The catalyst for conversion of hydrocarbons and method thereof

 

The invention relates to the field of petrochemicals. Described is a catalyst for the conversion of hydrocarbons, which includes x-ray amorphous carbon obtained by evaporation of carbon-containing material and having the following characteristics: the temperature at which oxidation in air Tbut320°C; the temperature of the maximum rate of oxidation of TMCO590°C; the temperature of the end oxidation in air - Tco630°C; initial rate of hydrogenolysis at 700°C in the absence of a catalyst, activating hydrogen, Vbeg2,08 wt.% carbon/h; maximum amount of MnO-4-Jonah spent in contact with 1 g of the above-mentioned carbon in solution16 mmol. The method of producing catalyst includes evaporation in an atmosphere of helium carbon-containing material while applying to it the flow of energy 50-300 watts/mm2sedimentation is formed by evaporation fullerenelike soot, the extraction of the above-mentioned fullerene soot with an organic solvent, separating the precipitate, washing and subsequent drying. Technical result: the catalyst for conversion of hydrocarbons, imicheskih poisons.

2 N. and 24 C.p. f-crystals, 3 ill.

The present group of inventions relates to the catalysts used for the conversion of hydrocarbons, and in particular to catalysts for reactions involving C-H communication hydrocarbons and help break these ties with the formation of compounds containing multiple bonds, and to methods of producing such catalysts.

Such catalysts can be used in the dehydrogenation reactions of hydrocarbons and the processes in which these reactions are carried out, particularly in 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 in dehydrocyclization6+-alkanes with the formation of benzene and its homologues.

Activation is very strong C-H communication alkanes priori is a difficult task. The presence in the molecule of an alkane several almost equal energy of C-H linkages involves low selectivity in dehydrogenation reactions. Resulting from the dehydrogenation of alkenes undergo dehydrogenation transformations which result on the catalyst surface Deposit depleted VA deactivates the catalyst, therefore, its activity and selectivity change over time. The struggle with the formation of coke is one of the main tasks of the processes of hydrocarbon processing.

Known dehydrogenation catalyst and dehydrocyclization alkanes containing chromate aluminum (5-60 wt.% in terms of CR2Oz) on the carrier (see RF patent №492115, IPC B 01 J 23/26 published 27.01.2002 year).

The disadvantage of this catalyst are significant losses of raw materials for coke and gas (hydrogen and light hydrocarbons).

There is a method of preparation of the catalyst dehydrogenation and dehydrocyclization alkanes, consisting in the application of active phase in the form of chromate aluminum on the pre-calcined alumina or the product of dehydration of hydrargillite (see RF patent №677168, IPC B 01 J 21/04, 07 With 5/32 published 27.01.2002 year).

The catalyst, obtained in a known manner, leads, as above, to a significant loss of raw material for coke and gas.

A known catalyst for conversion of hydrocarbons comprising oxides of Nickel, titanium, aluminum and boron in the following ratio, wt.%: Nickel oxide 10,5-13,5; titanium oxide of 0.2-0.6; boron oxide 0.3 to 0.9, and the alumina - other (see RF patent №2157730, IPC B 01 J 37/Berezovaya coke and light hydrocarbons, sensitivity to sulfur compounds and the inability to use raw materials containing alkenes.

A known method of producing catalyst for conversion of hydrocarbons, which consists in the impregnation of the support with a solution of nitrate salts of Nickel and aluminum and annealing the obtained catalyst mass at 400-500°C. the Medium is prepared by forming mixture comprising alumina, titanium hydride, boric acid and carbon black with the addition of the binder mixture of paraffin wax and oleic acid, molding at a pressure of 0.4-0.2 MPa and a temperature of 70-75C with subsequent crop has wilted and annealing (see RF patent №2157730, IPC B 01 J 37/02, B 01 J 23/755 published 20.10.2000,).

When the conversion of hydrocarbons in the presence of a catalyst, obtained in a known manner, there is considerable loss of raw materials to the formation of coke and gas, deactivation of the catalyst formed coke and reducing mezhregionalnogo cycle.

Catalytic activation of C-H linkages on the basis of carbon are poorly understood. B. L. Moldovan employees, apparently first discovered the catalytic activity of carbon materials, in particular activated charcoal and coke, dehydrocyclization n-octane and Diisobutyl the velocity of the liquid of 0.1-0.15 h-1. In addition to these reactions, intensively proceeded cracking of paraffins and cycloparaffins (see B. Moldovan, F. Bezprozvanniy, ,Comoser, M. Kobylka. - Journal of General chemistry. - 1937, T. 7, No. 13, S. 1840-1847).

The disadvantage of this catalyst is a low activity, which also decreases in time, which is probably associated with the formation of coke. Dilution of the feedstock with hydrogen does not lead to inhibition of coke formation.

One of these catalysts is coke, which was obtained by pyrolysis gasoline at 600(See B. Moldovan, F. Bezprozvanniy, ,Comoser, M. Kobylka. - Journal of General chemistry. - 1937, T. 7, No. 13, S. 1840-1847).

A known catalyst for the reforming of naphtha (naphtha, a product of the distillation of crude oil with the number of carbon atoms of more than 6, not containing alkenes), which represents the activated carbon without processing or saturated with carbonates or hydroxides of alkali metals (Na, K, Li) and used in the temperature range 538-593C. Promotion of activated carbon carbonates or hydroxides of alkali metals reduces the speed of zakochany and allows you to regenerate the catalyst (see R. A. Sanford and B. S. Friedman, Ind. Eng. Chem., 1954, v.46. No. 12, pp. 2568-2571). Fault the catalyst in the reaction of dehydrogenation (output toluene from methylcyclohexane 15.1 per cent) and the process of dehydrocyclization (output of toluene from n-heptane 9.6%) and the inability to suppress zakochany. So, when diluted feedstock with hydrogen or steam at a molar ratio of diluent to hydrocarbon, 2.4, loss of raw material for coke reach 2.3 per cent.

All coals with increasing flow rate of the raw material rapidly lost activity, which is associated with koksoobrazovaniya and decrease in the specific surface of the catalyst (see N.And.Shuykin, T. I. Naryshkin, DAN SSSR, 1960, I. 135, No. 1, S. 105-108).

A known catalyst for the aromatization of n-hexane and n-octane, which is the composition ZrO2and carbon obtained by the method of Sol - gel (see N.Preiss, L.-M. Berger, K. Szulzewsky. - Carbon. - 1996, V. 34, No. 1, R. 109-119) with subsequent annealing at different temperatures in the helium atmosphere. The most preferred catalytic activity of the sample is characterized by a specific surface 141 m2/g, the adsorption (desorption) of hydrogen 92-93 mmol/g and desorption of ammonia 0.21 mmol/g Aromatization of n-hexane and n-octane in the presence of a known catalyst proceeded only in the atmosphere of hydrogen, but not nitrogen. The conversion of n-hexane at its flavoring was 20.7%, the selectivity for benzene to 66.7% in the gas phase was observed comparable amounts of alkanes C1-C4and alkenes With2-C4methylpentane and Methylcyclopentane. Converstion, contains mostly comparable amounts of ethylbenzene and o-xylene, and 91.2% (see D. L. Hoang, H. Preiss, C. Parlitz, F. Krumeich, H. Lieske, Appl.Catal. A. General, 1999, V. 182, No. 2, R. 385-397; A. Trunschke, D. L. Hoang, J. Radnik, K.-W. Brzezinka, A. Bruckner, H. Lieske, Appl. Catal. A. General, 2001, V. 208, No. 2, P. 381-392).

The disadvantages of the known catalyst: low (not more than 35.5 per cent) degree of conversion of the alkane, the need for dilution of the feedstock with hydrogen in connection with zakoksovanie, the inability to apply for aromatization of cyclohexane and its homologues.

Calcined at high temperatures and containing oxycarbide zirconium catalyst conducts mainly catalytic cracking (with the formation of alkanes C1-C4and alkenes C2-C1and isomerization of n-octane.

It should be noted that carbon-based catalysts typically operate at higher (>500(C) in comparison with the known industrial reforming catalysts (450-470C) temperatures and have low isomerization activity.

Known catalyst for dehydrogenation and hydrogenation, including hydrogenolysis of the hydrocarbon adopted for the prototype representing the fullerenes General formula Cnwhere n=50-120. The catalyst is dissolved in the raw material or in the case of insoluble is giving catalyst in the form of a solution largely prevents the formation of insoluble products, in particular coke. However, the known catalyst prototype is only active in the dehydrogenation hydroaromatics compounds, but not of alkanes. Unknown applicability of known catalyst for dehydrogenation of cyclohexane and its homologues, which eliminates the use of a known catalyst for dehydrocyclization alkanes. The fullerene sublimation reduces the temperature by use of the known catalyst. The formation of a stable fullerene hydrides by heating with hydroaromatics connection leads to justified doubts regarding the possibility of dehydrogenation hydroaromatics compounds with high degrees of conversion. The experiments show that the fullerene and the fullerene epoxides catalyze the cracking of alkanes, but not their dehydration.

A method of obtaining a catalyst in the form of a mixture of fullerenes adopted for the prototype, including the evaporation of carbon or graphite in the chamber with the inert gas pressure of 200 Torr ohmic heating and concentrated solar radiation to the surface temperature 3000-4000With the collection of fullerene soot from the walls of the chamber or removing it from the inert gas and the subsequent extraction of fullerenes from it organizabon prototype catalyst in the form of a mixture of fullerenes is only active in the dehydrogenation hydroaromatics compounds, but not alkanes. Unknown applicability of known catalyst for dehydrogenation of cyclohexane and its homologues, which eliminates the use of a known catalyst for dehydrocyclization alkanes. The fullerene sublimation reduces the temperature by use of the known catalyst. The formation of a stable fullerene hydrides by heating with hydroaromatics connection leads to justified doubts regarding the possibility of dehydrogenation hydroaromatics compounds with high degrees of conversion. The experiments show that fullerenes and fullerene epoxides catalyze the cracking of alkanes, but not their dehydration.

The task, which directed the claimed invention is to provide such a catalyst for the conversion of hydrocarbons and method of producing the catalyst used for the conversion of hydrocarbons would have a wide range of actions, in particular, has been active in the dehydrogenation of alkanes and cycloalkanes and dehydrocyclization alkanes, not deaktivirovana in the processing of pentane and alkenes, was not subject to zakochani did not contain noble metals, was insensitive to conventional catalytic poisons - sulfur compounds, AI for hydrocarbons the substance of the claimed invention is the catalyst for conversion of hydrocarbons includes x-ray amorphous carbon obtained by evaporation of carbon-containing material and having the characteristics of:

the onset temperature of oxidation in air - Tbut320;

the temperature of the maximum rate of oxidation of TMCO590;

the temperature of the end oxidation in air - Tco630;

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

limit the number of IGOs-4-Jonah spent in contact with 1 g of the above-mentioned carbon in solution16 mmol.

Evaporation of carbon-containing material may be carried out, for example, under the action of laser radiation or under the action of an electric arc.

Preferably, x-ray amorphous carbon had a temperature Tbut=280S and temperature TMCO=508C.

The above-mentioned x-ray amorphous carbon is a m is th density0.05 g/cm3.

The catalyst can optionally contain, in addition to x-ray amorphous carbon, inert granular material, for example, in the form of particles with a size of 0.25 to 1.00 mm, which, given the hydrodynamic resistance of the fine material, contributes to the ease of use of the catalyst in a flow-type apparatus. As a granular material in the catalyst may be introduced, for example, quartz or ceramics.

In the catalyst of the 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 - the Rest

The catalyst may be in the form of pellets formed from a mixture of x-ray amorphous carbon with a binder.

As a binder can be introduced neutral gel hydroxide of metal selected from the group of aluminum, magnesium, zirconium, titanium, hafnium.

The binder may be a mixture of neutral gels at least two hydroxides of metals selected from the group of aluminum, magnesium, zirconium, titanium, hafnium.

As a binder can also be entered hydrogel metal selected from the group of aluminum, magnesium, zirconium, realisator can be introduced natural hydrogel.

As a binder in the catalyst may be introduced clay.

In the catalyst of the x-ray amorphous carbon and a binder may be contained in the following ratio, wt.%:

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

The Rest of the binder

The formation of granules is carried out, for example, extrusion of the wet mass and subsequent crop has wilted at room temperature and annealing at a temperature of 200-550With the vacuum. The annealing in an atmosphere of air causes oxidation of the active component - ray amorphous carbon, annealing at temperatures above 550With undesirable, as available in the original x-ray amorphous carbon unpaired multiple bonds converted into conjugated aromatic, are formed graphitized particles and loss of catalytic activity.

In part of the way being claimed invention is that the method of obtaining the above-described catalyst includes evaporation in an atmosphere of helium carbon-containing material while applying to it the flow of energy 50-300 watts/mm2sedimentation is formed by evaporation fullerenelike soot extraction of fullerenes from the soot organic solvent, the temperature of 150-200C.

The carbonaceous material in the present method can be used graphite.

Evaporation in an atmosphere of helium carbon-containing material can be conducted, for example, in arc electric discharge energy flow 50-300 watts/mm2created in a cylindrical reactor with coaxial electrodes when the ratio of the diameter of the reactor R to the electrode diameter d equal to (10-20):1. When the energy flow is less than 50 W/mm2the rate of evaporation of carbon and selectivity of the evaporation process on the x-ray amorphous carbon is very low. When the flow of energy greater than 300 W/mm2the selectivity of the evaporation process on the x-ray amorphous carbon is reduced because of the increased selectivity graphitized particles and the graphite.

At least one of the electrodes may be made of graphite. In this case, is made of graphite electrode serves voltage of positive polarity and move it towards the opposite electrode at a rate of 0.2-6.0 mm/min.

Evaporation of carbon-containing material is predominantly carried out at a pressure of helium 100-760 mm RT.article.

The claimed invention illustrated by the drawings, where Fig.1 shows the change in mass of the sample (in %) in almost the =280With temperature TMCO=508C and the temperature of the end of the oxidation of Tco=630C, obtained by evaporation of the energy flux of 300 W/mm2(1) a catalyst having a specific surface area of 210 m2/g, temperature Tbut=320With temperature TMCO=590S and temperature Tco=900With obtained when the energy flux of 50 W/mm2(2) for the catalyst that is obtained when the energy flow < 50 W/mm2(3); for glass carbon (4) and graphite (5) when it is programmed heating. Vertical lines mark the area of oxidation of x-ray amorphous carbon (I); the oxidation of the graphitized particles (II); the oxidation of graphite (III);

in Fig.2 shows the spectra of x-ray diffraction of the 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 spectrum 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 regardless of the production method, the reactivity and catalytic activity contains data e is between hard water, since water was discovered in absolute methanol after washing x-ray amorphous carbon, a vacuum at 100With over 10 hours In one cycle “deep vacuum at 150With the adsorption of dry air, hydrogen and oxygen does not exceed the measurement error.

The specific surface of the catalyst is depending on the conditions of receiving 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 can turn neprevyshenie graphite, which is determined by the slow decrease of the mass above 670With, and graphitized particles (not fully converted graphite) detected by the mass loss of the temperature range 645-670C (see Fig.1). Graphite is visible also on a sharp line 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 is 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 Fig.3). The line is close to Lorentzian in the center, has a wide wings. On the second integral of the EPR spectrum (or the area under the integral form of the line) determined that the catalyst contains, depending on the conditions of reception (2-5)1020the spin of a mole of carbon, i.e., 1 paramagnetic center (HRC) at 1000-3000 carbon atoms. The value of g-factor (2,0022) paramagnetic centers induced defects such as dangling C-C bonds.

In addition to dangling bonds, the catalyst contains unpaired multiples of C=C bond, detectable interaction with the ion IGOs-4in a neutral environment (Wagner's reaction) and Br2. The concentration of detectable multiples of C=C bonds greatly higher than dangling, and is most active in the catalysis of the samples according to the calculation of a double C=C bond to 5 carbon atoms.

High reactivity of the inventive catalyst (abnormally low temperatures at the beginning and end oxidation in air, oxidation and bromination, in solution, the hydrogenolysis is IU unpaired multiple bonds, in the catalyst, there are defects such as dangling bonds. These functional groups in the catalyst determine its catalytic activity and are manifested in reactivity. Probably the dehydrogenation conversion of hydrocarbons in the presence of the inventive catalyst flow-type reaction with hydrogen transport when alkane acts as a hydrogen donor and a catalyst - acceptor, turning at the temperature of dehydrogenation and dehydrocyclization in a relatively unstable hydride form. It is quite reasonable, because we are first shown the hydrogenolysis of the inventive catalyst in the absence of activating hydrogen catalyst at temperatures700Since, however, up to 400Not detected chemisorption of hydrogen the catalyst.

The combination of all the above features of the claimed catalyst 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 Tbut<300With, but not exposed �ttp://img.russianpatents.com/chr/176.gif">With inactive in the reactions of dehydrogenation and dehydrocyclization alkanes.

The inventive catalyst is also characterized by well-developed surface and a low bulk density (up to 0.05 g/cm3and without mixture with granular material or a binder suitable for use in conditions of stagnant reactor. In the flow reactor to avoid increasing the gas-dynamic resistance or entrainment of the catalyst with a gas stream 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 a molded 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 be used hydroxide gels or hydrogels metals selected from the group of aluminum, magnesium, zirconium, titanium, hafnium, and various types of clay. Unsuitable as a binder aluminosilicates, zeolites and other solid acids, causing cracking of the raw materials and the deposition of coke on catalyses mechanical strength and resistant to abrasion.

Use as catalyst x-ray amorphous carbon with the above characteristics to activate C-H bonds allows to recycle used only 15-20% paraffins, to avoid the formation of coke on the catalyst surface and not to dilute the feedstock with hydrogen. The catalyst does not contain transition and noble metals and little susceptible to conventional catalytic poisons - sulfur compounds. This is typical of the usual catalysts reforming activity in the dehydrogenation of cyclohexane and its homologues.

The inventive catalyst according to the present invention is obtained by evaporation in an atmosphere of 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 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 the precipitate, wash it with ether and dried.

When heart and soul is, the quartz or ceramic) with a particle size of 0.25-1.00 mm, preferably in the following ratio, wt.%:

X-ray amorphous carbon 1,65 - to 99.00

Inert granular material Else

The catalyst may be prepared in the form of a molded, as described above, the units of the x-ray amorphous carbon and a binder, for example a neutral gel hydroxide or neutral hydrogel of a metal selected from the group of aluminum, magnesium, zirconium, titanium, hafnium or mixtures of gels or hydrogels.

X-ray amorphous carbon and binder are preferably mixed to form the following ratio, wt.%:

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

The Rest of the binder

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 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 when the pressure 100-760 Torr. 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.

At the of Lerida cannot be decontaminated, interacting with each other. Slower supply graphite electrode and greater than 300 W/mm2input energy contribute to full 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, dangling bonds and other reactive fragments, 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 pressure of the inert gas, less than 100 Torr (i.e., high concentrations of reactive clusters of activated carbon), frequent collision-energy-rich carbon particles lead to the interaction of the cluster x-ray amorphous carbon with one another and circuit uncompensated valences and double bonds, which contributes to the formation of the product with low reactivity. 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 protectional obtain catalyst - x-ray amorphous carbon is illustrated by the following examples.

Example 1. In the apparatus with a diameter of 85 mm evaporated graphite rod with a diameter of 6 mm at a feed rate of 1.0 mm/min, the strength of 65 amps and voltage 38,7 In and helium pressure of 100 Torr. Condensed fullerensoderzhashchie soot were subjected to exhaustive extraction with toluene to conventional Soxhlet extractions were washed with ether and dried at 150C in vacuum, obtaining x-ray amorphous carbon (a yield of 60.5%) with onset temperature oxidation in air 320With the temperature of the end oxidation in air 630C, the temperature of maximum rate of oxidation 650With subjected to hydrogenolysis by molecular hydrogen in the absence of a catalyst at a temperature of 700C with an initial speed of 0.05 mol/h

Example 2. In the apparatus with a diameter of 85 mm evaporated graphite rod with a diameter of 6 mm at a feed rate of 6.0 mm/min, amperage 212 a and a voltage of 40 V and a helium pressure of 700 Torr. Condensed fullerensoderzhashchie soot were subjected to exhaustive extraction with toluene to conventional Soxhlet extractions were washed with ether and dried at 200With in a vacuum, getting 6.gif">C, the temperature of maximum rate of oxidation 508With subjected to hydrogenolysis in the absence of activating hydrogen catalysts at a temperature of 700With a muzzle velocity of 0.1 mol/h

The invention is also illustrated by the following examples of use of the inventive catalyst.

Example 1. In a tubular flow reactor is placed in a fixed layer, a catalyst consisting of 0.05 g ray amorphous carbon, characterized by Tbut=320C; TMCO=590C; Tco=630C and Vbeg=2,08 wt.% carbon/h, with an average concentration of non-conjugate double bonds at least one of 6 carbon atoms and 2.95 g of crushed quartz with particle size 0.25-0.5 mm (1.66% of x-ray amorphous carbon, 98.34 per cent granular material). The reactor is rinsed with an inert gas for 0.5 h to remove air and thermostatic at a temperature of 550With, after which miss saturated with 22With a pair of n-hexane in an argon (content of n-hexane 20 mol.%).

The resulting hydrocarbon product contains (in mol.%) the source of n-hexane 46,9, benzene 39,3, coal,8 and methane to 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 2. 1.0 g of x-ray amorphous carbon, characterized by Tbut=280C; TMCO=508C; Tco=630C and Vbeg=2,08 wt.% carbon/h, with an average concentration of non-conjugate double bonds in one to 5 carbon atoms, free of fullerenes With60and C70, 0.1 g of crushed ceramic particle size of 0.75-1.0 mm (99,0% x-ray amorphous carbon, 1% granular material) and 65 g (0.5 mol) of 1,2-dihydronaphthalene was placed in a vessel equipped with a reflux condenser, and boil for 2 hours After removal of x-ray amorphous carbon and ceramics in solution detected 12.3 g (0,096 mol) of naphthalene. The degree of conversion of initial 1,2-dihydronaphthalene was 19.2%.

Example 3. In the conditions of example 1 over a catalyst in the form of an extrudate with a diameter of 5 mm, consisting of 1.2 g of x-ray amorphous carbon, characterized by Tbut=280C; TMCO=508C; Tco,=630C and Vbeg=2,08 wt.% carbon/h, with an average conc the ub> and 1.8 g of neutral aluminum hydroxide (40% x-ray amorphous carbon, 60% binder), missed saturated with 22With a pair of n-octane. The hydrocarbon portion of the product contained (in mol.%) the original n-octane 3,7, xylenes 56,8, toluene and 4.8, benzene 2, hydrocarbons With719,3, hydrocarbons With65,8, hydrocarbons With51,2, hydrocarbons With43,9, 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%, the selectivity of the cracking products 34%.

Example 4. In the conditions of example 1 over a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 0.05 g enterohemorrhagic carbon, characterized by Tbut=290C; TMCO=520C; Tco=630C and Vbeg=2,08 wt.% carbon/h, with an average concentration of non-conjugate double bonds in one to 5 carbon atoms, free of fullerenes With60and C70and 2.95 g of neutral titanium hydroxide (1.66% of x-ray amorphous carbon, 98.34 per cent binder), missed saturated with 22With a pair of extraction of gasoline (boiling within 80-125

Example 5. In the conditions of example 1 over a catalyst consisting of 0.05 g ray amorphous carbon, characterized by Tbut=280C; TMCO=508C; Tco=630C and Vbeg=2,08 wt.% carbon/h, with an average concentration of non-conjugate double bonds at least one of 6 carbon atoms and 2.95 g of silica with a particle size of 0.25-0.50 mm (1.66% of x-ray amorphous carbon, 98.34 per cent granular material), missed saturated with 22With a pair of n-pentane. The hydrocarbon portion of the product contained by 83.4 mol.% the source of n-pentane, and 5.8 mol.% benzene, 2,4 mol.% isomers of pentane, 1,5 mol.% hydrocarbons With4that 2.8 mol.% propylene, 1,2 mol.% propane, 0.6 mol.% ethylene, 2,2 mol.% ethane and 0.5 mol.% of methane. 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%.

PR is SJ Tbut=280C; TMCO=508C; Tco=630C and Vbeg=2,08 wt.% carbon/h, with an average concentration of non-conjugate double bonds at least one of 6 carbon atoms and 2.95 g of silica with a particle size of 0.25-0.50 mm, missed saturated with 22With a pair of n-heptane. The hydrocarbon portion of the product contained (in mol.%) the source of n-heptane 21,2, toluene 7,8, benzene 25,5, hydrocarbons With68,8, hydrocarbons With510,2, hydrocarbons With45,8, propylene 8,0, propane 5,8, ethylene 1,4, ethane 4.1 and methane to 0.6. The conversion of the original n-heptane was 78,8%, the selectivity for benzene 32.3%, selectivity to toluene of 9.9%.

Example 7. In the conditions of example 1 was used as catalyst 3.0 g of crushed quartz. The hydrocarbon portion of the product contained only neprevyshenie the original n-hexane, i.e. quartz at 550With not catalyzes the dehydrogenation, dehydrocyclization, cracking and isomerization of n-hexane.

Example 8. In the conditions of example 1 above 3.0 g of extrudate with a diameter of 3 mm, consisting of neutral aluminum hydroxide missed saturated with 22With a pair of n-heptane. Hydrocarbon hydrocarbon With40,3, propane 0,5, ethylene 0,7, ethane 0.1 and methane 0,1. The conversion of the original n-heptane was 2.5%. Aromatic products are missing, there are only products with the number of carbon atoms is less than 7, i.e., the cracking products.

Example 9. In the conditions of example 1 used a catalyst consisting 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 10. In a quartz ampoule volume of 50 cm3were placed 0.1 g of fullerene C60the ampoule was evacuated to a residual pressure of 0.01 Torr and filled with 100 Torr of vapor of n-hexane. The ampoule was sealed and kept 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 contained 100 Torr ethane and 200 Torr of Athena, which indicates that multiple cracking of hexane.

Example 11. In the conditions of example 1 used a catalyst consisting of 0.1 g of fullerene epoxides With60and 2.9 g of crushed quartz, missed saturated with 22With a pair of Ghana 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 12. In the conditions of example 1 over a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 1.0 g of x-ray amorphous carbon, characterized by Tbut=310C; TMCO=520S; Kthen=630C and Vbeg=2,08 wt.% carbon/h, with an average concentration of non-conjugate double bonds one to 6 carbon atoms, free of fullerenes With60and C70and 2.0 g of neutral zirconium hydroxide (33.3% of x-ray amorphous carbon, 66,7% binder), missed nasyshennye at 22With a couple of clohexane. Hydrocarbon reaction products contained 5.5% of cyclohexane and 91.1% of benzene and 3,4% of hydrocarbons With6. The degree of conversion of cyclohexane to 94.5%, the selectivity for dehydrogenation product - benzene was 96,4%.

Example 13. In the conditions of example 1 over a catalyst in the form of an extrudate with a diameter of 3 mm, consisting of 0.9 g x-ray amorphous carbon, characterized by Tbut=320C; TMCO=580With; Tothen=630C and VNarodnogo from fullerenes With60and C70and 2.1 g of neutral zirconium hydroxide (30,0% x-ray amorphous carbon, 70.0% of binder), missed with a bulk velocity of 40 cm3/min (1000 h-1) butene-butane fraction of the following composition (in 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, With1-3-hydrocarbons 0,3,5-7-hydrocarbons of 0.9. The exit gas contained (in 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%.

Claims

1. The catalyst for conversion of hydrocarbons, including x-ray amorphous carbon obtained by evaporation of carbon-containing material and having the following characteristics: the temperature at which oxidation in air Tbut320°C; the temperature of the maximum rate of oxidation of TMCO590°C; the temperature of the end oxidation in air Tco630°C; initial rate of hydrogenolysis at 700°C in the absence of a catalyst, activating hydrogen, Vbeg2,08 wt.% carbon/h; maximum 805.gif">16 mmol.

2. The catalyst p. 1, characterized in that the evaporation of carbon-containing material is carried out under the action of laser radiation.

3. The catalyst p. 1, characterized in that the evaporation of carbon-containing material is carried out under the action of an electric arc.

4. The catalyst according to any one of paragraphs.1-3, characterized in that the said x-ray amorphous carbon has a temperature Tbut=280°C and the temperature TMCO=508C.

5. The catalyst according to any one of paragraphs.1-4, 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.

6. The catalyst according to any one of paragraphs.1-4, characterized in that the catalyst additionally contains an inert granular material.

7. The catalyst p. 6, characterized in that the said granular material consists of particles with a size of 0.25 to 1.00 mm

8. The catalyst p. 6, characterized by the fact that, as mentioned granular material introduced quartz.

9. The catalyst p. 6, characterized by the fact that, as mentioned granular material introduced ceramics.

10. Cat is the following ratio, wt.%:

X-ray amorphous carbon 1,65-to 99.00

Inert granular material Else

11. The catalyst according to any one of paragraphs.1-4, characterized in that the catalyst is made in the form of pellets formed from a mixture of x-ray amorphous carbon with a binder.

12. The catalyst according to p. 11, characterized by the fact that, as mentioned binder introduced neutral gel metal hydroxide selected from the group of aluminum, magnesium, zirconium, titanium, hafnium.

13. The catalyst according to p. 11, which as mentioned binder is introduced a mixture of neutral gels at least two metal hydroxides selected from the group of aluminum, magnesium, zirconium, titanium, hafnium.

14. The catalyst according to p. 11, 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.

15. The catalyst according to p. 11, characterized by the fact that, as mentioned binder is introduced a mixture of neutral hydrogels at least two metals selected from the group of aluminum, magnesium, zirconium, titanium, hafnium.

16. The catalyst PP.14 and 15, characterized in that, as mentioned hydrogel introduced natural hydrogel.

17. The catalyst is mu PP.11-17, 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 catalyst according to any one of paragraphs.11-18, characterized in that the said molded pellets enterohemorrhagic carbon with a binder is subjected to heat treatment at temperatures of 200-550°C in vacuum.

20. The method of producing catalyst under item 1, including evaporation in an atmosphere of helium carbon-containing material while applying to it the flow of energy 50-300 watts/mm2sedimentation is formed by evaporation fullerenelike soot, the extraction of the above-mentioned fullerene soot with an organic solvent, separating the precipitate, washing and subsequent drying.

21. The method according to p. 20, characterized in that the drying is carried out in the vacuum at a temperature of 150-200°C.

22. The method according to p. 20, characterized in that the carbonaceous material used graphite.

23. The method according to p. 20, characterized in that the evaporation in the atmosphere of helium carbon-containing material are in the field of electric arc discharge with a flow of energy 50-300 watts/mm2created in a cylindrical reactor with SP.22, characterized in that at least one of these electrodes are made of graphite.

25. The method according to p. 23, characterized by the fact that made of graphite mentioned electrode serves voltage of positive polarity and move it towards the opposite electrode at a rate of 0.2-6.0 mm/min.

26. The method according to any of paragraphs.19-24, characterized in that the evaporation of carbon-containing material is carried out at a pressure of helium 100-760 Torr.

 

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