EA007871B1 - 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 selected from Group 3 of the Periodic Table of Elements, the Lanthanide series of elements and the Actinide series 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. For example, IZ No. 5367100 describes the use of zeolite, Ζ8Μ-5, to convert methanol to olefin (olefins); IZ No. 4062905 discusses the conversion of methanol and other oxygen-containing substances to ethylene and propylene using crystalline aluminosilicate zeolites, for example zeolite T, 5, erionite and chabazite; IZ No. 4079095 describes the use of material Ζ8Μ-34 for converting methanol to hydrocarbon products, such as ethylene and propylene; and IZ No. 4310440 describes the production of light olefin (s) from alcohol using crystalline aluminophosphate, often referred to as A1PO ₄ .

Some of the molecular sieves most effective for converting methanol to olefin (olefins) are silica aluminophosphate (ZARO) molecular sieves. Silicon aluminophosphate molecular sieves have a microporous crystalline structure with a three-dimensional skeleton of the angular socialized tetrahedral units [H1O ₂ ], [A1O ₂ ] and [PO ₂ ]. Synthesis of ZARA 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 IZ 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 ZARO molecular sieves, undergo rapid coking and, therefore, require frequent regeneration, usually involving exposure of the catalyst to 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.

IZ 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 these into a hydrocarbon product rich in C4 isoso compounds.

IZ No. 6180828 discusses the use of modified molecular sieves 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.

IZ 5417949 relates to a process for converting harmful nitrogen oxides in an oxygen-containing effluent stream to nitrogen and water using a molecular sieve and a binder from a metal oxide, where the preferred binder is titanium dioxide, and the molecular sieve is aluminosilicate.

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.

Kapd and 1psh in the work of the EGGSSy BGSAKS η and IsherGoG As1bPs1os1Sb Op 111s Sch1sGpa1 kigGass Oh N1ZARO-34 SügyaSpea S1a1u11y 111s with the Tssyposys11 Tebube. Satianu18 Beykk 53, ss. 171-176 (1998) write that the selectivity with respect to the form during the conversion of methanol to ethylene over No.-ZARO-34 can be increased, and the formation of coke is reduced by grinding the catalyst with MDO, CaO, BaO or Ck ₂ O on microspheric non-porous 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 007871 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 III of the Periodic Table of the Elements, elements of the lanthanide series and elements of the actinide series, where this metal oxide at 100 ° C absorbs carbon dioxide in the amount of at least 0.03, and, as a rule, at least 0.04 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.

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

Preferred molecular sieves include silicoaluminophosphate.

Another object of the invention is a molecular sieve catalytic composition comprising a Group III metal oxide and an element oxide from the lanthanide or actinide series, 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 physically mixing the first particles, including the molecular sieve, with the second particles, including at least one metal oxide selected from Group III of the Periodic Table of the Elements, elements of the lanthanide series and elements of a series of actinides, where this metal oxide at 100 ° C absorbs carbon dioxide in an amount of at least 0.03 mg / m ² of metal oxide particles.

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

Another object of the invention is a method of producing olefin (olefins) by converting a starting material, such as an oxygen-containing substance, expediently an alcohol, for example methanol, into one or more olefins in the presence of a catalytic composition comprising a molecular sieve and at least one oxide of a metal selected from the group III of the Periodic Table of the elements, elements of the lanthanide series and elements of the actinide series, where this metal oxide at 100 ° C absorbs carbon dioxide in an amount of at least 0.03 mg / m ² about metal oxide.

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 sieve with the active metal oxide of Group III of the Periodic Table of the Elements (if you use the IUPAC format described in the work of the CBC Napbiook! Syesh181gu rbysk, edition 78th, CBC RgS55. Vosa Va1o, E1op6a (1997)) and / or elements of a number of lanthanides or actinides leads to the formation of a catalytic composition with an increased yield of olefins and / or with a longer service life, when it is used in the conversion of starting materials, such as oxygen-containing substances, and more specifically anolyte into olefin (s). In addition, the resulting catalytic composition is characterized by higher selectivity for propylene and the yield of smaller amounts of undesirable ethane and propane, together with other undesirable compounds, such as aldehydes and ketones, and specifically acetaldehyde.

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, the zeolite frame type and molecular sieves of the zeolite type, the structure of which is established, are designated by a three-letter code and are described in A11ac o! 2nd Btashemutk Turek, 5th edition, Ekeuet, Lopbop, Epd1apb (2001), which is fully incorporated into this description by reference.

Non-limiting examples of preferred molecular sieves, in particular for use in the conversion of the starting material, including oxygen-containing substances, to olefin (olefins), include sieves with frameworks of the types LEB, LEC BEA, SLE, EEE BAI, BEV, SC, LTA, HB, MEB , MYU MY, MTT, Μνν, TAM and ΤΟΝ. In one preferred embodiment, the molecular sieve used in the catalytic composition of the invention has an AEE or CHA topology, or a combination thereof, most preferably the CHA topology.

The materials of crystalline molecular sieves have a 3-dimensional four-linked frame structure in the corner of a common tetrahedron [TO ₄ ], where T denotes any tetrahedrally

- 007871 coordinated cation, such as tetrahedral [8U ₄ ], [A1O ₄ ] and [PO ₄ ] links. Molecular sieves that can be used in the present invention have a frame that includes tetrahedral units [A1O ₄ ] and [PO ₄ ], i.e. aluminophosphate (A1PO) molecular sieve, or tetrahedral units [8U ₄ ], [A1O ₄ ] and [PO ₄ ], i.e. silicon aluminophosphate (8APO) molecular sieve. The most preferred molecular sieves that can be used in the present invention are silicon aluminophosphate (8APO) molecular sieves or substituted, preferably metal-substituted, 8APO molecular sieves. Examples of acceptable metal substituents are alkali metal of Group I of the Periodic Table of the Elements, alkaline earth metal of Group II of the Periodic Table of the Elements, rare earth metal of Group III 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 8APO and APRO 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, 8APO-31, 8APO-34, 8APO-35, 8APO-36, 8APO-37, 8APO-40, 8APO-41, 8APO-42, 8APO-44 (I8 No. 6162415), 8APO-47, 8APO-56 , ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37, ALPO-46 and the metal-containing forms of these molecular sieves. Of these, one or a combination of 8APO-18, 8APO-34, 8APO35, 8APO-44, 8APO-56, APRO-18 and APPO-34 and their metal-containing derivatives, in particular one or a combination of 8ARO-18 sieves, are particularly effective molecular sieves. , 8APO-34, ALPO-34 and ALPO-18, as well as their metal-containing derivatives, and especially one or a combination of 8ARO-34 and APRO-18, 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 AO 98/15496, published April 16, 1998, both of which are fully incorporated into the present description as references. So, for example, 8APO-18, APRO-18 and KIA-18 have a framework like АА, and 8APO-34 possesses a frame like СНА. Thus, the molecular sieve used in the present invention may include at least one interlocked phase with frameworks of types АА and СНА, mainly, when the ratio between framework of type СНА and frame of type АА, as determined by the IGERX method described in the published application I8 number 2002-0165089, exceeds 1: 1.

In a preferred embodiment, in which the silica sieve serves as a molecular sieve, 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.

Metal oxides.

The metal oxides that can be used in the present invention are oxides of Group III metals and metals of the lanthanide or actinide series, which, at 100 ° C, absorb carbon dioxide in an amount of at least 0.03 mg / m ² of metal oxide, in particular at least measure 0.04 mg / m ² 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 0.05 to 1 mg / m ² of metal oxide. When used in combination with a molecular sieve, such active metal oxides provide advantages in catalytic conversion processes, primarily the conversion of oxygen-containing substances to olefins.

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, carbon dioxide adsorption is determined using Meile TSA / 8ITA 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 in a helium current at 100 ° C at the target adsorption temperature, the sample is exposed to 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, a sample of metal oxide in those

- 3 007871 3 minutes are treated with a stream of helium. 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 L8TM Ό 3663 standard, the specific surface area of the sample is determined.

Preferred metal oxides of the group III include oxides of scandium, yttrium and lanthanum, and the preferred metal oxides of the lanthanide series or actinide include cerium oxides, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and thorium . The most preferred active metal oxides are scandium oxide, lanthanum oxide, yttrium oxide, cerium oxide, praseodymium oxide, neodymium oxide, and mixtures thereof, especially mixtures of lanthanum oxide and cerium oxide.

In one embodiment, effective metal oxides are those oxides of metals of group III and / or metals of lanthanide and actinide series, which, when used in combination with a molecular sieve in a catalytic composition, effectively lengthen the effective service life of the catalytic composition. Quantitative lengthening of the service life of the catalytic composition is set according to the increase in service life (SS), which is determined using the following equation:

_t catalyst service life in combination with active metal oxide (oxides)

X1U ” ^_ ...

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 insignificant or zero, or usually shortens the service life of the catalytic composition, as a result of which such an oxide is characterized by an ESD value less than or equal to 1. The active metal oxides of the invention are those of Group III metal oxides and actinides, which, when used in combination with a molecular sieve, provide a molecular sieve catalyst composition that characterized SCCP value greater than 1. By definition, the catalyst composition of the molecular sieve which is not combined with an 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 50, in particular from 1.5 to 20. 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.

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 nitrate, halide, 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 a Group III metal oxide are also alkoxides, for example, yttrium n-propoxide.

In one embodiment, the oxide of a metal of group III or the oxide of an element of a lanthanide or actinide series is hydrothermally treated under conditions that include a temperature of at least 80 ° C, preferably at least 100 ° C. Hydrothermal treatment can be carried out in a closed pressure vessel exceeding atmospheric pressure. However, the preferred treatment method involves using an open vessel under reflux conditions. Mixing a Group III metal oxide or an oxide of a number of lanthanides or actinides in a liquid medium, for example, under the influence of boiling liquid and / or a mixer, promotes the effective interaction of the oxide with the liquid medium. The preferred duration of contacting the oxide with the liquid medium is at least 1 hour, preferably at least 8 hours. The preferred pH value of the liquid medium for this treatment is about 6 or higher, more preferably 8 or higher. 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 ₄ ⁺ , Ν ⁺ , K ⁺ , Md ²⁺ and Ca ²⁺ ), pyridine and its derivatives, as well as alkyl / hydroxylamines.

In another embodiment, an active oxide of a metal of group III or an active oxide of an element of a lanthanide or actinide series is prepared by exposing a liquid solution, such as an aqueous solution, including a source of metal ions, such as a metal salt, to conditions sufficient to cause precipitation of the hydrated solid precursor. 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, the preferred precipitant is a base, such as sodium hydroxide and ammonium hydroxide.

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The temperature at which the liquid medium is maintained during the precipitation is usually less than or equal to 200 ° C, in particular 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 solid oxide material. 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

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 is usually converted into a binder from alumina by heat treatment.

Alumochlorohydrol, a hydroxylated aluminum-based sol, including 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 is a number from 5 to 40, p is a number from 2 to 15, and x is a number from 0 to 30. In one embodiment, the binder is the product A11 ₃ O ₄ (OH) ₂₄ C1 ₇ -12 (H ₂ O) described in work 6.M. ^ Negtap et al., 81iF. 8shT. δει. APF 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, enrage, diasporas, and transition aluminas, 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 # 1 with 8676, available from Ba1o S11epis1 Co., Neuperville, Illinois, and Yuaso1 ΑΕ20Ό \ ν. available at the company уuaso1 Тpo Tesbolo1od1ek, 1ps., Ashland, 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 P1x1e, MsYatee, Seogeshcha and Nopf. 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.

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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 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 about 5 to 60%, and more preferably from 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 of, for example, straight chain and branched olefin (s); 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 obtained hydrocarbon products, exceeds 30 wt.%, In particular, exceeds 35 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, reducing the amounts formed ethane and propane exceeds 10%, in particular, exceeds 20%, for example, exceeds 30%, and mostly 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. Absolute partial pressure of the source

- 7 007871 material, excluding all the diluent used 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.

Mass hourly rate (MES), which is defined as the total weight of the starting material, 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 release 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, typically 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

- 8 007871 its original 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 in the transformation in the interval between the two last reference 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 silicon-alumino phosphate molecular sieve, 8APO-34, designated as M8A, 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: 0.2 ₈ O ₂ / A1 ₂ O ₃ / P ₂ O ₅ / 0.9 K1 / 1.5 K2 / 50 H ₂ O was first prepared by mixing a certain amount of Sopbe Riga 1 8B product with deionized water with obtaining 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 fibo A840 (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, 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, and the catalytic layer was diluted with quartz to minimize the formation of hot spots in the reactor.

Example 1

A sample of Ba (KO ₃ ) ₃ -HH ₂ O (L1bps11 Sieshtea1 Compounds) was calcined in air at 700 ° C for 3 hours to obtain lanthanum oxide.

Example 2

g LA (MO ₃ ) ₃ -HH ₂ O (company L1bps11 Syettle1 Sotrap) with stirring was dissolved in 500 ml of distilled water. The pH was adjusted to 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 catalyst was calcined at 600 ° C in a stream of air for 3 hours to obtain lanthanum oxide (LA ₂ O ₃ ).

Example 3

g V (YU _{3) 3} -6H ₂ O was dissolved with stirring in 500 ml of distilled water. The pH was adjusted to 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 catalyst was calcined at 600 ° C in a stream of air for 3 hours to obtain yttrium oxide (U ₂ O ₃ ).

Example 4

Sample 8c (YAO ₃ ) ₃ -HH ₂ O (L1bps11 Syetu-1 Sotrap) was calcined in air at 700 ° C for 3 hours to obtain scandium oxide (8c ₂ O ₃ ).

Example 5

g Ce (UDs _{3) 3} -6H ₂ O was dissolved with stirring in 500 ml of distilled water. The pH was adjusted to 8 by the addition of concentrated ammonium hydroxide. Then this suspension was packed into 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 catalyst was calcined at 600 ° C in a stream of air for 3 hours to obtain cerium oxide (Ce2O3).

- 9 007871

Example 6

g Pr (HOZ) s-6N ₂ O with stirring, dissolved in 500 ml of distilled water. The pH was adjusted to 8 by the addition of concentrated ammonium hydroxide. Then this suspension was packed into 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 catalyst was calcined at 600 ° C in a stream of air for 3 hours to obtain praseodymium oxide (Pr ₂ O ₃ ).

Example 7

g HT (CO _{3) 3} -6H ₂ O was dissolved with stirring in 500 ml of distilled water. The pH was adjusted to 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 catalyst was calcined at 600 ° C in a stream of air for 3 hours to obtain neodymium oxide (Xc1 ₂ O ₃ ).

Example 8

g Ce (\ O _{3) 3} -611 ₂ O and 7.0 g of Ra (\ O _{3) 3} -6H ₂ O was dissolved with stirring in 500 ml of distilled water. Another solution was prepared containing 20 g of concentrated ammonium hydroxide and 500 ml of distilled water. These two solutions were combined 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 catalyst was calcined in a stream of air for 3 hours at 700 ° C to obtain a mixed metal oxide, nominally containing 5% by weight of lanthanum, calculated on the final weight of the mixed metal oxide.

Example 9

g Ce (\ O ₃₎ -611 ₂ O ₃ and 30.0 g of Ra (\ O _{3) 3} -6H ₂ O was dissolved with stirring in 500 ml of distilled water. Another solution was prepared containing 20 g of concentrated ammonium hydroxide and 500 ml of distilled water. These two solutions were combined 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 catalyst was calcined in a stream of air for 3 hours at 700 ° C to obtain a mixed metal oxide, nominally containing 5% by weight of cerium, based on the final weight of the mixed metal oxide.

Example 10

The carbon dioxide absorption by the oxides of examples 1 to 9 was determined using the MeIleG / 8ΌΤΆ 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.

Table 1

Example The dry weight of the catalyst (mg) Absorbed CO ₂ (mg) Specific surface area (m ² / g) CO ₂ absorption (mg CO ₂ / m ² ) one 22 0.1846 40 0,210 2 31 0.6487 38 0.551 3 24 0.3296 80 0.172 four 20 0.0490 33 0.074 five 143 0.7714 57 0.095 6 50 0.3136 24 0.261 Ί 41 0.6491 18 0.880 eight 130 0.8407 51 0.127 9 42 1.2542 46 0.649

Comparative example 11.

In this comparative example 11 (cf. note 11), the molecular sieve catalyst composition prepared in example A was tested in the process of example B using 50 mg

- 10 007871 molecular sieve catalyst composition without active metal oxide. The results of the experiment are presented in table. 2 and 3.

Example 12

In this example, the molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg molecular sieve catalyst composition with 10 mg La ₂ O ₃ obtained by decomposing the nitrate in Example 1. The components mixed well, and then diluted with sand to form a bed for the reactor. The results of this experiment are presented in Table. 2 and 3, showing that the addition of LA ₂ O ₃ , the active oxide of a metal of Group III, increased the service life by 149%. The ethane selectivity decreased by 36%, and the propane selectivity decreased by 32%, 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 molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg molecular sieve catalyst composition with 10 mg La ₂ O ₃ prepared by precipitation in Example 2.

The components were well mixed, and then diluted with sand to form a layer for the reactor. The results of this experiment are presented in Table. 2 and 3, showing that the addition of LA ₂ O ₃ , obtained by precipitation, of an active oxide of a metal of Group III, increased the service life by 340%. The ethane selectivity decreased by 55%, and the propane selectivity decreased by 44%, which was assumed to be due to a significant decrease in the reaction rates with the transition of hydrogen.

Example 14

In this example 14, the molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg molecular sieve catalyst composition with 10 mg мг ₂ Υ ₃ obtained in Example 3. The components were well mixed, and then diluted with sand to form a reactor bed. The results of this experiment are presented in Table. 2 and 3, showing that adding Υ _{2 3} , an active oxide of a metal of group III, increased the service life by 1090%. The ethane selectivity decreased by 45%, and the propane selectivity decreased by 28%, which was thought to be due to a significant decrease in the reaction rates with the transition of hydrogen.

Example 15

In this example 15, the molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg molecular sieve catalyst composition with 10 mg 8e ₂ O ₃ prepared in Example 4. The components were well mixed, and then diluted with sand to form a reactor bed. The results of this experiment are presented in Table. 2 and 3, showing that the addition of 8e ₂ O ₃ , an active oxide of a metal of group III, increased the service life by 167%. The ethane selectivity decreased by 27%, and the propane selectivity decreased by 21%, which was assumed to be due to a significant decrease in the reaction rates with the transition of hydrogen.

Example 16

In this example 16, the molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg molecular sieve catalyst composition with 10 mg Ce ₂ O ₃ obtained in Example 5. The components were well mixed, and then diluted with sand to form a reactor bed. The results of this experiment are presented in Table. 2 and 3, showing that the addition of Се2О3, the active metal oxide of the lanthanide series, increased the service life by 630%. The ethane selectivity decreased by 50%, and the propane selectivity decreased by 34%, which was assumed to be due to a significant decrease in the reaction rates with the transition of hydrogen.

Example 17

In this example 17, the molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg molecular sieve catalyst composition with 10 mg Pr ₂ O ₃ obtained in Example 6. The components were well mixed, and then diluted with sand to form a reactor bed. The results of this experiment are presented in Table. 2 and 3, showing that the addition of Pr ₂ O ₃ , the active metal oxide of the lanthanide series, increased the service life by 640%. The ethane selectivity decreased by 51%, and the propane selectivity decreased by 38%, which was assumed to be due to a significant decrease in the reaction rates with the transition of hydrogen.

Example 18

In this example 18, the molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg of a molecular sieve catalyst composition with 10 mg Ib ₂ O ₃ obtained in Example 7. The components were well mixed, and then diluted with sand to form a reactor bed. The results of this experiment are presented.

- 11 007871 in the table. 2 and 3, showing that adding Νά _{2 3} , the active metal oxide of the lanthanide series, increased the service life by 340%. The ethane selectivity decreased by 49%, and the propane selectivity decreased by 34%, which was assumed to be due to a significant decrease in the reaction rates with the transition of hydrogen.

Example 19

In this example 19, the molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg mixed metal oxide prepared in Example 8. The components were well mixed and then diluted sand to obtain a layer for the reactor. The results of this experiment are presented in Table. 2 and 3, showing that the addition of 5% BaO _x / Ce ₂ O ₃ , an active metal oxide of the lanthanide series modified with a Group III metal oxide, increased the service life by 450%. The ethane selectivity decreased by 47%, 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 20

In this example, the molecular sieve catalyst composition prepared in Example A was tested in the process of Example B using 40 mg of the molecular sieve catalyst composition with 10 mg mixed metal oxide prepared in Example 9. The components were well mixed and then diluted sand to obtain a layer for the reactor. The results of this experiment are presented in Table. 2 and 3, showing that the addition of 5% CeO _x / Ba ₂ O ₃ , an active oxide of a Group III metal modified with an oxide of an element of the lanthanide series, increased the service life by 260%. The ethane selectivity decreased by 56%, and the propane selectivity decreased by 45%, which was assumed to be due to a significant decrease in the reaction rates with the transition of hydrogen.

table 2

Example The composition of the layer in the reactor Life Cycle Rate (PUS) The main olefin (%) c ₂ ⁼ / s ₃ ⁼ Purity C ₃ (%) Wed. eleven 100% M8A 1.0 72.99 0.90 94.1 12 80% M8A / 20% LA ₂ O ₃ 2.5 73.84 0.81 96.1 13 80% M8A / 20% LA ₂ O ₃ 4.4 73.78 0.74 96.9 14 80% M8A / 20% _{2 3} 11.9 73.68 0.76 96.0 15 80% М8А / 20% 8с ₂ О ₃ 2.7 73.74 0.81 95.5 sixteen 80% M8A / 20% CE ₂ O ₃ 7.3 70,51 0,69 96.3 17 80% M8A / 20% Pr ₂ O ₃ 7.4 72.37 0.72 96.6 18 80% M8A / 20% _{2 3} 4.4 72.57 0.71 96.3 nineteen 80% М8А / 20% Lao _х / Се ₂ О ₃ 5.5 70.64 0.73 96.4 20 80% M8A / 20% CeO _x / La ₂ O ₃ 3.6 70,52 0.71 96.9

Table 3

Example The composition of the layer in the reactor CH ₄ with ₂ ⁼ C ₂ ° with ₃ ⁼ Sz ° from ₄ from ₅ + Wed. 100% M8A 2.04 34.50 0.78 38.49 2.43 14.01 3.82 12 80% M8A / 20% LA ₂ O ₃ 1.61 33.05 0.50 40.79 1.65 14.96 4.51 13 80% M8A / 20% LA ₂ O ₃ 1.38 31.43 0.35 42.35 1.37 15.03 5.51 14 80% M8A / 20% _{2 3} 1.39 31.85 0.43 41.83 1.74 14.43 5.61 15 80% М8А / 20% 8с ₂ О ₃ 1.67 33.08 0.57 40.66 1.93 14.49 4.45 sixteen 80% M8A / 20% CE ₂ O ₃ 2.05 28,89 0.39 41.62 1.61 15.29 6.83 17 80% M8A / 20% Pr ₂ O ₃ 1.59 30.18 0.38 42.19 1.51 15.22 6.06 18 80% M8A / 20% _{2 3} 1.64 30.2 0.40 42.37 1.61 15,13 5.68 nineteen 80% М8А / 20% Lao _х / Се ₂ О ₃ 2.62 29.85 0.41 40.80 1.52 14.07 7.14 20 80% M8A / 20% CeO _x / La ₂ O ₃ 2.13 29,16 0.34 41.36 1.34 14.86 7.92

- 12 007871

Claims (8)

1. A method of preparing a catalytic composition for converting the starting material into one or more olefins, comprising physically mixing the first particles, including a molecular sieve, with second particles, including at least one metal oxide selected from group III of the Periodic table of elements, elements of a number of lanthanides and actinide series elements, wherein the metal oxide at 100 ° C absorbs carbon dioxide in an amount of at least 0.03 mg / m ² metal oxide particles and said metal oxide is in the dried or calcined state. 2. The method according to claim 1, in which the metal oxide selected from group III of the Periodic table of elements, elements of a number of lanthanides and elements of a number of actinides, is scandium oxide, lanthanum oxide, yttrium oxide, cerium oxide, praseodymium oxide, neodymium oxide and their mixtures. 3. The method according to claim 2, in which the metal oxide is a mixture of lanthanum oxide and cerium oxide. 4. The method according to any one of the preceding paragraphs, wherein said second particles are prepared 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 of 400 to 900 ° C. 5. The method according to any one of the preceding paragraphs, in which the molecular sieve is an aluminophosphate (A1PO) molecular sieve or a silicon aluminophosphate (8APO) molecular sieve. 6. The method according to any one of the preceding paragraphs, in which the molecular sieve has the topology of AEE or the topology of CHA, or a combination thereof. 7. The method according to any one of the preceding paragraphs, in which the source material includes one or more oxygen-containing substances. 8. The method according to any one of the preceding paragraphs, in which the starting material includes alcohol.