JP2005518929A - Molecular sieve compositions, their catalysts, their production and use in conversion processes - Google Patents

Abstract

The present invention relates to a catalyst composition, a process for producing the catalyst composition, and a feed, preferably an oxygenated feed, into one or more olefins, preferably ethylene and / or propylene. It relates to the use of the catalyst composition in conversion. The catalyst composition contains a molecular sieve and at least one oxide of a metal from group 4, optionally combined with at least one metal from groups 2 and 3 of the periodic table of elements.

Description

Detailed Description of the Invention

  The present invention relates to molecular sieve compositions and catalysts containing the molecular sieve compositions, the synthesis of such compositions and catalysts, and the use of such compositions and catalysts in conversion processes to produce olefins.

  Olefins are traditionally produced from petroleum feedstocks by catalytic cracking or steam cracking. Their cracking processes, particularly steam cracking, produce light olefins such as ethylene and / or propylene from various hydrocarbon feedstocks. Ethylene and propylene are important petrochemical products useful in various processes for producing plastics and other chemical compounds.

  In the petrochemical industry, it has been known for some time that oxygenates, especially alcohols, can be converted to light olefins. A preferred alcohol for light olefin production is methanol, and a preferred method of converting a methanol-containing feedstock to light olefins, primarily ethylene and / or propylene, involves contacting the feedstock with a molecular sieve catalyst composition.

There are many different types of molecular sieves known to convert oxygenate-containing feedstocks to one or more olefins. For example, US Pat. No. 5,367,100 describes the use of zeolite, ZSM-5, to convert methanol to olefins, and US Pat. No. 4,062,905 describes crystalline materials. US Pat. No. 4,079,095 describes the conversion of methanol and other oxygenates to ethylene and propylene using aluminosilicate zeolites such as zeolite T, ZK5, erionite and shabasite. the shown methanol, use of ZSM-34 for conversion to hydrocarbon products such as ethylene and propylene have been described, in U.S. Patent No. 4,310,440, often with AlPO ₄ The production of light olefins from alcohols using crystalline aluminophosphates is described.

Some of the most useful molecular sieves for converting methanol to olefins are silicoaluminophosphate (SAPO) molecular sieves. The silicoaluminophosphate molecular sieve has a three-dimensional microporous crystalline framework structure of [SiO ₂ ], [AlO ₂ ] and [PO ₂ ] angle-sharing tetrahedral units. The synthesis of the SAPO molecular sieve, its incorporation into the catalyst, and its use in converting the feedstock to olefins, particularly when the feedstock is methanol, is described in US Pat. No. 4,499,327, 677,242, 4,677,243, 4,873,390, 5,095,163, 5,714,662 and 6,166,282, All of which are fully incorporated herein by reference.

  When used for the conversion of methanol to olefins, most molecular sieves, including SAPO molecular sieves, undergo rapid coking, and thus frequent regeneration of the catalyst typically upon exposure to high temperatures and steam generating environments. Need. As a result, current methanol conversion catalysts tend to have a limited useful life, and thus molecular sieve catalyst compositions that exhibit increased life, particularly when used in the conversion of methanol to olefins. Need to provide.

No. 4,465,889, methanol, dimethyl ether or mixtures thereof, for use in converting to iso -C ₄ rich compound hydrocarbon products, thorium, zirconium or titanium metal oxide A catalyst composition containing a silicate molecular sieve impregnated with a product is described.

  U.S. Pat. No. 6,180,828 describes the use of modified molecular sieves to produce methylamines from methanol and ammonia, where, for example, silicoaluminophosphate molecular sieves are zirconium oxide, Formulated with one or more modifiers such as titanium oxide, yttrium oxide, montmorillonite or kaolin.

  U.S. Pat. No. 5,417,949 relates to a process for converting harmful nitrogen oxides in oxygen-containing effluents to nitrogen and water using molecular sieves, metal oxide binders, wherein preferred binders are titania. And the molecular sieve is aluminosilicate.

  European Patent Publication EP-A-312981 discloses a zeolite embedded in an inorganic refractory matrix material on a silica-containing support material and at least one oxide of beryllium, magnesium, calcium, strontium, barium or lanthanum, Disclosed is a process for cracking a vanadium-containing hydrocarbon feed stream using a catalyst composition, preferably containing a physical mixture with magnesium oxide.

Effects of Decrease in Number of Acid Sites Located on the PO-Kine and Inui by Y-SAP-34 Crystalline Catalyst by the 17 In the conversion of methanol to ethylene in the catalyst, the catalyst is ground with MgO, CaO, BaO or Cs ₂ O (BaO is most preferred) on non-porous silica in microspheres, thereby increasing shape selectivity and coke formation. It is disclosed that can be reduced.

  PCT Patent Application Publication No. WO 98/29370 includes a small pore non-zeolite molecular sieve containing a metal selected from the group consisting of lanthanide series elements, actinide series elements, scandium, yttrium, group 4 metals, group 5 metals and combinations thereof. The conversion of oxygenates to olefins is disclosed.

In one aspect, the present invention resides in a catalyst composition comprising a molecular sieve and at least one oxide of a metal selected from Group 4 of the Periodic Table of Elements, wherein the metal oxide is at 100 ° C. has at least 0.03 mg / metal oxide ^{m 2,} typically at least 0.035 mg / metal oxide ^{m 2} to the carbon dioxide uptake.

  Preferably, the catalyst composition may also contain at least one of a binder and a matrix material different from the metal oxide.

  The catalyst composition may also contain an oxide of a metal selected from groups 2 and 3 of the periodic table of elements. In one embodiment, the Group 4 metal oxide comprises zirconium oxide and the Group 2 and / or Group 3 metal oxide is one or more oxides selected from calcium oxide, barium oxide, lanthanum oxide, yttrium oxide, and scandium oxide. Including things.

  Preferably, the molecular sieve conveniently contains silicoaluminophosphate.

  In another aspect, the present invention resides in a molecular sieve catalyst composition comprising an active Group 4 metal oxide and Group 2 metal oxide and / or Group 3 metal oxide, a binder, a matrix material, and a silicoaluminophosphate molecular sieve.

In yet another aspect, the present invention provides that the first particles containing a molecular sieve contain a Group 4 metal oxide and that at 100 ° C., at least 0.03 mg / m ² of metal oxide particles m ² is taken up. A method of producing a catalyst composition comprising physically mixing with second particles having.

  Preferably, the hydrated precursor of the Group 4 metal oxide is precipitated from the solution containing the metal ions and the hydrated precursor is heated at a temperature of at least 80 ° C. for 10 days or less. Said second particles are produced by water treatment and then calcination of the hydrated precursor at a temperature in the range of 400 ° C to 900 ° C.

In another aspect, in the presence of a molecular sieve and a catalyst composition containing at least 0.03 mg / m2 metal oxide m ² active group 4 metal oxide having carbon dioxide uptake at 100 ° C. Relates to a process for producing olefins, preferably by converting a feedstock such as an alcohol, for example methanol, into one or more olefins.

  In yet another aspect, the present invention provides a feed to one or more olefins in the presence of a molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material, and a mixture of metal oxides different from the binder and matrix material. Concerning how to convert.

  In one embodiment, the catalyst composition has a Lifetime Enhancement Index (LEI) greater than 1, such as greater than 1.5, wherein the LEI is herein the life of the catalyst composition. , Defined as the ratio to the lifetime of the same catalyst composition in the absence of active metal oxide.

  The present invention relates to molecular sieve catalyst compositions and their use in the conversion of hydrocarbon feeds, particularly oxygenated feeds, to olefins. A catalyst having a longer life when used in the conversion of a feedstock such as oxygenate, and more particularly methanol, to olefins by blending a molecular sieve with one or more active metal oxides. It has been found that a composition is obtained. The resulting catalyst composition also has a higher amount of desirable lower olefins, especially propylene, and a lesser amount of undesirable ethane and propane, as well as other undesirable aldehydes and ketones, especially acetaldehyde. It has a tendency to form with the compound.

  Preferred active metal oxides are Group 4 metals (for example zirconium) of the periodic table of elements using the IUPAC format described in CRC Handbook of Chemistry and Physics, 78th edition, CRC Press (Boca Raton, Florida) (1997). And hafnium). In some cases it has been found that improved results are obtained when the catalyst composition also contains at least one oxide of a metal selected from groups 2 and / or 3 of the periodic table of elements. It was done.

Molecular sieves Molecular sieves are classified by the Structure Commission of the International Zeolite Association according to the rules of the IUPAC Commission on Zeolite Nomenclature. According to this classification, the framework-type zeolite and zeolite-type molecular sieve, for which the structure has been established, have been given the three letter code, Atlas of Zeolite Framework Types, 5th edition, Elsevier (London, UK) (2001) Which is fully incorporated herein by reference.

  In particular, non-limiting examples of preferred molecular sieves for use in the conversion of oxygenate-containing feedstocks to olefins include skeletal species, AEL, AFY, AEI, BEA, CHA, EDI, FAU, FER, GIS, LTA , LTL, MER, MFI, MOR, MTT, MWW, TAM and TON. In one preferred embodiment, the molecular sieve used in the catalyst composition of the present invention has an AEI topology or a CHA topology or a combination thereof, and most preferably has a CHA topology.

The crystalline molecular sieve material has an angle-sharing [TO ₄ ] tetrahedral three-dimensional four-linked framework structure, where T is a [SiO ₄ ], [AlO ₄ ] and / or [PO ₄ ] tetrahedral unit. Such a cation coordinated as a tetrahedron. The molecular sieve useful in the present invention conveniently contains a framework comprising [AlO ₄ ] and [PO ₄ ] tetrahedral units, ie, an aluminophosphate (AlPO) molecular sieve, or. Conveniently containing a framework comprising [SiO ₄ ], [AlO ₄ ] and [PO ₄ ] tetrahedral units, ie a silicoaluminophosphate (SAPO) molecular sieve. Most preferably, the molecular sieve useful in the present invention is a silicoaluminophosphate (SAPO) molecular sieve or a substituted, preferably metal, SAPO molecular sieve. Examples of suitable metal substituents are alkali metals of group 1 of the periodic table, alkaline earth metals of group 2 of the periodic table, lanthanide series: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, erbium, dysprosium , Holmium, thulium, ytterbium and lutetium; and scandium or yttrium, Group 3 rare earth metals, Group 4 to Group 12 transition metals of the Periodic Table, or a mixture of any of these metal species.

Preferably, the molecular sieve used in the present invention has a pore system defined by an 8-membered ring of [TO ₄ ] tetrahedron and has a pore size of less than 5 angstroms, such as 3 angstroms to 5 angstroms, for example 3 angstroms It has an average pore size of from ~ 4.5 Angstroms, especially from 3.5 Angstroms to 4.2 Angstroms.

  Non-limiting examples of SAPO and AlPO molecular sieves useful in the present invention include SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO. -34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44 (US Pat. No. 6,162,415), SAPO-47, SAPO-56, One or a combination of AlPO-5, AlPO-11, AlPO-18, AlPO-31, AlPO-34, AlPO-36, AlPO-37, AlPO-46 and their metal-containing molecular sieves are included. Among them, particularly useful molecular sieves are SAPO-18, SAPO-34, SAPO-35, such as SAPO-18, SAPO-34, AlPO-34 and AlPO-18 and one or combinations of their metal-containing derivatives. , SAPO-44, SAPO-56, AlPO-18 and AlPO-34 and their metal-containing derivatives or combinations thereof, in particular SAPO-34 and AlPO-18 and their metal-containing derivatives or combinations thereof. is there.

  In one embodiment, the molecular sieve is an commensal material having two or more separate crystalline phases within one molecular sieve composition. In particular, symbiotic molecular sieves are described in US Patent Application Publication No. 2002-0165089 and PCT Patent Application Publication WO 98/15496 published on April 16, 1998, both of which are incorporated herein by reference. . For example, SAPO-18, AlPO-18, and RUW-18 have an AEI skeleton, and SAPO-34 has a CHA skeleton. Thus, the molecular sieve used in the present invention may contain at least one alternating phase of AEI and CHA framework species, and in particular CHA framework species pairs determined by the DIFFaX method disclosed in US Patent Application Publication No. 2002-0165089. The ratio of AEI skeleton species is greater than 1: 1.

  Preferably, when the molecular sieve is a silicoaluminophosphate, the molecular sieve is not more than 0.65, such as 0.65 to 0.10, preferably 0.40 to 0.10, more preferably 0.32. Having a Si / Al ratio of from 0.10 to 0.10, most preferably from 0.32 to 0.15.

Active Metal Oxides Active metal oxides useful in the present invention are metal oxides different from typical binders and / or matrix materials that provide advantages in catalytic conversion processes when used in combination with molecular sieves. is there. Preferred metal oxides are Group 4 metals, such as zirconium and / or hafnium, alone or Group 2 metal (eg, magnesium, calcium, strontium and barium) oxides and / or Group 3 metals (lanthanide series elements). And an actinide series element) (for example, yttrium, scandium and lanthanum) in combination with an oxide of a metal oxide. The most preferred active Group 4 metal oxides are zirconium metal oxides alone or in combination with calcium oxide, barium oxide, lanthanum oxide and / or yttrium oxide. In general, silicon, aluminum and combinations thereof are not preferred.

In particular, the active metal oxide, when used in combination with a molecular sieve in the catalyst composition, extends the useful life of the catalyst composition, particularly in the conversion of a feedstock containing methanol to one or more olefins. It is a metal oxide that is different from typical binders and / or matrix materials that are effective in this. The quantification of the extension in the catalyst composition is:

(Wherein the lifetime of the catalyst or catalyst composition in the same process under the same conditions is the catalyst composition until the conversion of the feedstock by the catalyst composition falls below some defined level, e.g. 10%. Is the Lifetime Enhancement Index (LEI) defined by the cumulative amount of feed processed per gram of product. Inert metal oxides have little or no effect on the life of the catalyst composition or shorten the life of the catalyst composition and thus have a LEI of 1 or less. Thus, the active metal oxides of the present invention are metal oxides that are different from typical binders and / or matrix materials that, when used in combination with molecular sieves, provide molecular sieve catalyst compositions having an LEI greater than 1. . By definition, a molecular sieve catalyst composition that is not combined with an active metal oxide has a LEI equal to 1.0.

  By including an active metal oxide in combination with a molecular sieve, a catalyst composition having a LEI, such as 1.5 to 10, ranging from greater than 1 to 20 can be produced. Typically, the catalyst composition according to the invention is greater than 1.1, for example in the range of 1.2 to 1.5, more particularly greater than 1.3, greater than 1.5. LEI values greater than 2, such as greater than 7, are indicated.

Particularly useful metal oxides in the present invention have at 100 ° C., of at least 0.03 mg / metal oxide ^{m 2,} such as at least 0.035 mg / metal oxide ^{m 2,} the carbon dioxide uptake. Although the upper limit of carbon dioxide uptake of metal oxides is not critical, in general, metal oxides useful in the present invention are less than 10 mg / metal oxide m ² , 5 mg / metal oxide at 100 ° C. with carbon dioxide, such as less than m ² . Typically, metal oxides useful in the present invention have a carbon dioxide uptake of 0.04 to 0.2 mg / m ² of metal oxide.

  In order to determine the carbon dioxide uptake of the metal oxide, the following procedure is employed. The sample of metal oxide is dehydrated by heating to about 200 ° C. to 500 ° C. in flowing air until a constant weight, “dry weight”, is obtained. The temperature of the sample is then reduced to 100 ° C. and carbon dioxide is passed through the sample continuously or intermittently until a constant weight is obtained again. The increase in sample weight in mg / mg sample based on the dry weight of the sample is the amount of carbon dioxide adsorbed.

In the examples described below, carbon dioxide adsorption is measured using a Mettler TGA / SDTA 851 thermogravimetric analysis system under ambient pressure. The metal oxide sample is dehydrated in flowing air to 500 ° C. for 1 hour. The temperature of the sample is lowered to about 100 ° C. in flowing helium. After equilibrating the sample in flowing helium at the desired adsorption temperature, the sample is subjected to 20 separation pulses (approximately 12 seconds / pulse) of a gas mixture containing 10 wt% carbon dioxide and the balance being helium. . After each pulse of adsorbed gas, the metal oxide sample is flushed with flowing helium for 3 minutes. After treatment at 500 ° C., the increase in weight in mg / mg adsorbent based on the weight absorbed is the amount of carbon dioxide adsorbed. The surface area of the sample is measured by the method of Brunauer, Emmett and Teller (BET) published as ASTM D3663, giving carbon dioxide uptake in mg carbon dioxide / m ² metal oxide.

Conveniently, the active carbon has greater than ^{10m 2 / g, 10m 2 /} g , such as up to greater than 300 meters ² / g, such as ^{20 m} 2 / g to 250 meters ² / g, a BET surface area. Preferably, the active metal oxide has at least ^{20 m} 2 / g, such as ^{20 m} 2 / g to 250 meters ² / g, a BET surface area. More particularly, the active metal oxides, greater than ^{20 m} 2 / g, such as greater than ^{25 m} 2 / g, in particular greater than ^{30 m} 2 / g, contains zirconium oxide having a BET surface area.

  Active metal oxides are produced by various methods. The active metal oxide is preferably prepared from an active metal oxide precursor such as a halide, a metal salt such as nitrate sulfate or acetate. Other suitable metal oxide sources include compounds that form metal oxides during calcination, such as oxychlorides and nitrates. Alkoxides, such as zirconium-n-propoxide, are also suitable sources of Group 4 metal oxides. A preferred source of Group 4 metal oxide is hydrated zirconia. The expression hydrated zirconia is intended to mean a substance that contains a zirconium atom that is covalently bonded to another zirconium atom by a bridging oxygen atom, and further contains an available hydroxyl group.

In one embodiment, the hydrated zirconia is hydrothermally treated under conditions comprising a temperature of at least 80 ° C, preferably at least 100 ° C. Hydrothermal treatment is typically performed in a closed vessel at a pressure higher than atmospheric pressure. However, the preferred mode of treatment involves the use of an open vessel under reflux conditions. For example, agitation of a hydrated Group 4 metal oxide in a liquid medium by the action and / or agitation of a refluxing liquid promotes effective interaction of the hydrated oxide with the liquid medium. To do. The time of contact of the hydrated oxide with the liquid medium is conveniently a time, such as at least 1 hour, at least 8 hours. The liquid medium for this treatment has a pH, such as about 6 or more, 8 or more. Non-limiting examples of suitable liquid media include water, hydroxide solutions (including hydroxides of NH ₄ ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ ), carbonates and bicarbonates (NH ₄ ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ carbonates and bicarbonates), pyridine and their derivatives, and alkyl / hydroxylamine.

  When a mixture of a Group 4 metal oxide with a Group 2 metal oxide and / or a Group 3 metal oxide is prepared, a first liquid solution containing a source of Group 4 metal ions is added to the Group 2 metal and And / or can be formulated with a liquid solution containing a source of Group 3 metal ions. The blending of the two solutions can be performed under conditions sufficient to result in the coprecipitation of the hydrated precursor of the mixed oxide material as a solid from the solution. Alternatively, the source of Group 4 metal ions and the source of Group 2 metal and / or Group 3 metal ions can be combined into a single solution. This solution is then subjected to conditions sufficient to result in the coprecipitation of the hydrated precursor into the solid mixed oxide material, such as by the addition of a precipitant to the solution.

  The temperature at which the liquid medium is maintained during precipitation is generally in the range below 200 ° C., from 0 ° C. to below 200 ° C. A specific range of temperature for precipitation is 20 ° C to 100 ° C. The resulting gel is then hydrothermally treated at at least 80 ° C, preferably at least 100 ° C. The hydrothermal treatment is typically performed at atmospheric pressure. In one embodiment, the gel is hydrothermally treated for up to 10 days, such as up to 5 days, such as up to 3 days.

  The metal oxide hydrated precursor is then recovered, for example, by filtration or centrifugation, washed and dried. The resulting material can then be calcined, for example in an oxidizing atmosphere, at a temperature of at least 400 ° C., such as at least 500 ° C., for example 600 ° C. to 900 ° C., in particular 650 ° C. to 800 ° C. An active metal oxide material or an active mixed metal oxide. The calcination time is typically a time of 48 hours or less, such as 1.0 to 10 hours, such as 0.5 to 24 hours. In one embodiment, the calcination is performed at about 700 ° C. for 1-3 hours.

  In other embodiments, the Group 4 metal oxide and the Group 2 metal oxide and / or Group 3 metal oxide are prepared separately and then contacted together to produce a mixed metal oxide, Can be contacted with a molecular sieve. For example, the group 4 metal oxide can be contacted with the molecular sieve before introducing the group 2 metal oxide and / or the group 3 metal oxide, or the group 2 metal oxide before introducing the group 4 metal oxide. An oxide and / or a Group 3 metal oxide can be contacted with the molecular sieve.

  When the catalyst composition contains a Group 4 metal oxide and a Group 3 metal oxide, the ratio of Group 4 metal oxide to Group 3 metal oxide is the total moles of Group 4 metal oxide and Group 3 metal oxide. Can be in the range of 1,000: 1 to 1: 1, such as 500: 1 to 2: 1, preferably 100: 1 to 3: 1, more preferably 75: 1 to 5: 1. . Further, the catalyst composition contains 1 to 25% by weight, preferably 1 to 20% by weight, more preferably 1 to 15% by weight, based on the total weight of the mixed metal oxides. Thus, the Group 3 metal oxide is a lanthanum or yttrium metal oxide, and the Group 4 metal oxide is a zirconium metal oxide.

  When the catalyst composition contains a Group 4 metal oxide and a Group 2 metal oxide, the molar ratio of the Group 4 metal oxide to the Group 2 metal oxide is the total moles of the Group 4 metal oxide and the Group 2 metal oxide. Range from 1,000: 1 to 1: 2, 500: 1 to 2: 3, preferably 100: 1 to 1: 1, more preferably 50: 1 to 2: 1. obtain. In addition, the catalyst composition contains 1 to 25 wt%, preferably 1 to 20 wt%, more preferably 1 to 15 wt% of Group 2 metal oxide based on the total moles of mixed metal oxide. The Group 2 metal oxide is calcium oxide and the Group 4 metal oxide is a zirconium metal oxide.

Catalyst Composition The catalyst composition of the present invention comprises any one of the previously described molecular sieves and one or more previously described active metal oxides, optionally a binder and / or different from the active metal oxide. Contains matrix material. Typically, the weight ratio of molecular sieve to active metal oxide in the catalyst composition is 5% to 800%, preferably 10% to 600%, more preferably 20% to 500%, Most preferably, it is 30 to 400% by weight.

  There are many different binders useful for producing the catalyst composition of the present invention. Non-limiting examples of binders useful alone or in combination include various types of hydrated alumina, silicas and / or other inorganic oxide sols. One preferred alumina-containing sol is aluminum chlorohydrol. The inorganic oxide sol acts like a glue that combines the synthesized molecular sieve and other materials such as a matrix, especially after heat treatment. Upon heating, the inorganic oxide sol, preferably an inorganic oxide sol having a low viscosity, is converted to an inorganic oxide binder component. For example, alumina sol is converted to an aluminum oxide binder after heat treatment.

Aluminum chlorohydrol, hydroxylated aluminum based sol having a chloride counterion, the general _{formula, Al m O n (OH)} o Cl p · x (H 2 O)
Wherein m is 1 to 20, n is 1 to 8, o is 5 to 40, p is 2 to 15, and x is 0 to 30. In one embodiment, the binder comprises G.I. M.M. Stud. Surf. Sci. and Catal. 76, 105-144 (1993), Al ₁₃ O ₄ (OH) ₂₄ Cl ₇ · 12 (H ₂ O). In other embodiments, the one or more binders are aluminum oxyhydroxide, γ-alumina, boehmite, diaspore, and α-alumina, β-alumina, γ-alumina, δ-alumina, ε-alumina, κ-alumina and It is blended with one or more other alumina materials such as transition aluminas such as rho-alumina, aluminum trihydroxides such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.

  Non-limiting examples of commercially available colloidal alumina sols include Nalco Chemical Co. (Nalco 8676 and Nyacol Nano Technology Inc. available from Naperville, Ill.). Nyacol AL20DW available from (Ashland, Massachusetts).

  If the catalyst composition contains a matrix material, the matrix material is preferably different from the active metal oxide and binder. The matrix material is typically effective in reducing the overall catalyst cost and acts as a heat sink during regeneration, increasing the density of the catalyst composition, catalyst physical properties such as crush strength and abrasion resistance. Increase physical properties.

  Non-limiting examples of matrix materials useful in the present invention include one or more non-active metal oxides including beryllia, quartz, silica or sol and mixtures thereof, such as silica-magnesia, silica-zirconia, silica-titania, Silica-alumina and silica-alumina-tria are included. In one embodiment, the matrix material is a natural clay such as materials from the montmorillonite and kaolin families. These natural clays include bentonite and kaolins known as, for example, Dixie clay, McNamee clay, Georgia clay and Florida clay. Non-limiting examples of other matrix materials include halloysite, kaolinite, dickite, nacrite or anauxite. Matrix materials such as clay can be subjected to well-known modification processes such as calcination and / or acid treatment and / or chemical treatment.

In a preferred embodiment, the matrix material is a clay or clay seed composition, in particular clay or a clay seed composition having a low content of iron or titania, most preferably kaolin. Kaolin has been found to form a high solids content slurry that can be pumped, has a low fresh surface area, and easily fits together compactly because of the plate-like structure. The preferred average particle size of the matrix material, most preferably kaolin, is 0.1 μm to 0.6 μm and has a D ₉₀ particle size distribution of less than 1 μm.

  When the catalyst composition contains a binder or matrix material, the catalyst composition is typically 1 wt% to 80 wt%, preferably 5 wt% to 60 wt%, based on the total weight of the catalyst composition. More preferably 5% to 50% by weight of molecular sieve.

  When the catalyst composition contains a binder and a matrix material, the weight ratio of binder to matrix material is typically 1:15 to 1: 5, such as 1:10 to 1: 4, in particular 1: 6 to 1: 5. The amount of binder is typically from about 2% to about 30%, from about 5% to about 20%, in particular from about 7%, based on the total weight of the binder, molecular sieve and matrix material. % To about 15% by weight.

  The catalyst composition is typically 0.5 g / cc to 5 g / cc, such as 0.7 g / cc to 5 g / cc, for example 0.7 g / cc to 4 g / cc, in particular 0.8 g / cc. It has a density in the range of cc to 3 g / cc.

In preparing the catalyst composition- blended catalyst composition, the molecular sieve is first synthesized and then the Group 2 metal oxide or mixture of Group 2 metal oxide and Group 3 metal oxide described above. And preferably physically mixed in a substantially dry, dried or calcined state. Most preferably, the molecular sieve and the active metal oxide are physically mixed in their calcined state. Homogeneous physical mixing can be done by any method known in the art, such as mixing using a mixer muller, drum mixer, ribbon / paddle blender, kneader and the like. A chemical reaction between the molecular sieve and the metal oxide is unnecessary and is generally not preferred.

  When the catalyst composition contains a matrix and / or binder, the molecular sieve is first conveniently formulated into the catalyst precursor along with the matrix and / or binder and then the active metal oxide is formulated. Formulated with a precursor. The active metal oxide can be added as unsupported particles or can be added in combination with a support such as a binder or matrix material. The resulting catalyst composition can then be formed into particles of useful shape and size by well known techniques such as spray drying, pelletizing, extrusion and the like.

  In one embodiment, the molecular sieve composition and the matrix material are combined with a liquid, optionally with a binder, to produce a slurry and then mixed to produce a substantially homogeneous mixture containing the molecular sieve composition. . Non-limiting examples of suitable liquids include water, alcohols, ketones, aldehydes and / or esters. The most preferred liquid is water. The slurry of molecular sieve composition, binder and matrix material is then fed to a production unit device such as a spray dryer that forms the catalyst composition into the required shape, eg, microspheres.

  Once the molecular sieve catalyst composition has been produced in a substantially dry state or in a dried state, a heat treatment such as calcination is usually performed to further cure and / or activate the produced catalyst composition. Typical calcination temperatures are in the range of 400 ° C. to 1,000 ° C., preferably 500 ° C. to 800 ° C., more preferably 550 ° C. to 700 ° C. A typical calcination environment is air (which may contain a small amount of water vapor), nitrogen, helium, flue gas (oxygen-poor combustion products) or any combination thereof.

  In a preferred embodiment, the catalyst composition is at a temperature of 600 ° C. to 700 ° C. in nitrogen, typically 30 minutes to 15 hours, preferably 1 hour to about 10 hours, more preferably about 1 hour to about 5 Heat is applied for a period of time, most preferably from about 2 hours to about 4 hours.

The catalyst composition described in where the catalyst composition is used is, for example, a naphtha feedstock to light olefins (US Pat. No. 6,300,537) or higher molecular weight (MW) hydrocarbons. Cracking to low MW hydrocarbons; for example, hydrocracking heavy oils and / or cyclic feeds; for example, isomerization of aromatic compounds such as xylene; for example, polymer products of one or more olefins Polymerization to produce; reforming; hydrogenation; dehydrogenation; for example, dewaxing of hydrocarbons to remove linear paraffins; eg to separate their isomers of alkyl aromatics For example, alkylation of aromatic hydrocarbons such as benzene and alkylbenzenes; for example, alkyl exchange of combinations of aromatic compounds and polyalkylaromatic hydrocarbons; dealkylation; water Decyclizing; for example, toluene, disproportionation to produce benzene and xylenes; for example, oligomerization of straight and branched chain olefins; useful in a variety of ways, including and dehydrocyclization.

  Preferred methods include a method of converting naphtha into a mixture of highly aromatic compounds; a method of converting light olefins to gasoline, distillate and lubricant; a method of converting oxygenates to olefins; Methods of converting to olefins and / or aromatics; and methods of converting unsaturated hydrocarbons (ethylene and / or acetylene) to aldehydes for conversion to alcohols, acids and esters.

  The most preferred method of the present invention is the conversion of the feedstock to one or more olefins. Typically, the feedstock has an aliphatic portion of 1 to about 50 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and most preferably 1 to 4 carbon atoms. One or more aliphatic moiety-containing compounds, preferably one or more oxygenates.

  Non-limiting examples of suitable aliphatic moiety-containing compounds include alcohols such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide, and methylamine. Various alkyl amines, alkyl ethers such as dimethyl ether, diethyl ether and methyl ethyl ether, alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehydes, and acetic acid The acids are included. Preferably, the feedstock contains methanol, ethanol, dimethyl ether, diethyl ether or combinations thereof, more preferably methanol and / or dimethyl ether, most preferably methanol.

  When using the various feedstocks described above, particularly feedstocks containing oxygenates such as alcohols, the catalyst composition of the present invention converts the feedstock primarily into one or more olefins. It is effective to do. The olefin produced typically has 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. And most preferably ethylene and / or propylene.

  Typically, the catalyst composition of the present invention comprises a feed containing one or more oxygenates, typically greater than 50% by weight, typically based on the total weight of hydrocarbons in the product. It is effective to convert to a product containing olefin (s) greater than 60%, such as greater than 70%, preferably greater than 80%. Furthermore, the amount of ethylene and / or propylene produced, based on the total weight of hydrocarbons in the product, is typically greater than 40% by weight, such as greater than 50% by weight, preferably greater than 65% by weight, More preferably more than 78% by weight. Typically, the amount of ethylene produced in weight percent, based on the total weight of the hydrocarbon product produced, is greater than 20 weight percent, such as greater than 30 weight percent, such as greater than 40 weight percent. Also, the amount of propylene produced in wt%, based on the total weight of the hydrocarbon product produced, is greater than 20 wt%, such as greater than 25 wt%, such as greater than 30 wt%, preferably 35 More than weight percent.

  When using the catalyst composition of the present invention for the conversion of feedstocks containing methanol and dimethyl ether to ethylene and propylene, compared to similar catalyst compositions under the same conversion conditions but without active metal oxide components Thus, it has been found that the production of ethane and propane is reduced by more than 10%, such as more than 20%, for example more than 30%, in particular in the range of 30% to 40%.

  In addition to oxygenate components such as methanol, the feedstock is generally non-reactive with the feedstock and molecular sieve catalyst composition, typically to reduce the feedstock concentration. It may contain one or more diluents used in Non-limiting examples of diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, water, essentially non-reactive paraffins (especially alkanes such as methane, ethane and propane), Essentially non-reactive aromatic compounds as well as mixtures thereof are included. The most preferred diluents are water and nitrogen, with water being particularly preferred.

  The method includes 200 ° C. to 1,000 ° C., such as 250 ° C. to 800 ° C., 250 ° C. to 750 ° C., conveniently 300 ° C. to 650 ° C., preferably 350 ° C. to 600 ° C., more preferably 350 ° C. It can be performed at a wide range of temperatures, such as in the range of 550 ° C.

  Similarly, the method can be performed over a wide range of pressures, including self-pressure. Typically, the partial pressure of the feed, excluding the diluent in the feed used in the process, is in the range of 0.1 kPaa to 5 MPaa, preferably 5 kPaa to 1 MPaa, more preferably 20 kPaa to 500 kPaa.

The hourly weight superficial velocity (WHSV), defined as the total weight of the feedstock excluding diluent, per hour per weight of molecular sieve in the catalyst composition is 1 hour- ^{1 to} 5,000 hours- ¹ , preferably 2 hours ^{-1 to} 3,000 hours ⁻¹ , more preferably 5 hours ^{−1 to} 1,500 hours ⁻¹ , most preferably 10 hours ^{−1 to} 1,000 hours ⁻¹ . In one embodiment, the WHSV is at least 20 hours ⁻¹ and in the range of 20 hours ^{−1 to} 300 hours ⁻¹ when the feedstock contains methanol and / or dimethyl ether.

  The process of the present invention is conveniently used as a fixed bed process, more typically as a fluidized bed process (including turbulent bed process), such as a continuous fluidized bed process, particularly as a continuous high speed fluidized bed process. Done.

  In one practical embodiment, the process is performed as a fluidized bed process using a reactor system, a regeneration system, and a recovery system. In such a process, fresh feedstock, optionally containing one or more diluents, is fed along with the molecular sieve catalyst composition to one or more rising-up reactors in the reactor system. The feedstock is converted to a gas effluent in the riser reactor and enters a separating vessel in the reactor system along with the coked catalyst composition. The coked catalyst composition is separated from the gaseous effluent in a separation vessel, typically with the aid of a cyclone, and then separated into the stripping zone, typically in the lower part of the separation vessel. Supply to the ripping zone. In the stripping zone, the coked catalyst composition is contacted with a gas such as steam, methane, carbon dioxide, carbon monoxide, hydrogen and / or an inert gas such as argon, preferably steam, and coke. The adsorbed hydrocarbon is recovered from the converted catalyst composition, and then the coked catalyst composition is introduced into the regeneration system.

  In the regeneration system, the coked catalyst composition is coke from the coked molecular sieve catalyst composition, preferably 0.5% by weight, based on the total weight of the coked catalyst composition entering the regeneration system. It is contacted with a regeneration medium, preferably a gas containing oxygen, under regeneration conditions that can be combusted to a level below. For example, the regeneration conditions can include a temperature in the range of 450 ° C to 750 ° C, preferably 550 ° C to 700 ° C.

  The regenerated catalyst composition withdrawn from the regeneration system is blended with the new molecular sieve catalyst composition and / or recycled molecular sieve catalyst composition and / or feed and / or new gas or liquid and fed to the riser reactor. Returned.

  The gas effluent is removed from the separation system and passed through a recovery system to separate and purify light olefins, particularly ethylene and propylene, in the gas effluent.

  In one practical embodiment, the process of the present invention forms part of an integrated process for producing light olefins from hydrocarbon feedstocks, particularly methane and / or ethane. The first step of the process is to pass a gas feed through a synthesis gas production zone, preferably in combination with water vapor, to produce a synthesis gas stream that typically contains carbon dioxide, carbon monoxide and hydrogen. The synthesis gas stream is then generally contacted with a heterogeneous catalyst, typically a copper-based catalyst, at a temperature in the range of 150 ° C. to 450 ° C. and a pressure in the range of 5 MPa to 10 MPa. Convert to a nate-containing stream. After purification, the oxygenate-containing stream can be used as a feed in the previously described process for producing light olefins such as ethylene and / or propylene. A non-limiting example of this integrated method is described in EP-B-0933345, the description of which is fully incorporated herein by reference.

  In other, more fully integrated methods, optionally in combination with the previously described integrated methods, the olefins produced are directed to one or more polymerization processes to produce various polyolefins.

  In order to provide a better understanding of the present invention, including the typical advantages of the present invention, the following examples are provided.

  In the examples, LEI is defined as the ratio of the lifetime of a molecular sieve catalyst composition containing an active metal oxide to the lifetime of the same molecular sieve containing no metal oxide. To determine LEI, lifetime is defined as the cumulative amount of oxygenate that is preferably converted to one or more olefins per gram of molecular sieve until the conversion rate drops to about 10% of the initial value. Is done. If the transformation does not drop to 10% of its initial value by the end of the experiment, the lifetime is estimated by linear extrapolation based on the rate of reduction in the transformation at the last two data points in the experiment.

“Major olefin” is the sum of the selectivity to ethylene and propylene. “C ₂ ⁼ / C ₃ ⁼ ” is the ratio of ethylene selectivity to propylene selectivity calibrated during the run. "C ₃ purity" is calculated by dividing the propylene selectivity in the total propylene selectivity and propane selectivity. Methane (CH ₄ ), ethylene (C ₂ ⁼ ), ethane (C ₂ ⁰ ), propylene (C ₃ ⁼ ), propane (C ₃ ⁰ ), C ₄ classes (C ₄ ′ s) and C ₅ + classes (C The selectivity for ₅ + 's) is the calibrated average selectivity during the run. C ₅ + s is noted that consist _{C 5} ethers, _{C 6 to} acids and _{C 7} acids only. The selectivity values are corrected for coke as is well known, so they do not add up to 100% in the table.

Example A
Preparation of Molecular Sieve A silicoaluminophosphate molecular sieve, SAPO-34, designated MSA, was crystallized in the presence of tetraethylammonium hydroxide (R1) and dipropylamine (R2) as organic structure indicators or templating agents. following:
_{0.2SiO 2 / Al 2 O 3 /} P 2 O 5 /0.9R1/1.5R2/50H 2 O
Was prepared by first mixing an amount of Condea Pural SB with deionized water to form a slurry. To this slurry was added an amount of phosphoric acid (85%). Their addition was carried out with stirring to produce a homogeneous mixture. To this homogeneous mixture, Ludox AS40 (40% SiO ₂ ) was added, then R1 was added with mixing to produce a homogeneous mixture. To this homogeneous mixture was added R2, and the resulting mixture was then crystallized by heating to 170 ° C. for 40 hours with stirring in a stainless steel autoclave. Thereby, a slurry of crystalline molecular sieve was obtained. The crystals were then separated from the mother liquor by filtration. The molecular sieve crystals were then mixed with a binder and matrix material and particles were produced by spray drying.

Example B
Conversion Method All the conversion data given is obtained using a microflow reactor consisting of a stainless steel reactor [1/4 inch (0.64 cm) outer diameter] located in a furnace supplying vaporized methanol. It was. The reactor was maintained at a temperature of 475 ° C. and a pressure of 25 psig (172.4 kPag). The flow rate of methanol was such that the flow rate of methanol on a weight basis per g of molecular sieve, also known as the hourly superficial velocity (WHSV), was 100 hours- ¹ . The product gas exiting the reactor was collected and analyzed using gas chromatography. The catalyst loading was 50 mg and the catalyst bed was diluted with quartz to minimize reactor hot spots.

Example 1
The ZrOCl ₂ · 8H ₂ O in 1,000g are dissolved with stirring in distilled water 3.0 liters. Another solution was prepared containing 400 g of concentrated NH ₄ OH and 3.0 liters of distilled water. Both solutions were heated to 60 ° C. The two heated solutions were combined at a rate of 50 ml / min using nozzle mixing. The final complex pH was adjusted to about 9 by the addition of concentrated ammonium hydroxide. The slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product produced was collected by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined in flowing air at 700 ° C. for 3 hours to produce an active zirconium oxide material.

Example 2
500 g of ZrOCl ₂ .8H ₂ O and 84 g of La (NO ₃ ) ₃ .6H ₂ O were dissolved in 3.0 liters of distilled water with stirring. Another solution was prepared containing 260 g of concentrated NH ₄ OH and 3.0 liters of distilled water. Both solutions were heated to 60 ° C. and then combined using nozzle mixing at a rate of 50 ml / min to produce the final mixture, slurry. The pH of the final mixture was adjusted to about 9 by the addition of concentrated ammonium hydroxide. The slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The resulting product was collected by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined in flowing air at 700 ° C. for 3 hours and an active mixed containing a nominal 10 wt% La (lanthanum) based on the final weight of the mixed metal oxide. Metal oxide was produced.

Example 3
50 g of ZrOCl ₂ .8H ₂ O was dissolved in 300 ml of distilled water with stirring. Other solutions containing 4.2g of La (NO ₃₎ distilled water ₃ · 6H ₂ O and 300ml was prepared. The two solutions were combined with stirring to produce the final mixture. The final mixture pH was adjusted to about 9 by the addition of concentrated ammonium hydroxide (28.9 g). The slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The resulting product was collected by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this resulting product was calcined in flowing air at 700 ° C. for 3 hours and an active mixed containing a nominal 5 wt% La based on the final weight of the mixed metal oxide. Metal oxide was produced.

Example 4
500 g of ZrOCl ₂ .8H ₂ O and 70 g of Y (NO ₃ ) ₃ .5H ₂ O were dissolved in 3.0 liters of distilled water with stirring. Another solution was prepared containing 260 g of concentrated NH ₄ OH and 3.0 liters of distilled water. Both solutions were heated to 60 ° C. and then combined at a rate of 50 ml / min using nozzle mixing to produce the final mixture. The pH of the final mixture, slurry, was adjusted to about 9 by the addition of concentrated ammonium hydroxide. The slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The resulting product was collected by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of the resulting product is calcined in flowing air at 700 ° C. for 3 hours, and contains an active containing nominally 10 wt% Y (yttrium), based on the final weight of the mixed metal oxide. A mixed metal oxide was produced.

Example 5
500 g ZrOCl ₂ .8H ₂ O and 56 g Ca (NO ₃ ) ₂ .4H ₂ O were dissolved in 3,000 ml distilled water with stirring. Another solution was prepared containing 260 g concentrated NH ₄ OH and 3,000 ml distilled water. The two solutions were combined with stirring. The final complex pH was adjusted to about 9 by the addition of concentrated ammonium hydroxide (160 g). The slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The resulting product was collected by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined in flowing air at 700 ° C. for 3 hours and an active mixed containing a nominal 5 wt% Ca (calcium) based on the final weight of the mixed metal oxide. Metal oxide was produced.

Example 6
70g of _{TiOSO 4 · xH 2 SO 4 ·} xH 2 O and (x = 1) are dissolved with stirring in distilled water of 400 ml. Another solution was prepared containing 12.8 g CeSO ₄ and 300 ml distilled water. The two solutions were combined with stirring. The final complex pH was adjusted to about 8 by addition of concentrated ammonium hydroxide (64.3 g). The slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product produced was collected by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined in flowing air at 700 ° C. for 3 hours and an active mixed metal oxidation containing a nominal 5 wt% Ce based on the final weight of the mixed metal oxide. Product was produced.

Example 7
5 g of HfOCl ₂ xH ₂ O was dissolved in 100 ml of distilled water with stirring. The pH of the final complex was adjusted to about 9 by addition of concentrated ammonium hydroxide (4.5 g). The slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product produced was collected by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this catalyst was calcined in flowing air at 700 ° C. for 3 hours to produce active hafnium oxide.

Example 8
5 g HfOCl ₂ of · xH ₂ O and 0.62 g La a _{(NO 3) 3 · 6H 2} O of are dissolved with stirring in distilled water of 100 ml. The final complex pH was adjusted to about 9 by the addition of concentrated ammonium hydroxide (3.5 g). The slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The resulting product was collected by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined in flowing air at 700 ° C. for 3 hours and an active mixed metal oxidation containing a nominal 5 wt% La based on the final weight of the mixed metal oxide. Product was produced.

Example 9
Carbon dioxide uptake of the oxides of Examples 1-8 was measured using a Mettler TGA / SDTA 851 thermogravimetric analysis system under ambient pressure. First, the metal oxide sample was dehydrated in flowing air to about 500 ° C. for 1 hour, after which carbon dioxide uptake was measured at 100 ° C. The surface area of the sample was measured by the method of Brunauer, Emmett and Teller (BET), and the carbon dioxide uptake was expressed by the carbon dioxide mg / metal oxide m ² shown in Table 1.

Example 10 (comparative example)
The performance of the control, the molecular sieve of Example A, MSA is shown in Tables 2 and 3 using a 50 mg charge in the reactor and under the conditions described in Example B.

Example 11
In this example, the catalyst composition consisted of 40 mg of Example A MSA and 10 mg of Example 1 active zirconium oxide. The catalyst composition and the active mixed metal oxide were mixed well and then diluted with quartz to form the reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. The results indicate that the addition of active zirconium oxide to the catalyst bed significantly increased the lifetime of the molecular sieve composition and reduced the amount of undesirable ethane and propane.

Example 12
In this example, the catalyst composition was composed of 40 mg of Example A MSA and 10 mg of active mixed metal oxide containing 10 wt% La described in Example 2. The catalyst composition and the active mixed metal oxide were mixed well and then diluted with quartz to form the reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. The data in Tables 2 and 3 are as implied by an LEI value of 2 by constituting 20% of the catalyst composition loading with an active mixed metal oxide containing 10% by weight La, The lifetime of the molecular sieve composition is doubled and there is a net increase of 1.7% in the main olefins on an absolute basis, most of which is due to an increase of 2.76% in propylene and 1.07% in ethylene It shows that it compensates for a slight reduction of. The selectivity of ethane was reduced by 39% and the selectivity of propane was reduced by 37%, indicating that the hydrogen transfer reaction was significantly reduced.

Example 13
In this example, the catalyst was composed of 30 mg of MSA of Example A and 20 mg of active mixed metal oxide containing 10% by weight La as described in Example 2. The catalyst composition and the active mixed metal oxide were mixed well and then diluted with quartz to form the reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. The data in Tables 2 and 3 show that constituting 40% of the catalyst composition loading with an active mixed metal oxide containing 10 wt% La results in a lifespan of the SAPO-34 catalyst composition of 440% It shows an increase. This selectivity trend for catalyst loading is similar to the selectivity seen in Example 8.

Example 14
In this example, the catalyst composition consisted of 40 mg of MSA of Example A and 10 mg of active mixed metal oxide containing 10 wt% Y as described in Example 4. The catalyst composition and the active mixed metal oxide were mixed well and then diluted with quartz to form the reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. The substitution of yttrium for lanthanum has the effect of further increasing LEI. However, the improvement in selectivity was not as dramatic as seen with lanthanum, and the increase in main olefins was 1.2% on an absolute basis.

Example 15
In this example, the catalyst was composed of 40 mg of MSA of Example A and 10 mg of active mixed metal oxide containing 5 wt% La described in Example 3. The catalyst composition and the active mixed metal oxide were mixed well and then diluted with quartz to form the reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. The active mixed metal oxide containing 5 wt% lanthanum oxide is much more powerful in increasing LEI than the active mixed metal oxide of Example 8 containing 10 wt% La. Seems to have a good effect.

Example 16
In this Example 16, the catalyst was composed of 40 mg of MSA of Example A and 10 mg of active mixed metal oxide containing 5 wt% Ca as described in Example 5. The catalyst composition and the active mixed metal oxide were mixed well and then diluted with quartz to form the reactor bed. The results of this experiment in the reactor and conditions described in Example B are shown in Tables 2 and 3. An active mixed metal oxide containing 5 wt% calcium oxide increased the lifetime of the molecular sieve composition by 223%.

Example 17 (comparative example)
In this comparative example, the catalyst composition consisted of 40 mg of the MSA of Example A and 10 mg of amorphous mixed metal oxide, amorphous silica / alumina. The molecular sieve catalyst composition and inert mixed metal oxide catalyst were mixed well and then diluted with quartz to form a reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. This Comparative Example 17 shows that when an inert mixed metal oxide is used, the LEI is reduced to a value of less than 1.0 compared to Example 11 of the present invention. There is also a 1.07% loss in main olefin selectivity and no significant reduction in ethane and propane production.

Example 18
In this example, the catalyst composition consisted of 40 mg of the MSA of Example A and 10 mg of active mixed metal oxide containing Ce and titania as described in Example 6. The catalyst composition and the active mixed metal oxide were mixed well and then diluted with quartz to form the reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. The presence of active mixed metal oxide increased the lifetime of the molecular sieve composition by 134%.

Example 19
In this example, the catalyst composition consisted of 40 mg of the MSA of Example A and 10 mg of the active hafnium metal oxide described in Example 7. The catalyst composition and active metal oxide were mixed well and then diluted with quartz to form a reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. The data in Tables 2 and 3 show that the active hafnium metal oxide constitutes 20% of the catalyst composition loading, which increased the molecular sieve life by 126%. The selectivity to ethane was reduced by 40% and the selectivity for propane was reduced by 46%, indicating that the hydrogen transfer reaction was significantly reduced.

Example 20
In this example, the catalyst composition was composed of 40 mg of the MSA of Example A and 10 mg of active mixed metal oxide containing 5 wt% La described in Example 8. The catalyst composition and the active mixed metal oxide were mixed well and then diluted with quartz to form the reactor bed. The results of testing this catalyst composition in the method of Example B are shown in Tables 2 and 3. The data in Tables 2 and 3 increased the lifetime of the molecular sieve by 150% by composing 20% of the catalyst composition loading with an active mixed metal oxide containing 5 wt% La. The selectivity to ethane was reduced by 51% and the selectivity for propane was reduced by 51%, suggesting that the hydrogen transfer reaction was significantly reduced.

Claims (25)

A catalyst composition comprising a molecular sieve and at least one metal oxide selected from Group 4 of the Periodic Table of Elements, wherein the metal oxide is at least 0.03 mg / m ² of metal oxide at 100 ° C., A catalyst composition having carbon dioxide uptake. The catalyst composition of claim 1, wherein the metal oxide has a carbon dioxide uptake of at least 0.035 mg / metal oxide m ² at 100 ° C. 5. The catalyst composition according to claim 1 or 2, wherein the metal oxide has a carbon dioxide uptake of less than 10 mg / metal oxide m ² at 100 ° C. The catalyst composition according to any one of claims 1 to 3, further comprising an oxide of a metal selected from Group 2 and Group 3 of the periodic table. One or more oxides in which the Group 4 metal oxide contains zirconium oxide and the Group 2 metal oxide and / or Group 3 metal oxide is selected from calcium oxide, barium oxide, lanthanum oxide, yttrium oxide, and scandium oxide. The catalyst composition according to claim 4, comprising: 6. The catalyst composition according to any one of claims 1 to 5, wherein the metal oxide has a surface area greater than 10 m < ² > / g. The catalyst composition according to any one of claims 1 to 6, further comprising at least one of a binder and a matrix material different from the metal oxide. A molecular sieve catalyst composition comprising an active Group 4 metal oxide and / or Group 3 metal oxide, a binder, a matrix material and a silicoaluminophosphate molecular sieve. The catalyst composition of claim 8, wherein the binder is alumina sol and the matrix material is clay. The group 4 metal oxide includes zirconium oxide, and the group 2 and / or group 3 metal oxide includes one or more oxides selected from calcium oxide, lanthanum oxide, yttrium oxide, and scandium oxide. Alternatively, the catalyst composition according to claim 9. The catalyst composition according to any one of claims 1 to 10, wherein the molecular sieve contains an aluminophosphate or a silicoaluminophosphate. The catalyst composition according to claim 11, wherein the molecular sieve contains a CHA framework type molecular sieve and / or an AEI framework type molecular sieve. The first particles containing the molecular sieve are physically combined with the second particles containing group 4 metal oxide and having at least 0.03 mg / m ² of metal oxide particles having carbon dioxide uptake at 100 ° C. A method of producing a catalyst composition comprising mixing. The method of claim 13, wherein the second particles have a surface area greater than 10 m ² / g. 15. A method according to claim 13 or claim 14, wherein the first particles comprise a silicoaluminophosphate molecular sieve, the binder comprises an alumina sol, and the matrix material comprises clay. The method according to any one of claims 13 to 15, wherein the second particles also contain a Group 2 metal oxide and / or a Group 3 metal oxide. A hydrated precursor of a Group 4 metal oxide is precipitated from a solution containing the metal ions, the hydrated precursor is hydrothermally treated at a temperature of at least 80 ° C. for 10 days or less, and The method of any one of claims 13 to 16, wherein the second particles are produced by calcining the hydrated precursor to a temperature in the range of 400 ° C to 900 ° C. One or more feedstocks in the presence of a molecular sieve and a catalyst composition containing at least 0.03 mg / m ² metal oxide m ² active group 4 metal oxide with carbon dioxide uptake at 100 ° C. Method to convert to olefin. 19. The method of claim 18, wherein the catalyst composition has a Lifetime Enhancement Index (LEI) greater than 1. 20. A method according to claim 18 or claim 19, wherein the molecular sieve is silicoaluminophosphate. 21. A process according to any one of claims 18 to 20, wherein the catalyst composition also contains active group 2 metal oxides and / or group 3 metal oxides. The method according to any one of claims 18 to 21, wherein the feedstock contains methanol and / or dimethyl ether. A process for converting a feedstock to one or more olefins in the presence of a molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material, and a mixture of metal oxides different from the binder and matrix material. 24. The method of claim 23, wherein the mixture of metal oxides comprises a Group 4 metal oxide in combination with a Group 2 metal oxide and / or a Group 3 metal oxide. 18. A process for converting a feedstock to one or more olefins in the presence of a catalyst composition produced by the process of any one of claims 13-17.