KR20040089679A - Catalyst compositions comprising molecular sieves, their preparation and use in conversion processes - Google Patents

Abstract

The present invention relates to catalyst compositions, methods for their preparation and their use in the conversion of raw materials, preferably oxygenated raw materials, to one or more olefin (s), preferably ethylene and / or propylene. The catalyst composition comprises at least one oxide and a molecular sieve of a metal selected from Group 3, lanthanum-based and actinium-based elements of the Periodic Table of Elements.

Description

Catalyst compositions comprising molecular sieves, methods for their preparation and their use in the conversion process {CATALYST COMPOSITIONS COMPRISING MOLECULAR SIEVES, THEIR PREPARATION AND USE IN CONVERSION PROCESSES}

Olefins are typically prepared from petroleum raw materials by catalytic or steam cracking processes. This cracking process, in particular steam cracking, produces light olefin (s) such as ethylene and / or propylene from various hydrocarbon sources. Ethylene and propylene are important petrochemical products useful in a variety of processes for the production of plastics and other chemical compounds.

In the petrochemical industry it has been known for some time that oxygenates, especially alcohols, are convertible to lower olefin (s). Preferred alcohols for the production of lower olefins are methanol, and preferred processes for converting the methanol-containing feedstock into lower olefin (s), primarily ethylene and / or propylene, include contacting the feedstock with the molecular sieve catalyst composition.

There are many different types of molecular sieves known to convert oxygenate-containing feedstock into one or more olefin (s). For example, US Pat. No. 5,367,100 describes the conversion of methanol to olefin (s) using zeolite, ZSM-5; US Patent No. 4,062,905 describes the conversion of methanol and other oxygenates to ethylene and propylene using crystalline aluminosilicate zeolites such as zeolite T, ZK5, erionite and carbazite; US Patent No. 4,079,095 describes the use of ZSM-34 to convert methanol into hydrocarbon products such as ethylene and propylene; US Pat. No. 4,310,440 describes the preparation of lower olefin (s) from alcohols using crystalline aluminophosphate (often referred to as AlPO ₄ ).

Some of the most useful molecular sieves that convert methanol to olefin (s) are silicoaluminophosphate (SAPO) molecular sieves. Silicoaluminophosphate molecular sieves contain three-dimensional microporous crystalline framework structures of [SiO ₄ ], [AlO ₄ ] and [PO ₄ ] corner covalent four-sphere units. Their use in the synthesis of SAPO molecular sieves, blending them into catalysts and converting raw materials (particularly where the raw material is methanol) to olefins is described in US Pat. Nos. 4,499,327, 4,677,242, 4,677,243, 4,873,390 , 5,095,163, 5,714,662 and 6,166,282, all of which are incorporated herein by reference in their entirety.

When used for the conversion of methanol to olefins, most molecular sieves, including SAPO molecular sieves, undergo rapid coking and require frequent regeneration, which typically involves exposing the catalyst to high temperature and vapor environments. As a result, current methanol conversion catalysts tend to have a limited useful life, and therefore there is a need to provide molecular sieve catalyst compositions that exhibit increased life, especially when used in the conversion of methanol to olefins.

US Pat. No. 4,465,889 discloses molecular sieves comprising silicalite molecular sieves impregnated with thorium, zirconium or titanium metal oxides used to convert methanol, dimethyl ether or mixtures thereof into hydrocarbon products rich in iso-C ₄ compounds. Describe the composition.

U. S. Patent No. 6,180, 828 describes the preparation of methylamines from methanol and ammonia using modified molecular sieves, where, for example, silicoaluminophosphate molecular sieves comprise one or more modifiers such as zirconium oxide, titanium oxide, yttrium oxide, In combination with montmorillonite or kaolinite.

US Pat. No. 5,417,949 relates to a process for converting toxic nitrogen oxides in an oxygen containing effluent to nitrogen and water using molecular sieves and metal oxide binders, wherein the preferred binder is titania and the molecular sieve is alumino Silicate.

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

Kang and Inui, [ Effects of decrease in number of acid sites located on the external surface of Ni-SAPO-34 crystalline catalyst by the mechanochemical method , Catalysis Letters 53, pages 171-176 (1998)]. Silver shape selectivity can be enhanced and coke formation can be catalyzed by MgO, CaO, BaO or Cs ₂ O, most preferably BaO and catalysts on microspheres nonporous silica in the conversion of methanol to ethylene on Ni-SAPO-34. It is disclosed that it can be relaxed by milling.

WO 98/29370 discloses olefins of oxygenated on a metal containing pore non-zeolitic molecular sieve selected from the group consisting of lanthanides, actinides, scandium, yttrium, Group 4 metals, Group 5 metals or combinations thereof. Initiate the conversion to.

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

In one embodiment, the present invention comprises at least one oxide of a metal selected from Group 3, lanthanide and actinium-based elements and a molecular sieve of the Periodic Table of the Elements, wherein the metal oxide is 0.03 mg (carbon dioxide) / m 2 (at 100 ° C.). Metal oxide), typically a catalyst composition having a carbon dioxide adsorption amount of at least 0.04 mg (carbon dioxide) / m 2 (metal oxide).

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

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

Preferably, the molecular sieve may conveniently comprise silicoaluminophosphate.

In another aspect, the present invention relates to a catalyst composition comprising an oxide, a binder, a matrix material and a silicoaluminophosphate molecular sieve of a Group 3 metal oxide and / or a lanthanide or actinium based element.

In another embodiment, the present invention comprises at least one oxide of a metal selected from Group 3, lanthanide and actinium-based elements of the Periodic Table of Elements, wherein the metal oxide is 0.03 mg (carbon dioxide) / m 2 (metal oxide) at 100 ° C. And a second particle having an adsorption amount of carbon dioxide or more, and a first particle including a molecular sieve.

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

In another embodiment, the present invention comprises at least one oxide of a metal selected from Group 3, lanthanide and actinium-based elements and a molecular sieve of the Periodic Table of the Elements, wherein the metal oxide is 0.03 mg (carbon dioxide) / m 2 at 100 ° C. A method for preparing olefin (s) by converting a raw material, such as an oxygenate, conveniently an alcohol, such as methanol, into one or more olefin (s) in the presence of a catalyst composition having an adsorption amount of carbon dioxide above (metal oxide). will be.

In other embodiments, the catalyst composition has a lifetime enhancement index (LEI) of 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 catalytically active metal oxides.

The present invention relates to molecular sieve catalyst compositions and their use in the process of converting hydrocarbon feedstocks, especially oxygenated feedstocks, to olefin (s). Molecular sieves can be prepared from Group 3 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 / or of lanthanide or actinium-based elements. By combining with at least one active metal oxide selected from the oxides, enhanced olefin yield and / or longer lifespan can be obtained in use in the process of converting oxygenates, more particularly raw materials such as methanol, to olefin (s). It was found that a catalyst composition having was produced. The resulting catalyst composition also has higher propylene selectivity and tends to be obtained with small amounts of unwanted ethane and propane and other undesirable compounds such as aldehydes and ketones, specifically acetaldehyde.

Molecular sieve

Molecular sieves have been classified by the Structural Committee of the International Zeolite Association in accordance with the IUPAC Committee's rules for zeolite nomenclature. According to this classification, the three-letter code is assigned to framework-structured zeolite and zeolite molecular sieves and is incorporated herein by reference in its entirety, the Atlas of Zeolite Framework Types, 5th edition, Elsevier, London, England (2001).

Non-limiting examples of preferred molecular sieves, particularly for the use of oxygenates containing raw materials to olefin (s), are skeletal AEL, AEI, BEA, CHA, EDI, FAU, FER, GIS, LTA, LTL, MER, MFI , MOR, MTT, MWW, TAM and TON. In a 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, most preferably has a CHA topology.

The crystalline molecular sieve material is a corner-covalent [TO ₄ ] glomerulus where T is any quaternary coordinated cation, such as 3 of [SiO ₄ ], [AlO ₄ ] and / or [PO ₄ ] glomerular units. It has a four-dimensional skeletal structure. Molecular sieves useful in the present invention are [AlO ₄ ] and [PO ₄ ] glomerular units, ie aluminophosphate (AIPO) molecular sieves, or [SiO ₄ ], [AlO ₄ ] and [PO ₄ ] glomerular units, ie silicoalumi It simply includes a backbone comprising nophosphate (SAPO) molecular sieve. Most preferably, molecular sieves useful herein are silicoaluminophosphate (SAPO) molecular sieves or substituted, preferably metal substituted SAPO molecular sieves. Examples of suitable metal substituents include lanthanide elements: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, erbium, dysprosium, holmium, thulium, ytterbium and lutetium; Group 1 alkali metals of the periodic table of elements, group 2 alkaline earth metals of the periodic table of elements, group 3 rare earth metals of the periodic table of elements, including scandium or yttrium, group 4 to 12 transition metals of the periodic table of elements, or any mixture of these metal species to be.

Preferably, the molecular sieve as used herein has a pore system defined by an 8 membered ring of [TO ₄ ] glomerulus and has a range of less than 5 ms, such as in the range of 3 ms to 5 ms, such as 3 ms to 4.5 ms and especially 3.5 ms to It has an average pore size of 4.2 mm 3.

Non-limiting examples of SAPO and AIPO molecular sieves useful herein 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, A1PO-5, AlPO-11, AlPO-18, A1PO-31, A1PO-34, AlPO-36, A1PO-37, AlPO-46, and metal-containing molecular sieves thereof, or combinations thereof. Of course, particularly useful molecular sieves are SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, A1PO-18 and A1PO-34 and their metal-containing molecular sieves or combinations thereof, such as One or a combination of SAPO-18, SAPO-34, AlPO-34 and A1PO-18 and their metal containing molecular sieves, in particular one or their SAPO-34 and A1PO-18 and their metal containing molecular sieves Combinations.

In an embodiment, the molecular sieve is an intergrowth material having two or more distinct crystal phases in one molecular sieve composition. In particular, coalescing molecular sieves are described in US Patent Application Publication Nos. 2002-0165089 and International Publication No. WO 98/15496, issued April 16, 1998, which are hereby incorporated by reference in their entirety. For example, SAPO-18, AIPO-18 and RUW-18 have an AEI structure type, and SAPO-34 has a CHA skeleton. Thus, the molecular sieves used herein provide for the association of AEI and CHA skeletons, in particular the ratio of the CHA skeleton to the AEI skeleton determined by the DIFFaX method described in US Patent Application Publication No. 2002-0165089. It may include one or more phases.

Preferably, if the molecular sieve is silicoaluminophosphate, the molecular sieve is Si / Al of 0.65 or less, such as 0.65 to 0.10, preferably 0.40 to 0.10, more preferably 0.32 to 0.10, most preferably 0.32 to 0.15. Have rain.

Metal oxide

Metal oxides useful herein are oxides of Group 3 metals and lanthanum and actinium metals with carbon dioxide adsorption at 100 ° C. of at least 0.03 mg (carbon dioxide) / m 2 (metal oxide), such as at least 0.04 (carbon dioxide) / m 2 (metal oxide). . Although the upper limit in the carbon dioxide adsorption amount of the metal oxide is not important, generally metal oxides useful herein have a carbon dioxide adsorption amount of less than 10 mg (carbon dioxide) / m 2 (metal oxide), such as 5 mg (carbon dioxide) / m 2 (metal oxide) at 100 ° C. Will be less than). Typically, metal oxides useful herein have a carbon dioxide adsorption amount of 0.05 to 1 mg (carbon dioxide) / m 2 (metal oxide). When used in combination with molecular sieves, such active metal oxides offer advantages in catalytic conversion processes, especially in the conversion of oxygenates to olefins.

In order to measure the carbon dioxide adsorption amount of the metal oxide, the following procedure is adopted. The sample of the metal oxide is dehydrated by heating the sample to 200 ° C. to 500 ° C. in flowing air until a constant weight, ie “dry weight” is obtained. The temperature of the sample is then reduced to 100 ° C. and the carbon dioxide is continuously or intermittently passed over the sample repeatedly until a constant weight is obtained. The increase in weight of the sample (mg) / weight of the sample (mg) based on the dry weight of the sample is the amount of carbon dioxide adsorbed.

In the examples reported below, the carbon dioxide adsorption amount is measured using a Mettler TGA / SDTA 851 thermogravimetric system under ambient pressure. The metal oxide sample is dehydrated at 500 ° C. in flowing air for 1 hour. The temperature of the sample is then reduced to 100 ° C. in flowing helium. After the temperature of the sample is equilibrated to the desired adsorption temperature in the flowing helium, 20 individual pulses (about 12 seconds / pulse) of a gas mixture comprising 10% by weight of carbon dioxide and the remaining amount of helium are applied to the sample. After each pulse of adsorbent gas, the metal oxide sample is flushed with flowing helium for 3 minutes. The increase in weight (mg) of sample per mg of adsorbent based on adsorbent weight after treatment at 500 ° C. is the amount of carbon dioxide adsorbed. The surface area of the sample was measured according to the methods of Brunauer, Emmet and Teller (BET) as disclosed in ASTM D3663, and the carbon dioxide adsorption amount expressed in carbon dioxide (mg) / metal oxide area (m 2). To provide.

Preferred Group 3 metal oxides include oxides of scandium, yttrium and lanthanum, and preferred oxides of lanthanum or actinium metals include cerium, praseodymium, neodymium, samarium, europium, galdorlinium, terbium, dyspro Calcium, holmium, erbium, thulium, ytterbium, lutetium and thorium. Most preferred active metal oxides are 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, useful metal oxides are oxides of Group 3 metals and / or lanthanum and actinium-based metals that are effective in extending the useful life of the catalyst composition when used in combination with molecular sieves in the catalyst composition. Quantification of catalyst life extension is measured by the Life Improvement Index (LEI) defined by Equation 1:

In the above formula, in the same process under the same conditions, the lifetime of the catalyst or catalyst composition is the accumulation of processed raw material per gram of catalyst composition until the conversion of the raw material by the catalyst composition falls slightly below a predetermined level, eg 10%. Inert metal oxides have little or no effect on the life of the catalyst composition, or shorten the life of the catalyst composition and will therefore have an LEI of 1 or less. The active metal oxide of the present invention is a Group 3 metal oxide comprising lanthanum and actinium oxides, and when used in combination with a molecular sieve, it is a metal oxide that provides a molecular sieve catalyst composition having an LEI of greater than one. By definition, molecular sieve catalyst compositions that are not combined with active metal oxides will have an LEI of 1.0.

When including active metal oxides in combination with molecular sieves, it has been found that catalyst compositions can be produced having LEIs greater than 1-50, such as in the range of 1.5-20. Typically the catalyst composition according to the invention exhibits LEI values greater than 1.1, such as 1.2 to 15, more specifically greater than 1.3, such as greater than 1.5, such as greater than 1.7, such as greater than 2.

The active metal oxide (s) can be prepared using various methods. Active metal oxides are preferably prepared from active metal oxide precursors such as metal salts such as halides, nitrates, sulfates or acetates. Other suitable sources of metal oxides include compounds that form metal oxides during calcination, such as oxychloride and nitrate. Alkoxides are also suitable sources of Group 3 metal oxides, such as yttrium n-propoxide.

In one embodiment, the Group 3 metal oxide or the lanthanum or actinium-based oxides are hydrothermally treated under conditions comprising a temperature of at least 80 ° C, preferably at least 100 ° C. Hydrothermal treatment can typically take place in a sealed vessel at a pressure greater than atmospheric pressure. However, preferred modes of treatment include using open containers under reflux conditions. Stirring Group III metal oxides or lanthanide or actinium based oxides in the liquid medium, eg by the movement of liquid reflux and / or agitation, promotes effective interaction of the hydrated oxide with the liquid medium. The contact period of the hydrated oxide with the liquid medium is conveniently at least 1 hour, such as at least 8 hours. The liquid medium for this treatment typically has a pH of at least about 6, such as at least 8. Non-limiting examples of suitable liquid media include water, hydroxide solutions (including hydroxides of NH ₄ ⁺ , Na ⁺ , K ⁺ , Mg ⁺ and Ca ²⁺ ), carbonate and bicarbonate solutions (NH ₄ ⁺ , Na ⁺ , K ⁺ , Carbonates and bicarbonates of Mg ⁺ and Ca ²⁺ ), pyridine and derivatives thereof, alkyl / hydroxyl amines.

In another embodiment, a liquid solution, such as an aqueous solution comprising a source of metal ions, such as a metal salt, is treated under conditions sufficient to cause precipitation of the hydrated precursor of the solid oxide material, such as by adding a precipitant to the solution to activate the active group III. Metal oxides or oxides of lanthanum or actinium are prepared. Conveniently, precipitation is carried out at a pH above 7. For example, the precipitant may be a base such as sodium hydroxide or ammonium hydroxide.

The temperature the solution maintains during precipitation is generally in the range of 200 ° C. or lower, such as 0 ° C. to 200 ° C. The specific temperature range 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. Hydrothermal treatment typically takes place 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 hydrated precursor of the metal oxide (s) is then recovered, washed and dried, for example by filtration or centrifugation. The resulting material is then calcined at temperatures of at least 400 ° C., such as at least 500 ° C., such as 600 ° C. to 900 ° C., and especially 650 ° C. to 800 ° C., in an oxidizing atmosphere, for example, to form active metal oxides or active mixed metal oxides. Can be. The calcination time is typically 48 hours or less, such as 0.5 to 24 hours, such as 1.0 to 10 hours. In one embodiment, the calcination is conducted at about 700 ° C. for 1 to 3 hours.

Catalyst composition

The catalyst composition of the present invention comprises any one of the molecular sieves previously described and one or more of the active metal oxides described above, optionally with a binder and / or matrix material different from the active metal oxide (s). do. Typically, the weight ratio of molecular sieve to active metal oxide in the catalyst composition is 5% to 800% by weight, preferably 10% to 600% by weight, more preferably 20% to 500% by weight, most preferably Preferably in the range of 30% to 400% by weight.

There are many different binders useful for forming the catalyst composition of the present invention. Non-limiting examples of binders useful in singular or combination form include various types of hydrated alumina, silica and / or other inorganic oxide sol. One preferred alumina containing sol is aluminum chlorohydrol. The molecular sieves and other materials from which the inorganic oxide sol has been synthesized act as glue, for example together with the matrix, in particular after heat treatment. Upon heating, the inorganic oxide sol, which preferably has a low viscosity, is converted to the inorganic oxide binder component. For example, the alumina sol will be converted to aluminum oxide binder after heat treatment.

The hydroxylated aluminum sol containing aluminum chlorohydrol, chloride counter ion has the formula Al _m O _n (OH) _o Cl _p x (H ₂ O) {wherein m is 1-20 and 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 is described in GMWolterman, et al. , Stud. Surf. Sci. and Catal. , 76, pages 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 oxide, γ-alumina, boehmite, diaspora and transitional aluminas such as α-alumina, β-alumina, γ-alumina, δ-alumina, ε-alumina, κ-alumina , ρ-alumina, aluminum trihydroxide such as one or more other alumina materials such as gibbsite, vialite, nordrandite, doelite and mixtures thereof.

Non-limiting examples of commercially available colloidal alumina sol include Nalco 8676 available from Nalco Chemical Corp., Naperville, Ill. And Nyacol AL20DW, available from Niacol Nano Technologies, Massachusetts Ashland.

If the catalyst composition contains a matrix material, it is preferably different from the active metal oxide and any binder. Typically the matrix material is effective in reducing the overall catalyst cost, acting as a thermal sink during regeneration, densifying the catalyst composition, increasing the physical properties of the catalyst such as crush strength and wear resistance.

Non-limiting examples of matrix materials useful herein include beryllia, quartz, silica or sol, and mixtures thereof, such as silica-magnesia, silica-zirconia, silica-titania, silica-alumina, and silica-alumina-toria. At least one inert metal oxide. In an embodiment, the matrix material is natural clay, such as those of the montmorillonite and kaolin class. These natural clays include subbentonites and kaolin, known for example Dixie, McNamee, Georgia and Florida clays. Non-limiting examples of other matrix materials include halosite, kaolinite, dickite, nacrite, or anoxite. Matrix materials such as clays may be treated by known reforming processes such as calcination and / or acid treatment and / or chemical treatment.

In a preferred embodiment, the matrix material is in particular clays or claylike compositions having a low iron or titania content, most preferably kaolin. Kaolin is known to form a high solids content pumpable slurry, have a low fresh surface area, and easily coalesce together due to 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 the D ₉₀ particle size distribution is less than 1 μm.

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

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

Typically the catalyst composition is in the range of 0.5 g / cc to 5 g / cc, such as 0.6 g / cc to 5 g / cc, such as 0.7 g / cc to 4 g / cc, especially 0.8 g / cc to 3 g / cc. Has a density.

Catalyst composition formulation

In the preparation of the catalyst composition, the molecular sieves are first synthesized and then physically mixed with the active metal oxide, preferably in a dry, dried or calcined state. Most preferably the molecular sieve and active metal oxide are physically mixed in their calcined state. Intimate physical mixing can be performed by any method known in the art, such as mixing using a mixer muller, drum mixer, ribbon / paddle blender, kneader, and the like. Chemical reactions between the molecular sieve and the metal oxide (s) are unnecessary and generally undesirable.

If the catalyst composition contains a matrix and / or a binder, the molecular sieve is conveniently initially formulated with the matrix and / or binder with the catalyst precursor and then the active metal oxide is combined with the formulated 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 a shape and size useful by known techniques such as spray drying, pelletization, extrusion, and the like.

In one embodiment, the molecular sieve composition and the matrix material may be combined with the liquid to form a slurry, optionally together with a binder, and then mixed to create 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 forming unit, such as a spray dryer, which forms the catalyst composition in the desired shape, such as microspheres.

Once the molecular sieve catalyst composition is formed in a substantially dry or dried state, heat treatment, such as calcination, is typically carried out to further harden and / or activate the formed 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. Typical calcination environments are air (which may include small amounts of water vapor), nitrogen, helium, flue gas (oxygen-depleted combustion products), or any combination thereof.

In a preferred embodiment, the catalyst composition is in nitrogen for a period of time, typically from 30 minutes to 15 hours, preferably from 1 hour to about 10 hours, more preferably from about 1 hour to about Heated for 5 hours, most preferably about 2 to 4 hours.

Use of catalyst composition

Such catalyst compositions include, for example, cracking from naphtha feed to lower olefin (s) (US Pat. No. 6,300,537) or cracking from high molecular weight (MW) hydrocarbons to low molecular weight hydrocarbons; For example hydrocracking of heavy oil and / or cyclic raw materials; Isomerization of aromatics such as for example xylene; For example polymerizing one or more olefin (s) to produce a polymer product; Reformation; Hydrogenation; Dehydrogenation; Dewaxing of hydrocarbons such as to remove straight chain paraffins; Absorption of alkyl aromatic compounds, such as to separate isomers; Alkylation of aromatic hydrocarbons such as, for example, benzene and alkylbenzenes; Transalkylation of aromatic and polyalkylaromatic hydrocarbon combinations, for example; Dealkylation; Hydrodecylization; Disporportionation of toluene, for example to produce benzene and xylene; Oligomerization of, for example, straight and branched chain olefin (s); And dehydrodecylization.

Preferred processes include converting naphtha into a higher aromatic mixture; Conversion of the lower olefin (s) to gasoline, distillate and lubricating oil; Converting oxygenates to olefin (s); Conversion of lower paraffins to olefins and / or aromatics; And converting unsaturated hydrocarbons (ethylene and / or acetylene) to aldehydes for conversion to alcohols, acids and esters.

The most preferred process of the present invention is to convert the raw material into one or more olefin (s). Typically, the raw material has, for example, an aliphatic moiety of 1 to about 50 carbon atoms, preferably 1 to about 20 carbon atoms, more preferably 1 to about 10 carbon atoms, most preferably 1 to 4 carbon atoms At least one aliphatic-containing compound containing, and preferably at least one oxygenate.

Non-limiting examples of suitable aliphatic-containing compounds include alcohols such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide, alkylamines such as methylamine, alkyl ethers such as dimethyl Ethers, diethyl ether and methylethyl ether, alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehyde and various acids such as acetic acid. Preferably, the raw material comprises methanol, ethanol, dimethyl ether, diethyl ether or combinations thereof, more preferably methanol and / or dimethyl ether, most preferably methanol.

The use of the various raw materials mentioned above, in particular raw materials containing oxygenates, such as alcohols, is effective for the catalyst composition of the invention to convert the raw materials into mainly one or more olefin (s). The resulting olefin (s) typically have 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, Most preferably ethylene and / or propylene.

Typically, the catalyst composition of the present invention comprises a raw material containing at least one oxygenate of more than 50%, typically more than 60%, such as more than 70% by weight, based on the total weight of hydrocarbons in the product. Preferably effective for conversion to products containing greater than 80% by weight of olefin (s). In addition, 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 78% by weight. Exceeds% Typically, the amount (wt%) of ethylene produced is greater than 30 wt%, such as greater than 35 wt%, such as greater than 40 wt%, based on the total weight of hydrocarbons in the resulting product. Also, based on the total weight of hydrocarbons in the resulting product, the amount (wt%) of propylene produced is greater than 20 wt%, such as greater than 25 wt%, such as greater than 30 wt%, preferably 35 wt% Exceeds.

The use of the catalyst composition of the present invention to convert raw materials comprising methanol and dimethyl ether into ethylene and propylene is not compatible with ethane and propane as compared to similar catalyst compositions at the same conversion conditions without active metal oxide component (s). It has been found that production is reduced by more than 10%, such as more than 20%, such as more than 30%, in particular in the range of 30% to 40%.

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

The process includes a wide range of temperatures, such as 200 ° C. to 1000 ° C., such as 250 ° C. to 800 ° C., 250 ° C. to 750 ° C., and conveniently 300 ° to 650 ° C., preferably 350 ° C. to 600 ° C., more Preferably it may be carried out at 350 ℃ to 550 ℃.

Similarly, the process can be carried out at a wide range of pressures, including autogenous pressures. Typically, the partial pressure of the raw materials excluding any diluent 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 weight time space velocity (WHSV), defined as the total weight of raw material (no diluent) per hour of molecular sieve in the catalyst composition, is between 1 hr ^-1 and 5000 hr ^-1 , preferably between 2 hr ^-1 and 3000 hr ^-1 , more preferably 5 hr ^-1 to 1500 hr ^-1 , most preferably 10 hr ^-1 to 1000 hr ^-1 . In one embodiment, the WHSV is at least 20 hr ⁻¹ and 20 hr ⁻¹ to 300 hr ⁻¹ when the feed contains methanol and / or dimethyl ether.

The process of the present invention is conveniently carried out as a fixed bed process, more typically as a fluidized bed process (including turbulent bed processes), as a continuous fluidized bed process, in particular as a continuous high speed fluidized bed process. do.

In one practical embodiment, the process is carried out in a fluid bed process using a reactor system, a regeneration system and a recovery system. In this process, fresh raw material, optionally having one or more diluent (s), is fed together with the molecular sieve catalyst composition to one or more riser reactor (s) of the reactor system. In the riser reactor (s) the raw material is converted along the caulked catalyst composition into a gas effluent that enters the dispensing vessel of the reaction system. The caulked catalyst composition is separated from the gas effluent, typically with the help of a cyclone, in a separation vessel and then fed to a stripping zone, typically at the bottom of the separation vessel. In the stripping zone, the caulked catalyst composition is a coking in which gas, such as steam, methane, carbon dioxide, carbon monoxide, hydrogen, and / or an inert gas such as argon, and hydrocarbons adsorbed in contact with steam, is subsequently introduced into the regeneration system. From the resulting catalyst composition.

In the regeneration system, the coked catalyst composition is regenerated under regeneration conditions, which can burn coke from the coked catalyst composition to a level of preferably less than 0.5% by weight based on the total weight of the caulked molecular sieve catalyst composition entering the regeneration system. Contact with a medium, preferably a gas containing oxygen. For example, the regeneration conditions may include a temperature range of 450 ° C to 750 ° C, preferably 550 ° C to 700 ° C.

The regenerated catalyst composition from the regeneration system is contacted with the fresh molecular sieve catalyst composition and / or recycled molecular sieve catalyst composition and / or raw material and / or fresh gas or liquid and returned to the riser reactor (s).

The gas effluent exits the separation system and is passed through a recovery system for separating and purifying the lower olefin (s), in particular ethylene and propylene, from the gas effluent.

In one practical embodiment, the process of the present invention forms part of an integrated process for producing lower olefin (s) from hydrocarbon raw materials, in particular methane and / or ethane. The first step in the process passes a gaseous feedstock, preferably in combination with a water stream, to a synthesis gas production zone to produce a synthesis gas stream, typically comprising carbon dioxide, carbon monoxide and hydrogen. The synthesis gas stream then contains oxygenates by contact with heterogeneous catalysts, typically copper-based catalysts, at temperatures ranging from 150 ° C. to 450 ° C. and pressures ranging from 5 MPa to 10 MPa. Switch to the stream. After purification, the oxygenate containing stream can be used as a raw material in the process for producing lower olefin (s) such as ethylene and / or propylene. Non-limiting examples of such integration processes are described in EP-B-0 933 345, which is incorporated herein by reference in its entirety.

In another more fully integrated process, optionally in combination with the integrated process, the resulting olefin (s) is directed to one or more polymerization processes to produce various polyolefins.

The following examples are provided to provide an easy understanding of the present invention including representative advantages of the present invention.

In an embodiment, LEI is the ratio of the lifetime of the molecular sieve catalyst composition containing the active metal oxide (s) compared to the lifetime of the same molecular sieve catalyst composition lacking the metal oxide (s) (LEI defined as 1). Is defined. To measure LEI, life is defined as the accumulation of oxygenates, preferably converted to one or more olefin (s) per gram of molecular sieve, until the conversion rate drops to about 10% of its initial value. If the conversion does not drop to 10% of the initial value by the end of the experiment, the lifetime is estimated by linear extrapolation based on the rate of conversion reduction for the last two data points in the experiment.

"Prime olefin" is the sum of the selectivities for ethylene and propylene. The ratio "C ₂ ⁼ / C ₃ ⁼ " is the ratio of weighted ethylene to propylene selectivity in performance. "C ₃ purity" is calculated by dividing propylene selectivity by the sum of propylene and propane selectivity. The selectivity for methane, ethylene, ethane, propylene, propane, C ₄ 's and C ₅ +' s is the weighted average selectivity in performance. Note that C ₅ + 's consist only of C ₅ ' s, C ₆ 's, and C ₇ ' s. As they are known, they are corrected for coke, so the selectivity values do not add up to 100% in the table.

Example A

Preparation of Molecular Sieves

In the presence of tetraethyl ammonium hydroxide (R1) and dipropylamine (R2) as an organic structural indicator or templating agent, the silicoaluminophosphate molecular sieve designated SAPA, SAPO-34, was crystallized. A predetermined amount of Condea Pural SB was first mixed with deionized water to form a slurry to prepare a mixture of the following molar ratios: 0.2 SiO ₂ / Al ₂ O ₃ / P ₂ O ₅ / 0.9 R 1 / 1.5 R 2/50 H ₂ O. A predetermined amount of phosphoric acid (85%) was added to this slurry. This addition was carried out under stirring to form a homogeneous mixture. Ludox AS40 (40% SiO ₂ ) was added to this homogeneous mixture and then R1 was added with mixing to form a homogeneous mixture. After adding R2 to this homogeneous mixture, the resulting mixture was crystallized by heating with stirring at 170 ° C. for 40 hours in a stainless steel autoclave. This gave a slurry of crystalline molecular sieves. The crystals were then separated from the mother liquor by filtration. The molecular sieve crystals were then mixed with the binder and the matrix material to form particles by spray drying.

Example B

Conversion process

All conversion data presented were obtained using a microflow reactor consisting of a stainless steel reactor (outer diameter of 1/4 inch (0.64 cm)) placed in a furnace fed with vaporized methanol. The reactor was maintained at a temperature of 475 ° C. and a pressure of 25 psig (172.4 kPag). The flow rate of methanol is such that the flow rate of methanol per gram of molecular sieve, based on weight, also known as weight time space velocity (WHSV), is 100 h ⁻¹ . The product gas exiting the reactor was collected and analyzed using gas chromatography. The catalyst load was 50 mg and the catalyst bed was diluted with quartz to minimize the hot spot of the reactor.

Example 1

A sample of La (NO ₃ ) ₃ .xH ₂ O (Aldrich Chemical Company) was calcined at 700 ° C. in air 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 of the final composite was adjusted to about 9 by addition of concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product formed was recovered by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined at 600 ° C. in flowing air for 3 hours to produce lanthanum oxide (La ₂ O ₃ ).

Example 3

50 g of Y (NO ₃ ) ₃ .6H ₂ O (Aldrich Chemical Company) was dissolved in 500 ml of distilled water with stirring. The pH of the final composite was adjusted to about 9 by addition of concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product formed was recovered by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined at 600 ° C. in flowing air for 3 hours 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 at 700 ° C. in air for 3 hours to produce scandium oxide (Sc ₂ O ₃ ).

Example 5

50 g of Ce (NO ₃ ) ₃ .6H ₂ O was dissolved with stirring in 500 ml of distilled water. The pH of the final composite was adjusted to about 8 by addition of concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product formed was recovered by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined at 600 ° C. in flowing air for 3 hours to produce cesium oxide (Ce ₂ O ₃ ).

Example 6

50 g of Pr (NO ₃ ) ₃ .6H ₂ O was dissolved with stirring in 500 ml of distilled water. The pH of the final composite was adjusted to about 8 by addition of concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product formed was recovered by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined at 600 ° C. in flowing air for 3 hours to produce praseodymium oxide (Pr ₂ O ₃ ).

Example 7

50 g of Nd (NO ₃ ) ₃ .6H ₂ O was dissolved with stirring in 500 ml of distilled water. The pH of the final composite was adjusted to about 9 by addition of concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The formed product was recovered by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined at 600 ° C. in flowing air for 3 hours to produce neodymium oxide (Nd ₂ O ₃ ).

Example 8

39 g of Ce (NO ₃ ) ₃ .6H ₂ O and 7.0 g of La (NO ₃ ) ₃ .6H ₂ O were dissolved with stirring in 500 ml of distilled water. Another solution was prepared containing 20 g of concentrated ammonium hydroxide and 500 ml of distilled water. These two solutions were combined at a rate of 50 ml / min using a nozzle mixer. The pH of the final composite was adjusted to about 9 by addition of concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product formed was recovered by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined at 700 ° C. in flowing air for 3 hours to produce an active mixed metal oxide containing nominally 5% by weight of lanthanum based on the final weight of the mixed metal oxide.

Example 9

9 g of Ce (NO ₃ ) ₃ .6H ₂ O and 30.0 g of La (NO ₃ ) ₃ .6H ₂ O were dissolved in 500 ml of distilled water with stirring. Another solution was prepared containing 20 g of concentrated ammonium hydroxide and 500 ml of distilled water. These two solutions were combined at a rate of 50 ml / min using a nozzle mixer. The pH of the final composite was adjusted to about 9 by addition of concentrated ammonium hydroxide. This slurry was then placed in a polypropylene bottle and placed in a steam box (100 ° C.) for 72 hours. The product formed was recovered by filtration, washed with excess water and dried at 85 ° C. overnight. A portion of this product was calcined at 700 ° C. in flowing air for 3 hours to produce an active mixed metal oxide containing nominally 5% by weight of cerium based on the final weight of the mixed metal oxide.

Example 10

The carbon dioxide adsorption amount of the oxides of Examples 1 to 9 was measured using a Mettler TGA / SDTA 851 thermogravimetric system under ambient pressure. The metal oxide sample was first dehydrated at 500 ° C. in flowing air for 1 hour, and then the adsorption amount of carbon dioxide was measured at 100 ° C. The surface area of the sample was determined according to the method of Brunauer, Emmet and Teller (BET), to determine the amount of carbon dioxide adsorption provided in Table 1, expressed in carbon dioxide (mg) / metal oxide area (m 2). to provide.

Example 11 (comparative example)

In this Comparative Example 11 (CEx. 11), the molecular sieve catalyst composition produced in Example A was tested in the process of Example B using 50 g of a molecular sieve catalyst composition lacking an active metal oxide. The results of the runs are reported in Tables 2 and 3.

Example 12

In this example, the molecular sieve composition produced in Example A was tested in the process of Example B using 10 mg of La ₂ O ₃ and 40 mg of the molecular sieve catalyst composition produced through nitrate decomposition in Example 1. . The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, where the addition of active Group 3 metal oxides La ₂ O ₃ increased the lifetime by 149%. The selectivity for ethane was reduced by 36% and the selectivity for propane was reduced by 32%, which meant that the hydrogen transfer reaction was significantly reduced.

Example 13

In this example, the molecular sieve composition produced in Example A was tested in the process of Example B using 10 mg of La ₂ O ₃ and 40 mg of the molecular sieve catalyst composition produced through precipitation in Example 2. The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, in which the addition of La ₂ O ₃ , an active Group 3 metal oxide produced through precipitation, increased the lifetime by 340%. The selectivity to ethane was reduced by 55% and the selectivity to propane was reduced by 44%, which meant that the hydrogen transfer reaction was significantly reduced.

Example 14

In this Example 14, the molecular sieve composition produced in Example A was tested in the process of Example B using 10 mg of Y ₂ O ₃ and 40 mg of the molecular sieve catalyst composition produced in Example 3. The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, where the addition of active Group 3 metal oxides Y ₂ O ₃ increased the lifetime by 1090%. The selectivity to ethane was reduced by 45% and the selectivity to propane was reduced by 28%, which meant that the hydrogen transfer reaction was significantly reduced.

Example 15

In this Example 15, the molecular sieve composition produced in Example A was tested in the process of Example B using the 10 mg Sc ₂ O ₃ and 40 mg molecular sieve catalyst composition produced in Example 4. The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, where the addition of an active Group 3 metal oxide, Sc ₂ O ₃ , increased the lifetime by 167%. The selectivity to ethane was reduced by 27% and the selectivity to propane was reduced by 21%, which meant that the hydrogen transfer reaction was significantly reduced.

Example 16

In this Example 16, the molecular sieve composition produced in Example A was tested in the process of Example B using 10 mg of Ce ₂ O ₃ and 40 mg of the molecular sieve catalyst composition produced in Example 5. The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, where the addition of active Group 3 metal oxides Ce ₂ O ₃ increased the lifetime by 630%. The selectivity for ethane was reduced by 50% and the selectivity for propane was reduced by 34%, which meant that the hydrogen transfer reaction was significantly reduced.

Example 17

In this Example 17, the molecular sieve composition produced in Example A was tested in the process of Example B using 10 mg of Pr ₂ O ₃ and 40 mg of the molecular sieve catalyst composition produced in Example 6. The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, where the addition of Pr ₂ O ₃ , an active Group 3 metal oxide, increased the lifetime by 640%. The selectivity to ethane was reduced by 51% and the selectivity to propane was reduced by 38%, which meant that the hydrogen transfer reaction was significantly reduced.

Example 18

In this Example 18, the molecular sieve composition produced in Example A was tested in the process of Example B using 10 mg of Nd ₂ O ₃ and 40 mg of the molecular sieve catalyst composition produced in Example 7. The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, where the addition of Nd ₂ O ₃ , an active Group 3 metal oxide, increased the lifetime by 340%. The selectivity to ethane was reduced by 49% and the selectivity to propane was reduced by 34%, which means that the hydrogen transfer reaction was significantly reduced.

Example 19

In this Example 19, the molecular sieve composition produced in Example A was tested in the process of Example B using 10 mg of the mixed metal oxide produced in Example 8 and 40 mg of the molecular sieve catalyst composition. The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, in which the addition of 5% LaO _x / Ce ₂ O ₃ , an active lanthanide metal oxide modified by Group 3 metal oxides, increased the lifespan by 450%. The selectivity to ethane was reduced by 47% and the selectivity to propane was reduced by 37%, indicating that the hydrogen transfer reaction was significantly reduced.

Example 20

In this Example 20, the molecular sieve composition produced in Example A was tested in the process of Example B using 10 mg of the mixed metal oxide produced in Example 9 and 40 mg of the molecular sieve catalyst composition. The components were mixed well and then diluted with sand to form a reaction bed. The results of this experiment are shown in Tables 2 and 3, in which the addition of 5% CeO _x / La ₂ O ₃ , an active Group 3 metal oxide modified with lanthanide oxides, increased the lifetime by 260%. The selectivity to ethane was reduced by 56% and the selectivity to propane was reduced by 45%, which meant that the hydrogen transfer reaction was significantly reduced.

Claims (18)

Carbon dioxide adsorption amount of at least 0.03 mg (carbon dioxide) / m 2 (metal oxide) of the metal oxide including at least one oxide of a metal selected from Group 3 of the periodic table of the elements, lanthanide elements and actinium elements, and molecular sieves; Catalyst composition having a. The method of claim 1, The catalyst composition has a carbon dioxide adsorption amount of at least 0.04 mg (carbon dioxide) / m 2 (metal oxide) at 100 ° C. The method according to claim 1 or 2, The catalyst composition having a carbon dioxide adsorption amount of less than 10 mg (carbon dioxide) / m 2 (metal oxide) at 100 ° C. The method according to any one of claims 1 to 3, A catalyst composition further comprising at least one of a binder and a matrix material different from the metal oxide. A catalyst composition comprising an oxide of a Group 3 metal oxide and / or a lanthanide or actinium based element, a binder, a matrix material and a silicoaluminophosphate molecular sieve. The method according to claim 4 or 5, A catalyst composition wherein the binder is an alumina sol and the matrix material is clay. The method according to any one of claims 1 to 6, A catalyst composition 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 method according to any one of claims 1 to 7, The catalyst composition wherein the metal oxide is yttrium oxide. The method according to any one of claims 1 to 8, A catalyst composition wherein the molecular sieve comprises aluminophosphate or silicoaluminophosphate. The method of claim 9, A catalyst composition wherein the molecular sieve comprises a CHA skeletal molecular sieve and / or an AEI skeletal molecular sieve. At least one oxide of a metal selected from Group 3, lanthanide and actinium-based elements of the Periodic Table of Elements, wherein the metal oxide has a carbon dioxide adsorption amount of at least 0.03 mg (carbon dioxide) / m 2 (metal oxide particles) at 100 ° C; A method for producing a catalyst composition comprising physically mixing two particles with a first particle comprising molecular sieves. The method of claim 11, Wherein said first particle comprises a silicoaluminophosphate molecular sieve, a binder comprising an alumina sol, and a matrix material comprising clay. The method according to claim 11 or 12, A hydrated precursor of the metal oxide is precipitated from a solution containing ions of the metal, and the hydrated precursor is hydrothermally treated at a temperature of 80 ° C. or higher for up to 10 days, and then a temperature of 400 ° C. to 900 ° C. A method for producing the second particle by calcining a hydrated precursor in the range. Carbon dioxide adsorption amount of at least 0.03 mg (carbon dioxide) / m 2 (metal oxide) of the metal oxide including at least one oxide of a metal selected from Group 3 of the periodic table of the elements, lanthanide elements and actinium elements, and molecular sieves; In the presence of a catalyst composition having a polymer; The method of claim 14, Wherein the catalyst composition has a lifetime enhancement index (LEI) of greater than one. The method according to claim 14 or 15, The molecular sieve is silicoaluminophosphate. The method according to any one of claims 14 to 16, Wherein the raw material comprises methanol and / or dimethyl ether. A process for converting a feedstock into at least one olefin (s) in the presence of a catalyst composition prepared by the method of any one of claims 11 to 13.