RU2448080C2 - Method for heterogeneous catalytic partial dehydrogenation of hydrocarbon to undergo dehydrogenation - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method for heterogeneous catalytic partial dehydrogenation, where an input stream of a gaseous reaction mixture containing the hydrocarbon to be dehydrogenated passes through a solid catalyst layer in a column, and the input stream of the gaseous reaction mixture in the column is formed by adding a gas I to the input stream being fed to the solid catalyst layer in the column, where gas I contains molecular hydrogen and the hydrocarbon to be dehydrogenated. An input gas II containing molecular oxygen is added before the solid catalyst layer.

EFFECT: method provides completely satisfactory homogenisation of CO₂ concentration after passing through an inert layer.

39 cl, 18 dwg

Description

The present invention relates to a method for heterogeneous catalytic partial dehydrogenation of at least one dehydrogenated hydrocarbon to at least one dehydrogenated hydrocarbon, in which for the purpose of partial dehydrogenation of at least one hydrocarbon to be dehydrogenated, the entire volume of the input stream of the reaction gas mixture containing molecular oxygen, molecular hydrogen and at least one hydrocarbon to be dehydrogenated is carried through the solid layer mash, located in a mine with a predetermined cross-section, which includes, when looking in the direction of the flow of the input gas stream of the reaction gas mixture, first filling with inert molded products, and then catalytically active filling with at least one molded catalyst product, formed so that for the reaction combustion of molecular hydrogen with molecular oxygen to produce water and / or for the combustion reaction of a hydrocarbon contained in the input stream of the reaction gas mixture with oxygen to about carbon monoxide and water, it provides less activation energy in the inlet section than for dehydrogenation of at least one hydrocarbon to be dehydrogenated to at least one dehydrogenated hydrocarbon, so that part (usually at least 1 mol.%, or at least 2 mol%, or at least 3 mol%, or at least 4 mol%, or at least 5 mol%) of at least one dehydrogenated hydrocarbon to be dehydrated to at least one dehydrogenated hydrocarbon, and input OK, the reaction gas mixture in the mine is created by adding molecular oxygen inlet to the solid catalyst layer to the molecular hydrogen entering the mine in volumetric stream V1 to the solid catalyst bed and to the inlet stream I containing at least one hydrocarbon to be dehydrogenated gas II with a total flow volume of V2.

In addition, the present invention relates to a device for implementing the method according to the invention, as well as a method for partial oxidation of at least one dehydrogenated hydrocarbon.

As used herein, the term “dehydrogenated hydrocarbon” refers to hydrocarbons whose molecules contain at least two (“two”, preferably from the point of view of application) hydrogen atoms less than the hydrocarbon molecules to be dehydrogenated. Otherwise, the term "hydrocarbon" means substances whose molecules are built only by elements of carbon and hydrogen.

Thus, dehydrogenated hydrocarbons include, in particular, acyclic and cyclic aliphatic hydrocarbons, in the molecule of which there are one or several C-C double bonds.

Examples of such aliphatic dehydrogenated hydrocarbons are propene, isobutene, ethylene, 1-butene, 2-butene and butadiene. Those. dehydrogenated hydrocarbons, in particular, include single unsaturated linear (n-alkenes) or branched aliphatic hydrocarbons (eg, isoalkenes), as well as cycloalkenes. In addition, alkapolyenes (for example, dienes and trienes), whose molecules contain more than one double bond between carbon atoms, are classified as dehydrogenated hydrocarbons. Dehydrated hydrocarbons should also include hydrocarbon compounds derived from alkyl aromatic compounds, for example ethylbenzene or isopropylbenzene, by dehydrogenation of alkyl substituents. These are, for example, compounds such as styrene or α-methyl styrene.

In the most general sense, dehydrogenated hydrocarbons are valuable starting materials (raw materials) for the synthesis of, for example, functionalized compounds suitable for radical polymerization (for example, acrylic acid from propene and methacrylic acid from isobutene), and their polymerization products. Such functionalized compounds can, for example, be created by partial oxidation of dehydrogenated hydrocarbons. Dehydrated hydrocarbons, however, are also suitable for the production of compounds such as methyl tert-butyl ether (an isobutene derivative, which, for example, can be used as a fuel additive to produce an octane number). Dehydrogenated hydrocarbons are, however, suitable for polymerization and as such.

The hydrocarbons to be dehydrated in this text are, in particular, acyclic and cyclic alkanes, but also olefins (in which it is necessary to increase the number of double bonds between carbon atoms). Partial dehydrogenation of n-butenes to heterogeneous catalysis butadiene should be mentioned as an example.

Those. The term “hydrocarbons to be dehydrogenated” in this text means, for example, hydrocarbons with the general stoichiometric formula C _n H _{2n + 2} , where n> 1 and n≤20, as well as with stoichiometric characteristics C _n H _2n , where n> 1 and n≤20, and with stoichiometric characteristics C _n H _2n-2 , where n> 2 and n≤20, and n is integer, in particular alkanes with 2-16 carbon atoms, such as ethane (before ethylene), propane (to propylene), n-butane, isobutane (to isobutene), n-pentane, isopentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n -tridecan, n- tetradecane, n-pentadecane and n-hexadecane.

In particular, however, all that is said in the present text, as hydrocarbons subject to dehydrogenation, refers to alkanes with 2-6 carbon atoms, and in particular to hydrocarbons with 2-4 carbon atoms (in particular alkanes). Those. in this text, the hydrocarbons to be dehydrogenated are primarily ethane, propane, n-butane and isobutane, but also 1-butene and 2-butene.

Partial dehydrogenation of a heterogeneous catalysed hydrocarbon in this text means dehydrogenation (conventional), in which at least the intermediate formation of free molecular hydrogen occurs, and, therefore, the dehydrogenation step takes place endothermally (exothermic combustion of hydrogen can be used as the next step). In contrast, in partial oxidation with heterogeneous catalysis, the removal of hydrogen from the hydrocarbon to be dehydrogenated due to the presence of oxygen occurs directly in the form of water (H ₂ O). Therefore, the dehydrogenation step of partial oxidation with heterogeneous catalysis is distinguished in principle by exothermic flow.

In addition, the partial dehydrogenation with heterogeneous catalysis in this text is dehydrogenation in the solid catalyst layer.

Typically, for the partial (conventional) dehydrogenation of at least one hydrocarbon to be dehydrogenated (e.g. propane), relatively high reaction temperatures are necessary. The resulting turnover is usually limited by thermodynamic equilibrium. Typically, the reaction temperature is between 300 and 800 ° C. Or between 400 and 700 ° C. For a molecule, for example one propane, dehydrogenated to propylene, one hydrogen molecule is produced. High temperatures and removal of the reaction product H ₂ , as well as a decrease in partial pressure due to dilution with inert substances, favor an equilibrium in the sense of at least one dehydrogenated hydrocarbon as the final product. Moreover, in the present text, inert gas (inert dilution gas) generally means a component of the reaction gas mixture, which, under the conditions of the corresponding reaction, generally behaves chemically inert and, when each inert component of the reaction gas mixture is considered separately, remains chemically unchanged more than 95 mol.%, preferably more than 97 mol.% or more than 99 mol.%. Examples of typical inert dilution gases are N ₂ , H ₂ O, CO ₂ , noble gases such as He, Ne and Ar, as well as mixtures of these gases, etc.

Since the partial dehydrogenation of at least one hydrocarbon (for example, propane) to be dehydrogenated to at least one dehydrogenated hydrocarbon results in a dehydrogenation step endothermally, the heat (energy) required for the desired reaction temperature is communicated to the reaction gas in advance and / or during dehydrogenation with heterogeneous catalysis.

Partial dehydrogenation with heterogeneous catalysis is easiest to implement in a shaft-shaped reactor. By such a shaft is meant a reaction space enclosed by a material envelope in contact with the reaction space, which is equipped with at least one first opening for supplying the reaction gas mixture to the reaction space and at least one second opening for collecting at least one product gas stream from the reaction space. At least one solid catalyst bed is located in the reaction space (in the shaft) through which the reaction gas mixture flows. During the residence time in the solid catalyst bed, the desired partial dehydrogenation of at least one hydrocarbon to be dehydrogenated to at least one dehydrogenated hydrocarbon occurs.

A sufficient dehydrogenation turnover is achieved even when the mine (reactor) is insulated from its surroundings (quasi-adiabatic conditions are provided), the reaction gas mixture is heated to a temperature (starting temperature) of 350 or 400 to 800 ° C (often from 500 to 700 ° C) or from 550 to 650 ° C) and conduct the reaction gas mixture in only one adiabatic passage through at least one solid catalyst layer located in the reaction space (in the shaft (reactor)).

Depending on the turnover and the selected inert dilution, the reaction gas is cooled by approximately 30-200 ° C with a single pass through the solid catalyst layer.

Additionally, it is advisable to use water vapor as an inert diluent gas in the reaction gas mixture for partial dehydrogenation with heterogeneous catalysis for two reasons. Firstly, water vapor has a relatively high molar heat capacity, which reduces the degree of cooling indicated above in the framework of such a joint application.

With a reduced degree of cooling, a reduced initial temperature is often sufficient for the required level of turnover. This is advisable in view of the fact that in partial dehydrogenation reactions of at least one hydrocarbon to be dehydrogenated, as the initial temperature rises through undesirable side reactions, the formation increases, incl. small amounts of heavy boiling high molecular weight organic compounds (thermal decomposition products), up to elemental hydrocarbons, deposited on the surface of the catalyst and thus deactivating it. However, the carbon deposited on the surface of the catalyst, with increasing partial dehydrogenation temperature with heterogeneous catalysis in the presence of water vapor as an inert dilution gas, is constantly, at least partially, or completely removed by the principle of coal gasification.

The dehydrogenation of a hydrocarbon (e.g. propane) with heterogeneous catalysis in a shaft type reactor (with adiabatic communication with the external environment) is advisable then (as with a dehydrogenation revolution per one passage of the reaction gas mixture through the reactor, not exceeding 30 mol.%, And with values of more than 30 mol.% (for example, up to 40 mol.%, or up to 50 mol.%, or up to 60 mol.%)), when the reactor is multi-stage.

Such a multi-stage reactor includes more than one solid catalyst layer (closed reaction space) that catalyzes dehydrogenation, which layers are arranged sequentially in the mine one after another. The number of catalyst layers can be, for example, from 1 to 20, it is advisable from 2 to 8, or from 3 to 6. As a rule, the solid catalyst layers are then located one after the other radially or along the axis.

A particularly simple option is to place solid catalyst layers along the axis of the catalyst in the shaft, one after the other, in the direction of flow of the reaction gas. However, it is possible to arrange them in annular slots between cylindrical gratings inserted concentrically into each other in the shaft. You can also place annular slots in the shaft in the segments one above the other and conduct the reaction gas after the radial passage of one segment to the next, located above or below.

On the way from one solid catalyst bed to another, the reaction gas can be subjected to intermediate heating (to externally control temperature changes), for example, passing it through indirect heat exchangers (for example, heat exchangers) located in the mine between sections of the solid layer and working on hot gases and / or liquids ribs, or heat exchanger plates, or heat exchangers in the form of tube bundles).

If the shaft reactor is otherwise operating in adiabatic mode, then for dehydrogenation revolutions (for example, propane → propylene revolutions) not exceeding 40 mol% for a single passage of the reaction gas through the shaft reactor (for example, when using the catalysts described in applications for German patent DE-A 102005044916 and DE-A 19937107, in particular, given as examples), as a rule, it is sufficient to introduce the reaction gas mixture into the shaft (into the reaction-protected enclosure containing solid catalyst layers) completely heated to a temperature of 350, or 400, or from 450 to 550 ° C (preferably from 400 to 500 ° C), and inside the shaft (around the catalyst layers located in it) at least maintain the temperature in this range using indirect heat transfer (external control of temperature changes). This also has a particularly favorable effect on the service life of the solid catalyst layers before regeneration.

From the point of view of application technology, however, it is more reasonable to carry out the aforementioned intermediate heating directly (internal control of temperature changes). For this, to the reaction gas mixture (to the reaction gas), it is possible to move along the shaft along the mine path, for example, after passing through the first solid catalyst layer in the direction of the reaction gas stream, and also between subsequent solid catalyst layers in the direction of the reaction gas stream, preferably in a limited amount, in each case, add a gas containing molecular oxygen, thereby creating a stream of a reaction gas mixture containing molecular oxygen, molecular hydrogen and at least one n hydrocarbon to be dehydrogenated.

If a catalyst bed next to the flow of this reaction gas mixture containing at least one molded article from the catalyst (for example, by proper selection of the active mass) is formed so that it is at least in the inlet region in the direction of flow of the reaction gas mixture containing molecular oxygen, molecular hydrogen and at least one hydrocarbon to be dehydrogenated, provided lower activation energy for the molecular oxygen combustion reaction molecular hydrogen to form water and / or for the combustion reaction of a hydrocarbon with oxygen contained in the reaction gas mixture to form carbon oxides and water, than to dehydrogenate at least one hydrocarbon to be dehydrogenated, then when the reaction gas mixture passes through a solid catalyst bed in a solid firstly, limited exothermic combustion of molecular hydrogen and / or soda contained in the reaction gas mixture will primarily occur zhaschegosya in the reaction gas mixture of hydrocarbon and molecular oxygen (to produce water - or H ₂ O as H ₂ O and carbon oxides). The heat of reaction generated in this case heats the reaction gas mixture and can be used for further passage of the reaction gas mixture through a solid catalyst bed, mainly including endothermic dehydrogenation. The resulting combustion products, such as: CO ₂ , H ₂ O, as well as N ₂ , possibly accompanying the molecular oxygen necessary for combustion, form the desired inert diluent gases.

In the reaction gas mixture formed earlier and containing molecular hydrogen, leaving the solid catalyst layer, it is then possible, before entering the next solid catalyst layer in the direction of the reaction gas mixture flow, to again add gas containing molecular hydrogen, in a limited volume, etc. .

A shift in the balance between the combustion of hydrogen and the combustion of a hydrocarbon upon entering a mixture containing molecular oxygen, molecular hydrogen and at least one hydrocarbon to be dehydrogenated is possible first of all by selecting a catalyst in the inlet region (in the direction of the flow of the reaction mixture of gases) with catalytic activity. As catalysts that relatively specifically (selectively) catalyze the combustion of molecular hydrogen and / or hydrocarbon, for example, those mentioned in US patent applications US-A 4,788,371, US-A 4,886,928, US-A 5,430,209, US-A can be used 5,530,171, US-A 5,527,979 and US-A 5,563,314.

The dominance of "hydrogen burning" is usually preferable to the dominance of "hydrocarbon burning" because it provides both increased selectivity for the formation of at least one dehydrogenated hydrocarbon compound and an increased dehydrogenation rate based on a single passage of the reaction gas through a multi-stage reactor. As a rule, it is ensured when the backfill with catalytic activity contains only dehydrogenation catalysts as catalysts (in particular, those recommended, and especially those given as examples in the German patent application DE-A 19937107), since they usually capable of catalyzing not only the dehydrogenation of a hydrocarbon to be dehydrogenated (for example, propane), but also the combustion of molecular hydrogen and hydrocarbons with molecular oxygen. In this case, the combustion of hydrogen proceeds much faster than the dehydrogenation of at least one hydrocarbon to be dehydrogenated (for example, propane), and much faster than the combustion of such in the case of competition for these catalysts (i.e., under such conditions they provide the lowest with a significant margin - activation energy for the combustion of molecular hydrogen).

Depending on the volume of the combustion reaction (also depending on the amount of added molecular oxygen), the total reaction during a single passage of the reaction gas mixture through a multi-stage reactor from the point of view of the total thermal effect (ie relative to the gross thermal effect ) can be either endothermic (negative) or autothermal (mostly zero) or exothermic (positive).

In this case, the burning of molecular hydrogen delivers approximately two times the amount of heat compared with that used for its formation in the framework of dehydrogenation.

Of course, between the two solid catalyst beds, both the principle of external temperature control and the principle of internal control can be used. The isothermal qualities of the partial dehydrogenation of at least one heterogeneous catalysis hydrocarbon can also be improved by placing steps in the reaction space between the solid catalyst layers of closed embedded structures (for example, in the form of pipes), which are advisable, but not necessary, to be evacuated before filling. Such embedded structures can also be placed in a particular solid catalyst bed. These structures contain proper solids or liquids that evaporate or melt when a certain temperature is exceeded and thus consume heat, and when the temperature drops below this value, they condense again and generate heat. In order to further improve the isothermal characteristics outside the envelope surface of the shaft-shaped reactor, in principle, it is possible to additionally ensure the movement of fluid (gaseous or liquid) coolants. From the point of view of the application technique, however, significant costs arise, due to which, as a rule, it is preferable to perform adiabatically with the external environment.

It goes without saying that the described internal temperature control measures can also be used to heat the reaction gas mixture supplied to the first solid catalyst layer in the direction of flow of the reaction gas mixture to the desired reaction temperature. For these purposes, it is possible to add molecular hydrogen from another source to the mine reactor containing at least one hydrocarbon to be dehydrogenated and sent to a shaft reactor. However, one can do without such an addition of hydrogen. In this case, internal temperature control can mainly be carried out only by burning a hydrocarbon. Often, the reaction gas mixture supplied to the first solid catalyst bed can be brought to the reaction temperature in another way. For example, the initial gas flows from which the reaction gas mixture is fed to the first solid catalyst bed may initially have a corresponding temperature. In addition, these feed streams may initially contain molecular oxygen, so that the problem of adding a gas containing molecular oxygen to the gas mixture entering the first solid catalyst layer in the flow direction does not arise.

In principle, methods for partially dehydrogenating at least one dehydrogenated hydrocarbon to at least one heterogeneous catalysis dehydrogenated hydrocarbon in a shaft reactor configured as a multi-stage solid-bed reactor with internal control of temperature changes are known (cf., for example, patent applications Germany DE-A 102005061626, DE-A 102005057197, DE-A 102005052923, DE-A 102005052917, DE-A 102005022798, DE-A 102005009885, DE-A 102005010111, DE-A 102004032129, DE-A 102005013039, 03 / 076370, German patent application DE-A 10211275, international application WO 01 / 96270 and the technical level cited in these publications).

From the aforementioned publications, there is also known a method for such execution of a single solid catalyst bed of a multistage reactor, in which a catalyst bed with catalyst activity including at least one catalytic molded catalyst article is coated with inert molded articles in the direction of flow of the reaction gas stream mixtures to add to the gas stream entering such a solid catalyst bed and containing molecular water One and at least one hydrocarbon to be dehydrogenated, a gas containing molecular oxygen necessary for internal temperature control, before this gas stream reaches a solid catalyst bed (i.e., an inert bed (bed from inert molded articles) covering the bed itself with the catalytic bed activity).

The specified description of the technical level leaves, however, a completely open question in what way, i.e. how to add a gas stream containing molecular oxygen on an industrial scale.

However, according to the results of our own studies, the method of adding a gas stream containing molecular oxygen to a gas stream containing molecular hydrogen and at least one hydrocarbon subject to dehydrogenation entering the mine onto an appropriate solid catalyst bed is important for implementing the method on an industrial scale for various reasons .

Firstly, where gas containing molecular oxygen is added, local zones of increased oxygen concentration arise. In the most unfavorable cases, they can be of the kind that will lead to the local formation of flammable (explosive) gas mixtures, which is undesirable from the point of view of application technology, which means that the existence of these mixtures should be short-lived in any case, and from the point of view of localization strictly limited. In addition, even before the desired combustion with heterogeneous catalysis, the reaction gas mixture obtained after addition is characterized by an elevated temperature (which additionally increases during the combustion with heterogeneous catalysis). Therefore, before the reaction gas mixture containing molecular oxygen reaches the solid catalyst bed, the reaction gas mixture usually undergoes undesirable homogeneous radical reactions (for example, undesired exothermic homogeneous radical reactions of partial oxidation and / or oxidation of a hydrocarbon; local evolution of reaction heat generated when these adverse reactions, causes a local temperature increase, the result of which is usually the activation of unwanted thermal decomposition of hydrocarbons) with a wide range of by-products, which reduces the selectivity for the final product and, as a rule, also reduces the life of the catalyst. Selectivity in the final product, reduced to such an extent, is a disadvantage especially when at least one product that is the target of the reaction, i.e. at least one dehydrogenated hydrocarbon must undergo the following reaction (for example, partial oxidation with heterogeneous catalysis). Within the solid catalyst bed, such undesirable radical side reactions are generally suppressed, since the significant internal surface of the solid bed backfill plays the role of a radical scavenger. The severity of such undesirable radical reactions, as a rule, exponentially increases with increasing reaction time.

In this regard, there have already been proposals to add a gas containing molecular oxygen only directly into the inert bed covering the catalytically active bed. This method of operation, however, is unfavorable in the sense that when the gas containing molecular oxygen is distributed inside an inert bed, a centralized feed distribution system (for example, a piping system with outlet openings) encounters in an inert bed a resistance that is distributed mainly randomly (depending on whether any inert molded product closes the given outlet of the piping system and to what extent). This may undesirably lead to local comparative differences in the flows of the incoming gas containing molecular oxygen. In the worst case scenario, this can lead to the fact that when a gas containing molecular oxygen is adjusted, in the sense of supplying the total quantity per unit time, no gas containing molecular oxygen flows from some of the outlet openings - and a gas containing molecular oxygen enters the outlet hydrogen and at least one hydrocarbon to be dehydrogenated. In addition, inert molded products can adversely affect individual flows exiting the outlet openings, and in the extreme case even remove the local feed stream from the solid catalyst layer.

When a reaction gas mixture containing added molecular oxygen enters a bed located behind an inert bed in the direction of flow, which has catalytic activity itself, an uneven distribution of oxygen in the reaction gas mixture leads to bedding with catalytic activity, due to local catalysis, to differences in the degrees of combustion. They are accompanied by corresponding local differences in heat production. Local temperature rises, however, cause accelerated local aging of the backfill with catalytic activity. Although a possible increase in the length of the inert filling in the direction of flow allows one to achieve mainly a homogeneous distribution of molecular oxygen in the reaction gas mixture when it enters the filling with catalytic activity, such an increase in the length of the inert filling is accompanied by an increase in pressure loss of the reaction gas mixture during the passage of filling, which, after all, it requires increasing compressor power. In addition, with an increase in the residence time of the reaction gas in an inert bed, undesired side reactions can also develop. This is especially significant when the inner surface of the inert bed is relatively limited.

The objective of the present invention, therefore, is to propose the method described in the preamble of this publication, which will be as complete and as possible as economical as possible, i.e. in a simple and least costly manner, takes into account the details specified in the preamble and minimizes the size of the inert filling. The approach described in US patent application US-A 2,584,391 does not solve the problem, since it focuses on the method implemented in the catalytic fluidized bed.

The theoretical presentation of the patent application of Germany DE-A 102004024957 also does not provide a solution to the problem. First, it deals with heterogeneous catalysis oxidation, in which the reaction gas mixture containing molecular oxygen is fed directly into the bed with catalytic activity. In addition, there are breaks in the feed system. In addition, this requires a system of bundles of pipes with expensive tube sheets (bottoms), the production of which requires a relatively high cost.

International application WO 2004/074222 does not offer assistance in solving the problem. So, it contains the requirement that the gas, which includes molecular oxygen, and the gas stream containing at least one hydrocarbon to be dehydrogenated, go strictly parallel to each other flows, which requires a relatively complex device. In addition, parallel flow management requires a relatively long mixing area.

The German patent application DE-A 102004003070, again, does not contribute to the solution of the problem, since it is associated with oxidation with heterogeneous catalysis, in which the reaction gas mixture is fed directly to the bed with catalytic activity.

Therefore, as a solution to the problem that has not been solved at the current technical level, a method is presented for partial dehydrogenation of at least one hydrocarbon to be dehydrogenated to at least one heterogeneous catalysis dehydrogenated, in which for the purpose of partial dehydrogenation of at least one hydrocarbon to be dehydrogenated the volume of the input stream of the reaction gas mixture containing molecular oxygen, molecular hydrogen and at least one dehydrogenated The hydrocarbon is passed through a solid catalyst bed located in a mine with a predetermined cross-section, which includes - when looking in the direction of the flow of the reaction gas inlet stream - first backfill from inert molded products, and then the catalytically active backfill of at least at least one molded catalyst product, formed so that for the reaction of combustion of molecular hydrogen with molecular oxygen to form water and / or for the reaction of combustion of a hydrocarbon containing of the reaction gas mixture in the inlet stream, with oxygen to carbon oxides and water, it provides lower activation energy in the inlet section than for dehydrogenation of at least one dehydrogenated hydrocarbon to at least one dehydrogenated hydrocarbon, so that part (as a rule at least 1 mol.%, or at least 2 mol.%, or at least 3 mol.%, or at least 4 mol.%, or at least 5 mol.%) of at least one subject hydrocarbon dehydrogenation about at least one dehydrogenated hydrocarbon, and the input stream of the reaction gas mixture in the mine is created by the fact that the molecular hydrogen entering the mine in the volumetric stream V1 on the solid catalyst layer, and the input stream I containing at least one hydrocarbon to be dehydrogenated , to the solid catalyst layer add molecular oxygen-containing inlet gas II with a total volume of stream V2, characterized in that the inlet gas II is supplied in the form of gas flows II flowing from most of the outlet the holes A of the piping system located in the direction of the inlet gas flow II in front of the solid catalyst bed so that

a) The totality of the directions of the majority M of all the inlet gas flows II flowing from the outlet openings A under conditions of an imaginary absence of the inlet gas stream I make an angle α equal to 90 ± 60 ° with the direction of the inlet gas stream I;

b) The distance D of the majority M of all outlet openings A from the solid catalyst layer, taking into account the flow rate W of the gas inlet stream I in the mine, is less than the induction time J of the reaction gas mixture (this is a gas mixture constituting the input stream of the reaction gas mixture) times 2 · W, or equal to it;

c) When projecting the centers of gravity of most M of all the outlet openings A in the direction of the gas inlet stream I onto the projection plane E perpendicular to the direction of the gas inlet stream I flow for at least 75% (preferably at least 80%, preferably at least for 85%, or at least 90%, it is advisable - at least 95% or even better for 100%) of the projection area captured by the inlet gas stream I, the number of ZA centers of gravity of the outlet openings located on an arbitrary square meter is not less than 10;

d) Separate inlet gas flows II flowing from the outlet openings A belonging to the number ZA of the centers of gravity of the outlet openings A (for example, volumetric or mass flows) deviate from their number average by no more than 50% (when calculated based on the number average );

, иe) Within the limits of the number ZA of the outlet openings, the distance d from one center of gravity of the outlet opening to the nearest to the center of gravity of the outlet opening to it closest to it (in the projection plane E) is not more than

, and

f) The ratio V1: V2≥8 is satisfied.

In the method according to the invention, it is in principle possible to add the inlet gas II (in the case of, for example, air) at a temperature of, for example, 20 ° C. (outside temperature).

According to the invention, however, it is advisable (this ensures a uniform distribution of gas density over the outlet openings A) so that the difference ΔT _II ^I (modulo) between the temperature of the inlet gas stream I and the inlet gas II does not exceed 300 ° C. Preferably, ΔT _II ^I does not exceed 250 ° C, it is particularly preferred that it does not exceed 200 ° C, it is even more preferred that it does not exceed 150 ° C, it is particularly advisable that it does not exceed 100 ° C, it is highly preferred that the difference was not more than 75 ° C, it is extremely advisable that it does not exceed 50 ° C, even better - it does not exceed 30 ° C, and best of all, that it is ≤20 ° C, or ≤10 ° C, or 0 ° C.

If both temperatures are not identical, then the temperature of the input stream I, as a rule, is higher.

In particular, the above is true if the temperature of the input stream I satisfies the condition ≥350 ° C (for example, ≥375 ° C, or ≥400 ° C, or ≥425 ° C, or ≥450 ° C, or ≥475 ° C, or ≥500 ° C, or ≥525 ° C, or ≥550 ° C, or ≥600 ° C). As a rule, this temperature does not exceed 800 ° C, often does not exceed 700 ° C.

The solid catalyst layer located in the mine during the implementation of the method according to the invention may be the only solid catalyst layer located in the shaft reactor, or one of the many solid catalyst layers in the shaft reactor, made in the form of a multi-stage reactor. If this solid catalyst bed is the first in a shaft reactor when viewed in the direction of the reaction gas stream, then the reaction gas inlet stream usually does not yet contain dehydrogenated hydrocarbon. If, when implementing the method according to the invention, this solid catalyst layer is the one following the first in the direction of the reaction gas stream, then the input stream of the reaction gas mixture (the gas stream entering this solid catalyst layer) is normal, however, will contain and how much at least one dehydrogenated hydrocarbon. The solid catalyst layer in the implementation of the method according to the invention may also be in the multistage reactor the last solid catalyst layer in the direction of flow of the reaction gas.

This means that, in principle, the method according to the invention can be applied to all solid catalyst layers present in a multi-stage reactor.

The inlet reaction gas mixture, which is already fed to the first solid catalyst bed in the shaft reactor in the direction of the reaction gas flow, may, however, also for various reasons contain at least one dehydrogenated hydrocarbon. For example, when, when working as described in international application WO 03/076370 or in the German patent application DE-A 10211275, the gas product stream exiting the dehydrogenation reactor is divided into two parts with the same composition and one of the parts is returned to the reaction the gas mixture supplied to the dehydrogenation reactor as a dehydrogenation circulating gas, and the second part is further used in another way (for example, in order to partially oxidize the dehydrogenated hydrocarbon obtained in the reaction space with heterogeneous catalysis).

Accordingly, the foregoing is also true for the gas inlet stream I, which together with the molecular oxygen-containing inlet gas II constitutes the inlet stream of the reaction gas mixture supplied to the solid catalyst bed during the implementation of the method according to the invention.

In principle, it is possible to use both pure molecular oxygen and a mixture of molecular oxygen and an inert gas (for example, air) as input gas II when implementing the method according to the invention. As such inert gases, for example, molecular nitrogen, carbon dioxide, noble gases and / or water vapor can be used.

From the point of view of application technology, it is advisable that the inlet gas II was a mixture of air and water vapor. The use of mixtures of molecular oxygen with an inert gas as input gas II is more expedient in comparison with the use of pure molecular oxygen in this capacity insofar as this reduces the risk of explosion when mixing the input gas II with the input gas stream 1 of the region of the outlet openings A. In addition, the additional use of inert gas in the inlet gas II makes it possible to increase the total volume flows V2, which is expedient in the sense of stability (uniformity) when adding the inlet gas II to the inlet gas stream I. If, however, an increase in the proportion of inert gas in the resulting gas stream partial dehydrogenation of at least one heterogeneous catalysis hydrocarbon is undesirable (for example, if with the further use of at least one dehydrogenated hydrocarbon it turns out to be ballast m, for the movement of which costs are necessary), then this share in the inlet gas II should be minimized.

The appropriate inlet gases II during the implementation of the method according to the invention may, for example, contain the following components:

from 0 to 80 vol.% water vapor,

from 10 to 97 vol.% N ₂ and

from 3 to 25 vol.% O ₂ .

In this case, the possible composition variations of the inlet gas II can be as follows:

from 15 to 80 vol.% H ₂ O,

from 20 to 85 vol.% N ₂ and

from 5 to 25 vol.% O ₂ ;

or

from 15 to 60 vol.% H ₂ O,

from 20 to 80 vol.% N ₂ and

from 5 to 20 vol.% O ₂ .

The ratio of the volumetric flow V1 (in Nm ³ / h; Nm ³ is the volume in m ³ that the corresponding amount of gas would occupy under normal conditions (0 ° C, 1 atm)) and the volumetric flow V2 (also in Nm ³ / h) when implementing the method according to the invention satisfies the condition ≥8. It is advisable that it be not less than 10, particularly preferably not less than 15, and very preferably not less than 20. Often the ratio V1: V2 when implementing the method according to the invention also satisfies the condition ≥25 or ≥30, or ≥40 or ≥50 . Typically, however, the ratio V1: V2 when implementing the method according to the invention satisfies the condition ≤500, often ≤400 or ≤300, often also ≤200 or ≤100.

Typically, when implementing the method according to the invention, the solid catalyst layer has in the direction of flow of the reaction gas mixture not only a coating layer of inert material, but also a final layer of inert molded products. The reason is that, for example, in the case of using an axial multistage reactor, the solid catalyst layer typically lies on a gas permeable grating shelf, the cell size of which is larger than the size of the molded catalyst products.

If the solid catalyst layer in the mine during the implementation of the method according to the invention is the first (and possibly the only) solid catalyst layer in the mine reactor in the direction of the flow of the initial gas stream I, then the incoming gas stream I moving in the mine with a volumetric value stream V1 typically corresponds to an inlet gas stream supplied to a shaft reactor to dehydrogenate at least one heterogeneous catalysed hydrocarbon to be dehydrogenated. Typically, it contains at least 5% by volume of at least one hydrocarbon to be dehydrogenated (e.g., propane). In addition, it may contain, for example:

a) N ₂ ;

b) N ₂ and H ₂ O;

c) N ₂ , H ₂ O and H ₂ ;

d) N ₂ , H ₂ O, CO ₂ and H ₂ or

e) N ₂ , H ₂ O, CO, CO ₂ and H ₂ .

In addition to this, it may also already contain limited amounts of molecular oxygen.

If, however, the solid catalyst layer in the implementation of the method according to the invention is a layer following this first solid catalyst layer in the shaft reactor in the direction of the reaction gas stream, then the incoming gas stream I will normally correspond to the reaction gas mixture leaving the previous solid the catalyst bed in the direction of the flow of the reaction gas, which usually in addition to the aforementioned gases contains at least one dehydrogenated hydrocarbon. As a rule, in this case it will not contain molecular oxygen.

By the majority M of all the outlet openings A (and the individual flows of the inlet gas II flowing out of them) in this publication, we should mean those outlet openings A (and the separate flows of the inlet gas II flowing out of them), of which more than 50% preferably more than 60 or 70%, particularly preferably more than 80 or 90%, and very preferably 100%) of the total volumetric flow V2, provided that among the individual inlet gas streams II flowing from them within the total amount all individual input streams There is not a single gas II that is smaller than the largest of the individual inlet gas flows II that do not belong to this majority of M.

According to the invention, it is preferable that all individual inlet gas streams II flowing from the outlet openings A have the same dimensions within production capabilities.

The geometric characteristics of the outlet openings A, when implementing the method according to the invention, can, in principle, be arbitrary. Those. it is possible to use both outlet A in the form of polygons (for example, triangular, quadrangular, pentagonal, hexagonal, etc.), and round (for example, elliptical or round). It is advisable that when implementing the method according to the invention, uniform outlet parameters (including size) are given to all outlet openings A. According to the invention, round outlet openings A (“holes”) are preferred. It is advisable that the maximum length L (in the case of round outlet openings - their diameter) of outlet A (this is the longest straight line segment connecting two points lying on the line bordering this outlet A) satisfies the condition ≥0 when implementing the method according to the invention , 1 mm and up to ≤5 cm. the possible values of L are ≥0.2 mm to ≤4 cm, and ≥0.3 mm to ≤3 cm, or ≥0.4 mm to ≤2 cm, or ≥0.5 mm to ≤1 cm, often ≥1 mm and up to ≤5 mm.

It is advisable that the area (cross-section) of the outlet openings A be within (π · L ² ) / 2, and the boundaries of the above ranges should be substituted as L.

If the ratio R formed by the maximum length L of the outlet A * and the smallest length K of this outlet A * (this is the shortest straight line passing through the center of gravity of the outlet A * and connecting two points lying on the line bounding this outlet A * ), i.e. R = L: K, ≥5 (usually R <5 and ≥1), then this is the outlet A * (for example, if the outlet A * is a slit), for the purposes of the present invention, it should be replaced by uniform round virtual holes in the calculations And in the amount of n, which is calculated as follows:

,

,

where π = the ratio of the circumference to its diameter,

U = length of the outlet circuit A *, and

F = outlet area A *.

If n is not an integer, then it is rounded to the nearest integer (in the case of "1.50" and similar rounding is performed upward).

The diameter d _{h of the} aforementioned virtual outlet openings A is calculated as follows:

This number is designated as the hydraulic diameter of the outlet A *.

The centers of gravity of these virtual circular exit openings A are located on the straight line segment G, the length of which corresponds to the largest size (greatest length) L, and which passes through the center of gravity of the outlet A * in such a way that this center of gravity divides the length G in half, and the segment G itself, being at least extended, intersects the contour of the outlet A * twice, and the straight line G forms a right angle with the direction of the gas inlet flow I. The centers of gravity n of the virtual outlet openings should be evenly distributed over the segment G, and the center of gravity of the outlet A * itself should form the center (center of gravity, midpoint) of this distribution.

The expression "in conditions of an imaginary absence" of the inlet gas stream I means that when implementing the method according to the invention, the (separate) inlet gas stream II flowing from the outlet A changes its direction when it meets the inlet gas stream I. Therefore, to establish the angle α, the direction of the flow (separate stream) of the inlet gas II flowing from a given outlet orifice A, which would take place if, for the otherwise otherwise unchanged process conditions, the inlet gas stream I would be absent .

According to the invention, it is advisable that for most M all of the outlet openings A (or for the inlet gas flows II emanating from them), the angle α is 90 ± 50 °, preferably 90 ± 40 °, particularly preferably 90 ± 30 °, even more preferably 90 ± 20 °, very preferably 90 ± 10 °, even better 90 ± 5 °, and best of all - 90 °. For the direction of this (separate) stream of the inlet gas II flowing from the outlet, the direction of the central stream is taken.

According to the invention, the outlet openings A must be in front of the solid catalyst bed. Those. Outlets A must not be blocked by inert molded products. Moreover, it is advisable that the beam drawn from the center of gravity of the outlet A, perpendicular to the direction of flow of the inlet gas I, does not come into contact with any inert molded product for at least two ways (preferably four, especially preferably at least six, and very preferably at least eight) hydraulic diameters d _h of the outlet A (d _h = 4 · F / U), and best of all - at any distance. Otherwise, according to the invention, it is preferable that the outlet openings A are as close as possible to the solid catalyst layer.

In this publication, the shortest straight line connecting the center of gravity of the outlet with the point at which the inert molded product comes into contact with the inert coating bedding of the solid catalyst layer is taken to remove D of outlet A from the solid catalyst layer.

According to the invention, the distances D from the majority M of all outlet openings A to the solid catalyst layer, taking into account, when calculating, the velocity W (in m / s) of the inlet gas stream I (= the volume stream of the inlet gas I divided by the minimum cross-sectional area through which this volume flow (which is the area covered by the inlet gas stream I on a plane perpendicular to the inlet gas stream I through which the inlet gas stream I flows, taking into account the fact that centers t the holes of the outlet openings A)) in the shaft should be less than or equal to the induction time J (in s) of the inlet reaction gas mixture, multiplied by 2 · W. Those. for most M of all the outlets A, the condition must be fulfilled: D≤2 · W · J.

In this case, the induction time J should be understood as follows.

If an induction gas mixture that has the same molecular oxygen content and the hydrocarbon to be dehydrogenated (in each case vol.%) As the input stream of the reaction gas mixture, and which is created by means of the hydrocarbon to be dehydrogenated (or its mixture with molecular nitrogen) as source gas 1 add molecular oxygen in the form of source gas 2 in the form of air (either as pure molecular oxygen, or as a mixture of it with molecular nitrogen) (i.e. from gases other than mol oxygen and hydrocarbon to be dehydrogenated, the induction gas mixture contains only molecular nitrogen), and which has the same temperature T ^R and is at the same pressure P ^R as the input stream of the reaction gas mixture, provide itself the oxygen content (O ₂ ) in this induction gas mixture decreases as a function of time. The induction time J of the input stream of the reaction gas mixture in this case is the time during which the oxygen concentration in the corresponding induction gas mixture decreases to 70% of its initial value (absolute value).

A simple way to determine the induction time J experimentally is as follows.

A Y-shaped mixing nozzle made of quartz glass (tube inner diameter 0.6 cm; wall thickness 1 mm; fork angle 90 °; both branches of the branching are twisted into a spiral, each stretched length of 2 m; tube length Y- a branching mixing nozzle of 0.5 m) is placed in a furnace (for example, in a furnace with infrared emitters or in a circulation furnace), where it is heated to a temperature of T. Initial gas 1 is supplied to one of the branches of the fork, and the second - source gas 2. At the end of the quartz tube Y-image Nogo mixing nozzle carrier branching set valve gear which opens when the pressure P ^R. The volumetric flows of both feed gases are measured relative to each other so that, after connecting the tubes, an induction gas mixture of the desired composition is formed. Absolute volume flows are set so that the oxygen content in the induction gas mixture upon exiting the carrier tube of the Y-shaped mixing nozzle (mixing tube) is only 70% of the calculated initial value. Based on the flow rate and the length of the quartz mixing tube, J is obtained as the quotient of dividing the length by the flow rate. Moreover, as a rule, the volume flow of the induction gas mixture in the mixing tube will be less than 10 m ³ / h. The oxygen concentration at the outlet of the carrier tube of the Y-shaped mixing nozzle (mixing tube) can be determined using a lambda probe (λ probe). The latter can be performed as an element of Nernst. We are talking about a ceramic sensor, one side of which is placed in the flow of the induction gas mixture, and the other in the oxygen standard. For example, ambient air can be used as such a reference. At elevated temperature T ^{R, the} ceramic probe material, which usually consists of zirconium oxide with yttrium addition, acquires the ability to conduct negative oxygen ions. The difference in the concentration of molecular oxygen in both gases causes ion diffusion in the probe. Due to this, on a platinum electrode located in the probe between its outer and inner sides, it is possible to relieve the voltage — probe voltage. This voltage is described by the Nernst equation and is a direct measure of the oxygen concentration in the flow of the induction gas mixture at the outlet of the carrier tube of a Y-shaped mixing nozzle (mixing tube).

An alternative is to use a resistance lambda probe. In this case, the sensitive element usually consists of a ceramic material based on titanium dioxide, which has the properties of a semiconductor. In this case, “oxygen holes” become the charge carriers — places where there is no oxygen acting as donors. In the presence of oxygen in the environment, the holes are filled, and the number of free charge carriers decreases. Oxygen ions do not significantly contribute to conductivity; on the contrary, oxygen reduces the number of free charge carriers. At a high oxygen concentration, the sensor material has high resistance. The signal is received from a voltage divider with a fixed resistance.

Manufacturers of lambda probes are, for example, Robert Bosch GmbH, as well as Denso and NGK.

By the center of gravity of the outlet in this publication is meant the imaginary center of gravity with uniform filling (area) of the hole with mass.

According to the invention, it is preferable that the condition D≤1 · W · J is fulfilled for most M of all outlet openings A, more preferably D≤0.5 · W · J. It is highly preferred that the condition D≤0.2 · W · J be valid for most of all outlets A. Even better, for the majority of all outlets A, the condition D≤0.05 · W · J is valid. It is particularly advisable that this condition is always true for all outlets A. In addition, according to the invention, it is advisable that for all outlets A the value of D is the same.

The strict need, however, for the same value for all outlets A to be D is not.

If, however, the projection of the centers of gravity of most M of all the outlet openings A in the direction of the gas inlet stream I onto the projection plane E is perpendicular to the direction of the gas inlet stream I flow, then at least 75% (preferably at least 80%, better - at least 85%, or at least 90%, it is advisable - at least 95% or even better for 100%) the projection area captured by the inlet gas stream I, the number of ZA centers of gravity of the outlet openings located on an arbitrary square meter should be at least 10. According to the invention, it is advisable that the condition ZA≥20 or ≥30, preferably ZA≥40 or ≥50, particularly preferably ZA≥60 or ≥70, very preferably ZA≥80 or ≥90 or ≥100. It is advisable according to the invention to choose large values of ZA (as a rule, an increase in ZA entails a decrease in the maximum size L of the outlet openings A). In principle, when implementing the method according to the invention, ZA can be up to 100,000 or more. For reasons of cost-effectiveness, however, ZA is typically less than 10,000, often less than 1,000.

.Within the limits of the number ZA of the outlet openings, the distance d from one center of gravity of the outlet opening to the closest center of gravity of the outlet opening to it (in the projection plane E) should not exceed

.

, или не больше чем

, или не больше чем

.Those. according to the invention d should be no more than

, or no more than

, or no more than

.

).Of course, the number ZA of the centers of gravity of the outlet openings can also be evenly distributed over the projection area covered by the inlet gas stream I on the projection plane E (

)

Furthermore, according to the invention, it is advantageous for the outlet openings not to be opposite each other, so that the inlet gas flows II flowing from these outlet openings A would be directed oppositely to each other.

In addition, according to the invention, it is essential that the individual flows (for example, volume or mass) of the inlet gas II flowing from the outlet openings A belonging to the number ZA of the centers of gravity of the outlet openings deviate from their number average value (averaged over the number ZA) of not more than by 50% (preferably not more than 40%, particularly preferably not more than 30%, very preferably not more than 20% or not more than 10%, even better - not more than 5% , and best of all - they would not deviate at all). In this case, the deviation is calculated based on the number average value.

According to the invention, it is advisable that when implementing the method according to the invention, the shaft geometrically represented a straight (not beveled) cylinder, i.e. two equal (congruent) bases lying in parallel planes, the points of which are connected by parallel straight lines perpendicular to the planes of both bases. Within the framework of cylindrical geometrical parameters, an elliptical cylinder is preferable, and first of all, a cylinder having a circle as a base.

It goes without saying that the use of the method according to the invention also includes the situation where, in addition to injecting a gas containing molecular oxygen according to the invention, in front of the solid catalyst bed, a gas containing molecular oxygen is also added to the inert coating bed.

According to the invention, another requirement is that, based on a single passage of the stream of the initial reaction gas mixture through the solid catalyst bed, a part of at least one hydrocarbon to be dehydrogenated, namely at least 1 mol, contained in the stream of the initial reaction gas mixture. %, or at least 2 mol.%, or at least 3 mol.%, or at least 4 mol.%, or at least 5 mol.% (preferably at least 7 mol.%, particularly preferably - at least 9 mol.%, and extremely pre meaningfully at least 11 mol.%), was subjected to dehydrogenation to at least one dehydrogenated hydrocarbon. Usually, however, the above fraction in molar percent satisfies the condition of ≤20 mol%.

In the General case, the stream of the initial reaction gas mixture contains, as a rule, at least 5 vol.% At least one hydrocarbon to be dehydrogenated. Often, this volume fraction, with appropriate values, satisfies the condition of ≥10 vol.%, Often ≥15 vol.%, And most often ≥20 vol.%, Or ≥25 vol.%, Or ≥30 vol.%. As a rule, however, this volume fraction with the corresponding values satisfies the condition ≤90 vol.%, For the most part ≤80 vol.% And often ≤70 vol.%. Like all numerical data in this publication, the above values are true, in particular, in the case of using propane as a hydrocarbon to be dehydrogenated and propylene as a dehydrogenated hydrocarbon. Of course, they are also true when the hydrocarbon to be dehydrated is isobutane and the dehydrogenated hydrocarbon is isobutene.

Typically, the amount of inlet gas II added to the inlet gas stream I, when implementing the method according to the invention, is measured so that the resulting reaction gas mixture, calculated on the amount of hydrocarbon and dehydrogenated hydrocarbon (for example, propane and propylene) to be dehydrated, contained therein contained from 0.01 or 0.5 to 30 vol.% molecular oxygen.

According to the invention, it is advisable that the molar content of molecular oxygen in the stream of the initial reaction gas mixture is not more than 50 mol.% Of the amount (in moles) of molecular hydrogen contained therein.

As a rule, the molar content of molecular oxygen in the stream of the initial reaction gas mixture, relative to the amount (in moles) of molecular hydrogen contained in it, is from 10 to 40 mol.%, Often from 15 to 35 mol.% And often from 20 to 30 mol.%.

According to the invention, it is advisable that when implementing the method according to the invention, when passing the stream of the initial reaction gas mixture through the solid catalyst bed, all molecular oxygen (or at least 95 mol% of it) contained in the stream of the initial reaction gas mixture was used to burn molecular hydrogen containing in the stream of the initial reaction gas mixture.

From the point of view of the application technique, it is advisable that when implementing the method according to the invention, when passing the flow of the initial reaction gas mixture through the solid catalyst bed using molecular oxygen, approximately half the amount of molecular hydrogen that, in the case of a multi-stage reactor, was formed in the previously passed solid catalyst bed .

The initial pressure of the stream of the initial reaction gas mixture when it enters the solid catalyst layer during the implementation of the method according to the invention is, as a rule, from 1.5 to 6 bar, often from 2 to 5 bar, and in many cases from 3 to 4 bar.

The temperature of the flow of the initial reaction gas mixture when it enters the solid catalyst layer during the implementation of the method according to the invention is, as a rule, from 300 to 700 ° C, often from 350 to 600 ° C, and in many cases from 400 to 500 ° C.

In the present text, “loading of a solid catalyst bed catalyzing a reaction step with a reaction gas” in the most general sense means the amount of reaction gas in normative liters (= Nl; volume in liters that an appropriate amount of reaction gas mixture would occupy under normal conditions, i.e. e. at 0 ° C and 1 atm), which in one hour passes through one liter of the solid catalyst layer. The load can also be calculated from only one of the components of the reaction gas.

In this case, this is the volume of this component in Nl / l · h that passes through a liter of the solid catalyst layer per hour (a clean filling of inert material is not included in the calculation in the solid catalyst layer). The load can also be calculated only relative to the amount of catalyst that is contained in the solid catalyst layer, which includes the catalyst itself, diluted with an inert material (in this case, a special note is given).

In principle, the method according to the invention can be implemented at a load on the solid catalyst layer (relative to the total amount of catalyst contained therein) by both the reaction gas and at least one hydrocarbon to be dehydrogenated (e.g., propane) contained therein, from 100 up to 10000 h ^-1 (Nl / l · h, abbreviated h ^-1 ), often from 300 to 5000 h ^-1 , i.e. in many cases, from 500 to 3000 h ^-1 (mainly regardless of the desired turnover of at least one hydrocarbon to be dehydrogenated).

When implementing the method according to the invention, the input gas stream I, as a rule, enters the solid catalyst layer located in the mine, mainly vertically. Those. the angle β between the direction of flow of the inlet gas I in the shaft and the plane superimposed on the surface of the solid catalyst layer to which the stream enters is usually 90 ± 30 °, preferably 90 ± 20 °, particularly preferably 90 ± 10 °, very preferably 90 ± 5 °, and best of all - 90 °.

When implementing the method according to the invention, the area (backfill) in the shaft of the solid catalyst layer to which the stream enters is not less than 1 m ² . In many cases, it satisfies the condition of ≥2 m ² , or ≥3 m ² , or ≥4 m ^2, or ≥5 m ² . Of course, the indicated area may also satisfy the condition of ≥10 m ² , or ≥20 m ² , or ≥30 m ² . In the so-called world scale installations, the aforementioned area can also be at least 40 m ² or 50 m ² . Values of this area exceeding 100 m ² are more likely an exception.

In principle, all dehydrogenation catalysts known at the current technical level as used for dehydrogenation with heterogeneous catalysis can be used as catalysts for backfilling with catalytic activity. They can be roughly divided into two groups. Firstly, these are catalysts having an oxide nature (for example, chromium oxide and / or alumina), and secondly, those consisting of supported on a support, usually oxide (for example, zirconium oxide, alumina, dioxide silicon, titanium dioxide, magnesium oxide, lanthanum oxide and / or cerium oxide), a metal, as a rule, relatively noble (for example, platinum). Among other things, you can use all dehydrogenation catalysts that are recommended in international patent application WO 01/96270, European application EP-A 731077, German patent applications DE-A 10211275, DE-A 10131297, international application WO 99/46039, application for US patent US-A 4,788,371, European application EP-A 705136, international application WO 99/29420, US patent applications US-A 4,220,091, US-A 5,430,220, US-A 5,877,369, European application EP-A 117146, patent applications Germany DE-A 19937196, DE-A 19937105, US patent applications US-A 3,670,044, US-A 6,566,573 and in international application WO 94/29021. Moreover, these catalysts for the above reasons may be the only catalysts in the catalytically active filling when implementing the method according to the invention. In principle, backfill with catalytic activity may consist solely of molded articles having catalytic activity. Of course, backfill with catalytic activity can also consist of molded articles having catalytic activity, diluted with inert molded articles. These inert molded products can be made, for example, from calcined clays (aluminosilicates) or steatite (for example, C 220 manufactured by CeramTec), or other (preferably mainly pore-free) materials of the high-temperature ceramic class, such as aluminum oxides, dioxide silicon, titanium dioxide, magnesium oxide, lanthanum oxide, cerium oxide, mixed zinc oxide and aluminum, thorium dioxide, zirconium dioxide, silicon carbide or other silicates, such as magnesium silicate, or mixtures of the above materials. When implementing the method according to the invention, the aforementioned materials can also be used for an inert coating, and, if necessary, for the backfill of the solid catalyst layer.

Advantageously, the inert coating bedding of the solid catalyst layer for the method according to the invention is such that no more than 35 mol% (preferably ≤30 mol%, particularly preferably ≤25 mol%) pass through this inert bed with the feed of the reaction gas mixture. , even better, ≤20 mol%, particularly suitable ≤15 mol%, even more suitable ≤10 mol%, and very preferably ≤5 mol% or 0 mol%) of molecular oxygen contained therein.

In particular, the catalysts (examples 1, 2, 3 and 4 of the German patent application DE-A 19937107) can be used as catalysts (for example, the only ones) for catalytic backfill of a solid catalyst layer in the method according to the invention.

We are talking about dehydrogenation catalysts that contain from 10 to 99.9 wt.% Zirconium oxide, from 0 to 60 wt.% Alumina, silicon dioxide and / or titanium dioxide and from 0.1 to 10 wt.% at least one element of the first or second main group, one of the elements of the third side group, one element of the eighth side group of the periodic system of elements, lanthanum and / or tin, so that the sum of weight percentages is 100 wt.%.

In a preferred embodiment, the aforementioned dehydrogenation catalysts comprise at least one side group element VIII, at least one main group I and II element, at least one main group III and / or IV element and at least one side III element groups including lanthanides and actinides. Preferably, as an element of the side group VIII, the active mass of the dehydrogenation catalysts contains platinum and / or palladium, particularly preferably platinum. Preferably, as the elements of the main group I and II, the active mass of the aforementioned dehydrogenation catalysts contains potassium and / or cesium. As elements of the side group III, including lanthanides and actinides, the active mass of the aforementioned dehydrogenation catalysts preferably contains lanthanum and / or cerium. As elements of the III and / or IV main group, the active mass of the aforementioned dehydrogenation catalysts preferably contains one or more elements belonging to the group comprising boron, gallium, silicon, germanium, tin and lead, particularly preferably tin. It is highly preferred that the active mass of the aforementioned dehydrogenation catalysts contains at least one representative of the aforementioned element groups.

In general, dehydrogenation catalysts can be filaments (a typical diameter is from 0.1 or 1 to 10 mm, preferably from 1.5 to 5 mm; a usual length is from 1 to 20 mm, preferably from 3 to 10 mm) , tablets (preferably the same sizes as the threads) and / or catalyst rings (outer diameter and height in each case, usually from 2 to 30 mm or up to 10 mm, a suitable wall thickness is from 1 to 10 mm, or up to 5 mm , or up to 3 mm).

There are no fundamental limitations either regarding the geometric parameters of the catalysts (especially in the case of supported catalysts), or regarding the geometric parameters of inert molded products. Particularly often used are solid cylinders, hollow cylinders (rings), balls, cones, pyramids and cubes, as well as threads, wheels, sprockets and monoliths.

The maximum size of molded products from the catalyst, as well as inert molded products (the longest straight line connecting two points located on the surface of the molded product) can be from 0.5 mm to 100 mm, often from 1.5 mm to 80 mm, and in many cases from 3 mm to 50 mm or up to 20 mm.

Finally, the catalysts described in German patent application No. 102005044916, made as particularly suitable for use (for example, as the only catalysts) for having a catalytic activity of filling the solid catalyst layer when implementing the method according to the invention.

In the framework of the method according to the invention, the removal of high-boiling high molecular weight organic compounds deposited on the catalyst surface, up to carbon, which lead to catalyst deactivation, and catalyst regeneration can be carried out by occasionally passing oxygen-containing gas through the solid catalyst layer at an elevated temperature and thus practically burning out precipitated substances.

The catalysts recommended in this publication can be regenerated after long-term operation in a simple way, first (at the first stage of regeneration) by passing through the solid layer of the catalyst diluted with nitrogen and / or (preferably) water vapor air having an inlet temperature of 300 to 600 ° C (in extreme in cases - also up to 750 ° C), often from 400 to 450 ° C. In this case, the load of the catalyst by the regeneration gas (calculated on the total amount of the regenerating catalyst) can be, for example, from 50 to 10,000 h ^-1 , and the oxygen content in the regeneration gas can be from 0.5 to 20 vol.%.

Then, in the next stages of regeneration, under otherwise unchanged conditions of regeneration, air can be used as a regeneration gas. From the point of view of the application technique, it is advisable to purge the catalyst before regeneration with an inert gas (for example, N ₂ , in particular industrial nitrogen, containing up to 1 vol.% O ₂ , H ₂ O, or mixtures thereof).

Then, as a rule, it is generally useful to continue regeneration using pure molecular hydrogen or molecular hydrogen diluted with an inert gas (preferably with water vapor and / or nitrogen, the hydrogen content must satisfy the condition ≥1 vol .-%), with the otherwise unchanged regeneration conditions .

According to the invention, it is advisable that the ratio of the bed length X (in the direction of flow of the initial reaction gas mixture) of the inert coating layer of the solid catalyst layer and the distance d in the projection plane E, i.e. X: d, would satisfy the condition ≥0.05, preferably ≥0.07, and especially advisable ≥0.1. Often this aforementioned X: d ratio satisfies the condition ≥0.2, or ≥0.3, or ≥0.5, or ≥1 when implementing the method according to the invention. Usually, however, this X: d ratio for the most part does not exceed 10, and in many cases it does not exceed 5.

For the purposes of the method according to the invention, it is advisable that when the reaction gas mixture enters the bed of the catalyst layer which has proper catalytic activity and is located after the inert bed in the flow direction, the distribution of molecular oxygen in the reaction gas mixture is as uniform as possible. It is preferable that the difference between the highest local volumetric concentration of molecular oxygen and the lowest local volumetric concentration of molecular oxygen in the reaction gas mixture, relative to the average volumetric concentration of molecular oxygen in the reaction gas mixture upon entering the reaction gas mixture in the catalyst bed with the actual catalytic activity, be no more than more than 200%, preferably not more than 150%, particularly preferably not more than 100%, and extremely preferably not more than 50%, or not more than 25%.

Typical values of the induction time J when implementing the method according to the invention can satisfy the condition ≤2000 ms, or ≤1000 ms, or ≤500 ms, or ≤100 ms, or ≤50 ms, or ≤20 ms, or ≤10 ms. Typically, the values of the induction time J when implementing the method according to the invention, however, satisfy the condition of ≥1 ms.

In principle, the cross-section of the pipeline system through which the inlet gas II is supplied can be arbitrary when implementing the method according to the invention. Those. the section can be, for example, round (for example, round or oval or elliptical), or polygonal (for example, triangular, quadrangular or hexagonal, etc.).

From the point of view of the application technique, it is advisable that the cross-section of the pipelines through which the inlet gas II arrives at the place where the outlet openings A are is polygonal. Preferably triangular or quadrangular. It is particularly preferable that the cross-section of the pipelines (channels) through which the inlet gas II arrives at the place where the outlet openings A are located is square or rectangular (in this case, the outlet openings A are as close as possible to the edge of the quadrangle that is closest to solid catalyst bed). The reason for the above lies in the fact that when using the indicated cross section in the form of a polygon, it is easier to produce (set) both exact and uniform deletions D and angles α for all outlet openings A. With respect to outlet openings A themselves, it is preferable that of the indicated polygonal cross-sectional shape, they were rounded (round), and it is preferable that the diameter of all outlet openings A be the same. Moreover, according to the invention, it is preferable that D be the same for all outlet openings A. Furthermore, according to the invention, it is advisable that the angle α also be the same for all outlet openings A and be 90 ° ± 5 ° or equal to 90 °. Further, when implementing the method according to the invention, it is advisable that all the inlet gas flows II flowing out from the outlet openings A are identical, and ideally, with respect to the surface (plane) of the solid catalyst layer to which the reaction gas mixture inlet flows Outlets A were also evenly distributed on this plane.

If, when implementing the method according to the invention in a shaft reactor designed as a multi-stage reactor, the solid catalyst layer is one that follows the other (previous) solid catalyst layer in the direction of the reaction gas flow, then it is advisable to implement the method according to the invention that the previous solid catalyst layer (its filling) was as uniform as possible, homogeneous (especially with respect to the length of the filling in the direction of flow of the reaction gas). The consequence of this as uniform as possible execution of the preceding solid catalyst layer is a substantially uniform flow of the reaction gas through the preceding solid catalyst layer and the resulting maximum uniform pressure level over the entire inlet gas stream I of the method according to the invention.

Thus, it is possible to achieve common advantages for the entire method according to the invention. In particular, so that the maximum local differences in pressure encountered within the flow of the inlet gas I between the outlet openings A are less than the pressure losses occurring during the outflow of separate flows of the inlet gas II from the outlet openings A, or in the worst case be equal to these losses. If the losses are, for example, 5 mbar, according to the invention it is advisable that the above-mentioned maximum pressure differences encountered are not more than 3 mbar.

It should be added here that when implementing the method according to the invention, the piping system through which the inlet gas II enters is expediently implemented so that the pressure reduction that occurs on the way from the inlet gas II inlet to the pipeline system until the inlet gas II arrives at the outlet A , was as small as possible (in particular, with respect to pressure loss during passage of exit openings A; as a rule, this pressure reduction should be no more than one fifth, preferably not more than one tenth, from pressure loss), and - in the case of uniform execution of the outlet openings A - as uniform as possible (especially when the adjustment of the inlet gas supply II is based on the total supply quantity). Such a slight decrease in pressure occurs, for example, when the length of the piping system and the flow rate in the system are kept as low as possible, and the flow cross section in the piping system is at a high level.

If the method according to the invention is used in a multi-stage reactor on several solid catalyst beds (if necessary, on all those in the reactor, or on all except one), it is preferable to supply the inlet gas II through a separate piping system in front of each solid catalyst bed. In principle, however, these independent piping systems can be supplied (powered) from a single source of inlet gas II.

As a rule, however, they are supplied with inlet gases II that differ from each other (in composition).

As the material from which the equipment necessary for the method according to the invention is made, it is possible, in particular, to use steel grades recommended in German application No. 102005061626. In particular, from the side in contact with the product, also stainless steel type DIN 1.4841.

The method according to the invention is especially suitable when it is implemented in a shaft reactor made in the form of a multi-stage reactor, and in this case on all solid catalyst layers located in the shaft reactor, possibly with the exception of the first solid catalyst layer in the shaft reactor in the flow direction reaction gas. The last exception occurs, as a rule, when the reaction gas supplied to the shaft reactor already contains at least one hydrocarbon to be dehydrogenated, if necessary - in sufficient quantity - molecular hydrogen, as well as molecular oxygen as required. Usually, the latter occurs when the reaction gas supplied to the shaft reactor, designed as a multi-stage reactor, includes residual gas, which includes oxygenate (for example, non-reacted molecular oxygen) and originating from partial dehydrogenation at least one dehydrogenated hydrocarbon (e.g., propane) to at least one dehydrogenated hydrocarbon (e.g., propylene) partially oxidizing the at least one dehydrides hydrocarbon (for example, propylene with the formation of acrolein and / or acrylic acid as the final product), accompanied by a (residual) hydrocarbon to be dehydrogenated, remaining after the partial oxidation products are separated from the desired product from the gas mixture. By the complete oxidation (burning) of a dehydrated and / or dehydrogenated hydrocarbon in this publication is meant the complete conversion of the carbon contained in a hydrocarbon into carbon oxides (CO, CO ₂ ), and the hydrogen contained therein into H ₂ O; all other than this conversion of a dehydrogenated and / or subject to dehydrogenation of a hydrocarbon under the influence of molecular oxygen in this text are combined into the concept of "partial oxidation"; additional exposure to ammonia means ammoxidation, which is also included in the concept of partial oxidation.

The reaction gas fed to the shaft reactor may, for example, be a mixture of fresh hydrocarbon to be dehydrogenated (e.g. fresh propane) and the aforementioned residual gas (which typically also contains steam). If necessary, however, H ₂ , H ₂ O and / or O ₂ can be added to the reaction gas before it is fed to the shaft reactor, designed as a multi-stage reactor; for example, before the reaction gas enters the multi-stage reactor, it is possible to add dehydrogenation circulating gas according to the international application WO 03/076370 or the German patent application DE-A 10211275.

The design of such a shaft reactor, designed as a multi-stage reactor (cf. figures 1 and 2), can be (as in general when implementing the method according to the invention) the following (the digital indices below refer to figures 1-17 that are part of this application ; the dimensions given relate to the specific embodiment of such a reactor, given as an example. It goes without saying that such axial multistage reactors can also be manufactured in larger or smaller sizes; the number of solid layers is catalyzed Ra can also be increased or decreased).

From the external environment (i.e., from the environment), a multi-stage axial reactor, hereinafter cited as an example, is delimited by a shell (1) in the form of a straight circular cylinder (if the end points of the parallel radii of two equal circles lying in two parallel planes are connected to each other with the other segments that are perpendicular to both parallel planes of the circles (lower and upper bases (the upper is the first of the circles, counting in the direction of the reaction gas flow) of the circular cylinder), then a straight (not beveled) round cyl NDR, also called the cylinder of revolution; the straight line on which the centers of the circles lie is called the axis of the circular cylinder), which is closed both from above and below by covers (2, 3) having a torosperic (box-like) shape according to DIN 28011 (collectively, the shell and lids form the forming of the pressure tank). Under the lower torospherical bottom (lower cover), the tank is held under pressure by a frame, which, in turn, is supported by four to eight supports. The shell thickness is 30 mm. The outer diameter of the shell of a round cylinder is 6070 mm. The distance between the lower and upper surface (bases) of the cylinder is 2640 mm. The height of both the top and bottom covers is 1350 mm (being measured in each case from the center of the round bottom or top base in each case to the point of maximum removal of the cover). The wall thickness of the upper cover (3) is uniform and amounts to 30 mm, the wall thickness of the lower cover (2) begins with a value of 30 mm, and uniformly increases up to 45 mm in the direction of the nozzle of the gas outlet pipe.

The top cover ends with a centrally located inlet gas pipe fitting (4). Its inner diameter is 1200 mm. Similarly, the bottom cover ends with a centrally located fitting for the exhaust gas pipe (5). Its internal diameter is 1400 mm. The height of each nozzle is 240 mm (if appropriate insulating materials are placed on the outside of the pressure vessel wall for thermal insulation (with a layer thickness, for example, from 300 to 500 mm), then the height of the nozzle increases accordingly, since from the point of view of application technology it is advisable that the fitting protrudes from the insulating layer). Where the bottom cover ends with an outlet gas pipe fitting (5), the cover is additionally equipped with a reinforcing ring (6), which is welded to the cover and to the fitting. Its outer diameter is 1900 mm and its thickness is 50 mm. While the bottom cover of the reactor is preferably connected to the cylindrical shell by welding, between the cylindrical shell and the top cover of the reactor is preferably a flange connection (7) (between the peripheral flange (8) of the cylindrical shell and a similar peripheral flange on the cover (9)) with a sealing collar [ welding] (10). 5 is a longitudinally enlarged view of a portion of a flange joint including a sealing collar (10) (the latter are usually made of steel sheets having a thickness of about 2 mm; similar sealing collars are also presented in international application WO 2004/067164). The gas leak through the used flange connection should be less than 10 ^-4 mbar · l / s. The implementation of the top cover detachable facilitates the loading of inert molded products and / or catalyst and their removal, for example, in the case of partial or complete replacement of the catalyst.

In order to minimize the residence time of the reaction gas inlet gas (4) supplied through the pipe fitting, which contains at least one hydrocarbon and molecular oxygen to be dehydrogenated, in the inner space of the upper cover of the reactor (3) (and thereby mainly prevent undesired side reactions in the reaction gas, which already has an elevated temperature), the inner space of the lid is reduced with a concave intermediate lid (11), the shape of which can correspond, for example, a lateral surface (with a thickness of 15 mm) of a straight truncated round cone or two located on each other straight truncated round cones.

It is advisable to ensure the rigidity of the connection of the top cover and the truncated cone using radially located ribs (cf. international application WO 2004/067164).

The circumference of the upper base of the truncated cone corresponds to the lower circumference of the fitting of the inlet gas pipe (4). Of course, the intermediate cover may also be convex in the direction of the generatrix of the cylindrical shell, as shown, for example, in FIG. 5 and FIG. 7, as well as in FIG. 9 of international application WO 2004/067164. It is advisable that the narrowed intermediate cap (11) would reduce the internal volume of the cap available for the reaction gas by at least 50 vol.%, But normally not more than 90 vol.%, Of its value in the absence of an intermediate cap. The intermediate cover (11) is joined by welding. From the point of view of application technology, it is advisable that from the circumference of the intermediate cover itself, from 3 to 36 through holes are placed, the cross-sectional area of which would be from 1 to 8 cm ² . Through these openings, the space R enclosed between the intermediate cover and the reactor cover communicates with the remaining internal volume of the cover. To mainly prevent the flow of the reaction gas through these through holes into the space R, the space R is continuously purged with an inert gas (preferably molecular nitrogen, for example, industrial nitrogen containing up to 1 vol.% O ₂ , water vapor or mixtures thereof) through 1-12 pipelines (53) in the cap and exhaust (added to the reaction gas) through the through holes. Typically, this inert gas stream in total is less than 1 vol.%, In most cases even less than 0.1 or less than 0.01 vol.%, Of the volumetric flow of the reaction gas (in Nm ³ ).

The pipeline supplying the reaction gas is provided with a gas-tight connection to the inlet gas pipe fitting (4) by means of flanges, as well as the pipeline diverting the gas production stream, with the outlet gas pipe fitting (5). From the point of view of application technology in both cases it is advisable to use a sealing collar. Alternatively, the supply pipe can also be directly connected to the fitting of the inlet gas pipe (4) by welding.

For proper and safe operation, the above-mentioned pipelines are preferably equipped with devices to compensate for elongation effects that may occur, for example, due to changes in temperature, and it is advisable to use compensators that differ in the lateral way of operation.

Such expansion joints, as a rule, of a multilayer structure, can be made of the same material as the pipeline itself. Particularly appropriate, however, is the embodiment (in the general case: a gas-permeable rigid inner pipe and a gas-tight elastic outer shell (gas-tight elastic outer pipe)), including the inner part of the pipe in contact with the transported gas and preferably made of stainless steel, material number according DIN: 1.4893, having, according to the purpose of the application, a gas-permeable expansion joint, and located on the outside, a gas-tight elastic, corrugated part, which is at least Partially made of a material capable of withstanding special mechanical and temperature loads, such as material 1.4876 (designation according to VdTÜV-Wb 434), or 1.4958 / 1.4959 (designation according to DIN 17459), or INCOLOY 800 N, or 800 HAT, or nickel-based material 2.4816 (alternative designation Alloy 600) or 2.4851 (alternative designation Alloy 601).

Otherwise, all parts of the multistage reactor in question can be made of stainless steel, material number according to DIN: 1.4893, or of other stainless steel recommended or mentioned in German application 102005061626. In particular, from the side in contact with the product - also made of stainless steel type 1.4841 to DIN.

The inner space of the lower cover by installing twelve plates (walls) (12) on the inner wall of the cover along the entire height of the cover is divided into twelve (alternatively, eight, six or four, or three, or sixteen) identical sectors (chambers) are also possible. The shape of the plates on the side where they are in contact with the inner wall of the lid (the back of this plate) corresponds to the bulge of the lid. The thickness of the plates is uniform and is 30 mm. In addition to the back, each installed plate also has edges K and C. The edges K are parallel to the axis of the round cylinder of the shell and extend 1400 mm from the inner wall of the lower cover to the base of the round cylinder of the shell, to which the edges K are perpendicular. The edges K form the frontal surfaces of the respective plates facing the inside of the cover. The edges C touch the base of the round cylinder of the shell and complete the individual plates on top. Like the aforementioned base surface itself, they form a right angle with the corresponding edge K, i.e. they extend along the radii of this circle-shaped base surface. However, although the length of these radii is 3010 mm, the length of edges C is only 2460 mm. The edge C does not protrude beyond the edge K, but ends flush with it where it meets the edge K. This means that the edges K of the plates placed opposite to each other (their edges C are located on the diameter of the base surface of the round cylinder common to them) do not touch each other and are located at a distance of 1100 mm from each other.

The lower end of the edges K ends on the contour line of the outlet fitting of the gas pipe.

If the edges C of two plates adjacent to each other are extended until they intersect each other, then in each case these edges form an angle of 30 °. Thus, two adjacent plates in each case form, together with the inner wall of the lid on which they are placed, a chamber that is open both in the direction of the base of the round cylinder of the shell and in the direction of the central axis of the lower cover (which is an extension of the axis of symmetry of the round cylinder of the shell way down). In addition, the plates may contain through holes through which adjacent chambers communicate with each other. Since the twelve plates are held on the inner wall of the lower cover only by gravity, and are not connected to the inner wall of the lower cover by a weld, the position of the twelve plates and their location relative to each other are stabilized by means of spacers (13) placed (welded) between each two adjacent plates.

Where the plane of the base of the round cylinder of the shell and the lower cover meet each other, a support ring (14) having a support width of 60 mm is horizontally (welded to the inner wall of the lower cover). The thickness (height) of the support ring is 20 mm.

Where the plates from the bottom are joined with the support ring, they have a cutout of the corresponding shape, into which the support ring enters without gaps, so that the edge C and the supporting surface of the support ring are at the same height, and the supporting surface continues that part of the edge C on which the cutout no.

To accommodate various solid catalyst beds in the above-described high-pressure tank, an appropriate number of cylindrical blocks are placed in it.

Moreover, by “ring” is meant a portion of the plane bounded by two concentric rings having radii different from each other. If two congruent (coincident) rings located in parallel planes (upper and lower rings) connect the end points of the parallel radii of the outer circles and the end points of the parallel radii of the inner circles by segments, we get a “ring cylinder”. The segments connecting the endpoints of both inner circles are called the inner generators of the annular cylinder (their combination forms the inner side surface (shell)), and the segments connecting the endpoints of both outer circles are called the outer generators of the annular cylinder (their combination forms the outer side surface (shell )). If the generators are perpendicular to both circles, then the annular cylinder is called straight or not beveled. The segment connecting the centers of the rings is called the axis of the annular cylinder. If the straight annular cylinder is intersected by two planes parallel to the lower and upper rings, spaced apart by a distance H, then between the planes of the block having the shape of an annular cylinder, a height H occurs, which also has an upper ring and a lower ring.

The thickness of the outer shell of the blocks in the form of an annular cylinder used for the described pressure tank is 20 mm, and the thickness of the inner shell of the blocks in the form of an annular cylinder used for the described pressure tank is 30 mm. Their height H is equal to 850 mm (exception: the height H of the first block in the form of an annular cylinder in the direction of flow of the reaction gas is 710 mm). The radius of the inner circle of the above-mentioned blocks in the form of an annular cylinder (the distance from the center of the circle to the inner shell of the blocks in the form of an annular cylinder) is 600 mm, the radius of the outer circle of the above-mentioned blocks in the form of an annular cylinder (the distance from the center of the circle to the outer shell of the blocks in the form of an annular cylinder) equals 2900 mm. The distance between the outer shell of the blocks in the form of an annular cylinder and the inner shell of the blocks in the form of an annular cylinder is thus 2270 mm.

The space bounded by the inner shell is called the inner space of the block in the form of an annular cylinder. The space between the outer and inner shell is called the intermediate space of the block in the form of an annular cylinder.

Twelve dividing walls W _T (15) having a thickness of 30 mm divide the intermediate space of the block in the form of an annular cylinder into twelve identical sector spaces.

The height H of the individual partition walls corresponds to the height H of the block. The length T of the separation wall is equal to the distance between the outer shell of the block in the form of an annular cylinder and the inner shell of the block in the form of an annular cylinder. Accordingly, the dividing wall is welded in its height H to both the outer shell and the inner one. The height H of the separation wall is perpendicular to the upper and lower rings of the block in the form of an annular cylinder. The length T of the separation wall extends radially from the outer shell to the inner shell and ends, if you mentally extend it, on the axis of the block in the form of an annular cylinder. If, in the aforementioned manner, the two dividing walls adjacent to each other are extended until they intersect with each other, then they form an angle of 30 °.

If a segmented block in the form of an annular cylinder is inserted into the described high-pressure tank, it simply fits onto the support ring (14), so that on one side there is a gap of 50 width between the cylindrical shell of the high-pressure tank and the outer shell of the block in the form of an annular cylinder mm, and on the other hand, the separation walls of the block in the form of an annular cylinder and the plates of the lower cover of the block stand on top of each other (or one above the other, i.e. on the coating), i.e. the axis of the cylindrical shell and the block in the form of an annular cylinder coincide. In the direction of the reaction gas flow, the lower ring is located after the upper ring of the mounted segmented block in the form of an annular cylinder.

In each case, there are ten straight (not curved) transverse (bearing) walls Q (54) between adjacent dividing walls W _T , having a height of 200 mm and a thickness of 20 mm. The connection of the bearing walls with the dividing walls W _{T is} carried out by welding. The length of the supporting walls naturally increases in accordance with the distance between them and the inner shell of the block in the form of an annular cylinder, that is, with a decrease in the distance between them and the outer shell of the block in the form of an annular cylinder.

From the point of view of application technology, it is advisable that within the same sector space between the supporting walls Q there are equal gaps.

The bearing walls Q have such a shape that the distance from their lower edge to the lower ring of the segmented block in the form of an annular cylinder is 40 mm.

In addition, there are through holes O in the transverse walls Q, and it is advisable that their center be located at half the height of the transverse wall. With increasing distance from the inner shell of the block in the form of an annular cylinder, the number of through holes O on the transverse wall increases. It is advisable to perform transverse walls Q located in different sector spaces, located at the same distance from the inner shell of the block in the form of an annular cylinder, congruent. Preferably, the through holes O are round.

A lattice sector made exactly along it, which carries a solid catalyst layer, is placed on the supporting structure created in this way within one sector space.

Typically, molded articles of the catalyst are not poured directly onto the grating sector (if necessary, a grid of metal wire (for example, stainless steel, from which the pressure tank is made) with a small cell size is also placed on the grate). This is because molded catalyst articles typically have smaller linear dimensions than lattice cells. In the case of the described reactor, it is advisable that the cell size of the used lattice sectors is from 2 or 3 to 7 mm, for example 4 mm

Accordingly, first inert balls of Steramit C 220 manufactured by CeramTec with a diameter of 5 mm are poured at the same height of 50 mm for all lattice sectors, followed by backfill of shaped products with catalytic activity. Another inert filling of balls made of the same steatite, but with a diameter of 2 to 3 mm, is poured onto this inert filling to a height of 25 mm, followed by a filling of shaped products with catalytic activity. As molded articles of the catalyst, for example, yarns with a diameter of 1.5 mm and a length distributed over a Gaussian in the range from 10 mm to 15 mm are used, and the maximum distribution is approximately 12.5 mm (stoichiometric ratio of elements (distribution of active elements, including the carrier, by weight), as well as the procedure for manufacturing the catalyst precursor and activating it to the active catalyst, otherwise correspond to those described in example 4 of the German patent application DE-A 10219879).

The filling height of the molded catalyst articles is uniform and amounts to 300 mm (it can be uniform in a simple manner, for example, by applying a holey metal sheet or grate to the finished filling (on the upper ring) and removing the molded catalyst products protruding from its openings). Then, the solid catalyst layer is covered with backfill from rings made of Steatit C 220 manufactured by CeramTec (to the upper ring of the segmented block in the form of an annular cylinder). The geometric characteristics of steatite rings are 7 mm × 7 mm × 4 mm ((outer diameter) × (height) × (inner diameter)), and the filling height is uniform and is 200 mm (exception: in the case of the first block in the form of an annular cylinder in in the direction of flow of the reaction gas, this backfill height is only 60 mm).

The uniformity of the height of the inert fillings can be achieved in a simple way, for example, by laying on each lattice sector the measured backfill remaining in the inert layer (16), shown in Fig. 6, the height of which is equal to the fill height, so that the inert fill can simply be smoothed along it to a single value . Typically, the wall thickness of this rail is from 0.3 to 2 cm. Similar measured backfill rails can also be used for backfilling with active products.

As an alternative to steatite rings, solid steatite cylinders of 7 mm × 7 mm ((outer diameter) × (height)) can also be used. As another alternative, steatite balls with a diameter of 5 mm to 6 mm can be used.

On this last in the direction of flow (lowermost) block in the form of an annular cylinder loaded with a solid catalyst layer, two more loaded in a solid layer of catalyst block in the form of an annular cylinder are placed. The dividing walls W _{T of} all the blocks in the form of an annular cylinder are superimposed on each other, i.e. just like the outer and inner shells.

Where blocks in the form of an annular cylinder stand on top of each other, there are inevitably thin gas-permeable seams. It is advisable to fill the space (gap) between the shell in the form of a round cylinder (1) of the high pressure tank and the outer shell of the blocks in the form of a ring cylinder with insulating material (for example, mineral wool or glass wool), which is placed on the support ring (14).

At the height of the upper ring of the corresponding block in the form of an annular cylinder, a shell in the form of a round cylinder (1) of a high pressure tank and an outer shell of a block in the form of an annular cylinder loaded with a solid catalyst layer in each case are connected to each other by a welded sealing sleeve (17), ensuring gas impermeability. The figure 7 presents an enlarged image of a welded sealing sleeve (17) in longitudinal section. It is designed in such a way that it is able to compensate for thermal contraction and expansion (both in the process of dehydrogenation and in the framework of catalyst regeneration, significant changes in temperature take place) of the corresponding block in the form of an annular cylinder without breaking and without losing tightness. At the height of the lower ring of the corresponding block in the form of an annular cylinder, there is no such seal, therefore, gas penetrates from there into the space (gap) between the shell in the form of a round cylinder (1) of the high pressure tank and the outer shell (18) of this block in the form of a ring cylinder providing pressure equalization.

Under the cover (upper) ring of the block in the form of an annular cylinder, the lowest (last) in the direction of flow of the reaction gas, but above the lower ring of the same block in the form of an annular cylinder, in the inner space of the block in the form of an annular cylinder to weld with gas impermeability the bottom (19) extends to the entire annular section of this inner space and, accordingly, is round. Where two ring cylinders stand on top of each other, above the lower ring of the block in the form of a ring cylinder, the upper one in the direction of flow of the reaction gas, in the corresponding inner space of the block in the form of a circular cylinder, a steel hood (tape) is welded to the inner shell, protruding below the weld above the gap, which is between the blocks located one above the other in the form of an annular cylinder, overlapping it. The tape is about 8 mm thick and 60 mm wide.

Otherwise, the inner spaces of the blocks in the form of an annular cylinder located one above the other together form a common, non-beveled inner space (20) of a cylindrical shape, closed from the bottom by a bottom (19), and from above opening into the top cover.

In this common interior space (20) pipes (21) pass through which the inlet gas II (inlet gas supply pipes II) necessary for the method according to the invention flows. The remaining volume of the total internal space (20) around the inlet gas supply pipes II is filled with quartz sand, the grain size of which is from 0.3 to 1.2 mm (alternatively, crushed oxide ceramics, its granules or balls (or other small molded products) from it; it is preferable that the filling does not contain dust, which can be achieved, for example, by washing it with water and then drying (for example, drying with a flame). The filling ends a little lower (about 1 cm) of the upper ring of the first block in the form of an annular cylinder in the direction of flow of the reaction gas. The feed gas II is supplied between the first and second (in the direction of flow of the reaction gas), as well as between the second and third layers of the solid catalyst layer.

The input (22) of the pipes (21) into the reactor is realized through the upper cover of the reactor (3) through the inlet fittings (23) located in it and rigidly welded with it.

The outer diameter of the walls is 168.3 mm, and the wall thickness can be from 2 to 7 mm. In each case, between these two solid catalyst layers, three such pipes (inlet gas supply pipes II) supply the inlet gas II. Within one such group of inlet gas supply pipes II, they are fed with inlet gas II from the same source. Typically, however, the composition of the inlet gas II, which is supplied (in the direction of flow) between the first and second solid catalyst layer, and the composition of the inlet gas II, which is fed between the second and third solid catalyst layer, are different from each other and come from different sources .

The input gas supply volume II for each group of three input gas supply pipes II in each case is controlled by the total amount.

The seal of the inlet of the inlet gas supply pipe II to the upper reactor lid is shown in section in FIG. 8. It is realized using external and internal flange connections. The transition of the pipe supplying the inlet gas II to the inlet fitting (23) is divided into three parts. Three parts are the pipe section in the inlet fitting (24), the pipe section outside the inlet fitting (25) and the pipe section in the intermediate disk (26). The internal flange connection provides a gas-tight connection of the lower pipe section from below with the pipe section in the intermediate disk, and the external flange connection, on the one hand, provides a seal (insulation) of the inlet fitting from the environment, and at the same time provides a gas-tight connection of the upper pipe section from above with the pipe section in intermediate disk. As a sealing material, it is possible to use, for example, materials based on mica, treated graphite, or metal seals. The above construction allows you to remove the top cover of the reactor after the external flange connection, without the need to change the position of the pipes (21) in the reactor.

An alternative embodiment of a seal for entering the inlet gas supply pipe II into the upper reactor lid is shown in longitudinal section in FIG. 9.

The transition of the pipe supplying the inlet gas II to the inlet fitting (23) is divided into two parts. Two parts are the pipe section in the inlet fitting (27) and the pipe section outside the inlet fitting (28). The inner diameter of the latter exceeds the inner diameter of the former by 10 to 30 mm. A gas-tight transition between them is realized by means of a flange connection. To do this, an outer flange is welded to the upper end of the nozzle, which reaches the portion of the pipe held inside the nozzle, protruding from this flange by 10 to 30 mm and fixed to the flange using a welded sealing sleeve (29). An outer flange is also welded to the lower end of the pipe section outside the inlet fitting (28). As a sealing material, it is possible to use, for example, materials based on mica, treated graphite, or metal seals.

At the height of the through holes O of the transverse walls Q of the first block in the form of an annular cylinder in the direction of flow of the reaction gas and at the height of the through holes of the transverse walls Q of the second block in the form of an annular cylinder in the direction of flow of the reaction gas in the inner shell of this block in the form of an annular cylinder in each In this case, there are three MO vias, the centers of which are located at the vertices of an equilateral triangle. In each case, three inlet gas supply pipes II are rotated through these openings of the MO (they are hermetically welded into these openings), which then pass through the through holes O of the transverse walls Q along the radii in the direction of the outer shell of this block in the form of an annular cylinder until they meet with an II KR (30) distribution ring inlet gas pipe placed in this block in the form of an annular cylinder, to which they are welded, and which has the same external and internal diameter as the inlet gas supply pipes brought to it aza II. The annular distribution pipe KR extends at the height of the through holes O of the given block in the form of an annular cylinder through viaduct-like through holes in the respective partitions W _T , but it is not welded to the viaduct bridges.

The gap width between the KR distribution pipe and the through hole is from about 4 to 15 mm.

The length of the inlet gas supply pipe II, calculated from its entrance into the upper reactor cover to the corresponding distribution ring pipe KR, is at least 3 and not more than 6 m. The outer diameter of the circle described by both distribution ring pipes is 2860 mm. The corresponding inner diameter is 2560 mm.

While the passage of the supply pipes of the inlet gas II through the vias of the MO is provided by seals, this does not apply to the corresponding passage through the vias of O. This is implemented with a message.

The width of the gap can be from 2 to 10 mm.

From the distribution ring pipe KR (30), the inlet gas distribution pipes II, conducted through the through holes O, lead radially to the outer as well as to the inner shell of the block in the form of an annular cylinder.

The outer diameter of the distribution pipes ranges from 80 to 110 mm and can be, for example, 88.9 mm. The thickness of the walls of the distribution pipes is in the range from 2.1 to 6.3 mm.

Between the transverse walls Q of the block in the form of an annular cylinder, the distribution pipes (32) are rotated downward in the direction of the lower ring of the block in the form of an annular cylinder.

Directly under the supporting structure of the first unit in the direction of the reaction gas flow and the second in the direction of the reaction gas flow (but not under the supporting structure of the third in the direction of the reaction gas flow), a block in the form of an annular cylinder are equipped with outlet openings A square metering boxes (31), with ribs a, b and c, the faces of which are represented by three pairs of congruent rectangles, into which boxes the distribution pipes open, as shown in longitudinal section in figure 10 ( an off the wall thickness of boxes dosage is from 1 to 3 mm, preferably - from 1.5 to 2.5, and advantageously - 2 mm). In dosing (distribution) boxes having short ribs a, as a rule, only one distribution pipe opens. In dosing (distribution) boxes with long ribs a, up to three distribution pipes open. The length of the ribs c for all dosing boxes is the same and is 40 mm, and the length of the ribs b is also the same for all dosing boxes and is 150 mm. In contrast, the length of the ribs a for different boxes is different. For all boxes, one of two pairwise congruent rectangles a × b in each case is at the level of the lower ring of the block in the form of an annular cylinder.

All ribs with are perpendicular to the plane of the lower ring and are directed to the upper ring belonging to this block in the form of an annular cylinder. The ribs of all the boxes are parallel. The distance between two adjacent dosing boxes is 130 mm. In this sequence, the metering boxes are distributed over the entire cross section of the inner space of the block in the form of an annular cylinder. The ribs a extend along the secant from one side of the outer shell of the block in the form of an annular cylinder to the other side of the outer shell. If at the same time they meet with the inner shell of the block in the form of an annular cylinder, then the dosing box ends shortly before the inner shell, and on the opposite side of the circumference of the inner shell it continues in the form of a new (separate) dosing box with a similar rib length a. On the inner side of the outer shell, as well as on the outer side of the inner shell of the block in the form of an annular cylinder, there are holders (33), preferably made with a geometric closure, on which dosing boxes are fixed in the middle of the b × c rectangle. In figures 11 (side view) and 12 (top view) presents an example of such a holder made with a geometric closure.

In the case of metering polyhedra (preferably regular 12-gons) with gas permeability along all 360 ° of the circle, for example, you can focus on the following dimensions:

Edge length b: 160 mm;

Edge length s: 40 mm;

The thickness of the walls of the metering boxes: 2 mm;

The distance between the metering boxes located one after another along the radius (interval): 125 mm;

Inner diameter of outlet openings A: 2.5 mm;

The distance between the two outlet holes A adjacent to the “beads” (from center to center): the same, equal to 60 mm;

The distance from the imaginary "string of beads" to the edge a, facing the lower ring of the block in the form of an annular cylinder: 10 mm; and

The outlet openings A of the radially opposite rectangles a × c of the distribution boxes next to each other in the radial direction are located opposite each other.

From the point of view of the application technique, it is advisable to supply the metering polyhedra with an inlet gas II containing molecular oxygen so that the points of introduction into the same polyhedron are uniformly distributed along the contour of the polyhedron. The number of these introduction points for the same polyhedron can be, for example, 2, or 3, or 4, or 5, or 6, or 7, or more. With an increase in the number of insertion points, the pressure value at specific outlet openings A of the polyhedron is more and more evenly distributed. Figure 18 schematically shows such a structure of a dosage polyhedron.

In an alternative embodiment, the dispensing boxes can be distributed over the cross-section of the inner space of the block in the form of an annular cylinder not in secants, but in the form of concentric polygons or concentric circles, like a web. In this case, it is possible to produce solid polygons or circles extending over the entire 360 ° angle (one metering polygon or one metering circle), or in the form of separate metering boxes.

It is advisable to place the dosage boxes in the same (congruent) for both blocks in the form of an annular cylinder.

Outlets A are located on the rectangle sides a × c of the metering boxes (distribution boxes) having the shape of parallelepipeds. They are all round and their inner diameter is in the range of 2 to 4 mm, preferably 3 mm.

Outlets A are located on both congruent sides-rectangles a × c of the metering box (distribution box), arranged like beads strung on a thread, the “thread” being located at a distance of 5 mm from the edge a, facing the lower ring of the block in the form of an annular cylinder , and parallel to this edge a. The distance from one outlet A to the closest outlet in the “beads” is always (measured from the center to the center) 100 mm (as an alternative, another uniform distance lying in the range of 50 to 100 mm is also possible). In the described reactor, the total number of outlet openings A of all dosing (distribution) boxes placed in one block in the form of an annular cylinder is about 2000 (if the distance between two adjacent outlet “A” beads is chosen less than 100 mm, then the total number of outlet openings And it can be up to 10,000 or up to 5000). Edges a, facing the lower ring of the block in the form of an annular cylinder, should not protrude from the bottom of the lower ring. In conclusion, it should be pointed out that where the dosing (distribution) boxes meet the dividing walls W _T , in these dividing walls W _T there are corresponding openings for these dosing (distribution) boxes, and between the internal contour of the opening and the external contour of the dosing (distribution) box there is a gas permeable gap of about 1 cm in size. Outlets A of radially opposite rectangles a × c of the distribution boxes next to each other in the radial direction radial direction, located opposite each other.

In principle, the total number of outlet openings A, as already mentioned, can be the same in different blocks in the form of an annular cylinder.

However, these values may differ from each other. Those. in the direction of flow of the reaction gas from one block in the form of an annular cylinder to another block in the form of an annular cylinder, this total may increase or decrease.

Partial dehydrogenation of at least one heterogeneous catalysed hydrocarbon to be dehydrogenated according to the invention in the described multi-stage axial reactor and it is advisable to control it by measuring temperatures in various catalyst beddings of a particular solid catalyst layer.

The height of the catalytically active bed of molded catalyst products of the solid catalyst layer of the above-described axial multistage reactor in the direction of the reaction gas flow is 300 mm (30 cm) (of course, a multistage reactor in full accordance with the plan can also be designed for a bed height different from 30 cm (for example , 40 cm). A backfill height of 40 cm is recommended, for example, in cases where threads with a diameter of 3 mm are used as molded catalyst products, which ensure a smaller pressure drop; an increase in the filling height gives the advantage of reducing the diameter of the inner space of the blocks in the form of an annular cylinder to 5.47 m, which leads to a decrease in the area of blowing of the catalyst filling to 21.6 m ² ).

Temperature measurements are taken in the direction of the reaction gas flow at the following heights of the catalytically active backfill:

0 cm;

7.5 cm;

15 cm;

22.5 cm and

30 cm

If the height of the backfill from molded articles with catalytic activity differs from 300 mm (for example, 240 mm, or 260 mm, or 280 mm), then temperature measurements are carried out at five heights, respectively, equally distributed over this height of the backfill.

For this, perpendicular to the axis of the corresponding block in the form of an annular cylinder (i.e. horizontally, in the radial direction) through the shell (1) of a straight circular cylinder, as well as through the outer shell of a block in the form of an annular cylinder, a triple catalytically backfill is introduced at the level of each of of the aforementioned heights Sh, three guide fingers (34) for inserting a triple thermocouple (a triple thermocouple performs simultaneous temperature measurements at three different depths (usually lying at an equal distance from each other)) input ah), cf. figure 13. A separate guide pin extends up to the inner shell of the block in the form of an annular cylinder and is closed from the solid catalyst layer. Those. the interior of the guide pin does not come in contact with the reaction gas. The inner diameter of each guide pin is in the range of 3 to 5 mm, and the outer diameter of the guide pin is from 6 to 8 mm. Three guide fingers (34) located at the same height of the backfill Sh are distributed along the circumference of the shell (1) so that the guide fingers following each other along the circumference of the shell, if they are mentally extended to intersect each other, are located at an angle of 120 ° to each other. The guide fingers located at the heights of the filling Sh, which are next to each other in the flow direction, do not overlap with the previous three guide fingers, but are shifted by 90 ° relative to them. In this case, the direction of the aforementioned shift (clockwise or counterclockwise) is maintained over the entire height of the bed with catalytic activity, so that the guide fingers overlap each other at heights Sh = 0 cm and Sh = 30 cm, as shown in Fig. 14.

The temperatures measured at the filling heights Sh = 0 cm and Sh = 30 cm are used as a measure to adjust the dosage of the inlet gas II before the solid catalyst bed in which the temperature is measured. A change in the molar ratio between the hydrocarbon to be dehydrogenated and the dehydrogenated hydrocarbon in the area from the entry of the reaction gas into the inlet pipe fitting (4) to the outlet of the reaction gas from the exhaust gas pipe fitting (5) gives an indicator of the dehydrogenation turnover related to a single passage through the reactor. The injection of the input gases II is carried out so as to achieve the desired dehydrogenation turnover.

In figures 13 and 14 in detail shows the introduction of the guide finger (34) in longitudinal section.

It can be seen that the guide pin (34) within the solid catalyst layer passes inside the - also closed - protective finger (35) having an inner diameter in the range from 4 to 7 mm and an outer diameter from 6 to 9 mm. The gap between the outer wall of the guide finger and the inner wall of the protective finger should be as small as possible. If necessary, the remaining gap is filled with heat-conducting paste for high temperatures. A protective finger is welded in the inner wall (36) of the outer shell of the block in the form of an annular cylinder to ensure gas impermeability, so that the reaction gas cannot penetrate into the slot (38) between the shell (1) and the outer shell of the block in the form of an annular cylinder. Outside the shell (1), the guide pin extends along the axis of symmetry of the purge pipe (37), whose inner diameter is approx. 45 mm and the outer diameter is 50.8 mm. The length of the guide pin is 2000 mm, and the length of the purge pipe is 400 mm. The purge pipe is hermetically closed by a flange (39), into which a guide pin enters through the seal using the clamping ring (40).

From the outside of the sheath (1), the purge pipe is hermetically welded. The passage of the guide pin (34) through the shell (1) is not leakproof. An inert gas (preferably molecular nitrogen, for example, industrial nitrogen containing up to 1 vol.% O ₂ , water vapor or mixtures thereof) is supplied through a fitting (41) welded to the purge pipe, which, when the guide pin (34) passes through the shell (1) ) gets access to the gap between the shell (1) and the outer shell of the block in the form of an annular cylinder (inert gas is supplied indirectly through the gap (38) to part of the purge pipes). In addition, figure 13 shows a welded sealing sleeve 17.

Typically, these inert gas flows generally comprise less than 1 vol.%, Often even less than 0.1 or less than 0.01 vol.%, Of the volumetric flow of the reaction gas (in Nm ³ ).

In figures 15 and 16 are shown in longitudinal section two bipods stabilized by a transverse strut. They consist of tubes having an outer diameter of 6 mm and a wall thickness of 1 mm. The tubes forming both legs are inserted into the support plates (43) (30 mm × 10 mm × 20 mm ((width) × (height) × (depth)). Where the legs meet together and, if necessary, in the middle transverse struts, perpendicular to the plane of the cut introduced short bushings (42).

Before backfilling the solid catalyst layer, a plurality of such bipeds are mounted on the trellised sector. Through the above-mentioned bushings (42), protective fingers are passed in order to stabilize the horizontal position of the guide fingers for thermocouples and prevent them from sagging.

The guide fingers located one above the other (Sh = 0 cm, Sh = 30 cm) can be supported on the same biped, as shown in figure 16.

It is advisable to further improve the adiabatic qualities of the described multi-stage axial reactor by placing appropriate heat-insulating materials (for example, fiberglass or mineral wool with a layer thickness, for example, from 300 to 500 mm) on the outer surface of the pressure vessel wall. These materials can be placed, for example, with the help of holders fixed (for example, welded) on the outer wall.

Partial dehydrogenation of propane to propylene with heterogeneous catalysis, mentioned before the description of the design of the shaft reactor, made in the form of a multi-stage reactor, can be implemented in this multi-stage reactor, for example, as follows.

116,306 Nm ³ / h of reaction gas is supplied through the inlet gas pipe fitting to the multi-stage reactor, which includes the following components (inert gas flows N ₂ into the reactor cover and purge pipes (27) are neglected here, since their total amount is less than 0.01 vol.%, from the amount of reaction gas (in Nm ³ )):

propane 34.44 vol.% propylene 0.2 vol.% N ₂ 52.8 vol.% O ₂ 3.04 vol.% CO ₂ 1.61 vol.% With 0.39 vol.% H ₂ 0.09 vol.% ethane 0.12 vol.% H ₂ O 7.22 vol.% isobutene 0.01 vol.% acrylic acid 0.04 vol.% acrolein 0.02 vol.% acetic acid 0.02 vol.%

The reaction gas has a temperature of 394 ° C and is at a pressure of 3.10 bar at the inlet.

Between the first and second solid catalyst layers in the direction of the reaction gas flow through the outlet openings A of the respective distribution boxes, 2930 Nm ³ / h of air-water vapor mixture containing the following components is supplied as inlet gas II 1:

water 34.9 vol.% N ₂ 51.4 vol.% O ₂ 13.7 vol.%

The temperature of the inlet gas II 1 is 450 ° C, and the pressure is 2.9 bar.

Between the second and third solid catalyst layers in the direction of the reaction gas flow through the outlet openings A of the respective distribution boxes, 2600 Nm ³ / h of air-water vapor mixture containing the following components is supplied as inlet gas II 2:

water 54.33% vol. N ₂ 36.09 vol.% O ₂ 9.58 vol.%

The temperature of the inlet gas II 2 is 450 ° C, and the pressure is 2.8 bar.

A mixture of gaseous products containing the following components comes out through a fitting of the outlet pipe (5) from a multistage reactor in an amount of 120754 Nm ³ / h.

propane 24.95 vol.% propylene 5.77 vol.% N ₂ 49.865 vol.% O ₂ 0 vol.% CO ₂ 3.03 vol.% With 0.35 vol.% H ₂ 4.13 vol.% methane 0.01 vol.% ethane 0.11 vol.% ethylene 0.01 vol.% H ₂ O 11.98 vol.%, acrylic acid 0.01 vol.%

The temperature of the gaseous mixture of products is 501 ° C, the gaseous mixture of products is under a pressure of 2.71 bar.

As an input gas stream I 1, a gas mixture containing the following components flows out from the first in the direction of the reaction gas stream of the solid catalyst layer in an amount of 120754 Nm ³ / h (which corresponds to a flow velocity W1 of 1.1 m / s) containing the following components:

propane 30.16% vol. propylene 3.03 vol.% N ₂ 51.03 vol.% O ₂ 0 vol.% CO ₂ 2.36 vol.% With 0.372 vol.% H ₂ 2.14 vol.% methane 0.001 vol.% ethane 0.116 vol.% ethylene 0.004 vol.% H ₂ O 9.75 vol.% acrylic acid 0.022 vol.%

The temperature of the input stream I 1 is 496 ° C, and its pressure is 2.9 bar.

As the input gas stream I 2, from the second in the direction of the reaction gas stream of the solid catalyst layer in an amount of 127180 Nm ³ / h (which corresponds to a flow velocity W1 of 1.33 m / s), a gas mixture containing the following components flows out:

propane 26.85 vol.% propylene 4.65 vol.% N ₂ 50.29 vol.% O ₂ 0 vol.% CO ₂ 2.75 vol.% With 0.359 vol.% H ₂ 3.34 vol.% methane 0.002 vol.% ethane 0.113 vol.% ethylene 0.005 vol.% H ₂ O 11.13 vol.% acrylic acid 0.013 vol.%

The temperature of the inlet gas stream I 2 is 496 ° C, and its pressure is 2.8 bar.

The directions of all individual inlet gas streams II 1 exiting the outlet openings A 1 (these are the outlet A in the distribution boxes for the inlet gas II 1 of the first block in the form of an annular cylinder in the direction of the reaction gas stream) in the imaginary absence of the inlet gas stream I 1 form with the input gas stream 11, the angle α equal to 90 °.

The directions of all individual inlet gas flows II 2 exiting the outlets A 2 (these are the outlets A in the distribution boxes for the inlet gas II 2 of the second block in the form of an annular cylinder in the direction of the first reaction gas stream) in the imaginary absence of the inlet gas stream I 2, form an angle α equal to 90 ° with the inlet gas stream I 2.

The induction time J 1 of the input reaction gas mixture 1 (enters the second block in the form of an annular cylinder in the direction of flow of the reaction gas) is 0.735 seconds.

If the temperature of the inlet reaction gas mixture 1 is increased to 550 ° C, the induction time is reduced to 0.15 seconds.

Similarly, an increase in pressure, as well as an increase in temperature, shortens the induction time J.

The induction time J 2 of the input reaction gas mixture 2 (enters the third block in the form of an annular cylinder in the direction of flow of the reaction gas) is 0.761 seconds.

If the temperature of the inlet reaction gas mixture 2 is increased to 550 ° C, the induction time is reduced to 0.15 seconds.

The distance D1 between all outlet openings A1 and the proper solid catalyst bed is 5 mm.

The distance D2 between all A2 outlets and the proper solid catalyst bed is 5 mm.

In alternative embodiments, it is possible, however, to set any identical values of both D 1 and D 2 in the range from 5 mm to 10 mm.

When projecting all the outlet openings A1 in the direction of the inlet gas stream I 1 onto the projection plane E1 perpendicular to the direction of the inlet gas stream I 1, the number ZA1 of the centers of gravity of the outlet openings located in the projection area covered by the inlet stream I 1 on any arbitrary m ² less than 50.

The distance from one center of gravity of the outlet to the nearest center of gravity of the outlet is then no more than 100 mm in the projection plane.

When projecting all the outlet openings A2 in the direction of the inlet gas stream I 2 onto the plane of projection E2 perpendicular to the direction of the inlet gas stream I 2, the number ZA2 of the centers of gravity of the outlet openings located in the projection area covered by the inlet stream I 2 on any arbitrary m ² less than 50.

The distance from one center of gravity of the outlet to the nearest center of gravity of the outlet is then no more than 100 mm in the projection plane.

When the input stream of the reaction gas 1 passes through a solid catalyst layer located in the second annular cylinder block in the direction of the reaction gas stream, 6.19 mol% of the propane contained in the input stream of the reaction gas 1 is converted to propylene.

When the input stream of the reaction gas 2 passes through a solid catalyst layer located in the third annular cylinder block in the direction of the reaction gas stream, 3.09 mol% of the propane contained in the input stream of the reaction gas 2 is converted to propylene.

The product gas mixture leaving the multi-stage reactor through the outlet pipe fitting (5) can be used in a manner known per se to subject propylene contained therein, accompanied by propane contained therein, to subsequent partial oxidation with heterogeneous catalysis, with the aim of producing acrolein and / or acrylic acid.

You can act as described in the German patent applications DE-A 102005061626, DE-A 102005057197, DE-A 102005052923, DE-A 102005052917, DE-A 102005022798, DE-A 102005009885, DE-A 102005010111, DE- A 102004032129, DE-A 102005013039, DE-A 10211275, international applications WO 01/96270 and WO 03/076370, German patent application DE-A 102005056377 and in accordance with the current technical level described in these publications. In particular, it is possible to act as described in German patent applications DE-A 102004032129 and DE-A 102005013039 or in DE-A 102005022798.

Then, the final product is usually separated from the gas mixture of the products of partial oxidation, and at least a portion of the residual gas containing propane and, if necessary, not having passed the conversion of propylene, is returned to partial dehydrogenation with heterogeneous catalysis to form the reaction gas supplied to the gas inlet fitting pipes of an axial multistage reactor.

In a manner similar to the above, the axial multistage reactor 116309 Nm ³ / h of reaction gas supplied through the inlet gas pipe has been formed; by combining (for example, as shown in figure 10 of international application WO 2004/067164) crude propane in an amount of 8063 Nm ³ / h and with specification

propane ≥98.0 vol.% propylene ≤0.11 vol.% n-butane <0.001 vol.% isobutane <0.05 vol.% ethane <1.5 vol.% ethylene <0.02 vol.% other C ₄ hydrocarbons <0.001 vol.%

at a temperature of 20 ° C and a pressure of 4 bar, and 102961 Nm ³ / h of residual gas of such partial oxidation, which at a temperature of 104 ° C and a pressure of 3.3 bar is characterized by the following composition:

propane 31.18 vol.% propylene 0.215 vol.% N ₂ 59.69 vol.% O ₂ 3.44 vol.% CO ₂ 1.81 vol.% With 0.444 vol.% H ₂ 0.098 vol.% ethane 0.06 vol.% ethylene 0.003 vol.% H ₂ O 2.96 vol.% acrylic acid 0.04 vol.% acrolein 0.03 vol.% acetic acid 0.03 vol.%

To combine both gas flows, they are intensively mixed with each other, for example, using a static mixer built into the pipeline.

It is advisable that the aforementioned combination and the feed time into the inlet gas pipe fitting be as close as possible to each other in time.

When combining, a gas mixture first appears, characterized by P = 3.21 bar and T = 95.7 ° C. By indirect heat exchange with a gas mixture of products (S) leaving the outlet fitting of the gas pipe, the temperature is brought to 394 ° C. and the inlet pressure is set to 3.10 bar.

Separation of the final product from the gas mixture of products obtained by partial oxidation in the gas phase of propylene to acrolein and / or acrylic acid can be carried out in a manner known per se during at least one separation step. In this case, they usually act as follows: at the main separation stage, at least one final product is transferred from the gas phase to the liquid phase (if necessary, the gas mixture of the products is first cooled). This can be done, for example, by partial or complete, and also, if necessary, fractionated condensation of the final product (for example, acrolein and / or acrylic acid) and / or by absorption (absorption) of at least one final product from the product gas mixture in an aqueous or organic solvent (i.e., fractionated condensation and / or absorption with water or an aqueous solution can also be superimposed). Fractional condensation and / or absorption with water or an aqueous solution is generally preferred as the main separation step. If the end product is acrylic acid and / or acrolein, suitable absorbents can be, for example, water, aqueous solutions of lower carboxylic acids, as well as hydrophobic organic solvents, such as mixtures of diphenyl and diphenyl ether (e.g. Diphyl ^® ) or mixtures Diphyl (75 to 99.9% by weight) and dimethyl phthalate (0.1 to 25% by weight). In the case of acrylic acid, the product gas mixture containing the final product is preferably subjected to fractional condensation. As examples of the main separation step (especially in the case of acrylic acid), the methods described in the following publications (cf., for example, European applications EP-A 1388533, EP-A 1388532, German patent application DE-A 10235847, European application EP-A 792867, international application WO 98/01415, European applications EP-A 1015411, EP-A 1015410, international applications WO 99/50219, WO 00/53560, WO 02/09839, German patent application DE-A 10235847 , international application WO 03/041833, German patent application DE-A 10223058, DE-A 10243625, DE-A 10336386, European application EP-A 854129, US patent application US-A 4317926, patent applications German tent DE-A 19837520, DE-A 19606877, DE-A 190501325, DE-A 10247240, DE-A 19740253, European applications EP-A 695736, EP-A 982287, EP-A 1041062, EP-A 117146, applications German patent DE-A 4308087, DE-A 4335172, DE-A 4436243, DE-A 19924532, DE-A 10332758, as well as DE-A 19924533). In addition, the separation of acrylic acid can be carried out similarly as described in European applications EP-A 982287, EP-A 982289, DE-A 10336386, German patent applications DE-A 10115277, DE-A 19606877, DE-A 19740252 , DE-A 19627847, European applications EP-A 920408, EP-A 10 68174, EP-A 1066239, EP-A 1066240, international applications WO 00/53560, WO 00/53561, German patent application DE-A 10053086 and European application EP-A 982288. It is preferable to carry out the separation as described in FIG. 7 of international application WO / 0196271, or as described in the German patent application DE-A 102004032129 and its equivalent patents. Suitable separation methods are also the methods described in publications of international applications WO 2004/063138, WO 2004/035514, German patent applications DE-A 10243625 and DE-A 10235847. Further processing of the obtained crude acrylic acid can be carried out, for example, as described in international applications WO 01/77056, WO 03/041832, WO 02/055469, WO 03/078378 and WO 03/041833.

A common feature of the aforementioned separation methods is that, for example, in the head of, for example, a separation column containing specific devices having a separation ability, a gaseous mixture of products containing, according to direct or indirect cooling, is supplied at least one final product, usually a residual gas stream is obtained that mainly contains those components of the gaseous mixture of products whose boiling point at normal occurrence (1 bar) does not exceed -30 ° C (i.e., are difficult to condense or highly volatile components).

In the lower part of the separation column, components of a gaseous mixture of products with lower volatility are usually obtained in the condensed phase, including the desired at least one final product, and by-products with volatility similar to the final product.

The components of the residual gas are usually primarily propane, possibly propylene that has not undergone partial oxidation, molecular oxygen, and also inert dilution gases, which are often used in partial oxidation, such as nitrogen and carbon dioxide. Depending on the separation method used, water vapor may be contained in the residual gas either only in trace amounts or in amounts up to 20 vol.% Or more. This gas can be (and usually is) supplied as described.

It is worth mentioning here again that the main step in separating acrylic acid from the gas mixture of partial oxidation products containing acrylic acid as the final product is preferably carried out by subjecting the gas mixture to the products, optionally cooled by direct and / or indirect cooling, in a separation column, containing specific devices with separation ability, upward fractionated condensation with a lateral discharge of crude acrylic acid (for example, in itself) and / or absorbed water or an aqueous solution, as described as an example in international application WO 2004/035514 and German patent application DE-A 10243625. The selected crude acrylic acid is then preferably crystallized in suspension, and the resulting suspension crystallized acrylic acid is preferably separated from the mother liquor using a wash column. In this case, it is advisable to use as a washing liquid a melt of crystals of acrylic acid, previously separated in a wash column. In addition, it is preferable that the wash column is one with forced transportation of the crystal layer. The use of a hydraulic wash column (e.g., TNO columns) or a mechanical wash column is particularly preferred. You can follow the details set forth in international applications WO 01/77056, WO 03/041832, as well as WO 03/041833. Those. the remaining mother liquor is preferably returned to fractionated condensation (cf. also European application EP-A 1015410). The release of by-products as a flushing stream is usually below the side outlet for crude acrylic acid.

Using just one crystallization step, acrylic acid can be obtained in this way with a purity of at least 99.8 wt.%, Which is excellent for the manufacture of superabsorbents based on sodium polyacrylates.

Otherwise, the requirements profile for the method according to the invention corresponds to that specified in the patent applications of Germany DE-A 10245585 and DE-A 10246119.

The methods of the invention are also generally those in which the partial dehydrogenation with heterogeneous catalysis according to the invention is followed by at least one partial oxidation of at least one heterogeneous catalysed dehydrogenated hydrocarbon.

In the figures from 1 to 17 presents the following:

Figure 1: Oblique projection of a longitudinal section of a shaft reactor, made in a multi-stage form and suitable for use according to the invention.

Figure 2: Front view of a longitudinal section of a shaft reactor, made in a multi-stage form and suitable for use according to the invention.

Figure 3: Top view of a block in the form of an annular cylinder without a grill.

Figure 4: Top view of the block in the form of an annular cylinder with a grid and superimposed on such a mesh of metal wire.

Figure 5: Flange connection between the shell in the form of a round cylinder (1) and the top cover of the reactor.

Figure 6: Measured backfill rack.

Figure 7: Welded sealing sleeve between the shell in the form of a round cylinder (1) and the outer shell of the block in the form of an annular cylinder at the height of the upper ring.

Figure 8: The transition of the pipe supplying the inlet gas II, in the inlet fitting of the upper cover of the reactor, made in three parts.

Figure 9: The transition of the pipe supplying the inlet gas II, in the inlet fitting of the upper cover of the reactor, made in two parts.

Figure 10: Transition of distribution pipes to distribution boxes.

Figure 11: Side view of the holder for the distribution box, made with a geometric circuit.

Figure 12: Top view of the holder shown in figure 11.

Figure 13: Insertion of the thermocouple into the solid catalyst bed.

Figure 14: Introduction to the solid catalyst layer of two thermocouples located one above the other with overlapping.

Figure 15: Bipod for supporting the guide pin of the thermocouple.

Figure 16: Two-leg for supporting the guide fingers of the thermocouple of two thermocouples located in a solid layer one above the other with overlapping.

Figure 17: Simulation of a shaft reactor.

Example

We used a simulated mine reactor (44) in the form of a parallelepiped. The inner space of the parallelepiped with a wall thickness of 3 mm (all elements of the simulated reactor were made of stainless steel 1.4541) had the following dimensions. The base area is 840 mm (rib a) × 900 mm (rib b). The height (rib c) of the simulated reactor in the form of a parallelepiped was 1200 mm.

60 cm above the base of the reactor simulator (the size data refer to the distance from the surface of the base to the upper rib a * of the metering boxes (distribution boxes)) in the interior of the simulated reactor, with their own longitudinal rib b * parallel to rib b, three identical the shape of the parallelepipeds of the metering box (45) with a rectangular section a * × c *. The wall thickness of these metering boxes was 2 mm. The ribs a * were parallel to the ribs a and had a length of 15 cm. The ribs c * were parallel to the ribs c and had a length of 4 cm. The distance between the two dosing boxes was 13 cm. The middle of the three dosing boxes was placed with the edge a * in the center of the width of the box a = 840 mm. The rib length b * was 900 mm. The surfaces a * × c * of the dosage boxes in each case were welded to the surfaces a × c. The simulated parallelepiped-shaped reactor was open at the top (i.e. did not have a lid), and at the bottom it was closed on four sides.

On both rectangular sides with the * × b * dosing box, there were round exit holes A (46) with a diameter of 3 mm, arranged like beads strung on a thread, the “thread” being 5 mm from the rib b * facing the a × surface b, and was parallel to this edge.

The distance from one outlet A to the nearest one in the “beads” of outlet A was (measured from the center to the center) 10 cm. The outlet A of the opposite rectangles with * × b * adjacent rectangular boxes were located opposite each other ("In the light").

A hole metal sheet (47) was superimposed on the dosing boxes (45) (along the a × b section), the sheet being 3 mm thick. The holes had a uniform oval shape. Their diameter was 3 mm and the longitudinal size was 1.5 cm. The proportion of holes in a hole sheet was about 30% (percentage of holes in% = (sum of permeable areas / total area) × 100). The centers of the holes were evenly distributed over the squares.

An inert backfill (48) with a height of 20 cm made of steatite rings 7 mm × 7 mm × 4 mm in size ((outer diameter) × (height) × (inner diameter)) was applied to the hole sheet. A uniform metal mesh consisting of longitudinally and transversely passing metal wire was imposed on this backfill.

The distance between the two parallel metal wires closest to each other was 2 mm. A lattice (49) was superimposed on this metal mesh, which, like the metal mesh, extended over the entire a × b section. The height of the lattice (parallel to the edge c) was 10 cm. The rest of the lattice had a cellular structure. A single cell had a square section, the internal area of which was 3 cm × 3 cm. The thickness of the lattice walls was 1 mm.

Under the dosing boxes there was a supply pipe (50), which ran parallel to the edge a (the distance to the nearest edge a was 10 cm) and was introduced into the b × c wall through the corresponding hole and hermetically welded into it. The cross section of the supply pipe was square, 10 cm × 10 cm. In length, it extended to the end of the rib a * of the third metering box.

Under a specific distribution box in the supply pipe, there was a circular hole with a diameter of 8 cm, which coincided in its position with the corresponding (located in the center) round hole in the surface a * × b * facing the base a × b, and was connected to it by welding. The length of the supply pipeline was 800 m.

40 m ³ / h of a mixture (simulating inlet gas II), consisting of 10 vol.% CO ₂ and 90 vol.% Air (T = 25 ° C, P = 1.1 bar), were fed into the supply pipe.

At 10 cm, a perforated metal sheet (51) was welded onto the parallelepiped-shaped reactor feed pipe, which extended over the entire cross-sectional area a × b. The holes in the hole sheet (3 mm thick) had a diameter of 1 cm. The centers of the holes were evenly distributed over the squares. The proportion of holes in the hole sheet was 6%.

Under the aforementioned hole sheet, a round fitting (52) (300 mm inner diameter) was inserted into the simulated reactor in the form of a parallelepiped. The distance from it to the base a × b was 5 cm. The distance from it to the nearest surface a × b was 10 cm.

The surface (wall) b × s through which the nozzle was inserted was opposite the surface b × s through which the feed pipe passed (if you mentally extend the feed pipe and the nozzle in the corresponding flow directions, the extension lines will be almost one above the other) .

Using fittings, 2500 m ³ / h of air (T = 25 ° C. P = 1.1 bar) was drawn into a simulated parallelepiped reactor simulator (simulated gas inlet stream I).

Using an Ultramat 22P apparatus manufactured by Siemens (the apparatus draws in a gas mixture and passes it through a cuvette, determining its CO ₂ content by UV spectroscopy using a calibration comparison cuvette), the CO ₂ content was determined in separate square cells of the mesh lattice.

The number average concentration of CO ₂ was 0.16 vol.%.

The maximum measured CO ₂ was 0.30 vol.%.

The minimum measured CO ₂ was 0.02 vol.%.

A longitudinal section of a simulated reactor in the form of a parallelepiped is presented in figure 17.

U.S. Provisional Patent Application No. 60/787165, filed March 30, 2006, and US Provisional Patent Application No. 60/791207, filed April 12, 2006, are incorporated into this application by reference. Substantial changes and deviations from the present invention are possible in the contents of the above publications. Thus, it can be considered that the invention, within the framework of the attached claims, can also be implemented otherwise than specifically indicated therein.

Claims (39)

1. The method of heterogeneous catalytic partial dehydrogenation of at least one acyclic or cyclic hydrocarbon of alkanes or olefins to be dehydrogenated to at least one dehydrogenated acyclic or cyclic aliphatic hydrocarbon with one or more double C-C bonds in the molecule, in which, for the purpose of partial dehydrogenation, at least one hydrocarbon to be dehydrogenated the entire volume of the input stream of the reaction gas mixture containing molecular acid the kind, molecular hydrogen, and at least one hydrocarbon to be dehydrogenated, is passed through a solid catalyst layer located in a shaft with a predetermined cross-section, which includes, when looking in the direction of the flow of the reaction gas inlet stream, first backfill from inert molded articles of length X, and then the catalytically active backfill following it with at least one molded catalyst product, formed so that for the reaction of combustion of molecular hydrogen with molecular with formation of water and / or for the combustion reaction of the hydrocarbon contained in the input stream of the reaction gas mixture with oxygen to carbon oxides and water, it provides at least an inlet energy at least in the input section than for dehydrogenation of at least one hydrocarbon to be dehydrogenated to at least one dehydrogenated hydrocarbon such that part of the at least one hydrocarbon to be dehydrogenated is dehydrated to at least one dehydrated carbon hydrogen, and the input stream of the reaction gas mixture in the mine is created by adding to the molecular hydrogen entering the mine in the bulk stream V1 to the solid catalyst layer and the input stream I containing at least one hydrocarbon to be dehydrogenated to the solid catalyst layer molecular oxygen inlet gas II with a total volume of stream V2, characterized in that the gas inlet II is supplied in the form of gas streams II flowing out of a plurality of outlet openings A of the pipe system located in the direction of the inlet gas flow I in front of the solid catalyst bed so that:
a) the directions of the majority M of all the inlet gas flows II flowing from the outlet openings A, under conditions of an imaginary absence of the inlet gas stream I, make an angle α equal to 90 ± 60 ° with the direction of the inlet gas stream I;
b) the distance D of the majority M of all outlet openings A from the solid catalyst layer, taking into account the flow rate W of the gas inlet stream I in the mine, is less than the induction time J of the reaction gas mixture (this is a mixture of gases composing the input stream of the reaction gas mixture) times 2 · W , or equal to it;
c) when the projection of the centers of gravity of the majority M of all the outlet openings A in the direction of the gas inlet flow I onto the projection plane E is perpendicular to the direction of the gas inlet flow I for at least 75% of the projection area captured by the inlet gas flow I, the number ZA of the gravity of the outlet located on an arbitrary square meter is at least 10;
d) individual inlet gas flows II flowing from the outlet openings A, belonging to the number ZA of the centers of gravity of the outlet openings A, deviate from their number average value by no more than 50% (when calculating based on the number average value);
e) within the limits of the number ZA of the outlet openings, the distance d from one center of gravity of the outlet to the nearest to it (in the projection plane E) center of gravity of the outlet is not more than

, and
f) the ratio V1: V2≥8 is satisfied, and
g) the ratio of X is satisfied: d≥0.1 and ≤5. 2. The method according to claim 1, characterized in that the inlet gas II contains the following components:
from 0 to 80 vol.% water vapor,
from 10 to 97 vol.% N ₂ ,
from 3 to 25 vol.% O ₂ . 3. The method according to claim 1 or 2, characterized in that the inlet gas II contains the following components:
from 15 to 60 vol.% H ₂ O,
from 20 to 80 vol.% N ₂ ,
from 5 to 20 vol.% O ₂ . 4. The method according to claim 1 or 2, characterized in that the ratio V1: V2≥15 is satisfied. 5. The method according to claim 1 or 2, characterized in that the ratio V1: V2≥20 is fulfilled. 6. The method according to claim 1 or 2, characterized in that the longitudinal size L of the outlet A is not less than 0.1 mm and not more than 5 cm. 7. The method according to claim 1 or 2, characterized in that the longitudinal size L of the outlet A is not less than 1 mm and not more than 5 mm. 8. The method according to claim 1 or 2, characterized in that the directions of the majority M of all the inlet gas flows II flowing from the outlet openings A in the conditions of an imaginary absence of the inlet gas stream I comprise an angle α with the direction of the inlet gas stream I equal to 90 ± 30 °. 9. The method according to claim 1 or 2, characterized in that the directions of the majority M of all the inlet gas flows II flowing from the outlet openings A in the conditions of an imaginary absence of the inlet gas stream I comprise an angle α equal to 90 ± with the direction of the inlet gas stream I 10 °. 10. The method according to claim 1 or 2, characterized in that the majority M of all outlet openings A satisfies the condition D≤0.5 · W · J. 11. The method according to claim 1 or 2, characterized in that the majority M of all outlet openings A satisfy the condition D≤0.2 · W · J. 12. The method according to claim 1 or 2, characterized in that ZA≥30. 13. The method according to claim 1 or 2, characterized in that ZA≥50. 14. The method according to claim 1 or 2, characterized in that ZA≥100. 15. The method according to claim 1 or 2, characterized in that the distance d is not more than

. 16. The method according to claim 1 or 2, characterized in that the distance d is not more than

. 17. The method according to claim 1 or 2, characterized in that the individual flows of the inlet gas II flowing from the outlet openings A, belonging to the number ZA of the centers of gravity of the outlet openings, deviate from their number average by no more than 30%. 18. The method according to claim 1 or 2, characterized in that the individual flows of the inlet gas II flowing from the outlet openings A, which are among the ZA centers of gravity of the outlet openings, deviate from their number average by no more than 10%. 19. The method according to claim 1 or 2, characterized in that under the majority M of all the outlet openings A and the individual flows of the inlet gas II flowing from them, it should be understood that those outlet openings A and the separate flows of the inlet gas II flowing out of them, from which together account for more than 70% of the total volumetric flow V2, with the condition that among the individual inlet gas flows II flowing out of them, there is not one within the total number of all individual inlet gas flows II that would be less than the largest of the individual input g streams for II, not belonging to the majority of M. 20. The method according to claim 1 or 2, characterized in that under the majority M of all the outlet openings A and the individual flows of the inlet gas II flowing from them, it should be understood that those outlet openings A and the separate flows of the inlet gas II flowing out of them, from which together account for more than 90% of the total volumetric flow V2, with the condition that among the individual inlet gas flows II flowing out of them, there is not one within the total number of all individual inlet gas flows II that would be less than the largest of the individual input g streams for II, not belonging to the majority of M. 21. The method according to claim 1 or 2, characterized in that when projecting the centers of gravity of most M of all the outlet openings A in the direction of the gas inlet stream I onto the projection plane E is perpendicular to the direction of the gas inlet stream I flow for at least 85% of the projection area, captured by the inlet gas stream I, the number ZA of the centers of gravity of the outlet openings located on an arbitrary square meter is at least 10. 22. The method according to claim 1 or 2, characterized in that when projecting the centers of gravity of most M of all the outlet openings A in the direction of the gas inlet stream I onto the projection plane E is perpendicular to the direction of the gas inlet stream I flow for at least 95% of the projected area, captured by the inlet gas stream I, the number ZA of the centers of gravity of the outlet openings located on an arbitrary square meter is at least 10. 23. The method according to claim 1 or 2, characterized in that the input stream of the reaction gas mixture is conducted through a solid catalyst bed, taking into account that at least 2 mol% of the at least one hydrocarbon to be dehydrogenated therein is subjected to dehydrogenation to at least one dehydrogenated hydrocarbon. 24. The method according to claim 1 or 2, characterized in that the input stream of the reaction gas mixture is conducted through a solid catalyst layer, taking into account that at least 5 mol% of the at least one hydrocarbon to be dehydrogenated therein is subjected to dehydrogenation to at least one dehydrogenated hydrocarbon. 25. The method according to claim 1 or 2, characterized in that the input stream of the reaction gas mixture contains at least 5 vol.% At least one hydrocarbon to be dehydrogenated. 26. The method according to claim 1 or 2, characterized in that the input stream of the reaction gas mixture contains at least 10 vol.% At least one hydrocarbon to be dehydrogenated. 27. The method according to claim 1 or 2, characterized in that the molar content of molecular oxygen in the input stream of the reaction gas mixture is not more than 50 mol.% The amount contained (in moles) of molecular hydrogen. 28. The method according to claim 1 or 2, characterized in that when passing the input stream of the reaction gas mixture through the solid catalyst bed, at least 95 mol% of the molecular oxygen contained in the input stream of the reaction gas mixture was used to burn molecular hydrogen contained in reaction gas inlet stream. 29. The method according to claim 1 or 2, characterized in that the temperature of the input stream of the reaction gas mixture when it enters the solid catalyst layer is from 300 to 700 ° C. 30. The method according to claim 1 or 2, characterized in that the load on the solid catalyst layer (relative to the total amount of catalyst contained in it) by at least one hydrocarbon to be dehydrogenated is from 100 to 10,000 Nl / l · h. 31. The method according to claim 1 or 2, characterized in that the induction time J does not exceed 2000 ms. 32. The method according to claim 1 or 2, characterized in that the induction time J does not exceed 100 ms. 33. The method according to claim 1 or 2, characterized in that the cross-section of the pipeline system through which the inlet gas II enters, where the outlet holes A are, is polygonal. 34. The method according to claim 1 or 2, characterized in that the cross-section of the pipeline system through which the inlet gas II enters, where the outlet openings A are, is quadrangular. 35. The method according to claim 1 or 2, characterized in that the outlet openings A are round. 36. The method according to claim 1 or 2, characterized in that the difference ΔT _II ^I between the temperature of the incoming gas stream I and the inlet gas II does not exceed 300 ° C. 37. The method according to claim 1 or 2, characterized in that at least one hydrocarbon to be dehydrogenated is propane. 38. The method according to claim 1 or 2, characterized in that at least one dehydrogenated hydrocarbon is propylene. 39. The method according to claim 1 or 2, characterized in that it is implemented in a shaft reactor, made in the form of a multi-stage reactor.

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