JP2005518930A - 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 it, and its use in the conversion of a feed, preferably an oxygenated feed, into one or more olefins, preferably ethylene and / or propylene. About. The catalyst composition comprises a molecular sieve and at least one oxide of a metal selected from the group 3 of the periodic table of elements, the lanthanide series of elements and the actinide series 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 ₄ ], [AlO ₄ ] and [PO ₄ ] 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 to convert methanol to olefins, most molecular sieves, including SAPO molecular sieves, undergo rapid coking and thus typically undergo frequent regeneration with exposure to high temperatures and steam environments of the catalyst. I 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 A catalyst composition containing a silicate molecular sieve impregnated with an oxide 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.

  US 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, where the preferred binder is titania. Yes, 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 to increase shape selectivity and coke formation It is disclosed that can be reduced.

  PCT patent application publication WO 98/29370 describes 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 an oxide of a metal selected from at least one group 3 of the periodic table of elements, a lanthanide series of elements, an actinide series of elements, oxide has at 100 ° C., of at least 0.03 mg / metal oxide ^{m 2,} typically at least 0.04 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.

  In one embodiment, the metal oxide is selected from lanthanum oxide, yttrium oxide, scandium oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, thorium oxide, and mixtures thereof.

  Preferably, the molecular sieve conveniently contains silicoaluminophosphate.

  In another aspect, the invention resides in a molecular sieve catalyst composition comprising a Group 3 metal oxide and / or an oxide of a lanthanide series element or an actinide series element, a binder, a matrix material, and a silicoaluminophosphate molecular sieve.

In yet another aspect, the present invention contains at least one oxide containing a metal selected from the group 3 of the periodic table of elements, the lanthanide series of elements, and the actinide series of elements. A method of producing a catalyst composition comprising physically mixing with second particles wherein the metal oxide incorporates at least 0.03 mg / m ² of metal oxide particles m ² at 100 ° C. In the method.

  Preferably, the hydrated precursor of the metal oxide is precipitated from a solution containing the metal ions, and the hydrated precursor is hydrothermally treated at a temperature of at least 80 ° C. for 10 days or less. The second particles are then produced by calcining the hydrated precursor at a temperature in the range of 400 ° C. to 900 ° C.

In another aspect, there is a catalyst composition comprising a molecular sieve and an oxide of a metal selected from at least one group 3 of the periodic table of elements, a lanthanide series of elements and an actinide series of elements, wherein the metal oxide is One feedstock such as oxygenate, conveniently an alcohol such as methanol, in the presence of a catalyst composition having carbon dioxide uptake of at least 0.03 mg / m ² of metal oxide at 100 ° C. The present invention relates to a method for converting to olefin.

  In one embodiment, the catalyst composition has a Lifetime Enhancement Index (LEI) greater than 1, such as greater than 1.5. LEI is defined herein as the ratio of the lifetime of the catalyst composition to the lifetime of the same catalyst composition 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. The molecular sieve is a group of elements of the Periodic Table of Elements [CRC Handbook of Chemistry and Physics, 78th Edition, CRC Press (Boca Raton, Fla.) (1997) using the IUPAC format] and / or lanthanide series elements or By combining with active metal oxides from actinide series elements, increased olefin yields and / or when used to convert feeds such as oxygenates, more particularly methanol, to olefins. Or it has been found that a catalyst composition having a longer lifetime is provided. The resulting catalyst composition is also more propylene-selective and tends to produce only a small amount of undesirable ethane and propane, along with other undesirable compounds such as aldehydes and ketones, particularly acetaldehyde. .

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, 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 sieves useful in the present invention conveniently contain a framework comprising [AlO ₄ ] and [PO ₄ ] tetrahedral units, ie aluminophosphate (AlPO) molecular sieves, or [SiO ₄ ], [ Conveniently containing a framework comprising 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 SAPO molecular sieve substituted, preferably substituted with metal. Examples of suitable metal substituents are group 1 alkali metals of the periodic table of elements, alkaline earth metals of group 2 of the periodic table of elements, lanthanide series: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, erbium , Dysprosium, holmium, thulium, ytterbium and lutetium; and any of the rare earth metals of group 3 of the periodic table of elements including scandium or yttrium, transition metals of groups 4 to 12 of the periodic table of elements or any of these metal species It is a mixture.

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 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 alternate 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.

Metal Oxides The metal oxides useful in the present invention are at least 0.03 mg / m ² metal oxide m ² elemental periodic group III metals, lanthanide series metals and actinide series at 100 ° C. with uptake of carbon dioxide. It is a metal oxide. 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 / m ² of carbon dioxide in metal oxide m ² at 100 ° C. such as carbon dioxide in the metal oxide m ^2, with incorporation. Typically, metal oxides useful in the present invention have a carbon dioxide uptake of 0.05 to 1 mg / m ² of metal oxide. When used in combination with molecular sieves, such active metal oxides provide advantages in catalytic conversion processes, particularly in the conversion of oxygenates to olefins.

  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 about 500 ° C. for 1 hour. The temperature of the sample is then lowered to the desired adsorption temperature of 100 ° C. in flowing helium. After equilibrating the sample in flowing helium at 100 ° C., the sample is subjected to 20 separation pulses (about 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 the weight of the sample in mg / mg adsorbent based on the weight of adsorption is the amount of carbon dioxide adsorbed. Surface area of the sample, Brunauer, published as ASTM D3663, measured by the method of Emmett and Teller (BET), is given carbon dioxide uptake with carbon dioxide mg / metal oxide ^{m 2.}

  Preferred Group 3 metal oxides include oxides of scandium, yttrium and lanthanum, and preferred oxides of lanthanide or actinide series metals include cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprodium, Oxides of holmium, erbium, thulium, ytterbium, ruthelium and thorium are included. The most preferred active metal oxides include scandium oxide, lanthanum oxide, yttrium oxide, cerium oxide, praseodymium oxide, neodymium oxide and mixtures thereof, in particular mixtures of lanthanum oxide and cerium oxide.

In one embodiment, the useful metal oxide, when used in combination with a molecular sieve in the catalyst composition, is an oxidation of a Group 3 metal and / or a lanthanide and actinide series metal that is effective in extending the useful life of the catalyst composition. It is a thing. The quantification of the extension in the catalyst composition life is given by the following formula:

(Wherein the lifetime of the catalyst or catalyst composition is measured in the same process under the same conditions, and the catalyst composition until the conversion of the feedstock by the catalyst composition is reduced by some defined level, for example 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. The active metal oxides of the present invention are Group 3 metal oxides, including lanthanide and actinide series oxides, which when used in combination with molecular sieves, give molecular sieve catalyst compositions having a 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 range of LEI, such as 1.5 to 20, in the range of greater than 1 to 50 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 15, more particularly greater than 1.3, greater than 1.5, such as greater than 1.5. The LEI value is greater than 2, such as greater.

  Active metal oxides can be produced using various methods. The active metal oxide is preferably prepared from an active metal oxide precursor such as a metal salt such as nitrate, halide, 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 yttrium-n-propoxide, are also suitable sources of Group 3 metal oxides.

In one embodiment, the Group 3 metal oxide or lanthanide or actinide series oxide is hydrothermally treated under conditions comprising a temperature of at least 80 ° C, preferably at least 100 ° C. The hydrothermal treatment can be performed in a closed container 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, stirring a Group 3 metal oxide or a lanthanide or actinide series oxide in a liquid medium by the action and / or stirring of a refluxing liquid promotes effective interaction of the oxide with the liquid medium. To do. The time of contact of the oxide with the liquid medium is preferably at least 1 hour, preferably at least 8 hours. The liquid medium for this treatment has a pH of about 6 or higher, preferably about 8 or higher. Non-limiting examples of suitable liquid media include water, hydroxide solutions (including hydroxides of NH ₄ ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ ), carbonate and bicarbonate solutions (NH ₄ ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ carbonates and bicarbonates), pyridine and their derivatives, and alkyl / hydroxylamines.

  In other embodiments, the active Group 3 metal oxide or the lanthanide or actinide series of active oxide is a liquid solution, such as an aqueous solution containing a source of metal ions, such as a metal salt. By subjecting it to conditions sufficient to result in precipitation of a hydrated precursor solid oxide material, such as by addition of a precipitant to. Conveniently, the precipitation is performed at a pH higher than 7. For example, the precipitating agent is preferably a base such as sodium hydroxide or ammonium hydroxide.

  The temperature at which the liquid medium is maintained during precipitation is generally a temperature, such as a range of 0 ° C. to 200 ° C., up to 200 ° C. A specific range of temperature for precipitation is 20 ° C to 100 ° C. The resulting gel is then hydrothermally treated at a temperature of 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. To produce a solid oxide material. The calcination time is typically 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.

Catalyst Composition The catalyst composition of the present invention comprises one or more molecular sieves as described above and one or more active metal oxides as described above, 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% by weight. It is preferably 10% to 600% by weight, more preferably 20% to 500% by weight, and most preferably 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).

  When 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 between 0.1 μm and 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 ratio. 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.

Method of making a catalyst composition In making a catalyst composition, a molecular sieve is first synthesized and then an active metal oxide, preferably in a substantially dry, dried or calcined state. Physically mixed with active metal oxides at 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 to 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 30 weight percent, such as greater than 35 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 a feedstock containing methanol and dimethyl ether to ethylene and propylene, compared to a similar catalyst composition under the same conversion conditions but without an active metal oxide component 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, a new 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 gaseous effluent in the riser reactor and enters a separating vessel in the reactor system 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 stripped into the stripping zone, typically in the lower part of the separation vessel. Supply to the area. 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 less than 0.5% by weight, based on the total weight of the coked molecular sieve catalyst composition entering the regeneration system, preferably from the coked catalyst composition. To a level, contact is made with a regeneration medium, preferably a gas containing oxygen, under regeneration conditions where the coke can be combusted. 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 combined with the integrated methods described above, 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 having an LEI of 1 and is defined as the ratio of the lifetime of the molecular sieve catalyst composition containing 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. R2 was added to this homogeneous mixture, 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
A sample of La (NO ₃ ) ₃ xH ₂ O (Aldrich Chemical Company) was calcined in air at 700 ° C. for 3 hours to produce lanthanum oxide.

Example 2
50 g of La (NO ₃ ) ₃ xH ₂ O (Aldrich Chemical Company) was dissolved in 500 ml of distilled water with stirring. The pH was adjusted to 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 catalyst was calcined at 600 ° C. for 3 hours in flowing air to produce lanthanum oxide (La ₂ O ₃ ).

Example 3
_{Y (NO 3) 3 · 6H} 2 O, and dissolved with stirring 50g of distilled water 500 ml. The pH was adjusted to 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 catalyst was calcined at 600 ° C. for 3 hours in flowing air to produce yttrium oxide (Y ₂ O ₃ ).

Example 4
A sample of Sc (NO ₃ ) ₃ xH ₂ O (Aldrich Chemical Company) was calcined in air at 700 ° C. for 3 hours to produce scandium oxide (Sc ₂ O ₃ ).

Example 5
_{Ce (NO 3) 3 · 6H} 2 O, and dissolved with stirring 50g of distilled water 500 ml. The pH was adjusted to 8 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 catalyst was calcined at 600 ° C. for 3 hours in flowing air to produce cerium oxide (Ce ₂ O ₃ ).

Example 6
_{Pr (NO 3) 3 · 6H} 2 O, and dissolved with stirring 50g of distilled water 500 ml. The pH was adjusted to 8 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 catalyst was calcined in flowing air at 600 ° C. for 3 hours to produce praseodymium oxide (Pr ₂ O ₃ ).

Example 7
_{Nd (NO 3) 3 · 6H} 2 O, and dissolved with stirring 50g of distilled water 500 ml. The pH was adjusted to 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 catalyst was calcined at 600 ° C. for 3 hours in flowing air to produce neodymium oxide (Nd ₂ O ₃ ).

Example 8
Ce (NO ₃ ) ₃ · 6H ₂ O, 39 g and La (NO ₃ ) ₃ · 6H ₂ O, 7.0 g were dissolved in 500 ml of distilled water with stirring. Another solution was prepared containing 20 g of concentrated ammonium hydroxide and 500 mg of distilled water. The two solutions were combined at a rate of 50 ml / min using a nozzle mixer. 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 catalyst was calcined in flowing air at 700 ° C. for 3 hours to produce a mixed metal oxide containing 5% by weight lanthanum based on the final weight of the mixed metal oxide. .

Example 9
Ce (NO ₃ ) ₃ · 6H ₂ O, 9 g and La (NO ₃ ) ₃ · 6H ₂ O, 30.0 g were dissolved in 500 ml of distilled water with stirring. Another solution was prepared containing 20 g of concentrated ammonium hydroxide and 500 mg of distilled water. The two solutions were combined at a rate of 50 ml / min using a nozzle mixer. 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 catalyst was calcined in flowing air at 700 ° C. for 3 hours to produce a mixed metal oxide containing 5% by weight of cerium based on the final weight of the mixed metal oxide. .

Example 10
Carbon dioxide uptake of the oxides of Examples 1-9 was measured using a Mettler TGA / SDTA 851 thermogravimetric analysis system under ambient pressure. Initially, the metal oxide samples were dehydrated to about 500 ° C. in flowing air for 1 hour, after which carbon dioxide uptake was measured at 100 ° C. The surface areas of these samples were measured by the method of Brunauer, Emmett and Teller (BET), and the carbon dioxide uptake was expressed as mg carbon dioxide / metal oxide m ² and is shown in Table 1.

Comparative Example 11
In this comparative example 11 (CEx.11), the molecular sieve catalyst composition produced in Example A was tested by the method of Example B using 50 mg of the molecular sieve catalyst composition containing no active metal oxide. The results of the implementation are shown in Tables 2 and 3.

Example 12
In this example, the molecular sieve catalyst composition produced in Example A was used as the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of La ₂ O ₃ produced by nitrate decomposition in Example 1. Tested. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which show that the lifetime increased by 149% with the addition of La ₂ O ₃ , an active Group 3 metal oxide. The selectivity to ethane is reduced by 36% and the selectivity to propane is reduced by 32%, indicating a significant reduction in the hydrogen transfer reaction.

Example 13
In this example, the molecular sieve catalyst composition produced in Example A was prepared by the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of La ₂ O ₃ produced by precipitation in Example 2. Tested. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which show that the lifetime was increased by 340% by the addition of La ₂ O ₃ produced by precipitation, an active Group 3 metal oxide. ing. The selectivity to ethane is reduced by 55% and the selectivity to propane is reduced by 44%, indicating a significant reduction in the hydrogen transfer reaction.

Example 14
In Example 14, the molecular sieve catalyst composition produced in Example A was tested by the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of Y ₂ O ₃ produced in Example 3. did. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which show that the lifetime increased by 1090% with the addition of Y ₂ O ₃ , an active Group 3 metal oxide. The selectivity to ethane is reduced by 45% and the selectivity to propane is reduced by 28%, indicating a significant reduction in the hydrogen transfer reaction.

Example 15
In this Example 15, the molecular sieve catalyst composition produced in Example A was tested by the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of Sc ₂ O ₃ produced in Example 4. did. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which show that the lifetime increased by 167% with the addition of Sc ₂ O ₃ , an active Group 3 metal oxide. The selectivity to ethane is reduced by 27% and the selectivity to propane is reduced by 21%, indicating a significant reduction in the hydrogen transfer reaction.

Example 16
In this Example 16, the molecular sieve catalyst composition produced in Example A was tested by the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of Ce ₂ O ₃ produced in Example 5. did. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which show that the lifetime increased by 630% with the addition of Ce ₂ O ₃ , an active lanthanide metal oxide. The selectivity to ethane is reduced by 50% and the selectivity to propane is reduced by 34%, indicating a significant reduction in the hydrogen transfer reaction.

Example 17
In this Example 17, the molecular sieve catalyst composition produced in Example A was tested by the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of Pr ₂ O ₃ produced in Example 6. did. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which show that the lifetime was increased by 640% with the addition of Pr ₂ O ₃ , an active lanthanide metal oxide. The selectivity to ethane is reduced by 51% and the selectivity to propane is reduced by 38%, indicating a significant reduction in the hydrogen transfer reaction.

Example 18
In this Example 18, the molecular sieve catalyst composition produced in Example A was tested by the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of Nd ₂ O ₃ produced in Example 7. did. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which show that the lifetime was increased by 340% with the addition of Nd ₂ O ₃ , an active lanthanide metal oxide. The selectivity to ethane is reduced by 49% and the selectivity to propane is reduced by 34%, indicating a significant reduction in the hydrogen transfer reaction.

Example 19
In this Example 19, the molecular sieve catalyst composition produced in Example A was prepared by the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of the mixed metal oxide produced in Example 8. Tested. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which show that by adding 5% LaO _x / Ce ₂ O ₃ , an active lanthanide metal oxide modified with a Group 3 oxide, 450% %, Indicating that the life has increased. The selectivity to ethane is reduced by 47% and the selectivity to propane is reduced by 37%, indicating a significant reduction in the hydrogen transfer reaction.

Example 20
In this Example 20, the molecular sieve catalyst composition produced in Example A was subjected to the method of Example B using 40 mg of the molecular sieve catalyst composition containing 10 mg of the mixed metal oxide produced in Example 9. Tested. The ingredients were mixed well and then diluted with sand to produce a reactor bed. The results of this experiment are shown in Tables 2 and 3, which are obtained by adding 5% CeO _x / La ₂ O ₃ , an active Group 3 metal oxide modified with a lanthanide series oxide, 260%, indicating increased lifetime. The selectivity to ethane is reduced by 56% and the selectivity to propane is reduced by 45%, indicating a significant reduction in the hydrogen transfer reaction.

Claims (18)

A catalyst composition comprising a molecular sieve and an oxide of a metal selected from at least one group 3 of the periodic table of elements, a lanthanide series of elements and an actinide series of elements, wherein the metal oxide is at 100 ° C. A catalyst composition having a carbon dioxide uptake of at least 0.03 mg / m ² of metal oxide. The catalyst composition of claim 1, wherein the metal oxide has a carbon dioxide uptake of at least 0.04 mg / m ² of metal oxide at 100 ° C. 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 at least one of a binder and a matrix substance different from the metal oxide. A molecular sieve catalyst composition comprising a Group 3 metal oxide and / or an oxide of a lanthanide element or an actinide series element, a binder, a matrix material, and a silicoaluminophosphate molecular sieve. The catalyst composition according to claim 4 or 5, wherein the binder is alumina sol and the matrix material is clay. 7. The metal oxide according to claim 1, wherein the metal oxide is selected from lanthanum oxide, yttrium oxide, scandium oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, thorium oxide, and mixtures thereof. The catalyst composition. The catalyst composition according to any one of claims 1 to 7, wherein the metal oxide is yttrium oxide. The catalyst composition according to any one of claims 1 to 8, wherein the molecular sieve contains an aluminophosphate or a silicoaluminophosphate. The catalyst composition according to claim 9, wherein the molecular sieve contains a CHA framework type molecular sieve and / or an AEI framework type molecular sieve. Physically mixing the first particle containing the molecular sieve with at least one second particle containing an oxide of a metal selected from the group 3 of the periodic table of elements, the lanthanide series of elements and the actinide series of elements A method of producing a catalyst composition, wherein the metal oxide has an uptake of carbon dioxide of at least 0.03 mg / metal oxide m ² at 100 ° C. 12. The method of claim 11, wherein the first particles comprise a matrix material comprising a silicoaluminophosphate molecular sieve, a binder comprising alumina sol and clay. Precipitating the hydrated precursor of the metal oxide from the solution containing the metal ions and hydrothermally treating the hydrated precursor at a temperature of at least 80 ° C. for 10 days or less; The method of claim 11 or claim 12, wherein the second particles are produced by calcining the hydrated precursor at a temperature in the range of 400 ° C to 900 ° C. A catalyst composition comprising a molecular sieve and an oxide of a metal selected from at least one group 3 of the periodic table of elements, a lanthanide series of elements and an actinide series of elements, wherein the metal oxide is at 100 ° C. A process for converting a feedstock to one or more olefins in the presence of a catalyst composition having carbon dioxide uptake of at least 0.03 mg / m ² of metal oxide. 15. The method of claim 14, wherein the catalyst composition has a Lifetime Enhancement Index (LEI) greater than 1. 16. A method according to claim 14 or claim 15 wherein the molecular sieve is silicoaluminophosphate. 17. A method according to any one of claims 14 to 16, wherein the feedstock contains methanol and / or dimethyl ether. 14. 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 11-13.