RU2231516C1 - Hydrocarbon dehydrogenation and dehydrocyclization process - Google Patents

Abstract

FIELD: petrochemical processes.

SUBSTANCE: feedstock stream comes into contact with catalyst based on X-ray amorphous catalytic prepared by evaporation of carbon-containing material and showing following characteristics: in-air oxidation commencement temperature ≤ 320^оС, maximum oxidation rate temperature ≤ 590^оС, in-air oxidation end temperature ≤ 630^оС, initial hydrogenolysis rate at 700^оС in absence of hydrogen-activating catalyst ≥ 2.08 wt % carbon/h, limiting amount of MnO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ ion consumed in contact with 1 g of above-mentioned carbon in solution ≥ 16 mmole at 350-600^оС and pressure 0.01 to 0.15 mPa.

EFFECT: enabled processing of hydroaromatic compounds, alkanes, and cyclo-C₆-alkanes to produce dehydrogenation of cyclo-C₆-alkanes and dehydrocyclization of alkanes.

24 cl, 3 dwg, 16 ex

Description

The present invention relates to processes for the conversion of hydrocarbons, in particular to dehydrogenation and dehydrocyclization of hydrocarbons, and processes where these transformations are carried out, in particular to the dehydrogenation of C ₂ -C ₅ alkanes to produce alkenes, cyclo-C ₅ alkanes to cycloalkenes and cycloalkadiene, cyclo-C ₆ alkanes to benzene and its homologues, as well as to dehydrocyclization of C ₆₊ alkanes to form benzene and its homologs.

Dehydrogenation and dehydrocyclization processes include activation and subsequent cleavage of the C-H bond. Since C – H bonds in alkanes are almost equivalent in binding energy, it is a priori difficult to count on the high selectivity of the dehydrogenation stage. Alkenes resulting from dehydrogenation also undergo further dehydrogenation transformations, resulting in the formation on the catalyst surface of hydrogen-depleted densification products - precursors of carbonaceous deposits, usually called coke. Coke deactivates the catalyst, its activity and selectivity change over time. Prevention of coke formation is one of the main tasks of hydrocarbon processing.

Dehydrocyclization and dehydrogenation, like the traditional reforming process, due to the active deposition of coke, is usually carried out when the feedstock is diluted with hydrogen or water vapor with a clear predominance of diluent (molar ratio of hydrogen / hydrocarbon up to 5/1). The role of such a diluent is probably to remove freshly formed coke as a result of its hydrogenation or steam reforming. Dilution of the feed (its low concentration in the reaction zone) reduces the degree of conversion per passage and requires an increase in contact time, for example, an increase in pressure in the reaction apparatus. An increase in hydrogen pressure reduces the amount of coke deposited, but causes side reactions of hydrocracking and hydrogenolysis. The unpleasant side of increasing the total pressure and hydrogen pressure is a decrease in the already low proportion of dehydrogenation and dehydrocyclization reactions that occur with an increase in the number of particles and with the evolution of hydrogen. In real reforming processes in all reactions, including undesirable ones, no more than 15-20% of the alkanes of the feed are converted. In addition, prior to use, the reforming feedstock is subjected to additional preparation — removal of catalytic poisons (sulfur compounds), non-processable pentanes (depentanization), and deactivating alkenes catalyst.

A known method of converting normal hexane to benzene on a Cr ₂ O ₃ -Al ₂ O ₃ -Na ₂ O catalyst at a temperature of 550-580 ° C, a pressure in the range of 300 - 1500 Torr, a molar hydrogen / hydrocarbon ratio of 3/1, and the volumetric flow rate of raw materials in terms of liquid in the range of 0.2-2.0 h ^-1 (see UK patent No. 1009511, IPC C 07 C 5/00, published 10.11.1965).

The disadvantages of this method are the need for dilution of the feedstock with hydrogen, a low degree of conversion of the feedstock, large losses for coke and gas, reaching 15.3%, the associated catalyst deactivation and reduction in its activity, overcome by increasing the process temperature.

A known method of processing petroleum feeds (see US patent No. 5013423, IPC C 10 G 35/06, 1991), in which the feed is brought into contact with a non-acidic dehydrogenation catalyst in the presence of hydrogen under conditions of temperature and pressure and at a clock feed rate, providing dehydrocyclization. The catalyst contains a platinum group metal on an indium-containing zeolite carrier, which has a crystal structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50.

At process temperatures of more than 427 ° C in the presence of hydrogen, the resulting product has a higher octane number and aromatic hydrocarbon content than the initial reforming product. The disadvantages of the process are the low degree of conversion of the feed, the high content of benzene (25-30 vol.%) In the target product, the deposition of coke on the catalyst and the need to dilute the feed with hydrogen.

A known method of processing a pentane fraction to produce liquefied petroleum gas by direct interaction with an acidic crystalline aluminosilicate with a silica / alumina ratio of more than 12, having a peak temperature of desorption of hydrazine in the process of raising the temperature to more than 650 ° C (see Japanese Patent Application N 3-54717, IPC C 10 G 11 / 05.1993).

The disadvantages of this method is the need for separation and disposal of by-products obtained in quantities of up to 12 vol. %, as well as in progressive coking of the catalyst with a time-varying composition of reaction products, the absence of dehydrogenation processes, the impossibility of dehydrocyclization and cracking of the feedstock.

A known method for the conversion of heavy hydrocarbons (see RF application No. 97107731, IPC C 10 G 47/32, 01 J 23/78, published 05/20/1999), including the supply of heavy hydrocarbon feed to the reaction zone and its conversion to the catalytically active phase. The catalytically active phase includes a first metal and a second metal, where the first metal is a base metal of group VIII and the second metal is an alkali metal. In the method, the feedstock is contacted with water vapor at a pressure of less than or about 2.1 MPa to obtain a hydrocarbon product having a reduced boiling point. Typically, the first metal is selected from the group consisting of iron, cobalt, nickel and mixtures thereof, and the second metal is selected from the group consisting of potassium, sodium and mixtures thereof. In this case, at least one of the metals is fixed on the carrier. The carrier material is mesoporous selected from the group consisting of silicon dioxide, natural and artificial aluminosilicates, aluminum oxides, coke from petroleum or coal, and carbon-based materials obtained from plant or animal sources.

The disadvantages of this method are the cracking of raw materials, the need for dilution, steam conversion of the raw materials with the formation of synthesis gas, progressive coking and associated catalyst deactivation.

A known method of processing hydrocarbon feedstocks based on aliphatic hydrocarbons (see RF patent No. 2152977, IPC C 10 G 35/095, published July 20, 2000), comprising supplying the feedstock to the reaction zone, diluting it with hydrocarbon gas and carrying out the process at elevated temperature, mainly 320-420 ° C, in the presence of an aluminosilicate catalyst, followed by isolation of the desired products from the catalysis. As an aluminosilicate catalyst, an alumina-cobalt-molybdenum zeolite-containing catalyst is used having the composition (wt.%): Zeolite ZSM-11 with a silicate module 17 ÷ 60 - 15 - 45, cobalt oxide 2-6, molybdenum oxide 8-14, binder - the rest. As a hydrocarbon diluent gas, desulphurized natural gas is used and the process is conducted under a pressure of 1.5-2.0 MPa to obtain a catalysis containing target aromatic hydrocarbons, C ₃ -C ₅ hydrocarbons, C ₁ -C ₂ hydrocarbons in an amount of not more than 1 wt.%, followed by separation of the hydrocarbon fraction used as an octane increasing additive or high-octane gasoline, and C ₃ -C ₄ liquefied hydrocarbons.

The disadvantages of the process are the necessity of introducing a diluent - natural gas with its preliminary preparation (desulfurization or hydrotreating), which complicates the process, high (1.5-2.0 MPa) pressure of the process, which proceeds with an increase in the number of particles, which causes a decrease in the degree of conversion of raw materials, the need to purify raw materials from pentanes, the impossibility of processing alkenes or raw materials containing them, the unsuitability of the process for the processing of cycloalkanes, the sensitivity of the catalyst to conventional catalytic poisons - sulfur compounds.

A known method of reforming naphtha (ligroin, an oil distillation fraction with a carbon number of more than 6, not containing alkenes), which consists in using activated carbon as a catalyst without treatment or impregnated with carbonates or hydroxides of alkali metals (Na, K, Li) in the temperature range 538 -593 ° C. Promotion slightly reduces the rate of coke deposition, and also allows for regeneration (see RA Sanford and BS Friedman, Ind. Eng. Chem. 1954. V.46, No. 12, pp.2568-2571). The disadvantages of the known catalyst: low (no more than 20%) alkane conversion, low activity of the promoted catalyst in dehydrogenation (15.1% yield of toluene from methylcyclohexane) and dehydrocyclization (9.6% yield of toluene from n-heptane) and the inability to suppress coking. So, when diluting raw materials with hydrogen or steam at a molar ratio of diluent and hydrocarbon equal to 2.4, the loss of raw materials for coke reaches 2.3%.

A known method of dehydrogenation, as well as hydrogenolysis of a hydrocarbon, adopted as a prototype (see US patent No. 5336828, IPC C 07 C 5/327, published 09/09/1994), which includes contacting the feed with a catalyst representing at least one soluble fullerene C _n , where n = 50-120, while maintaining the reaction mixture at a temperature in the range from 25 to 500 ° C and a pressure in the range of 1-1500 Torr. Mentioned fullerene is dissolved in the feed if the feed is a liquid capable of dissolving fullerene, or in an additional solvent, which is also a solvent for hydrocarbon.

Use in a known prototype method of a catalyst in the form of a solution prevents the formation of coke.

The disadvantages of the known prototype method are as follows. The known prototype catalyst is active only in the dehydrogenation of hydroaromatic compounds, but not alkanes. The applicability of the known catalyst for the dehydrogenation of cyclohexane and its homologues is unknown, which excludes the use of the known catalyst for the dehydrocyclization of alkanes. The sublimation of fullerene (SK Mathews, M. Sai Baba et al. Fullerene Science and Technology. 1993. No 1 (1). P.101-109; MV Korobov, LN Sidorov, J. Chem. Termodynamics. 1994. V.26. P.61-73) reduces the temperature of use of the known catalyst and narrows the range of dehydrogenation reactions that are thermodynamically possible. So, in particular, fullerene and fullerene epoxides catalyze cracking of alkanes, but not their dehydrogenation. The formation of stable fullerene hydrides when heated with a hydroaromatic compound leads to reasonable doubts about the possibility of dehydrogenation of hydroaromatic compounds with high degrees of conversion.

The problem to which the invention is directed is the development of such a method of dehydrogenation and dehydrocyclization of hydrocarbons, which would ensure the processing of not only hydroaromatic compounds, but alkanes and cyclo-C ₆ alkanes, carrying out dehydrogenation of cyclo-C ₆ alkanes and dehydrocyclization of alkanes.

The problem is solved in that the method of dehydrogenation and dehydrocyclization of hydrocarbons involves contacting the feed stream with a catalyst based on X-ray amorphous carbon obtained by evaporation of a carbon-containing material and having the following characteristics:

temperature of the onset of oxidation in air T _but ≤ 320 ° C;

temperature of the maximum oxidation rate T _mso = 590 ° C;

temperature of the end of oxidation in air T _ko ≤ 650 ° C;

initial hydrogenolysis rate at 700 ° C in the absence of a hydrogen activating catalyst, V _beg ≥ 2.08% wt. carbon / h;

-иона, расходуемое при контакте с 1 г упомянутого углерода в растворе, - не менее 16 ммоль при температуре от 350 до 600° С и давлении от 0,01 до 0,15 мПа.limit amount

the ion consumed in contact with 1 g of the aforementioned carbon in solution is at least 16 mmol at a temperature of 350 to 600 ° C and a pressure of 0.01 to 0.15 MPa.

Contacting the feed stream with the catalyst can be carried out by feeding the feed at an hourly average volumetric rate in terms of liquid from 0.1 to 10 h ^-1 , and the catalyst can be obtained, for example, by evaporation of a carbon-containing material under the influence of an electric arc or under the action of laser radiation .

The contacting of the feed stream is preferably carried out with a catalyst based on X-ray amorphous carbon having a temperature T _but = 280 ° C. and a temperature T _mso = 508 ° C.

Used in the inventive method, X-ray amorphous carbon may have a specific surface area S = 210-280 m ² / g and bulk density ρ ≤ 0.05 g / cm ³ .

The catalyst may additionally contain an inert granular material, mainly consisting of particles with a size of 0.25-1.00 mm As an inert granular material, quartz or ceramic can be introduced.

X-ray amorphous carbon and inert granular material can be taken in the following ratio, wt.%:

X-ray amorphous carbon 1.65-99.00;

inert granular material rest.

In the inventive method, a catalyst in the form of granules formed from a mixture of X-ray amorphous carbon with a binder can be used.

As a binder, a neutral metal hydroxide gel selected from the group of aluminum, magnesium, zirconium, titanium, hafnium, or a mixture of neutral gels of at least two metal hydroxides selected from the above group can be introduced into the catalyst.

As a binder, a neutral metal hydrogel selected from the above group, or a mixture of at least two such neutral metal hydrogels, or a natural hydrogel can be introduced into the catalyst.

After molding, the granular catalyst is heat treated in vacuum at temperatures from 200 to 550 ° C.

In the inventive method, X-ray amorphous carbon and a binder can be taken in the following ratio, wt.%:

X-ray amorphous carbon 1.65-40.00;

binding rest.

In the inventive method can be used raw materials containing alkanes as the main components with the number of carbon atoms not less than 6.

As raw materials in the inventive method can be used oil, raw materials of the reforming process, including unstabilized products of the reforming process, as well as reforming products after separation of aromatic compounds.

The inventive method of dehydrogenation and dehydrocyclization of hydrocarbons is based on the use of a catalyst based on X-ray amorphous carbon and is illustrated by drawings, where

figure 1 shows the dependence of the oxidation state used in the inventive method of the catalyst having a specific surface area of 278 m ² / g, temperature T _but = 280 ° C, T _mso = 508 ° C and T _ko = 630 ° C obtained by evaporation by an energy flow of 200 W / mm ² (1); a catalyst having a specific surface area of 210 m ² / g, temperature T _but = 320 ° C, T _mso = 590 ° C and T _ko = 900 ° C (2) obtained with an energy flow of 50 W / mm ² , the catalyst obtained at an energy flow of less than 50 W / mm ² (3); glassy carbon (4) and graphite (5) as a function of temperature (I is the oxidation region of X-ray amorphous carbon; II is the oxidation region of graphitized particles; III is the oxidation region of graphite); temperatures T _but , T _mso and T _ko in FIG. 1 are marked for catalyst (1);

figure 2 shows the x-ray diffraction spectra of 1 - catalyst (1), catalyst (2) and catalyst (3) (designations (1), (2) and (3) are the same as in figure 1);

figure 3 shows the spectra of electron paramagnetic resonance (EPR) of the catalyst (1), catalyst (2) and catalyst (3) (symbols (1), (2) and (3) are the same as in figure 1).

The catalyst used in the inventive method of dehydrogenation and dehydrocyclization of hydrocarbons, regardless of the method of preparation, its reactivity and catalytic activity, contains, according to elemental analysis, 95-97% wt. carbon, about 1.5% hydrogen and 3-4% oxygen. Hydrogen and oxygen are present in the form of hard to remove water, since water was detected in absolute methanol after washing X-ray amorphous carbon evacuated at 100 ° C for 10 hours. As a result of one cycle, “deep vacuum at 150 ° C - adsorption of dry air” contains hydrogen and oxygen does not exceed the measurement error.

The specific surface area of the catalyst is, depending on the production conditions, 210-280 m ² / g (for fine graphite, for comparison, 6 m ² / g). Upon receipt of the catalyst at energy flows less than 50 W / mm ² , it can include graphite that has not been converted due to the low energy flow, which is determined by the slow loss of mass above 670 ° C and graphitized particles (not fully converted graphite), detected by weight loss in the temperature range 645-670 ° C (see figure 1). Graphite is also determined by the sharp line 002 of graphite in the X-ray diffraction spectra (see figure 2). The presence of graphitized particles and graphite dramatically reduces the reactivity of the catalyst. The catalyst obtained by evaporation of a carbon-containing material under the influence of an energy flux of 50-300 W / mm ² and having high catalytic activity does not contain graphite itself and graphitized particles, as evidenced by the absence of graphite line 002 (see Fig. 2) and the temperature of the end of oxidation 630 ° C (see figure 1).

The EPR spectrum of the catalyst in vacuum is a singlet line with a width of 0.19 mT and a g-factor of 2.0022 (see figure 3). The line is close to Lorentz in the center, has wide wings. According to the second integral of the EPR spectrum (or the area under the integrated line shape), it was determined that the catalyst contains, depending on the production conditions, (2-5) · 10 ²⁰ spin per 1 mol of carbon, i.e. 1 paramagnetic center (PC) for 1000-3000 carbon atoms. According to the g-factor (2.0022), paramagnetic centers are caused by structural defects such as dangling C – C bonds.

в нейтральной среде) и по взаимодействию с Вr₂. При контакте рентгеноаморфного углерода с ионом

в нейтральной среде наблюдается уменьшение концентрации иона

в растворе, расход иона

в нейтральной среде на 1 г рентгеноаморфного углерода превышает 16 ммоль. Прочие углеродные материалы, в частности графит, стеклоуглерод, активированные угли, не взаимодействуют с ионом

(ион

не расходуется при контакте с прочими углеродными материалами). Концентрация обнаруживаемых по взаимодействию с ионом

кратных С=С-связей значительно выше, чем оборванных, и составляет по расчету для наиболее активных в катализе образцов одну двойную С=С-связь на 5 углеродных атомов.In addition to dangling bonds, the catalyst contains non-conjugated multiple C = C bonds detected by the Wagner reaction (interaction with an ion

in a neutral environment) and the interaction with Br ₂ . Upon contact of X-ray amorphous carbon with an ion

in a neutral environment there is a decrease in ion concentration

in solution, ion consumption

in a neutral medium per 1 g of X-ray amorphous carbon exceeds 16 mmol. Other carbon materials, in particular graphite, glassy carbon, activated carbon, do not interact with the ion

(and he

not consumed by contact with other carbon materials). The concentration detected by the interaction with the ion

multiple C = C bonds is much higher than dangling ones, and is calculated for the most active samples in catalysis as one double C = C bond per 5 carbon atoms.

X-ray amorphous carbon in the absence of hydrogen-activating catalysts at a temperature of ≥ 700 ° С undergoes hydrogenolysis, which is not observed for other carbon materials, including fullerenes, at 1000 ° С.

The high reactivity of the catalyst used in the inventive method (an abnormally low temperature of the onset of oxidation and a high average rate of oxidation in air, oxidation and bromination in solution, hydrogenolysis in the absence of hydrogen activating catalysts) indicate the presence in its structure of non-conjugated multiple bonds that are absent in the structure of others carbon materials.

These structural features of the catalyst determine its catalytic activity and are manifested in reactivity. It is likely that the dehydrogenation transformations of hydrocarbons in the presence of a catalyst proceed as reactions involving the transfer of hydrogen from an alkane to a catalyst with the formation of relatively unstable hydride forms of active X-ray amorphous carbon. This is quite reasonable, since we first discovered the hydrogenolysis of the claimed catalyst with molecular hydrogen in the absence of a hydrogen activating catalyst, but the chemisorption of hydrogen by the catalyst in the temperature range of 50-400 ° C was not found.

The combination of all the above characteristics of the catalyst is a necessary and sufficient condition for its activity in dehydrogenation and dehydrocyclization reactions. The absence of any characteristic does not allow to obtain the desired technical effect. Thus, for example, pyrolyzed graphite oxide having a Т _but up to 300 ° С is not subjected to non-catalytic hydrogenolysis by molecular hydrogen even at a temperature of 700 ° С, and is not active in alkane dehydrogenation and dehydrocyclization reactions.

Used in the inventive method, the catalyst is also characterized by a sufficiently developed surface and low bulk density (up to 0.05 g / cm ³ ) and in its pure form is not suitable for operation in a flow reactor. In order to avoid an increase in gas-dynamic resistance or entrainment of the catalyst with a gas stream, in this case a mixed catalyst can be used with the addition of an inert granular material, for example, quartz or ceramics, to the X-ray amorphous carbon.

It is preferable to use the catalyst in granular form. X-ray amorphous carbon practically does not give durable granules during pressing. The formation of X-ray amorphous carbon with a binder allows you to get durable granules. As a binder in the formation of a catalyst based on X-ray amorphous carbon, hydroxide gels or hydrogels of metals selected from the group: aluminum, magnesium, zirconium, titanium, hafnium, and various types of clay can be used. Aluminosilicates, zeolites and other solid acids that cause cracking of raw materials and coke deposition on the catalyst are not suitable as binders.

The use of X-ray amorphous carbon with the above characteristics as a catalyst in the method of dehydrogenation and dehydrocyclization of hydrocarbons makes it possible to process alkanes used only by 15-20%, to avoid coke formation on the catalyst surface and not to dilute the raw material with hydrogen. In addition, alkenes or raw materials containing them, in particular unstabilized (i.e., not subjected to hydrogenation to remove alkenes by converting them to alkanes), raw materials (for example, unstabilized straight-run gasoline) or reforming products ( catalysate before separation of aromatic compounds or raffinate after separation) or a feed containing pentanes. In addition, cyclohexane and its homologues are successfully processed by this method by dehydrogenation. According to this method, the catalyst used does not contain transition and noble metals and is little susceptible to conventional catalytic poisons - sulfur compounds.

The catalyst used in the inventive method of dehydrogenation and dehydrocyclization is obtained by the evaporation process in a helium atmosphere of a raw material containing a chemical element carbon. Evaporation is carried out when an energy stream of 50-300 W / mm ^{2 is} supplied to the carbon-containing material. The source of such a flow of energy may be an electric arc discharge, laser radiation, or microwave radiation. Graphite is most preferred as a carbon-containing material. The evaporation products in the form of fullerene-containing soot are precipitated and extracted from it fullerenes with an organic solvent according to known methods. Then the insoluble precipitate is separated, washed with ether and dried.

If necessary, the obtained X-ray amorphous carbon is mechanically mixed with an inert granular material (for example, quartz or ceramic) with a particle size of 0.25-1.00 mm, preferably in the above ratio. It is preferable to use a catalyst in the form of granules formed from a mixture of X-ray amorphous carbon with a binder in the above ratio and subjected to heat treatment in vacuum at a temperature of from 200 to 550 ° C.

As an example of the evaporation of carbon-containing material, the following is the process of electric arc evaporation of graphite.

Graphite in the form of a solid cylindrical rod is placed in a cylindrical chamber with a ratio of the diameter of the chamber and the diameter of the evaporated rod equal to (10-20): 1. The chamber is filled with helium mainly at a pressure of 100-760 mm RT. Art. Direct current energy is supplied to the rod with an energy flow in an arc of 50 to 300 W / mm ² at a translational speed of the evaporated graphite electrode from 0.2 to 6.0 mm / min.

The above process parameters are necessary to create conditions under which X-ray amorphous carbon clusters cannot be deactivated by interacting with each other. A slower supply of a graphite electrode and a greater than 300 W / mm ² input energy flux contribute to the complete atomization of carbon and the thermodynamic nonequilibrium of the formed X-ray amorphous carbon clusters. The X-ray amorphous carbon clusters formed in the arc, having uncompensated valencies, open double bonds and other reactive fragments of the structure, are cooled and “quenched” while maintaining a thermodynamically nonequilibrium state along the path and on the cooled chamber walls. With a short path to the chamber walls (with a ratio of the diameters of the chamber and the rod less than 10: 1) and an inert gas pressure less than 100 mm Hg. Art. (i.e., a high concentration of reactive active carbon clusters), frequent collisions of energy-rich carbon particles lead to the interaction of X-ray amorphous carbon clusters with each other and the closure of uncompensated valencies and double bonds, which contributes to the formation of a product with a low reactivity. In addition, a high (10: 1 or more) ratio of the diameters of the chamber and the rod and a large volume of the reaction apparatus are associated with the fact that the vaporized compact graphite with a density of 1.5-2.0 g / cm ^{3 is} transformed into highly dispersed X-ray amorphous carbon with a low ( less than 0.05 g / cm ³ ) bulk density.

The inventive method of dehydrogenation and dehydrocyclization is as follows.

) близки к молекулярным. Сырье, в зависимости от условий и агрегатного состояния, находится в виде отдельных молекул (в случае пара или газа) или молекулярных агрегатов (в случае жидкости). Таким образом, взаимодействие сырья и катализатора протекает на границе раздела фаз твердое - газ или твердое - жидкость. В силу описанных выше причин (наноразмеры частиц катализатора) взаимодействие сырья и катализатора осуществляется на псевдомолекулярном уровне. В результате такого взаимодействия, несомненно, протекающего постадийно, например, путем хемосорбции с диссоциацией связи С-Н алкана или циклоалкана, алкан или циклоалкан подвергается дегидрированию и превращается в алкен или циклоалкен.The catalyst is a solid, but its particle size (about 40 nm = 400

) are close to molecular. Raw materials, depending on the conditions and state of aggregation, are in the form of individual molecules (in the case of steam or gas) or molecular aggregates (in the case of liquid). Thus, the interaction of the feedstock and the catalyst proceeds at the solid-gas or solid-liquid interface. For the reasons described above (nanosized catalyst particles), the interaction of the feedstock and catalyst is carried out at a pseudomolecular level. As a result of this interaction, which undoubtedly proceeds stepwise, for example, by chemisorption with dissociation of the CH alkane or cycloalkane bond, the alkane or cycloalkane undergoes dehydrogenation and turns into an alkene or cycloalkene.

The raw material of the claimed process according to the state of aggregation is most often a liquid or, less commonly, a gas. Liquid is usually supplied by a metering pump. In the case of liquids with high saturated vapor pressure, the supply can be carried out by bubbling an inert gas (preferably nitrogen or argon) through the liquid. In this case, the feed mixture contains up to 50% of the feed. Hydrogen and helium cannot be used for these purposes.

Raw materials at a temperature in the range of 350-600 ° C and a pressure of 76-1140 Torr are brought into contact with X-ray amorphous carbon, which has the above characteristics. X-ray amorphous carbon may be introduced on its own; in the form of a mechanical mixture with an inert granular material; in the form of granules previously formed from a mixture with a binder. The type of catalyst is determined by the task and the type of process. X-ray amorphous carbon in itself can only be used in a static system. In this case, the process temperature is limited by the thermal stability of the feed. At such temperatures, mainly thermodynamically possible reactions of the dehydrogenation of hydroaromatic compounds to aromatic. Dehydrogenation of alkanes (or their dehydrocyclization) and cycloalkanes is favored by higher process temperatures when possible types of raw materials are steam.

Evaporation and heating of steam to the reaction temperature in the catalyst bed unproductive reduces the temperature of the catalytic layer. Therefore, usually a catalytic reaction is preceded by evaporation and heating of the feed to the reaction temperature. During the experiments, the heating and evaporation of the raw materials were carried out in an evaporator-heater combined with a catalytic reactor, i.e. the evaporator-heater was the previous layer of ceramic packing in front of the catalytic layer. The steam heated on the nozzle layer enters the catalyst layer, passes through it, turning into reaction products. To ensure the passage of gases, the catalyst must be a mechanical mixture of X-ray amorphous carbon with granular material or granules formed from a mixture of X-ray amorphous carbon with a binder.

The reaction products condense and separate liquid products from gaseous products using a refrigerator-separator.

The inventive method of dehydrogenation and dehydrocyclization is illustrated by the following examples.

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16,0 ммоль, и 2,95 г дробленого кварца с размерами частиц 0,25-0,5 мм (1,65% рентгеноаморфного углерода, 98,65% инертного зернистого материала, объем 2,4 см³). Реактор продувают аргоном снизу вверх в течение 0,5 ч, термостатируют в токе аргона при 550° С и пропускают снизу вверх с объемной скоростью 40 см³/мин (1000 ч^-1) бутен-бутановую фракцию состава (% мол.): н-бутан 23,5, изо-бутан 10,3, бутен-1 39,5, бутен-2 8,7, изо-бутен 14,9, бутадиен-1,3 1,6, C_1-3-углеводороды 0,3, С_5-7-углеводороды 0,9. Выходящий газ содержит (% мол.): н-бутан 20,0, изо-бутан 8,5, бутен-1 21,1, бутен-2 9,2, изо-бутен 14,2, бутадиен-1,3 5,0, С_1-3-углеводороды 11,6, С_5-7-углеводороды 1,5, водород 9,6. Степень конверсии бутанов составила 15-17%, бутена-1 46,0%.Example 1. In a tubular flow reactor is placed alternately 4.0 cm ^{3 of} quartz; cork made of basalt fabric; the catalyst, which is a mechanical mixture of 0.05 g of X-ray amorphous carbon with characteristics: T _but = 320 ° C; T _mso = 580 ° C; T _to = 630 ° C, V _beg = 2.1% wt. carbon / h, and the limit amount

ion consumed in contact with 1 g of the aforementioned carbon in solution, 16.0 mmol, and 2.95 g of crushed quartz with particle sizes of 0.25-0.5 mm (1.65% X-ray amorphous carbon, 98.65% inert granular material, volume 2.4 cm ³ ). The reactor was purged with argon from the bottom up for 0.5 h, thermostated in an argon stream at 550 ° C and passed from the bottom up with a bulk velocity of 40 cm ³ / min (1000 h ^-1 ) butene-butane fraction composition (mol%): n butane 23.5, iso-butane 10.3, butene-1 39.5, butene-2 8.7, iso-butene 14.9, butadiene-1.3 1.6, C _1-3 hydrocarbons 0 , 3, C _5-7 hydrocarbons 0.9. The exhaust gas contains (mol%): n-butane 20.0, iso-butane 8.5, butene-1 21.1, butene-2 9.2, iso-butene 14.2, butadiene-1.3 5 0, C _1-3 hydrocarbons 11.6, C _5-7 hydrocarbons 1.5, hydrogen 9.6. The degree of conversion of butanes was 15-17%, butene-1 46.0%.

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16 ммоль, и 2,4 г дробленого кварца с размерами частиц 0,5-0,75 мм (1,66% рентгеноаморфного углерода, 98,34% зернистого материала, объем катализатора 2,4 см³); пробку из базальтовой ткани; 5 см³ дробленой керамики с размером частиц 0,75-1,0 мм. Реактор продувают сверху вниз аргоном в течение 0,5 ч для удаления воздуха и термостатируют при температуре 5,50° С, после чего пропускают насыщенные при 22° С пары н-гексана в аргоне с объемной скоростью 40 см³/мин (1000 ч^-1 по газу, 1 ч^-1 по жидкому н-гексану).Example 2. In a tubular flow reactor, one by one the catalyst is placed, which is a mechanical mixture of 0.6 g of X-ray amorphous carbon with characteristics: T _but = 320 ° C; T _mso = 590 ° C; _Tco = 630 ° C, V _beg = 2.08% wt. carbon / h, and the limit amount

-ionic ion consumed in contact with 1 g of the aforementioned carbon in solution, 16 mmol, and 2.4 g of crushed quartz with particle sizes of 0.5-0.75 mm (1.66% X-ray amorphous carbon, 98.34% granular material, catalyst volume 2.4 cm ³ ); cork made of basalt fabric; 5 cm ³ crushed ceramics with a particle size of 0.75-1.0 mm The reactor is flushed from top to bottom with argon for 0.5 h to remove air and thermostated at a temperature of 5.50 ° C, after which n-hexane vapors saturated at 22 ° C are passed in argon at a volume velocity of 40 cm ³ / min (1000 h ^{- 1} for gas, 1 h ^-1 for liquid n-hexane).

The resulting hydrocarbon product contains (mol%): starting n-hexane 46.9, benzene 39.3, hydrocarbons C ₆ 2.1, hydrocarbons C ₅ 0.2, hydrocarbons C ₄ 3.7, propylene 3.0, propane 1.1, ethylene 1.8 and methane 1.8. The degree of conversion of the starting n-hexane was 54.1%, the benzene selectivity 72.6%, the isomerization selectivity 3.8%, the cracking product selectivity 11.6%.

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16,6 ммоль, и 18 г нейтрального гидроксида алюминия (40% рентгеноаморфного углерода, 60% связующего, объем катализатора 37,5 см³); 50 см³ дробленого кварца с размерами частиц 0,5-0,75 мм. Реактор продувают сверху вниз аргоном в течение 0,5 ч для удаления воздуха и термостатируют при температуре 550° С, после чего подают н-октан с объемной скоростью 37,5 мл/ч (1 ч^-1 по жидкому н-октану). Давление в реакторе составило 760 Торр (0,1 мПа). Углеводородная часть продукта содержит (% мол.): исходный н-октан 3,7, ксилолы 56,8, толуол 4,8, бензол 2, углеводороды С₇ 19,3, углеводороды С₆ 5,8, углеводороды C₅ 1,2, углеводороды С₄ 3,9, пропилен 1,0, пропан 0,6, этилен 0,2, этан 0,6 и метан 0,14. Степень конверсии исходного н-октана составила 96,3%, селективность по ароматическим углеводородам 66%.Example 3. In a tubular flow reactor, the catalyst is placed alternately in the form of an extrudate with a diameter of 5 mm, consisting of 12 g of X-ray amorphous carbon with characteristics: T _but = 280 ° C; T _mso = 508 ° C; _Tco = 630 ° C, V _beg = 2.08% wt. carbon / h, and the limit amount

-ionic ion consumed in contact with 1 g of the aforementioned carbon in solution, 16.6 mmol, and 18 g of neutral aluminum hydroxide (40% X-ray amorphous carbon, 60% binder, catalyst volume 37.5 cm ³ ); 50 cm ³ crushed quartz with particle sizes of 0.5-0.75 mm. The reactor is flushed from top to bottom with argon for 0.5 h to remove air and thermostat at a temperature of 550 ° C, after which n-octane is supplied at a space velocity of 37.5 ml / h (1 h ^-1 in liquid n-octane). The pressure in the reactor was 760 Torr (0.1 MPa). The hydrocarbon portion of the product contains (mol%): starting n-octane 3.7, xylenes 56.8, toluene 4.8, benzene 2, hydrocarbons C ₇ 19.3, hydrocarbons C ₆ 5.8, hydrocarbons C ₅ 1, 2, hydrocarbons C ₄ 3.9, propylene 1.0, propane 0.6, ethylene 0.2, ethane 0.6 and methane 0.14. The degree of conversion of the starting n-octane was 96.3%, and the selectivity for aromatic hydrocarbons was 66%.

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16,4 ммоль, и 29,5 г нейтрального гидроксида титана (1,66% рентгеноаморфного углерода, 98,34% связующего, 38 см³) и 50 см³ керамических колец диаметром 4 мм и термостатированный при 550° С подавали экстракционный бензин (пределы выкипания 80-125° С, 55%мол. С₆, 30% С₇ 10% C₈) с объемной скоростью 114 мл/ч (3 ч^-1). Давление в реакторе составило 760 Торр (0,1 мПа). Углеводородные продукты реакции, наряду с непревращенными исходными (в сумме 44,5% мол.) содержат (% мол.): бензол 10,8, толуол 20,4, ксилолы+этилбензол 15,5, продукты крекинга в сумме 5,0. Степени превращения исходных С_6-8-углеводородов составили 54, 55 и 45% соответственно. Исходное сырье с октановым числом 13 превращено в продукт с октановым числом 78 (по исследовательскому методу).Example 4. In the conditions of example 3 into a reactor filled with a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 0.5 g of X-ray amorphous carbon with characteristics: T _but = 290 ° C; T _mso = 520 ° C; _Tco = 630 ° C, V _beg = 2.08% wt. carbon / h, and the limit amount

ion consumed in contact with 1 g of the aforementioned carbon in solution, 16.4 mmol, and 29.5 g of neutral titanium hydroxide (1.66% X-ray amorphous carbon, 98.34% binder, 38 cm ³ ) and 50 cm ^{3 of} ceramic extraction rings with a diameter of 4 mm and thermostatically controlled at 550 ° C were supplied (boiling range 80-125 ° C, 55 mol% C ₆ , 30% C ₇ 10% C ₈ ) at a volumetric rate of 114 ml / h (3 h ^-1 ) The pressure in the reactor was 760 Torr (0.1 MPa). The hydrocarbon reaction products, along with the unconverted initial (in the amount of 44.5 mol%), contain (mol%): benzene 10.8, toluene 20.4, xylenes + ethylbenzene 15.5, cracked products in the amount of 5.0. The degree of conversion of the initial C _6-8 hydrocarbons was 54, 55 and 45%, respectively. The feedstock with an octane number of 13 was converted into a product with an octane number of 78 (according to the research method).

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16,6 ммоль, и 0,03 г кварца с размерами частиц 0,25-0,50 мм (99,0% рентгеноаморфного углерода, 1,0% зернистого материала), через реактор пропускают при 550° С насыщенные при 22° С пары н-пентана в аргоне с объемной скоростью 2,0 см³/мин (50 ч^-1 по газу, 0,1 ч^-1 по жидкому н-пентану). Давление в реакторе составило 760 Торр (0,1 мПа). Углеводородная часть продукта содержит (% мол.) исходный н-пентан 83,4, бензол 5,8, изомеры пентана 2,4, углеводороды С₄ 1,5, пропен 2,8, пропан 1,2, этен 0,6, этан 2,2 и метан 0,5. Степень конверсии исходного н-пентана составила 16,6%, селективность по бензолу 34,9%, селективность изомеризации 14,1%, селективность по продуктам крекинга 52,9%.Example 5. In the conditions of example 2, using as a catalyst a mechanical mixture consisting of 3.0 g of X-ray amorphous carbon, characterized by T _but = 280 ° C; T _mso = 508 ° C; T _ko = 630 ° C; V _beg = 2.08% wt. carbon / h, and the limit amount

ion consumed in contact with 1 g of the aforementioned carbon in solution, 16.6 mmol, and 0.03 g of quartz with particle sizes of 0.25-0.50 mm (99.0% X-ray amorphous carbon, 1.0% granular material ), n-pentane vapors saturated at 22 ° С are passed through a reactor at 550 ° С in argon with a space velocity of 2.0 cm ³ / min (50 h ^-1 for gas, 0.1 h ^-1 for liquid n-pentane) . The pressure in the reactor was 760 Torr (0.1 MPa). The hydrocarbon portion of the product contains (mol%) starting n-pentane 83.4, benzene 5.8, pentane isomers 2.4, hydrocarbons C ₄ 1.5, propene 2.8, propane 1.2, ethene 0.6, ethane 2.2 and methane 0.5. The conversion of the starting n-pentane was 16.6%, the benzene selectivity was 34.9%, the isomerization selectivity was 14.1%, and the cracking product selectivity was 52.9%.

Example 6. Under the conditions of example 2 at 550 ° C, 3.0 g of crushed quartz is used as a catalyst. The hydrocarbon portion of the product contains only the unconverted starting n-hexane, i.e. quartz at 550 ° C does not catalyze dehydrogenation, dehydrocyclization, cracking, and isomerization of n-hexane.

Example 7. Under the conditions of Example 3, using 3.0 g of an extrudate with a diameter of 3 mm consisting of neutral aluminum hydroxide as a catalyst, n-heptane vapors saturated at 22 ° C in argon were passed through a reactor at 550 ° C. The hydrocarbon portion of the product contains (mol%): starting n-heptane 97.5, hydrocarbons C ₆ 0.4, hydrocarbons C ₅ 0.4, hydrocarbons C ₄ 0.3, propane 0.5, ethene 0.7, ethane 0.1 and methane 0.1. The degree of conversion of the starting n-heptane was 2.5%. There are no aromatic products; there are only products with less than 7 carbon atoms, i.e. cracking products.

Example 8. Under the conditions of Example 2, a mechanical mixture of 0.1 g of graphite and 2.9 g of crushed quartz was used as a catalyst at 550 ° C. The hydrocarbon portion of the product contained only the unconverted starting n-hexane, i.e. carbon graphite at 550 ° C does not catalyze dehydrogenation, dehydrocyclization, cracking and isomerization of n-hexane.

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16,3 ммоль, и 24,0 г нейтрального гидроксида алюминия (20,0% рентгеноаморфного углерода, 80,0% связующего, 38 см³) и 50 см³ керамических колец диаметром 4 мм и термостатированный при 550° С, подавали стабилизированное сырье риформинга - гидрогенизат прямогонного бензина с пределами выкипания 96-157° С с объемной скоростью 114 мл/ч (3 ч^-1). Давление в реакторе составило 760 Торр (0,1 мПа). Углеводородные продукты реакции содержат (% мол.): углеводороды С_1-4 12,4, углеводороды C₅ 3,9, углеводороды С₆ 4,5, углеводороды С₇ 4,0, бензол 3,8, толуол 28,2, ксилолы+этилбензол 55,6. Выход жидкого катализата составил 87,6%.Example 9. In the conditions of example 3 into a reactor filled with a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 6.0 g of X-ray amorphous carbon with characteristics: T _but = 290 ° C; T _mso = 520 ° C; T _ko = 630 ° C; V _beg = 2.08% wt. carbon / h, and the limit amount

ion consumed in contact with 1 g of the aforementioned carbon in solution, 16.3 mmol, and 24.0 g of neutral aluminum hydroxide (20.0% X-ray amorphous carbon, 80.0% binder, 38 cm ³ ) and 50 cm ^{3 of} ceramic rings with a diameter of 4 mm and thermostatically controlled at 550 ° C, stabilized reforming feed was supplied - straight-run gasoline hydrogenate with boiling limits of 96-157 ° C with a volumetric rate of 114 ml / h (3 h ^-1 ). The pressure in the reactor was 760 Torr (0.1 MPa). Hydrocarbon reaction products contain (mol%): hydrocarbons C _1-4 12.4, hydrocarbons C ₅ 3.9, hydrocarbons C ₆ 4.5, hydrocarbons C ₇ 4.0, benzene 3.8, toluene 28.2, xylenes + ethylbenzene 55.6. The yield of liquid catalysis was 87.6%.

Example 10. 0.1 g of C ₆₀ fullerene is placed in a 50 cm ³ quartz ampoule, the ampoule is vacuumized to a residual pressure of 0.01 Torr and 100 Torr of n-hexane vapor is blown. The ampoule is sealed and kept under static conditions at 530 ° C for 6 hours. According to the analysis in the absence of benzene and the starting n-hexane, the gas sample contains 100 Torr ethane and 200 Torr ethene, which indicates multiple cracking of hexane in the presence of C ₆₀ fullerene.

-иона, расходуемое при контакте с 1 г упомянутого углерода в растворе, 16,6 ммоль, ампулу вакуумируют до остаточного давления 0,01 Торр и напускают 100 Торр паров н-гексана. Ампулу запаивают и выдерживают в статических условиях при 530° С в течение 2 ч. Газовая проба согласно анализу содержит, кроме водорода, 23 Торр исходного н-гексана, 71 Торр бензола, 3 Торр этена и 3 Торр бутана. Степень конверсии н-гексана 77%, селективность по бензолу 92,2%, селективность по продуктам крекинга 7,8%.Example 11. In a quartz ampoule with a volume of 50 cm ³ put 0.1 g of X-ray amorphous carbon, characterized by T _but = 280 ° C; T _mso = 508 ° C; _Tco = 630 ° C, V _beg = 2.08% wt. carbon / h, and the limit amount

-ionic ion, consumed in contact with 1 g of the aforementioned carbon in solution, 16.6 mmol, the ampoule is evacuated to a residual pressure of 0.01 Torr and 100 Torr of n-hexane vapor is released. The ampoule is sealed and kept under static conditions at 530 ° C for 2 hours. The gas sample according to the analysis contains, in addition to hydrogen, 23 Torr of the starting n-hexane, 71 Torr of benzene, 3 Torr of ethene and 3 Torr of butane. The conversion of n-hexane is 77%, the selectivity for benzene is 92.2%, the selectivity for cracking products is 7.8%.

Example 12. Under the conditions of Example 2, a mechanical mixture of 0.1 g of fullerene C ₆₀ epoxides and 2.9 g of crushed quartz was used as a catalyst, and hexane vapor in argon saturated at 22 ° C was passed at 550 ° C. The pressure in the reactor was 760 Torr (0.1 MPa). The hydrocarbon reaction products contain, along with unconverted starting hexane (43.7 mol.%), Only alkanes C ₁ -C ₅ alkenes and C ₂ -C _5, i.e. the conversion of hexane was 56.3%, and the selectivity for cracking products was 100%.

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16 ммоль, и 20 г нейтрального гидроксида циркония (33,3% рентгеноаморфного углерода, 66,7% связующего, 38 см³) и 50 см³ дробленого кварца с размерами частиц 0,75-1,0 мм и термостатированный при 550° С, подают циклогексан с объемной скоростью 380 мл/ч (10 ч^-1). В реакторе с помощью вентиля тонкой регулировки поддерживают давление 1140 Торр (0,15 мПа). Углеводородные продукты реакции содержат (мол.%): циклогексан 5,5, бензол 91,1 и углеводороды С₆ 3,4. Степень конверсии циклогексана 94,5%, селективность по продукту дегидрирования - бензолу - составила 96,4%.Example 13. In the conditions of example 3 into a reactor filled with a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 10 g of X-ray amorphous carbon, characterized by T _but = 310 ° C; T _mso = 520 ° C; _Tco = 630 ° C, V _beg = 2.08% wt. carbon / h, and the limit amount

ion consumed in contact with 1 g of the aforementioned carbon in solution, 16 mmol, and 20 g of neutral zirconium hydroxide (33.3% X-ray amorphous carbon, 66.7% binder, 38 cm ³ ) and 50 cm ^{3 of} crushed quartz with particle sizes 0.75-1.0 mm and thermostatically controlled at 550 ° C, serves cyclohexane with a bulk velocity of 380 ml / h (10 h ^-1 ). In the reactor, using a fine adjustment valve, a pressure of 1140 Torr (0.15 MPa) is maintained. Hydrocarbon reaction products contain (mol.%): Cyclohexane 5.5, benzene 91.1 and hydrocarbons C ₆ 3.4. The degree of conversion of cyclohexane is 94.5%, the selectivity for the dehydrogenation product — benzene — was 96.4%.

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16,4 ммоль, и 24,0 г нейтрального гидроксида алюминия (20,0% рентгеноаморфного углерода, 80,0% связующего, 38 см³) и 50 см³ керамических колец диаметром 4 мм и термостатированным при 550° С, подают рафинат (остаток после экстракции ароматических углеводородов из продуктов риформинга) с пределами выкипания 80-142° С, с объемной скоростью 114 мл/ч (3 ч^-1). Углеводородные продукты реакции содержат (%мол.): углеводороды С_1-4 22,7, углеводороды С₅ 0,5, углеводороды С₆ 0,4, углеводороды С₇ 0,5, бензол 29,3, толуол 14,0, ксилолы+этилбензол 0,4. Выход жидкого катализата составил 77,4%.Example 14. In the conditions of example 3 into a reactor filled with a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 6.0 g of X-ray amorphous carbon with characteristics: T _but = 290 ° C; T _mso = 520 ° C; T _ko = 630 ° C; V _beg = 2.08% wt. carbon / h, and the limit amount

ion consumed in contact with 1 g of the aforementioned carbon in solution, 16.4 mmol, and 24.0 g of neutral aluminum hydroxide (20.0% X-ray amorphous carbon, 80.0% binder, 38 cm ³ ) and 50 cm ^{3 of} ceramic rings with a diameter of 4 mm and thermostatically controlled at 550 ° C, raffinate is fed (the residue after extraction of aromatic hydrocarbons from reforming products) with boiling limits of 80-142 ° C, with a bulk velocity of 114 ml / h (3 h ^-1 ). Hydrocarbon reaction products contain (mol%): hydrocarbons C _1-4 22.7, hydrocarbons C ₅ 0.5, hydrocarbons C ₆ 0.4, hydrocarbons C ₇ 0.5, benzene 29.3, toluene 14.0, xylenes + ethylbenzene 0.4. The yield of liquid catalysis was 77.4%.

-иона, расходуемого при контакте с 1 г упомянутого углерода в растворе, 16 ммоль, и 20 г нейтрального гидроксида циркония (33,3% рентгеноаморфного углерода, 66,7% связующего, 38 см³) и 50 см³ дробленого кварца с размерами частиц 0,75-1,0 мм при температуре 600°С подавали циклогексан с объемной скоростью 380 мл/ч (10 ч^-1). В реакторе поддерживали давление 760 Торр (0,1 мПа). Углеводородные продукты реакции содержат (мол.%): циклогексан 3,5, бензол 88,1 и углеводороды С₆ 0,4, углеводороды С₄ 4,0 и углеводороды C₂ 4,0. Степень конверсии циклогексана 96,5%, селективность по бензолу (продукт дегидрирования) составляет 91,3%.Example 15. In the conditions of example 3 into a reactor filled with a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 10 g of X-ray amorphous carbon, characterized by T _but = 310 ° C; T _mso = 520 ° C; T _ko = 630 ° C; V _beg = 2.08% wt. carbon / h, and the limit amount

ion consumed in contact with 1 g of the aforementioned carbon in solution, 16 mmol, and 20 g of neutral zirconium hydroxide (33.3% X-ray amorphous carbon, 66.7% binder, 38 cm ³ ) and 50 cm ^{3 of} crushed quartz with particle sizes Cyclohexane was supplied at 0.75-1.0 mm at a temperature of 600 ° C with a bulk velocity of 380 ml / h (10 h ^-1 ). A pressure of 760 Torr (0.1 MPa) was maintained in the reactor. Hydrocarbon reaction products contain (mol%): cyclohexane 3.5, benzene 88.1 and hydrocarbons C ₆ 0.4, hydrocarbons C ₄ 4.0 and hydrocarbons C ₂ 4.0. The degree of conversion of cyclohexane is 96.5%, the selectivity for benzene (dehydrogenation product) is 91.3%.

-иона, расходуемым при контакте с 1 г упомянутого углерода в растворе, 16,1 ммоль, и 20 г нейтрального гидроксида циркония (33,3% рентгеноаморфного углерода, 66,7% связующего, 38 см³) и 50 см³ дробленого кварца с размерами частиц 0,75-1,0 мм при температуре 350° С подавали циклогексан с объемной скоростью 38 мл/ч (1,0 ч^-1 по жидкому циклогексану). С помощью маностата и водоструйного насоса в реакторе поддерживают давление 76 Торр (0,01 мПа). Углеводородные продукты реакции содержат (мол.%): циклогексан 20,2, бензол 66,5, углеводороды С₆ 0,2, углеводороды С₄ 6,5 и углеводороды С₂ 6,6. Степень конверсии циклогексана 79,8%, селективность по бензолу составила 83,4%.Example 16. In the conditions of example 3 into a reactor filled with a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 10 g of X-ray amorphous carbon, characterized by T _but = 310 ° C; T _mso = 520 ° C; T _ko = 630 ° C; V _beg = 2.08% wt. carbon / h and limit amount

ion consumed in contact with 1 g of the aforementioned carbon in solution, 16.1 mmol, and 20 g of neutral zirconium hydroxide (33.3% X-ray amorphous carbon, 66.7% binder, 38 cm ³ ) and 50 cm ^{3 of} crushed quartz with with a particle size of 0.75-1.0 mm at a temperature of 350 ° C., cyclohexane was supplied at a volumetric rate of 38 ml / h (1.0 h ^-1 in liquid cyclohexane). Using a manostat and a water-jet pump, a pressure of 76 Torr (0.01 MPa) is maintained in the reactor. The hydrocarbon reaction products contain (mol%): cyclohexane 20.2, benzene 66.5, hydrocarbons C ₆ 0.2, hydrocarbons C ₄ 6.5 and hydrocarbons C ₂ 6.6. The degree of conversion of cyclohexane is 79.8%, the selectivity for benzene was 83.4%.

Claims (24)

1. A method of dehydrogenation and dehydrocyclization of hydrocarbons, comprising contacting a feed stream with a catalyst based on X-ray amorphous carbon obtained by evaporation of a carbon-containing material and having the following characteristics: temperature of onset of oxidation in air T _but ≤ 320 ° C; temperature of the maximum oxidation rate T _mso ≤ 590 ° C; temperature of the end of oxidation in air T _ko ≤ 630 ° C; initial hydrogenolysis rate at 700 ° C in the absence of a hydrogen activating catalyst, V _beg ≥ 2.08 wt.% carbon / h; limit amount

an ion consumed in contact with 1 g of the aforementioned carbon in a solution of ≥ 16 mmol; at a temperature of 350 to 600 ° C and a pressure of 0.01 to 0.15 MPa. 2. The method according to claim 1, characterized in that the contacting of the feed stream with the aforementioned catalyst is carried out when the feed is supplied with the hourly average space velocity in terms of liquid from 0.1 to 10 h ^-1 . 3. The method according to any one of claims 1 and 2, characterized in that the contacting of the feed stream is carried out with said catalyst obtained by evaporation of said carbon-containing material by an electric arc. 4. The method according to any one of claims 1 and 2, characterized in that the contacting of the feed stream is carried out with said catalyst obtained by evaporation of said carbon-containing material under the action of laser radiation. 5. The method according to any one of claims 1 to 4, characterized in that said X-ray amorphous carbon has temperatures T _but = 280 ° C and T _mso = 508 ° C. 6. The method according to any one of claims 1 to 5, characterized in that said X-ray amorphous carbon has a specific surface area S = 210-280 m ² / g and bulk density ρ ≤ 0.05 g / cm ³ . 7. The method according to any one of claims 1 to 5, characterized in that the catalyst further comprises an inert granular material. 8. The method according to claim 7, characterized in that the said granular material consists of particles with a size of 0.25-1.00 mm 9. The method according to any one of claims 7 to 8, characterized in that quartz is introduced as said granular material. 10. The method according to any one of claims 7 to 8, characterized in that ceramics are introduced as said granular material. 11. The method according to any one of claims 7 to 10, characterized in that said X-ray amorphous carbon and said granular material are taken in the following ratio, wt.%: X-ray amorphous carbon 1.65-99.00 Inert granular material Else 12. The method according to any one of claims 1 to 5, characterized in that the catalyst is made in the form of granules formed from a mixture of the aforementioned X-ray amorphous carbon with a binder, heat-treated in a vacuum in the temperature range 200-550 ° C. 13. The method according to p. 12, characterized in that as the binder is introduced a neutral gel of a metal hydroxide selected from the group of aluminum, magnesium, zirconium, titanium, hafnium. 14. The method according to p. 12, characterized in that as the binder is introduced a mixture of neutral gels of at least two metal hydroxides selected from the group: aluminum, magnesium, zirconium, titanium, hafnium. 15. The method according to p. 12, characterized in that as the said binder introduced a neutral hydrogel of a metal selected from the group of aluminum, magnesium, zirconium, titanium, hafnium. 16. The method according to p. 12, characterized in that, as said binder, a mixture of at least two neutral metal hydrogels is selected from the group: aluminum, magnesium, zirconium, titanium, hafnium. 17. The method according to item 12, characterized in that as the hydrogel mentioned introduced natural hydrogel. 18. The method according to any one of paragraphs.12-17, characterized in that said X-ray amorphous carbon and said binder are taken in the following ratio, wt.%: X-ray amorphous carbon 1.65-40.00 Binder Else 19. The method according to any one of claims 1 to 18, characterized in that the feed contains alkanes as the main components with the number of carbon atoms not less than 6. 20. The method according to any one of claims 1 to 18, characterized in that oil is used as a raw material. 21. The method according to any one of claims 1 to 18, characterized in that the raw materials of the reforming process are used as raw materials. 22. The method according to item 21, characterized in that as the raw materials use unstabilized raw materials of the reforming process. 23. The method according to any one of claims 1 to 18, characterized in that the products of the reforming process are used as raw materials. 24. The method according to item 23, characterized in that as a raw material use reforming products after separation of aromatic compounds.

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