The method of dehydrogenation and dehydrocyclization hydrocarbons

 

Usage: petrochemistry. Essence: carry out the contacting of the flow of the feedstock with the catalyst on the basis of x-ray amorphous carbon obtained by evaporation of carbon-containing material and having the following characteristics: the temperature at which oxidation in air Tbut320C; the temperature of the maximum rate of oxidation of TMCO590C; the temperature of the end oxidation in air Tco630C; initial rate of hydrogenolysis at 700In the absence of a catalyst, activating hydrogen, Vbeg2,98%wt. carbon/h; maximum number of-Jonah spent in contact with 1 g of the above-mentioned carbon in solution,16 mmol, at a temperature of from 350 to 600C and a pressure of from 0.01 to 0.15 MPa. Effect: method provides processing hydroaromatics compounds, alkanes and cyclo-C6-alkanes, carrying out the dehydrogenation cyclo-C6-alkanes and dehydrocyclization alkanes. 1 C. and 23 C. hydrocarbons, in particular dehydration and dehydrocyclization hydrocarbons, and processes, where these transformations are carried out, particularly to the dehydrogenation of alkanes C2-C5obtaining alkenes, cyclo-C5-alkanes to cycloalkenes and cycloalkanes, cyclo-C6-alkanes to benzene and its homologues, as well as to dehydrocyclization6+-alkanes with the formation of benzene and its homologues.

The processes of dehydrogenation and dehydrocyclization include activation and subsequent rupture of C-H bond. Because the C-H bond in alkanes almost equal to the energy, a priori it is difficult to expect high selectivity stage dehydrogenation. Resulting from the dehydrogenation of alkenes also undergo further dehydrogenation transformations, culminating in the formation on the catalyst surface depleted in hydrogen products seal precursor carbonaceous deposits, usually referred to as coke. Cox deactivates the catalyst, its activity and selectivity change over time. Preventing the formation of coke is one of the main tasks of the processes of hydrocarbon processing.

Dehydrocyclization and dehydration, as well as traditional process, the reef is om with clear predominance of diluent (the molar ratio of hydrogen/hydrocarbon to 5/1). The role of such a diluent, probably, is to remove the fresh coke in hydrogenation or steam reforming. Dilution of the raw material (its low concentration in the reaction zone) reduces the degree of conversion per pass and requires an increase in contact time, for example, by increasing the pressure in the reaction apparatus. The increased pressure of the hydrogen reduces the number otlichayushchegosya coke, but causes adverse reactions of hydrocracking and hydrogenolysis. Unpleasant side increasing total pressure and hydrogen pressure - reducing already low share of the reactions of dehydrogenation and dehydrocyclization occurring with increasing number of particles and release of hydrogen. In real processes of reforming all reactions, including unwanted, becomes no more than 15-20% of alkanes raw materials. In addition, to use the raw material reforming unit is subjected to additional training - remove catalytic poisons (sulfur compounds), not processed pentane (dependance) and deactivating the catalyst alkenes.

There is a method of conversion of normal hexane in benzene catalyst CR2About3-Al2O3-Na2O at a temperature of 550-580With, the pressure is on, the liquid is in the range of 0.2 to 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, the low degree of conversion of raw materials, large losses on coke and gas, reaching 15.3%, and the resulting deactivation of the catalyst and reduce its activity, overcome by increasing the process temperature.

A method of refining of crude oil (see U.S. patent No. 5013423, IPC With 10 G 35/06, 1991), in which the raw material is brought into contact with the non-acidic dehydrogenation catalyst in the presence of hydrogen under conditions of temperature and pressure and with an hourly feed rate of raw materials, providing dehydrocyclization. The catalyst contains a platinum group metal containing indium zeolite carrier, which has a crystalline structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, ZSM-50.

At process temperatures of more than 427In the presence of hydrogen the resulting product has a higher octane number and the content of aromatic hydrocarbons than the original product of the reformer. Disadvantages of the process are of a low degree of conversion of raw materials, high content of benzene (about 25-30. %) of the target product, the deposition of coke on the catalyst and the liquefied petroleum gas by direct interaction with the acidic crystalline aluminosilicate with a ratio of silica/alumina of more than 12, having a peak temperature of desorption of hydrazine in the process of increasing the temperature to more than 650(See U.S. Pat. Japan on the application N 3-54717, IPC With 10 G 11/05,1993).

The disadvantages of this method is the need for separation and recycling of by-products obtained in an amount up to about 12. % and the progressive coking of the catalyst with time-varying composition of the reaction products, the lack of dehydrogenation processes, the impossibility of dehydrocyclization and cracking of the feedstock.

A known method of converting heavy hydrocarbons (see RF application No. 97107731, IPC C 10 G 47/32, 01 J 23/78, published 20.05.1999), including the filing of a heavy hydrocarbon feedstock in the reaction zone and its conversion to a catalytically active phase. The catalytically active phase includes the first metal and a second metal where the first metal is a base metal of group VIII and the second metal is an alkaline metal. The way to carry out the contacting of the feedstock with steam at a pressure less than or approximately equal to 2.1 MPa, to produce a hydrocarbon product having a reduced boiling point. Usually the first metal chosen from the group consisting of iron, koballa least one of the metals is fixed on the carrier. The material of mesoporous media is selected from the group consisting of silicon dioxide, natural and synthetic silicates, alumina, coke from petroleum or coal and materials based on carbon derived from plant or animal sources.

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

A method of refining hydrocarbon-based aliphatic hydrocarbons (see RF patent №2152977, IPC With 10 G 35/095 published 20.07.2000), including the supply of raw materials in the reaction zone, the dilution of the hydrocarbon gas and carrying out the process at elevated temperatures, mainly 320-420Since, in the presence of an aluminosilicate catalyst, followed by separation of catalyzate target products. As aluminosilicate catalyst used allocability zeolite-containing catalyst having the composition (wt.%): zeolite ZSM-11 with silicate module 1760 - 15 - 45 cobalt oxide 2-6, molybdenum oxide 8-14, binding - rest. As prevolution catalyzate, containing the target aromatic hydrocarbons, hydrocarbons3-C5, hydrocarbons, C1-C2not more than 1 wt.%, followed by separation of the hydrocarbon fractions used as increasing the octane number of supplements or high-octane gasoline, and liquefied hydrocarbons With3-C4.

The disadvantages are the necessity of introducing the diluent - natural gas with its pre (desulfurization or Hydrotreating), which complicates the process, high (1.5 to 2.0 MPa) pressure process occurring with increasing number of particles, which causes a decrease in the degree of conversion of the raw materials, the need for cleaning materials from pentane, the impossibility of processing alkenes or raw materials containing them, the unsuitability of the process for processing cycloalkanes, the sensitivity of the catalyst to a conventional catalytic poisons - sulfur compounds.

There is a method of reforming naphtha (naphtha, fraction distillation of crude oil with the number of carbon atoms of more than 6, not containing alkenes), which consists in using as a catalyst of activated carbon without processing or saturated with carbonates or hydroxides of alkali metals (Na, K, Li) in the temperature range 538-593

There is a method of dehydrogenation and hydrogenolysis of the hydrocarbon adopted for the prototype (see U.S. patent No. 5336828, IPC C 07 C 5/327, published 09.08.1994), which includes the contact of the feedstock with a catalyst comprising a at least one soluble fullerene Cnwhere n=50-120, while maintaining the reaction mixture at a temperature in the range from 25 to 500C and a pressure in the range 1-1500 Torr. The above-mentioned fullerene is dissolved in the raw material, if the substrate is a liquid, capable of dissolving the fullerene, or additional solvent which is a solvent for hydrocarbons.

The use of the known method is the prototype of the catalyst in the form of a solution prevents the formation of coke.

The challenge which seeks the invention is to provide such a method of dehydrogenation and dehydrocyclization hydrocarbons, which would be processed not only hydroaromatics connections, but alkanes and cyclo-C6-alkanes, carrying out the dehydrogenation cyclo-C6-alkanes and dehydrocyclization alkanes.

The problem is solved in that pic is on the basis of x-ray amorphous carbon, obtained by evaporation allentsteig material and has the following features:

the onset temperature of oxidation in air Tbut320;

the temperature of the maximum rate of oxidation of TMCO=590;

the temperature of the end oxidation in air Tco650;

initial rate of hydrogenolysis at 700In the absence of a catalyst, activating hydrogen, Vbeg2,08% wt. carbon/h;

limit the number of-Jonah spent in contact with 1 g of the above-mentioned carbon in solution, not less than 16 mmol at a temperature of from 350 to 600C and a pressure of from 0.01 to 0.15 MPa.

The contacting of the flow of the feedstock with the catalyst can be carried out by feeding a raw material with an average hourly volumetric rate in terms of fluid from 0.1 to 10 h-1and the catalyst can be obtained, for example, by evaporation of carbon-containing material under the action of an electric arc or under the action of laser radiation.

The contacting of the flow of raw materials predpochtite the img src="https://img.russianpatents.com/chr/176.gif">S and temperature TMCO=508C.

Used in the claimed method x-ray amorphous carbon may have a specific surface area S=210-280 m2/g and bulk density0.05 g/cm3.

The catalyst can optionally contain inert granular material, mainly consisting of particles with a size of 0.25 to 1.00 mm In an inert granular material may be a quartz or ceramics.

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

x-ray amorphous carbon 1,65-to 99.00;

inert granular material things.

In the present method can be applied to the catalyst in the form of pellets formed from a mixture of x-ray amorphous carbon with a binder.

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

As a binder in the catalyst may be introduced neutral hydrogel of a metal selected from the above group, ylvania granular catalyst is subjected to heat treatment in vacuum at temperatures from 200 to 550C.

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

x-ray amorphous carbon 1,65-40,00;

the rest of the binder.

In the present method can be used raw material containing as the main components of alkanes with the number of carbon atoms is not less 6.

As raw material in the present method can be used oil, raw material reforming process, including unstabilized, the products of the reforming process and the products of reforming after separation of aromatic compounds.

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

in Fig.1 shows the dependence of the oxidation rate used in the claimed method of the catalyst having a specific surface area of 278 m2/g, temperature Tbut=280S, TMCO=508C and Tco=630C, obtained by evaporation of the energy flux of 200 W/mm2(1); a catalyst having a specific surface area of 210 m2/g, temperature Tbut=320S, TMCO=2, catalyst, obtained when the energy flow < 50 W/mm2(3) glass carbon (4) and graphite (5) from temperature (I - region of the oxidation of x-ray amorphous carbon; II - region of the oxidation graphitized particles; III - region of the oxidation of graphite); temperature TbutTMCOand Tcoin Fig.1 marked for catalyst (1);

in Fig.2 shows x-ray diffraction spectra of 1 - catalyst (1), catalyst (2) and the catalyst (3) (labels (1), (2) and (3) are the same as those in Fig.1);

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

The catalyst used in the present method of dehydrogenation and dehydrocyclization hydrocarbons, regardless of the production method, the reactivity and catalytic activity, contains according to elemental analysis, 95-97 wt.%. carbon, about 1.5% of hydrogen and 3-4% oxygen. Hydrogen and oxygen are present in hard water, because the water was discovered in absolute methanol after washing x-ray amorphous carbon, a vacuum at 100With over 10 hours In one cycle “deep does not exceed the measurement error.

The specific surface of the catalyst is, depending on the conditions of receipt, 210-280 m2/g (fine graphite, for comparison, 6 m2/g). Upon receipt of the catalyst when the energy flows less than 50 W/mm2he cannot be turned due to the low flow of energy graphite, which is determined by the slow decrease of the mass above 670And graphitized particles (not fully converted graphite) detected by the mass loss of the temperature range 645-670C (see Fig.1). Graphite is also defined by sharp lines 002 graphite in the spectra of x-ray diffraction (see Fig.2). The presence of graphitized particles and graphite dramatically reduces the reactivity of the catalyst. The catalyst obtained by evaporation of carbon-containing material under the action of the flow of energy 50-300 watts/mm2and having high catalytic activity, does not contain the actual graphite and graphitized particles, as evidenced by the absence of line 002 graphite (see Fig.2) and the temperature of the end of the oxidation 630C (see Fig.1).

Range of EPR catalyst in a vacuum is a singlet line width 0,19 MT and g-factor 2,0022 (see under integral form of the line) is defined, the catalyst contains, depending on the conditions of receipt, (2-5)1020spin on 1 mol of carbon, i.e., 1 paramagnetic center (HRC) at 1000-3000 carbon atoms. The value of g-factor (2,0022) paramagnetic centers induced by structural defects of the type of dangling C-C bonds.

In addition to dangling bonds, the catalyst contains unpaired multiples of C=C-bond, detectable by the reaction Wagner (interaction with ionin a neutral environment) and interaction with the Br2. Contact x-ray amorphous carbon with ionin neutral medium, a decrease in ion concentrationin solution, the ow ionin neutral medium, 1 g of x-ray amorphous carbon is greater than 16 mmol. Other carbon materials, in particular graphite, glass carbon, activated carbons, do not interact with the ion(ionnot consumed by contact with other carbon materials). The concentration of detectable interaction with ionmultiple C=C-bonds is significantly higher than dangling, and is rashly carbon in the absence of activating hydrogen catalysts at temperatures700With that undergoes hydrogenolysis, for other carbon materials, including fullerenes, not observed when 1000C.

High reactivity is used in the claimed method of the catalyst (abnormally low onset temperature oxidation and high average rate of oxidation in air, oxidation and bromination, in solution, the hydrogenolysis in the absence of activating hydrogen catalysts) indicate the presence of unpaired structure of multiple bonds that are missing in the structure of other carbon materials.

These features of the structure of the catalyst determine its catalytic activity and are manifested in reactivity. Probably the dehydrogenation conversion of hydrocarbons in the presence of catalyst flow-type reaction with the transfer of hydrogen from the alkane to the catalyst with the formation of relatively unstable hydride forms of active x-ray amorphous carbon. It is quite reasonable, since we first discovered the hydrogenolysis of the inventive catalyst with molecular hydrogen in the absence of activating hydrogen catalyst, however, is not found chemisorption of hydrogen the catalyst in inator is a necessary and sufficient condition of its activity in the reactions of dehydrogenation and dehydrocyclization. The absence of any characteristics not possible to obtain the desired technical effect. For example, paralizovannaya oxide graphite, with Tbut300With not subjected to the non-catalytic hydrogenolysis of molecular hydrogen at temperatures as low as 700With not active in the reactions of dehydrogenation and dehydrocyclization alkanes.

Used in the inventive method, the catalyst is also characterized by well-developed surface and a low bulk density (up to 0.05 g/cm3and in its pure form is not suitable for operation under conditions of flow reactor. To avoid increasing the gas-dynamic resistance or entrainment of the catalyst with the gas flow in this case can be used mixed catalyst with the addition of x-ray amorphous carbon is inert granular material, such as quartz or ceramic.

It is preferable to use the catalyst in granular form. X-ray amorphous carbon does not give a solid granules during pressing. Forming x-ray amorphous carbon with a binder allows you to get a solid granules. As a binder in forming catalyst on the basis of x-ray amorphous carbon can bian, hafnium, and various types of clay. Not suitable as a binder aluminosilicates, zeolites and other solid acids, causing cracking of the raw materials and the deposition of coke on the catalyst.

The use of x-ray amorphous carbon with the above characteristics as a catalyst in the method of dehydrogenation and dehydrocyclization hydrocarbons lets you recycle used only 15-20% alkanes, to avoid the formation of coke on the catalyst surface and not to dilute the feedstock with hydrogen. In addition, the processing in this way can be subjected to alkenes or raw materials containing them, in particular non-stabilized (i.e. not subjected to hydrogenation to remove alkenes by turning them into alkanes), raw materials (for example, unstabilized naphtha) or the products of reforming (catalysate to the separation of aromatic compounds or the raffinate after their separation) or raw materials containing pentane. In addition, the processing in this way by dehydrogenation successfully subjected cyclohexane and its homologues. This method is used, the catalyst does not contain transition and noble metals and little susceptible to conventional catalytic poisons - sulfur compounds.

Premiere helium raw materials, containing the chemical element carbon. The evaporation of the lead supplying the carbon-containing material flow energy 50-300 watts/mm2. The source of this energy flow can be electric arc discharge, laser light or microwave radiation. Most preferred as the carbonaceous material is graphite. The products of evaporation in the form of fullerenelike carbon black precipitated and extracted from it the fullerene organic solvent by known methods. Then separate nerastvorim precipitate, washed with ether and dried.

If necessary, the resulting x-ray amorphous carbon is mechanically mixed with inert granular material (e.g., quartz or ceramics) with a particle size of 0.25-1.00 mm, preferably in the above ratio. Preferably the use of the catalyst in the form of pellets formed from a mixture of x-ray amorphous carbon with a binder in the above ratio and subjected to a heat treatment in vacuum at a temperature of from 200 to 550C.

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

Graphite in the form of a solid cylindrical rod made the Roux is filled with helium mainly when the pressure 100-760 mm RT. Art. To the rod down energy to DC energy flow in an arc from 50 to 300 W/mm2when the speed of the translational movement evaporated graphite electrode from 0.2 to 6.0 mm/min.

The above process parameters necessary to create the conditions under which clusters are x-ray amorphous carbon cannot be decontaminated, interacting with each other. Slower supply graphite electrode and greater than 300 W/mm2, stream energy input help to complete atomization of carbon and thermodynamic nonequilibrium formed clusters are x-ray amorphous carbon. Formed in an arc clusters are x-ray amorphous carbon, having uncompensated valence disclosed double bond and the other of the reactive fragment patterns, cooled, and "hardened" with thermodynamically non-equilibrium state on the road and on the cooled walls of the chamber. When the short path to the chamber walls (when the ratio of the diameters of the camera and stud < 10:1) and the inert gas pressure < 100 mm RT. senior (i.e., high concentrations of reactive clusters of activated carbon), frequent collision-energy-rich carbon particles lead to vzaimodeystvij links, which leads to the formation of product with low reactivity. In addition, high (10:1 or more) the ratio of the diameters of the chamber and a rod and a large amount of the reaction device is connected with the fact that evaporated compact graphite with a density of 1.5-2.0 g/cm3turns into a fine x-ray amorphous carbon is low (less 0.05 g/cm3) bulk density.

The inventive method of dehydrogenation and dehydrocyclization is as follows.

The catalyst is a solid, however, the size of its particles (40 nm=400) is close to the molecular. Raw materials, depending on conditions and the state of aggregation is in the form of individual molecules (in the case of a steam or gas) or molecular aggregates (if liquid). Thus, the interaction of raw materials and catalyst flows at the phase boundary solid - gas or solid - liquid. Based on the above reasons (nano catalyst particles) interaction of raw materials and the catalyst is carried out on pseudomolecular level. As a result of such interaction, undoubtedly, flowing Paladino, for example, by chemisorption with the dissociation of the C-H alkane or cycloalkane, alkane and the ECCA aggregate state is most often a liquid or rare gas. Fluid flow is usually a metering pump. In the case of liquids with high vapour pressure 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 raw materials. Hydrogen and helium cannot be used for these purposes.

Raw materials at a temperature in the range of 350-600And pressure 76-1140 Torr lead in contact with the x-ray amorphous carbon, which has the above characteristics. X-ray amorphous carbon may be introduced by itself; in the form of a mechanical mixture with inert granular material; in the form of granules, pre-formed from a mixture with a binder. Type of catalyst is determined by the goal and process type. X-ray amorphous carbon itself can only be used in a static system. In this case, the process temperature is limited by thermal stability of the raw material. At these temperatures thermodynamically possible, mainly reactions of dehydrogenation hydroaromatics compounds in the aromatic. The dehydrogenation of alkanes (or their dehydrocyclization) and cycloalkanes is favored by higher temperatures processhave catalyst unproductive reduces the temperature of the catalytic layer. So typically the catalytic reaction is preceded by evaporation and the substrate is heated to the reaction temperature. In our experiments, heating and evaporation of the raw materials was carried out in the evaporator-heater, combined with a catalytic reactor, i.e., the evaporator-heater was a previous on-the-go raw material layer ceramic nozzles in front of the catalyst layer. Warmed up on the packing layer steam enters the catalyst bed, held it, turning into the reaction products. The catalyst thus to ensure the passage of gases 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 the liquid products from the gaseous products by using cooler-separator.

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

Example 1. In a tubular flow reactor is placed alternately 4.0 cm3quartz; the plug of basalt fabric; the catalyst comprising a mechanical mixture of 0.05 g of x-ray amorphous carbon with the following characteristics: Tbut=320C; Tmelingo number-Jonah spent in contact with 1 g of the above-mentioned carbon in solution, 16.0 mmol, and 2.95 g of crushed quartz with particle size 0.25-0.5 mm (1,65% x-ray amorphous carbon, 98,65% inert granular material, the volume of 2.4 cm3). The reactor was rinsed with argon from the bottom up for 0.5 h, thermostatic in a stream of argon at 550With and flow from the bottom up with a bulk velocity of 40 cm3/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, C1-3-hydrocarbons 0,3,5-7-hydrocarbons of 0.9. The exit gas contains (mol%): n-butane 20,0, ISO-butane 8,5, butene-1 21,1, butene-2 and 9.2, ISO-butene 14,2, butadiene-1,3 5,0, C1-3-hydrocarbons 11,6,5-7-hydrocarbons 1,5 hydrogen to 9.6. The conversion of butane was 15-17%, butene-1 46,0%.

Example 2. In a tubular flow reactor are placed alternately, the catalyst comprising a mechanical mixture of 0.6 g of x-ray amorphous carbon with the following characteristics: Tbut=320C; TMCO=590C; Tco=630With Vbeg=2,08% wt. carbon/h, and limit the number of-Jonah spent at stake is thereamong carbon 98.34 per cent of the granular material, the amount of catalyst 2.4 cm3); the plug of basalt fabric; 5 cm3crushed ceramics with a particle size of 0.75 to 1.0 mm, the Reactor is blown from top to bottom with argon for 0.5 h to remove air and thermostatic at a temperature of 5.50With, after which miss saturated with 22With a pair of n-hexane in argon with a bulk velocity of 40 cm3/min (1000 h-1gas, 1 h-1in liquid n-hexane).

The resulting hydrocarbon product contains (mol%): the original n-hexane 46,9, benzene, 39,3, hydrocarbons62,1, hydrocarbons50,2, hydrocarbons43,7, propylene 3,0, propane, 1,1, ethylene 1.8 and methane, 1,8. The conversion of the original n-hexane amounted to 54.1%, the selectivity for benzene to 72.6%, the selectivity of isomerization of 3.8%, the selectivity of the cracking products of 11.6%.

Example 3. In a tubular flow reactor is placed alternately with the catalyst in the form of an extrudate with a diameter of 5 mm, consisting of 12 g of x-ray amorphous carbon with the following characteristics: Tbut=280C; TMCO=508C; Tco=630With Vbeg=2,08% wt. carbon/h, and limit the number of3); 50 cm3crushed quartz with particle sizes of 0.5-0.75 mm, the Reactor is blown from top to bottom with argon for 0.5 h to remove air and thermostatic at a temperature of 550With, then served n-octane with a bulk velocity of 37.5 ml/h (1 h-1for liquid n-octane). The pressure in the reactor amounted to 760 Torr (0.1 MPa). The hydrocarbon portion of the product contains (mol%): the original n-octane 3,7, xylenes 56,8, toluene and 4.8, benzene, 2, hydrocarbons719,3, hydrocarbons65,8, hydrocarbons, C51,2, hydrocarbons43,9, propylene 1,0, propane 0.6 ethylene 0,2, ethane 0.6 and methane 0,14. The conversion of the original n-octane was 96,3%, the selectivity for aromatic hydrocarbons 66%.

Example 4. In the conditions of example 3 in 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 the following characteristics: Tbut=290C; TMCO=520C; Tco=630With Vbeg=2,08% wt. carbon/h, and limit the number of-Jonah spent in contact with 1 g of the above-mentioned carbon in solution, 16.4 mmol, and 29.5 g of neutral GI diameter of 4 mm and temperature-controlled at 550With filed extraction gasoline (boiling within 80-125With 55 mol%. With6, 30% With710% C8with a bulk velocity of 114 ml/h (3 h-1). The pressure in the reactor amounted to 760 Torr (0.1 MPa). Hydrocarbon reaction products, along with neprevzaidennymi source (total of 44.5% mol.) contain (mol%): benzene 10,8, toluene 20,4, xylene+ethylbenzene 15,5, the cracking products in the amount of 5.0. The degree of conversion of the initial6-8-hydrocarbons was 54, 55 and 45%, respectively. Feedstock with an octane number 13 turned into a product with an octane rating of 78 (research method).

Example 5. In the conditions of example 2, using as catalyst a mechanical mixture consisting of 3.0 g of x-ray amorphous carbon, characterized by Tbut=280C; TMCO=508C; Tco=630S; Vbeg=2,08% wt. carbon/h, and limit the number of-Jonah spent in contact with 1 g of the above-mentioned carbon in a solution of 16.6 mmol, 0.03 g of silica with a particle size of 0.25-0.50 mm (99,0% x-ray amorphous carbon, 1.0% of a granular material), passed through the reactor at 550With saturated at 22-1for liquid n-pentane). The pressure in the reactor amounted to 760 Torr (0.1 MPa). The hydrocarbon portion of the product contains (in% mol.) the source of n-pentane by 83.4, benzene, 5,8, isomers of pentane 2,4, hydrocarbons41,5, propene 2,8, propane 1,2, Aten 0.6 ethane and 2,2 methane of 0.5. The conversion of the source of n-pentane was 16.6%, the selectivity for benzene 34,9%, the selectivity of the isomerization of 14.1%, the selectivity of the cracking products of 52.9%.

Example 6. In the conditions of example 2 at 550To use as a catalyst 3.0 g of crushed quartz. The hydrocarbon portion of the product contains only neprevyshenie the original n-hexane, i.e. quartz at 550With not catalyzes the dehydrogenation, dehydrocyclization, cracking and isomerization of n-hexane.

Example 7. In the conditions of example 3, using as catalyst 3.0 g of extrudate with a diameter of 3 mm, consisting of neutral aluminum hydroxide is passed through the reactor at 550°C saturated with 22With a pair of n-heptane in argon. The hydrocarbon portion of the product contains (mol%): the original n-heptane 97,5, hydrocarbons60,4, hydrocarbons50,4, hydrocarbons40,3, propane 0,5, Aten 0,7, ethane 0.1 and methane 0,1. The conversion of the original n-heptane SOS is roducti cracking.

Example 8. In the conditions of example 2 were used at 550With as catalyst a mechanical mixture of 0.1 g of graphite and 2.9 g of crushed quartz. The hydrocarbon portion of the product contained only neprevyshenie the original n-hexane, i.e., graphite is composed of carbon, at 550With not catalyzes the dehydrogenation, dehydrocyclization, cracking and isomerization of n-hexane.

Example 9. In the conditions of example 3 in a reactor filled with a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 6.0 g x-ray amorphous carbon with the following characteristics: Tbut=290C; TMCO=520C; Tco=630S; Vbeg=2,08%wt. carbon/h, and limit the number of-Jonah spent in contact with 1 g of the above-mentioned carbon in solution, 16.3 mmol, and 24.0 g of neutral aluminum hydroxide (20.0% of the x-ray amorphous carbon, 80.0% of binder, 38 cm3) and 50 cm3ceramic rings with a diameter of 4 mm and temperature-controlled at 550With, gave stable raw material reforming, hydrogenation product of gasoline with a boiling within 96-157With volumetric speed (mol%): hydrocarbons With1-412,4, hydrocarbons, C53,9, hydrocarbons64,5, hydrocarbons74,0, benzene, 3,8, toluene 28,2, xylene+ethylbenzene 55,6. The yield of liquid catalyzate amounted to 87.6%.

Example 10. In a quartz ampoule volume of 50 cm3place 0.1 g of fullerene C60the ampoule vacuum to a residual pressure of 0.01 Torr and putting 100 Torr vapor of n-hexane. The vial sealed and incubated under static conditions at 530With over 6 hours of a Gas sample according to the analysis in the absence of benzene and the source of n-hexane contains 100 Torr ethane and 200 Torr of Athena, which indicates that multiple cracking of hexane in the presence of fullerene C60.

Example 11. In a quartz ampoule volume of 50 cm3place 0.1 g of x-ray amorphous carbon, characterized by Tbut=280C; TMCO=508C; Tco=630With Vbeg=2,08%wt. carbon/h, and limit the number of-Jonah spent in contact with 1 g of the above-mentioned carbon in a solution of 16.6 mmol, ampoule vacuum to a residual pressure of 0.01 Torr and putting 100 Torr vapor of n-hexane. The vial sealed and incubated under static conditions at 530

Example 12. In the conditions of example 2 using as the catalyst a mechanical mixture of 0.1 g of fullerene epoxides With60and 2.9 g of crushed quartz and miss at 550With saturated at 22With a couple of hexane in argon. The pressure in the reactor amounted to 760 Torr (0.1 MPa). Hydrocarbon reaction products contain, along with neprevzaidennymi source hexane (43,7 mol.%), only alkanes C1-C5and alkenes With2-C5, i.e., the degree of conversion of hexane was 56,3%, and the selectivity of the cracking products 100%.

Example 13. In the conditions of example 3 in 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 Tbut=310C; TMCO=520C; Tco=630With Vbeg=2,08% wt. carbon/h, and limit the number of-Jonah spent in contact with 1 g of the above-mentioned carbon in solution, 16 mmol) and 20 g of neutral zirconium hydroxide (33.3% of x-ray amorphous carbon, 66,7 the 550With serves cyclohexane with a bulk velocity of 380 ml/h (10 h-1). In the reactor using the on / off valve support pressure 1140 Torr (0.15 MPa). Hydrocarbon reaction products contain (mol.%): cyclohexane 5,5, benzene to 91.1 and hydrocarbons With63,4. The degree of conversion of cyclohexane to 94.5%, the selectivity for the product of the dehydrogenation to benzene was 96,4%.

Example 14. In the conditions of example 3 in a reactor filled with a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 6.0 g x-ray amorphous carbon with the following characteristics: Tbut=290C; TMCO=520C; Tco=630S; Vbeg=2,08% wt. carbon/h, and limit the number of-Jonah spent in contact with 1 g of the above-mentioned carbon in solution, 16.4 mmol, and 24.0 g of neutral aluminum hydroxide (20.0% of the x-ray amorphous carbon, 80.0% of binder, 38 cm3) and 50 cm3ceramic rings with a diameter of 4 mm and temperature-controlled at 550With serving the raffinate (the residue after extraction of aromatic hydrocarbons from the products of the reforming) with limits boiling 80-142With a bulk velocity of 114 ml/h (3 h-16
0,4, hydrocarbons70,5, benzene, 29,3, toluene 14,0, xylene+ethylbenzene is 0.4. The yield of liquid catalyzate amounted to 77.4%.

Example 15. In the conditions of example 3 in 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 Tbut=310C; TMCO=520C; Tco=630S; Vbeg=2,08% wt. carbon/h, and limit the number of-Jonah spent in contact with 1 g of the above-mentioned carbon in solution, 16 mmol) and 20 g of neutral zirconium hydroxide (33.3% of x-ray amorphous carbon, 66,7% of the binder, 38 cm3) and 50 cm3crushed quartz with a particle size of 0.75-1.0 mm at a temperature of 600°C was applied cyclohexane with a bulk velocity of 380 ml/h (10 h-1). In the reactor kept the pressure 760 Torr (0.1 MPa). Hydrocarbon reaction products contain (mol.%): cyclohexane 3,5, benzene 88,1 and hydrocarbons With60,4, hydrocarbons44.0 and a hydrocarbon, C24,0. The degree of conversion of cyclohexane to 96.5%, the selectivity for benzene (product of dehydrogenation) is 91.3 percent.

Example 16. In the conditions of example 3 in a reactor filled with a catalyst in the form of �hr/176.gif">C; TMCO=520C; Tco=630S; Vbeg=2,08% wt. carbon/h and the maximum number of-Jonah spent in contact with 1 g of the above-mentioned carbon in a solution of 16.1 mmol) and 20 g of neutral zirconium hydroxide (33.3% of x-ray amorphous carbon, 66,7% of the binder, 38 cm3) and 50 cm3crushed quartz with a particle size of 0.75-1.0 mm at a temperature of 350With filed cyclohexane with a volume rate of 38 ml/h (1,0 h-1on liquid cyclohexane). Using manostat and water-jet pump in the reactor support pressure of 76 Torr (0.01 MPa). Hydrocarbon reaction products contain (mol.%): cyclohexane 20,2, benzene, 66,5, hydrocarbons60,2, hydrocarbons46.5 and hydrocarbons With26,6. The degree of conversion of cyclohexane was 79.8%, selectivity to benzene was of 83.4%.

Claims

1. The method of dehydrogenation and dehydrocyclization hydrocarbons, comprising contacting the stream of feedstock with the catalyst on the basis of x-ray amorphous carbon obtained by evaporation of carbon-containing material and having the following characteristics: the temperature of the oxidation on the spine of oxidation of TMCO590C; the temperature of the end oxidation in air Tco630C; initial rate of hydrogenolysis at 700In the absence of a catalyst, activating hydrogen, Vbeg2,08 wt.% carbon/h; maximum number of-Jonah spent in contact with 1 g of the above-mentioned carbon in solution16 mmol; at a temperature of from 350 to 600C and a pressure of from 0.01 to 0.15 MPa.

2. The method according to p. 1, characterized in that the contacting of the flow of raw materials with the said catalyst is carried out at a material with hourly average volumetric rate in terms of fluid from 0.1 to 10 h-1.

3. The method according to any of paragraphs.1 and 2, characterized in that the contacting of the flow of raw material is carried out with the aforementioned catalyst, obtained by evaporation of the aforementioned carbonaceous material under the action of an electric arc.

4. The method according to any of paragraphs.1 and 2, characterized in that the contacting of the flow of raw material is carried out with the aforementioned catalyst obtained by evaporation upon kersulis fact, the above-mentioned x-ray amorphous carbon has a temperature Tbut=280C and TMCO=508C.

6. The method according to any of paragraphs.1-5, characterized in that the said x-ray amorphous carbon has a specific surface area S=210-280 m2/g and bulk density0.05 g/cm3.

7. The method according to any of paragraphs.1-5, characterized in that the catalyst additionally contains an inert granular material.

8. The method according to p. 7, characterized in that the said granular material consists of particles with a size of 0.25 to 1.00 mm

9. The method according to any of paragraphs.7-8, characterized by the fact that, as mentioned granular material introduced quartz.

10. The method according to any of paragraphs.7-8, characterized by the fact that, as mentioned granular material introduced ceramics.

11. The method according to any of paragraphs.7-10, characterized in that the said x-ray amorphous carbon and the above-mentioned granular material is taken in the following ratio, wt.%:

X-ray amorphous carbon 1,65-to 99.00

Inert granular material Else

12. The method according to any of paragraphs.1-5, characterized in that the catalyst is made in the form of pellets, molding and the temperature range 200-550C.

13. The method according to p. 12, characterized by the fact that, as mentioned binder introduced neutral gel hydroxide of metal selected from the group of aluminum, magnesium, zirconium, titanium, hafnium.

14. The method according to p. 12, characterized by the fact that, as mentioned binder is introduced a mixture of neutral gels at least two hydroxides of metals selected from the group of: aluminum, magnesium, zirconium, titanium, hafnium.

15. The method according to p. 12, characterized by the fact that, as mentioned 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 by the fact that, as mentioned binder is introduced a mixture of at least two neutral hydrogels metals selected from the group of: aluminum, magnesium, zirconium, titanium, hafnium.

17. The method according to p. 12, characterized by the fact that, as mentioned hydrogel introduced natural hydrogel.

18. The method according to any of paragraphs.12-17, characterized in that the said x-ray amorphous carbon and the above-mentioned binder is taken in the following ratio, wt.%:

X-ray amorphous carbon 1,65-40,00

The Rest of the binder

19. The method according to any of paragraphs.1-18, characterized in that b according to any one of paragraphs.1-18, characterized in that is used as raw material oil.

21. The method according to any of paragraphs.1-18, characterized in that is used as raw material raw material process of reforming.

22. The method according to p. 21, characterized in that the raw material use non-stabilized raw material of the process of reforming.

23. The method according to any of paragraphs.1-18, characterized in that is used as raw material products of the process of reforming.

24. The method according to p. 23, characterized in that is used as raw material products of the reforming process after separation of the aromatic compounds.

 

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