Mesoporous carbon-supported copper-based catalyst, method for production and use thereof

FIELD: chemistry.

SUBSTANCE: present invention relates to a mesoporous carbon-supported copper-based catalyst, a method for production and use thereof in catalytic dehydrogenation of a compound with a C2-C12 alkyl chain to convert said compound to a compound with a corresponding alkenyl chain. The catalyst contains mesoporous carbon, a copper component and an auxiliary element supported on said mesoporous carbon. One or more auxiliary elements (in form of oxides) are selected from a group consisting of V2O5, Li2O, MgO, CaO, Ga2O3, ZnO, Al2O3, CeO2, La2O3, SnO2 and K2O. The amount of the copper component (calculated as CuO) is 2-20 wt % based on the total weight of the catalyst. The amount of the auxiliary element (calculated as said oxide) is 0-3 wt %. The amount of the mesoporous carbon is 77.1-98 wt % based on the total weight of the catalyst. The method of producing the catalyst involves: (1) a step of contacting a copper component precursor, auxiliary element precursor and mesoporous carbon in a given ratio to form an intermediate product and (2) a step of calcining the intermediate product to obtain the mesoporous carbon-supported copper-based catalyst.

EFFECT: catalyst is cheap, environmentally safe and has high thermal stability and caking resistance with considerably high and relatively stable catalytic activity.

19 cl, 47 ex

 

This application claims the priority of Chinese patent application No. 201110371388.2 on November 21, 2011, the contents of which are fully incorporated herein by reference.

The technical field

The present invention relates to catalysts based on copper, specifically to put on mesoporous coal catalysts based on copper. This invention relates to the preparation of catalysts based on copper, deposited on mesoporous carbon, and their use in the dehydrogenation of compounds with alkyl chain C2-C12.

Background of invention

The dehydrogenation cheaper compounds with alkyl chain C2-C12(for example, ethane, butene, isobutane, ethyl benzene, ethylcyclohexane etc., called hereinafter the compounds with alkyl chain) in appropriate more valuable connections with alkenylphenol chain attracts increasing attention from industry and science. For example, isobutene, one of the olefins, C4a very important starting material for the industrial organic chemistry - traditionally are mainly in the apparatus for producing ethylene by cracking petroleum streams or in the apparatus for catalytic cracking of heavy crude oil at refineries. Because in the modern chemical industry is growing need for isobutene as vhodnosti, was developed the method of obtaining isobutene of isobutane by dehydrogenation, which was the third-ranking among the world's primary source of isobutene.

Dehydrogenation of isobutane on the prior art in an industrial scale is usually carried out in the absence of oxygen using a catalyst based on Cr or Pt. For example, you can specify the way Catofin from ABB Lummus, the way Oleflex from UOP company, the way Star from Philips, the way from Linde company Linde and the way FBD-4 from the firm Snamprogetti.

These methods of the prior art are faced with such problems as the use of toxic catalysts based on Cr or expensive Pt catalysts, which leads to an appreciation of the way or to the problems of environmental pollution. In addition, since the dehydrogenation reaction are thermodynamic limit, these methods of the prior art provide a relatively low conversion of isobutane. The conversion can be increased by increasing the reaction temperature, however, a relatively high reaction temperature usually causes sintering of the catalyst, the coke deposition and deactivation of the catalyst. Therefore, there is still a need to increase thermal stability of the catalysts of the prior art.

More attention is attracted by dehydration in an atmosphere of CO2 . Ogonowski et al. compared the activity in the dehydrogenation of isobutane catalysts V-Mg-O surface 21 m2g-1at the reaction temperature of 600°C in an inert atmosphere (In) activity in the atmosphere of CO2. These results show that the catalyst shows increased activity in the dehydrogenation in an atmosphere of CO2when the conversion of isobutane to 13% and the selectivity of formation of isobutene above 80% (Catalysis Communications, Vol.11, 2009, pp.132-136). Shimada et al. found that the conversion of isobutane can reach even 23% at 600°C in the presence deposited on activated carbon Fe2O3when the selectivity of the formation of isobutene 80%. Unfortunately, the activity of this catalyst is declining rapidly, and after 3 hours, the conversion of isobutane is reduced to 13% (Applied Catalysis A: General, Vol.168, 1998, pp.243-250). Ding et al. found that catalysts containing deposited on activated carbon Cr2O3and deposited on activated carbon NiO, have a relatively high initial activity in the dehydrogenation of isobutane in an atmosphere of CO2but both catalyst relatively rapidly lose activity (Chinese Chemical Letters, Vol.19, 2008, pp.1059-1062; Journal of Molecular Catalysis A: Chemical, Vol.315, 2010, pp.221-225).

However, these catalysts of the prior art do not satisfy practical requirements due to insufficient high conversion of isobutene and selectives and education isobutene, so in this area remains a field for improvement. In addition, the difficult problem remains rapid deactivation of the catalyst.

The catalysts of the prior art have similar disadvantages when used in the dehydrogenation of other Akilov C2-C12in addition to isobutane.

Under such circumstances, in this area remains a need to develop a catalyst, particularly a catalyst for dehydrogenation of Akilov C2-C12that would be cheap, environmentally friendly and resistant to sintering with a noticeably high and relatively stable catalytic activity, which would solve the problems associated with the catalysts of the prior art.

The invention

Based on previous experience, the applicants have found that by the use of copper as the primary metal active component and applying it to mesoporous coal in combination with a suitable supporting element, if necessary, can successfully solve the above problems, as described in the present invention.

Specifically, the present invention includes the following options.

1. Deposited on mesoporous carbon catalyst based on copper, characterized in that the composition comprises mesoporous carbon, copper and support the positive element, applied to the specified mesoporous carbon,

moreover, an auxiliary element (oxide) is one or more elements which are selected from the group consisting of V2O5, Li2O, MgO, CaO, Ga2O3, ZnO, Al2O3CeO2La2O3, SnO2and K2O, preferably SnO2, Li2O, combination SnO2and Li2O, combination SnO2and K2O, the combination of Li2O and K2O or a combination of SnO2, K2O and Li2O,

the amount of the copper component in the calculation on the total weight of the catalyst (calculated as CuO) is 2-20 wt.%, preferably 3-15 wt.%,

the number of auxiliary element calculated on the total weight of the catalyst (calculated as specified oxides) is 0-3 .0 wt.%, preferably 0-2 .9 wt.%, more preferably 0.2-2.0 wt.%, and

the number of mesoporous carbon calculated on the total weight of the catalyst is 77.1-98 wt.%, preferably 83-96 .8 wt.%, more preferably the rest.

2. Deposited on mesoporous carbon catalyst based on copper in accordance with any of the above options, and the catalyst is practically consists of mesoporous carbon, the copper component and the auxiliary element.

3. Deposited on mesoporous carbon catalyst based on copper in accordance with any of the above options, and ECOPOLICY coal has a specific surface area by BET 900-3100 m 2g-1preferably 1200-3100 m2g-1the most probable pore size of 2-8 nm, pore volume of 0.4-3.2 lhs-1, preferably 1.0-2.1 lhs-1misoprostol 50-100%, preferably 75-100%.

4. Deposited on mesoporous carbon catalyst based on copper in accordance with any of the above options, and mesoporous coal is a coal one or more types chosen from the group consisting of mesoporous coal with an ordered pore structure, carbon nanotubes, carbon nanorods or mesoporous coal with disordered pore structure.

5. The method of obtaining deposited on mesoporous carbon catalyst based on copper, characterized in that it comprises the following stages:

(1) stage contacting of the copper precursor component (such as a soluble salt of copper, including a water-soluble salt of copper, one or more salts are selected from the group consisting of acetates of copper, copper sulphate, copper nitrate and copper halides, such as one or more salts are selected from the group consisting of acetates of copper nitrate and copper chloride copper), the predecessor of the auxiliary element (such as a water-soluble salt of the auxiliary element, such as one or more salts are selected from the group consisting of acetates, sulfates, no the preparations and halides auxiliary element, such as one or more salts are selected from the group consisting of sulfates, nitrates and chlorides of the auxiliary element), and mesoporous coal in a predetermined ratio to obtain deposited on mesoporous carbon catalyst based on copper, and

(2) the stage of calcination of the intermediate product to obtain deposited on mesoporous carbon catalyst based on copper,

moreover, an auxiliary element (oxide) is one or more oxides chosen from the group consisting of V2O5, Li2O, MgO, CaO, Ga2O3, ZnO, Al2O3CeO2La2O3, SnO2and K2O, preferably SnO2, Li2O, combination SnO2and Li2O, combination SnO2and K2O, the combination of Li2O and K2O or a combination of SnO2, K2O and Li2O,

a predetermined ratio such that deposited on mesoporous carbon catalyst based on copper, obtained after calcination, has the following composition,

the amount of copper in the calculation on the total weight of the catalyst (calculated as CuO) is 2-20 wt.%, preferably 3-15 wt.%,

the number of auxiliary element calculated on the total weight of the catalyst (calculated as above oxides) is 0-3 .0 wt.%, preferably 0-2 .9 wt.%, more preference is sustained fashion 0.2-2.0 wt.%, and

the number of mesoporous carbon calculated on the total weight of the catalyst is 77.1-98 wt.%, preferably 83-96 .8 wt.%, more preferably the rest.

6. The method according to any of the above options, in which the contacting is carried out in the presence of the reagent, forming complexes with metal, and the mass ratio of the reagent, forming complexes with metal, and the copper precursor component is in the range of 0.4-2.0.

7. The method according to any of the above options, in which the calcination is carried out in the atmosphere of inert gas containing no oxygen, at 500-750°C (preferably 560-690°C).

8. Application deposited on mesoporous carbon catalyst based on copper for any of these options or use deposited on mesoporous carbon catalyst based on copper, obtained by the method according to any of the above options, in the catalytic dehydrogenation of Akilov C2-C12for the conversion of the alkyl groups of C2-C12connection to the appropriate alkenylphenol group.

9. The use according to any one of the above options, in which the alkyl compound C2-C12is isobutane, and the application involves the step of contacting deposited on mesoporous carbon catalyst based on copper with a mixture of raw materials is isobutane and CO2to build the value of isobutane in isobutene by the reaction of catalytic dehydrogenation.

10. The use according to any one of the above options, in which the reaction is catalytic dehydrogenation is carried out in the following conditions: reaction temperature 550-650°C, preferably 560-610°C, pressure of the reaction 0.05-1.0 MPa, preferably 0.06 to 0.5 MPa, a space velocity of 0.5-8 LH-1cath-1, the molar ratio of isobutane and CO2from 1:0.5 to 1:11.

The effect of this invention

The method of obtaining deposited on mesoporous carbon catalyst based on copper is relatively simple and practically perform that eliminates the need for expensive or toxic metal components to obtain, and therefore, the catalyst is cheap and environmentally safe.

Compared with catalysts of the prior art the use of this deposited on mesoporous carbon catalyst based on copper can provide a significant increase in the conversion of compounds with alkyl chain and the selectivity of the formation of the corresponding compounds with alkenylphenol circuit (for example, the conversion of compounds with alkyl chain, for example, isobutane, can reach 35-70%, preferably 50-75% or more, and the selectivity of the formation of the corresponding compounds with alkenylphenol chain, for example, isobutene, can reach 70-98%, preferably 85-98%) despite the fact that the activity of the catalyst remains stable is Inoi for a relatively long time, highlighting the slow deactivation of the catalyst. Due to the high activity can significantly reduce the temperature of the formation reaction of the corresponding compounds with alkenylphenol chain of the compounds with alkyl chain in the presence of this deposited on mesoporous carbon catalyst based on copper, which will lead to significantly lower product costs and lower energy costs.

In addition, compared with the catalyst of the prior art on this deposited on mesoporous charcoal catalyst based on copper, which exhibits good thermal stability against sintering even at a relatively high temperature reactions and almost not baked, not coke deposition and deactivation, which facilitates a further increase in the conversion of compounds with alkyl chain (and also the selectivity of the formation of compounds with alkenylphenol chain).

Options inventions

Hereinafter the invention is described more fully with reference to specific cases. However, this invention can be implemented in various ways, and one should not assume that it is limited to the above options.

In the context of this invention, the terms "alkyl chain", "albanova chain", "Alchemilla chain" or "Allenova chain" etc. refer to alcelam, alkaram, alkenyl or alkenes is a straight chain or branched chain (acyclic), respectively.

According to this invention, the terms "conversion" and "selectivity" refers to the conversion of compounds with alkyl chain C2-C12and selectivity in a single pass of education corresponding compounds with alkenylphenol chain, i.e. the conversion and selectivity determined after contacting the fresh catalyst with fresh raw material from compounds with alkyl chain C2-C12(or fresh raw materials from compounds with alkyl chain C2-C12mixed with CO2) in a single pass in the dehydrogenation reaction, and not to existing conversion or selectivity, defined after repeated contact of raw materials from recycling with the specified catalyst in the reaction of dehydrogenation.

According to this invention, proposed is deposited on mesoporous carbon catalyst based on copper, which includes mesoporous carbon, copper component (as CuO) and a supporting element (in the form of the corresponding oxide)is deposited on a specified mesoporous carbon.

According to this invention, the copper component is on mesoporous coal mainly in the form of copper oxide. For example, in the calculation of C copper in the form of oxide is 50 wt.% or more, for example, 80 wt.% or more, 90 wt.% or more all copper based on the weight of the mesoporous carbon. The copper oxide may constitute uboy stable copper oxide, for example, CuO or the corresponding non-stoichiometric oxide of CuxO1-xwhere 0<x<1, for example, CuO. However, for ease of presentation and calculation of the copper component is designated as CuO.

According to this invention, based on the total weight of the catalyst, the amount of the copper component (calculated as CuO) may be 2-20 wt.%, for example, 3-15 wt.%.

Typically, according to this invention, an auxiliary element (in the form of its oxide) is one or more oxides chosen from the group consisting of V2O5, Li2O, MgO, CaO, Ga2O3, ZnO, Al2O3CeO2La2O3, SnO2and K2O. In this case, based on the total weight of the catalyst supporting element (calculated as specified oxide) may be 0-3 .0 wt.%, for example, 0-2 .9 wt.% or 0.2-2.0 wt.%.

Specifically, according to this invention, an auxiliary element (in the form of its oxide) is one or more oxides chosen from the following groups a and b,

Group A: V2O5, Li2O, MgO, CaO, Ga2O3, ZnO, Al2O3CeO2La2O3, SnO2and

Group b: K2O.

In this case, according to this invention, the supporting element selected from group a, based on ABSU the mass of catalyst (oxide) may be 0-3 .0 wt.%, for example, 0-2 .9 wt.% or 0.001-2.9 wt.%, for example, 0.2 to 2.0 wt.%. In addition, the number of auxiliary element selected from the group, calculated on the total weight of the catalyst (oxide) may be 0-3 .0 wt.%, for example, 0-2 .9 wt.%, 0.001-2.9 wt.%, 0.2-2.0 wt.%, the exact value of 1.2 wt.% or any value that can be rounded to values higher or lower than 1.2 wt.%, you can exclude from each of these intervals. Or alternatively, according to this invention, the supporting element selected from the group (as oxide), based on the total weight of the catalyst may be 0.001-1.1 wt.% or 1.3-2.9 wt.%.

According to this invention, the auxiliary element is on mesoporous coal mainly in the form of oxide auxiliary element. For example, based on a supporting element supporting element in the form of oxide (the oxide of the auxiliary element) in the calculation of the auxiliary element 50 wt.% or more, for example, 80 wt.% or more, for example, 90 wt.% or more auxiliary element based on the weight of the mesoporous carbon. Oxide auxiliary element can be any stable oxide of the specified auxiliary element, for example, the oxide represented by any of the above chemical formula, or the corresponding nastech amerykaski oxide, for example, SnyO2-ywhere 0<y<2, preferably an oxide represented by any of the above formula. However, for ease of presentation and calculations supporting element denote as above the corresponding oxide.

According to this invention, these support elements can be of the same type or a combination of two or more types. When using the combination of the molar ratio of the two auxiliary elements in combination may be, but is not limited to, from 1:10 to 10:1. According to this invention, the preferred SnO2, Li2O, combination SnO2and Li2O, combination SnO2and K2O, the combination of Li2O and K2O or a combination of SnO2, K2O and Li2O.

According to this invention, when using only one auxiliary element above the number refers to the number specified one auxiliary element, while when using a combination of two or more secondary elements, as indicated above, this number refers to the total amount of these auxiliary elements.

According to this invention, by using the auxiliary element can be more effectively solved the problem of falling activity relevant to catalysts predshestvuyuschego equipment, while the catalyst obtained according to the present invention, is characterized by its stable activity for a relatively long time. For example, when using the catalyst according to this invention to obtain the corresponding compounds with alkenylphenol chain C2-C12the reaction of dehydrogenation of compounds with alkyl chain C2-C12compared to the activity (expressed as the conversion of compounds with alkyl chain C2-C12for example, isobutane), identified through 1 hour after start of the reaction, the activity, some 3 hours after start of the reaction, is reduced by not more than 20%, preferably not more than 15%, e.g. not more than 10% or 5% or 2%. In addition, the selectivity of the formation of compounds with alkenylphenol chain in the presence of the catalyst remains almost constant during the reaction (for example, for 3 hours or more) within ±2% or less, preferably ±1% or less.

According to this invention, the amount of mesoporous carbon calculated on the total weight of the catalyst can be 77.1-98 wt.%, for example, 83-96 .8 wt.%, or the rest of the catalyst.

According to this invention, if the number mesoporous coal is the rest of the catalyst calculated on the total weight of the catalyst, the catalyst according to the present from which briteney consists almost entirely of mesoporous carbon, the copper component and an auxiliary component. "Almost" means that the catalyst along with mesoporous carbon, the copper component and the auxiliary element may also contain any unavoidable impurities or any side components, necessarily generated during preparation of the catalyst. Typically, the amount of these impurities or by-products is so low (only 1 wt.% or less)that it has virtually no impact or no significant impact on the maintenance of the catalyst activity.

According to one variant of the invention, deposited on mesoporous carbon catalyst based on copper in this invention does not contain expensive elements (for example, Pd, Pt, Au, Ag, Rh, Ir, Ru and the like), as well as toxic or environmentally harmful elements (such as Cr, Pb, Cd, As, Hg, Os, etc.), i.e. it is characterized by low cost and environmental safety.

According to this invention, the mesoporous carbon has a specific surface area by BET 900-3100 m2g-1preferably 1200-3100 m2g-1the most probable pore size of 2-8 nm, pore volume of 0.4-3.2 lhs-1, preferably 1.0-2.1 lhs-1misoprostol 50-100%, preferably 75-100%.

According to this invention, mesoporous coal one or more kinds selected from the group consisting of mesoporous coal with the have an order is authorized by the pore structure, carbon nanotubes, carbon nanorods or mesoporous coal with disordered pore structure (e.g., disordered mesoporous carbon, obtained by the carbonization of organic carbohydrates or metal halides).

Mesoporous coal produces industry (for example, under the trademark CMK-1 and CMK-3 industrial mesoporous coal with ordered pore structure) or can be obtained in a known manner (for example, you can refer to Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764).

According to this invention, no specific limitation to the particle size of the mesoporous carbon, if it satisfies the requirements for catalyst carrier. For example, the particles may have a size of, but not limited to, 10-10000 nm or 10-1000 nm or 10-100 nm. If mesoporous coal consists of particles with non-spherical shape, the size refers to the size along the long axis or length, it is obvious that the experts in this field.

According to this invention, if it is not to be limited to any theory, it can be assumed that the use of mesoporous carbon as a carrier of the catalyst will have a relatively large specific surface area and larger pore size, which facilitates rapid diffusion of reactants and products in the channels of the pores. Compared with the catalyst of the prior art is ehniki (for example, with the conventional catalyst deposited on activated carbon) proposed a catalyst based on copper, deposited on mesoporous carbon, has a relatively superior heat resistance and is not sintered even at a relatively high reaction temperature, it is not deposited coke and not going decontamination, which facilitates a further increase in the conversion of compounds with alkyl chain (and the selectivity for formation of compounds with alkenylphenol chain).

According to this invention, a method of obtaining deposited on mesoporous carbon catalyst based on copper, characterized in that it comprises the following stages:

(1) stage contacting of the precursor of the copper component, the predecessor of the auxiliary element and mesoporous coal in a predetermined ratio, preferably in the presence of a dispersing medium, for example, water) and the intermediate product (hereinafter called the stage of contact), and

(2) the stage of calcination of the intermediate product to obtain deposited on mesoporous carbon catalyst based on copper (hereinafter referred to as stage calcination).

According to this invention, a predetermined ratio should be such that deposited on mesoporous carbon catalyst based on copper after stage calcination had pointed to by the th above composition.

According to this invention, the term "precursor of the copper component" refers to a compound capable of forming the specified copper oxide (e.g., CuO), after annealing at a stage of annealing (2). Preferred is a water soluble salt of copper, such as water-soluble salt of copper, for example, one or more salts are selected from the group consisting of acetates of copper, copper sulphate, copper nitrate and copper halides, for example, one or more salts are selected from the group consisting of acetates of copper nitrate and copper chloride copper, for example, copper acetate(II)nitrate copper(II) or copper chloride(II), etc.

According to this invention, the predecessor of the copper component may be one type or a combination of two or more types.

According to this invention, the term "predecessor subsidiary element" refers to a compound capable of forming a specified oxide auxiliary element (for example, presents the specified chemical formula), after annealing at a stage of annealing (2). Preferred is a water soluble salt of the auxiliary element, including a water-soluble salt of the auxiliary element, such as one or more salts are selected from the group consisting of acetates, sulfates, nitrates and halides auxiliary ale is NTA, for example, one or more salts are selected from the group consisting of sulfates, nitrates and chlorides of the auxiliary element, such as SnCl4, SnSO4, LiNO3, KNO3CH3COOLi or CH3COOK, etc.

According to this invention, it is possible to use the predecessor subsidiary element of the same type or a combination of two or more types.

According to this invention, there are no specific limitations to the sequence or ordering contact with each other starting components (i.e. the predecessor of the copper component, the predecessor of the auxiliary component and mesoporous carbon) at the stage of contact. In addition, according to this invention, no particular limitation on how to conduct a stage of contact, to ensure sufficient contact of the source components and the formation of a homogeneous intermediate product. For example, it is sufficient to mix the associated source components to homogeneity by any means known in this area (if necessary, with stirring).

If necessary for a more dense and uniform contact or for the convenience of contacting stage contacting can be carried out in the presence of a dispersing medium, such as water. Then the intermediate floor is given in the form of a suspension.

Stage contacting is carried out at any temperature in the range of 0-90°C., for example, from room temperature to about 80°C, but this is not the limit. Stage contacting you spend so long in order to obtain a homogeneous intermediate product, usually within 0.05-5 hours without restrictions.

According to this invention, the obtained intermediate product, especially in the form of suspensions, dried by any method known in this field (for example, when 60-150°C or 70-120°C)to remove the dispersion medium (e.g. water), which was introduced during the preparation of the catalyst. According to this invention, the dried product is for simplicity referred to as an intermediate product.

According to this invention, the stage of contacting can be performed in the presence of the reagent, forming complexes with metal (preferably water-soluble reagent, forming complexes with metal), stabilizer and reagent for establishing pH, etc.

According to this invention, the mass ratio of the reagent, forming complexes with metal, and the copper precursor component may be 0.4-2.0. The reagent, forming complexes with metal, contributes to the dispersion of active components (i.e. the copper component and the auxiliary element) on mesoporous angle that increases the activity of the catalyst.

The reagent, forming complexes with metal, can serve as a polybasic carboxylic acid and a polybasic alcohol and polyamine, etc. you Can use the reagent, forming complexes with the metal of one type or a combination of two or more types. When using the combination, the mass ratio of all reagents, forming complexes with metal, and the copper precursor component is in the range of 0.4-2.0.

An example of a polybasic carboxylic acid is an acid with alanovoy group C2-20and 2-10 (preferably 3-6) carboxyl groups, for example, oxalic acid, succinic acid, etc. is Also an example of a polybasic carboxylic acid is albanova group C2-20with one or more (e.g., 1-6) hydroxyl groups, for example, malic acid, tartaric acid, citric acid, etc. Another example of the polybasic carboxylic acid is polycarboxilic(poly)amine obtained by the gap specified alanovoy chain With2-20with one or more nitrogen atoms, for example, nitrilotriacetic acid, EDTA, etc.

An example of a polybasic alcohol is albanova group C2-20with 2-10 (preferably 3-6) hydroxyl groups, for example, ethylene glycol, or the polymer specified polybasic alcohol, for example, polyethylene glycol, or polyhydroxy the Il(poly)amine, educated in the interrupt specified alanovoy chain C2-20one or more nitrogen atoms, for example, monoethanolamine, triethylamine, etc.

Example polyamine is Ethylenediamine, Diethylenetriamine, Triethylenetetramine etc.

An example of a stabilizer known in this field, is ammonium chloride, ammonium sulfate, etc. Reagent to install pH is hydrochloric acid, ammonia, etc.

According to this invention, the reagent, forming complexes with metal (and also the stabilizer and the reagent for ustanovlenija pH, both of which do not necessarily apply if necessary), you can enter at the stage of contact for contact with the mesoporous carbon with or before or after the introduction of the copper precursor component and/or the precursor auxiliary element without any specific limitations.

According to this invention, the predecessor of the copper component and/or the precursor auxiliary element and/or a reagent forming complexes with metal, can be applied in the form of a solution. For convenience, preferred is an aqueous solution. To this end, the predecessor of the copper component and/or the precursor auxiliary element and the reagent, forming complexes with the metal dissolved in the solution separately and then the respective races of the thieves enter into contact simultaneously or one after another or prepared as a mixed solution of two or three components, and then the mixed solution is injected through the probe without any specific restrictions. At the same time or after the specified operation mentioned stabilizer and a reagent for establishing pH, etc. enter, if necessary by any method known in this field, known as the rule number.

According to one variant of the present invention, the stage of contacting includes:

(1a) the Stage of measuring, mixing and dissolution in water of a given amount of copper precursor component, the predecessor of the auxiliary element and the reagent, forming complexes with metal, and the mass ratio of the reagent, forming complexes with metal, and the copper precursor component is in the range of 0.4-2.0; if necessary, the solution is not necessarily to add the right amount of stabilizer reagent for establishing pH, etc. and get water solution.

(1b) the Stage of mixing the aqueous solution with a given number mesoporous coal under stirring and receive suspensions and

(1c) the Stage of drying the suspension (for example, when 60-150°C or 70-120°C) and obtain an intermediate product.

According to this invention, the "predetermined amount" of copper precursor component, the predecessor of the auxiliary element and mesoporous coal is such that it is deposited on mesoporous carbon catalyst based on copper, obtained the settlement of the th stage of calcination, has a composition satisfying the above requirements without additional restrictions. Therefore, the person skilled in the art can determine the appropriate "predetermined amount" of each source component on the basis of these requirements without any specific limitations.

According to this invention, the obtained intermediate product is calcined at a stage of annealing in the following way to obtain a catalyst based on copper, deposited on mesoporous carbon, according to this invention. During combustion of 50 wt.% or more, for example, 80 wt.% or more, for example, 90 wt.% or more all copper (calculated as Cu)contained in the precursor of the copper component, deposited on mesoporous carbon, can be converted into the specified copper oxide and 50 wt.% or more, for example, 80 wt.% or more, for example, 90 wt.% or more of the entire auxiliary element (calculated on a supporting element)contained in the precursor auxiliary element deposited on mesoporous carbon, can be converted into the oxide of the specified corresponding auxiliary element.

According to this invention, the copper content of the component and the supporting element thus obtained deposited on mesoporous charcoal catalyst based on copper, you can define the traditional method of elemental analysis, for example, ICP (inductively coupled plasma) or XRF (x-ray fluorescence analysis), etc. in the form of the corresponding oxide.

Stage calcination is carried out in the atmosphere of inert gas containing no oxygen, at 500-750°C (preferably 560-690°C). Usually calcined within 3-8 hours, and this is not the limit. The term "in the atmosphere of inert gas containing no oxygen" refers to the atmosphere of N2high purity Ar atmosphere of high purity or the atmosphere of high purity, in which the concentration of O2is constant at a level of less than 0.1 vol.%.

According to this invention, the invention relates to the use of this catalyst based on copper, deposited on mesoporous carbon, according to the present invention or the application deposited on mesoporous carbon catalyst based on copper, obtained as described above according to this invention, in the catalytic dehydrogenation of alkyl compounds C2-C12for the conversion of alkyl compounds C2-C12in appropriate alkeneamine connection.

Examples of alkyl compounds C2-C12are any connection with one or more groups C2-C12for example, with an organic skeleton (for example, ethers, hydrocarbons, esters, heterocyclic link is, silicones, silanes, polymers, cellulose and the like) or inorganic skeleton (for example, such esters as titanates, silicates, silicon atom, atom, magnesium atom of aluminum and the like, containing one or more groups with the alkyl chain C2-C12). Preferred are hydrocarbon, C0-30with one or more alkyl groups, C2-C12.

Examples of the hydrocarbon, C0-30are alkanes C1-30type of methane, ethane, propane and the like, cyclic alkanes, such as cyclopropane, CYCLOBUTANE, cyclohexane and the like, alkenes C2-30such as Eten, propene, etc., cycloalkene C2-30such as cyclobutene, cyclohexene etc., alkynes C2-30for example, ethyn, identical propyne and the like, and aromatic hydrocarbons like benzene, toluene, ethylbenzene, naphthalene, styrene, etc.

According to this invention, in the case of hydrocarbon With0i.e. the expression "hydrocarbon With0with one or more alkyl chains C2-C12" refers to alkanal C2-C12for example, alkaram C2-C6for example, ethane, propane, n-butane, tertiary butane, n-pentane, isopentane, n-hexane, etc.

According to this invention, it is obvious that each of the one or more alkyl groups, C2-C12is the side group in the alkyl skeleton of compound C2-C12.

According to this invention, it is preferable that the alkyl compound C2-C12contained 1-5 (preferably 1-3 or 1 or 2 alkyl groups, C2-C12. Examples of alkyl groups C2-C12are ethyl, n-propyl, isopropyl, n-butyl, isobutyl, emop-butyl, n-pentyl and the like, and preferable are alkyl groups of C2-C6for example, ethyl.

According to this invention include hydrocarbon, C0-30with one or more alkyl groups, C2-C12preferred are hydrocarbon, C0-30containing one ethyl group, for example, ethane, propane, isobutane, isopentane, benzene, ethylcyclohexane etc.

You can use alkyl compounds C2-C12one type or two or more types.

According to the application of the present invention, a catalyst based on copper, deposited on mesoporous carbon, according to this invention or supported on mesoporous carbon catalyst based on copper, obtained by the method according to this invention, in contact with alkyl compounds C2-C12(or with a mixture of raw materials from alkyl compounds C2-C12and CO2) for the conversion of the alkyl groups of C2-C12in appropriate alkenylphenol group by reaction of dehydrogenation.

Contacting syshestvyut by any means, known in this field (for example, the choice of the reaction when contacting, the choice of the reactor type, the method of introduction of the catalyst or alkyl compounds C2-C12or a mixture of raw materials etc), so there is no need to describe him except for the following reaction conditions of catalytic dehydrogenation.

According to this invention, the reaction conditions for the catalytic dehydrogenation include a reaction temperature 450-700°C, preferably 520-650°C, pressure of the reaction 0.05-10.0 MPa, preferably 0.8-1.0 MPa, a space velocity of 0.5-40 LH-1cath-1, preferably 1-10 LH-1cath-1. Using the mixture of raw materials, the molar ratio of alkyl compounds C2-C12(for example, ethane, propane, isobutane, isopentane, ethyl benzene, ethylcyclohexane or their combinations), and CO2is from 1:0.1 to 1:40, preferably from 1:0.5 to 1:20.

Optionally, prior to contacting with the catalyst of alkyl compounds C2-C12or mixed feedstock can be preheated before varying between 250 and 600°C, for example, 320-500°C.

According to this invention, when the alkyl compound C2-C12contains only one alkyl group of C2-C12this one alkyl group of C2-C12exposed catalyst on the hydrogenation. If alkyl compound C2-C12contains two or more alkyl groups, C2-C12then apparently at least one (or all, but not necessarily) of two or more alkyl groups, C2-C12subjected to catalytic dehydrogenation, while in some cases it is necessary to degidrirovanii all of the two or more alkyl groups, C2-C12.

In addition, when the catalytic dehydrogenation of alkyl groups of C2-C12usually removing two hydrogen atoms and it turns into a corresponding alkeneamine connection C2-C12. The result is alkeneamine connection C2-C12usually contains only one double bond in the carbon-carbon, but this is not the limit. For the position of the double bond carbon-carbon alkenylphenol group C2-C12there are no specific restrictions, for example, it may be a terminal position or a position adjacent to the terminal position in alkenylphenol group C2-C12but this is not the limit.

According to one particular variant of this invention, the alkyl compound C2-C12is isobutane. Finally, according to this invention, a method of obtaining isobutene, characterized in that it includes a step of contacting opisanog the above deposited on mesoporous carbon catalyst based on copper in this invention or supported on mesoporous carbon catalyst based on copper, received specified by the method according to this invention, a mixed raw material of isobutane and CO2for the conversion of isobutane in isobutene by the reaction of catalytic dehydrogenation.

According to this invention, the reaction conditions for the catalytic dehydrogenation preferably include: a reaction temperature 550-650°C, preferably 560-610°C, pressure of the reaction 0.05-1.0 MPa, preferably 0.06 to 0.5 MPa, a space velocity of 0.5-8 LH-1cath-1, the molar ratio of isobutane and CO2from 1:0.5 to 1:11. Optionally, prior to contacting with the catalyst mixed raw materials can be pre-heated to 300-500°C, for example, 320-450°C.

Examples

This invention is hereinafter described in more detail with reference to the following examples, but is by no means limited to them.

Example 1

42.4 g of copper nitrate(II) and 44.6 g of citric acid was dissolved in 600 ml of water, received a mixed solution, and then to the specified solution was added 158.8 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min in a thermostatic water bath at 70°C, dried at 150°C, probalily at 680°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 99 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, consisting of isobutane and CO2with a molar ratio of isobutane and CO21:6, followed by reaction under the following conditions: a reaction temperature of 630°C, pressure of the reaction of 0.1 MPa and a space velocity of 5 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction is 58% and the selectivity of the formation of isobutene equal to 88.6%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 48%, and the selectivity of the formation of isobutene 89.2%.

Comparative example 1

42.4 g of copper nitrate(II) and 44.6 g of citric acid was dissolved in 600 ml of water, received a mixed solution and then to this solution was added 158.8 g of activated carbon with a specific surface area of 1420 m2g-1and a most probable pore size of 0.8 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 150°C, probalily at 680°C in nitrogen atmosphere for 5 hours and got deposited on activated carbon catalyst based on copper, containing a measured quantity of CuO, equal to 10.1 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340 is With, consisting of isobutane and CO2with a molar ratio of isobutane and CO21:6, followed by reaction under the following conditions: a reaction temperature of 630°C, pressure of the reaction of 0.1 MPa and a space velocity of 5 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, is 33% and the selectivity of the formation of isobutene equal 89.1%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 14%, and the selectivity of the formation of isobutene 90.2%.

Example 2

10.0 g of copper acetate(II) and 20.1 g of citric acid dissolved in 1150 ml of water, received a mixed solution, and then to the specified solution was added 214.5 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) with a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 120°C, probalily at 680°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 2.0 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 300°C, from isobutane and CO2with a molar ratio of isobutane and CO equal to 1:4, followed by reaction under the following conditions: a reaction temperature of 630°C, pressure of the reaction of 0.1 MPa and a space velocity of 4 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 37% and the selectivity of the formation of isobutene 89.0%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 24%, and the selectivity of the formation of isobutene 91.2%.

Example 3

21.4 g of copper nitrate(II) and 38.6 g of citric acid was dissolved in 600 ml of water, received a mixed solution, and then to the specified solution was added 158.8 g disordered mesoporous carbon a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764). Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 120°C, probalily at 680°C in nitrogen atmosphere for 3 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 5.0 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO21:6, followed by reaction under the following conditions: a reaction temperature of 630°C, the providing of the reaction of 0.1 MPa and a space velocity of 5 LH -1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 48% and the selectivity of the formation of isobutene 90.4%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 38%, and the selectivity of the formation of isobutene 91.2%.

Example 4

74.4 g of copper chloride(II) and 30.4 g of citric acid was dissolved in 600 ml of water, received a mixed solution and then to this solution was added 176.8 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) with a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 120°C, probalily at 680°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 20.0 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 300°C, from isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:4, followed by reaction under the following conditions: a reaction temperature of 630°C, pressure of the reaction of 0.1 MPa and a space velocity of 4 LH-1cath-1. In the conversion of isobutane is determined after 1 hour, the donkey start of the reaction, was 42% and the selectivity of the formation of isobutene 86.0%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 30%, and the selectivity of the formation of isobutene 89.5%.

Example 5

12.7 g of copper nitrate(II), 0.5 g of SnCl2and 5.1 g of citric acid dissolved in 2149 ml of water, received a mixed solution and then to this solution was added 173.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 120°C, probalily at 690°C in nitrogen atmosphere for 3 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 3.0 wt.%, and a measured quantity of SnO2equal to 0.2 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 320°C, isobutane and CO2with a molar ratio of isobutane and CO21:11, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 5 LH-1cath-1.

In the conversion of isobutane is determined after 1 hour after start of the reaction, was 52% and the selectivity of the formation of isobutene 89.7%, while the conversion of the Isobe is Ana, it is determined by 3 h after start of the reaction, equal to 43%, and the selectivity of the formation of isobutene 90.5%.

Comparative example 1

12.6 g of copper nitrate(II) and 5.1 g of citric acid dissolved in 2149 ml of water, received a mixed solution and then to this solution was added 173.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 120°C, probalily at 690°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 3.0 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 320°C, isobutane and CO2with a molar ratio of isobutane and CO21:11, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and a space velocity of 5 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 48% and the selectivity of the formation of isobutene 90.3%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 31%, and the selectivity of the formation of isobutene 90.8%.

Example 6

26.0 g of copper nitrate(II), 1.4 g SnC 2and 26.0 g of citric acid dissolved in 2149 ml of water, received a mixed solution, and then this solution was added 207.6 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 80°C, probalily at 610°C in nitrogen atmosphere for 8 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 5.1 wt.%, and a measured quantity of SnO2equal to 0.5 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO21:6, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 3 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 57% and the selectivity of the formation of isobutene 85.3%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 52%, and the selectivity of the formation of isobutene 89.4%.

Example 7

27.5 g of copper acetate(II), 1.7 g SnSO4and 55.0 g of citric acid was dissolved in 600 ml of water, received a mixed solution and then the this solution was added 105.6 g CMK-3 - mesoporous carbon a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 680°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 9.9 wt.%, and a measured quantity of SnO2equal to 0.9 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 450°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:4, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 3 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 56% and the selectivity of the formation of isobutene 89.97%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 56%, and the selectivity of the formation of isobutene 89.9%.

Example 8

20.2 g of copper chloride(II), 2.6 g SnSO4and 40.0 g of citric acid dissolved in 700 ml of water, received a mixed solution and to this solution was added 105.6 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) is attached to the second surface 1230 m 2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 680°C in nitrogen atmosphere for 3 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 10.1 wt.%, and a measured quantity of SnO2equal to 1.5 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 380°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:2, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and a space velocity of 5 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 68% and the selectivity of the formation of isobutene 83.9%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 59%, and the selectivity of the formation of isobutene 90.8%.

Example 9

34.6 g of copper acetate(II), 2.9 g of SnCl2and 26.0 g of citric acid were dissolved in 1000 ml of water, received a mixed solution and then to this solution was added 98.7 g industrial mesoporous carbon (LD-7, Nanjing Linda Activated Carbon Co., Ltd) with a specific surface area of 980 m2g-1and a most probable pore size of 2.2 nm. the ATEM and the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 110°C, probalily at 560°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 12.9 wt.%, and a measured quantity of SnO2equal to 2.0 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 320°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:0.5, followed by reaction under the following conditions: a reaction temperature of 550°C, pressure of the reaction of 0.1 MPa and a space velocity of 8 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 38% and the selectivity of the formation of isobutene 96.7%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 35%, and the selectivity of the formation of isobutene 98.1%.

Example 10

43.6 g of copper nitrate(II), 2.1 g of SnCl2and 44.6 g of citric acid dissolved in 650 ml of water, received a mixed solution and then to this solution was added 103.4 g industrial mesoporous carbon (LD-7, Nanjing Linda Activated Carbon Co., Ltd) with a specific surface area of 980 m2g-1and a most probable pore size of 2.2 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 640°C in an atmosphere of azo is within 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 15.0 wt.%, and a measured quantity of SnO2equal to 1.5 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:8, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and a space velocity of 5 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 70% and the selectivity of the formation of isobutene 87.1%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 61%, and the selectivity of the formation of isobutene 89.3%.

Example 11

26.0 g of copper nitrate(II), 1.4 g of metavanadate ammonium and 26.0 g of citric acid were dissolved in 800 ml of water, received a mixed solution and then to this solution was added 230.6 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 80°C, probalily at 630°C in nitrogen atmosphere for 8 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 4.3 wt.%, and a measured quantity V 2O5equal to 0.4 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO21:6, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 51% and the selectivity of the formation of isobutene 86.1%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 43%, and the selectivity of the formation of isobutene 89.3%.

Example 12

30.3 g of copper chloride(II), 13.3 g LiNO3and 44.6 g of citric acid was dissolved in 600 ml of water, received a mixed solution and then to this solution was added 158.8 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 150°C, probalily at 680°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 9.7 wt.%, and a measured quantity of Li2O, is equal to 1.6 wt.%. The catalyst was loaded into a reactor with a fixed bed and this is the reactor gave a mixed raw material, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO21:6, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 59% and the selectivity of the formation of isobutene 91.2%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 55%, and the selectivity of the formation of isobutene 91.6%.

Example 13

30.3 g of copper nitrate(II), 19.3 g LiNO3and 44.6 g of citric acid were dissolved in 800 ml of water, received a mixed solution and then to this solution was added 158.8 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 150°C, probalily at 670°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 7.8 wt.%, and a measured quantity of Li2O, equal to 2.1 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO 21:6, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 56% and the selectivity of the formation of isobutene 92.4%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 51%, and the selectivity of the formation of isobutene 92.7%.

Example 14

38.3 g of copper nitrate(II), 5.2 g LiNO3and 49.6 g of citric acid dissolved in 700 ml of water, received a mixed solution and then to this solution was added 152.7 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 150°C, probalily at 680°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 9.2 wt.%, and a measured quantity of Li2O equal to 0.5 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 350°C from isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:10, followed by reaction under the following conditions: a reaction temperature of 600°C, giving the giving the reaction of 0.1 MPa and space velocity 1 LH -1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 57% and the selectivity of the formation of isobutene 90.4%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 53%, and the selectivity of the formation of isobutene 91.2%.

Example 15

19.0 g of copper nitrate(II), 1.4 g of Mg(NO3)2and 26.0 g of citric acid dissolved in 2149 ml of water, received a mixed solution and then to this solution was added 210.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 80°C, probalily at 610°C in nitrogen atmosphere for 8 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 3.5 wt.%, and a measured quantity of MgO, equal to 0.9 wt.%. The catalyst was loaded into a reactor with a moving bed of catalyst in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO21:6, followed by reaction under the following conditions: a reaction temperature of 620°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the conversion of isobutane defined che is ez 1 hour after start of the reaction, was 51% and the selectivity of the formation of isobutene 85.3%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 41%, and the selectivity of the formation of isobutene 86.2%.

Example 16

28.2 g of copper acetate(II), 2.1 g of CaCl2and 31.0 g of citric acid were dissolved in 1000 ml of water, received a mixed solution and then to this solution was added 220.3 g industrial mesoporous carbon (LD-7, Nanjing Linda Activated Carbon Co., Ltd) with a specific surface area of 980 m2g-1and a most probable pore size of 2.2 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 110°C, probalily at 560°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 4.9 wt.%, and a measured quantity of CaO equal to 0.4 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 320°C, isobutane and CO2with a molar ratio of isobutane and CO21:9, followed by reaction under the following conditions: a reaction temperature of 620°C, pressure of the reaction of 0.1 MPa and a space velocity of 10 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction was 50% and the selectivity of the formation of isobutene 87.1%, at the time as the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 40%, and the selectivity of the formation of isobutene 88.4%.

Example 17

19.2 g of copper nitrate(II), 3.5 g of gallium nitrate(III) and 34.6 g of citric acid dissolved in 650 ml of water, received a mixed solution and then to this solution was added 197.6 g industrial mesoporous carbon (LD-7, Nanjing Linda Activated Carbon Co., Ltd) with a specific surface area of 980 m2g-1and a most probable pore size of 2.2 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 640°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 3.8 wt.%, and a measured quantity of Ga2O3equal to 0.4 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:8, followed by reaction under the following conditions: a reaction temperature of 620°C, pressure of the reaction of 0.1 MPa and a space velocity of 3 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 54% and the selectivity of the formation of isobutene 86.7%, while the conversion of isobutane, it is determined by 3 h after the beginning of R the shares, equal to 48%, and the selectivity of the formation of isobutene 88.1%.

Example 18

21.6 g of copper nitrate(II), 4.2 g of Zn(NO3)2and 40.6 g of citric acid dissolved in 650 ml of water, received a mixed solution and then to this solution was added 103.4 g industrial mesoporous carbon (LD-7, Nanjing Linda Activated Carbon Co., Ltd) with a specific surface area of 980 m2g-1and a most probable pore size of 2.2 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 640°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 4.1 wt.%, and a measured quantity of ZnO equal to 0.8 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:10, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and a space velocity of 3 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 55% and the selectivity of the formation of isobutene 85.1%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 48%, and the selectivity of the formation of isobutene 88.6%.

Example 19

34.0 g of copper nitrate(II), 4.1 g of Al(NO3)3and 19.2 g of citric acid dissolved in 650 ml of water, received a mixed solution and then to this solution was added 240.1 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 640°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, 5.8 wt.%, and a measured quantity of Al2O3equal to 0.3 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 390°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:10, followed by reaction under the following conditions: a reaction temperature of 620°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 59% and the selectivity of the formation of isobutene 87.91%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, 50%, and the selectivity of the formation of isobutene 88.6%.

Example 20

29.2 g of copper nitrate(II), 2.0 g of cerium nitrate and 48.6 g of citric keys which the notes were dissolved in 1200 ml of water, got mixed solution and then to this solution was added 298.0 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 640°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 3.7 wt.%, and a measured quantity of CeO2equal to 0.3 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO21:9, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 4 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction was 62% and the selectivity of the formation of isobutene 85.0%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 55%, and the selectivity of the formation of isobutene 87.6%.

Example 21

22.2 g of copper nitrate(II), 2.0 g LaCl3and 24.6 g of citric acid were dissolved in 1000 ml of water, received a mixed solution and then to this solution was added 298.0 g CMK-3 - mesoporous carbon is with a specific surface area of 1320 m 2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 640°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 2.8 wt.%, and a measured quantity of La2O3equal to 1.1 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:10, followed by reaction under the following conditions: a reaction temperature of 630°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 69% and the selectivity of the formation of isobutene 84.8%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 59%, and the selectivity of the formation of isobutene 86.6%.

Example 22

42.4 g of copper nitrate(II), 4.0 g of KNO3and 44.6 g of citric acid was dissolved in 600 ml of water, received a mixed solution and then to this solution was added 158.8 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 m is n on temperature-controlled water bath at 70°C, dried at 150°C, probalily at 670°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 9.9 wt.%, and measured the number of K2O, is equal to 0.9 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:4, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 55% and the selectivity of the formation of isobutene 90.4%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 51%, and the selectivity of the formation of isobutene 90.6%.

Example 23

34.8 g of copper nitrate(II), 9.8 g KNO3and 44.6 g of citric acid was dissolved in 600 ml of water, received a mixed solution and then to this solution was added 188.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 80°C, dried at 120°C, probalily at 660°C in nitrogen atmosphere for 6 hours and got nanesennya mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 7.5 wt.%, and measured the number of K2O, equal to 2.1 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:10, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 51% and the selectivity of the formation of isobutene 91.1%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 46%, and the selectivity of the formation of isobutene 91.7%.

Example 24

12.7 g of copper nitrate(II), 0.9 g of SnCl2, 1.2 g LiNO3and 7.1 g of citric acid dissolved in 2149 ml of water, received a mixed solution and then to this solution was added 173.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 80°C, dried at 120°C, probalily at 690°C in nitrogen atmosphere for 3 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 3.0 wt.%, measured SnO 2equal to 0.3 wt.%, and a measured quantity of Li2O, equal to 0.1 wt%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 320°C, isobutane and CO2with a molar ratio of isobutane and CO21:11, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 3 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 56% and the selectivity of the formation of isobutene 90.7%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 54%, and the selectivity of the formation of isobutene 91.2%.

Example 25

12.7 g of copper nitrate(II), 0.9 g of SnCl2, 1.2 g KNO3and 9.3 g of citric acid dissolved in 2149 ml of water, received a mixed solution and then to this solution was added 173.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 80°C, dried at 120°C, probalily at 690°C in nitrogen atmosphere for 3 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 3.0 wt.%, a measured quantity of SnO2equal to 0.3 wt.%, and edit the counter the number of K 2O equal to 0.3 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:8, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 61% and the selectivity of the formation of isobutene 91.7%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 58%, and the selectivity of the formation of isobutene 92.3%.

Example 26

18.9 g of copper nitrate(II), 0.9 g LiNO3, 1.2 g KNO3and 10.1 g of citric acid dissolved in 2000 ml of water, received a mixed solution and then to this solution was added 173.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 120°C, probalily at 690°C in nitrogen atmosphere for 3 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 4.1 wt.%, a measured quantity of Li2O, equal to 0.1 wt.%, and measured the number of K2O equal to 0.3 wt.%. Kata is isator loaded in a reactor with a fixed bed in the reactor gave a mixed raw material, preheated to 320°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:5, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 59% and the selectivity of the formation of isobutene 87.7%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 56%, and the selectivity of the formation of isobutene 92.3%.

Example 27

18.9 g of copper nitrate(II), 1.8 g of SnCl2, 2.4 g LiNO3, 2.7 g KNO3and 20.1 g of citric acid dissolved in 2000 ml of water, received a mixed solution and then to this solution was added 148.8 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 120°C, probalily at 630°C in nitrogen atmosphere for 3 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 4.6 wt.%, a measured quantity of SnO2equal to 0.8 wt.%, a measured quantity of Li2O equal to 0.3 wt.%, and measured the number of K2O equal to 0.7 wt.%. The catalyst was loaded into a reactor with a fixed bed and in which the reactor gave a mixed raw material, pre-heated to 350°C from isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:4, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 61% and the selectivity of the formation of isobutene 91.4%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 59%, and the selectivity of the formation of isobutene 92.3%.

Example 28

37.5 g of copper nitrate(II) and 48.7 g of tartaric acid was dissolved in 600 ml of water, received a mixed solution and to this solution was added 210.3 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 140°C, probalily at 670°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 6.8 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 330°C, isobutane and CO2with a molar ratio of isobutane and CO2equal to 1:10, followed by reaction under the following conditions: rate is the atur reaction 650°C, the pressure of the reaction 0.08 MPa and space velocity 4 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 65% and the selectivity of the formation of isobutene 69.6%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 55%, and the selectivity of the formation of isobutene 70.2%.

Example 29

42.2 g of copper nitrate(II), 4.2 g of KNO3and 55.5 g of ethylene glycol were dissolved in 600 ml of water, received a mixed solution and to this solution was added 196.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 150°C, probalily at 680°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 8.1 wt.%, and measured the number of K2O equal to 0.8 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO21:9, followed by reaction under the following conditions: a reaction temperature of 650°C, pressure of the reaction 0.08 MPa and space velocity 2 LH-1cath-1. In the converse which I isobutane, certain 1 hour after start of the reaction, was 74% and the selectivity of the formation of isobutene 71.1%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 71%, and the selectivity of the formation of isobutene 71.6%

Example 30

39.2 g of copper nitrate(II), 6.0 g of cerium nitrate(III) and 51.6 g of citric acid dissolved in 1200 ml of water, received a mixed solution and to this solution was added 285.0 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 660°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 5.1 wt.%, and a measured quantity of CeO2equal to 1.0 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isobutane and CO2with a molar ratio of isobutane and CO21:11, followed by reaction under the following conditions: a reaction temperature of 645°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the conversion of isobutane is determined after 1 hour after start of the reaction, was 72% and the selectivity of the formation and is of obucina 68.1%, while the conversion of isobutane, it is determined by 3 h after start of the reaction, equal to 67%, and the selectivity of the formation of isobutene 68.8%

Example 31

The catalyst of example 25 was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, ethane and CO2with a molar ratio of ethane and CO2equal to 1:8, followed by reaction under the following conditions: a reaction temperature of 650°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the result, the conversion of ethane determined after 1 hour after start of the reaction, was 72% and the selectivity of the formation of ethane 70.3%, while the conversion of ethane, it is determined by 3 h after start of the reaction, equal to 68%, and the selectivity of the formation of ethane 71.2%.

Example 32

32.7 g of copper nitrate(II) and 48.7 g of glycerol were dissolved in 600 ml of water, received a mixed solution and then to this solution was added 158.8 g CMK-3, a mesoporous carbon a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 140°C, probalily at 660°C in nitrogen atmosphere for 6 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 7.8 wt.%. The catalyst was loaded into reactor fixed bed in the reactor gave a mixed raw material, preheated to 330°C, propane and CO2with a molar ratio of propane and CO2equal to 1:10, followed by reaction under the following conditions: a reaction temperature of 580°C, pressure of the reaction 0.09 MPa and space velocity 3 LH-1cath-1. In the result, the conversion of propane, some within 1 hour after start of the reaction, was 27% and the selectivity of the formation of propane 95.1%, while the conversion of propane, some 3 hours after start of the reaction, equal to 22%, and the selectivity of the formation of propane 95.3%.

Example 33

29.6 g of copper chloride(II), 4.6 g of SnCl2and 40.0 g of ethylene glycol were dissolved in 1400 ml of water, received a mixed solution and to this solution was added 210.2 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) with a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 660°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 7.5 wt.%, and a measured quantity of SnO2equal to 1.5 wt.%. The catalyst was loaded into a fluidized bed reactor and in the reactor gave a mixed feedstock, preheated to 380°C, propane and C 2with a molar ratio of propane and CO2equal to 1:10, followed by reaction under the following conditions: a reaction temperature of 590°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the result, the conversion of propane, some within 1 hour after start of the reaction was 33% and the selectivity of the formation of propane 92.3%, while the conversion of propane, some 3 hours after start of the reaction, equal to 26%, and the selectivity of the formation of propane 93.2%.

Example 34

23.6 g of copper nitrate(II), 9.2 g of Mg(NO3)2and 36.0 g of citric acid were dissolved in 1600 ml of water, received a mixed solution and then to this solution was added 232.1 g disordered mesoporous carbon a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764). Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 80°C, probalily at 640°C in nitrogen atmosphere for 8 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 4.0 wt.%, and a measured quantity of MgO, equal to 1.6 wt.%. The catalyst was loaded into a reactor with a moving bed in the reactor gave a mixed feedstock, preheated to 340°C, propane and CO2with a molar ratio disappear to the and and CO 21:7, followed by reaction under the following conditions: a reaction temperature of 610°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the result, the conversion of propane, some within 1 hour after start of the reaction, was 31% and the selectivity of the formation of propane 93.3%, while the conversion of propane, some 3 hours after start of the reaction, equal to 25%, and the selectivity of the formation of propane 93.6%.

Example 35

The catalyst of example 26 was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 350°C, propane and CO2with a molar ratio of propane and CO2equal to 1:4, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the result, the conversion of propane, some within 1 hour after start of the reaction was 33% and the selectivity of the formation of propane 94.1%, while the conversion of propane, some 3 hours after start of the reaction, equal to 31%, and the selectivity of the formation of propane 94.6%.

Example 36

35.1 g of copper nitrate(II) and 34.7 g of ethylene glycol were dissolved in 1000 ml of water, received a mixed solution and then to this solution was added 200.1 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) with the additional surface 1230 m 2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 140°C, probalily at 660°C in nitrogen atmosphere for 6 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 6.8 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 330°C, isopentane and CO2with a molar ratio of isopentane and CO2equal to 1:5, followed by reaction under the following conditions: a reaction temperature of 560°C, pressure of the reaction 0.09 MPa and space velocity 3 LH-1cath-1. In the conversion of isopentane determined after 1 hour after start of the reaction, was 42% and the selectivity of the formation of isopentane 74.2%, while the conversion of isopentane, and it is determined by 3 h after start of the reaction, equal to 33%, and the selectivity of the formation of isopentane 74.8%.

Example 37

33.3 g of copper nitrate(II), 3.3 g of metavanadate ammonium and 26.0 g of oxalic acid was dissolved in 1100 ml of water, received a mixed solution and then to this solution was added 211.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water Banari 70°C, dried at 80°C, probalily at 650°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 6.0 wt.%, and a measured quantity of V2O5equal to 1.0 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 340°C, isopentane and CO2with a molar ratio of isopentane and CO21:6, followed by reaction under the following conditions: a reaction temperature of 560°C, pressure of the reaction 0.09 MPa and space velocity 1 LH-1cath-1. In the conversion of isopentane determined after 1 hour after start of the reaction, was 49% and the selectivity of the formation of isopentane and isopentane 80.6%, while the conversion of isopentane, and it is determined by 3 h after start of the reaction, equal to 43%, and the selectivity of the formation of isopentane and isopentane 81.2%.

Example 38

33.3 g of copper nitrate(II), 3.3 g of metavanadate ammonium, 6.0 g LiNO3and 26.0 g of oxalic acid was dissolved in 1100 ml of water, received a mixed solution and then to this solution was added 211.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 80°is, he probalily at 650°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO equal to 6.0 wt.%, and a measured quantity of V2O5equal to 1.0 wt.%, and a measured quantity of Li2O equal to 0.5 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 330°C, isopentane and CO2with a molar ratio of isopentane and CO21:11, followed by reaction under the following conditions: a reaction temperature of 560°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the conversion of isopentane determined after 1 hour after start of the reaction, was 51% and the selectivity of the formation of isopentane and isopentane amounted to a total of 83.6%, while the conversion of isopentane, and it is determined by 3 h after start of the reaction, equal to 49%, and the selectivity of the formation of the amount of isopentane and isopentane 84.2%.

Example 39

The catalyst from example 27 was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 330°C, isopentane and CO2with a molar ratio of isopentane and CO2equal to 1:8, followed by reaction under the following conditions: a reaction temperature of 550°C, pressure of the reaction of 0.1 MPa and the volume is of MNA speed 1 LH -1cath-1. In the conversion of isopentane determined after 1 hour after start of the reaction, was 48% and the selectivity of the formation of the amount of isopentane and isopentane 80.2%, while the conversion of isopentane, and it is determined by 3 h after start of the reaction, equal to 46%, and the selectivity of the formation of the amount of isopentane and isopentane 80.6%.

Example 40

35.1 g of copper chloride(II) and 34.7 g of ethylene glycol were dissolved in 1000 ml of water, received a mixed solution and then to this solution was added 210.2 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) with a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 140°C, probalily at 640°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 8.9 mass %. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 350°C., from ethyl benzene and CO2with a molar ratio of ethylbenzene and CO2equal to 1:8, followed by reaction under the following conditions: a reaction temperature of 490°C, pressure of the reaction 0.08 MPa and space velocity 3 LH-1cath-1. In financial p is Tata conversion of ethylbenzene, certain 1 hour after start of the reaction, was 58% and the selectivity of the formation of styrene 94.1%, while the conversion of ethylbenzene, it is determined by 3 h after start of the reaction, 50%, and the selectivity of the formation of styrene 94.9%.

Example 41

35.1 g of copper chloride(II), 6.4 Zn(NO3)2and 45.6 g of citric acid dissolved in 1200 ml of water, received a mixed solution and then to this solution was added 210.2 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) with a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 640°C. in a nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 8.7 mass %, and a measured quantity of ZnO, 1.0%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 350°C., from ethyl benzene and CO2with a molar ratio of ethylbenzene and CO2equal to 1:4, followed by reaction under the following conditions: a reaction temperature of 500°C, pressure of the reaction 0.09 MPa and space velocity 6 LH-1cath-1. In the result, the conversion of ethylbenzene determined after 1 h the s after start of the reaction, was 58% and the selectivity of the formation of styrene 93.9%, while the conversion of ethylbenzene, it is determined by 3 h after start of the reaction, equal to 53%, and the selectivity of the formation of styrene 94.4%.

Example 42

40.3 g of copper chloride(II), 5.1 g of Zn(NO3)2, 3.8 g KNO3and 45.6 g of citric acid dissolved in 1200 ml of water, received a mixed solution and then to this solution was added 230.3 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) with a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 160°C, probalily at 660°C in nitrogen atmosphere for 6 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 9.1 mass %, a measured quantity of ZnO, equal to 0.8%, and a measured quantity of K2O equal to 0.6 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 350°C., from ethyl benzene and CO2with a molar ratio of ethylbenzene and CO2equal to 1:8, followed by reaction under the following conditions: a reaction temperature of 470°C, the pressure of the reaction 0.08 MPa and space velocity 3 LH-1cath-1. In the result, the conversion of ethylbenzene, particularly the I within 1 hour after start of the reaction, was 47% and the selectivity of the formation of styrene 96.1%, while the conversion of ethylbenzene, it is determined by 3 h after start of the reaction, equal to 44%, and the selectivity of the formation of styrene 96.8%.

Example 43

18.9 g of copper nitrate(II), 1.8 g of SnCl2, 2.4 g LiNO3, 2.7 g KNO3and 20.1 g of ethylene glycol were dissolved in 2000 ml of water, received a mixed solution and then to this solution was added 148.8 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 120°C, probalily at 590°C in nitrogen atmosphere for 3 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 4.5 mass %, a measured quantity of SnO2equal to 0.9%, a measured quantity of Li2O equal to 0.3 wt.%, and measured the number of K2O equal to 0.7 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 350°C., from ethyl benzene and CO2with a molar ratio of ethylbenzene and CO2equal to 1:4, followed by reaction under the following conditions: a reaction temperature of 480°C, pressure of the reaction of 0.1 MPa and a space velocity of 2 LH-1cath-1. In the result, the conversion of ethylbenzene, opredelennyje 1 hour after start of the reaction, was 62% and the selectivity of the formation of styrene 96.4%, while the conversion of ethylbenzene, it is determined by 3 h after start of the reaction, equal to 59%, and the selectivity of the formation of styrene 96.9%.

Example 44

33.0 g of copper acetate(II) and 34.7 g of citric acid were dissolved in 1000 ml of water, received mixed dissolve then to this solution was added 190.3 g disordered mesoporous carbon (obtained according to the Journal of Materials Chemistry, Vol.19, 2009, pp.7759-7764) with a specific surface area of 1230 m2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 140°C, probalily at 620°C in nitrogen atmosphere for 8 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 6.9 mass %. The catalyst was loaded into a reactor with a moving bed in the reactor gave a mixed feedstock, preheated to 340°C, from ethylcyclohexane and CO2with a molar ratio of ethylcyclohexane and CO2equal to 1:5, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction 0.08 MPa and space velocity 2 LH-1cath-1. In the conversion of ethylcyclohexane determined after 1 hour after start of the reaction, was 56% and the selectivity of the formation of ethylcyclohexane 72.2%, at the time as conversion of ethylcyclohexane, it is determined by 3 h after start of the reaction, equal to 47%, and the selectivity of the formation of ethylcyclohexane 73.2%.

Example 45

34.0 g of copper acetate(II), 6.1 g of Al(NO3)3and 39.2 g of citric acid dissolved in 1200 ml of water, received a mixed solution and then to this solution was added 230.1 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 6.0 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 100°C, probalily at 630°C in nitrogen atmosphere for 6 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, 5.8 mass %, and a measured quantity of Al2O3equal to 0.7 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 330°C, from ethylcyclohexane and CO2with a molar ratio of ethylcyclohexane and CO2equal to 1:10, followed by reaction under the following conditions: a reaction temperature of 620°C, pressure of the reaction of 0.1 MPa and a space velocity of 3 LH-1cath-1. In the conversion of ethylcyclohexane determined after 1 hour after start of the reaction, was 58% and the selectivity of the formation of vinylcyclohexane 76.3%, while the conversion of ethylcyclohexane determined after 3 h p is after the beginning of the reaction, equal to 49%, and the selectivity of the formation of vinylcyclohexane 76.8%.

Example 46

43.3 g of copper acetate(II), 2.8 g of metavanadate ammonium, 6.0 g of cerium nitrate(III) and 34.0 g of oxalic acid was dissolved in 1100 ml of water, received a mixed solution and then to this solution was added 211.2 g CMK-3 - of mesoporous carbon with a specific surface area of 1320 m2g-1and a most probable pore size of 4.3 nm. Then the mixture was stirred 10 min at the temperature-controlled water bath at 70°C, dried at 80°C, probalily at 650°C in nitrogen atmosphere for 5 hours and got deposited on mesoporous carbon catalyst based on copper, containing a measured quantity of CuO, equal to 7.6 mass %, a measured quantity of V2O5equal to 0.8 wt.%, and a measured quantity of CeO2equal to 1.1 wt.%. The catalyst was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 350°C from ethylcyclohexane and CO2with a molar ratio of ethylcyclohexane and CO21:11, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and a space velocity of 8 LH-1cath-1. In the conversion of ethylcyclohexane determined after 1 hour after start of the reaction, was 57% and the selectivity of the formation of vinylcyclohexane 76.2%, while the conversion of ethylcyclohexane is, it is determined by 3 h after start of the reaction, equal to 51%, and the selectivity of the formation of vinylcyclohexane 77.5%.

Example 47

The catalyst from example 27 was loaded into a reactor with a fixed bed in the reactor gave a mixed feedstock, preheated to 330°C, from ethylcyclohexane and CO2with a molar ratio of ethylcyclohexane and CO2equal to 1:8, followed by reaction under the following conditions: a reaction temperature of 600°C, pressure of the reaction of 0.1 MPa and space velocity 1 LH-1cath-1. In the conversion of ethylcyclohexane determined after 1 hour after start of the reaction, was 67% and the selectivity of the formation of the sum of vinylcyclohexane and ethylcyclohexane 80.2%, while the conversion of ethylcyclohexane defined in 3 hours after start of the reaction is equal to 65%, and the selectivity of the formation of vinylcyclohexane and ethylcyclohexane together 80.8%.

1. Deposited on mesoporous carbon catalyst based on copper for catalytic dehydrogenation of compounds with alkyl chain C2-C12including mesoporous carbon, a copper component and an auxiliary element, applied to the specified mesoporous carbon,
one or more support elements (as oxides) are selected from the group consisting of V2O5, Li2O, MgO, Cao, Ga2O3, ZnO, Al2About3 CeO2La2O3, SnO2and K2O,
the amount of the copper component (calculated as CuO) is 2-20 wt.% calculated on the total weight of the catalyst, the number of auxiliary element (based on the specified oxide) is 0-3 wt.% and the number mesoporous coal is 77.1-98 wt.% calculated on the total weight of the catalyst.

2. Deposited on mesoporous carbon catalyst based on copper according to claim 1, in which one or more support elements (as oxide) selected from the group consisting of SnO2, Li2O, combination SnO2and Li2O, combination SnO2and K2O, the combination of Li2O and K2O and combinations SnO2, K2O and Li2O.

3. Deposited on mesoporous carbon catalyst based on copper according to claim 1, in which the amount of the copper component (calculated as CuO) is 3-15 wt.% calculated on the total weight of the catalyst, the number of auxiliary element (based on the specified oxides) is 0.2-2.0 wt.% and the number mesoporous coal is 83-96 .8 wt.%.

4. Deposited on mesoporous carbon catalyst based on copper according to claim 1, in which the number mesoporous coal is the rest mass of the catalyst.

5. Deposited on mesoporous carbon catalyst based on copper according to claim 1, which consists mainly mesoporous carbon, copper com is Ananta and auxiliary element.

6. Deposited on mesoporous carbon catalyst based on copper according to claim 1, in which the mesoporous carbon has a specific surface area by BET 1200-3100 m2g-1the most probable pore size of 2-8 nm, pore volume 1.0-2.1 ml g-1and misoprostol 75-100%.

7. Deposited on mesoporous carbon catalyst based on copper according to claim 1, in which one or more mesoporous carbons selected from the group consisting of mesoporous coal with an ordered pore structure of carbon nanotubes, carbon nanorods or mesoporous carbon disordered porous structure.

8. The method of obtaining deposited on mesoporous carbon catalyst based on copper, characterized in that it includes:
(1) stage contacting of the precursor of the copper component, the predecessor of the auxiliary element and mesoporous coal in a predetermined ratio with the formation of an intermediate product, and
(2) the stage of calcination of the intermediate product and get deposited on mesoporous carbon catalyst based on copper, in which one or more support elements (as oxide) selected from the group consisting of V2O5, Li2O, MgO, Cao, Ga2O3, ZnO, Al2About3CeO2La2O3, SnO2and K2O, preferably SnO2, Li2O, combination SnO2and Li2O combination SnO 2and K2O, the combination of Li2O and K2O or a combination of SnO2, K2O and Li2O,
the specified value is such that it is deposited on mesoporous carbon catalyst based on copper, obtained after calcination, has the following composition,
the amount of the copper component (calculated as CuO) is 2-20 wt.% calculated on the total weight of the catalyst,
the number of auxiliary component (based on the specified oxide) is 0-3 .0 wt.% calculated on the total weight of the catalyst and the amount of mesoporous coal is 77.1-98 wt.%.

9. The method according to claim 8, in which the copper precursor component is a water-soluble salt of copper and a predecessor of the auxiliary element is a water-soluble salt of the auxiliary element.

10. The method according to claim 9, in which a water-soluble salt of copper selected from the group consisting of acetates of copper, copper sulphate, copper nitrate and copper halides, and water-soluble salt of the auxiliary element selected from the group consisting of acetates, sulfates, nitrates and halides of the auxiliary element.

11. The method of claim 8 in which the supporting element (oxide) selected from the group consisting of SnO2, Li2O, combination SnO2and Li2O, combination SnO2and K2O, the combination of Li2O and K2O and combine the AI SnO 2, K2O and Li2O.

12. The method according to claim 8, in which the calculation on the total weight of the catalyst, the amount of the copper component (calculated as CuO) is 3-15 wt.%, calculated on the total weight of the catalyst, the number of auxiliary element (based on the specified oxide) is 0.2-2.0 wt.% and the number mesoporous coal is 83-96 .8 wt.% calculated on the total weight of the catalyst.

13. The method according to claim 8, in which the number mesoporous coal is the rest mass of the catalyst.

14. The method according to claim 8, in which the contacting is carried out in the presence of the reagent, forming complexes with metal, and the mass ratio of the reagent, forming complexes with metal, and the copper precursor component is in the range of 0.4-2.0.

15. The method according to claim 8, in which the calcination is carried out in the atmosphere of inert gas containing no oxygen, when 560-690°C.

16. Application deposited on mesoporous carbon catalyst based on copper according to claim 1 or the use deposited on mesoporous carbon catalyst based on copper, obtained by the method according to claim 8, in the catalytic dehydrogenation of compounds with alkyl chain C2-C12for the conversion of compounds with alkyl chain C2-C12in connection with the corresponding alkenylphenol chain.

17. The application of clause 16, wherein the connection with the alkyl is Noah chain C 2-C12is isobutane and which involves the step of contacting deposited on mesoporous carbon catalyst based on copper with a mixed raw material of isobutane and CO2for the conversion of isobutane in isobutene by the reaction of catalytic dehydrogenation.

18. The application 17, wherein the reaction conditions of catalytic dehydrogenation are as follows: the reaction temperature 550-650°C, pressure of the reaction 0.05-1.0 MPa, a space velocity of 0.5-8 l g-1cath-1, the molar ratio of isobutane and CO2from 1:0.5 to 1:11.

19. Use p, in which the reaction conditions of catalytic dehydrogenation are as follows: the reaction temperature 560-610°C, pressure of the reaction 0.06-0.5 MPa, a space velocity of 0.5-8 l g-1cath-1, the molar ratio of isobutane and CO2from 1:0.5 to 1:11.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: described is a method of producing C3-C5 olefin hydrocarbons via dehydrogenation of corresponding C3-C5 paraffin hydrocarbons or mixtures thereof in the presence of a catalyst which contains chromium oxide, zinc oxide, aluminium oxide and additionally a aluminium-magnesium spinel and at least tin oxide in amount of 0.1-3.0 wt %. Before the regeneration step, reaction products are removed from the catalyst by first passing C1-C5 hydrocarbons or mixtures thereof and then nitrogen through the catalyst. The catalyst contains chromium oxide, zinc oxide, aluminium oxide, aluminium-magnesium spinel and tin oxide, with the following ratio of components in terms of oxides, wt %: Cr2O3 - 10.0-30.0, ZnO - 10.0-40.0, SnO2 - 0.1-3.0, MgO - 1.0-25.0, Al2O3 - the balance. The catalyst can further contain a manganese compound in amount of 0.05-5.0 wt %.

EFFECT: high efficiency of the process of producing olefin hydrocarbons.

3 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: method is characterised by contacting a gas stream containing at least one of said hydrocarbons with a dehydrogenation catalyst containing gallium and platinum and deposited on a support made of aluminium oxide or aluminium oxide and silicon dioxide, at reaction temperature in a direct-flow, upward stream with weight ratio of catalyst to hydrocarbon of 5 to 100 in a dehydrogenation reactor, wherein the average contact time of the hydrocarbon with the catalyst in the zone of the dehydrogenation reactor ranges from 1 s to 4 s, and temperature and pressure in the dehydrogenation reactor range from 570 to 750°C and from 41.4 (6.0) to 308 (44.7) kPa (psia); and moving the hydrocarbon and the catalyst from the dehydrogenation reactor into a separation device, wherein the average contact time of the hydrocarbon with the catalyst at reaction temperature in the separation device is less than 5 s, and the full average contact time between the hydrocarbon, catalyst and the formed hydrocarbons is less than 10 s; and moving the catalyst from the separation device into a regenerator, where the catalyst is brought into contact with an oxygen-containing regenerating stream and additional fuel.

EFFECT: method has short contact time between the hydrocarbon and the catalyst.

7 cl, 5 dwg

FIELD: chemistry.

SUBSTANCE: disclosed is a method of determining resistance of an alkyl aromatic hydrocarbon dehydrogenation catalyst to catalyst poisons, said catalyst containing an alkali metal, the method involving treating the catalyst with a mixture which contains an alkyl aromatic hydrocarbon and 1-10% aqueous hydrochloric acid solution in ratio of 1:2…1:3, at temperature of 550-650°C, holding the sample for 3 hours; in order to dehydrogenate the alkyl aromatic hydrocarbons, the dealkylisation degree is determined using the formula: α=n(Me+)inn(Me+)recn(Me+)in, where α is the dealkylisation degree; n(Me+) is the amount of the alkaline promoter, mol. The method enables to predict loss of an alkaline promoter when using the catalyst at a formulation adjustment step without conducting long-term tests.

EFFECT: method for rapid determination of resistance of an alkyl aromatic hydrocarbon dehydrogenation catalyst, which contains an alkali metal, to catalytic poisons.

1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: initial hydrocarbon raw material is initially separated and first part of initial raw material is introduced into first zone of dehydration reaction, which functions without oxidation re-heating, and obtained as a result output flow is introduced into second zone of dehydration reaction, which functions without oxidation re-heating. Obtained as a result output flow from second zone of dehydration reaction, together with second part of initial raw material is introduced into third zone of dehydration reaction, which functions with oxidation re-heating.

EFFECT: increased method productivity.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: present invention relates to a catalyst and a method for continuous oxidative dehydrogenation of paraffins to corresponding olefins, specifically ethane to ethylene. Described is a catalyst for continuous oxidative dehydrogenation of ethane to ethylene, which contains a mixed oxide catalyst phase which contains ions of metals such as vanadium, molybdenum, niobium, tellurium or antimony, deposited on a support in form of an inert gas-permeable porous ceramic membrane with a deposited mixed oxide catalyst phase on the outer side of the membrane surface. Described also is a method for continuous oxidative dehydrogenation of ethane to ethylene in the presence of the disclosed catalyst by feeding an ethane-containing gas onto the outer side of the membrane surface coated with catalyst, and an oxygen-containing gas is fed onto the inner side of the membrane surface which is not coated with catalyst at temperature of 300°C-550°C, pressure ranging from atmospheric pressure to 10 MPa and volume rate of feeding material of 500-2000 h-1.

EFFECT: increase in ethylene selectivity to 98% and output of the process from 800 to 1400-2240 g/h per kg catalyst, high process safety since it enables to separate the hydrocarbon stream from the stream of oxygen-containing gas, thereby minimising the probability of their mixing, thus preventing formation of explosive mixtures.

4 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of controlling activity of a catalyst for dehydrogenation of higher n-paraffins. The method involves controlling catalyst activity by increasing the rate of feeding water into a reactor and is characterised by that, the flow rate of water is further adjusted depending on the type of catalyst, wherein the ratio of the equilibrium constant when varying the process temperature to the equilibrium constant at the initial temperature must equal to one: Ki+1Ki=(nCO(i+1)*nCO(1)*)63(n1H2O+nCO(1)*nH2O(i+1)+nCO(i+1)*)28(n1H2O+nH2(1)*nH2O(i+1)+nH2(i+1)*)28=1, where Ki+1, K1 denote the equilibrium constant at Ti+1 and T1, Pa21; nH2O(i+1),n1H2O is the initial amount of H2O at Ti+1 and T1, mole; n*CO(i+1), n*CO(1) is the equilibrium amount of CO at Ti+1 and T1, mole; nH2(i+1)*,nH2(1)* is the equilibrium amount of H2 at Ti+1 and T1, mole.

EFFECT: high efficiency of the process.

2 cl, 1 tbl, 3 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a material which is suitable as a support for an alkane dehydrogenation catalyst, a method of producing said material and a method for catalytic dehydrogenation of alkane-containing gas mixtures. Described is a material for catalytic dehydrogenation of gas mixtures which contain C2-C6 alkanes and may contain hydrogen, water vapour, oxygen or any mixture of said gases, wherein primarily alkenes and hydrogen, and additionally water vapour, can be obtained, which: a) consists of ceramic foam obtained from oxide or non-oxide ceramic materials or a mixture of oxide and non-oxide ceramic materials, b) wherein the oxide ceramic materials used are calcium aluminate, silicon dioxide, tin dioxide or zinc aluminate or a mixture of said substances, c) to provide catalytic activity, the material is saturated with at least one catalytically active substance and d) the catalytically active material contains platinum, tin or chromium or mixtures thereof. Described is a method of producing said material by applying a starting ceramic substance, mixed during production with a suitable additive as an auxiliary agent, in form of a suspension onto a prepared starting polyurethane material, after which the obtained material is sintered and saturated with catalytically active material. Described is a method of dehydrogenating alkane-containing gas mixtures (versions) using the disclosed material.

EFFECT: considerable reduction in hydraulic resistance of the catalyst, significant improvement in availability of catalytically active material, increase in thermal and mechanical stability of the material.

14 cl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of dehydrogenating alkanes, according to which a mixture containing hydrocarbons, particularly alkanes, which can contain water vapour, is continuously fed through a catalyst bed at ordinary dehydrogenation conditions. The many-hours-long dehydrogenation step is followed by a step with bleeding of oxygen-free gas through a reactor layer in order to blow and remove reaction gas from the reactor layer, and this is followed by a step for bleeding oxygen-containing regeneration gas in order to remove deposits on the catalyst formed during the dehydrogenation reaction. This is followed by a step for bleeding oxygen-free gas in order to blow and remove regeneration gas from the reactor. Duration of bleeding oxygen-containing gas during catalyst regeneration is equal to or less than 70% of the total duration of regeneration, total regeneration time is equal to 1 hour and regeneration starts after a seven-hour step of obtaining the product. The method is characterised by that regeneration starts with a five-minute blowing step, followed by a step for regeneration with a gas which contains oxygen and water vapour for 20 minutes, followed by an additional blowing step.

EFFECT: method enables to preserve catalyst activity and selectivity with respect to the desired process and after many regeneration cycles.

12 cl, 5 ex, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to dehydrogenation catalysts. Described is a dehydrogenation catalyst for dehydrogenating gaseous hydrocarbons, which contains platinum, one or more auxiliary metals selected from a group consisting of tin, germanium, gallium, indium, zinc and manganese, an alkali metal or an alkali-earth metal and a halogen component, which are deposited on a support consisting of aluminium oxide having theta-crystallinity of 90% or higher, said support having 5-100 nm mesopores and 0.1-20 mcm macropores, and platinum density per unit surface area of the catalyst is equal to 0.001-0.009 wt %/m2.

EFFECT: high catalyst activity.

8 cl, 3 tbl, 3 dwg, 3 ex

FIELD: oil and gas industry.

SUBSTANCE: invention refers to the method for obtaining lower olefinic hydrocarbons and includes pyrolysis of hydrocarbon raw material in presence of metallic catalyst applied to the carrier located inside the reactor. The method is characterised by the fact that propane-butane hydrocarbon mixture is used as hydrocarbon raw material, and nanostructure particles of metals formed on inner carrier surface are used as catalyst.

EFFECT: use of the present invention allows increasing ethylene and propylene output and excluding the coke formation.

7 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to field of catalysis. Described is method of obtaining metal oxide on substrate, suitable for application as precursor for catalyst or sorbent, which includes the following stages: (i) impregnation of substrate material with metal nitrate solution in solvent, (ii) keeping impregnated material in gas mixture, containing nitrogen oxide, at temperature within the range to remove solvent from impregnated material with simultaneous drying and stabilisation of metal nitrate on substrate, with obtaining dispersed on substrate metal nitrate and (iii) calcination of dispersed on substrate metal nitrate to realise its decomposition and formation of metal oxide on substrate, where calcinations is performed in gas mixture, which consists of one or several inert gases and nitrogen oxide, and concentration of nitrogen oxide in gas mixture is within the range 0.001-15 vol.%.

EFFECT: increased catalytic activity of obtained products.

12 cl, 4 dwg, 11 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of catalysis. Described is method of obtaining catalyst, which includes impregnation of metal oxide substrate material with platinum compound, drying below the point of said platinum compound decomposition, burning in gas flow, which contains NO and inert gas. Described is application of said catalyst as oxidation catalyst, and catalyst unit in the system of exhaust gas purification.

EFFECT: increased activity and selectivity of CO and NO oxidation.

17 cl, 3 dwg, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of catalysis. Described is method of creating efficient platinum-free catalytic coating on ceramic units for neutralisation of waste gases of autotractor diesel engines, which includes formation of substrate with large value of specific surface on ceramic honeycomb carriers.

EFFECT: increase of catalyst activity.

2 cl, 4 dwg, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: described are methods of chrome catalyst activation, which include increasing chrome catalyst temperature in, at least, bilinear changing, which contains increase of chrome catalyst temperature at first speed during first period of time to first temperature on first site of changing of bilinear changing; and increase of chrome catalyst temperature at second speed during second period of time from said first temperature to second temperature on second site of changing of bilinear changing, which follows directly after first area of changing, and first speed is larger, than second speed, and first period precedes second period; with first temperature being in the range from approximately 650°C to approximately 750°C, with second temperature being in the range from approximately 750°C to approximately 850°C. Method of obtaining polyolefines in presence of catalyst, activated by claimed method, is described.

EFFECT: increased efficiency of catalyst activation.

19 cl, 13 dwg, 17 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: described is a catalyst for selective oxidation of carbon monoxide in a mixture with ammonia, containing 0.7-1.2 wt % gold, 0.8-5.0 wt % Fe3+ and a crystalline theta-modification of aluminium oxide (θ-Al2O3) - the balance. Described are methods of producing said catalyst.

EFFECT: obtaining a catalyst with high activity and selectivity in oxidation of CO while reducing activity in ammonia conversion.

3 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: described is a catalyst for selective oxidation of carbon monoxide in a mixture with ammonia, containing 0.5-1.0 wt % gold, 1.0-5.0 wt % ruthenium and aluminium oxide - the balance. Described is a method of preparing said catalyst.

EFFECT: high selectivity in oxidising CO in a mixture with ammonia while reducing ammonia conversion.

3 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: described is a method of preparing a catalyst for producing aromatic hydrocarbons by converting hydrocarbon gases, which involves depositing molybdenum on a support which is zeolite HZSM-5, via impregnation thereof with an aqueous solution of a molybdenum salt, followed by calcination in air at temperature of 500-600°C, wherein the zeolite HZSM-5 in powder form is first subjected to dealumination via thermal-steam treatment in an air current with steam partial pressure of 10-60 kPa at temperature of 450-550°C, and the obtained zeolite HZSM-5 with total content of molybdenum of 2-5 wt % is mixed with an inert material which actively absorbs microwave energy, based on a metal oxide or carbide, with weight ratio of the components of 2-4:1, respectively. Disclosed is a method of producing aromatic hydrocarbons in the presence of the catalyst obtained using the method described above.

EFFECT: low power consumption while simplifying implementation of the process using an active catalyst.

6 cl, 1 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: described is a method of preparing a catalyst for complete oxidation of hydrocarbons by depositing platinum or palladium on a calcined sulphated zirconium oxide support via impregnation thereof with an aqueous solution of a platinum or palladium compound, followed by calcination in air at temperature of 300-500°C and reduction in a hydrogen current at temperature of 300-500°C, wherein the sulphated zirconium oxide support is further modified with gallium ions via deposition thereof from aqueous gallium nitrate solution. Described is use of the catalyst obtained using the method described above for complete oxidation of hydrocarbons.

EFFECT: obtaining a high-quality catalyst for purifying air from hydrocarbon impurities, which enables hydrocarbon conversion.

9 cl, 1 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: described is a method of preparing a catalyst for oxidative condensation of methane to C2+ hydrocarbons, which involves depositing manganese and sodium tungstate on a silicon dioxide support via successive impregnation thereof with aqueous solutions of manganese nitrate and then sodium tungstate, followed by calcination in air at temperature of 800°C, wherein the obtained composition Mn - Na2WO4/SiO2 with total content of manganese of 1-2 wt % and sodium tungstate of 3-5 wt % is mixed with an inert material which actively absorbs microwave energy, based on a metal carbide with weight ratio of components of 2-4:1, respectively. Described is a method for oxidative condensation of methane to C2+ hydrocarbons in the presence of a catalyst obtained using the method described above.

EFFECT: high conversion of methane and high selectivity with respect to C2+ hydrocarbons.

6 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of catalyst. Described is method of preparing bimetal gold-copper catalyst of oxidation, which includes successive stages of application of precursors of metals on carrier, and thermal processing, as gold and copper precursors applied are anion and cation complexes, which formed in interaction with each other poorly soluble compound of complex salt in accordance with the law on electroneutrality.

EFFECT: increase of catalyst activity.

7 cl, 2 tbl, 9 ex

FIELD: oil and gas industry.

SUBSTANCE: catalytic additive includes zeolite ZSM-5 in a hydrogen form with silica modulus in the range from 25 up to 40 and the matrix which components include activated bentonite clay, aluminium hydroxide of pseudo-boehmitic modification treated by the nitric acid and amorphous alumosilicate with the following content of components, in wt %: zeolite ZSM-5 - 30-60; bentonite clay - 20-40; aluminium hydroxide - 10-40; amorphous alumosilicate - 10-20. The method of catalytic additive manufacturing includes ionic exchange of cations in zeolite ZSM-5 by ammonia cations, zeolite mixing with the matrix components which include boehmitic modification and amorphous alumosilicate, spray drying and ignition.

EFFECT: improving properties of catalytic additive.

2 cl, 3 tbl, 7 ex

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