EA007873B1 - Catalyst compositions comprising molecular sieves, their preparation and use in conversion processes - Google Patents

Abstract

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

Description

The present invention relates to molecular sieve compositions and their containing catalysts, to the synthesis of such compositions and catalysts, and to the use of such compositions and catalysts in conversion processes to produce olefin (s).

Olefins are traditionally obtained from petroleum feedstocks in catalytic cracking or steam cracking processes. As a result of such cracking processes, in particular steam cracking, a light olefin (s) such as ethylene and / or propylene are obtained from a variety of hydrocarbon feedstocks. Ethylene and propylene are important finished industrial petrochemical products that can be used in a variety of processes for the production of plastics and other chemical products.

For some time now, it has been known in the petrochemical industry that oxygen-containing substances, mainly alcohols, can be converted into light olefin (s). The preferred alcohol for producing light olefins is methanol, and a preferred method for converting a methanol-containing starting material to a light olefin (s), mainly ethylene and / or propylene, involves contacting the starting material with a molecular sieve catalyst composition.

It is known that starting materials, including oxygen-containing substances, are converted into one or more olefins by molecular sieves of many different types. So, for example, in υδ No. 5367100 the use of zeolite, Ζ8Μ-5, for the conversion of methanol to olefin (olefins) is described; ϋδ No. 4062905 discusses the conversion of methanol and other oxygen-containing substances to ethylene and propylene using crystalline aluminosilicate zeolites, for example, zeolite T, ΖΚ5, erionite and chabazite; υδ No. 4079095 describes the use of ΖδΜ-34 material for the conversion of methanol to hydrocarbon products such as ethylene and propylene; and υδ No. 4310440 describes the preparation of light olefin (s) from alcohol using crystalline aluminophosphate, often referred to as A1PO ₄ .

Some of the most effective molecular sieves for converting methanol to olefin (olefins) are silicoaluminophosphate (δита) molecular sieves. The silicoaluminophosphate molecular sieves have a microporous crystalline structure with a three-dimensional skeleton of angled socialized tetrahedral units [δίΟ ₂ ], [Α1Ο ₂ ] and [PO ₂ ]. The synthesis of δΑΡΟ molecular sieve, the preparation of a catalyst from it and its use in the conversion of the starting material to olefin (olefins), especially when the starting material is methanol, are described in patents υδ No. 4499327, 4677242, 4677243, 4873390, 5095163, 5714662 and 6166282, which are all fully incorporated herein by reference.

When they are used in the conversion of methanol to olefins, most molecular sieves, including δита molecular sieves, undergo rapid coking and, therefore, require frequent regeneration, usually involving exposure to high temperatures and saturated steam. As a result, modern catalysts for the conversion of methanol have a limited effective life, due to which there is a need to create a catalytic composition based on a molecular sieve, which exhibits an extended service life, in particular, when used in the process of converting methanol to olefins.

Υδ No. 4465889 describes a catalytic composition comprising a silicalite molecular sieve impregnated with an oxide of a metal such as thorium, zirconium and titanium, intended for use in the conversion of methanol, dimethyl ether or a mixture thereof into a hydrocarbon product rich in C4 iso compounds.

Υδ No. 6180828 discusses the use of a modified molecular sieve for producing methylamines from methanol and ammonia, where, for example, a silicoaluminophosphate molecular sieve is combined with one or more modifiers such as zirconium oxide, titanium oxide, yttrium oxide, montmorillonite or kaolinite.

υδ No. 5417949 relates to a method for converting harmful nitrogen oxides in an oxygen-containing effluent into nitrogen and water using a molecular sieve and a binder of metal oxide, where the preferred binder is titanium dioxide and aluminosilicate is the molecular sieve.

EP-A 312981 describes a method for cracking vanadium-containing hydrocarbon feed streams using a catalyst composition comprising a physical mixture of a zeolite embedded in an inorganic refractory matrix material and at least one of the oxides of beryllium, magnesium, calcium, strontium, barium or lanthanum, preferably magnesium oxide, on a silica-containing carrier material.

Kaid and Iish in the work of EGeSb OG Besgeak ίη and BogGas AS1b kbek 1os1eb op 1ye ex1egia1 kigGase OG N1δΑΡΟ-34 sg81aoshe sa1a1uk1 bu 1ye teesaiosyes1s1 te! Yob, Sa1eb1u8. 171-176 (1998) write that the selectivity with respect to the form during the conversion of methanol to ethylene over Νί-δΑΡΟ-34 can be increased, and the coke formation is reduced by grinding the catalyst with Μ§Ο, CaO, BaO or Sk ₂ O on microspherical non-porous dioxide silicon, with BaO being most preferred.

International Publication No. XVΟ 98/29370 describes the conversion of oxygen-containing substances to olefins over a non-zeolitic molecular sieve with small pores containing a metal.

- 1 007873 selected from the series including lanthanides, actinides, scandium, yttrium, metals of group 4, metals of group 5 and their combinations.

In one embodiment, an object of the invention is a catalytic composition comprising:

(a) a metal oxide that has a specific surface area of more than 20 m ² / g, which is calcined at a temperature above 200 ° C and which, when saturated with acetone and is in contact with this acetone for 1 h at 25 ° C, converts more than 80% acetone;

(b) a binder;

(c) matrix material; and (d) a molecular sieve having an average pore size of less than 5 A.

A suitable molecular sieve has a framework comprising at least tetrahedral units [A1O ₄ ] and [PO ₄ ], and more specifically, a framework comprising at least tetrahedral units [8ίΟ ₄ ], [A1O ₄ ] and [PO ₄ ], such as silicoaluminophosphate.

In one embodiment, the metal oxide includes magnesium oxide.

In another embodiment, an object of the invention is a catalytic composition comprising a molecular sieve and at least one metal oxide selected from group 2 of the Periodic Table of the Elements, where this metal oxide absorbs carbon dioxide in an amount of at least 0.03 mg / m at 100 ° C. ² metal oxides.

In a suitable embodiment, the catalyst composition also includes at least one metal oxide selected from group 3 of the Periodic Table of the Elements, such as yttrium oxide, lanthanum oxide, scandium oxide, and mixtures thereof.

In another embodiment, an object of the invention is a method for preparing a catalyst composition, the method comprising physically mixing the first particles comprising a molecular sieve and second particles comprising at least one metal oxide selected from group 2 of the Periodic Table of the Elements, where this metal oxide is at 100 ° C absorbs carbon dioxide in an amount of at least 0.03 mg / m ² metal oxide.

In another embodiment, an object of the invention is a method for preparing a catalyst composition, the method comprising combining a silicoaluminophosphate molecular sieve, a binder, a matrix material and at least one metal oxide, which, when saturated with acetone and is in contact with this acetone for 1 h at 25 ° C, converts more than 25% acetone.

However, in another embodiment, an object of the invention is a method for preparing a catalyst composition, this method comprising: (a) combining a molecular sieve, a binder and a matrix material to obtain a catalyst precursor and (b) adding a metal oxide to the catalyst precursor which is calcined at temperature in the range from 200 to 700 ° C.

In one embodiment, the metal oxide is magnesium oxide, which is physically mixed with a molecular sieve synthesized from a reaction mixture comprising at least one structural directing agent and at least two of such materials as a silicon source, a phosphorus source, and an aluminum source.

In yet another embodiment, an object of the invention is a method for converting a starting material into one or more olefins in the presence of a molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material and an active metal oxide, which when saturated with acetone and is in contact with this acetone for 1 h at 25 ° C, converts more than 80% acetone.

However, in yet another embodiment, an object of the invention is a method for producing one or more olefins, the method comprising contacting a starting material comprising at least one oxygen-containing substance with a catalytic composition comprising a small pore molecular sieve, a binder, a matrix material , magnesium oxide, which is calcined in the temperature range from 200 to 600 ° C, and a metal oxide of group 3.

The invention relates to a catalyst composition, its synthesis and its use in the conversion of hydrocarbon starting materials, in particular oxygen-containing starting materials, to olefin (olefins). It was found that combining a molecular sieve with a specific metal oxide leads to the formation of a catalyst composition with a longer catalyst life when it is used in the process of converting starting materials, such as oxygen-containing substances, and more specifically methanol, into olefin (olefins). In addition, the resulting catalyst composition is characterized by a higher selectivity for propylene and the yield of less undesirable ethane and propane. A preferred metal oxide is a group 2 metal oxide, absorbing carbon dioxide at 100 ° C. in an amount of at least 0.03 mg / m ^{2 of} this metal oxide, and / or a metal oxide that is capable of converting more than 80% acetone at room temperature. In one embodiment, the metal oxide is magnesium oxide, which has a specific surface area of more than 20 m ² / g and which is calcined at temperatures above 200 ° C. This unexpected result is further improved when a group 3 metal oxide (e.g., scandium, lanthanum or yttrium) is combined with magnesium oxide of the Periodic Table of Elements,

- 2,007,873 compiled using the IUPAC format described in the work of SCS NapBoock o £ Sieshtu and Ryuz1sz, 78th edition, SKS Przegz, Vosa RaUp. Iopba (1997).

Molecular sieves.

Molecular sieves are classified by the Structural Commission of the International Association of Zeolites in accordance with the rules of the IUPAC Commission on the nomenclature of zeolites. In accordance with this classification, zeolite of the frame type and molecular sieves of the zeolite type, the structure of which is established. are denoted by a three-letter code and are described in A11az about £ 2ее1е Ртate ^ open Turez, 5th edition, E1ееу1ет, Лопбоп, Епд1апб (2001), which is fully incorporated into this description by reference.

Non-limiting examples of preferred molecular sieves, particularly for use in processes for converting a starting material including oxygen-containing substances into olefins (olefins) include frame types AE, ΑΡΥ, AE1, BEA, CHA, ΕΌΙ, PAI, PEK, ΟΙ8, LTA, LI , MEK, ΜΡΙ, IOC, MTT, MAA, TAM and ΤΟΝ. In one preferred embodiment, the molecular sieve used in the catalyst composition of the invention has an AE1 topology, or a CHA topology, or a combination thereof, most preferably a CHA topology.

The materials of crystalline molecular sieves have a three-dimensional four-bound framework structure located in the corner of a common tetrahedron [TO ₄ ], where T denotes any tetrahedrally coordinated cation, such as tetrahedral units [8ίΟ ₄ ], [A1O ₄ ] and [PO ₄ ]. The molecular sieves that can be used in the present invention have a framework comprising tetrahedral units [A1O ₄ ] and [PO ₄ ], i.e. aluminophosphate (A1RO) molecular sieve or tetrahedral units _[4 occupies 8], [A1O _4] and [PO _4], i.e., silicoaluminophosphate (8APO) molecular sieve. The most preferred molecular sieves that can be used in the present invention are silicoaluminophosphate (8APO) molecular sieves or substituted, preferably metal substituted, 8APO molecular sieves. Examples of suitable metal substituents are alkali metal of group 1 of the Periodic table of elements, alkaline earth metal of group 2 of the periodic table of elements, rare earth metal of group 3 of the periodic table of elements, including lanthanides (lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, erbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium), scandium or yttrium, transition metals of groups 4 to 12 of the Periodic Table of the Elements and mixtures of any of these metals.

The preferred molecular sieve used in the present invention has a pore system defined by 8-membered rings of the tetrahedron [TO ₄ ] and has an average pore size of less than 5 A, in particular in the range from 3 to 5 A, for example from 3 to 4.5 And, in particular, from 3.5 to about 4.2 A.

Non-limiting examples of 8APO and APO molecular sieves that can be used in the present invention include one or a combination of products such as 8APO-5, 8APO-8, 8APO-11, 8APO-16, 8APO-17, 8APO-18, 8APO- 20, 8ARO-31, 8ARO-34, 8ARO-35, 8ARO-36, 8ARO-37, 8ARO-40, 8ARO-41, 8ARO-42, 8ARO-44 (I8 No. 6162415), 8ARO-47, 8ARO-56 , ALO-5, ALO-11, ALO18, ALO-31, ALO-34, ALO-36, ALO-37, ALO-46 and metal-containing forms of these molecular sieves. Of these, particularly effective molecular sieves are one or a combination of 8ARO-18, 8ARO-34, 8ARO-35, 8ARO-44, 8ARO-56, ALO-18 and ALO-34 sieves and their metal derivatives, in particular one or a combination of 8APO sieves -18, 8APO-34, ALRO-34 and ALRO-18, as well as their metal-containing derivatives, and especially one or a combination of sieves 8ARO-34 and ALO-18, as well as their metal-containing derivatives.

In one embodiment, the molecular sieve is an intergrowth material having two or more distinct crystalline phases within a single molecular sieve composition. Thus, in particular, fused molecular sieves are described in patent application I8 No. 2002-0165089 and application AO 98/15496, published April 16, 1998, both of which are fully incorporated into this description by reference. So, for example, 8APO-18, ALRO-18 and KIA-18 have a frame of type AE1, and 8APO-34 has a frame of type CHA. Thus, the molecular sieve used in the present invention may include at least one intergrown phase with frameworks of types AE1 and CHA, preferably when the ratio between the framework of type CHA and the framework of type AE1, as determined by the I1PPAX method described in published application I8 No. 2002-0165089, exceeds 1: 1.

In a preferred embodiment, in which the molecular sieve is silicoaluminophosphate, the molecular sieve has a ratio of 81 / A1 less than or equal to 0.65, in particular from 0.65 to 0.10, preferably from 0.40 to 0.10, more preferably from 0.32 to 0.10, and most preferably from 0.32 to 0.15.

In one particular embodiment, the molecular sieve is 8APO-18, 8APO-34, or an intergrowth variant thereof, in which the skeleton of these molecular sieves consists essentially of tetrahedral units [81O ₄ ], [A1O ₄ ] and [PO ₄ ] and therefore , free from additional wireframe elements such as nickel.

Oxides of metals.

The metal oxides of the invention are those metal oxides that differ from typical binders and / or matrix materials, which, when used in combination with

- 3 007873 molecular sieves, provide advantages in catalytic conversion processes. Thus, in particular, metal oxides that can be used according to the present invention are oxides which, when they are saturated with acetone and allowed to stand in contact with acetone for 1 h at room temperature (about 25 ° C), convert more than 80% acetone, for example more than 85%, in particular more than 90%, and in some cases more than 95%. There are many methods for determining the conversion of acetone, and one such method is the application of ¹³ C-NMR of a solid. In this method, the metal oxide is first dehydrated under vacuum while heating using a stepwise temperature program. As a rule, the highest temperature created during the dehydration process is 400 ° C. Then, the metal oxide is saturated with acetone-2- ¹³ C at ambient temperature (approximately 25 ° C) using conventional techniques to a vacuum line. The metal oxide with adsorbed acetone-2- ¹³ C without any contact with air or moisture is transferred to the rotor 7millimetrovy NMR. After the sample was kept at 25 ° C for 1 h, quantitative ¹³ C-NMR spectral data of a solid was obtained to determine the acetone conversion by rotation at a magic angle.

Suitable metal oxides are group 2 metal oxides, either alone or in combination with group 3 metal oxides, which at 100 ° C. absorb carbon dioxide in an amount of at least 0.03 mg / m ² metal oxide, in particular at least 0 , 35 mg / m ² metal oxide. Although the upper limit for the absorption of carbon dioxide by metal oxide is not critical, usually the metal oxides that can be used according to the present invention at 100 ° C contain carbon dioxide in an amount of less than 10 mg / m ² metal oxide, in particular less than 5 mg / m ² metal oxide.

In order to determine the absorption of carbon dioxide by metal oxide, the following method is chosen, in which the system is used thermogravimetric analysis Mey1et ΤΟΆ / 8ΌΤΆ 851 under normal pressure. The metal oxide sample is dehydrated for 1 h in a stream of air to about 500 ° C. Next, the temperature of the sample in a helium stream is reduced to 100 ° C. After the sample reaches an equilibrium state in the helium stream at the target adsorption temperature, 20 separate pulses (approximately 12 s / pulse) of the gaseous mixture, including 10 wt.% Carbon dioxide, are exposed to the sample, and the rest is helium. After each pulse of adsorption gas, the metal oxide sample is treated with a helium stream for 3 minutes. The weight gain of the sample, expressed in mg / mg of adsorbent in terms of the mass of adsorbent after treatment at 500 ° C, is the amount of adsorbed carbon dioxide. In order to establish the absorption of carbon dioxide in milligrams of carbon dioxide / m ² metal oxide in accordance with the Braunauer-Emmett-Teller (BET) method published in the form of A8TM 3663 standard, the specific surface area of the sample is determined.

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 MDO, even more preferably a combination of MDO and a group 3 metal oxide, has a specific surface area, as determined in accordance with the Braunauer-Emmett-Teller (BET) method, published as standard L8TM Ό 3663, more than 20 m ² / g, in particular more than 50 m ² / g, for example more than 80 m ² / g and even more than 200 m ² / g. Suitable metal oxides are those metal oxides that have a specific surface area of more than 20 m ² / g, which are calcined to temperatures above 200 ° C and capable of converting more than 25%, in particular more than 50%, for example more than 80%, of acetone, at room temperature .

In another embodiment, the metal oxide, preferably magnesium oxide, even more preferably MDO and a group 3 metal oxide, are calcined at a temperature in the range from 200 to 700 ° C., in particular from about 250 to 650 ° C., for example in the range from 300 to 600 ° C, and, as a rule, from 350 to 550 ° C.

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

Active metal oxides can be prepared using a variety of methods. Active metal oxides can be obtained from precursors of active metal oxides, such as metal salts, preferably metal salts of group 2 or group 3 as precursors. Other suitable sources of Group 2 metal oxide include compounds that form these metal oxides during calcination, such as oxychlorides and nitrates. Additional suitable sources of group 2 or group 3 metal oxides include salts containing metal cations of group 2 or group 3 metals, such as halides, nitrates, and acetates. Alkoxides are also sources of Group 2 or Group 3 metal oxides.

In one method, an active metal oxide is prepared by thermal decomposition of metal-containing compounds, such as magnesium oxalate and barium oxalate, at high temperatures, such as 600 ° C., in an air stream. Thus, the obtained metal oxides are usually characterized by a low specific BET specific surface area, for example, less than 30 m ² / g.

In another method, an active metal oxide is prepared by hydrolysis of metal-containing compounds, followed by dehydration and calcination. For example, MdO is hydroxylated by mixing

- 4 007873 oxide with deionized water, which leads to the formation of a white suspension. This slurry on a hot plate is slowly heated to dryness to give a white powder. This white powder is then dried in a vacuum oven at 100 ° C for at least 4 hours, in particular for 12 hours. The dried white powder is then calcined in air at a temperature of at least 400 ° C, in particular at least 500 ° C, and, as a rule, at least 550 ° C. The thus obtained active metal oxides are usually characterized by a greater specific BET surface area (ranging from 30 to 300 m ² / g) than those obtained by thermal decomposition of the precursors of active metal oxides.

However, in another embodiment, the active metal oxide is prepared according to the so-called airgel method (Koreg, O.V., Hadayu, I., νοίοάίη, A. and K1abiyiye, K. 1. SIET. Ma1eg. 1997, 9, 2468 -2480). In this method, powdered MD in a stream of nitrogen is reacted with anhydrous methanol to obtain a solution of MD (OCH ₃ ) ₂ in methanol. The resulting solution of MD (OCH ₃ ) ₂ is introduced into toluene. Then, with vigorous stirring, water is added dropwise to form a solution of MD (OH) ₂ in methanol / toluene. The resulting colloidal suspension of MD (OH) _{2 is} placed in an autoclave, the dry pressure is increased to 100 psi (690 kPa) and slowly heated to a final gauge pressure of about 1000 psi (6895 kPa). The supercritical solvent is discharged into the atmosphere to obtain a fine white powder MD (OH) 2. By extracting this fine white powder at 400 ° C. under vacuum, nanocrystalline MgO is obtained. Active metal oxides prepared in this way have the highest BET specific surface area, usually greater than 300 m ² / g.

There are various methods for producing mixed group 2 metal oxides and group 3 metal oxide precursors, for example wet impregnation, treatment to initial moisture and coprecipitation.

In one embodiment, mixed metal oxides are prepared by impregnating a group 3 metal oxide precursor with a group 2 metal oxide. In a typical preparation process, a group 3 metal oxide precursor, such as ba (acetylacetonate) ₃ , is dissolved in an organic solvent such as toluene. The solvent is used in an amount sufficient to fill the volume of the mesopores and macropores of the group 2 metal oxide. The solution of the group 3 metal oxide precursor is added dropwise to the group 2 metal oxide. The wet mixture is dried in a vacuum oven for 1 to 12 hours to remove the solvent . Next, the prepared solid mixture is calcined, for example, at a temperature of 400 ° C, high enough to decompose the group 3 metal oxide precursor to oxide.

In another embodiment, the mixed oxide is prepared by processing to an initial moisture content. Typically, a Group 3 metal oxide precursor, such as lanthanum acetate, is dissolved in deionized water. The solution was added dropwise to the metal oxide of group 2. The mixture was dried in a vacuum oven at 50 ° C for 1 to 12 hours. The dried mixture was crushed and calcined at 550 ° C in air for 3 hours.

However, in another embodiment, the mixed metal oxide is prepared by coprecipitation. An aqueous solution including Group 2 and Group 3 metal oxide precursors is subjected to sufficient conditions to precipitate a hydrated solid oxide material precursor, in particular by adding sodium hydroxide or ammonium hydroxide. The temperature at which the liquid medium is maintained during coprecipitation, as a rule, is from 20 to 100 ° C. Then, the resulting gel is hydrothermally treated at temperatures between 50 and 100 ° C for several days. Hydrothermal treatment, as a rule, proceeds under a pressure exceeding atmospheric.

After that, the prepared material is isolated, for example, by filtration or centrifugation, washed and dried. Then, the prepared material is calcined at a temperature above 200 ° C, preferably above 300 ° C, more preferably above 400 ° C, and most preferably above 450 ° C.

The composition of the molecular sieve.

The catalyst composition of the invention includes any one of the molecular sieves described above and one or more active metal oxides described above, optionally in conjunction with a binder and / or matrix material other than the active metal oxide (s). As a rule, the mass ratio between the active metal oxide (s) and molecular sieve in the catalyst composition is in the range from 1 to 800 wt.%, In particular from 5 to 200 wt.%, Mainly from 10 to 100 wt.%.

There are many different binders that can be used in the preparation of catalytic compositions. Non-limiting examples of binders that can be used alone or in combination include hydrated alumina, silica, and / or various types of inorganic oxide sols. One preferred sol-containing alumina is aluminochlorhydrol. Inorganic oxide sol acts like glue that binds synthesized molecular sieves and other

- 5 007873 materials, such as a matrix, especially after heat treatment. When heated, an inorganic oxide sol, preferably having a low viscosity, is converted into an inorganic binder component. For example, an alumina sol is usually converted to alumina by heat treatment.

Alumochlorohydrol, a hydroxylated aluminum sol, including a chloride counterion, corresponds to the general formula L1 _t O _p (OH) _o C1 _p -x (H ₂ O), in which t denotes a number from 1 to 20, η denotes a number from 1 to 8 , o denotes a number from 5 to 40, p denotes a number from 2 to 15, and x denotes a number from 0 to 30. In one embodiment, the binder is the product A1 ₁₃ O ₄ (OH) ₂₄ Cl ₇ T2 (H ₂ O) described in the work of S.M. \ Wo11egtap et al., § Щб. §PC. δει. apb Sa! a1., 76, ss. 105-144 (1993), which is incorporated herein by reference. In another embodiment, one or more binders are combined with one or more other alumina materials, non-limiting examples of which include, but are not limited to, aluminum oxyhydroxide, γ-alumina, boehmite, diaspores, and transition aluminas such as α-alumina, β- alumina, γ-alumina, δ-alumina, ε-alumina, κ-alumina and ρ-alumina, aluminum trihydroxide such as gibbeite, bayerite, nordstrandit, doyelite and mixtures thereof.

In another embodiment, the binder is an alumina sol, comprising mainly alumina, optionally containing a certain amount of silicon. However, in yet another embodiment, the binder is peptized alumina obtained by treating an alumina hydrate such as pseudoboehmite with an acid, preferably an acid that does not contain halogen, resulting in a sol or aluminum ion solution. Non-limiting examples of commercially available colloidal alumina sols include Ba1co 8676, available from Ba1co Siethuya Co., Naperville, Illinois, and Liuco12020, available at Liuco1 Liapo Teslino1. 1ps., Ashland, Massachusetts.

When the catalyst composition includes matrix material, it is preferably different from the active metal oxide and any binder. Matrix materials, as a rule, effectively reduce the total cost of the catalyst, act as heat sinks, promoting thermal protection of the catalyst composition, for example, during regeneration, densifying the catalyst composition, increasing the strength of the catalyst, in particular crush resistance and abrasion resistance.

Non-limiting examples of matrix materials include one or more of the following: inactive metal oxides, including beryllium oxide, quartz, silicon dioxide, sols and mixtures thereof, for example silicon dioxide / magnesium oxide, silicon dioxide / zirconia, silicon dioxide / titanium dioxide, silicon dioxide / alumina and silica / alumina / thorium dioxide. In one embodiment, matrix clays are natural clays, such as clays from the montmorillonite and kaolin families. These natural clays include subbentonites and those kaolins that are known, for example, as clays P1x1e, McAatee, Ceotsche and Nopba. Non-limiting examples of other matrix materials include halloysite, kaolinite, dicit, nakrit and anoxite. Matrix material, such as clay, is treated by implementing well-known modification methods, such as calcination and / or acid treatment and / or chemical treatment.

In a preferred embodiment, the matrix material is clay or a clay type composition, preferably clay or a clay type composition having a low content of iron or titanium dioxide, and the most preferred matrix material is kaolin. Kaolin has been found to form sludge capable of pumping with a high solids content, it has a small fresh surface area, and due to its lamellar structure it is easily compacted. A preferred average particle size of the matrix material, most preferably kaolin, is from about 0.1 to about 0.6 μm with a particle size distribution of Ό ₉₀ less than about 1 μm.

When the catalyst composition comprises a binder or matrix material, this catalyst composition typically contains from 1 to 80%, in particular from 5 to 60%, and preferably from 5 to 50%, by weight of the molecular sieve, based on the total weight of the catalytic composition.

When the catalyst composition comprises a binder and a matrix material, the mass ratio between the binder and the matrix material is usually from 1:15 to 1: 5, in particular from 1:10 to 1: 4, and mainly from 1: 6 to 1: 5. The amount of binder, as a rule, is from 2 to 30 wt.%, In particular from 5 to 20 wt.%, And mainly from 7 to 15 wt.%, In terms of the total weight of the binder, molecular sieve and matrix material. It was found that with a high sieve content and a low matrix content, the operational properties of the molecular sieve catalyst composition improve, while with a lower sieve content and a high matrix content, the abrasion resistance of the composition increases.

The catalyst composition, as a rule, has a density in the range from 0.5 to 5 g / cc, in particular from 0.6 to 5 g / cc, for example from 0.7 to 4 g / cc, mainly in the range from 0.8 to

- 6 007873 g / cc.

A method of preparing a catalyst composition.

In preparing the catalyst composition, a molecular sieve is first prepared, and then it is physically mixed with the group 2 metal oxide described above, or with a mixture of the group 2 and group 3 metal oxides, preferably in a substantially dry, dried or calcined state. In a most preferred embodiment, the molecular sieve and the active metal oxides are physically mixed in their calcined state. Not based on any particular theory, it is believed that homogeneous mixing of a molecular sieve and one or more active metal oxides improves conversion processes using a molecular sieve composition and a catalyst composition of the invention. Homogeneous mixing can be achieved by any method known in the art, such as mixing using a mixer with crushing rolls, a drum mixer, a tape / paddle mixer, a plasticizer, etc. The need for chemical interaction between the molecular sieve and oxide (oxides) metal is absent, but, in general, it is not preferred.

When the catalyst composition comprises a matrix and / or a binder, it is preferable to first prepare a catalyst precursor with a matrix and / or a binder based on a molecular sieve, and then the active metal oxide is combined with the prepared precursor. The active metal oxide may be added in the form of particles not supported on the carrier, or may be added in combination with a carrier, such as a binder and matrix material. Further, by well-known methods, such as spray drying, granulation, extrusion, etc., particles of effective shape and size can be formed from the resulting catalyst composition.

In one embodiment, the molecular sieve composition and the matrix material, optionally with a binder, are combined with the liquid to form a suspension, and then mixed to form a substantially homogeneous mixture containing the molecular sieve composition. Non-limiting examples of suitable liquids include water, alcohol, ketones, aldehydes and / or esters. The most preferred liquid is water. Then, a suspension of the molecular sieve, binder, and matrix material composition is sent to a molding unit, such as a spray dryer, in which the catalyst composition is shaped to the desired shape, for example microspheres.

After molding the molecular sieve catalyst composition in a substantially dry or dried state to further solidify and / or activate this molded catalyst composition, heat treatment is usually carried out at elevated temperatures, such as calcining. Typical calcination temperatures are in the range from 400 to 1000 ° C., in particular from 500 to 800 ° C., for example from 550 to 700 ° C. A typical calcination medium is air (which typically includes a small amount of water vapor), nitrogen, helium, flue gas (a combustion product with a lack of oxygen), or any combination thereof.

In a preferred embodiment, such a catalyst composition is maintained in nitrogen at a temperature of from 600 to 700 ° C. Exposure at elevated temperature is carried out over a period of time, usually from 30 minutes to 15 hours, in particular from 1 to 10 hours, for example from 1 to 5 hours, and mainly from 2 to

hours

The process for applying molecular sieve catalyst compositions.

The catalyst compositions described above can be used in a variety of processes, including cracking, for example, the starting gasoline-naphtha fraction to a light olefin (s) (see I8 No. 6300537) or high molecular weight (BM) hydrocarbons to lower (NM) hydrocarbons; hydrocracking, for example, heavy petroleum products and / or cyclic feedstock; isomerization of, for example, aromatic compounds such as xylene; polymerizing, for example, one or more olefins to obtain a polymer product; reforming; hydrogenation; dehydrogenation; dewaxing, for example, hydrocarbons to remove straight chain paraffins; absorption of, for example, alkyl aromatic compounds to isolate their isomers; alkylating, for example, aromatic hydrocarbons such as benzene and alkylbenzene, optionally with propylene, to produce cumene or long chain olefins; transalkylation, for example, combinations of aromatic and polyalkyl aromatic hydrocarbons; dealkylation; hydrodecyclization; the disproportionation of, for example, toluene to obtain benzene and paraxylene; oligomerization of, for example, a straight chain and branched olefin (s); and dehydrocyclization.

Preferred processes include processes for converting a benzene-naphtha fraction into highly aromatic mixtures; conversion of light olefin (s) to gasoline, distillates and lubricants; the conversion of oxygen-containing substances to olefin (olefins); converting light paraffins to olefins and / or aromatic compounds; and converting unsaturated hydrocarbons (ethylene and / or acetylene) to aldehydes for conversion to alcohols, acids and esters.

The most preferred method of the invention is to convert the starting material into one or more olefins. Typically, the starting material includes one or more compounds containing aliphatic residues, and preferably one or more oxygen-containing

- 7,007873 substances, whereby the aliphatic residue contains from 1 to about 50 carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.

Non-limiting examples of suitable aliphatic residual compounds include alcohols such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide, alkyl amines such as methylamine, aliphatic ethers such as dimethyl ether, diethyl ether and diethyl ether alkyl halides such as methyl chloride and ethyl chloride, alkyl ketones such as dimethyl ketone, formaldehydes and various acids such as acetic acid. Preferred starting materials include methanol, ethanol, dimethyl ether, diethyl ether or a combination thereof, more preferably methanol and / or dimethyl ether, and most preferably methanol.

By using the various starting materials discussed above, in particular the starting material including an oxygen-containing substance such as alcohol, the catalyst composition of the invention effectively converts the starting material mainly into one or more olefins. The resulting olefin (s) typically contains from 2 to 30 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably from 2 to 6 carbon atoms, even more preferably from 2 to 4 carbon atoms, and most preferably represents ethylene and / or propylene.

Typically, the catalyst composition of the invention effectively converts a starting material comprising one or more oxygen-containing substances into a product containing more than 50 wt.%, Typically more than 60 wt.%, In particular more than 70 wt.%, And preferably more than 80 wt.%, olefin (olefins) in terms of the total mass of hydrocarbons in this product. Moreover, the amount of ethylene and / or propylene produced, calculated on the total weight of hydrocarbons in this product, is usually greater than 40 wt.%, For example greater than 50 wt.%, Preferably greater than 65 wt.%, And more preferably greater than 78 wt. .%. As a rule, the amount of ethylene produced in mass percent, calculated on the total weight of the obtained hydrocarbon products, exceeds 20 wt.%, In particular, exceeds 30 wt.%, For example, exceeds 40 wt.%. In addition, the amount of obtained propylene in mass percent, calculated on the total weight of the obtained hydrocarbon products exceeds 20 wt.%, In particular exceeds 25 wt.%, For example, exceeds 30 wt.%, And preferably exceeds 35 wt.%.

It has been found that in comparison with a similar catalytic composition under the same conversion conditions, but without the active metal oxide as component (s), when using the catalytic composition of the invention to convert the starting material containing methanol and dimethyl ether to ethylene and propylene, a decrease in the amount of formed ethane and propane exceeds 10%, in particular exceeds 20%, for example, exceeds 30%, and is preferably in the range from 30 to 40%.

In addition to an oxygen-containing component, such as methanol, the starting material may include one or more diluents, typically used to reduce the concentration of the starting material, which is usually unreactive with the starting material or molecular sieve catalyst composition. Non-limiting examples of diluents include helium, argon, nitrogen, carbon monoxide, carbon dioxide, water, substantially non-reactive paraffins (mainly alkanes such as methane, ethane and propane), substantially non-reactive aromatic compounds and mixtures thereof. The most preferred diluents are water and nitrogen, with water being particularly preferred.

The proposed method can be carried out in a wide temperature range, in particular in the range from 200 to 1000 ° C, for example from 250 to 800 ° C, including the range from 250 to 750 ° C, it is advisable from 300 to 650 ° C, preferably from 350 to 600 ° C, and more preferably 350 to 550 ° C.

Similarly, the proposed method can be implemented in a wide range of pressures, including spontaneously creating pressure. The absolute partial pressure of the starting material, excluding all the diluent contained in it, used in this method, as a rule, is in the range from 0.1 kPa to 5 MPa, preferably from 5 kPa to 1 MPa, and more preferably from 20 to 500 kPa.

The mass hourly velocity (MES), which is defined as the total mass of the starting material, excluding all diluents, per hour per mass of molecular sieve in the catalyst composition, can be in the range from 1 to 5000 h ^-1 , preferably from 2 to 3000 h ^-1 , more preferably from 5 to 1500 h ^-1 , and most preferably from 10 to 1000 h ^-1 . In one embodiment, the MOE is at least 20 h ⁻¹ , and when the starting material includes methanol and / or dimethyl ether, it is in the range from 20 to 300 h ⁻¹ .

The method according to the invention is expediently carried out in the form of a process with a fixed bed or, more typically, in the form of a process with a fluidized bed (including a process with a turbulent bed), in particular as a continuous process with a fluidized bed, and mainly a continuous process with a fluidized bed and high speed flow.

- 8 007873

In one practical embodiment, this method is carried out in the form of a fluidized bed process using a reactor system, a regeneration system, and a recovery system. In such a method, fresh feed, optionally with one or more diluents, is sent together with a molecular sieve catalyst composition to one or more vertical pipe reactors in a reactor system. The source material in the vertical pipe reactor (s) is converted into a gaseous effluent, which, together with the coked catalyst composition, enters the separation vessel in the reactor system. The coked catalyst composition is isolated from the gaseous effluent within the separation vessel, typically by cyclones, and then sent to the stripping zone, typically in the lower part of the separation vessel. In the stripping zone, the coked catalyst composition is contacted with a gas such as water vapor, methane, carbon dioxide, carbon monoxide, hydrogen and / or an inert gas such as argon, preferably water vapor, to separate adsorbed hydrocarbons from the coked catalyst composition, which then introduced into the regeneration system.

In a regeneration system, a coked catalyst composition is brought into contact with a regeneration medium, preferably an oxygen-containing gas, under regeneration conditions that allow coke to be burned out of the coked catalyst composition, preferably to a level below 0.5% by weight, based on the total weight of the coked catalyst composition compositions based on a molecular sieve entering the regeneration system. So, for example, regeneration conditions may include a temperature in the range from 450 to 750 ° C, and preferably from 550 to 700 ° C.

The regenerated catalyst composition withdrawn from the regeneration system is combined with a fresh molecular sieve catalyst composition and / or a molecular sieve catalyst composition returned to the process, and / or starting material, and / or fresh gas or liquids and returned to a vertical pipe reactor (reactors).

The gaseous effluent is diverted from the separation system and passed through a recovery system to recover and purify the light olefin (s), in particular ethylene and propylene contained in the gaseous effluent.

In one practical embodiment, the process of the invention forms part of a combined process for producing light olefin (s) from hydrocarbon feedstocks, in particular methane and / or ethane. The first step in this process is to supply a gaseous feed, preferably in combination with a stream of water, to a synthesis gas production zone to produce a synthesis gas stream, typically including carbon dioxide, carbon monoxide and hydrogen. The synthesis gas stream is then converted into a stream comprising an oxygen-containing substance, usually by contacting with a heterogeneous catalyst, typically a copper catalyst, at a temperature in the range of 150 to 450 ° C. and under pressure in the range of 5 to 10 MPa . After purification, a stream comprising an oxygen-containing substance can be used as a starting material in the process described above to produce light olefin (s), such as ethylene and / or propylene. Non-limiting examples of this combined process are presented 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 combined processes described above, the resulting olefin (s) are sent to one or more polymerization processes to produce various polyolefins.

In order to provide an even better understanding of the essence of the present invention, including its inherent advantages, the following examples are given.

Example A. Preparation of a molecular sieve.

A silicoaluminophosphate molecular sieve, 8-0-34, designated M8A, was crystallized in the presence of tetraethylammonium hydroxide (K.1) and dipropylamine (K2) as organic structural directing agents or template agents. A mixture of the following composition in molar ratios: 0.2810 ₂ / A1 ₂ 0 ₃ / Р ₂ 0 ₅ / 0.9 К1 / 1,5 К2 / 50Н ₂ О was first prepared by mixing a certain amount of Soibea Riga 1 8B product with deionized water to obtain a suspension . A certain amount of phosphoric acid (85%) was added to this suspension. These additions were made with stirring to give a homogeneous mixture. To this homogeneous mixture was added the product LIBOCH-840 (40% 81O ₂ ), followed by the addition of component K1 with stirring to obtain a homogeneous mixture. Component K2 was added to this homogeneous mixture. This homogeneous mixture was then crystallized in a stainless steel autoclave by holding it at 170 ° C for 40 hours with stirring. As a result, a suspension of crystalline molecular sieve was formed. Then the crystals were isolated from the mother liquor by filtration. Thereafter, molecular sieve crystals were mixed with a binder and matrix material, and the particles were formed by spray drying.

Example B. The process of transformation.

All of the presented catalytic data or conversion data was obtained using

- 9 007873 a microflow reactor, comprising a stainless steel reactor (with an external diameter of 1/4 inch (0.64 cm)), placed in a furnace to which evaporated methanol was fed. Methanol conversion reactions were carried out at 475 ° C, under gauge pressure of 25 psi (172 kPa) and MOE 100 (with respect to the amount of 8APO-34). A typical amount of the prepared product 8APO 34 described in Example A was 95 mg, in order to minimize the reaction exotherm in the reactor, the layer in the reactor was diluted with 1 g of silica sand. For the catalyst composition of the invention, a molecular sieve and a metal oxide, in particular, a physical mixture of the molecular sieve M8A of Example A and an active metal oxide were used.

The effluent from the reactor was collected in a Valveo loop valve to collect 15 samples. The collected samples were analyzed by a gas chromatograph installed on the production line (NeYey Raekagb 6890) equipped with a flame ionization detector. An O-column was used as the chromatographic column. The coefficients used as responses are listed in the following table. one.

Table 1

C1 C ₂ = C ₂ ° with ₃ = η ° CH ₃ OH (CH ₃ ) ₂ O from ₄ from ₅ Sat from ₇ 1,103 1,000 1,070 1.003 1,052 3,035 2,639 0,993 0,999 1.006 1,000

Concepts C ₄ , C ₅ +, etc. are carbon atoms in a hydrocarbon. It should be noted that the selectivity, denoted as C ₅ +, is determined by the sum of C ₅ , C ₆ and C ₇ . Mass average values (selectivity) were calculated based on 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; and y _; respectively indicate the yield and the number of grams of methanol fed / g molecular sieve. The reduced catalyst life (g methanol / g molecular sieve) is the total amount of methanol converted. It should be noted that both the service life and the Ministry of Emergencies are given in terms of the weight of the sieve 8ARO-34. The amount of converted methanol in cases where the degree of conversion was less than 10 wt.% Was not taken into account in the calculations. Dimethyl ether was not taken into account as a product, and instead, in the calculations of selectivity and conversion, it was considered as unreacted methanol.

Example 1. Control experiment.

In this Example 1, the catalyst composition consisted of a molecular sieve designated M8A, as described in Example A. The catalyst was diluted with quartz to form a layer for the reactor. The results of this experiment in the reactor and the conditions discussed above in Example B are presented in Table. 2.

table 2

C1 C ₂ = from? Sz = FROM? C _{4 C5} ⁺ C ₂ + s Service life, g / g 1.77 37.65 0.29 39.80 0.63 13.04 6.82 77.45 16.34

Example 2. Obtaining MdO and determining the conversion of acetone.

MDO was prepared as follows. 5.0 g of MdO (98%, AC8 grade for reactions from A1c1ps11) were mixed with 150 ml of deionized water to give a white suspension. This white suspension was slowly heated to dryness on a hot plate. The dried cake was broken into pieces and crushed to a fine powder. The powder was additionally dried in an oven at 120 ° C for 12 hours. Next, the white powder was calcined at 550 ° C in air for 3 hours. The thus obtained active metal oxide, MgO, had a relatively large specific surface area (BET area: approximately 250 m ² / g). MDO powders were sieved to obtain particles of different sizes. In the conversion process as described in Example B, particles with sizes ranging from 75 to 150 microns were used.

0.25 g of this obtained MgO was loaded into a glass tube and this tube was connected to a vacuum line through a 9 mm O-shaped coupling. Then, to remove water from MgO, this oxide was heated to 450 ° С and kept at 450 ° С for 2 h under vacuum. After cooling to room temperature, 25 ° C, saturated with MgO acetone-2- ¹³ C. Then, MgO adsorbed acetone-2- ¹³ C without any contact with air or moisture were charged in a 7-mm NMR rotor. Before determining the acetone conversion by NMR analysis, the sample was allowed to stand at room temperature (approximately 25 ° C) for 1 h. Experiments with ¹³ C-NMR of a solid were carried out in a 200 MHz NMR spectrometer with rotation under a magic angle. Mutual polarization spectral density was determined using a 1 second pulse delay at a 2 millisecond contact duration and 2000 scans. Quantitative single-pulse spectra were obtained using a 15-second pulse delay and at 400 or more scans. The test was repeated; The results of ¹³ C-NMR analysis showed that after 1 hour, on average, more than 80% acetone was consumed.

- 10 007873

Example 3. Molecular sieve and MdO.

In this Example 3, the molecular sieve catalyst composition described in Example 2 above included 33.6 wt.% MBA, 50.4 wt.% A binder and 16 wt.% MDO. This catalyst composition was mixed well and then diluted with quartz to form a reactor bed. The results of this experiment in the reactor and the conditions that were discussed above in example B are presented in table. 3. The data in table. 2 and 3 show that, due to the preparation of a catalytic composition with a MdO content of 16 wt.%, The life of the BARO-34 molecular sieve increased from 16.34 to 31.66 g / g molecular sieve, i.e. the increase was 94%.

Table 3

C1 with ₂ = C ₂ ° with ₃ = from ₃ ° C _{4 C5} ⁺ s ₂ + ₃ - Service life, g / g 1.73 36.86 0.27 40.74 0.53 14.01 5.87 77.59 31.66

Example 4. The mixture of MDO with a metal oxide of group 3 (5 wt.% Ba ₂ About ₃ ).

The introduction of Group 3 metal oxide, where Ba was the metal, into MDO with a large specific surface area was carried out by impregnation to initial moisture. 0.2261 g of lanthanum acetate was dissolved in approximately 1.9 ml of deionized water. The solution was added dropwise to 2.0146 g of MDO. The mixture was dried in a vacuum oven at 50 ° C for 1 h. The dried mixture was crushed and calcined at 550 ° C in air for 3 h. The content of La ₂ O ₃ was approximately 5 wt.%. Metal oxide powders were sieved to obtain particles of different sizes. Particles with sizes ranging from 75 to 150 microns were used in the conversion process.

Example 5. Molecular sieve and mixed metal oxides: 1, and ₂ About ₃ (5 wt.%) / MDO.

In this Example 5, the catalytic composition consisted of 33.6 wt.% MBA, 50.4 wt.% A binder and 16 wt.% MdO containing 5 wt.% Metal oxide of group 3, where the metal was Ba, as described in Example 4 above. This catalyst composition was mixed well and then diluted with quartz to form a reactor bed. The results of this experiment in the reactor and the conditions that were discussed above in example B are presented in table. 4. The data in table. 2 and 4 show that due to the content of 16 wt.% MDO in the catalytic composition, which included 5 wt.% Ba ₂ O ₃ , the life of the BARO-34 molecular sieve increased by more than 300%, from 16.34 to 65.90 g / g sieve.

Table 4

C1 with ₂ = from ₂ ° with ₃ = from ₃ ° from _{4 5} ⁺ s _{2 + 3} - Service life, g / g 1,59 34.54 0.23 42.02 0.50 14.24 6.87 76.56 65.90 ^a

^and The lowest conversion value was 30.69 wt.%, and the service life of this conversion was 57.57 g of methanol / g of sieve. Service life (65.90 g of methanol / g of sieve) was indicated by evaluating the extrapolation of the conversion from 30.69 to 10 wt.%.

Comparative example 6. Molecular sieve and BaO.

In this comparative example 6, 28.8 wt.% MBA, 43.2 wt.% A binder and 28 wt.% Barium acetate were mixed well, and then diluted with quartz to obtain a layer for the reactor. The reactor was heated to 550 ° C and kept at 550 ° C for 90 min in a stream of a mixture of 20 ml / min of oxygen and 50 ml / min of He. Under these conditions, barium acetate was decomposed to barium oxide. This molecular sieve catalyst composition was composed of 32 wt.% MBA, 48 wt.% A binder and 20 wt.% BaO. Next, the temperature in the reactor was reduced to 475 ° C and the catalytic composition of the yarn was removed during the conversion process under the conditions of Example B above. The results of the conversion process are presented in Table. 5. The data in table. 2 and 5 show that due to the preparation of a catalytic composition containing 20 wt.% BaO, the life of the molecular sieve BARO-34 increased by 43%.

Table 5

C1 with ₂ = from ₂ ° with ₃ = From ₃ ° C _{4 5} ⁺ s _{2 + 3} - Service life, g / g 1.74 37.19 0.27 40.36 0.55 13.57 6.32 77.55 23.36

CLAIM

Claims (9)

CLAIM 1. A catalytic composition prepared by a method comprising: (a) combining a silicoaluminophosphate molecular sieve and / or aluminophosphate molecular sieve, a binder and a matrix material to obtain a catalyst precursor and (b) adding at least one group 2 metal oxide to the catalyst precursor, which is calcined at a temperature in the range of 200 to 700 ° C. and which absorbs carbon dioxide at 100 ° C. in an amount of at least 0.03 mg / m ² of metal oxide. 2. The catalytic composition according to claim 1, in which the metal oxide of group 2 is used in combination with - 11 007873 group 3 metal oxide. 3. The catalytic composition according to claim 1 or 2, in which the metal oxide of group 2 is magnesium oxide. 4. The catalytic composition according to claim 2 or 3, in which the group 3 metal oxide is yttrium oxide, lanthanum oxide, scandium oxide, or a mixture thereof. 5. The catalytic composition according to claim 3 or 4, in which the magnesium metal oxide has a specific surface area of about 250 m ² / g 6. The catalytic composition according to claim 5, in which the magnesium oxide is calcined at a temperature of 550 ° C. 7. The catalytic composition according to claim 2, in which the combination of a group 3 metal oxide and a group 2 metal oxide is obtained by impregnating a group 3 metal oxide precursor of a group 2 metal oxide, drying and calcining at a sufficiently high temperature to decompose the group 3 metal oxide precursor to an oxide. 8. A method of converting a feed containing one or more oxygen-containing substances into one or more olefin (s), in which the conversion of the feed is carried out in the presence of a catalyst composition according to any one of claims 1 to 7. 9. The method of claim 8, in which one or more oxygen-containing substances is an alcohol.