Method of catalytic conversion of hydrocarbons into aromatic compounds on the catalyst containing silicon

 

(57) Abstract:

The invention relates to a method of catalytic conversion of hydrocarbons into aromatic compounds, which can be used for reforming of gasoline and the production of aromatic compounds. The invention: the feedstock in contact with a catalyst which contains a matrix consisting of gamma-modification of aluminum oxide or a mixture of gamma - and this-modifications of aluminum oxide, and 0.01-2 wt.% silicon, 0.1 to 15 wt.% at least one halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, 0.01 to 2 wt.% at least one noble metal selected from the group of platinum, from 0.005 to 10 weight. % of at least one promoting metal selected from the group consisting of tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten, and the catalyst is subjected to hydrothermal treatment at a temperature of from 300 to 1000C. in a gas atmosphere containing water vapor. The technical result is an increase in the yield of the target aromatic compounds and the octane number of the products of reforming. 29 C.p. f-crystals, 11 PL.

The invention relates to method the catalytic preframe the s and the production of aromatic compounds.

More specifically, the invention relates to a method of this type, using as a catalyst a multifunctional catalyst with a matrix of aluminum oxide.

Catalytic reforming is a process that provides an opportunity to increase the octane number of petroleum fractions, particularly heavy distillation of gasoline, by conversion of n-paraffins and naphthenes to aromatic hydrocarbons.

Thus, in the catalytic reforming process, on the one hand, there is a transformation of n-paraffins C7-C10in aromatics and light paraffins and, on the other hand, naphthenes C7-C10in aromatics and light paraffins. These reactions, in particular, illustrates the dehydrogenation conversion of cyclohexanol and dehydroisomerization of alkylcyclopentanes with the formation of aromatic compounds, such as methylcyclohexane forms toluene, and the conversion of n-paraffins in the cyclization in aromatic compounds, for example n-heptane forms toluene.

During catalytic reforming there are also reactions of cracking of heavy n-paraffins to lighter paraffins, which, in particular, preparing.

Finally, also the formation of coke as a result of condensation of aromatic rings with obtaining a solid, carbon-rich product, which is deposited on the catalyst surface.

These reforming catalysts have high sensitivity as to coke, and various poisons, which may reduce their activity: in particular to compounds of sulfur and nitrogen, metals and water.

When the deposition on the catalyst surface coke causes loss of catalyst activity over time, which leads to higher operating temperatures, reducing the yield of the product of reforming and increasing gas output.

For this reason, taking into account the regeneration of the catalyst, the catalytic reforming process can be carried out in two different ways: preregistration or cyclical manner and a continuous manner. In the first case the process is carried out in a fixed bed, and in the second case - in the movable catalyst bed.

In preregistration process in order to compensate for the loss of activity of the catalyst gradually increase the temperature, and then stop the operation of the installation in order to carry out the regeneration of the catalyst by del the process, the installation includes several successive reactors, each of them in turn excluded from work; coke deposits are removed from the catalyst derived from the process cycle, and the catalyst is subjected to regeneration, while the other reactors continue to operate.

In continuous reforming reactors used with a movable layer operate at low pressure (less than 1,53 MPa), which allows to significantly increase the yield of the product of reforming and hydrogen by stimulating reactions flavoring, instead of cracking reactions; on the other hand, significantly accelerates the formation of coke. The catalyst passes through the reactor and then through a regeneration section.

Processes for the production of aromatic compounds include reaction conversion of paraffinic and naphthenic hydrocarbons in the aromatic.

In these reactions, the conversion of hydrocarbons usually use bifunctional catalysts, such as platinum, deposited on chlorinated alumina, where the combination of the acid sites on chlorinated alumina required for isomerization reactions cyclopentane naphthenes and cyclization of paraffins, with platinum centers dehydr the tall, such as rhenium, tin or lead, have been described in U.S. patent 3 700 588 and 3 415 737.

As you can see from the above, the catalytic reforming process can be operated either using fixed or rolling catalyst layer.

In each case, the catalyst is subjected to regeneration treatment, carried out at high temperature and in the presence of water vapor and which, among other things, is Vigie coke, sudivshegosya on the catalyst. Unfortunately, such conditions lead to deactivation of the catalyst. Thus, it is important to solve the problem of improving the stability of the catalyst under these conditions.

Typically, the catalyst is in the form of extrudates or pellets, the size of which provides a relatively easy passage of the reactants and gaseous products. The deterioration of the catalyst, in particular as a result of abrasion in installations with a movable layer, leads to the formation of dust and grains of a smaller size. These fine grains prevent the flow of gas and cause a need to increase the pressure of the reactants at the inlet, and in some cases even required to cease operation of the installation. In addition, units with a movable layer as a consequence of such of fresh catalyst.

Therefore, the catalyst, such as a reforming catalyst must comply with a significant number of requirements, some of which may seem contradictory. First, the catalyst should be of maximal catalytic activity, which ensure high product yield, but this activity should be combined with the highest possible selectivity, in other words, must be suppressed reactions of cracking, yielding light products containing from 1 to 4 carbon atoms.

In addition, the catalyst should have a high stability against deactivation by coke deposits; the catalyst must also possess excellent resistance to poisoning when he was working in extreme conditions during the repeated operations of regeneration, which he should be.

In the case of a continuous reforming process, using reactors with a movable layer, as mentioned above, the catalysts also are being progressively intense wear due to friction, which leads to a significant reduction of their specific surface area and the formation of "stuff" that impairs the normal installation mode. Available the work to one or more of such requirements.

In addition, despite already implemented numerous improvements used bifunctional catalysts, the search continues for new catalysts that provides improved performance not only in terms of output in the reactions of transformation, but also in regard of service life of the catalyst.

The present invention specifically relates to a method for conversion of hydrocarbons with the use of a multifunctional catalyst, which has improved catalytic performance and longer service life in the reforming process and in the production of aromatic compounds.

According to the present invention, a method of converting hydrocarbons into aromatic compounds comprises contacting load of these hydrocarbons with a catalyst under conditions of temperature and pressure suitable for a specified transformation; this method differs in that the catalyst contains:

matrix containing the gamma-modification of aluminum oxide or a mixture of gamma - and this is a modification of aluminum oxide, and

- calculated on the total weight of the catalyst:

from 0.01 to 2 wt.% silicon

from 0.1 to 15 weight. % of at least one halogen, vibrantly from the group of platinum, and

0.005 to 10 weight. % of at least one promoting metal selected from the group consisting of tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten, and the catalyst is subjected to hydrothermal treatment at a temperature of from 300 to 1000oC in an atmosphere gas containing water vapor.

In one variant embodiment of the invention, the catalyst contains, in addition, from 0.001 to 10 weight. % of at least one alloying metal selected from the group consisting of alkali and alkaline earth metals, lanthanides, titanium, zirconium, hafnium, cobalt, Nickel and zinc.

It should be noted that in the continuation of this text, the content of silicon, halogen, noble metal, the promoting metal and alloying metal in the catalyst, expressed in weight percent based on the total weight of the catalyst, unless otherwise noted. Moreover, these levels correspond to the total content of the component (alloy metal, halogen, noble metal or the promoting metal) when the component contains several elements (Halogens or metals).

In this invention it is very important to primeneniye prevents a reduction in the specific surface area of the matrix oxide (oxide) aluminum, when the catalyst is subjected to regeneration treatment that is necessary for its operation in the reactions of conversion of hydrocarbons, but the catalyst with silicon has the disadvantage that it has a high kekirawa activity. Unexpectedly, the applicant has found that the hydrothermal treatment of the harsh conditions in the presence of water applied to this type of catalyst, ensures the prevention of the decrease of the specific surface area and improves the characteristics of the catalyst (suppressed cracking).

Preferably this hydrothermal treatment is carried out in a gaseous atmosphere containing not only water vapor but also halogen, such as chlorine.

The preferred catalyst of the invention contains:

a carrier consisting of a matrix of gamma-alumina or a mixture of gamma and ETA-alumina with the addition of silicon,

- at least one halogen,

- catalytically active metal, providing the dehydrating action of a catalyst comprising one or more noble metal from the platinum group, and

at least one promoting metal selected from the above metals.

In this izobreteniya General formula Al2O3nH2O where the value of n lies between 0 and 0.6, with a specific surface area of from 150 to 400 m2/g can be obtained by controlled dehydration of hydroxides of aluminum, in which the value of n lies between 1 and 3. The original amorphous hydroxides can exist in various forms, of which the most common are boehmite (n = 1), gibbsite and bayerite (n = 3). During the dehydrating conditions of processing these hydroxides can form several oxides of transition or modifications of aluminum oxide, such as forms, , , , , , and which differ mainly organization of their crystalline structure. During heat treatment of these different forms are mutual transformations obeying complex patterns and depending on working conditions. At high temperatures is the most stable alpha form, for which values of specific surface area and acidity is close to zero. In the reforming catalysts most commonly used gamma shape modifications of aluminum oxide, as it provides a compromise between the acid properties and thermal stability.

In accordance with the invention is used ha is uminia this modification can be obtained by firing bayerite in dry air at atmospheric pressure and at a temperature between 250 and 500oC, preferably between 300 and 450oC. the Obtained value of specific surface area, which depends on the final firing temperature is between 300 and 500 m2/year of aluminum Oxide of the gamma-modification is obtained by calcination of boehmite in air at a temperature of between 450 and 600oC. the Obtained value of the specific surface area gamma alumina is between 100 and 300 m2/,

The crystal structures of these two modifications of aluminum oxide similar to each other, but different. To identify structures can be used, in particular, the method of x-ray diffraction. These structures are defective spinel, and their configuration is slightly deviates from the cubic symmetry. This quadratic deformation minimum for this form and expressed much more clearly for the gamma-modification of aluminum oxide, elementary lattice which has the following parameters: a=b= 7.95 and c=7,79 .

In accordance with the invention, when using a mixture of gamma - and this-modifications of aluminum oxide, it may contain from 0.1 to 99% or more on 1 to 84 wt.% this is aluminum oxide. Preferably, this mixture contains from 3 to 70 weight. % and even better from 5 to 50 wt.% this is a modification of the oxide aluminiumalloy with the invention the matrix of alumina modified silica. The silicon content in the catalyst is from 0.01 to 2 wt.%, preferably from 0.01 to 1 wt.%.

Halogen or halogen free, used for acidification of the media may be in the amount of from 0.1 to 15 wt.% and preferably from 0.2 to 10% by weight of the catalyst. Preferably, use a single halogen, in particular chlorine.

The catalyst also contains one or more of the promoting metals whose purpose is the promotion of dehydrating activity of the noble metal from the platinum group and loss reduction of dispersion of the noble metal on the carrier surface, which is partially responsible for the deactivation of the catalyst.

The total content of the promoting metal is 0.005 to 10 wt.%, preferably from 0.01 to 1 wt.%.

The promoting metal is selected depending on the method of application of the catalyst.

Thus, when the catalyst is intended for use in the process fixed bed, the promoting metal is preferably selected from the group consisting of rhenium, manganese, chromium, molybdenum, tungsten, indium and thallium.

When the catalyst is intended for use in the process of moving bed, promote gallium.

Among them, the preferred metal for a process with a fixed layer is rhenium, and for a process with a movable layer of tin, as they provide the best promotion of catalytic activity.

In particular, rhenium increases the stability of the catalyst against deactivation by coke deposits. Thus, in the process fixed bed is used, a catalyst containing rhenium, as this increased stability allows you to extend the reaction cycles between two regenerations of the catalyst.

As for tin, it gives the opportunity to improve the performance of the catalysts that are used at low pressure. This improvement, along with reduced kekirawa activity tin-containing catalysts, improves the yield of products of reforming, especially in processes with continuous regeneration of the rolling layer of catalyst, operating at low pressure.

The total content of the promoting metal (metals) is 0.005 to 10 wt.%, preferably from 0.01 to 1 wt.%.

When the catalyst contains only one promoting metal, such as rhenium or tin, its content is preferably is of at least one noble metal from the platinum group in the amount of from 0.01 to 2 wt.% and preferably from 0.1 to 0.8 wt.%.

Noble metals that can be used are platinum, palladium, iridium, and platinum may be preferable.

In accordance with one embodiment of the invention, moreover, the catalyst contains from 0.001 to 10 wt.% at least one alloying metal selected from the group consisting of alkali and alkaline earth metals, lanthanides, titanium, zirconium, hafnium, cobalt, Nickel and zinc.

In this case, a matrix of alumina modified silica and one or more alloying metals.

Preferably, the alloying metal is only one of the following groups:

1) the group of alkali and alkaline earth metals,

2) the group of lanthanides and

3) the group containing titanium, zirconium, hafnium, cobalt, Nickel and zinc.

In the case of metals belonging to the first group (alkali and alkaline earth metals), the total content of the alloying metal in the catalyst is usually from 0.001 to 8 wt.%.

Used alkali metal may be lithium, sodium, potassium, rubidium and cesium; alkaline earth metals can be selected from beryllium, magnesium, calcium, strontium and barium.

Content is to isolates the catalyst of the invention.

So, in the case of a reactor with a fixed layer of the alloying metal in the catalyst is usually in the range of from 0.001 to 0.3 wt.% and preferably 0.005 to 0.3 wt.% or even better from 0.01 to 0.3 wt.%.

In the case of a reactor with a movable layer of the alloying metal in the catalyst increases and is usually more than 0.3 wt.% to 0.8 wt.%, preferably from more than 0.3 to 4 wt.% and even better from 0.7 to 4 wt.%.

Preferably, the alloying metal is an alkaline metal such as potassium.

In the case of alloying metals belonging to the second group (the lanthanides), the total content of the alloying metal in the catalyst is usually from 0.001 to 10 wt.%.

The group of the lanthanides or rare earths contains the elements of the group of lanthanum in the Periodic table of elements, atomic numbers between 57 and 71, such as lanthanum, cerium, neodymium and praseodymium.

The total content of the alloying metal from the second group also chosen, in particular, depending on the reactor, which will be used in the catalyst of the invention.

Thus, when the catalyst used in the reactor with a fixed bed, the alloying metal may be Afleet more than 0.5 wt.% up to 10 wt.% or even better from more than 0.5 to 4 wt.%, when the catalyst used in the reactor with a moving bed.

In the case of alloying metals belonging to the third group (titanium, zirconium, hafnium, cobalt, Nickel, and zinc), the total content of the alloying metal in the catalyst is usually from 0.001 to 10 wt.%.

The content of these metals is also chosen depending on the reactor, which will be used catalyst.

Thus, when the catalyst used in the reactor with a porous layer, the total content of the alloying metal of the third group is preferably from 0.001 to 0.7 wt.% and even better from 0.01 to 0.7 wt.%. Preferably the alloying metal is more than 0.7 wt.% up to 10 wt.% or even better from more than 0.7 to 4 wt.%, when the catalyst used in the reactor with a moving bed.

The catalyst of the invention can be prepared by deposition of various components in a matrix of aluminum oxide. The deposition of each component may be implemented fully or in part, on one or both forms of aluminum oxide matrix, before or after it is attached form. Components can be precipitated separately or simultaneously in any order.

Thus the us simultaneously on both forms of aluminum oxide or one of them, preferably this modification of aluminum oxide to mix both forms of aluminum oxide and prior to their formation.

It is also possible full or partial deposition of one or certain components on one or both forms of aluminum oxide, before they are mixed, and then carry out the deposition of the remaining components after mixing both forms of aluminum oxide, either before or after molding the mixture. When the deposition of one or more components to mix both forms of aluminum oxide, preferably carry out the deposition of silicon on this-modification of aluminum oxide.

However, in accordance with the invention usually prefer to mix both forms of aluminum oxide, before the deposition of the metal components and the halogen or Halogens.

The invention also provides a method of preparation of the catalyst of the invention, which comprises the following stages:

a) the preparation, if necessary the mixture, followed by molding matrix gamma - modification of aluminum oxide or a mixture of this - and gamma-modifications of aluminum oxide,

b) deposition of at least one of gamma - or ETA-modifications of aluminum oxide of one of the following components in weight percent, is

from 0.1 to 15 wt.%, preferably from 0.2 to 10 wt.% at least one halogen selected from the group consisting of fluorine, chlorine, bromine and iodine,

from 0.01 to 2 wt.% at least one noble metal from the platinum group, and

- 0.005 to 10 wt.% at least one promoting metal selected from the group consisting of tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten,

from 0.001 to 10 wt.%, if required, at least one alloying metal selected from the group consisting of alkali and alkaline earth metals, lanthanides, titanium, zirconium, hafnium, cobalt, Nickel and zinc.

Stages a) and b) can be carried out in any sequence, and the settling in stage b) can be carried out only partially to the stage a); they can be performed in any order; and

C) hydrothermal treatment of the catalyst obtained in stages a) and b), at a temperature between 300 and 1000oC in a gaseous atmosphere containing water vapor.

In the preferred embodiment of this method, first get a carrier consisting of aluminiumoxide matrix and silicon, and then it precipitated legious the s from the group of platinum.

In this case, the silicon can be precipitated on alumina or a mixture of aluminum oxide before or after molding.

Preferably, the precipitated silicon after forming a matrix of aluminum oxide.

The deposition of the various components of the catalyst can be carried out using traditional methods in liquid or gas phase, based on appropriate preceding compounds. When carry out the deposition of already formed aluminiumoxide matrix methods used can be, for example, dry impregnation, impregnation with an excess of a solution or ion exchange. If necessary, this operation is followed by drying and calcination at a temperature between 300 and 900oC, preferably in the presence of oxygen.

Thus, it is possible to precipitate silica from components such as alkyl tetrathionate, silicon alkoxides, Quaternary ammonium silicates, silanes, disilane, silicones, siloxanes, silicon halides, halogenoalkane and silicon in the form of microspherical or colloidal silicon dioxide. In the case where the silicon precursor is forcelimit, which can be represented by the formula M2/xSiF6where M is a cation of a metal or a nonmetal with Valens is d', cesium, rubidium, silver, thallium, protons and divalent - barium, magnesium, cadmium, copper, calcium, iron, cobalt, lead, manganese, strontium and zinc.

When the silicon is precipitated after the formation of the matrix of aluminum oxide, this deposition, preferably, carried out using the impregnation in an aqueous medium with an excess of an aqueous solution of the precursor. Then remove the impregnating solvent, for example by drying, and carry out the calcination in air at a temperature of, for example, between 300 and 900oC.

The precipitation of the alloying metal (or metals) from the first group, selected from alkali and alkaline earth metals, can be carried out using any technique and can be performed at any stage of the process of preparation of the catalyst. When this deposition is carried out after forming aluminiumoxide matrix, preferably using the operation impregnation in an aqueous medium with an excess of solution, followed by drying, to remove impregnating solvent, and annealed in air at a temperature of, for example, between 300 and 900oC.

Used precursor compounds may represent, for example, salts of alkali and alkaline-earth metal is dominant metal (or metals) of the second group (the lanthanides) can be carried out using any method known from the prior art, and can be done at any stage of the preparation of the catalyst. For example, in the case where this element from the group of the lanthanides or rare earths are precipitated after formation of the oxide or oxides of aluminum, containing, if necessary, other metals, you can use dry impregnation, impregnation with an excess of a solution or ion exchange. For a matrix that is already formed, the preferred method of introducing this additional element is impregnated in an aqueous medium using an excess of solution. In order to remove impregnating solvent after impregnation followed by drying and calcination in air at a temperature of, for example, between 300 and 900oC.

Used preceding compounds may represent, for example, halides, nitrates, carbonates, acetates, sulfates or oxalates of these elements.

The precipitation of the alloying element metal (or metals) of the third group consisting of titanium, zirconium, hafnium, cobalt, Nickel and zinc, the matrix of the catalyst used in the present invention, can be carried out using any method known from the prior art, and can be done on any article of aluminum oxide, containing, if necessary, other metals, you can use dry impregnation, impregnation with an excess of a solution or ion exchange. For a matrix that is already formed, the preferred method of introducing this additional element is impregnated in an aqueous medium using an excess of solution. In order to remove impregnating solvent after impregnation followed by drying and calcination in air at a temperature of, for example, between 300 and 900oC.

The deposition of silicon and at least one element selected from the group consisting of titanium, zirconium, hafnium, cobalt, Nickel and zinc, can be carried out independently from each other, or a transitional form of aluminum oxide or unshaped matrix, and this matrix contains from 0 to 99 weight. % this is a modification of aluminum oxide, and the remaining amount of the matrix to 100 wt.% is gamma-modification of aluminum oxide or again on the pre-formed matrix; the latter method is preferred.

The deposition of the noble metal or metals of the platinum group can also be carried out using traditional methods, in particular impregnation from aqueous or nonaqueous solution, code used, you can mention chloroplatinic acid, ammonium compounds, chloroplatinic ammonium, dicarboxylicacid platinum, hexahydroxy-platinum acid, palladium chloride and palladium nitrate.

In the case of platinum ammonium compounds may represent, for example examinee tetravalent platinum formula Pt(NH3)6X4, halogenating salt of platinum (IV), formula [PtX(NH3)5]X3, tetrachlorethylene platinum salts, of the formula PtX4(NH3)2X platinum complexes with halogen polyketone and halogenated compounds of the formula H[Pt(aca)2X], where the element X is a halogen selected from the group consisting of chlorine, fluorine, bromine and iodine, and preferably chlorine, and aca-group is a residue of the formula C5H7O2derived from acetylacetone.

Introduction noble metal of the platinum group is preferably carried out by impregnation using an aqueous or organic solution of one of the ORGANOMETALLIC compounds mentioned above. Among the organic solvents that can be used include paraffinic, naphthenic or aromatic hydrocarbons and galoidirovaniya given n-heptane, methylcyclohexane, toluene and chloroform. In addition, there may be used a mixture of solvents.

After the introduction of the noble metal, drying and calcination is preferably carried out, for example, at a temperature between 400 and 700oC.

The deposition of the noble metal or metals of the platinum group may be held at any time during the preparation of the catalyst. This can be done separately or simultaneously with the deposition of other components, for example, the promoting metal or metals. In this latter case, the impregnation can use solution containing all of the input components.

The deposition of the promoting metal or metals can also be carried out by traditional methods, on the basis of the foregoing compounds, such as halides, nitrates, acetates, tartratami, citrates, carbonates and oxalates of these metals. As a predecessor also suitable are any other salts or oxides of these metals, which are soluble in water, acid or other suitable solvent. As examples of such precursors can specify Renata, chromates, molybdates and wolframates. The promoting metal (or metals) may also be igami aluminum to molding, with subsequent annealing in air at temperatures between 400 and 900oC.

The introduction of the promoting metal or metals can also be performed by using a solution of organic compounds of these metals in the organic solvent. In this case, the deposition is preferably carried out after deposition of the noble metal (metals) from the group of platinum and calcination of the solid substance, followed by reduction with hydrogen (if required) at a high temperature, for example between 300 and 500oC. ORGANOMETALLIC compound selected from the group consisting of complexes indicated the promoting metal, in particular use polyketone complexes and hydrocarbide metals, such as alkyl, cycloalkyl, aryl, alkylaryl and arylalkylamine. In addition, can be used halogenated organic compounds. I can specifically be mentioned tetrabutyrate, in the case when the promoting metal is tin, tetraethyl lead, in the case when the promoting metal is lead, and triphenylene, in the case when the promoting metal is indium. Impregnating the solvent can be selected from the group consisting of paraffin, natinoality, containing from 1 to 12 carbon atoms in the molecule. We can cite the following examples of such solvent: n-heptane, methylcyclohexane and chloroform. It is also possible to use mixtures of the above solvents.

Halogen, such as chlorine, can be introduced into the catalyst at the same time as the other metal component, for example in cases when the previous connection is a halide of a metal of the platinum group, halides promoting metal or alkaline and alkaline earth metals. This introduction can be carried out by impregnation using an aqueous solution containing acid or halogenated salt. For example, can be precipitated chlorine, using a solution of hydrochloric acid. In addition, chlorine can be entered by calcination of the catalyst, for example, at a temperature between 400 and 900oC, in the presence of organic compounds containing halogen, such as for example carbon tetrachloride, methylene chloride and methylene chloride.

Obviously, you can enter at least two components of the catalyst, for example, on the basis of the solution containing the compounds, the precursors of these components. In addition, the components of the beam can be intermediate drying and/or calcination.

Forming a matrix of aluminum oxide can be carried out using methods of forming catalysts known from the prior art, such as for example extrusion, drop coagulation, coating, spray drying or tableting.

In a preferred embodiment, the method of preparation of the catalyst is characterized by the fact that it comprises the following successive stages:

a) forming the matrix of gamma-alumina or a mixture of gamma and ETA-alumina,

b) deposition of silicon on this matrix,

c) the possible deposition of at least one alloying metal, and

d) simultaneous or sequential deposition of:

at least one promoting metal selected from tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten,

at least one element selected from the group consisting of fluorine, chlorine, bromine and iodine, and

- at least one noble metal from the platinum group.

After the formation of the matrix and deposition of all catalyst components can make a final heat treatment at a temperature of between 300 and 1000oC, which can vklyuchit, preferably in the presence of free oxygen or air. Typically, this processing corresponds to the method of drying/annealing after deposition of the last component. After the formation of the matrix and deposition of all catalyst components hydrothermal treatment at a temperature of between 300 and 1000oC, preferably at temperatures between 400 and 700oC, in a gaseous atmosphere containing water vapor and, if desired, halogen, such as chlorine.

This processing may be performed in the layer through which the gas stream, or in a static atmosphere. Preferably, the gaseous atmosphere contains water and, if required, at least one halogen. The molar content of water is from 0.05 to 100%, preferably from 1 to 50%. The molar content of halogen is from 0 to 20%, preferably from 0 to 10% and more preferably from 0 to 2%. The duration of such processing is changed depending on conditions of temperature, partial pressure of water and the amount of catalyst. Mostly this value is between one minute and 30 hours, preferably between 1 and 10 hours Used gaseous atmosphere based on, for example, air, oxygen, or in the t an important role. As described in the examples below, in the presence of silicon, which protects aminoalkenes matrix from a reduction of the specific surface area during different regenerating treatment, thermal treatment of the catalyst of this type in harsh conditions, in the presence of water in an unexpected way provides protection reduce the specific surface area of the catalyst and at the same time improves its performance.

After the final heat treatment of the catalyst can be subjected to activation treatment in hydrogen atmosphere at high temperature, for example between 300 and 550oC.

This treatment in hydrogen atmosphere includes, for example, a slow increase in temperature in a stream of hydrogen until the maximum temperature recovery, which is usually between 300 and 550oC, preferably between 350 and 450oC, followed by keeping at this temperature for a period of time, which usually varies from 1 to 6 o'clock

In accordance with the invention described above, the catalyst used in the reactions for the conversion of hydrocarbons and more specifically to processes of reforming of gasoline and the production of aromatic connections obtained from the distillation of crude oil and/or other refining processes.

Processes for the production of aromatic compounds provide the basic raw material for petrochemical synthesis (benzene, toluene and xylene). These processes represent additional interest, giving the contribution to the production of significant amounts of hydrogen, which is necessary for processes for hydrogenation purification refining.

Both of these processes differ in the choice of operating conditions and the composition of raw materials.

Typical raw materials, processed in these processes, contains paraffin, naphthenic and aromatic hydrocarbons having from 5 to 12 carbon atoms in the molecule. This raw material is characterized by its density and weight of the composition, along with other indicators.

To implement these processes, the hydrocarbon feedstock is brought into contact with the catalyst of the present invention under appropriate conditions, for example at temperatures between 400 and 700oC, under a pressure varying from atmospheric to 4 MPa, using a rolling or stationary catalyst layer. When using a fixed catalyst layer, the pressure is between 1 and 2 MPa, and when the use is carried out at a mass flow of raw materials processed per unit mass of catalyst per hour in the range from 0.1 to 10 kg/kg / hour.

Part of the formed hydrogen recycle in accordance with the molar degree of recirculation, variable from 0.1 to 8. This degree of recirculation is a molar ratio of recirculating flow of hydrogen to the mass flow of raw materials.

Other characteristics and advantages of the invention can be represented more clearly when reading the following examples; it should be understood that these data are given to illustrate and not to limit the invention.

Example 1.

This example illustrates the obtaining of a catalyst which contains a matrix consisting of a mixture of gamma and ETA-alumina, which precipitated silicon, chlorine, tin, and platinum.

a) preparation of a matrix of aluminum oxide

First get a matrix by mechanical mixing powder of gamma-alumina having a specific surface area of 220 m2/g with this powder is aluminum oxide having a specific surface area of 320 m2/g, which is prepared by calcination bayerite. Share this-aluminum oxide is 10% by weight. Then this mixture is molded by extrusion and calcined in a stream of dry air for 3 hours at 520oC.

b) deposition of silicon
2H5)4. The concentration of this solution is 18.5 grams of silica per liter. This contacting is carried out at room temperature with stirring for 2 hours Then the solvent is evaporated under reduced pressure. Then the impregnated extrudates are dried at 120oC, 15 h and calcined 2 hours at a temperature of 530oC in a stream of dry air. So get the media corresponding to the invention.

c) the deposition of platinum, tin and chlorine

Then simultaneously precipitated platinum, tin and chlorine on the carrier by impregnation with aqueous chlorinated solution containing per 1 liter:

0.96 g of tin as tin chloride (II), SnCl2and

0,81 g of platinum in the form of H2PtCl6.

This solution is kept in contact with the carrier within 2 hours After centrifugation and drying for 4 h at 120oC impregnated carrier is calcined 3 h at 530oC in a stream of dry air.

d) the hydrothermal treatment

This is followed by hydrothermal treatment in the presence of water and chlorine. To this end, the catalyst is treated for 2 hours at a temperature of 510oC in the flow of 2000 l/h per 1 kg of solids. This air contains water and chlorine, which are injected into therefore, its 1% and 0.05%.

Characteristics of the obtained catalyst are shown in table 1.

Example 2

Use the same operating procedure as in Example 1 to prepare a catalyst having the same components, except that the method lacked the hydrothermal treatment, stage d.

Characteristics of the obtained catalyst are also shown in table 1.

Comparative example 1

This Example uses the same operating procedure as in Example 1, but in stage a) only apply gamma-alumina; the method was no stage b) deposition of silicon and the hydrothermal treatment, stage d).

Characteristics of the obtained catalyst are also shown in table 1.

Example 3

In this Example, the catalysts of Examples 1, 2 and Comparative example 1 was tested under the transformation of hydrocarbons having the following characteristics:

bulk density at 20oC 0,736 kg/l

the required octane rating of ~38

the content of paraffin hydrocarbons of 54.8 wt.%

the content of naphthenic hydrocarbons 33,1 wt.%

the content of aromatic hydrocarbons 12.1 wt.%

Use the following operating conditions:

temperature 500oC
P> At the end of the working period deactivated catalyst recovered by controlled combustion of coke and bring the chlorine up to about 1.10 wt.%. After this regeneration measure the value of the specific surface area of the carrier. Then after activation of the catalyst with hydrogen at high temperature are served raw materials in the new period. Thus, each catalyst was subjected to 5 cycles of regeneration. In the following table 2 shows the values of specific surface area corresponding to the first and last cycles, and the performance of the catalyst obtained after 15 h of each of these cycles.

When comparing the performance of the catalysts in Examples 1, 2 and catalyst of the prior art (Comparative example 1) found that the catalysts in Examples 1 and 2 give the best yield of aromatic compounds and the best indicators of the octane number of the product of the reformer. Also found that these improvements were achieved without reducing the yield of products of the reformer.

If now to conduct a review of the indicators after 5 cycles, it becomes evident that a reduction in the specific surface area of the catalysts in Examples 1 and 2 Gorazd the targets in the yield of aromatic compounds and the octane number.

Thus, the catalyst of the invention it is possible to obtain a product with the best octane number, and the product yield of the reformer does not change and remains stable after a few cycles.

Example 4

This example illustrates the obtaining of a catalyst which contains a matrix consisting of a mixture of gamma and ETA-alumina, which precipitated silicon, chlorine, potassium, rhenium and platinum.

a) preparation of a matrix of aluminum oxide

First get a matrix by mechanical mixing powder of gamma-alumina having a specific surface area of 220 m2/g with this powder is aluminum oxide having a specific surface area of 320 m2/g, which is prepared by calcination bayerite. Share this-aluminum oxide is 30% by weight. Then this mixture is molded by extrusion and calcined in a stream of dry air for 3 hours at 520oC.

b) deposition of silicon

After cooling, the calcined matrix it precipitated silica, bringing her into contact with ethanolic tetraethylorthosilicate Si(OC2H5)4. The concentration of this solution is 2.5 grams of silica per liter. This contacting is carried out at room those who installed the extrudates are dried at 120oC, 15 h and calcined 2 hours at a temperature of 530oC in a stream of dry air. So get the media corresponding to the invention.

c) deposition of potassium

Then the catalyst is brought into contact with an aqueous solution of potassium carbonate, K2CO3that contains 12.8 g of potassium per liter. This contacting is carried out at room temperature for 1 hour. Then the impregnated matrix is dried at 120oC, 15 h and calcined 2 hours at 530oC in a stream of dry air.

d) deposition of platinum and chlorine

Then simultaneously precipitated platinum and part of the chlorine on the carrier by impregnation chlorinated water solution containing per 1 liter:

to 8.20 g of chlorine as hydrogen chloride,

to 1.00 g of platinum in the form of H2PtCl6.

This solution is kept in contact with the carrier within 2 hours After centrifugation and drying for 4 h at 120oC impregnated carrier is calcined 3 h at 530oC in a stream of dry air.

e) deposition of rhenium and chlorine

Then simultaneously precipitated rhenium and the rest of chlorine by impregnation of a chlorinated water solution containing 1 l:

4,20 g of chlorine as hydrogen chloride,

1.50 g of rhenium inC in a stream of dry air.

f) the hydrothermal treatment

This is followed by hydrothermal treatment in the presence of water and chlorine. To this end, the catalyst is treated for 2 hours at a temperature of 510oC in the flow of 2000 l/h per 1 kg of solids. This air contains water and chlorine, which is introduced into the preheating zone above the layer of solids. The molar concentration of water and chlorine are respectively 1% and 0.05%.

Characteristics of the obtained catalyst are shown in table 3.

Example 5

Use the same operating procedure as in Example 4 to prepare a catalyst containing the same components except that in stage c) impregnating a solution containing 6.4 g of potassium per liter and no hydrothermal treatment, stage e).

Characteristics of the obtained catalyst are also shown in table 3.

Comparative example 2

This Example uses the same operating procedure as in Example 4, but in stage a) only apply gamma-alumina; no stage b) and (c) deposition of silicon and potassium, as well as the hydrothermal treatment, stage f).

Characteristics of the obtained catalyst is also shown in tablitas of a mixture of gamma-alumina and 8% this-alumina, which precipitated silicon, chlorine, potassium, tin and platinum.

This drug is used the same technique as in Example 4, using in stage a) 8% this-alumina, and instead of stages d) and e) conduct simultaneous deposition of platinum, tin and chlorine at one stage by impregnation of the matrix aqueous chlorinated solution containing per 1 liter:

0,81 g of platinum in the form of H2PtCl6and

0.96 g of tin as tin chloride (II).

This solution is kept in contact with the carrier within 2 hours After centrifugation and drying for 4 h at 120oC impregnated carrier is calcined 3 h at 530oC in a stream of dry air.

This is followed by hydrothermal treatment in the presence of water and chlorine, as in stage f) of Example 4.

Characteristics of the obtained catalyst are shown in table 3.

Example 7

Using the same operating procedure as in Example 6 to prepare a catalyst containing the same components except that in stage c) impregnating a solution containing 6.4 g of potassium per liter and no final hydrothermal treatment in the presence of water and chlorine.

Characteristics of the obtained catalyst t is todeco, as in Example 6, but in stage a) only apply gamma-alumina; no stage b) and (c) deposition of silicon and potassium, as well as the last stage f) for hydrothermal treatment in the presence of water and chlorine as described in Example 1.

Characteristics of the obtained catalyst are also shown in table 3.

Example 8

In this Example, the catalysts of Examples 4, 5 and Comparative example 2 was tested under the transformation of hydrocarbons having the following characteristics:

bulk density at 20oC 0,742 kg/l

the required octane number ~41

the content of paraffin hydrocarbons of 52.2 wt.%

the content of naphthenic hydrocarbons to 32.4 wt.%

the content of aromatic hydrocarbons of 15.4 wt.%

Use the following operating conditions:

temperature 500oC

the total pressure of 1.5 MPa

the mass flow of raw materials for 1 kg of catalyst 2.0 kg/h

the operating time of 100 hours

In the following table 4 shows the performance of the catalyst, expressed as yield (wt.%) and the required octane number of the product of the reformer.

When comparing the performance of the catalysts of Example 4 and Comparative example 2, on the one hand, and indicators of the catalysts of Examples 4 and 5 clearly better performance of the catalyst of the prior art (Comparative example 2).

In fact, the yield of light products of cracking C4 obtained during the testing of the two catalysts in Examples 4 and 5, significantly lower output C4 obtained for the catalyst of Comparative example 2.

So, you can see that the ratio of output of products of cracking C4 to the output of the aromatic compounds named in the above table. 2, as the ratio C4/aromatics below for the two catalysts in accordance with the invention. The selectivity of the catalysts in relation to the target aromatic products will increase at least decrease this ratio.

The catalysts of Examples 4 and 5 containing, in addition, this oxide of aluminum, silicon and potassium, as compared with the catalyst of Example 2 provide improved performance, particularly at reduced selectivity for products of cracking and therefore increasing their selectivity for aromatic products.

Example 9

In this Example, the catalysts of Examples 6, 7 and Comparative example 3 was tested under the transformation of hydrocarbons having the following characteristics:

bulk density at 20oC 0,736 kg/l

the required octane rating of ~38

the content of paraffin hydrocarbons of 54.8 wt.%
Use the following operating conditions:

the temperature of 495oC

the total pressure of 0.75 MPa

the mass flow of raw materials for 1 kg of catalyst 1.8 kg/h

the operating time of 100 hours

At the end of the working period deactivated catalyst recovered by controlled combustion of coke and bring the chlorine up to about 1.10 wt.%. After this regeneration measure the value of the specific surface area of the carrier. Then after activation of the catalyst with hydrogen at high temperature are served raw materials in the new period. Thus, each catalyst was subjected to 5 cycles of regeneration. In the following table 5 shows the values of specific surface area corresponding to the first and last cycles, and the performance of the catalyst obtained after 15 h of each of these two cycles.

When comparing the performance of the catalysts in Examples 6 and 7 with the performance of the catalyst of the prior art (Comparative example 3) found that the catalysts of Examples 6 and 7 give the best yield of aromatic compounds and the best indicators of the octane number of the product of the reformer. It may also be noted that these improvements were achieved without reducing the yield of products of the reformer.

If now the activity of the catalysts in Examples 6 and 7 is much less than the catalyst of the prior art. This is a smaller reduction has the best stability of yields of aromatic compounds and the octane number.

Example 10

This example illustrates the obtaining of a catalyst which contains a matrix consisting of a mixture of gamma and ETA-alumina, which precipitated silica, chloride, lanthanum, rhenium and platinum.

a) preparation of a matrix of aluminum oxide

First get a matrix by mechanical mixing powder of gamma-alumina having a specific surface area of 220 m2/g with this powder is aluminum oxide having a specific surface area of 320 m2/g, which is prepared by calcination bayerite. Share this-aluminum oxide is 40% by weight. Then this mixture is molded by extrusion and calcined in a stream of dry air for 3 hours at 520oC.

b) deposition of silicon

After cooling, the calcined matrix it precipitated silica, bringing her into contact with ethanolic tetraethylorthosilicate Si(OC2H5)4. The concentration of this solution is 2.5 grams of silica per liter. This contacting is carried out at room temperature with stirring during the C, 15 hours and calcined 2 hours at a temperature of 530oC in a stream of dry air.

c) deposition of lanthanum

Then the catalyst is brought into contact with an aqueous solution of lanthanum nitrate, La(NO3)36H2O, which contains 42 g of lanthanum per liter. This contacting is carried out at room temperature for 2 hours. Then the impregnated matrix is dried at 120oC, 15 h and calcined 2 hours at 530oC in a stream of dry air.

d) deposition of platinum and chlorine

Then simultaneously precipitated platinum and part of the chlorine on the carrier by impregnation chlorinated water solution containing per 1 liter:

to 8.20 g of chlorine as hydrogen chloride, and

1.0 g of platinum in the form of H2PtCl6.

This solution is kept in contact with the carrier within 2 hours After centrifugation and drying for 4 h at 120oC impregnated carrier is calcined 3 h at 530oC in a stream of dry air.

e) deposition of rhenium and chlorine

Then simultaneously precipitated rhenium and the rest of chlorine by impregnation of a chlorinated water solution containing 1 l:

4,20 g of chlorine as hydrogen chloride, and

1.50 g of rhenium in the form of rhenium chloride ReCl3.

After dry the treatment

This is followed by hydrothermal treatment in the presence of water and chlorine. To this end, the catalyst is treated for 2 hours at a temperature of 510oC in the flow of 2000 l/h per 1 kg of solid product. This air contains water and chlorine, which is introduced into the preheating zone above the layer of solids. The molar concentration of water and chlorine are respectively 1% and 0.05%.

Characteristics of the obtained catalyst are shown in table 6.

Example 11

Use the same operating procedure as in Example 10 to prepare a catalyst containing the same components except that in stage c) impregnating solution contains 21 g of lanthanum per liter and no hydrothermal treatment, stage f).

Characteristics of the obtained catalyst are also shown in table 6.

Example 12

This example illustrates the obtaining of a catalyst which contains a matrix consisting of a mixture of gamma-alumina, which precipitated silica, chloride, lanthanum, rhenium and platinum.

This drug is used the same procedure as in Example 10, but there is no stage f). At the stage a) apply only gamma-alumina, and the stage b) is carried out in the same conditions, the lead, as in Example 10.

Characteristics of the obtained catalyst are shown in table 6.

Example 13

Use the same operating procedure as in Example 12 to prepare a catalyst containing the same components, but provide one additional hydrothermal treatment under the same conditions as in Example 10, step f).

The chlorine content of the catalyst is 1.08 wt.%.

Comparative example 4

This Example uses the same operating procedure as in Example 10, but in stage a) only apply gamma-alumina and a lack of stage b) and (c) deposition of silicon and lanthanum, and the hydrothermal treatment, stage f).

Characteristics of the obtained catalyst are also shown in table 6.

Example 14

This example illustrates the obtaining of a catalyst which contains a matrix consisting of a mixture of gamma-alumina and 12% of this is aluminium oxide which is precipitated silica, chloride, lanthanum, tin, and platinum.

This drug is used the same procedure as in Example 10, using in stage a) 12 wt.% this-alumina, and instead of stages d) and e) conduct simultaneous deposition of platinum, tin and chlorine at one stage Cl6and

0.96 g of tin as tin chloride (II).

This solution is kept in contact with the carrier within 2 hours After centrifugation and wyszukiwania for 4 h at 120oC impregnated carrier is calcined 3 h at 530oC in a stream of dry air.

This is followed by hydrothermal treatment in the presence of water and chlorine, as in stage f) of Example 10, but the operating temperature is 500oC, and the molar concentration of water and chlorine respectively equal to 1.5% and 0.02%.

Characteristics of the obtained catalyst are shown in table 6.

Example 15

Use the same operating procedure as in Example 14 to prepare a catalyst containing the same components except that in stage c) impregnating solution contains 21 g of lanthanum per liter and no final hydrothermal treatment in the presence of water and chlorine, stage f).

Characteristics of the obtained catalyst are also shown in table 6.

Comparative example 5

This Example uses the same operating procedure as in Example 14, but in stage a) only apply gamma-alumina; no stage b) and (c) deposition of silicon and lanthanum, and the last stagetaitur also given in table 6.

Example 16

In this Example, the catalysts of Examples 10, 13 and Comparative example 4 was tested under the transformation of hydrocarbons having the following characteristics:

bulk density at 20oC 0,742 kg/l

the required octane number ~41

the content of paraffin hydrocarbons of 52.2 wt.%

the content of naphthenic hydrocarbons to 32.4 wt.%

the content of aromatic hydrocarbons of 15.4 wt.%

Use the following operating conditions:

temperature 490oC

the total pressure of 1.4 MPa

the mass flow of raw materials for 1 kg of catalyst 3.0 kg/h

In the following table 7 shows the performance of the catalyst, expressed as yield (wt.%) and the required octane number of the product of the reformer.

When comparing the performance of the catalysts of Example 10 and comparative Example 4, on the one hand, and the performance of the catalysts of Example 11 and Comparative example 4, on the other hand, it was found that the performance of the catalysts in Examples 10 and 11 significantly better performance of the catalyst of the prior art (Comparative example 4).

In fact, the yield of light products of cracking C4 obtained during the testing of the two catalysts in Examples 10 and 11, substantially nie output of products of cracking C4 to the output of the aromatic compounds, named in the table above as the ratio C4/aromatics below for the two catalysts in accordance with the invention. The selectivity of the catalysts in relation to the target aromatic products will increase at least decrease this ratio.

In addition, the catalysts of Examples 10 and 11, containing this-oxides of aluminium, silicon and lanthanum, in comparison with the catalyst of Comparative example 4, provide improved performance, particularly at reduced selectivity for products of cracking and therefore increasing their selectivity for aromatic products.

When comparing the performance of the catalysts in Examples 12 and 13 it can be noted that the catalyst of Example 13 provides improved performance compared with the catalyst of Example 12.

In fact, the catalyst of Example 13 gives significantly reduced the yield of products of cracking C4 and obviously increased the yield of aromatic compounds. The ratio of output of products of cracking C4 to the output of the aromatic compounds named in the table above as the ratio C4/aromatics, lower for the catalyst of Example 13. The selectivity of the catalysts in relation to the target aromatic products beat silicon and lanthanum. In addition, the catalyst of Example 13 is subjected to hydrothermal treatment. It provides superior performance in comparison with the catalyst of Example 12, in particular a reduced selectivity for products of cracking, and therefore increases its selectivity for aromatic products.

Example 17

In this Example, the catalysts of Examples 14, 15 and Comparative example 5 was tested under the transformation of hydrocarbons having the following characteristics:

bulk density at 20oC 0,736 kg/l

the required octane rating of ~38

the content of paraffin hydrocarbons of 54.8 wt.%

the content of naphthenic hydrocarbons 33,1 wt.%

the content of aromatic hydrocarbons 12.1 wt.%

Use the following operating conditions:

temperature 500oC

the total pressure of 0.40 MPa

the mass flow of raw materials for 1 kg of catalyst 2.0 kg/h

the operating time of 100 hours

At the end of the working period deactivated catalyst recovered by controlled combustion of coke and bring the chlorine up to about 1.10 wt.%. After this regeneration measure the value of the specific surface area of the carrier. Then after activation of the catalyst will vodorazdelnaya 5 cycles of regeneration. In the following table 8 shows the values of specific surface area corresponding to the first and last cycles, and the performance of the catalyst obtained after 15 h of each of these two cycles.

When comparing the performance of the catalysts in Examples 14 and 15 with the performance of the catalyst of the prior art (Comparative example 5) it can be noted that the catalysts of Examples 14 and 15 give the best yield of aromatic compounds and the best indicators of the octane number of the product of the reformer. It may also be noted that these improvements were achieved without reducing the yield of products of the reformer.

If now to conduct a review of the indicators after 5 cycles, it may be noted that the decrease in the specific surface area of the catalysts in Examples 14 and 15 is much smaller than that of the catalyst of the prior art. This is a smaller reduction has the best stability of yields of aromatic compounds and the octane number.

Example 18

This example illustrates the obtaining of a catalyst which contains a matrix consisting of a mixture of gamma and ETA-alumina, which precipitated silica, chloride, zirconium, rhenium and platinum.

a) preparation of the sid aluminum, having a specific surface area of 220 m2/g with this powder is aluminum oxide having a specific surface area of 320 m2/g, which is prepared by calcination bayerite. Share this-alumina is 20% by weight. Then this mixture is molded by extrusion and calcined in a stream of dry air for 3 hours at 520oC.

b) deposition of silicon

After cooling, the calcined matrix it precipitated silica, bringing her into contact with ethanolic tetraethylorthosilicate Si(OC2H5)4. The concentration of this solution is 2.5 grams of silica per liter. This contacting is carried out at room temperature with stirring for 2 hours Then the solvent is evaporated under reduced pressure. Then the impregnated extrudates are dried at 120oC, 15 h and calcined 2 hours at a temperature of 530oC in a stream of dry air.

c) deposition of Zirconia

Then the catalyst is brought into contact with an aqueous solution of circinelloides, ZnOCl28H2O that contains 26.7 g of zirconium per liter. This contacting is carried out at room temperature for 2 hours. Then the impregnated matrix is dried at 120oC, 15 h and calcined 2 hours at 530oC in a stream of dry air.


to 8.20 g of chlorine as hydrogen chloride, and

to 1.00 g of platinum in the form of H2PtCl6.

This solution is kept in contact with the carrier within 2 hours After centrifugation and drying for 4 h at 120oC impregnated carrier is calcined 3 h at 530oC in a stream of dry air.

e) deposition of rhenium and chlorine

Then simultaneously precipitated rhenium and the rest of chlorine by impregnation of a chlorinated water solution containing 1 l:

4,20 g of chlorine as hydrogen chloride, and

1.50 g of rhenium in the form of rhenium chloride ReCl3.

After drying the impregnated carrier is calcined 2 hours at 530oC in a stream of dry air.

f) the hydrothermal treatment

This is followed by hydrothermal treatment in the presence of water and chlorine. To this end, the catalyst is treated for 2 hours at a temperature of 510oC in the flow of 2000 l/h per 1 kg of solids. This air contains water and chlorine, which is introduced into the preheating zone above the layer of solids. The molar concentration of water and chlorine are respectively 1% and 0.05%.

Characteristics of the obtained catalyst are shown in table 9.

Approx the same components except that in stage c) impregnating a solution containing 13.3 g of zirconium per liter and no hydrothermal treatment, stage f).

Characteristics of the obtained catalyst are also shown in table 9.

Comparative example 6

This Example uses the same operating procedure as in Example 18, but in stage a) only apply gamma-alumina; no stage b) and (c) deposition of silicon and zirconium, as well as the stage f) for hydrothermal treatment.

Characteristics of the obtained catalyst are also shown in table 9.

Example 20

This example illustrates the obtaining of a catalyst which contains a matrix consisting of a mixture of gamma and ETA-alumina, which precipitated silica, chloride, zirconium, tin, and platinum.

This drug is used the same procedure as in Example 18, using in stage a) 8 wt.% this-alumina, and instead of stages d) and e) perform a one-stage simultaneous deposition of platinum, tin and chlorine by impregnation chlorinated water solution containing per 1 liter:

0,81 g of platinum in the form of H2PtCl6and

0.96 g of tin as tin chloride (II).

This solution leave contactroot the tel calcined 3 h at 530oC in a stream of dry air.

This is followed by hydrothermal treatment in the presence of water and chlorine, as in stage f) of Example 18.

Characteristics of the obtained catalyst are shown in table 9.

Example 21

Use the same operating procedure as in Example 20 to prepare a catalyst containing the same components except that in stage c) impregnating a solution containing 13.3 g of zirconium per liter and no final hydrothermal treatment in the presence of water and chlorine.

Characteristics of the obtained catalyst are also shown in table 9.

Comparative example 7

This Example uses the same operating procedure as in Example 20, but in stage a) only apply gamma-alumina; no stage b) and (c) deposition of silicon and zirconium, as well as the last stage f) for hydrothermal treatment in the presence of water and chlorine.

Characteristics of the obtained catalyst are also shown in table 9.

Example 22

In this Example, the catalysts of Examples 18, 19 and Comparative example 6 was tested under the transformation of hydrocarbons having the following characteristics:

bulk density at 20oC 0, is of naphthenic hydrocarbons to 32.4 wt.%

the content of aromatic hydrocarbons of 15.4 wt.%

Use the following operating conditions:

temperature 505oC

the total pressure of 1.3 MPa

the mass flow of raw materials for 1 kg of catalyst 4.0 kg/h

the operating time of 100 hours

In the following table 10 shows the performance of the catalyst, expressed as yield (wt.%) and the required octane number of the product of the reformer.

When comparing the performance of the catalysts of Example 18 and Comparative example 6, on the one hand, and the performance of the catalysts of Example 19 and comparative Example 6, on the other hand, it was found that the performance of the catalysts in Examples 18 and 19 significantly better performance of the catalyst of the prior art (Comparative example 6).

In fact, the yield of light products of cracking C4 obtained during the testing of the two catalysts in Examples 18 and 19, is significantly lower output C4 obtained for the catalyst of Comparative example 6.

So, you can see that the ratio of output of products of cracking C4 to the output of the aromatic compounds named in the table above as the ratio C4/aromatics below for the two catalysts in Examples 18 and 19. The selectivity of the catalysts in relation to catalizator Examples 18 and 19, containing ETA-alumina, silica, Zirconia, compared with the catalyst of Comparative example 6, provide improved performance, particularly at reduced selectivity for products of cracking and therefore increasing their selectivity for aromatic products.

Example 23

In this Example, the catalysts of Examples 20, 21 and Comparative example 7 was tested under the transformation of hydrocarbons having the following characteristics:

bulk density at 20oC 0,742 kg/l

the required octane number ~41

the content of paraffin hydrocarbons to 42.2 wt.%

the content of naphthenic hydrocarbons to 39.4 wt.%

the content of aromatic hydrocarbons of 16.4 wt.%

Use the following operating conditions:

temperature 505oC

the total pressure of 0.75 MPa

the mass flow of raw materials for 1 kg of catalyst 2.5 kg/h

the operating time of 100 hours

At the end of the working period deactivated catalyst recovered by controlled combustion of coke and bring the chlorine up to about 1.10 wt.%. After this regeneration measure the value of the specific surface area of the carrier. Then after activation of the catalyst with hydrogen at high is iclam work of regeneration. In the following table 11 shows the values of specific surface area corresponding to the first and last cycles and the performance of the catalyst obtained after 15 hours of work for each of these two cycles.

When comparing the performance of the catalysts in Examples 20 and 21 with the performance of the catalyst of the prior art (Comparative example 7) it can be noted that the catalysts of Examples 20 and 21 provide the best yield of aromatic compounds and the best indicators of the octane number of the product of the reformer. It may also be noted that these improvements were achieved without reducing the yield of products of the reformer.

If now to conduct a review of the indicators after 5 cycles, it may be noted that the decrease in the specific surface area of the catalysts in Examples 20 and 21 is much smaller than that of the catalyst of the prior art. This is a smaller reduction has the best stability of yields of aromatic compounds and the octane number.

Thus, the method in accordance with the invention makes it possible to significantly improve the results obtained in the conversion of hydrocarbons into aromatic compounds in terms of selectivity and stability-high volt the connection, including the contacting load of these hydrocarbons with a catalyst containing a matrix, silicon, halogen, noble metal of the platinum group, the promoting metal and subjected to heat treatment under conditions of temperature and pressure suitable for the above-mentioned transformations, characterized in that the catalyst contains: matrix containing the gamma-modification of aluminum oxide or a mixture of gamma - and this is a modification of aluminum oxide, calculated on the total weight of the catalyst is from 0.01 to 2 wt.% silicon, from 0.1 to 15 wt.% at least one halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, from 0.01 to 2 wt.% at least one noble metal from the platinum group and 0.005 to 10 wt.% at least one promoting metal selected from the group consisting of tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten, and the catalyst is subjected to hydrothermal treatment at a temperature of from 300 to 1000oC in an atmosphere gas containing water vapor.

2. The method according to p. 1, characterized in that the matrix of the catalyst contains from 3 to 70 wt.% this is a modification of aluminum oxide.

3. The method according to any of paragraphs.1 and 2, the best of the e of one of the alloying metal, selected from the group consisting of alkali and alkaline earth metals.

4. The method according to p. 3, wherein the alloying metal is potassium.

5. The method according to any of the p. 1 or 2, characterized in that the catalyst also contains calculated on the total weight of the catalyst is from 0.001 to 10 wt.% at least one alloying metal selected from the group consisting of titanium, zirconium, hafnium, cobalt, Nickel and zinc.

6. The method according to p. 5, wherein the alloying metal is zirconium.

7. The method according to any of the p. 1 or 2, characterized in that the catalyst also contains calculated on the total weight of the catalyst is from 0.001 to 10 wt.% at least one alloying metal selected from the group of lanthanides.

8. The method according to p. 7, wherein the alloying metal is lanthanum.

9. The method according to any of paragraphs. 1 to 8, characterized in that the silicon content in the catalyst is from 0.01 to 1 wt.%.

10. The method according to any of paragraphs.1 to 8, characterized in that the content of halogen in the catalyst is from 0.2 to 10 wt.%.

11. The method according to any of paragraphs.1 to 8, characterized in that the total content of noble metal is from 0.1 to 0.8 weight the t group, consisting of rhenium, manganese, chromium, molybdenum, tungsten, indium and thallium.

13. The method according to p. 12, characterized in that the promoting metal in the catalyst is rhenium.

14. The method according to any of paragraphs.1 to 8, characterized in that the promoting metal catalyst selected from the group consisting of tin, germanium, indium, antimony, lead, thallium and gallium.

15. The method according to p. 14, characterized in that the promoting metal in the catalyst is tin.

16. The method according to any of paragraphs.1 to 8, characterized in that the halogen in the catalyst is chlorine.

17. The method according to any of paragraphs.1 to 8, characterized in that the noble metal catalyst is platinum.

18. The method according to any of paragraphs.1 to 17, characterized in that the hydrothermal treatment, which is subjected to the catalyst, is carried out in the period from 1 min to 30 h in the atmosphere of gas containing from 0.05 to 100 mol.% water.

19. The method according to any of paragraphs.1 to 18, characterized in that the molar content of water is from 1 to 50%.

20. The method according to any of paragraphs.1, 18 and 19, characterized in that period hydrothermal treatment is from 1 to 10 hours

21. The method according to any of paragraphs.1 to 18, characterized in that at the holding of halogen gases in the atmosphere can reach up to 20 mol.%.

23. The method according to p. 21, characterized in that the halogen content in the atmosphere gas can reach up to 10 mol.%.

24. The method according to p. 21, characterized in that the halogen content can reach up to 2 mol.%.

25. The method according to any of paragraphs.1 and 18 to 24, characterized in that the atmosphere gas is air, oxygen, argon or nitrogen.

26. The method according to any of paragraphs.1 to 25, characterized in that the load of hydrocarbons contains paraffin, naphthenic and aromatic hydrocarbons having from 5 to 12 carbon atoms, and the load is brought into contact with the catalyst at a temperature of from 400 to 700oC and a pressure in the range from atmospheric up to 4 MPa.

27. The method according to any of the p. 12 or 26, characterized in that the pressure is from 1 to 2 MPa.

28. The method according to any of the p. 14 or 26, characterized in that the pressure is from 0.1 to 0.9 MPa.

29. The method according to any of paragraphs.26 to 28, characterized in that the load of hydrocarbons is brought into contact with the catalyst at a mass flow rate load in the range of from 0.1 to 10 kg of hydrocarbon per 1 kg of catalyst per hour.

30. The method according to any of paragraphs.1 to 29, characterized in that the conversion of hydrocarbons is kataliticheski

 

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The invention relates to a method for producing high-octane gasoline and aromatic hydrocarbons from hydrocarbons containing aliphatic olefins and paraffins, using a zeolite catalyst and can be used in the refining and petrochemical industry

The invention relates to a method of preparation of the catalysts for purification of exhaust gases from nitrogen oxides, in particular gases of metallurgical production, thermal power plants

The invention relates to the field of organic synthesis, namely the selective acetoxysilane 1,3-cyclopentadiene (CPD) in CIS-3,5-diacetoxyscirpenol (DACP)

The invention relates to the primary organic synthesis, and in particular to catalysts for diacetoxybiphenyl S-CIS-1,3-pen - tadiene in diacetoxybiphenyl

The invention relates to the production of catalysts for reforming of gasoline fractions

The invention relates to catalysts for hydrogenations of aromatic nitro compounds and can be used in the manufacture of dyes, upon receipt of the primary amines used in the manufacture of caprolactam, isocyanates, in the syntheses of means for plant protection

The invention relates to catalysts for hydrogenations of aromatic nitro compounds and can be used in the manufacture of dyes, upon receipt of the primary amines used in the manufacture of caprolactam, isocyanates, in the syntheses of means for plant protection

The invention relates to catalysts for hydrogenations of aromatic nitro compounds and can be used in the manufacture of dyes, upon receipt of the primary amines used in the manufacture of caprolactam, isocyanates, in the syntheses of means for plant protection

The invention relates to catalysts for hydrogenations of aromatic nitro compounds and can be used in the manufacture of dyes, upon receipt of the primary amines used in the manufacture of caprolactam, isocyanates, in the syntheses of means for plant protection
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