JP2005518928A - 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 making it, and a feed, preferably an oxygenated feed, in the conversion of one or more olefins, preferably ethylene and / or propylene. Regarding use. The catalyst composition comprises a molecular sieve and at least one metal oxide, such as magnesium oxide, that is saturated with acetone and converts more than 80% acetone when contacted with the acetone at 25 ° C. for 1 hour. contains.

Description

Detailed Description of the Invention

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

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

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

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

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

  When used to convert methanol to olefins, most molecular sieves, including SAPO molecular sieves, are subject to rapid coking and are therefore frequently associated with exposure of catalysts to high temperatures and steam generating environments. Requires regeneration. 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.

In one aspect, the present invention provides (a) a metal oxide having a surface area greater than 20 m ² / g and calcined at a temperature greater than 200 ° C., saturated with acetone, A metal oxide that converts more than 80% of acetone when contacted at 1 ° C. for 1 hour;
(b) a binder,
(c) matrix material and
(d) relates to a catalyst composition containing a molecular sieve having an average pore size of less than 5 angstroms.

The molecular sieve comprises a framework comprising at least [AlO ₄ ] and [PO ₄ ] tetrahedral units, more specifically, [SiO ₄ ], [AlO ₄ ] and [PO ₄ ] tetrahedral units, such as silicoaluminophosphate. Conveniently having a skeleton including.

  In one embodiment, the metal oxide includes magnesium oxide.

In another aspect, the present invention comprises a molecular sieve and at least one metal oxide selected from Group 2 of the Periodic Table of Elements, wherein the metal oxide is at least 0.03 mg / metal oxide m at 100 ° C. ^2. relates to a catalyst composition having carbon dioxide uptake.

  Conveniently, the catalyst composition also contains at least one oxide of a metal selected from group 3 of the periodic table of elements, such as yttrium oxide, lanthanum oxide, scandium oxide and mixtures thereof.

In another aspect, the present invention comprises physically mixing first particles comprising a molecular sieve with at least one second particle containing an oxide of a metal selected from Group 2 of the Periodic Table of Elements. wherein said metal oxide is at least 0.03 mg / metal oxide m ² at 100 ° C., with carbon dioxide uptake, to a method of preparing the catalyst composition.

  In another aspect, including blending with silicoaluminophosphate molecular sieve, binder, matrix material and at least one metal oxide, the metal oxide is saturated with acetone and contacted with said acetone at 25 ° C. for 1 hour. Sometimes relates to a process for producing a catalyst composition that converts more than 25% of acetone.

  In yet another aspect, the present invention provides (a) blending a molecular sieve, a binder and a matrix material to produce a catalyst precursor, and (b) subjecting the catalyst precursor to a temperature in the range of 200 ° C to 700 ° C. It relates to a method for producing a catalyst composition comprising adding a calcined metal oxide.

  In one embodiment, the metal oxide is magnesium oxide and physically synthesized with a molecular sieve synthesized from a reaction mixture containing at least one templating agent and at least two of a silicon source, a phosphorus source and an aluminum source. Mixed.

  In another aspect, a molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material and an active metal oxide, wherein the active metal oxide is saturated with acetone and contacted with said acetone at 25 ° C. for 1 hour. Sometimes relates to a process for converting a feedstock to one or more olefins in the presence of a molecular sieve catalyst composition that converts more than 80% of the acetone.

  In yet another aspect, the present invention involves calcining a feedstock containing at least one oxygenate to a small pore molecular sieve, a binder, a matrix material, magnesium oxide, and a temperature in the range of 200 ° C to 600 ° C. It relates to a process for producing one or more olefins comprising contacting with a catalyst composition containing a Group 3 metal oxide.

The present invention relates to molecular sieve catalyst compositions, their synthesis, and their use in the conversion of hydrocarbon feedstocks, particularly oxygenated feedstocks, to olefins. A catalyst composition having a longer catalyst life when used for the conversion of a feedstock such as oxygenate, more particularly methanol, by blending a molecular sieve with a specific metal oxide to an olefin. It was found to be brought about. Also, the resulting catalyst composition is more propylene selective and tends to produce lesser amounts of unwanted ethane and propane. Preferred metal oxides are capable of converting at least 0.03 mg / m ² metal oxide m 2 group 2 metal oxide with carbon dioxide uptake at 100 ° C. and / or more than 80% of acetone at room temperature. It is a metal oxide that can be produced. In one embodiment, the metal oxide is magnesium oxide having a surface area greater than 20 m ² / g and calcined at a temperature greater than 200 ° C. This unexpected result can be found in group III metals from 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) (eg, scandium). , Lanthanum or yttrium) is further increased when blended with magnesium oxide.

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

The crystalline molecular sieve material has an angle-sharing [TO ₄ ] tetrahedral three-dimensional four-linked framework structure, where T is a [SiO ₄ ], [AlO ₄ ] and / or [PO ₄ ] tetrahedral unit. Such a cation coordinated as a tetrahedron. Useful molecular sieves in the present invention, conveniently contain framework comprising [AlO _4] and [PO _4] tetrahedral units, i.e., whether it is 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 substituted, preferably metal, SAPO molecular sieve. 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 eight-membered ring of [TO ₄ ] tetrahedron, such as 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 , AlPO-5, AlPO-11, AlPO-18, AlPO-31, AlPO-34, AlPO-36, AlPO-37, AlPO-46 and their metal-containing molecular sieves or combinations thereof. Among them, particularly useful molecular sieves are SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, AlPO-18 and AlPO-34 and one or a combination of their metal-containing derivatives. Yes, such as one or a combination of SAPO-18, SAPO-34, AlPO-34 and AlPO-18 and their metal-containing derivatives, in particular one of SAPO-34 and AlPO-18 and their metal-containing derivatives or It is a combination.

  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.

In one particular embodiment, the molecular sieve is SAPO-18, SAPO-34, or the framework of the molecular sieve consists essentially of [SiO ₄ ], [AlO ₄ ] and [PO ₄ ] tetrahedral units, thus nickel These are alternate molecular sieves that do not contain any additional bone composition.

Metal Oxides Metal oxides useful in the present invention are metal oxides that are different from typical binders and / or matrix materials and, when used in combination with molecular sieves, provide metal oxides that benefit in catalytic conversion processes. It is. In particular, metal oxides useful in the present invention are saturated with acetone and, when contacted with acetone for 1 hour at room temperature (about 25 ° C.), more than 80% of acetone, for example more than 85%, 90% %, More than 95% in some cases, the amount of oxide to convert. There are various ways to determine the conversion of acetone, one such method is ¹³ C solid state NMR. In this method, first the metal oxide is dehydrated under vacuum while being heated by use of a stepwise temperature program. Typically, the highest temperature used in the dehydration operation is 400 ° C. The metal oxide is then saturated with acetone-2- ¹³ C at room temperature (about 25 ° C.) using conventional vacuum line techniques. The adsorbed metal oxide containing acetone-2- ¹³ C is transferred to a 7 mm NMR rotor without contact with air or moisture. Quantitative ¹³ C solid state NMR spectra using magic angle spinning have been observed to determine the conversion of acetone after the sample has been maintained at 25 ° C. for 1 hour.

Suitable metal oxides are Group 2 metal oxides, alone or in combination with Group 3 metal oxides, at 100 ° C., at least 0.03 mg / metal oxide m ² , at least 0.35 mg / metal. such as oxides m ^2, with a carbon dioxide uptake. Although the upper limit of carbon dioxide uptake of the metal oxide is not critical, in general, metal oxides useful in the present invention are less than 10 mg / metal oxide m ² , less than 5 mg / metal at 100 ° C. such as oxides m ^2, with a carbon dioxide uptake.

To determine the carbon dioxide uptake of metal oxides, the following procedure is employed 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. Next, the temperature of the sample is lowered to 100 ° C. in flowing helium. After equilibrating the sample in flowing helium at the desired adsorption temperature, the sample is subjected to 20 separation pulses (about 12 seconds / pulse) of a gas mixture containing 10% by weight 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 adsorbent weight is the amount of carbon dioxide adsorbed. The surface area of the sample is measured by the method of Brunauer, Emmett and Teller (BET) published as ASTM D3663, giving carbon dioxide uptake in mg carbon dioxide / m ² metal oxide.

  The most preferred group 2 metal oxide is magnesium oxide (MgO). Suitable Group 3 metal oxides include yttrium oxide, lanthanum oxide, scandium oxide, and mixtures thereof.

In one embodiment, the active metal oxide, preferably MgO, even more preferably the combination of MgO and a Group 3 metal oxide is greater than 20 m ² / g, such as greater than 50 m ² / g, for example It has a surface area measured by the method of Brunauer, Emmett and Teller (BET) published as ASTM D3663, greater than 80 m ² / g and even greater than 200 m ² / g. Suitable metal oxides have a surface area greater than 20 m ² / g calcined to temperatures above 200 ° C., and at room temperature, such as more than 25%, more than 50%, eg more than 80% of acetone. A metal oxide that can be converted.

  In other embodiments, the metal oxide, preferably magnesium oxide, even more preferably MgO and the Group 3 metal oxide are in the range of 200 ° C to 700 ° C, such as about 250 ° C to 650 ° C, such as 300 ° C to Calcination at a temperature in the range of 600 ° C, typically in the range of 350 ° C to 550 ° C.

In one embodiment, the magnesium metal oxide has a surface area of about 250 m ² / g and / or the magnesium oxide is calcined to about 550 ° C.

  Active metal oxides are produced using various methods. The active metal oxide can be made from an active metal oxide precursor, such as a metal salt, preferably a Group 2 or Group 3 metal salt precursor. Other suitable sources of Group 2 metal oxides include compounds that produce those metal oxides during calcination, such as oxychlorides and nitrates. Further suitable sources of Group 2 or Group 3 metal oxides include salts containing Group 2 or Group 3 metal cations such as halides, nitrates and acetates. Alkoxides are also a source of Group 2 or Group 3 metal oxides.

In one embodiment, the active metal oxide is produced by pyrolysis of metal-containing compounds, such as magnesium oxalate and barium oxalate, in flowing air at a high temperature such as 600 ° C. The metal oxides thus produced typically have a low BET surface area, for example less than 30 m ² / g.

In other methods, active metal oxides are produced by hydrolysis of metal-containing compounds followed by dehydration and calcination. For example, MgO is hydroxylated by mixing the oxide with deionized water to produce a white slurry. The slurry is slowly heated on a hot plate and dried to produce a white powder. The white powder is further dried in a vacuum oven at 100 ° C. for at least 4 hours, such as 12 hours. The dried white powder is then calcined in air at a temperature of at least 400 ° C., such as at least 500 ° C., typically at least 550 ° C. Active metal oxides produced in this way generally have a BET surface area (30 to 300 m ² / g) greater than that produced by pyrolysis of active metal oxide precursors.

In yet another embodiment, the active metal oxide is a so-called airgel process (Coper, OB, Lagadic, I., Volodin, A. and Chem. Mater. 1997, 9, 3468 by Klabunde, KJ.). -2480). In this method, Mg powder is reacted with anhydrous methanol under a nitrogen purge to produce a Mg (OCH ₃ ) ₂ solution in methanol. The resulting Mg (OCH ₃ ) ₂ solution is added to toluene. Water is then added dropwise to the Mg (OH) ₂ solution in methanol-toluene with vigorous stirring. The resulting colloidal suspension of Mg (OH) ₂ is placed in an autoclave, pressurized to 100 psig (690 kPag) with dry nitrogen and slowly heated to a final pressure of about 1,000 psig (6,895 kPag). The supercritical solvent is discharged and a fine white powder of Mg (OH) ₂ is produced. Nanocrystalline MgO is obtained by heating a fine white powder at 400 ° C. under vacuum. Active metal oxides so produced have the largest BET surface area, generally greater than 300 m ² / g.

  There are various methods for producing mixed metal oxides from Group 2 metal oxide precursors and Group 3 metal oxide precursors, such as wet dipping, initial wetting and coprecipitation.

In one embodiment, a mixed metal oxide is produced by immersing a Group 3 metal oxide precursor on the Group 2 metal oxide. In a typical preparation, a Group 3 metal oxide precursor such as La (acetylacetonate) ₃ is dissolved in an organic solvent such as toluene. The amount of solvent used is sufficient to fill the mesoporous and macroporous volume of the Group 2 metal oxide. A Group 3 metal oxide precursor solution is added dropwise to the Group 2 metal oxide. The wet mixture is dried in a vacuum oven for 1-12 hours to remove the solvent. The resulting mixture is then calcined at a temperature high enough to decompose the Group 3 metal oxide precursor to oxide, for example 400 ° C.

  In other embodiments, mixed oxides are produced by incipient wetness techniques. Typically, a Group 3 metal oxide precursor such as lanthanum acetate is dissolved in deionized water. The solution is added dropwise to the Group 2 metal oxide. The mixture is dried in a vacuum oven at 50 ° C. for 1-12 hours. The dried mixture is ground and calcined at 550 ° C. in air for 3 hours.

  In yet another embodiment, mixed metal oxides are produced by coprecipitation. An aqueous solution containing a Group 2 metal oxide precursor and a Group 3 metal oxide precursor results in the precipitation of a hydrated precursor of a solid oxide material, such as by addition of sodium hydroxide or ammonium hydroxide. To a sufficient condition. The temperature at which the liquid medium is maintained during coprecipitation is typically 20 ° C to 100 ° C. Next, the obtained gel is hydrothermally treated for several days at a temperature of 50 to 100 ° C. The hydrothermal treatment is typically performed at a pressure higher than atmospheric pressure.

  The resulting material is then recovered, for example, by filtration or centrifugation, washed and dried. The resulting material is then calcined at a temperature above 200 ° C., preferably above 300 ° C., more preferably above 400 ° C., most preferably above 450 ° C.

Molecular sieve composition The catalyst composition of the present invention comprises any one of the previously described molecular sieves and one or more active metal oxides, optionally different from the active metal oxide, a binder and And / or contained with a matrix material. Typically, the weight ratio of active metal oxide to molecular sieve in the catalyst composition is 1 wt% to 800 wt%, such as 5 wt% to 200 wt%, especially 10 wt% to 100 wt%. The range.

  There are many different binders that are useful in producing the catalyst composition. 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 Formulated with one or more other non-limiting examples of alumina materials such as transition aluminas such as rho-alumina, gibbsite, bayerite, nordstrandite, aluminum trihydroxide such as doyelite, and mixtures thereof. Is done.

  In other embodiments, the binder is an alumina sol, mainly an aluminum oxide, and optionally an alumina sol containing some silicon. In yet another aspect, the binder is peptized produced by treating alumina hydrate, such as pseudoboehmite, with an acid, preferably a halogen-free acid, to produce a sol or aluminum ion solution. Alumina. 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, for example, during regeneration, acts as a heat sink, shields heat from the catalyst composition, increases the density of the catalyst composition, Increase catalyst strength such as crush strength and wear resistance.

  Non-limiting examples of matrix materials 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. 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 the matrix material is 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 from about 0.1 μm to about 0.6 μm and has a D ₉₀ particle size distribution of less than about 1 μm.

  When the catalyst composition contains a binder or matrix material, the catalyst composition is typically 1% to 80% by weight, 5% to 60% by weight, based on the total weight of the catalyst composition. Such as 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 2% to 30%, such as 5% to about 20%, especially 7% to 15%, based on the total weight of binder, molecular sieve and matrix material. It is the amount by weight. Higher molecular sieve content and lower matrix content have been found to increase molecular sieve catalyst composition performance, while lower molecular sieve content and higher matrix content have been found to improve the abrasion resistance of molecular sieve catalyst compositions.

  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 formed and then a Group 2 metal oxide or a Group 2 metal oxide and a Group 3 metal oxide as described above. Preferably physically mixed in a substantially dry, dried or calcined state. Most preferably, the molecular sieve and the active metal oxide are physically mixed in their calcined state. Without being bound by any particular theory, it is believed that intimate mixing of the molecular sieve and one or more active metal oxides improves the conversion process using the molecular sieve composition and catalyst composition of the present invention. Homogeneous 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 at an elevated temperature is performed to further cure and / or activate the produced catalyst composition. Usually done. Typical calcination temperatures range from 400 ° C. to 1,000 ° C., such as 500 ° C. to 800 ° C., for example 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 heated in nitrogen at a temperature between 600 ° C and 700 ° C. The heating is typically performed for a period of time, for example 1 hour to 5 hours, in particular 2 hours to 4 hours, such as 30 minutes to 15 hours, 1 hour to 10 hours.

Methods for Using Molecular Sieve Catalyst Compositions The catalyst compositions described above can be used, for example, for naphtha feeds to light olefins (US Pat. No. 6,300,537) or higher molecular weight (MW). Cracking of hydrocarbons to lower MW hydrocarbons; for example, hydrocracking of heavy oils and / or cyclic feedstocks; for example, isomerization of aromatic compounds such as xylene; for example, one or more olefins Polymerization to produce polymer products; reforming; hydrogenation; dehydrogenation; eg dewaxing of hydrocarbons to remove linear paraffins; Absorption to separate isomers; for example, alkyls of aromatic hydrocarbons such as benzene and alkylbenzenes, optionally with propylene or with long chain olefins to form cumene For example, transalkylation of a combination of aromatic hydrocarbons and polyalkyl aromatic hydrocarbons; dealkylation; hydrogen decyclization; for example, disproportionation of toluene to produce benzene and p-xylene; It is useful in a variety of processes including, for example, oligomerization of linear and branched olefins; and dehydrocyclization.

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

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

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

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

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

  When using the catalyst composition of the present invention for the conversion of a feedstock containing methanol and dimethyl ether to ethylene and propylene, a similar catalyst composition under the same conversion conditions but without an active metal oxide component In comparison, it is 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 It can be in the range of 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 velocity 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 in a stripping zone, typically in the lower portion of the separation vessel. To supply. 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 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 a water stream, 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 feedstock 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 European patent 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.

Example A-Preparation of Molecular Sieve 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. Made it. following:
_{0.2SiO 2 / Al 2 O 3 /} P 2 O 5 /0.9R1/1.5R2/50H 2 O
Was prepared by first mixing an amount of Condea Pural SB with deionized water to form a slurry. To this slurry was added an amount of phosphoric acid (85%). Their addition was carried out with stirring to produce a homogeneous mixture. To this homogeneous mixture, Ludox AS40 (40% SiO ₂ ) was added, then R1 was added with mixing to produce a homogeneous mixture. To this homogeneous mixture was added R2. The homogeneous 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 catalyst data or conversion data given consisted of a stainless steel reactor [1/4 inch (0.64 cm) outer diameter] located in a furnace fed with vaporized methanol. Obtained using a microflow reactor. The methanol conversion reaction was performed at 475 ° C., 25 psig (172 kPag) and 100 WHSV (with respect to the amount of SAPO-34). A typical loading of the formulated SAPO-34 described in Example A was 95 mg and the reactor bed was diluted with 1 g of quartz sand to minimize the reaction exotherm in the reactor. In particular, the catalyst composition of the present invention used a molecular sieve and a metal oxide, a physical mixture of the MSA molecular sieve of Example A and an active metal oxide.

The effluent from the reactor was collected in a 15 sample loop Valco valve. The collected sample was analyzed by on-line gas chromatography (Hewlett Packard 6890) equipped with a flame ionization detector. The chromatographic column was a Q-column. The response factors used are listed in Table 1.

“C ₄ ′ s (C ₄ class), C ₅ + etc.” refers to the number of carbons in the hydrocarbon. The selectivity expressed as “C ₅ ′ + s (C ₅ + class)” is “C ₅ ′ s (C ₅ class), C ₆ ′ s (C ₆ class), C ₇ ′ s (C ₇ class)”. Note that it consists of the sum of The weight average (selectivity) is expressed by the following formula: x ₁ ^* y ₁ + (x ₂ −x ₁ ) ^* (y ₁ + y ₂ ) / 2 + (x ₃ −x ₂ ) ^* (y ₂ + y ₃ ) / 2 + ...
(Where x _i and y _i are yield and supplied methanol / molecular sieve g, respectively)
Calculated based on The reported catalyst lifetime (g methanol / g molecular sieve) is incrementally converted methanol. Note that both lifetime and WHSV were reported based on the weight of the SAPO-34 sieve. Methanol converted in less than 10 wt% conversion is not calculated in the calculation. Dimethyl ether was not calculated as product, but instead was treated as unreacted methanol in the selectivity and degree of conversion calculated.

Example 1-Control Experiment In this Example 1, the catalyst composition consisted of a molecular sieve labeled as MSA described in Example A. The catalyst was diluted with quartz to produce a reactor bed. The results of this experiment in the reactor and conditions described above in Example B are shown in Table 2.

Example 2-Preparation of MgO and measurement of acetone conversion MgO was prepared as follows. 5.0 g MgO (98%, ACS reagent grade from Aldrich) was mixed with 150 ml deionized water to produce a white slurry. The white slurry was slowly heated on a hot plate and dried. The dried cake was crushed into pieces and ground to a fine powder. The powder was further dried in an oven at 120 ° C. for 12 hours. The white powder was then calcined at 550 ° C. in air for 3 hours. Thus, the prepared active metal oxide, MgO, has a relatively large surface area (BET area of about 250 m ² / g). The MgO powder was sieved to obtain particles of various sizes. A particle size of 75 to 150 microns was used in the conversion method described in Example B.

This prepared MgO, 0.25 g, was loaded into a glass tube, and the glass tube was connected to a vacuum tube through a 9 mm O-ring connection. The MgO was then heated to 450 ° C. and kept under vacuum at 450 ° C. for 2 hours to remove water from the oxide. After cooling to room temperature and 25 ° C., the MgO was saturated with acetone-2- ¹³ C. did. Next, MgO with adsorbed acetone-2- ¹³ C was loaded into a 7 mm NMR rotor without contact with air and moisture. The sample was kept at room temperature (about 25 ° C.) for 1 hour and subjected to NMR measurement of acetone conversion. ¹³ C NMR experiments were performed on a 200 MHz solid state NMR spectrometer using Magic Angle Spinning. An orthogonal polarization spectrum was obtained using a 1 second pulse delay, a contact time of 2 minutes and a 2,000 scan number. A quantitative single pulse spectrum was obtained using a 15 second pulse delay and a scan number of 400 or more. The test was repeated and ¹³ C NMR results showed that, on average, more than 80% of the acetone was consumed after 1 hour.

Example 3 Molecular sieve and MgO
In this Example 3, the molecular sieve catalyst composition was composed of 33.6% by weight MSA, 50.4% by weight binder and 16% by weight MgO as described in Example 2. The catalyst composition was mixed well and then diluted with quartz to produce a reactor bed. The results of this experiment in the reactor and conditions described in Example B are shown in Table 3. The data in Tables 2 and 3 show that by constituting 16% by weight of the catalyst composition loading with MgO, the life of the SAPO-34 molecular sieve is increased from 16.34 g / g molecular sieve to 31.66 g / g molecular sieve, It shows an increase of 94%.

Example 4 - MgO 3 group metal oxide (5 wt% of _La 2 _{O 3)} and mixed metal is La to large surface area on the MgO, the loading of the Group 3 metal oxide was carried out by incipient wetness. 0.2261 g of lanthanum acetate was dissolved in about 1.9 ml of deionized water. The solution was added dropwise to 2.0146 g MgO. The mixture was dried in a vacuum oven at 50 ° C. for 1 hour. The dried mixture was ground and calcined at 550 ° C. in air for 3 hours. The weight percentage of La ₂ O ₃ is about 5%. The metal oxide powder was sieved to obtain particles of various sizes. A particle size of 75 to 150 microns was used in the conversion method.

Example 5 - Molecular sieve and mixed metal oxide: _La 2 _{O 3} (5 wt%) / MgO
In this Example 5, the catalyst composition was 33.6% by weight MSA, 50.4% by weight binder, and 5% by weight Group 3 metal oxide (the metal was the La described in Example 4). And 16% by weight MgO. The catalyst composition was mixed well and then diluted with quartz to produce a reactor bed. The results of this experiment in the reactor and conditions described in Example B are shown in Table 4. The data in Tables 2 and 4 show that the life of the SAPO-34 molecular sieve is 16.34 g / molecular sieve by comprising 16 wt% of the catalyst composition loading with MgO containing 5 wt% La ₂ O _3. It is shown that the increase from g to 65.90 g / g molecular sieve is more than 300%.

a. The lowest conversion measured was 30.69% by weight, with a lifetime of 57.57 g / g sieve at that conversion. Its reported lifetime (65.90 g methanol / g sieve) was estimated by extrapolating from 30.69 wt% to 10 wt% conversion.

Comparative Example 6-Molecular sieve and BaO
In this Comparative Example 6, 28.8 wt% MSA, 43.2 wt% binder, and 28 wt% barium acetate were mixed well and then diluted with quartz to produce a reactor bed. The reactor was heated to 550 ° C. and kept at 550 ° C. for 90 minutes in a flow of a mixture of 20 ml / min oxygen and 50 ml / min He. Under these conditions barium acetate was decomposed to barium oxide. The molecular sieve catalyst composition was composed of 32 wt% MSA, 48 wt% binder and 20 wt% BaO. The reactor temperature was then reduced to 475 ° C. and the catalyst composition was tested in the conversion process under the conditions of Example B. Table 5 shows the results of the conversion method. The data in Tables 2 and 5 show that the life of the SAPO-34 molecular sieve was increased by 43% by composing 20 wt% of the catalyst composition loading with BaO.

Claims (28)

(a) a metal oxide having a surface area greater than 20 m ² / g and calcined at a temperature higher than 200 ° C., saturated with acetone and contacted with said acetone at 25 ° C. for 1 hour , Metal oxides that convert more than 80% of acetone,
(b) a binder,
(c) matrix material and
(d) A catalyst composition containing a molecular sieve having an average pore size of less than 5 angstroms. The catalyst composition according to claim 1, wherein the surface area of the metal oxide is greater than 70 m ² / g. The catalyst composition according to claim 1 or 2, wherein the metal oxide is selected from Group 2 of the periodic table of elements. The catalyst composition according to claim 3, further comprising a Group 3 metal oxide. Molecular sieves, and at least one contains an oxide of a metal selected from Group 2 of the periodic table, metal oxides, at 100 ° C., of at least 0.03 mg / metal oxide m ^2, the carbon dioxide uptake A catalyst composition.   6. The catalyst composition of claim 5, wherein the metal oxide is saturated with acetone and converts more than 80% of the acetone when contacted with the acetone at 25 ° C. for 1 hour.   The catalyst composition according to claim 5 or 6, further comprising at least one of a binder and a matrix material different from the metal oxide.   The catalyst composition according to any one of claims 1 to 7, comprising a matrix material comprising a binder containing alumina sol and clay.   The catalyst composition according to any one of claims 5 to 8, further comprising a Group 3 metal oxide. The catalyst composition according to claim 4 or claim 9, wherein the Group 3 metal oxide is selected from yttrium oxide, lanthanum oxide, scandium oxide, and mixtures thereof. The catalyst composition according to any one of claims 1 to 10, wherein the metal oxide contains magnesium oxide. The catalyst composition according to any one of claims 1 to 11, wherein the molecular sieve comprises silicoaluminophosphate and / or aluminophosphate. (a) Silicoaluminophosphate molecular sieve and / or aluminophosphate molecular sieve, binder and matrix material are blended to form a catalyst precursor, (b) the catalyst precursor is heated to a temperature in the range of 200 ° C to 700 ° C. A process for producing a catalyst composition comprising adding at least one calcined metal oxide. Including compounding silicoaluminophosphate molecular sieve and / or aluminophosphate molecular sieve, binder, matrix material and at least one metal oxide, wherein the metal oxide is saturated with acetone and contacted with said acetone at 25 ° C. for 1 hour. To produce a catalyst composition that converts more than 25% of acetone. 15. A method according to claim 13 or claim 14, wherein the at least one metal oxide comprises magnesium oxide. Physically mixing the first particles comprising a molecular sieve with at least one second particle containing an oxide of a metal selected from Group 2 of the Periodic Table of Elements, wherein the metal oxide comprises 100 Process for producing a catalyst composition having an uptake of carbon dioxide of at least 0.03 mg / m ² of metal oxide at ° C. The method of claim 16, wherein the first particles and the second particles also contain at least one of a binder and a matrix. 18. A method according to claim 16 or claim 17, wherein the first particles comprise a matrix material comprising a silicoaluminophosphate molecular sieve, a binder comprising alumina sol, and clay. The method according to any one of claims 15 to 18, wherein the at least one metal oxide further contains at least one metal oxide selected from Group 3 of the periodic table of elements. 20. A process for converting a feedstock to one or more olefins in the presence of a catalyst composition produced by the process of any one of claims 13-19. A molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material and a metal oxide, wherein the metal oxide is saturated with acetone and more than 80% of acetone when contacted with said acetone at 25 ° C. for 1 hour Wherein the feedstock is converted to one or more olefins in the presence of a molecular sieve catalyst composition. The method of claim 21, wherein the metal oxide is calcined to a temperature in the range of 200 ° C to 700 ° C. 23. A method according to claim 21 or claim 22, wherein the metal oxide has a surface area greater than 70 m < ² > / g. 24. A method according to any one of claims 21 to 23, wherein the metal oxide has a carbon dioxide uptake of at least 0.03 mg / m ² of metal oxide at 100 ° C. 25. A method according to any one of claims 21 to 24, wherein the metal oxide comprises magnesium oxide. 26. The method of claim 25, wherein the catalyst composition also contains a Group 3 metal oxide. Contacting a feedstock containing at least one oxygenate with a catalyst composition comprising a small pore molecular sieve, a binder, a matrix material, and magnesium oxide calcined to a temperature in the range of 200 ° C to 700 ° C. A process for producing one or more olefins. 28. A process according to any one of claims 20 to 27, wherein the feedstock contains methanol and / or dimethyl ether.