaking -20- (16) (16) 200306890 or agitation. Once the crystalline molecular sieve product is Formed, usually a slurry, which can be recovered by any standard technique known in the art, such as by centrifugation or filtration, and the recovered crystalline product can be washed, such as washed with water, and It is then dried, for example in air. A crystallization method involves preparing Aqueous reaction mixture with excess template agent 'applies crystallization to the mixture under hydrothermal conditions to establish a balance between molecular sieve formation and dissolution, and then removes some excess template agent and / or organic base to inhibit molecular sieve dissolution. References, such as US 5, 2 9 6, 2 0, which is incorporated herein by reference. Other methods of synthesizing or improving molecular sieves are described in US 5, 8 7 9, 6 5 5 (Controlling the ratio of template to phosphorus ), US 6,005,155 (using a salt-free modifier), US 5,475,182 (acid extraction), US 5,962,762 (transition metal treatment), US 5,925,586 and 6,153,552 (phosphorus modification), US 5,925,800 (supported by stone), US 5,932,512 (fluorine treatment), US 6,046,3 73 (electromagnetic wave treatment or improvement), US 6,051,746 (multi-core aromatic modifier), US 6,22 5,254 (heating template agent), published on March 25, 2001 PCT WO 0 1/3 63 29 (synthesis of surfactants), PCT WO 01/25151 (phased acid addition) published on April 12, 2001, PCT WO 01 published on August 23, 2001 / 60746 (silicone oil), applied on August 15, 2001 US Patent No. 09/929949 (Cooling Molecular Sieve), US Patent No. 09 / 615,526 (including metal impregnation of copper) filed on July 13, 2000, and US Patent No. 09 (filed on 928) / 672,469 (conductive microfilter), and (17) 200306890 * »US Patent No. O9 / 7 548 i2 (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 template 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 template agent. Aluminum silicate and silicon aluminum phosphate molecular sieves have a high ratio of silicon (Si) to aluminum (A1) or a low ratio of silicon (Si) to aluminum (A1). However, for SAPO synthesis Si / A1 is better than rhenium. In one embodiment, the Si / Al ratio 分子 of the molecular sieve is less than 0 65, such as less than 0 40, such as less than 0 32, and especially less than 0 20: In another embodiment, the Si / Al ratio 分子 of the molecular sieve ranges from From about 0 65 to about 0 10, such as from about 0 40 to about 0 1 0, such as from about 0 3 2 to about 0 1 0, and especially from about 0 3 2 to about 0 1 5. Metal oxides The metal oxides of the present invention are metal oxides that are different from typical adhesives and / or matrix materials. When combined with molecular sieves, they are beneficial to catalytic conversion methods. In particular, the metal oxides useful herein are oxides of Group 2 metals, whether alone or in combination with Group 3 metal oxides, and the carbon dioxide intake of the Group 2 metal oxides is within 10% ( TC at least 0.003 mg / m2 metal oxide, such as at least 035 mg / m2 metal oxide. Although the upper limit of carbon dioxide uptake of metal oxides is not critical, generally, the carbon dioxide of metal oxides used herein At -22- (18) (18) 200306890 1 0 0 ° C, it will be less than 10 mg / rn2 metal oxide, such as less than 5 mg / m2 metal oxide. In order to measure the carbon dioxide intake of metal oxides, The following steps were taken using a Mettler TGA / SDTA 851 thermogravimetric analysis system at ambient pressure. A sample of metal oxides was dehydrated by heating in flowing air to approximately 500 ° C for 1 hour. After that, the temperature of the sample was at It was lowered to 100 ° C under flowing ammonia gas. After the sample reached equilibrium at the desired adsorption temperature and flowing helium gas, the sample was given a gas mixture containing 10% by weight carbon dioxide and the remainder being ammonia gas. 20 individual pulses of the substance (approximately 12 seconds / pulse). After each pulse of the adsorbed gas, the metal oxide sample was flushed with flowing ammonia for 3 minutes. The weight of the sample was increased to absorb the adsorbent after processing at 500 ° C Calculated by weight and expressed in mg / mg adsorbent, is the amount of adsorbed carbon dioxide. The surface area of the sample is measured according to the Brunauer, Emmett, and Teller (BET) method disclosed in ASTM D 3 663, providing carbon dioxide uptake, in mg carbon dioxide / m2 metal oxide is expressed. Suitable metal oxides are these metal oxides, the surface area of the metal oxide is greater than 20m2 / g, and it is calcined to greater than 200 ° C, and has a conversion greater than 25% at room temperature, such as Ability to be greater than 50%, such as greater than 80% acetone. The optimal Group 2 metal oxide is magnesium oxide (MgO). Suitable Group 3 metal oxides include yttrium oxide, lanthanum oxide, hafnium oxide, and mixtures thereof. In one embodiment, the active metal oxide is preferably MgO, more preferably a mixture of MgO and a Group 3 metal oxide, and its surface area is greater than (19) (19) 200306890 2 0 m 2 / g, for example, greater than 50. m2 / g, eg If it is greater than 80 m2 / g, and even greater than 200 m2 / g, it is measured in accordance with the Brunauer, Emmett, and Teller (BET) method disclosed in ASTM D 3663. In another embodiment, the metal oxide is preferably Magnesium oxide, more preferably MgO and a Group 3 metal oxide, has a temperature range from 200 ° C to 700 ° C, such as from about 25 ° C to 6 50 0 t, such as in the range from 3 00 ° C to 600 ° C, and typically from 3 5 0 5: to about 5 5 0 t :, is calcined. In one embodiment, the surface area of the magnesium metal oxide is about 250 m2 / g, and / or the magnesium oxide is calcined to about 55 CTC. In one embodiment, when the active metal oxide is saturated with acetone and contacted with the acetone at room temperature (about 25 ° C) for 1 hour, the metal oxide converts more than 80% acetone, such as more than 85%, such as Greater than 90%, and in some cases greater than 95%. There are various methods for determining the conversion of acetone, and one method is to use 13 C solid state NMR. In this method, the metal oxide is first dehydrated under vacuum while being heated using a stepwise temperature program. Typically, the maximum temperature used in the dehydration step is 400 ° C. Thereafter, the metal oxide is saturated with acetone-2-13C at room temperature (approximately 25 ° C) by using a conventional vacuum method technique. The metal oxide that adsorbs acetone-2-13C is moved to a 7-mm NMR rotor, which does not have any contact with air or moisture. After the sample was placed at 25 ° C for 1 hour, a quantitative 13C solid state NMR spectrum with magnetic angular rotation was obtained, and the conversion of acetone was measured. Various methods can be used to prepare the active metal oxide. The active metal oxide can be prepared from an active metal oxide precursor, such as a metal salt, preferably a Group 2 or Group 3 metal salt precursor. Other suitable sources for Group 2 metal oxides are -24- (20) (20) 200306890. Other suitable sources include compounds that form these metal oxides during calcination, such as chlorine oxides and nitrates. Additional suitable sources of Group 2 or Group 3 metal oxides include salts containing cations of Group 2 or Group 3 metals, such as halides, nitrates, and acetates. In one method, active metal oxides are prepared by pyrolyzing metal-containing compounds such as magnesium oxalate and barium oxalate at high temperatures, such as 600 ° C, and flowing air. Therefore, the metal oxides produced generally have a low BET surface area, for example, less than 30 m2 / g. In another method, active metal oxides are prepared by hydrolysis of metal-containing compounds, followed by dehydration and calcination. For example, Mg0 is hydrogenated by mixing oxides with deionized water to form a white material. The slurry was slowly heated to dryness on a hot plate to form a white powder. The white powder is further dried in a vacuum oven at 100 ° C for at least 4 hours, such as 12 hours. The dried white powder is then calcined in air at a temperature of at least 400 ° C, such as at least 500 ° C, and typically at least 50 ° C. Therefore, the active metal oxides produced generally have a higher B E T surface g area (between 30 and 300 m2 / g) than those produced by pyrolyzing the active metal oxide precursor. In another method, active metal oxides are prepared by the so-called aerogel method (K oper, OB, Lagadic, I, Volodin, A. and Klabunde, KJC hem Mater 1 997, 9, 2468-2480). . In this method,

The Mg powder was reacted with anhydrous methanol under nitrogen to form a methanol solution of Mg (〇CH3) 2. The obtained solution of Mg (0CΗ3) 2 was added with toluene. After that, water was added dropwise to a methanol-toluene solution of Mg (02) 2 in (25) (21) (21) 200306890 with vigorous stirring. The resulting colloidal suspension of Mg (OH) 2 was placed in a pressure cooker, pressurized with dry nitrogen to 1000 PS ig (690 k P ag), and slowly heated to a final pressure of about 1000 psig (6 8 9 5kPag). The supercritical solvent is discharged, producing Mg (OH) 2 as a fine white powder. Nanocrystalline MgO is obtained by heating a fine white powder at 400 ° C under vacuum. The resulting active metal oxide has a maximum BET surface area, typically greater than 300 m2 / g. Various methods exist for preparing mixed metal oxides from Group 2 and Group 3 metal oxide precursors, such as wet impregnation, incipient wetness, and coprecipitation. In one implementation, a mixed metal oxide is prepared by impregnating a Group 2 metal oxide with a Group 3 metal oxide. In a typical preparation, a Group 3 metal oxide precursor, such as lanthanum triethylsulfonyl acetate, is dissolved in an organic solvent, such as toluene. The solvent is used in an amount sufficient to fill the mesopores and macropores of the Group 2 metal oxide. The Group 3 metal oxide precursor solution is added dropwise to the Group 2 metal oxide. The wet mixture is dried in a vacuum oven for 1 to 12 hours to remove the solvent. The resulting solid mixture is then calcined at a temperature high enough to decompose the Group 3 metal oxide precursor g to its oxide, such as 400 ° C. In another embodiment, the mixed oxide is prepared by an incipient wetness technique. Typically, a Group 3 metal oxide precursor, such as lanthanum acetate, is dissolved in deionized water. The solution was added dropwise to the Group 2 metal oxide. The mixture was dried in a vacuum oven at 50 ° C for 1 to 12 hours. The dried mixture was decomposed and calcined in air at 50 ° C for 3 hours. In another embodiment, the mixed metal oxide is prepared by co-precipitation -26-(22) (22) 200306890. The water solubility of the Group 2 and Group 3 metal oxide precursors is also subjected to conditions sufficient to cause precipitation of the hydrated precursor of the solid oxide material ', for example, by adding sodium hydroxide or ammonium hydroxide. The temperature is typically from about 20 ° C to about 100 ° C, and the liquid medium is maintained during and at this temperature. The resulting gel is then at a temperature between 50 and 100. (: Hydrothermal treatment lasts for several days. Hydrothermal treatment typically occurs when the pressure is greater than atmospheric pressure. The obtained material is then recovered, such as by or centrifugation, and rinsed and dried. The obtained material is then heated at a temperature greater than 2 0 0 ° C, preferably more than 300 ° C, and more preferably more than 400 ° C, and most preferably more than 45 0 ° C, and calcined. Catalyst composition The catalyst composition of the present invention Including any one of the foregoing molecular sieves, and one or more of the above active metal oxides, optionally together with an adhesive and / or matrix material different from the active metal oxides. Typically, in the catalyst composition, the active metal oxidizes The weight ratio of the zeolite to the molecular sieve ranges from about 1% by weight to about 800% by weight, for example from about 5% by weight to about 200% by weight, especially from about 10% by weight to about 1,000% by weight. There are various adhesives used to form the catalyst composition. Non-limiting examples of adhesives include various types of hydrated alumina, silica, and / or other inorganic oxide sols, which can be used alone or in combination. Alumina containing The best sol is basic aluminum chloride. The inorganic oxide sol, like glue, binds the synthesized molecular sieve with other substances, such as a matrix, especially after heat treatment. By heating, the inorganic oxide sol, preferably- 27- (23) (23) 200306890 has low viscosity and is converted into an inorganic oxide adhesive component. For example, after heat treatment, alumina sol will be converted into an alumina adhesive. Basic aluminum chloride (containing chlorine counterion Alumina hydroxide-based sol) has the general formula AlmO ^ OHhClj ^ xfH ^ O), where m is 1 to 20, n is 1 to 8, 0 is 5 to 40, p is 2 to 15, and X is 0. To 30. In one embodiment, the adhesive is A11304 (0H) 24C17,12 (H20), which is described in GM Wolterman, et al, Stud Surf Sci and C at al, 76, pages 105-144 (1993), which This article is incorporated by reference. In another embodiment, one or more adhesives and one or more other non-limiting examples of alumina materials, such as aluminum oxyhydroxide, gamma-alumina, bauxite, gibbsite, and Transitional alumina, such as α-alumina, β-alumina, γ-alumina, δ_oxidation, ε-oxidation, κ-oxidation and ρ-oxidation, diammonium oxidation, such as dihydrate Ming mine, bay er it e, odordstrandite, doye 1 ite, and mixtures thereof are mixed. In another embodiment, the adhesive is an alumina sol, which advantageously includes alumina, optionally silica. In another embodiment, the adhesive is n-peptide-alumina, which prepares a sol or aluminum ion by treating an alumina hydrate (such as pseudo-alumina) with an acid, preferably an acid that does not contain a halogen. Solution. Non-limiting examples of commercially available colloidal alumina sols include Nalco 8676 commercially available from Nalco Chemical Co, Naperville, Illinois, and Nyacol nano Technologies, Inc.

The Nyacol AL20DWo catalyst composition of Ashland, Massachusetts includes a matrix material, which is preferably different from-28- (24) 200306890 metal oxides and any adhesives. The matrix material typically has a total cost and acts as a heat sink to assist the catalyst composition, such as shielding heat, hardening the catalyst composition, and increasing catalyst strength, such as abrasion resistance. Non-limiting examples of matrix materials include one or more compounds, the non-reactive metal oxides including barium oxide, silica, and mixtures thereof, such as silica-magnesium oxide, silicon; E stone-titanium oxide, silica-alumina, and In the case of silica, alumina, and oxygen, the matrix material is natural clay, such as those of the Lingling family. These natural clays include hypoxanthite and the soil. Non-limiting examples of matrix materials such as Dixie, McNamee, Georgia, and Prota include halositette dickite, pearlite, or terracotta clay such as clay, which can be applied Give known improvements, such as treatment and / or chemical treatment. In a preferred embodiment, the matrix material is a clay composition, especially a composition having a low content of iron or titanium dioxide, and most preferably, the matrix material is kaolin clay, which results in a pumpable, high solids content. The preferred average particle size of the slurry, its surface area, and its ease of compaction due to its flat structure (most preferably kaolin) are from 106 μm, and the D 9 particle size distribution is less than 1 μm. The catalyst composition includes an adhesive or a matrix material, and the ground contact includes from about 1% to about 80% by weight, for example, from effectively reducing the crushing strength and inactive metal oxide, silica or solvent during the regeneration of the catalyst. ί-Zirconia, hafnium silicide. In the famous Kaolin Rida clay such as Yimeng montmorillonite and Gao Φ. Its, Kaolin, Di. Matrix material, calcination and / or acid or clay type clay or clay type φ. Kaolin has been found to have low freshness. The matrix material ranges from 7 1 μm to about 5% by weight of the vehicle composition, typically from -29 to (25) (25) 200306890, about 60% by weight, and particularly from about 5% to 50% by weight of molecular sieves. Calculation of total catalyst composition weight. The catalyst composition includes an adhesive and a matrix substance, and the weight ratio of the adhesive to the matrix substance is typically from 1:15 to 1: 5, such as from 1:10 to 1: 4, and 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. And the total weight of the matrix material. It has been found that a high molecular sieve content and a low matrix material content will increase the performance of the sieve catalyst composition, while a low molecular sieve content and a high matrix material content will improve the abrasion resistance of the composition. Typical density of catalyst composition ranges from 0 5 g / cc to 5 g / cc, for example from 0 6 g / cc to 5 g / cc, for example from 0 7 g / cc to 4 g / cc, especially from 0 8 g / cc to 3g / cco Method for preparing catalyst composition In the preparation of catalyst composition, molecular sieve is formed first, and then mixed with the above-mentioned Group 2 metal oxide, or a mixture with Group 2 and Group 3 metal oxide , Preferably in a substantially dry, dried or calcined state, completely and 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 a hybrid honer, drum mixer, ribbon / pulp blender, kneader, or the like. Chemical reactions between molecular sieves and metal oxides are unnecessary. -30- (26) (26) 200306890 and usually are not preferred. The catalyst composition includes a matrix and / or an adhesive. The molecular sieve and the matrix and / or the adhesive are suitably formulated as a catalyst precursor, and then the active metal is mixed with the formulated precursor. The active metal oxide can be added as unsupported particles or as a mixture with a carrier such as an adhesive or matrix. The resulting catalyst composition can then be formed into particles of useful shape and size by known techniques, such as spray drying, curing, extrusion, and the like. In one embodiment, the molecular sieve composition and the matrix material are optionally mixed with an adhesive to form a slurry with a liquid, followed by mixing, 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 an embodiment, the -31-(27) (27) 200306890 slurry of the molecular sieve composition, adhesive and matrix material is mixed or honed to obtain a sufficiently uniform slurry of the secondary particles of the molecular sieve catalyst composition. Then, it is fed to a forming unit that generates a molecular sieve catalyst composition. In a preferred embodiment, the forming unit is a spray dryer. Typically, the forming unit is maintained at a temperature sufficient to remove most of the liquid from the slurry and from the resulting molecular sieve catalyst composition. When the catalyst composition is formed in this manner, the obtained catalyst composition is in the form of fine particles. When spray-drying is used as the forming agent, 'Typically, the slurry of the molecular decoration composition, matrix material and random adhesive is fed into a spray-drying container with a drying gas, and its average inlet temperature ranges from 200 ° C. To about 55 ° C, and outlet temperature range from 100 ° C to about 225 t. 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 herein as reference. Once the molecular sieve catalyst composition is formed in a substantially dry or dried state, the catalyst composition formed for further hardening and / or activation is usually heat-treated at a local temperature, such as calcination. A typical calcination temperature ranges from about 400 ° C to about 1,000 ° C, such as from about 500 ° C to about 800 ° C, such as from about 5 50 ° C to about 7 ° C. 0 0 ° C. Typical calcination environments are air (which may include small amounts of water vapor), nitrogen, helium, flue gas (oxygen-depleted combustion products -32- (28) (28) 200306890), or any combination thereof. In a preferred embodiment, the catalyst composition is heated under nitrogen at a temperature from about 600 ° C to about 700 ° C. The 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, for example, cracking of naphtha feed into light olefins (US 6,3 00,53 7) or larger molecular weight (MW) cracking of hydrocarbons into smaller MW hydrocarbons; hydrogen cracking, such as the cracking of heavy petroleum and / or cyclic feeds; isomerization, such as the isomerization of aromatics (such as xylene); polymerization, such as Polymerization of one or more olefins to produce a polymer product; reforming; hydrogenation; dehydrogenation; dehydration, such as dewaxing of hydrocarbons to remove linear alkanes; absorption, such as absorption of alkyl aromatics to separate out Its isomers; alkylation, such as aromatic hydrocarbons (such as benzene and alkylbenzene) optionally propylene alkylation to produce cumene, or long-chain olefins; alkyl transfer, such as aromatic and poly Alkyl transfer of a combination of alkyl aromatic hydrocarbons; dealkylation; hydrodecyclization; disproportionation, such as disproportionation of toluene to produce benzene and p-xylene; oligomerization, such as linear and branched Oligomerization of alkenes; and Hydrocyclization. Preferred methods include a method for converting naphtha into a highly aromatic mixture; a method for converting light olefins into gasoline, distillate and lubricating oil; and -33- (29) (29) 200306890 oxygenate conversion Methods for forming olefins; methods for converting light paraffins into olefins and / or aromatics; methods for converting unsaturated hydrocarbons (ethylene and / or acetylene) into aldehydes for conversion to alcohols, acids and esters. The preferred method of the present invention relates to a method for converting a feed to one or more olefins. Typically, the feed comprises one or more aliphatic-containing compounds. The aliphatic portion includes from 1 to 50 carbon atoms, such as from 1 to 20 carbon atoms, such as from 1 to 10 carbon atoms, and Especially from 1 to 4 carbon atoms. Non-limiting examples of aliphatic-containing compounds include alcohols such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, thioethers such as dimethylsulfide, alkylamines such as methylamine, and alkyl ethers For example, dimethyl ether, diethyl ether and methyl ether, alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehyde, and various acids such as acetic acid. In a preferred embodiment of the present invention, the feed comprises one or more oxygenates, and more specifically, one or more organic compounds containing at least one oxygen atom. In the most preferred embodiment of the present invention, the oxygenate in the feed is one or more alcohols, preferably aliphatic alcohols. The aliphatic portion of the alcohols has from 1 to 20 carbon atoms. It is preferably from 10 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms. Alcohols used as feedstock for the process of the present invention include lower linear and branched aliphatic alcohols and their unsaturated counterparts. Non-limiting examples of oxygenates include methanol, ethanol, n-propanol, Isopropanol, methyl ether, dimethyl ether, diethyl ether, diisopropyl ·, formaldehyde, dimethyl carbonate, dimethyl ketone, acetic acid, and mixtures thereof. -34- (30) (30) 200306890 In the preferred embodiment, the feed is selected from one or more of methanol, ethanol, monomethyl ether, monoethyl ether or a combination thereof, more preferably methyl alcohol and dimethyl ether. Ether, and most preferably methanol. The various feeds discussed above, especially feeds containing oxygenates, and 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 It is ethylene and / or propylene. The catalyst composition of the present invention is particularly used for a method generally called a gas conversion to an olefin (G T 0) or a method of converting methanol to an olefin (M τ 〇). In this method, the oxygenated feed, preferably a methanol-containing feed, is converted into one or more olefins 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% by weight based on the total weight of the hydrocarbons produced , Typically greater than 60 weight ° /. For example, more than 70% by weight, and preferably more 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, based on the total weight of the hydrocarbon products produced, and more Preferably it is greater 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, based on the total weight of the hydrocarbon products produced, is typically greater than 20% by weight, such as greater than 25% by weight, -35- (31) 200306890, such as greater than 30% by weight, It is preferably more than 35 wt%. It was found that compared with the similar catalyst group with no active metal oxide composition and the conversion conditions, the catalyst composition of the present invention was used to convert the feed containing methyl ether into ethylene and propylene, and the ethane and propylene produced were greater than 10%, For example, greater than 20%, such as greater than 30%, and the range from about 30% to 40%. In addition to the oxygenate component, such as methanol, the feed may contain a diluent, which is generally reactive with the feed or molecular sieve catalyst, and is typically used to reduce the concentration of the feed. Examples of diluent properties include ammonia, argon, nitrogen, carbon monoxide, carbon dioxide, non-reactive paraffins (especially alkanes, such as methane propane), substantially non-reactive aromatic compounds, and their optimal dilution The agents are water and nitrogen, and water is particularly preferred. Diluents, such as water, can be used in liquid or vapor form. The diluent can be added directly to the input reactor, or it can be added to the reactor, or together with the molecular sieve catalyst composition. The method of the present invention can be implemented in a wide temperature range from about 200 ° C to about 1 000 ° C, for example from about 250 ° C to about 250 ° C to about 7500 ° C, conveniently from about 3500 ° C ° C 'typically from about 3500 ° C to about 6 0 0 t :, and particularly from to about 5 5 0 ° C. Likewise, the method of the present invention can be carried out over a wide range of the pressure range including autogenous pressure. Typically, the partial pressure of the feed (excluding any of the diluents) in the process ranges from about 0% of the constituents in the phase methanol and dioxane to other non-restrictive water that is non-reflective, including one or more constituents, Essence, ethane and mixtures. The combination type is raw material, or it can be added directly. For example, the range of 8000 ° C to about 6 50 0 to 3 5 0 ° C lkPaa to (32) (32) 200306890 about 5Mpaa, such as from about 5kPaa to about IMPaa, and suitably from about 20kPaa To about 500kPaa. Weight space-time velocity (WHS V), defined as the total weight of the feed excluding any diluent / hour / weight of the molecular sieve in the catalyst composition, typically ranges from about 1 hr-l to about 5 000 hr-l, such as from about 2hr-1 to about 3,000hr-1, for example from about 5 hr-1 to about 15O00hr-1, and expediently from about 100hr-1 to about 1000hr-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 m / sec, such as greater than 0.05 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 carried out in a fixed bed method, or more typically in a fluidized bed method (including a turbulent moving bed method), such as a continuous fluidized bed method, and in particular, a continuous-bed 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 (33) (33) 200306890

Fluidization Engineering, D Kunii and 0 Levenspiel, Robert E Krieger Published Company, New York, New York 1977, all of which are incorporated herein by reference. The preferred reactor type is a riser reactor, which is generally described in Riser Reactor, Fluidization and Fluid-Particle System, pages 48 to 59, FA Zenz and DF Othmo, Reinhold Publishing Corporation, New York, 1 960, and US 6,166,282 (rapid fluidized bed reactor), and US patent application serial number 09/5 64,6 1 3, filed on May 4, 2000, 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 gas before being introduced into the riser reactor. The liquid is preferably water or methanol, and the gas is, for example, an inert gas , Such as nitrogen. -38- (34) (34) 200306890 In one embodiment, the amount of fresh feed that enters the reactor system in a liquid and / or vapor manner ranges from about 0.01 weight percent. To about 85% by weight, such as from about 1% to about 75% by weight. /. , More typically from about 5% to about 65% by weight, based on the total weight s of the feed containing any diluent therein. The liquid and vapor feeds may be of the same composition or may include the same or different feeds in various proportions, the feeds having the same or different diluents. The feed to the reactor system is partially or completely preferably converted into 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 olefins 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 zone, the coked catalyst composition g and gas, preferably one or a combination of a stream, methane, carbon dioxide, carbon monoxide, light or inert gas (such as argon), preferably a gas, phase Contact 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 scorched catalyst composition is regenerated under conventional temperature, pressure, and residence time conditions and re-39- (35) (35) 200306890, preferably containing Oxygen gas is in contact. Non-limiting examples of suitable regeneration media include one or more of oxygen, 03, S03, N20, NO, N02, N205, air, air diluted with nitrogen or carbon dioxide, oxygen, and water (US 6,245,703), carbon monoxide, and / Or hydrogen. Suitable regeneration conditions are those who have the ability to burn coke from the coking catalyst composition, preferably the coke is burned to a level of less than 0.05% by weight to input the coked molecular sieve catalyst to the regeneration system The total weight of the composition is calculated. For example, the regeneration temperature may range from about 200 ° C to about 150 ° C, such as from about 300 ° C to about 100 ° C, such as from about 450 ° C to about 7 5 0 ° C, and conveniently from about 5 5 0 ° C to about 7 0 0 ° C. The regeneration pressure may range from about 15 psia (103 kPaa) to about 500 psia (3 448 kPaa), such as from about 20 psia (138 kPaa) to about 2 50 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. 0 1 Molar% to about 5 Molar%, calculated as the total volume of 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 regeneration system, and passing the regenerated catalyst composition through a catalyst cooler to form a cooled regenerated catalyst composition. In an embodiment of -40- (36) (36) 200306890, the catalyst cooler is a heat exchanger ', and the heat exchanger is located inside or outside the regeneration system. Other methods of operating the regeneration system are described in US 6, 29, 9 1 6 (moisture control), which is incorporated herein by reference. Regenerated catalyst composition removed from the regeneration system, preferably from the catalyst cooler, and fresh molecular sieve catalyst composition and / or recycled molecular sieve catalyst composition and / or feed and / or fresh gas or liquid phase Mix and return to riser reactor. In one embodiment, the regeneration catalyst composition removed from the regeneration system is returned to the riser reactor directly, preferably after passing through the catalyst cooler. Carriers, such as inert gases, feed vapors, gases, and the like, can be used in a partially continuous or continuous manner to help introduce the regeneration catalyst composition to 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 compositions are described in Michela 1 L uge, EX perimenta 1 Techniques, Circulating Fluidized Beds, Grace, Avidan and Knowlton, eds, Blackie, 1 9 9 7 (336-337), which This article is incorporated by reference. The degree of coke on the catalyst composition was measured by removing the catalyst composition from the conversion method and measuring its carbon content. After regeneration, the typical degree of coke on the molecular sieve catalyst composition ranges from 0.001% by weight to about 15% by weight, such as from about 0.1% by weight to about 10% by weight, such as from about 0.02% by weight. To about 5% by weight, and expediently from about 0.33% to -41-(37) (37) 200306890 about 2% by weight 'calculated on a molecular weight basis. 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 typically include various separations, fractionation and / or distillation columns, columns, separators or units, and reaction systems, such as the manufacture of ethylbenzene (US 5,476,978) and other derivatization methods, such as the manufacture of aldehydes, ketones, and esters (US5 , 675, 04 1), and other combined equipment, such as various condensers, heat exchangers, refrigeration systems or cooling units, compressors, separation drums or pans, pumps, and the like, Non-limiting examples of columns, columns, separators, or units that are used in combination include one or more of the Jiayuan | removers (preferably high temperature methane distillers), ethane distillers, propane distillers , Scrubber (usually alkaline scrubber and / or quench tower), absorber, adsorber, membrane, ethylene (C2) separator, propylene (C3) separator, butene (C4) separator and And so on. Various recovery systems for preferential recovery of olefins, preferably light olefins such as ethylene, propylene and / or butene, are described in US 5,960,643 (second ethylene-rich stream), 1; 3 5,019,143, 5,452,581 and 5,082,481 (Membrane separation), US 5,6 72,1 9 7 (dependent on pressure adsorbent), US 6,069,288 (hydrogen removal), US 5,904,8 80 (in a single step, the recovered methanol is converted to hydrogen and carbon dioxide) US 5,927,063 (the recovered methanol is converted to a gas turbine power plant) and US 6,121,504 (direct product quenching), US 6,1 2 1,5 03 (highly purified olefins without ultra-rectification) ) And 1; 8, 6,293,998 (pressure-42- (38) (38) 200306890 force conversion adsorption), all of which are incorporated herein by reference. Other recovery systems containing purification systems (such as the purification of olefins) were described by Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 9, John Wiley & Sons, 1 996 pages 249-2 7 1 and 8 94- 899, which is incorporated herein by reference. Purification systems have also been described in, for example, US 6,271,42 8 (purification of diolefin streams), US 6,293,999 (separation of propylene from the C-house) and US Patent Application Serial No. 09/6 89 filed on October 20, 2000, 3 6; 3 (washing stream using hydration catalyst), 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 method, pass through a purification system that removes low levels of by-products or contaminants. Non-limiting examples of pollutants and by-products typically include polar compounds such as water, alcohols, carboxylic acids, ethers, carbon oxides, sulfur compounds such as hydrogen sulfide, carbonyl sulfide and thiols, ammonia and other nitrogen Compounds, rhenium, phosphine and chloride. Other pollutants or by-products include hydrogen and hydrocarbons, such as acetylene, methylacetylene, propadiene, butadiene, and butyne. Typically, in converting one or more oxygenates to olefins having 2 or 3 carbon atoms, minor amounts of hydrocarbons, especially olefins having 4 or more carbon atoms, are also produced. The content of C4 + hydrocarbons is usually less than 20% by weight, such as (39) (39) 200306890 to 10% by weight, such as less than 5% by weight, and particularly less than 2% by weight. /. Calculate the total weight of the effluent gas removed from the method to exclude water. Typically, a recovery system may therefore include one or more reaction systems to convert C 4 + impurities into useful products. A non-limiting example of this reaction system is described in US 5,9 5 5,64 (converting the product of 4 carbon atoms to butane-; [_ene), us 4,774,375 (isobutane and but-2-ene Converted into chemical gasoline), us 6, 〇49,017 (dimerization of n-butene), US 4,2 87,3 69 and 5,7 6 3,6 7 8 (higher olefins are carbonylated with carbon dioxide or Aldehyde production of condensed compounds), US 4,542,252 (multistage 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. A preferred light olefin prepared by any of the above methods is a high purity primary fine hydrocarbon product. The product includes a content greater than 80% by weight, such as generous < 90% by weight, such as greater than 95% by weight, such as An olefin having a single carbon number of at least about 99% by weight, based on the total weight of the olefin. In a practical embodiment, the process of the invention forms part of an integrated process for preparing light olefins from a hydrocarbon feed, preferably a gaseous hydrocarbon feed, especially methane and / or ethane. In the first step of the method, a gas feed is preferably mixed with a water stream, and a synthesis gas stream is prepared through the synthesis gas generation zone, typically including carbon dioxide, carbon monoxide, and hydrogen. Syngas products are known, and typical syngas temperatures range from about 700 ° C to about 1 200 t, and the syngas pressure ranges from about 2 MPa to about 100 MPa. . 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 joint gas stream is prepared via a reorganized stream of natural gas. The next step in the process involves contacting a syngas stream with a heterogeneous catalyst, typically a copper-based catalyst, in contact with each other to produce an oxygenate-containing stream, usually mixed with water. In one embodiment, the step of contacting is performed at a temperature ranging from about 150 ° C to about 45 ° C. and a pressure ranging from about 5 MPa to about 10 MPa. The oxygenate-containing stream or crude methanol, typically Includes alcohol products and various other ingredients, such as ethers, especially dimethyl ether, ketones, aldehydes, dissolved gases such as hydrogen, methane, carbon oxides, and nitrogen, and fuel oil. In the examples, the oxygenate-containing stream, crude methanol, is obtained by known purification methods, distillation, separation, and fractionation to obtain a purified oxygenate-containing stream, such as commercial grade A and AA methanol. A stream or 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 integrated process is It is described in EP-B-0 93 3345, 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 For each preparation One or more polymerization methods of polyenes. (Refer to, for example, US Patent Application Serial No. 09/6 1 5, 3 7 6, filed July 13, 2000, which (41) 200306890 is incorporated herein for polymerization In particular, at least the medium of the hydrocarbon, the agglomerate or its group, the type of catalyst, the catalyst composition method is olefin, and more traditional. Here the metallocene or coordinated Yin Jin Lu oxygen institute The above mentioned polymers of olefins, elastomeric olefins, and polypropylene are referred to as propylene chaos.) Methods include solution, gas phase, slurry phase, and high pressure methods, or a combination of gas phase or slurry phase polymerization of one or more olefins, The olefin is ethylene or propylene. These polymerization methods utilize polymerization catalysts that can include any of the molecular sieve catalysts discussed above. However, the preferred polymerization catalysts are Zieg-Natta, Feili Metal ·, metallocene-type and pre-polymerization catalysts, and mixtures thereof. In a preferred embodiment, the integration method includes polymerizing one or more olefins in a polymerization catalyst system reactor to prepare one or more polymerization products, wherein the one or more Many olefins have been used The above molecular sieves are prepared by converting alcohols, especially methanol. The preferred method of polymerization in a gas phase, and at least one of the olefins is ethylene or propylene. The catalyst system is a supported metallocene catalyst. In the embodiment, the supported metallocene catalyst system includes a carrier, a pentametal compound, and an activator. Preferably, the activator is a non-ionic or a gold oxide compound or a combination thereof, and most preferably, the activator is Polymers prepared by the polymerization method include linear low-density polyethylene, plastics, polyethylenes, low-density polyethylenes, and polypropylene copolymers. The polymers produced by the polyfluorene method, which use choline as a substrate, include Miscellaneous polypropylene, same-row polypropylene, opposing polypropylene, and block or collision copolymers. [Embodiments] -46- (42) (42) 200306890 Examples The following examples are provided to make the present invention, Get a better understanding of its representative advantages. Example A—Preparation of molecular sieve Shi Xijin Phosphate Molecular Sieve, SAPO-34, known as MSA, in the presence of tetraethylammonium hydroxide (R1) and dipropylamine (R2) serving as an organic structure pointing agent or template crystallization. A mixture consisting of the following mole ratios:

2S1O2 / AI2O3 / P2O5 / O 9R1 / 1.5R2 / 50H2〇 is prepared by mixing Condea Pural SB with deionized water to form a slurry. Phosphoric acid (8 5%) was added to the slurry. These adducts are stirred to form a homogeneous mixture. This homogeneous mixture was added to Ludox AS40 (40% SiO 2), followed by R 1 and mixed to form a homogeneous mixture. This homogeneous mixture was added to R2. The homogeneous mixture was then stirred in a stainless steel pressure cooker and heated to 170 ° C for 40 hours for crystallization. This provides a slurry of crystalline molecular sieve. The crystals were then separated from the mother liquor by filtration. The molecular sieve crystals are then mixed with the binder and matrix material, and formed into particles by spray drying. Example B-Conversion method uses a microflow reactor to obtain all catalysis or conversion data. The reactor consists of a stainless steel reactor (1/4 inch (0 64 cm) outside diameter) in a furnace -47- (43) (43) 200306890 configuration, vapor methanol is fed to a microflow reactor. The methanol conversion reaction was performed at a temperature of 47 5 ° C, a pressure of 25 psig (172 kPag), and 100 WHSV (about the content of SAPO-34). The typical content of the formulated SAP O 34 described in Example A was 95 mg, and the reactor bed was diluted with 1 g quartz sand to minimize the exothermic reaction in the reactor. In particular, for the catalyst composition of the present invention, a molecular sieve and a metal oxide, that is, a complete mixture of the M S A molecular sieve of Example A and a reactive metal oxide are used. The effluent from the reactor was collected in a 15-sample loop Valeo valve. The collected samples were analyzed by online gas phase tomography (Hewlett Packard 68 90) equipped with a flame ion detector. The chromatography column used was a Q-column. The response factors used are listed in Table 1 below. Table 1 C, c2 = C2 ° c3 = c3 ° CH3OH (ch3) 2o C4, s C5, s C6, s C7, s 1.103 1.000 1.070 1.003 1.052 3.035 2.639 0.993 0.999 1.006 1.000 The term "C4's, C5 +, etc." means a hydrocarbon Carbon number. Note that the selectivity labeled "C5 + 's" consists of the sum of C5's, C6's, and C7's. The weighted average (selectivity) is calculated by the following formula: Xl * y1 + (X2-xi) * (yi + y2) / 2 + (x3-x2) * (y2 + y3) / 2 +, where Xi And yi are the yield and g fed methanol / g molecular sieve, respectively. The reported catalyst life (g methanol / g molecular sieve) is the cumulative conversion of methanol. Note that both the life and WHSV are reported based on the weight of the SAP 〇-34 sieve. Methanol conversions below 10% by weight are not calculated. Dimethyl ether is not calculated as a product. Dimethyl ether is treated as unreacted methanol when calculating selectivity and conversion. -48- (44) (44) 200306890 Example 1-Comparative Experiment In this Example 1, the catalyst composition was composed of a molecular sieve labeled M S A as described in Example A. The catalyst was diluted with quartz to form a reactor bed. The experimental results obtained in the reactors and conditions discussed in Example B above are shown in Table 2.

Cl c2 = c2 ° c3 = c3 ° c4s C5 + s C 2 + 3 = lifetime g / g 1 7 7 3 7.65 0 29 39.80 0 63 13 04 6 82 77 45 16 34 Example 2-Preparation of 7MgO and measurement of acetone Conversion

MgO was prepared in the following manner. 50 g of MgO (98%, ACS reagent grade from Aldrich) was mixed with 150 ml of deionized water to form a white slurry. The white slurry was slowly heated to dryness on a hot plate. The dried cake is broken up and honed into a fine powder. The powder was further dried in the oven 1 20 ° C for 12 hours. The white powder was then calcined in air at 550 ° C for 3 hours. Therefore, the prepared active metal oxide (MgO) has a relatively high surface area (BET area of about 250 m2 / g). MgO powder is sieved to obtain particles of various sizes. Particle sizes between 75 and 150 microns were used in the conversion method described in Example B. 〇 2 5g of the prepared MgO was packed in a glass tube, which was connected to a vacuum line via a 9-mm 0-ring joint. MgO was then heated to -49- (45) (45) 200306890 4 50QC and held at 45 ° under vacuum. (: For 2 hours to remove water from the oxide. After cooling to room temperature (25 ° C), MgO is saturated with acetone-2-13C. MgO that adsorbs acetone-2-13C is moved to 7-mm NMR Rotate the film without any contact with air or moisture. Before measuring acetone conversion, the sample was placed at room temperature (about 25 ° C) for 1 hour. The 13C NMR experiment was performed with a 200 MHz solid-state NMR spectrometer. Equipped with magnetic angle rotation. Use 1-s pulse delay, 2-ms contact time and 2000 scan to obtain interleaved polarization spectrum. Use 15-s pulse delay and 400 or more scan to obtain quantitative single pulse spectrum The test was repeated and the results of 13 C NMR showed that, on average, more than 80% of the acetone was consumed after 1 hour.

Example 3-Molecular Sieve and MgO In this Example 3, the catalyst composition is composed of 36.6% by weight of MSA, 504% by weight of adhesive and 16% by weight of Mg 0 (described in Example 2 above). composition. The catalyst composition was mixed and then diluted with quartz to form a reactor bed. The results of this experiment in the reactors and conditions discussed in Example B above are shown in Table 3. The data in Tables 2 and 3 show that by constituting a 16.6% catalyst composition loaded with MgO, the life of SAPO-34 molecular sieve is increased from 16 34g / g molecular sieve to 31 66g / g molecular sieve, which is an increase of 9 4%. . -50- (46) (46) 200306890

Cl c2 = c2 ° c3 ° c4s C5 + s C 2 + 3 = lifetime g / g 1 73 3 6 8 6 0 27 40 74 0 53 14 01 5 87 7 7 5 9 3 166 Example 4_MgO and The Group 3 metal oxide is mixed to load the Group 3 metal oxide to a high surface area MgO through an incipient wetness method, wherein the metal is La. 0 226 1 g of lanthanum acetate was dissolved in about 9 ml of deionized water. The solution was added dropwise with 206 g of MgO. The mixture was dried in a vacuum oven at 50 ° C for 1 hour. The dried mixture was crushed and at 5 50. <: Calcined in air for 3 hours. The wt% of La203 is about 5%. The metal oxide powder is sieved to obtain particles of various sizes. Particles with sizes between 75 and 150 microns are used in the conversion method.

Example 5_Molecular sieve and mixed metal oxide: La203 (5 wt%) / MgO In this example 5, the catalyst composition is composed of 36.6% by weight of MSA, 504% by weight of the binder and contains 16 wt% MgO (where the metal is La, described in Example 4) of 5 wt% Group 3 metal oxide. The catalyst composition was thoroughly mixed and then diluted with quartz to form a reactor bed. The experimental results obtained in the reactors and conditions discussed in Example B above are shown in Table 4. The data in Tables 2 and 4 show that by constituting a 16% catalyst composition, the composition is loaded with MgO 'SAPO-34 molecular ornament containing 5% by weight of La203. The life span of the molecule is increased from 16 34 g / g molecular sieve to 6 5 90 g / g molecular sieve. , That is, an increase of more than 300%. -51-(47) (47) 200306890 Table 4

Cl c2 = c2 ° c3 = c3 ° C4S C5 + s C 2 + 3 = life g / s 1 5 9 3 4 5 4 0 23 42 02 0 50 14 24 6 87 76 5 6 6 5 90a a The minimum conversion rate is 306.9% by weight. In this conversion rate, the life is 5757 g of methanol / g molecular sieve. The reported lifetime (6590 g methanol / g molecular sieve) was calculated by extrapolating a conversion rate from 3 0.69% to 10% by weight.

Comparative Example 6-Molecular Sieve and BaO In this Comparative Example 6, 288% by weight of MS A, 432% by weight of an adhesive, and 2.8% by weight of barium acetate were thoroughly mixed, and then diluted with quartz. To form a reactor bed. The reactor was heated to 50 ° C. in a 20 ml / min oxygen and 50 ml / min He mixture stream and maintained at 5 50 CC for 90 minutes. Barium acetate is decomposed into barium oxide under these conditions. The molecular sieve composition is composed of 32% by weight of M S A, 48% by weight of a binder, and 20% by weight of BaO. The reaction temperature was lowered to 475 ° C after the catalyst temperature was reached. The catalyst composition was tested in the conversion method and under the conditions of Example B above. The results of the conversion method are shown in Table 5. The data in Tables 2 and 5 show that by constituting a catalyst composition of 20%, the life of the composition loaded with BaO'SAPO-34 molecular sieve is increased by 43%. -52-(48) 200306890

C! C2 = c2 ° C3 = Canal 3 C4S ^ ---, C5 + s C2 + 1 7 4 3 7 19 0 27 40 3 6 0 55 13 57 6 32 77 Lifetime g / g 2 3 3 6 When the present invention is described and illustrated by a particular embodiment, the surgeon will understand that the present invention is suitable for changing the 'no need for this explanation period' to use a mixture of piston flow, solid bed or flow in a single or multiple reactor system It is within the scope of the present invention to add multiple active metal oxides in different reaction zones to the synthesis mixture to prepare a sieve. Likewise, it is expected that molecular sieves will be used for the catalyst composition. For this reason, for the purpose of determining the actual scope, only the scope of the attached patent application is referred to. Learn the technique. For example, pre-bed method, special domain. Put one or more of the above molecules, one or more of the true nature of the present invention -53-

Claims (1)

(1) (1) 200306890, patent application scope 1 A catalyst composition, including (a) a metal oxide with a surface area greater than 20m2 / g, which has been calcined at a temperature greater than 200 ° C, and when The metal oxide was saturated with acetone and contacted with the acetone at 25 ° C for 1 hour. The metal oxide converted more than 80% of acetone; (b) an adhesive; (c) a matrix substance; and (d) an average pore. Molecular sieves with a size of less than 5 A. 2. The catalyst composition according to item 1 of the patent application scope, wherein the surface area of the metal oxide is greater than 70 m2 / g. 3. The catalyst composition according to item 1 of the patent application scope, wherein the molecular sieve is aluminophosphate and / or aluminophosphate molecular sieve. 4. The catalyst composition according to item 1 of the patent application scope, wherein the metal oxide includes magnesium oxide. 5 The catalyst composition according to item 4 of the patent application scope, further including a Group 3 metal oxide. 6—A catalyst composition including a molecular sieve and at least one oxide from a Group 2 metal of the periodic table, wherein the carbon dioxide intake of the metal oxide is at least 0.003 mg / 100 ° C m2 metal oxide. 7 The catalyst composition according to item 6 of the scope of patent application, wherein the carbon dioxide intake of the metal oxide is at least 10 (35 mg / m2 metal oxide at TC. 8) The catalyst composition, in which the carbon dioxide intake of the metal -54- (2) (2) 200306890 oxides is less than 10 mg / m2 metal oxides at the time of loot. The catalyst composition, wherein the carbon dioxide intake of the metal oxide is less than 5 mg / m2 metal oxide at 100 ° C. 10 As the catalyst composition of the sixth scope of the patent application, it also includes different At least one kind of adhesive and matrix material for the metal oxide. 1 1 The catalyst composition according to item 6 of the patent application scope, wherein the surface area of the metal oxide is larger than the surface area of the adhesive and / or matrix material. The catalyst composition according to item 6 of the patent application, wherein the surface area of the metal oxide is greater than 20 m 2 / g. 13 If the catalyst composition according to item 6 of the patent application, also includes an adhesive and a matrix substance, They are different from each other and different from the metal oxygen 14 The catalyst composition according to item 3 of the scope of patent application, wherein the adhesive includes alumina sol, and the matrix material includes clay. 15 The catalyst composition according to item 6 of the scope of patent application, wherein when the metal is The oxide was saturated with acetone and contacted with the acetone at 25 t for 1 hour, and the metal oxide converted more than 80% of acetone. 16 The catalyst composition according to item 6 of the patent application scope, wherein the metal oxide includes oxidation Magnesium. 17 If the catalyst composition in the scope of the patent application No. 6 includes a Group 3 metal oxide. 18 If the catalyst composition in the scope of the patent application No. 17, the Group 3 metal oxide is selected from Yttrium oxide, lanthanum oxide, hafnium oxide, and mixtures thereof -55- (3) (3) 200306890. 19 The catalyst composition according to item 6 of the patent application scope, wherein the molecular sieve includes a series of 2 or 3 selected from [Si04], [Al〇4] and [P〇4] unit composed of tetrahedral units. 2 〇 The catalyst composition of the scope of the patent application No. 6 wherein the molecular sieve includes silicoaluminophosphate. 2 1 If you apply for the catalyst composition in item 6 of the patent scope, The molecular sieve includes a molecular structure of the CHA structure type. 22 As a catalyst composition of the scope of application for item 21, the molecular sieve additionally includes a molecular structure of the AEI structure type. 23 For the composition of the catalyst of scope 6 of the patent application, wherein The weight ratio to the metal oxide ranges from 1% to 800%. 24-A method for preparing a catalyst composition, the method comprising: first particles containing a molecular sieve and at least one selected from the second element in the periodic table. The second particles of the group metal oxide are completely mixed, and the carbon dioxide intake of the metal oxide is at least 0 03 mg / m 2 metal oxide particles at 100 ° C. 25. The method of claim 24, wherein the surface area of the second particle is greater than 70 m2 / g. 26. The method of claim 24, wherein the first particles include silicoaluminophosphate molecular sieves and / or aluminophosphate molecular sieves. 27. The method of claim 24, wherein at least one of the first and second particles also includes at least one of an adhesive and a matrix substance. 28. The method of claim 27, wherein the first particle -56- (4) (4) 200306890 comprises a silicoaluminophosphate molecular sieve, a binder containing alumina sol, and a matrix material containing clay. 29. The method of claim 24, wherein when the metal oxide is saturated with acetone and contacted with the acetone at 25 ° C for 1 hour, the metal oxide converts more than 25% of acetone. 30. The method of claim 29, wherein the metal oxide includes magnesium oxide. 31. The method of claim 24, wherein the second particles further include at least one oxide selected from the group 3 metals of the periodic table. 3 2 —A method for preparing a catalyst composition, the method comprising mixing a molecular sieve, an adhesive, a matrix substance and at least one metal oxide, when the metal oxide is saturated with acetone and contacted with the acetone at 25 ° C 1 hour 'The metal oxide converted more than 25% of acetone. 33. The method of claim 32, wherein when the at least one metal oxide is saturated with acetone and contacted with the acetone at 25 ° C for 1 hour, the metal oxide converts more than 80% of acetone. 34. The method of claim 32, wherein the surface area of the at least one metal oxide is greater than 70 m2 / g. 35. The method according to item 32 of the scope of patent application, wherein the carbon dioxide intake of the at least one metal oxide is at least 0.003 mg / m2 metal oxide particles at 1000 ° C. 36. The method of claim 32, wherein the at least one metal oxide includes magnesium oxide. (5) (5) 200306890 3 7 The method according to item 36 of the scope of patent application, wherein the at least one metal oxide additionally includes at least one oxide selected from Group 3 metals in the periodic table. 38 — A method for preparing a catalyst composition, the method comprising (a) mixing a molecular sieve, an adhesive, and a matrix substance to produce a catalyst precursor; and (b) adding a metal oxide to the catalyst precursor, The metal oxide has been calcined in a temperature range from 200 ° C to 700 ° C. 39. The method of claim 38, wherein when the metal oxide is saturated with acetone and contacted with the acetone at 25 ° C for 1 hour, the metal oxide is converted to more than 25% of acetone. 40. The method according to item 38 of the scope of patent application, wherein the carbon dioxide intake of the metal oxide is at least 10 mg / m2 metal oxide particles at TC (TC). 4 1 The method according to item 8, wherein the metal oxide includes magnesium oxide. 42 The method according to item 41 of the patent application scope, wherein the method further comprises step (c) introducing a group 3 metal oxide selected from the group consisting of yttrium oxide, lanthanum oxide, and hafnium oxide. 43. A method for preparing a catalyst composition, the method comprising: (i) synthesizing a molecular sieve from a reaction mixture, the mixture including at least one templating agent and at least two selected from a sand source, a source, and a source; And (Π) recovering the molecular sieve synthesized in step (i); (ί Π) calcining -58- (6) (6) 200306890 magnesium oxide at a temperature ranging from about 200 to about 70 ° C Or a magnesium oxide precursor to generate active magnesium oxide; and (iv) physically mixing the molecular sieve recovered in step (i) and the active magnesium oxide. 44 The method according to item 43 of the scope of patent application, wherein the Carbon dioxide intake by active magnesium oxide 値The metal oxide is at least 0.003 mg / m2 at 100 ° C. 4 5 The method according to item 43 of the patent application, wherein the surface area of the active magnesium oxide ranges from about 70 m2 / g to about 600 m2 / g. 46 The method according to claim 43, wherein the molecular sieve and / or active magnesium oxide is mixed with an adhesive and / or matrix substance before step (vi). 47 The method according to claim 43 includes applying a third group Another step of introducing the metal oxide into the catalyst composition. 4 8-A method for converting the feedstock into one or more olefins in the presence of a molecular sieve catalyst composition, the catalyst composition including a molecular sieve, an adhesive, and a matrix substance And metal oxides, when the metal oxide is saturated with acetone and contacted with the acetone at 25 ° C for 1 hour, the metal oxide converts more than 80% of propidium. 4 9 According to the scope of patent application No. 48 A method in which the metal oxide is calcined to a temperature ranging from 20 (TC to 700 ° C. 5) The method according to item 48 of the patent application range, wherein the surface area of the metal oxide is greater than 70 m 2 / g. 5 1 Such as patent application The method according to item 48, wherein the carbon dioxide intake of the metal oxide is at least 0 03 mg / m2 metal-59- (7) (7) 200306890 oxide at 100 ° C. 52 The method according to item 48, wherein the metal oxide is magnesium oxide. 53 The method according to item 52 of the patent application, wherein the catalyst composition also includes a Group 3 metal oxide. 54 The application, such as patent application 48. The method of item 8 wherein the feed comprises methanol and / or dimethyl ether. 55 — A method for converting a feedstock into one or more olefins in the presence of a catalyst composition, which is prepared by a method according to item 24 of the scope of patent application. 56 — A method for converting a feedstock into one or more olefins in the presence of a catalyst composition, which is prepared by a method according to item 32 of the scope of patent application. 57 — A method of converting a feedstock into one or more olefins in the presence of a catalyst composition, which is prepared by a method according to item 38 of the scope of patent application. 58—A method for transforming the feedstock into one or more bright smoke in the presence of a catalyst composition '§ The catalyst composition is prepared by a method according to item 43 of the scope of patent application. 59 — 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 small pore molecular sieve, an adhesive Agent, matrix material, magnesium oxide and Group 3 metal oxide, the magnesium oxide has been calcined in a temperature range from 200 ° C to 700 ° C; -60- (8) (8) 200306890 (b) from the reaction The extrusion system discharges an effluent stream containing one or more olefins; and (c) passes the effluent stream through a recovery system; and (d) recovers at least the one or more olefins. 60. The method according to item 59 of the patent application, wherein the olefin includes ethylene and propylene, the molecular sieve is a silicoaluminophosphate molecular sieve, the feed includes methanol, the surface area of the magnesium oxide is greater than 80m2 / g, the adhesive is an alumina sol, and the matrix The substance is clay. 61. The method of claim 59, wherein the metal oxide converts more than 80% of acetone when the bell oxide is saturated with acetone and is in contact with the acetone for 1 hour. 62 — An integrated method for preparing one or more olefins, the integrated method comprising: (a) passing a hydrocarbon feed through a synthesis gas generation area to generate a synthesis gas stream; (b) contacting the synthesis gas stream with a catalyst to form an oxidation feedstock And (c) converting the oxidation feed to the one or more olefins in the presence of a molecular sieve catalyst composition comprising a small pore molecular sieve having an average pore size of less than 5A and a metal oxide having a surface area greater than 80 m2 / g Thing. 63. The method of claim 62, wherein the carbon dioxide intake of the metal oxide is 100100. (: At least 0.003 mg / m2 of metal oxide. -61-200306890 〇) 64 such as the scope of application for patent 62 additionally includes (d) in the presence of a polymerization catalyst] polyolefin. 65 If the scope of application for patent No. 62 includes methanol, olefins include ethylene and propylene magnesium, the magnesium oxide has been at a temperature from 300 ° C: an integrated method, wherein the method polymerizes one or more olefins into an integrated method, wherein Oxidation is carried out and the metal oxide is oxidized in the range of 5 7 5 ° C. -62- 200306890 Lu, (1), the designated representative of this case is: Figure _ (2), the component representative symbols of this representative map 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