EA007872B1 - 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 oxide of a metal from Group 4, optionally in combination with at least one metal from Groups 2 and 3, of the Periodic Table of Elements.

Description

The present invention relates to molecular sieve compositions and to catalysts containing them, 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 feedstock in catalytic cracking or steam cracking. As a result of such cracking processes, primarily steam cracking, light olefin (s), such as ethylene and / or propylene, are produced 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 in the petrochemical industry, it has been known that oxygen-containing substances, mainly alcohols, can be converted into light olefins (olefins). The preferred alcohol for producing light olefins is methanol, and the preferred method of converting the methanol-containing raw material to 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, convert one or more olefins into molecular sieves of many different types. So, for example, the use of zeolite, ΖδΜ-5, for the conversion of methanol to olefin (olefins) is described in υδ № 5367100; υδ No. 4062905 discusses the conversion of methanol and other oxygen-containing substances into ethylene and propylene using crystalline aluminosilicate zeolites, for example zeolite T, ΖΚ5, erionite and chabazite; I8 No. 4079095 describes the use of material Ζ8Μ-34 to convert methanol to hydrocarbon products, such as ethylene and propylene; and I8 No. 4310440 describes the production 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 silica aluminophosphate (8APO) molecular sieves. Silicon aluminophosphate molecular sieves have a microporous crystalline structure with a three-dimensional framework of angular socialized tetrahedral units [81О ₂ ], [АОО ₂ ] and [РО ₂ ]. Synthesis of 8APO molecular sieve, 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 I8 No. 4499327, 4677242, 4677243, 4873390, 5095163, 5714662 and 6166282 , which are all fully incorporated into this description as references.

When they are used in the process of converting methanol to olefins, most molecular sieves, including 8APO molecular sieves, undergo rapid coking and, therefore, require frequent regeneration, usually involving exposure to the catalyst at high temperatures and water-saturated environments. As a result, modern catalysts for the conversion of methanol have a limited effective service life, as a result of which there is a need to create a catalytic composition based on a molecular sieve that exhibits an increased service life, in particular, when used in the process of converting methanol to olefins.

I8 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 of them into a hydrocarbon product rich in C4 isoso compounds.

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

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

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

Qaid and 1Is in the work of the State Geology and Geology Association of геη and Gesegy ίί aab zyoz 1os1eb op Not Extirgia1 sigGas οί N1δARO-34 sguz! 171-176 (1998) write that the selectivity with respect to the form during the conversion of methanol to ethylene over No. ^ ARO-34 can be enhanced, and the formation of coke is reduced by grinding the catalyst with MgO, CaO, BaO or Cz ₂ O on microspherical nonporous silicon dioxide, with the most preferred Bao.

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

- 1 007872 brane from the series, including lanthanides, actinides, scandium, yttrium, metals of group IV, metals of group V, and their combinations.

In one embodiment, an object of the invention is a catalytic composition comprising a molecular sieve and at least one metal oxide selected from Group IV of the Periodic Table of Elements, where this metal oxide at 100 ° C absorbs carbon dioxide in an amount of at least 0.03, and, as a rule, at least 0.035 mg / m ² of metal oxide.

In a preferred embodiment, the catalytic composition also includes at least one of a binder and matrix material other than the aforementioned metal oxide.

The catalytic composition may also include an oxide of a metal selected from group II and group III of the Periodic Table of Elements. In one embodiment, the oxide of a metal of group IV includes zirconium oxide, and the oxide of a metal of group II and / or group III includes one or more oxides selected from calcium oxide, barium oxide, lanthanum oxide, yttrium oxide and scandium oxide.

Preferred molecular sieves include silicoaluminophosphate.

Another object of the invention is a molecular sieve catalytic composition comprising an active oxide of a metal of group IV and an oxide of a metal of group II and / or group III, a binder, a matrix material and a silicon aluminophosphate molecular sieve.

However, another object of the invention is a method for preparing a catalytic composition, this method comprising the step of physically mixing the first particles, including the molecular sieve, with the second particles, including a Group IV metal oxide and capable of absorbing carbon dioxide at 100 ° C in an amount at least 0.03 mg / m ² of metal oxide particles.

Preferably, said second particles are prepared causing precipitation from a solution containing ions of a Group IV metal, a hydrated precursor of said metal oxide, by hydrothermally treating a hydrated precursor at a temperature of at least 80 ° C for up to 10 days, and then calcining the hydrated precursor at a temperature in the range from 400 to 900 ° C.

Another object of the invention is a method for producing olefin (olefins) by converting a starting material, such as an oxygen-containing substance, expediently an alcohol, such as methanol, into one or more olefins in the presence of a catalytic composition comprising a molecular sieve and active oxide of a metal of group IV, having the ability ° C to absorb carbon dioxide in an amount of at least 0.03 mg / m ^{2 of} such a metal oxide.

However, another object of the invention is a method for converting a starting material to one or more olefins in the presence of a molecular sieve catalyst composition comprising a molecular sieve, a binder, a matrix material and a mixture of metal oxides other than the binder and matrix material.

In one embodiment, the catalytic composition has an increase in service life (SSI) greater than 1, in particular more than 1.5. In the present description, the SSI is defined as the ratio between the service life of a given catalyst composition and the service life of the same catalyst composition in the absence of an active metal oxide.

Objects of the invention are a catalytic composition based on a molecular sieve and its use in the conversion of hydrocarbon starting materials, in particular oxygen-containing starting materials, to olefin (olefins). It was found that the combination of molecular sieves with one or more active metal oxides leads to the formation of a catalytic composition with a longer service life, when it is used in the conversion of raw materials such as oxygen-containing substances, and more specifically methanol, to olefin (olefins). In addition, the resulting catalytic composition is characterized by the yield of increased amounts of desired lower olefins, mainly propylene, and smaller amounts of undesired ethane and propane, along with other undesirable compounds, such as aldehydes and ketones, and specifically acetaldehyde.

Preferred active metal oxides are those oxides that include metals of group IV (for example, zirconium and hafnium) of the Periodic Table of Elements compiled using the IUPAC format described in the SCS Napbiook ok Syeschschyy Rybysk edition, 78th edition, SKS Rhekk, Vos Carlo, Everton (1997). It has been found that in some cases improved results are obtained when the catalytic composition also contains at least one oxide of a metal selected from group II and / or group III of the Periodic Table of Elements.

Molecular sieves.

Molecular sieves are classified by the Structural Commission of the International Zeolite Association in accordance with the rules of the IUPAC Commission on Zeolite Nomenclature. In accordance with this classification, zeolite frame type zeolite and molecular sieves of zeolite type, the structure of which is established, are indicated by a three-letter code and are described in the work of Ayak ok 2eoshe Etashe ^ ot Turez, 5th edition, Ekkeut, bopbop, EpDapb (2001), which is in full The scope is incorporated herein by reference.

Non-limiting examples of preferred molecular sieves, especially for use

- 2 007872 in the processes of transformation of the source material, including oxygen-containing substances, into olefin (olefins), include sieves with frameworks of the types LE,, ΑΕΙ, BEA, SNA, ΕΌΙ, EAI, ΕΕΒ, 618, ЬТА, ЬЬ, МЕВ, ΜΕΙ , ΜΟΒ, MTT, Μ \ ν \ ν. TAM and ΤΟΝ. In one preferred embodiment, the molecular sieve used in the catalytic composition of the invention has a олог or CHA topology, or a combination thereof, most preferably the CHA topology.

Materials of crystalline molecular sieves have a 3 -dimensional, four-connected framework structure of corner-sharing is in tetra [TO _4], where T is any tetrahedrally coordinated cation such as tetrahedral units [8ίΟ _4], [Α1Ο _4] and [PO _4]. Molecular sieves that can be used in the present invention have a frame that includes tetrahedral [AU ₄ ] and [PO ₄ ] links, i.e. aluminophosphate (A1RO) molecular sieve or tetrahedral units [8ίΟ _4], [Α1Ο _4] and [PO _4], i.e., silicon aluminophosphate (8ΑΡΟ) molecular sieve. The most preferred molecular sieves that can be used in the present invention are silicon aluminophosphate (8ΑΡΟ) molecular sieves or substituted, preferably metal-substituted, 8ΑΡΟ molecular sieves. Examples of acceptable metal substituents are alkali metal of Group I of the Periodic Table of the Elements, alkaline earth metal of the Group ΙΙ Periodic Table of the Elements, rare earth metal of the Group of the Periodic Table of the 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 IV to XII 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 the 8-membered tetrahedron rings [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 8ΑΡΟ and ΑϋΡΟ molecular sieves that can be used in the present invention include one or a combination of products such as 8ΑΡΟ-5, 8ΑΡΟ-8, 8ΑΡΟ-11, 8ΑΡΟ-16, 8ΑΡΟ-17, 8ΑΡΟ-18, 8ΑΡΟ- 20, 8ΑΡΟ-31, 8ΑΡΟ-34, 8ΑΡΟ-35, 8ΑΡΟ-36, 8ΑΡΟ-37, 8ΑΡΟ-40, 8ΑΡΟ-41, 8ΑΡΟ-42, 8ΑΡΟ-44 (I8 No. 6162415), 8ΑΡΟ-47, 8ΑΡΟ-56 , ΑϋΡΟ-5, ΑϋΡΟ-11, ΑΙ.ΡΟ18, ΑϋΡΟ-31,-34, ΑϋΡΟ-36,-37, ΑϋΡΟ-46 and the metal-containing forms of these molecular sieves. Of these, one or a combination of 8ΑΡΟ-18, 8ΑΡΟ-34, 8ΑΡΟ-35, 8ΑΡΟ-44, 8ΑΡΟ-56, ΑϋΡΟ-18 and ΑϋΡΟ-34 and their metal-containing derivatives, in particular one or a combination of 8ΑΡΟ, are particularly effective molecular sieves. -18, 8ΑΡΟ-34, ΑϋΡΟ-34 and ΑϋΡΟ-18, as well as their metal-containing derivatives, and especially one or a combination of 8ΑΡΟ-34 and ΑϋΡΟ-18 sieves, as well as their metal-containing derivatives.

In one embodiment, the molecular sieve is an accrete material having two or more distinct crystalline phases within a single molecular sieve composition. Thus, in particular, the fused molecular sieves are described in patent application I8 No. 2002-0165089 and application νΟ 98/15496 published on April 16, 1998, both of which are fully incorporated into the present description as references. So, for example, 8ΑΡΟ-18, ΑϋΡΟ-18 and νυν-18 have a frame of the type ΑΕΕ and 8ΑΡΟ-34 has a frame like the SLEEP. Thus, the molecular sieve used in the present invention may include at least one interconnected phase with frameworks of types ΑΕI and CHA, mainly when the ratio between the framework of the CHA type and the framework of the type as determined by the OSHEX method described in the published application 8 No. 2002-0165089, greater than 1: 1.

In a preferred embodiment, in which the silica sieve serves as a molecular sieve, the molecular sieve has a ratio of 8Ϊ / Α1 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.

Active metal oxides.

The active metal oxides that can be used in the present invention are those metal oxides that differ from typical binders and / or matrix materials, which, when used in combination with a molecular sieve, provide advantages in catalytic conversion processes. Preferred active metal oxides are those metal oxides that contain Group IV metals, such as zirconium and / or hafnium, used either alone or in combination with a Group II metal oxide (for example, magnesium, calcium, strontium or barium) and / or Group III (including lanthanides and actinides), for example, yttrium, scandium, and lanthanum. The most preferred active Group IV metal oxide is a zirconium metal oxide, either alone or in combination with calcium oxide, barium oxide, lanthanum oxide and / or yttria. Typically, oxides of silicon, aluminum, and combinations thereof are not preferred.

Active metal oxides are, in particular, those metal oxides that differ from typical binders and / or matrix materials and which, when used in a catalytic composition in combination with a molecular sieve, effectively lengthen the effective service life of the catalytic composition, especially when turning the starting material, including methanol, into one or more olefins. The quantitative lengthening of the service life of the catalyst depends on the increase in service life (SS), which is determined using the following equation:

ПУСС _ Service life of the catalyst in combination with active metal oxide

Catalyst service life where the service life of the catalyst or catalyst composition in the same process and under the same conditions is expressed by the total amount of the processed starting material per gram of catalyst composition until the conversion of the starting material by the catalytic composition drops below a certain level, for example 10%. The effect of an inactive metal oxide on the service life of the catalytic composition is small, or zero, or usually shortens the service life of the catalytic composition, as a result of which such oxide is characterized by an EMP value less than or equal to 1. Thus, the active metal oxides of the invention are those metal oxides differ from typical binders and / or matrix materials, which, when used in combination with a molecular sieve, ensure the formation of a catalytic composition on Nove molecular sieve which is characterized by SCCP value greater than 1. By the definition of the catalyst composition, the molecular sieve, which is not aligned with the active metal oxide typically has SCCP value of 1.0.

It has been established that the inclusion of an active metal oxide in combination with a molecular sieve makes it possible to prepare a catalytic composition that has an EVA value in the range from more than 1 to 20, in particular from 1.5 to 10. As a rule, the catalytic compositions in accordance with the invention exhibit EVA values more than 1.1, for example in the range from 1.2 to 15, and more specifically more than 1.3, in particular more than 1.5, for example more than 1.7, in particular more than 2.

For example, metal oxides that can be used in the present invention, at 100 ° C., absorb carbon dioxide in an amount of at least 0.03 mg / m ² of metal oxide, in particular at least 0.035 mg / m ² of metal oxide. Although the upper limit of carbon dioxide absorption by metal oxide is not critical, metal oxides that can be used in the present invention usually contain less than 10 mg / m ² of carbon dioxide at 100 ° C, in particular less than 5 mg / m ² metal oxide. Metal oxides that can be used in the present invention generally have the ability to absorb carbon dioxide in an amount of from 0.04 to 0.2 mg / m ² of metal oxide.

In order to determine the absorption of carbon dioxide by a metal oxide, choose the following method. A sample of metal oxide is dehydrated in a stream of air by holding the sample at a temperature of 200 to 500 ° C to a constant mass, determining the dry mass. Next, the sample temperature is lowered to 100 ° C and carbon dioxide is passed through the sample either continuously or in pulses to the same mass. The weight gain of the sample, expressed in mg / mg of the sample based on the dry weight of the sample, is the amount of carbon dioxide adsorbed.

In the examples below, the adsorption of carbon dioxide is determined using the Meyler ΤΟΑ / δΌΤΑ 851 thermogravimetric analysis system under normal pressure. A sample of metal oxide is dehydrated for 1 hour in a stream of air at about 500 ° C. Next, the temperature of the sample in a stream of helium is reduced to 100 ° C. After the sample reaches an equilibrium state at a current of helium at the target adsorption temperature, the sample is affected by 20 individual pulses (approximately 12 s / pulse) of a gaseous mixture comprising 10 wt.% Of carbon dioxide, and the rest is helium. After each pulse of the adsorption gas, the metal oxide sample is treated with a stream of helium for 3 minutes. The weight gain of the sample, expressed in mg / mg of the adsorbent based on the weight of the adsorbent after treatment at 500 ° C, is the amount of adsorbed carbon dioxide. In order to establish the carbon dioxide absorption in milligrams of carbon dioxide / m ² of metal oxide in accordance with the Braunauer-Emmett-Teller method (BET), published as a standard ΑδΤΜ E 3663, the specific surface area of the sample is determined.

In a suitable embodiment, the active oxide (oxides) of the metal has a BET specific surface area of more than 10 m ² / g, in particular from more than 10 to 300 m ² / g. In a preferred embodiment, the active metal oxide (s) have a BET specific surface area of at least 20 m ² / g, in particular from 20 to 250 m ² / g. A more preferred active metal oxide (s) has a BET specific surface area of at least 25 m ² / g, in particular from 25 to 200 m ² / g. In a preferred embodiment, the active metal oxide (s) include zirconium oxide having a BET specific surface area of more than 20 m ² / g, in particular more than 25 m ² / g, and more specifically more than 30 m ² / g.

The active oxide (s) of the metal can be obtained using a variety of methods. In a preferred embodiment, the active metal oxide is prepared from a precursor of the active metal oxide, such as a metal salt, such as a halide, nitrate, sulfate, and acetate. Other acceptable sources of metal oxide include compounds that form a metal oxide during calcination, such as oxychlorides and nitrates. Acceptable sources of Group IV metal oxide

Alkoxides, such as zirconium n-propoxide, are also used. A preferred source of Group IV metal oxide is hydrated zirconia. The expression hydrated zirconia in its additional meaning is used to name the material including zirconium atoms, which are covalently bonded to other zirconium atoms by means of bridging oxygen atoms and additionally include the available hydroxyl groups.

In one embodiment, the hydrated zirconia is hydrothermally treated under conditions that include a temperature of at least 80 ° C, preferably at least 100 ° C. Hydrothermal treatment, as a rule, is carried out in a closed pressure vessel exceeding the atmospheric pressure. However, the preferred treatment method involves using an open vessel under reflux conditions.

Mixing a hydrated oxide of a metal of group IV in a liquid medium, for example, under the influence of a boiling liquid and / or a mixer, promotes the effective interaction of the hydrated oxide with a liquid medium. A suitable duration of contacting the hydrated oxide with the liquid medium is at least 1 hour, in particular at least 8 hours. The pH value of the liquid medium for this treatment is usually about 6 or more, in particular 8 or more. Non-limiting examples of acceptable liquid media include water, hydroxide solutions (including hydroxides ΝΗ ₄ ⁺ , Να '. K ⁺ , MD ^2+, and Ca ²⁺ ), solutions of carbonates and bicarbonates (including carbonates and bicarbonates NΗ ₄ ⁺ , Να', K ⁺ , Md ² 'and Ca ²⁺ ), pyridine and its derivatives, as well as alkyl / hydroxylamines.

In another embodiment, the active metal oxide is prepared, for example, by exposing a liquid solution, such as an aqueous solution, including a source of ions of a metal of Group IV, to conditions sufficient to cause precipitation of the hydrated precursor of the solid oxide material, in particular by adding a precipitant to the solution. In a suitable embodiment, the precipitation is carried out at a pH above 7. For example, a base such as sodium hydroxide and ammonium hydroxide can serve as a precipitant.

When it is necessary to prepare a mixture of a Group IV metal oxide with a Group II and / or III metal oxide, the first liquid solution comprising a source of a Group IV metal ion can be combined with a second liquid solution including a source of a Group II and / or Group III metal ion. This combination of the two solutions can be carried out under conditions sufficient to cause coprecipitation from the solution in the form of a solid of the hydrated precursor of the mixed oxide material. Alternatively, the source of ions of a metal of group IV and the source of ions of a metal of group II and / or group III can be combined in one solution. Then this solution can be affected by conditions sufficient to cause co-precipitation of the hydrated precursor in the form of a solid mixed oxide material, in particular by adding a precipitating agent to the solution.

The temperature at which the solution is kept during precipitation is usually below 200 ° C, for example in the range from 0 to below 200 ° C.

The specific temperature range for precipitation is from 20 to 100 ° C. Then the resulting gel is preferably hydrothermally treated at temperatures of at least 80 ° C, preferably at least 100 ° C. Hydrothermal treatment, as a rule, is carried out under atmospheric pressure. In one embodiment, the gel is hydrothermally treated for up to 10 days, in particular up to 5 days, for example up to 3 days.

Next, the hydrated precursor of the metal oxide (s) is isolated, for example, by filtration or centrifugation, washed and dried. Then, the prepared material can be calcined, in particular in an oxidizing atmosphere, at a temperature of at least 400 ° C, in particular at least 500 ° C, for example, from 600 to 900 ° C, and preferably from 650 to 800 ° C, to obtain active metal oxide or active mixed metal oxide. The duration of calcination is usually up to 48 hours, in particular, it lasts from 0.5 to 24 hours, for example, from 1.0 to 10 hours. In one embodiment, the calcination is carried out at about 700 ° C for 1 to 3 hours

In another embodiment, the oxide of the metal of group IV and the oxide of the metal of group II and / or group III are obtained separately, and then brought into contact with each other to obtain a mixed metal oxide, which is then brought into contact with a molecular sieve. For example, a Group IV metal oxide may be contacted with a molecular sieve prior to the introduction of a Group II and / or Group III metal oxide or, alternatively, a Group II and / or Group III metal oxide may be brought into contact with a molecular sieve before administration Group IV metal oxide.

When the catalytic composition comprises a Group IV metal oxide and a Group III metal oxide, the molar ratio between the metal oxide of Group 4 and the metal oxide of Group 3 may be in the range from 1000: 1 to 1: 1, in particular from 500: 1 to 2: 1, preferably from 100: 1 to 3: 1, more preferably from 75: 1 to 5: 1, calculated on the total number of moles of oxides of metals of Group IV and Group III. In addition, the catalytic composition may comprise from 1 to 25%, preferably from 1 to 20%, more preferably from 1 to 15%, by weight of a metal of group III, calculated on the total weight of the mixed metal oxide, in particular, when the oxide of a metal of group III is a metal oxide lan

- 5 007872 tane or yttrium, and the oxide of a metal of group IV is a zirconium metal oxide.

When the catalytic composition comprises a Group IV metal oxide and a Group II metal oxide, the molar ratio between the Group IV metal oxide and the Group II metal oxide may be in the range from 1000: 1 to 1: 2, in particular from 500: 1 to 2: 3, preferably from 100: 1 to 1: 1, and more preferably from 50: 1 to 2: 1, based on the total number of moles of oxides of metals of Group IV and Group II. In addition, the catalytic composition may include from 1 to 25%, preferably from 1 to 20%, and more preferably from 1 to 15%, by weight of the metal of group II in terms of the total weight of the mixed metal oxide, in particular, when the oxide of the metal group II is calcium oxide, and the metal oxide of group 4 is a zirconium metal oxide.

Catalytic composition.

The catalytic composition of the invention includes any one of the molecular sieves described above and one or more active metal oxides described above, optionally together with a binder and / or matrix material other than the active metal oxide (s). Typically, the mass ratio between the molecular sieve and the active metal oxide in the catalytic composition is in the range from 5 to 800 wt.%, Preferably from 10 to 600 wt.%, More preferably from 20 to 500 wt.%, And most preferably from 30 up to 400 wt.%.

There are many different binders that can be used in the preparation of the catalytic composition according to the invention. Non-limiting examples of binders that can be used alone or in combination include hydrated alumina, silica and / or other inorganic oxide sols of various types. One preferred alumina containing sol is aluminum chlorohydrol. An inorganic oxide sol acts like a glue that binds together synthesized molecular sieves and other materials, such as a matrix, especially after heat treatment. When heated, the inorganic oxide sol, preferably having a low viscosity, is converted into an inorganic oxide binder component. For example, an alumina sol as a result of heat treatment is usually converted to alumina.

Alumochlorohydrol, a hydroxylated aluminum-based sol, comprising a chloride counterion, corresponds to the general formula A1 _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 a product of A1 ₁₃ O ₄ (OH) ₂₄ C1 ₇ -12 (H ₂ O ), described in S.M. ^ Oh Notap et al., 81ib. 8shT. δοί. apb Ca1a1., 76, ss. 105-144 (1993). In another embodiment, one or more binders are combined with one or more other aluminum oxide materials, such as aluminum oxyhydroxide, γ-alumina, boehmite, diasporas, and transitional aluminum oxides, such as α-alumina, β-alumina, γ-oxide aluminum, δ aluminum oxide, ε-alumina, κ-alumina and ρ-alumina, aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, doyelite, and mixtures thereof.

Non-limiting examples of technically available colloidal alumina sols include products No. 11 with 8676, available from HaAlco C1st1ca1 Co., Naperville, NC. Illinois, and уuaso1 Ьb20i ^, available from уuaso1 апpoTos11po1oshche5. Ms. .. Ashland, pc. Massachusetts.

When the catalytic composition comprises a 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 during regeneration, compacting the catalytic composition and improving the physical properties of the catalyst, such as crush resistance and abrasion resistance.

Non-limiting examples of matrix materials that can be used in the present invention include one or more of the following substances: inactive metal oxides, including beryllium oxide, quartz, silica, sols, and mixtures thereof, such as silica / magnesia, silica / zirconia, silica / titania, silica / alumina and silica / alumina / thorium dioxide. In one embodiment, the matrix materials are natural clays, such as clays from the families of montmorillonite and kaolin. These natural clays include subbentonites and those kaolins, which are known, for example, as clays I1x1e, MsYatee, Ceotd1a and P1ot1ba. Non-limiting examples of other matrix materials include halloysite, kaolinite, dicite, nakrit, and anoxite. Matrix material, such as clay, can be subjected to treatment 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 a clay or a clay-type composition, in particular, has a low content of iron or titanium dioxide, and the most preferred matrix material is kaolin. Kaolin has been found to form pumpable sludge with a high content of solid particles, it has a small fresh surface area, and due to its lamellar structure it is easily compacted. The preferred average particle size of the matrix material, most preferably kaolin, is from

- 6 007872 about 0.1 to about 0.6 microns with a particle size distribution of Ό ₉₀ less than about 1 micron.

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

When the catalytic 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 preferably from 1: 6 to 1: 5. The amount of binder, as a rule, is from about 2 to about 30 wt.%, In particular from about 5 to about 20 wt.%, In particular from about 7 to about 15 wt.%, Calculated on the total weight of the binder, molecular sieve and matrix material.

The catalytic composition typically 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 of 0.8 to 3 g / cc.

Preparation of the catalytic composition.

When preparing the catalytic composition, a molecular sieve is first synthesized, and then it is physically mixed with the active metal oxide, preferably in a substantially dry, dried or calcined state. In the most preferred embodiment, the molecular sieve and active metal oxide are physically mixed in their calcined state. Homogeneous physical mixing can be achieved by any method known in the art, such as mixing using a mixer with crushing rollers, a drum mixer, a ribbon / paddle mixer, a kneader, and the like. There is no need for chemical interaction between the molecular sieve and the oxide (oxides) of the metal, and, in general, it is not preferred.

When the catalytic composition comprises a matrix and / or a binder, initially based on the molecular sieve, it is advisable to prepare the catalyst precursor with the matrix and / or binder, and then the active metal oxide is combined with the prepared precursor. The active metal oxide can be added in the form of unsupported particles or can be added in combination with a carrier such as a binder and matrix material. Further, using well-known methods such as spray drying, granulation, extrusion, etc., particles of effective shape and size can be formed from the resulting catalytic composition.

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

After forming the molecular sieve catalyst composition in a substantially dry or dried state, additional heat treatment, such as calcination, is usually performed to further solidify and / or activate this molded catalyst composition. Typical calcining temperatures are in the range of from 400 to 1000 ° C, preferably from 500 to 800 ° C, and more preferably from 550 to 700 ° C. A typical calcining environment is air (which may include a small amount of water vapor), nitrogen, helium, flue gas (a product of combustion with a lack of oxygen), or any combination thereof.

In a preferred embodiment, such a catalytic composition is kept in nitrogen at a temperature of from 600 to 700 ° C for a period of time, usually from 30 minutes to 15 hours, preferably from 1 to about 10 hours, more preferably from 1 to about 5 hours, and most preferably from about 2 to about 4 hours.

The use of a catalytic composition.

The catalytic composition described above can be used in a variety of processes, including cracking, for example, starting gasoline oligroin fraction to light olefin (s) (see I8 No. 6300537) or high molecular weight (HM) hydrocarbons to lower (LM) hydrocarbons; hydrocracking, for example, heavy oils and / or cyclic starting material; isomerization of, for example, aromatic compounds such as xylene; polymerizing, for example, one or more olefins to form a polymer product; reforming; hydrogenation; dehydrogenation; dewaxing, for example, hydrocarbons to remove straight-chain paraffins; absorbing, for example, alkyl aromatic compounds to isolate their isomers; alkylation of, for example, aromatic hydrocarbons such as benzene and alkyl benzenes; transalkylation, for example, combinations of aromatic and polyalkyl aromatic hydrocarbons; dealkylation; hydrodecyclization; disproportionating, for example, toluene to produce benzene and xylenes; oligomerization, for example

- 7 007872 measures of straight-chain and branched olefin (olefins); and dehydrocyclization.

Preferred processes include the conversion of the benzinoligroin fraction to highly aromatic mixtures; the conversion of light olefin (s) to gasoline, distillates and lubricants; the conversion of oxygen-containing substances into olefin (olefins); the conversion of light paraffins to olefins and / or aromatics and the conversion of 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 to one or more olefins. Typically, the starting material contains one or more aliphatic residues of the compounds, and preferably one or more oxygen-containing 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.

Nonlimiting examples of suitable aliphatic-containing compounds include alcohols such as methanol and ethanol, alkyl mercaptans such as methyl mercaptan and ethyl mercaptan, alkyl sulfides such as methyl sulfide, alkylamines such as methylamine, aliphatic ethers such as dimethyl ether, diethyl ether and methylethyl 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.

When using various raw materials discussed above, in particular a starting material comprising an oxygen-containing substance, such as an alcohol, the catalytic composition according to the invention effectively converts the starting material mainly to one or more olefins. The resulting olefin (s) generally 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.

As a rule, the catalytic composition according to the invention effectively converts a raw material comprising one or more oxygen-containing substances into a product containing more than 50% by weight, usually more than 60% by weight, in particular more than 70% by weight, and preferably more than 80 wt.%, olefin (olefins), calculated on the total weight 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 more than 40% by weight, for example more than 50% by weight, preferably more than 65% by weight, and more preferably more than 78% .%. As a rule, the amount of ethylene produced in mass percent, calculated on the total weight of the hydrocarbon products obtained, 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 established that in comparison with a similar catalytic composition under the same conditions of transformation, but without the active metal oxide as a component (components), when using the catalytic composition according to the invention for converting the starting material containing methanol and dimethyl ether into ethylene and propylene, the reduction of ethane and propane exceeds 10%, in particular it exceeds 20%, for example, it exceeds 30%, and mainly lies in the range from 30 to 40%.

In addition to the oxygen-containing component, such as methanol, the starting material may include one or more diluents, usually used to reduce the concentration of the starting material, which are usually not reactive 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), essentially non-reactive aromatics, 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 range of temperatures, in particular in the range from 200 to 1000 ° C, for example from 250 to 800 ° C, including the interval from 250 to 750 ° C, it is advisable from 300 to 650 ° C, preferably from 350 to 600 ° C, and more preferably from 350 to 550 ° C.

Similarly, the proposed method can be implemented in a wide range of pressures, including spontaneously generated pressure. The absolute partial pressure of the starting material, excluding all the diluent contained in it, used in this method, is usually 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.

Mass hourly speed (MES), which is defined as the total mass of the source material,

- 8 007872 excluding all diluents, per hour on the mass of molecular sieve in the catalytic 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 MES 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 as a fixed bed process or, more typically, as a fluidized bed process (including a turbulent bed process), in particular as a continuous fluidized bed process, and preferably a continuous fluidized bed process and high speed flow.

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 this method, fresh starting material, optionally with one or more diluents, together with the molecular sieve catalyst composition is sent to one or more vertical tube reactors in the reactor system. The source material in a vertical pipe reactor (s) is converted into a gaseous effluent stream, which, together with the coked catalytic composition, enters the separation vessel in the reactor system.

The coked catalytic composition is separated from the gaseous effluent inside the separation vessel, usually with cyclones, and then sent to the desorption zone, usually in the lower part of the separation vessel. In the desorption zone, the coked catalytic 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 the adsorbed hydrocarbons from the coked catalytic composition, which then injected into the regeneration system.

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

The regenerated catalyst composition discharged 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 the starting material and / or fresh gas or liquids and returned to the vertical tube. reactor (s).

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

In one practical embodiment, the process conducted according to the invention forms a part of the combined process for producing light olefin (s) from hydrocarbons, in particular methane and / or ethane. The first step in this process is to feed a gaseous starting material, preferably in combination with a stream of water, to the synthesis gas production zone to produce a synthesis gas stream, usually comprising carbon dioxide, carbon monoxide and hydrogen. Next, the flow of synthesis gas is converted into a stream comprising an oxygen-containing substance, usually by contacting a heterogeneous catalyst, usually with a copper-based catalyst, at a temperature in the range from 150 to 450 ° C and under a pressure in the range from 5 to 10 MPa . After purification, the stream comprising the oxygen-containing substance can be used as a starting material in the process that is presented above in the preparation of light olefin (s), such as ethylene and / or propylene. Non-limiting examples of this combined process are presented in EP-B 0933345, which is fully incorporated into the present description by reference.

In another more fully combined process, optionally in combination with the combined processes described above, the resulting olefin (olefins) is 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.

In these examples, the CCP is defined as the ratio between the service life of a molecular sieve catalytic composition comprising the active metal oxide (s) and the service life of a similar molecular sieve in the absence of a metal oxide defined as having a CES value of 1. In order to establish the CCP, the service life is expressed as as a cumulative amount of the oxygenate to be converted, preferably to one or more olefins, per gram of molecular sieve, until the conversion rate drops to level of about 10% of its initial value. If the transformation does not fall to 10% of its original value until the end of the experiment, the lifetime is estimated by linear extrapolation, based on the rate of decrease

- 9 007872 transformations on the interval between the two last base points in the experiment.

The primary olefin is the sum of the selectivities for ethylene and propylene. The ratio C ₂ = / C ₃ = is the ratio between the selectivities for ethylene and propylene, weighed during the experiment. The purity of C _{3 is} calculated by dividing the selectivity for propylene by the sum of the selectivity values for propylene and propane. The selectivity values for methane, ethylene, ethane, propylene, propane, C ₄ and C ₅ + are the average values of selectivity, weighted during the experiment. It should be noted that C ₅ + values consist only of C ₅ , C ₆ and C ₇ values. In the tables, the selectivity values do not add up to 100% in total, since, as is well known, they are adjusted for coke.

Example A. Preparation of molecular sieve.

A silicoaluminophosphate molecular sieve, ZARO-34, designated MZA, was crystallized in the presence of tetraethylammonium hydroxide (K1) and dipropylamine (K2) as organic structure-directing agents or templating agents. A mixture of the following composition in molar ratios: 0.2Z1O ₂ / A1 ₂ O ₃ / P ₂ O ₅ / 0.9 K1 / 1.5 K2 / 50H ₂ O was prepared first by mixing a certain amount of the product Soibea Riga 1 ZV with deionized water to form a suspension . An 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 Libox AZ40 (40% M1O ₂ ), followed by the addition of component K1 with stirring to obtain a homogeneous mixture. Component K2 was added to this homogeneous mixture, and then the resulting homogeneous mixture was crystallized in a stainless steel autoclave by aging at 170 ° C for 40 h with stirring. As a result, a suspension of crystalline molecular sieve was formed. Then the crystals were isolated from the mother liquor by filtration. After this, the molecular sieve crystals were mixed with a binder and a matrix material and the particles were spray dried.

Example B. The process of transformation.

All the data presented on the transformations were obtained using a microflow reactor that included a stainless steel reactor (with an external diameter of 1/4 inch (0.64 cm)) placed in a furnace into which evaporated methanol was fed. The reactor was maintained at a temperature of 475 ° C and a gauge pressure of 25 psi (172.4 kPa). The flow rate of methanol was such that the flow rate of methanol on a mass basis per gram of molecular sieve, also known as mass hourly rate (MES), was 100 h ^-1 . The resulting gases exiting the reactor were combined and analyzed using gas chromatography. The amount of catalyst was 50 mg, the catalytic layer was diluted with quartz in order to minimize the formation of hot spots in the reactor.

Example 1

1000 g of 2gОС1 ₂ -8Н ₂ О were dissolved with stirring in 3.0 l of distilled water. Another solution was prepared containing 400 g of concentrated ΝΗ.-OH and 3.0 liters of distilled water. Both solutions were heated to 60 ° C. The two heated solutions were combined by stirring in a nozzle at a feed rate of 50 ml / min. The pH of the final composite was adjusted to approximately 9 by the addition of concentrated ammonium hydroxide. Next, this suspension was packed in polypropylene bottles and placed in a steam chamber (100 ° C) for 72 hours. The resulting product was isolated by filtration, washed with excess water and dried overnight at 85 ° C. A part of this product was calcined in a stream of air for 3 hours at 700 ° C to obtain an active zirconia oxide material.

Example 2

500 g of 2gОС1 ₂ -8Н ₂ О and 84 g of ЛАЩО ₃ ) ₃ -6Н ₂ О were dissolved with stirring in 3.0 l of distilled water. Another solution was prepared containing 260 g of concentrated ΝΗ - ^ Η and 3.0 l of distilled water. Both solutions were heated to 60 ° C and then combined, stirring in a nozzle at a feed rate of 50 ml / min, to give a suspension as final mixture. The pH of the final mixture was adjusted to approximately 9 by the addition of concentrated ammonium hydroxide. Next, this suspension was packed in a polypropylene bottle and placed in a steam chamber (100 ° C) for 72 hours. The resulting product was isolated by filtration, washed with excess water and dried overnight at 85 ° C. A part of this product was calcined in a stream of air for 3 hours at 700 ° C to obtain an active mixed metal oxide, which nominally contained 10% by weight of la (lanthanum), calculated on the final weight of the mixed metal oxide.

Example 3

g of ₂ OCl ₂ -8H ₂ O was dissolved with stirring in 300 ml of distilled water. Preparing another solution containing 4.2 g aSchO _{3) 3} -6H ₂ O and 300 ml of distilled water. These two solutions were combined with stirring to give the final mixture. By adding concentrated ammonium hydroxide (28.9 g), the pH of the final mixture, the suspension, was adjusted to approximately 9. Next, this suspension was packed into a polypropylene bottle and placed for 72 hours in a steam chamber (100 ° C). Having formed

- 10 007872 The product was isolated by filtration, washed with excess water and dried overnight at 85 ° C. A part of this final product was calcined in a stream of air for 3 hours at 700 ° C to obtain an active mixed oxide of metals, nominally containing 5% by weight of L in terms of the final mass of the mixed oxide of metals.

Example 4

500 g of 2gОС1 ₂ -8Н ₂ О and 70 g ¥ (NO ₃ ) ₃ -5Н ₂ О were dissolved with stirring in 3.0 l of distilled water. Another solution was prepared containing 260 g of concentrated ΝΗ ₄ and 3.0 l of distilled water. Both solutions were heated to 60 ° C and then combined, stirring in a nozzle at a feed rate of 50 ml / min, to obtain the final mixture. By adding concentrated ammonium hydroxide, the pH of the final mixture, the suspension, was adjusted to about 9. Next, the suspension was packed in a polypropylene bottle and placed in a steam chamber (100 ° C) for 72 hours. The resulting product was isolated by filtration, washed with excess water and dried overnight at 85 ° C. A part of the obtained product was calcined in a stream of air for 3 hours at 700 ° C to obtain an active mixed metal oxide, nominally containing 10% by weight Υ (yttrium), calculated on the final weight of the mixed metal oxide.

Example 5

500 g Ζγ00 ₂ · 8Η ₂ 0 and 56 g of Ca (NO ₃ ) ₂ -4Н ₂ О were dissolved with stirring in 3000 ml of distilled water. Another solution was prepared containing 260 g ΝΗ ₄ and 3000 ml of distilled water. These two solutions were combined with stirring. The pH of the final composite was adjusted to approximately 9 by adding concentrated ammonium hydroxide (160 g). Next, this suspension was packed in polypropylene bottles and placed in a steam chamber (100 ° C) for 72 hours. The resulting product was isolated by filtration, washed with excess water and dried overnight at 85 ° C. A part of this product was calcined in a stream of air for 3 hours at 700 ° C to obtain an active mixed metal oxide, nominally containing 5% by weight of Ca (calcium), calculated on the final weight of the mixed metal oxide.

Example 6

g ΤίΟ8Ο ₄ · χΗ ₂ 8Ο ₄ · χΗ ₂ Ο (x = 1) was dissolved with stirring in 400 ml of distilled water. Another solution was prepared containing 12.8 g of Ce8O ₄ and 300 ml of distilled water. These two solutions were combined with stirring. By adding concentrated ammonium hydroxide (64.3 g), the pH of the final composite was adjusted to about 8. Then, this suspension was packed in polypropylene bottles and placed in a steam chamber (100 ° C) for 72 hours. The resulting product was isolated by filtration, washed with excess water and dried overnight at 85 ° C. A part of this product was calcined in a stream of air for 3 hours at 700 ° C to obtain an active mixed metal oxide, nominally containing 5% by weight of Ce, calculated on the final weight of the mixed metal oxide.

Example 7

g NGOS1 ₂ \ N ₂ O was dissolved with stirring in 100 ml of distilled water. By adding concentrated ammonium hydroxide (4.5 g), the pH of the final composite was adjusted to about 9. Next, this suspension was packed into a polypropylene bottle and placed in a steam chamber (100 ° C) for 72 hours. The resulting product was isolated by filtration, washed with excess water and dried overnight at 85 ° C.

A part of this catalyst was calcined in a stream of air for 3 hours at 700 ° C to obtain active hafnium oxide.

Example 8

g NGOS1 ₂ ^ xH ₂ O and 0.62 g LASCHO ₃ ) ₃ LH ₂ O were dissolved with stirring in 100 ml of distilled water. By adding concentrated ammonium hydroxide (3.5 g), the pH of the final composite was adjusted to about 9. Next, this suspension was packed into a polypropylene bottle and placed in a steam chamber (100 ° C) for 72 hours. The resulting product was isolated by filtration, washed with excess water and dried overnight at 85 ° C. A part of this catalyst was calcined in a stream of air for 3 hours at 700 ° C to obtain an active mixed metal oxide, which nominally contained 5 wt.% La, calculated on the final weight of the mixed metal oxide.

Example 9

The carbon dioxide absorption by the oxides of examples 1 to 8 was determined using the Meile TSL / 8 ETL 851 thermogravimetric analysis system under normal pressure. Samples of metal oxide were first dehydrated in a stream of air at about 500 ° C for 1 h, after which the absorption of carbon dioxide was determined at 100 ° C. In order to establish the absorption of carbon dioxide in milligrams of carbon dioxide / m ² metal oxide, the values of which are presented in table. 1, according to the Braunauer-Emmett-Teller method (BET), the specific surface area of the samples was determined.

- 11 007872

Table 1

Example Dry weight of catalyst (mg) mg CO ₂ Specific surface area (m ² / g) CO ₂ absorption (mg CO ₂ / m ² ) one 76 0.0980 29 0.045 2 115 0.7781 80 0.085 3 73 0.4243 89 0.065 four 97 0.3808 100 0.039 five 78 0.5399 85 0.081 6 43 0,1035 50 0.048 7 158 0.3704 25 0.094 eight 164 0.7359 60 0.075

Example 10 (comparative).

The performance properties of the control molecular sieve of Example A, M8A, using a 50-milligram amount in the reactor and under the conditions discussed above in Example B, are presented in Table. 2 and 3.

Example 11

In this example, the catalytic composition consisted of 40 mg M8A of Example A and 10 mg of active zirconium oxide of Example 1. These catalytic composition and active mixed metal oxide were mixed well and then diluted with quartz to form a layer for the reactor. The results of testing such a catalytic composition in the process of example B are presented in table. 2 and 3. These results show that the addition of active zirconium oxide to the catalytic layer significantly increased the service life of the molecular sieve composition and reduced the amount of unwanted ethane and propane.

Example 12

In this example, the catalytic composition consisted of 40 mg of M8A of Example A and 10 mg of active mixed metal oxide containing 10% by weight of Ba described in Example 2. This catalytic composition and active mixed metal oxide were well mixed and then diluted with quartz to form a layer for the reactor. The results of testing such a catalytic composition in the process of example B are presented in table. 2 and 3. The data in the table. 2 and 3 show that due to the introduction into the catalytic composition of 20% active mixed metal oxide containing 10 wt.% La, the service life of the molecular sieve was doubled, as indicated by its value of SS-2. In addition, the net increase in absolute ratio the main olefins were 1.7%, and most of this increase was achieved due to an increase in the yield of propylene by 2.76%, which was offset by a slight decrease in the yield of ethylene - by 1.07%.

The ethane selectivity decreased by 39%, and the propane selectivity decreased by 37%, which was assumed to be due to a significant decrease in the reaction rates with the transition of hydrogen.

Example 13

In this example, the catalyst consisted of 30 mg M8A of Example A and 20 mg of active mixed metal oxide containing 10% by weight of Ba, as described in Example 2. These catalytic composition and active mixed metal oxide were well mixed and then diluted with quartz to obtain layer for the reactor. The results of testing such a catalytic composition in the process of example B are presented in table. 2 and 3. The data table. 2 and 3 show that due to the introduction into the catalytic composition of 40% active mixed metal oxide containing 10 wt.% La, the service life of the catalytic composition based on 8APO-34 increased by 440%. Trends in selectivity with this catalyst content were similar to those observed in Example 8.

Example 14

In this example, the catalytic composition consisted of 40 mg of M8A from example A and 10 mg of active mixed metal oxide containing 10 wt.%, As described in example 4. The catalytic composition and the active mixed metal oxide were well mixed and then diluted with quartz with getting a layer for the reactor. The results of testing such a catalytic composition in the process of example B are presented in table. 2 and 3. The effect of replacing lanthanum with yttrium was even more

- 12 007872 NII PUS. However, improvements in selectivity were not as dramatic as those observed in the case of lanthanum, and the increase in respect of the main olefin in absolute terms was 1.2%.

Example 15

In this example, the catalyst consisted of 40 mg M8A of Example A and 10 mg of active mixed metal oxide containing 5% by weight of Ba, as described in Example 3. These catalytic compositions and active mixed metal oxide were well mixed and then diluted with quartz to obtain layer for the reactor. The results of testing such a catalytic composition in the process of example B are presented in table. 2 and 3. It is obvious that the active mixed metal oxide, containing 5 wt.% Lanthanum oxide, appeared to have a much stronger effect in the form of an increase in the CME than the active mixed metal oxide of example 8, which contained 10 wt.% La.

Example 16

In this example, the catalyst consisted of 40 mg M8A of example A and 10 mg of active mixed metal oxide containing 5 wt.% Ca, as set out in example 5. These catalytic composition and active mixed metal oxide were well mixed and then diluted with quartz to obtain layer for the reactor. The results of this experiment in the reactor and the conditions that were discussed above in Example B are presented in Table. 2 and 3. An active mixed metal oxide containing 5% by weight of calcium oxide increased the service life of the molecular sieve composition by 223%.

Example 17 (comparative).

In this comparative example, the catalytic composition consisted of 40 mg M8A of Example A and 10 mg of amorphous silicon dioxide / aluminum oxide, an inactive mixed metal oxide. This molecular sieve catalyst composition and inactive mixed metal oxide as catalysts were well mixed and then diluted with quartz to form a layer for the reactor. The results of testing such a catalytic composition in the process of Example B are also presented in Table. 2 and 3. This comparative example illustrates the reduction of the CCP when using inactive mixed metal oxide to a value less than 1.0 as opposed to example 11 of the invention. In addition, the loss of selectivity for the main olefin was 1.07%, and there was no significant reduction in the formation of ethane and propane.

Example 18

In this example, the catalytic composition consisted of 40 mg of M8A from example A and 10 mg of active mixed metal oxide containing Ce and titanium dioxide, as described in example 6. The catalytic composition and active mixed metal oxide were well mixed and then diluted with quartz to obtain layer for the reactor. The results of testing such a catalytic composition in the process of example B are presented in table. 2 and 3. The presence of an active mixed metal oxide increased the lifetime of the molecular sieve composition by 134%.

Example 19

In this example, the catalytic composition consisted of 40 mg M8A of Example A and 10 mg of active hafnium metal oxide described in Example 7. These catalytic composition and active metal oxide were well mixed and then diluted with quartz to form a layer for the reactor. The results of testing such a catalytic composition in the process of example B are presented in table. 2 and 3. The data in the table. 2 and 3 show that due to the introduction of 20% active hafnium metal oxide into the catalytic composition, the service life of the molecular sieve increased by 126%. The ethane selectivity decreased by 40%, and the propane selectivity decreased by 46%, which was thought to be due to a significant slowdown in the reactions with the transition of hydrogen.

Example 20

In this example, the catalytic composition consisted of 40 mg of M8A of Example A and 10 mg of active mixed metal oxide containing 5% by weight of Ba described in Example 8. This catalytic composition and active mixed metal oxide were well mixed and then diluted with quartz to form a layer for the reactor. The results of testing such a catalytic composition in the process of example B are presented in table. 2 and 3. The data in the table. 2 and 3 show that due to the introduction into the catalytic composition of 20% active mixed metal oxide containing 5 wt.% La, the service life of the molecular sieve was increased by 150%. The ethane selectivity decreased by 51%, and the propane selectivity decreased by 51%, which was thought to be due to a significant slowdown in the reactions with hydrogen transition.

- 13 007872

table 2

Example The composition of the layer in the reactor (wt.%) CUS The main olefin (%) C ₂ ⁼ / C ₃ ⁼ Purity C ₃ (%) 10 (compare) 100% M8A one 74.65 0.92 92.7 eleven 80% M8A / 20% ΖγΟ ₂ 2.64 74.79 0.82 96.1 12 80% M8A / 20% 10% la / 2gO ₂ 2.03 76.34 0.84 95.6 13 60% M8A / 40% 10% la / 7gO ₂ 5.41 75.50 0.85 94.6 14 80% M8A / 20% 10% Υ / ΖγΟ ₂ 2.79 75.81 0.85 94.9 15 80% M8A / 20% 5% la / yuO ₂ 4.85 75.84 0.84 94.8 sixteen 80% M8A / 20% 5% Ca / IGO ₂ 3.23 73.85 0.79 96.7 17 (compare) 80% M8A / 20% 8ΐΟ ₂ / Α1 _{2 3} 0.79 73.58 0.93 93.3 18 80% М8А / 20% Се / ТЮ ₂ 2.34 65.65 0.87 95.1 nineteen 80% М8А / 20% НЮ ₂ 2.26 72.98 0.71 96.2 20 80% M8A / 20% 5% La / NU ₂ 2.50 72.75 0.76 96.5

Table 3

Product selectivity (%) Example The layer in the reactor (wt.%) CH ₄ with ₂ ⁼ C ₂ ° with ₃ ⁼ From ₃ ° From ₄ C5 + 10 (compare) 100% M8A 1.5 35.82 0.95 38.83 3.05 14.50 2.12 AND 80% M8A / 20% ΖγΟ ₂ 1.5 33.74 0.53 41.05 1.68 14.79 3.31 12 80% M8A / 20% 10% la / yuO ₂ 1,3 34.75 0.58 41.59 1.93 14.96 2.46 13 60% M8A / 40% 10% L / gH ₂ 1.4 34.75 0.66 40.75 2.32 14.76 2.52 14 80% M8A / 20% 10% Υ / ΖγΟ ₂ 1,3 34.92 0.66 40.88 2.20 14.41 3.07 15 80% M8A / 20% 5% la / gyu ₂ 1.2 34,59 0.64 41.25 2.28 14.96 2.52 sixteen 80% M8A / 20% 5% Ca / IGO ₂ 1 ς * 9 ^ 32.65 η d? 41 7P • * 1 Δ2 * 5 ¹ 14 POISONS ς ΊΔ. ^ 9 ^ ' 17 (compare) 80% M8A / 20% 81O ₂ / A1 ₂ O ₃ 2.1 35.46 0.89 38.12 2.72 14.21 2.65 18 80% М8А / 20% Се / ТЮ ₂ 6.7 30.57 0.75 35.09 1.80 12.72 3.97 nineteen 80% М8А / 20% НЮ ₂ 1.9 31.62 0.52 41.36 1.65 14.64 4.93 20 80% M8A / 20% 5% La / NU ₂ 1.9 31.58 0.47 41.18 1.49 14.53 5.52

- 14 007872

Claims (11)

CLAIM 1. A catalytic composition prepared by a method comprising physically mixing the first particles, including a molecular sieve, with second particles, including a Group IV metal oxide and a Group II metal oxide and / or a Group III metal oxide, these second particles are in a dried or calcined state and carbon dioxide is absorbed at 100 ° C in an amount of at least 0.03 mg / m ² of metal oxide particles. 2. The catalytic composition according to claim 1, in which the oxide of a metal of group IV is zirconium oxide. 3. The catalytic composition according to claim 1 or 2, in which the oxide of a metal of group II and / or the oxide of a metal of group III is one or more oxides selected from calcium oxide, barium oxide, lanthanum oxide, yttrium oxide and scandium oxide. 4. The catalytic composition according to one of claims 1 to 3, in which the molecular sieve has an AER topology or CHA topology, or a combination thereof. 5. Catalytic composition according to one of claims 1 to 4, in which the molecular sieve is an aluminophosphate (A1PO) or silicon aluminophosphate (8APO) molecular sieve. 6. The catalytic composition according to one of the preceding paragraphs, in which the said second particles are prepared by precipitating a hydrated precursor of said Group IV metal oxide into the sediment from a solution containing the ions of the said metal, by hydrothermally treating the hydrated precursor at a temperature of at least 80 ° C for up to 10 days and subsequent calcination of the hydrated precursor at a temperature in the range from 400 to 900 ° C. 7. The catalytic composition according to claim 6, in which the source of the oxide of a metal of group IV is hydrated zirconia. 8. The catalytic composition according to any one of the preceding paragraphs, in which the second particles include an oxide of a metal of Group IV and an oxide of a metal of Group III and the molar ratio between the oxide of a metal of Group IV and an oxide of a metal of Group III is in the range from 500: 1 to 2: 1, preferably from 100: 1 to 3: 1, more preferably from 75: 1 to 5: 1, based on the total number of moles of Group IV metal oxides and Group III metal oxides. 9. The catalytic composition according to claims 1-7, in which the second particles comprise a Group IV metal oxide and a Group II metal oxide and the molar ratio between the Group IV metal oxide and the Group II metal oxide is in the range from 500: 1 to 2: 3, preferably from 100: 1 to 1: 1, more preferably from 50: 1 to 2: 1, based on the total number of moles of Group IV metal oxides and Group II metal oxides. 10. A method of converting a raw material comprising an oxygen-containing substance into one or more olefins, in which the conversion of the starting product is carried out in the presence of a catalytic composition according to any one of the preceding claims 1-9. 11. The method according to claim 10, in which the oxygen-containing substance is an alcohol.