WO2007091912A1 - Procédé pour produire des carburants de moteur - Google Patents

Procédé pour produire des carburants de moteur Download PDF

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WO2007091912A1
WO2007091912A1 PCT/RU2006/000066 RU2006000066W WO2007091912A1 WO 2007091912 A1 WO2007091912 A1 WO 2007091912A1 RU 2006000066 W RU2006000066 W RU 2006000066W WO 2007091912 A1 WO2007091912 A1 WO 2007091912A1
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catalyst
hydrocarbon gases
hydrogen
hydrocarbons
octane
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PCT/RU2006/000066
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English (en)
Russian (ru)
Inventor
Alexandr Sergeevich Bely
Alexandr Gennadievich Proskura
Dmitry Ivanovich Kiryanov
Mikhail Dmitrievich Smolikov
Vladimir Alexandrovich Likholobov
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Institut Problem Pererabotki Uglevodorodov Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk
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Priority to PCT/RU2006/000066 priority Critical patent/WO2007091912A1/fr
Publication of WO2007091912A1 publication Critical patent/WO2007091912A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal

Definitions

  • a method of obtaining components of motor fuels is a method of obtaining components of motor fuels.
  • the invention relates to the production of high-octane components of motor fuels, aromatic hydrocarbons and hydrogen from gasoline fractions of oil and gas condensate origin and C 1 -C 4 hydrocarbon gases and can be used in the oil refining and gas processing industries.
  • the disadvantage of this method is the low efficiency of the separation of hydrogen and hydrocarbon gases by the separation method, as well as the significant energy intensity of the process, due to the need to compress hydrocarbon gas from the separator of the second stage to the pressure in the reforming zone.
  • this method does not significantly eliminate the conversion of the original liquid feed to low-value C 1 -C 4 hydrocarbon gases.
  • the yield of the target high-octane liquid hydrocarbons is not more than 80-85 wt.% Calculated on raw materials.
  • the method includes biforming in the presence of a platinum-containing catalyst, followed by separation of liquid high-octane products and recirculation of C 1 -C 4 hydrocarbon gases to the biforming zone.
  • the mixture of gases formed in the process (hydrogen and C 1 -C 4 hydrocarbon gases) is separated by binding (absorption) of hydrogen upon contact with aromatic hydrocarbons in the catalytic hydrogenation zone, after which the liquid hydrogenation products (cyclohexane hydrocarbons) are separated from C 1 - C 4 - hydrocarbon gases.
  • Ci-C 4 - hydrocarbon gases are continuously recycled in a closed system from the hydrogenation zone to the biforming zone and vice versa without removing them from the process.
  • An additional amount of Ci-C 4 a hydrocarbon gas from an external source, is supplied to the recycle gas stream.
  • the hydrogen binding rate in the hydrogenation zone is maintained equal to the hydrogen evolution rate in the biforming zone.
  • the hydrogenation products are divided into liquid (hydrocarbons of the cyclohexane series) and gaseous C 1 -C 4 hydrocarbons in a gas-liquid separator. Bound hydrogen in the form of cyclohexane hydrocarbons is removed from the process. Cyclohexane hydrocarbons are sent to the catalytic dehydrogenation zone.
  • cyclohexane-type hydrocarbons are converted to aromatic hydrocarbons and hydrogen. Hydrogen is separated from aromatic hydrocarbons in a separator and removed from the process. Aromatic hydrocarbons are sent to the hydrogenation zone continuously to bind the hydrogen released during the biforming process. Dissolved in liquid high-octane products C 3 -C 4 - hydrocarbon gases are released in a distillation column and returned to the reaction bedforming zone for mixing with the feed (gasoline fraction).
  • the implementation of the two above-mentioned effects provides an increase in the output of the high-octane component to 92-98 wt.% Based on the gasoline fraction fed to the processing.
  • a disadvantage of the known method for the production of components of motor fuels is the rather fast dynamics of a decrease in the activity of the catalyst, especially in the initial period of the reaction cycle with the simultaneous introduction of C 1 -C 4 hydrocarbon gases into the reaction zone along with the liquid feed (gasoline).
  • the components of light hydrocarbon gases, co-adsorbing on the surface of the “fresh” catalyst form strongly adsorbed hydrocarbon fragments that are nucleating agents of coke and cause premature deactivation of the catalyst, thereby reducing the yield of high-octane products.
  • a mixture of gasoline fractions and C 1 -C 4 hydrocarbon gases is subjected to processing in a mass percentage of C 1 -C 4 ZC 5+ of at least 3 wt.% In C 5+ high-octane components of motor fuels.
  • This achieves the technical result of the proposed method, which manifests itself in an increase in the stability of the catalyst and an increase in the yield of high-octane gasolines.
  • the process in the second stage is carried out at a temperature of not less than 460 0 C and a partial pressure of hydrogen of not more than 1.5 MPa.
  • Another significant feature of the proposed method for the production of high-octane components of motor fuels is the constant supply of water and an organochlorine compound to the reactor zone in the second stage in such a way that the moisture content of the SHG is in the range from 10 to 25 ppm.
  • the deactivation rate of catalysts for dehydrogenation processes depends on the ratio of the rates of formation and regeneration (hydrogenation) of strongly adsorbed hydrocarbon fragments of a high degree of dehydrogenation on the surface of the catalyst (coke precursors).
  • One of the main conditions for good process stability is to ensure the equality of the rates of formation and hydrogenation of coke precursors on the catalyst [V. Durluakm, A. Velui, N. Ostrowski. Nef reformipat satellites of high resistapse to desivatiop // Nev Challepgers ip Catalysis. Portugalp Asademu of Scieps apd Arts. Nivi Sad. 1999. p. 89].
  • the rate of coke formation and hydrogenation depends on the amount and activity of hydrogen. By activity we mean the kinetic laws of activation and diffusion of (hydrogen) hydrogen over the surface, on which the rate of the self-regeneration process depends.
  • Simplified process of hydrogen activation can be represented as follows.
  • the activation of molecular hydrogen occurs on the metal component of the catalyst. This process consists of the stages of adsorption, dissociation, surface diffusion and interaction with hydrocarbons.
  • the rate of chemisorption and dissociation of hydrogen depends on the nature of the metal component.
  • the diffusion rate is determined by the degree of oxidation of the catalyst surface, which in turn is determined by the presence of oxidizing agents in the reaction zone.
  • water is used in astoichiometric amounts, its content in the WASH from 10 to 25 ppm. Once in the reaction zone, water dissociates into hydrogen and oxygen. The latter oxidizes the surface of the catalyst at elevated temperatures.
  • the degree of oxidation of the surface is determined by the water content in the reaction zone.
  • redox a continuous redox process (redox) is realized on the catalyst surface, the speed of which determines the diffusion rate of activated hydrogen over the surface and, as a result, the hydrogenation rate of coke precursors (catalyst self-regeneration rate).
  • organochlorine compounds are constantly fed along with water to the reaction zone so that a lower H 2 CVCl ratio is from 15 to 25. Under these conditions, the optimum hydrogen diffusion rates on the surface are reached and catalyst self-regeneration. This ensures high stability of the process in the second stage and, as a consequence, an increase in the production of high-octane components of motor fuels.
  • Another significant feature of the proposed method is the joint processing of C 1 -C 4 hydrocarbon gases and gasoline fractions on a catalyst containing, wt.%: Acid component of not less than 0.5 metal component, not less than 0.5 carrier, the rest to 100.
  • the catalyst may contain:
  • the catalyst may contain elements of groups VII and VIII in the ionic state in the oxidation state n> 0 [Belui A.S. New Post Office of Surface Comsitiop of Reformipat Satellite. Reast. Lipet. Catal. Lettt, 1996, V.57, JN ° 2, ⁇ .349].
  • the catalyst contains: aluminum oxide, aluminosilicates or mixtures thereof with a specific surface area of at least 200 m 2 / g.
  • An essential distinguishing feature of the proposed method for the joint processing of C 1 -C 4 hydrocarbon gases and gasoline fractions is the use of a catalyst in which metal and acid components are present together.
  • the function of the metal component is to carry out dehydrocyclization reactions of alkane molecules.
  • the function of the acid component is to weaken carbon-carbon bonds and to form dehydrogenated intermediates of extremely reactive carbon ions [Sauterfield CN. Neterohepeus Catalysis ip Pristise. McGraw-NS, Ips, 1980].
  • the function of the catalyst carrier is that it provides close contact between the acid and metal components and creates a developed mesoporous structure with a surface size of more than 200 m 2 / g. Together, this structure ensures the availability of active components for reagents and removes diffusion inhibitions of reactions.
  • the combined supply of a mixture of light C 1 -C 4 - and heavy C 5+ - hydrocarbons leads to joint chemisorption of light and heavy molecules on active centers, their conjugate activation and, as a result, integration of light molecules into longer ones and their further transformation into isoparaffin and aromatic hydrocarbons.
  • This process is carried out on the surface of the catalyst through a transition complex of light and heavy hydrocarbons, providing an increase in the efficiency of formation of high-octane components.
  • the catalyst is prepared in two stages.
  • the acid component is introduced into the catalyst by any known method, followed by drying and calcination of the obtained intermediate.
  • the acid component is introduced either by mixing the corresponding compounds with aluminum hydroxide, followed by molding into extrudates, drying and calcining, or treating the formed and calcined support with solutions of the appropriate reagents, followed by drying and calcination.
  • One of the essential conditions for obtaining high activity and selectivity of the catalyst is to obtain a defective crystalline structure of the acid carrier in the first stage of its preparation. This condition is provided by mixing aluminum hydroxide or a mixture of aluminum hydroxide and aluminosilicate clay with organic acids such as formic, acetic, oxalic, etc.
  • organic aluminum salts are formed, which decompose during high-temperature calcination and form defects in the crystal structure of the acid support.
  • the defect criterion is the true density of the carrier, which should be no more than 3.0-3.1 g / cm 3 .
  • the presence of a defect in the crystal structure of the acid support is the main condition for the formation of ionic metal forms with an oxidation state of n> 0 in the second stage of preparation of the catalyst.
  • Metal components from among metals of groups VII and VIII of the group are introduced in the second stage of preparation of the catalyst by impregnation of the acid carrier with solutions of the corresponding compounds.
  • a necessary condition for realizing the effects of strong metal-carrier interaction is the use of elevated (at least 80 0 C) temperatures and competitor acids.
  • the catalyst is then dried, calcined, reduced and sulphurized.
  • the amount of platinum group metals in the ionic state is determined by the adsorption method described in [Veli AS, Kiruapov DI, Smolikov MD, et. al. O 2 -adsorption apd (O 2 -H 2 ) -titration on electron deficient platinum in refonning catalysts. Kipet. Catal. Lett., 1994, V.53, M> l, p.l83].
  • TSU - hydrocarbons of the cyclohexane series (methylcyclohexane).
  • the reaction zone of the biforming reactor 1 is used with a reaction zone volume of 100 cm 3 .
  • a polymetallic biforming catalyst of the following composition is loaded into the reactor, wt.%: Platinum - 0.25; rhenium - 0.3; chlorine - 1.0; the carrier (aluminum oxysulfate) - the rest is up to 100.
  • the hydrogenation reactor 3 and dehydrogenation 4 load the same catalyst in an amount of 25 cm 3 each.
  • the catalysts in each reactor are reduced with hydrogen at 500 ° C, a pressure of 1.0 MPa, and a hydrogen feed rate of 10 nl / h.
  • the raw material for the process is a mixture of n-butane (3.0 wt.%) And a gasoline fraction of 105-185 0 C (100 wt.%) With a density of 0.743 g / ml, which are mixed with a hydrogen-containing gas and fed to the reaction bedforming zone at a temperature 495 0 C and a pressure of 2.2 MPa at a rate of 150 ml / h.
  • the reaction products from reactor 1 are cooled and served in the separator 2.
  • Hydrogen (80 vol.%) and light hydrocarbon gases from the separator 2 are fed into the hydrogenation reaction zone 3, which also serves toluene at a rate of 62 ml / h.
  • Liquid C 5+ hydrocarbons are sent for stabilization to distillation column 6, in which products are separated into C 3 -C 4 liquefied gases and stable high octane catalysis.
  • the catalyst is continuously withdrawn from the process, and liquefied gases are recycled to the inlet of the bioforming reaction zone.
  • Methylcyclohexane containing chemically bound hydrogen is subjected to dehydrogenation in reactor 4 at a temperature of 500 0 C, with the formation of toluene and hydrogen in a molar ratio of 1: 3.
  • Dehydrogenation products are separated into hydrogen and toluene in a separator 7.
  • Hydrogen is removed from the process.
  • the purity of hydrogen is above 97 vol.%
  • Liquid toluene is returned to the hydrogenation zone to separate hydrogen from C 1 -C 4 hydrocarbon gases from the biforming zone.
  • the basic principle of the biforming process is implemented, which consists in the fact that the hydrocarbon C 1 -C 4 gases formed in the process are not completely removed from the process as low-value by-products, but are intensively recycled to the reforming reaction zone, where they enter into joint transformations with macromolecular components of gasoline with the formation of high-octane components of motor fuels.
  • the main technical result of the biforming process is achieved, consisting in increasing the yield of the high-octane component to 92 wt.% Or more, based on the straight-run gasoline fraction submitted for processing.
  • FIG. 2 shows the data on the yield of octane-increasing aromatic hydrocarbons in the course of biforming for 100 hours, where:
  • Example 2 Illustrates the proposed method for the production of high-octane components of motor fuels, a catalyst and a method for its preparation.
  • a catalyst of the following composition is used, wt.%: Acid component (ZrOSO 4 ) - 0.65 metal component - 0.6 including: ionic platinum - 0.24 metal platinum - 0.06 rhenium - 0.3 carrier ( alumina) up to 100.
  • the catalyst is prepared in two stages.
  • the acid component is introduced into the catalyst by mixing a solution of a salt of sulfatocirconyl in acetic acid with aluminum hydroxide (modification of pseudoboehmite).
  • the ratio of acetic acid / AUON is 0.02 (calculated on calcined alumina).
  • the mixture is dried with stirring to a moisture content of 58 wt.%, Molded in stiffeners with a diameter of 2 mm, dried to a moisture content of 20 wt.%, calcined to a moisture content of 1.0 wt.%.
  • the true density of the product is 3.1 g / cm 3 .
  • the carrier is evacuated to a residual pressure of 0.01 V ⁇ Pa and moistened with water (80 ml of water per 100 g of carrier). Then the carrier is treated with 60 ml of an aqueous solution containing 0.3 g of platinum in the form of platinum chloride, 0.3 g of rhenium in the form of HReO 4 , 0.6 g of polar acid. The carrier is treated for 1 h at a temperature of 30 0 C, and then 1 h at 80 0 C. 0.03 g of oxalic acid and 0.15 g of hydrogen peroxide are added to the impregnation solution. Processing is continued for 0.5 hours with stirring.
  • the catalyst is loaded into the reactor 1 in an amount of 100 cm 3 .
  • the catalyst In the hydrogenation reactor 3 and dehydrogenation 4 load the catalyst of example 1.
  • the process of obtaining components of motor fuels is carried out in two stages.
  • the catalyst is run-in (aging) by feeding into the reactor 1 a mixture of a gasoline fraction (with a space velocity of 1.5 h "1 ) and hydrogen (once the system is filled with hydrogen to a pressure of 1.0 MPa) at a temperature of 400 0 C.
  • a gasoline fraction with a space velocity of 1.5 h "1
  • hydrogen once the system is filled with hydrogen to a pressure of 1.0 MPa
  • aromatization reactions of naphthenic hydrocarbons begin to take place.
  • the resulting hydrogen and hydrocarbon gases are removed from the process.
  • the temperature is gradually raised to 460 0 C (in 6 hours), and then to 480-485 0 C in 10-12 hours.
  • surface hydrocarbon fragment nt which act as intermediates in the formation of isoparaffin and aromatic hydrocarbons.
  • the aging process of the active surface is slow and it takes at least 24-36 hours to complete it, which is equivalent to processing at least 75 kg of raw materials per kg of catalyst.
  • the criterion for completing the aging process of the catalyst is stabilization of parameters the content of aromatic hydrocarbons in liquid products and their octane numbers.
  • the optimal parameters of the aging mode of the catalyst is the reformate production mode with an octane number of IOI not more than 93p., which is achieved when the content of aromatic hydrocarbons up to 63 wt.% at temperatures of 480-485 0 C.
  • the burned-in surface of the catalyst contains hydrocarbon intermediates of the aromatization reaction, which prevent the deep dehydrogenation of C 3 -C 4 alkanes and contribute to their conversion under conditions of joint conversion with gasoline into high-octane components of motor fuels.
  • the process proceeds stably, which ensures the goal of the proposed method is to increase the production of aromatic hydrocarbons, which are the main octane-raising components of motor fuels.
  • Stable operation of the catalyst is also ensured by the fact that water and an organochlorine compound from among dichloroethane, trichlorethylene, carbon tetrachloride are continuously pumped into the feed stream to the inlet of the reactor 1.
  • the water feed rate is maintained such that the moisture content of the WASH from the separator 2 is 10-25 ppm, and the molar ratio of H 2 CVCl is in the range of 15-25. This operation is necessary to maintain at an optimal level the acid function of the catalyst during continuous operation in the conditions of the bioforming reaction cycle. If the supply of water and chlorine to the reaction zone is absent (examples 1-3), as well as when the moisture content of the WASH is more than 25 ppm (example 5), the efficiency of the biforming process is reduced. The main parameters and results of the proposed method are shown in the table.
  • the average yield of high-octane component (BOK) under optimal conditions is 95 wt.% Calculated on the gasoline fraction with an octane number of IOC of 99.3 p., which indicates the achievement of the objectives of the present invention.
  • Example 3 Illustrates the influence of the conditions of the aging stage of a fresh catalyst.
  • the aging (running-in) method is carried out as in Example 2, with the difference that the aging time is reduced from 50 hours to 25 hours (from 75 kg to 50 kg of raw material per 1 kg of catalyst) and, in the final stage of aging, the conditions provided a more stringent mode compared with example 2.
  • the octane number was 98 p. with an aromatic hydrocarbon content of 69.5 wt.%. Therefore, the most optimal conditions for the aging of the catalyst is the mode with the production of BOK with an octane number of IOC no more than 93 p. In the amount of not less than 75 kg per 1 kg of catalyst.
  • Example 4 Illustrates the influence of process temperature on the yield and characteristics of the obtained high-octane product in the joint processing of C 1 -C 4 hydrocarbon gases with gasoline.
  • the processing method is the same as in example 2 with the difference that the processing is carried out in the bioforming reactor 1 (Fig. 1) at a temperature of 460 0 C.
  • the octane number of the IOC is 91 p.
  • the aim of the invention is achieved by carrying out the process at reaction temperatures of more than 460 0 C.
  • Example 5 The method is carried out as in example 2 with the difference that water is supplied to the biforming zone in an amount of 20 ppm, and chlorine in an amount of 0.5 ppm, based on raw materials.
  • the humidity of the WASH is 30 ppm, and the ratio of H 2 O / C1 is more than 40. From the table it follows that when carrying out the process in conditions of high humidity (more than 25 ppm) and with insufficient amounts of chlorine supplied to the system, the efficiency of the biforming process decreases.
  • the yield of BOK compared with example 2 is reduced from 95.0 wt.% To 92.8 wt.%, And the octane number of the IOC from 99.3 p. To 97 p.
  • Example 6 Illustrates the decrease in the efficiency of the bioforming process while reducing the amount of C 1 -C 4 hydrocarbon gas fed to the processing from 3 wt.% To 1.5 wt.%.
  • Ci-C 4 hydrocarbon gases and gasoline fraction Processing a mixture of Ci-C 4 hydrocarbon gases and gasoline fraction is carried out according to example 2 with the difference that the amount of gas supplied to the processing from an external source decreases from 3 wt.% To 1.5 wt.% With respect to the gasoline fraction. In this case, the BOK yield decreases from 95 wt.% To 91.5 wt.% 5 and the octane number from 99.3 p. To 96.5 p.
  • Example 7 Illustrates the effect of reducing in the composition of the catalyst an acid component of less than 0.5 wt.% And a metal component of less than 0.5 wt.%.
  • a catalyst of the following composition is used, wt.%: Acid component (ZrOSO 4 ) - 0.3; metal component Pt + - 0.3; carrier (aluminum oxide) - the rest is up to 100.
  • the catalyst is prepared in two stages.
  • the acid component is introduced by mixing a solution of a zirconyl sulfate salt (0.3 g of salt per 100 g of aluminum oxide) in acetic acid with aluminum hydroxide (modification of pseudoboehmite).
  • the ratio of acetic acid / AlOOH is 0.02.
  • the acid carrier is evacuated to a residual pressure of 0.01 MPa and moistened with water (80 g of water per 100 g of aluminum oxide).
  • the carrier is treated with 60 ml of an aqueous solution containing 0.3 g of platinum in the form of platinum chloride hydrochloric acid and 1.0 g of hydrochloric acid.
  • the carrier is treated with the solution with stirring for 1 h at a temperature of 30 0 C, and then 1 h at 80 0 C. 0.03 g of oxalic acid and 0.15 g of hydrogen peroxide are added to the impregnation solution. Processing is continued for 0.5 hours.
  • Example 8 Illustrates the proposed method using a catalyst of the following chemical composition, wt.%: Acid component AlOHCl 2 - 2,3; metal component - 0.6; including Pt + - 0.3;
  • the catalyst is prepared in two stages.
  • the acid component is introduced into the catalyst in the first stage in a known manner (SU 1019706, 01/22/1983).
  • the acid component 100 g of aluminum oxide is treated with a solution containing 7 g of hydrogen chloride dissolved in isopropyl alcohol. The interaction of hydrogen chloride with alumina is carried out in the mode of circulation of the solution through the carrier layer at room temperature for 2 hours. Then the solution is separated, the carrier is dried and calcined at 500 0 C to a residual moisture content of 2.0 wt.%.
  • the product contains 7.0 wt.% Chlorine and corresponds to the formula Al 19 O 23 AlOHCl 2 .
  • the carrier is evacuated to a residual pressure of 0.01 MPa and moistened with water (80 g of water per 100 g of aluminum oxide).
  • the carrier is then treated with 60 ml of an aqueous solution containing 0.3 g of platinum in the form of platinum chloride, 0.3 g of palladium in the form of palladium chloride and 0.8 g of hydrochloric acid.
  • the carrier is treated for 1 h at a temperature of 25 0 C, and then 1 h at 80 0 C.
  • the biforming process is carried out under the conditions given in the table.
  • water is continuously fed into the reactor 1 to maintain the WAG humidity at 25 ppm and dichloroethane to maintain a water / chlorine molar ratio of 25.
  • This example illustrates the possibility of reducing the process pressure from 2.2 MPa to 0.5 MPa.
  • Example 9 Use the catalyst of the following composition, wt.%: Acid component SnOCl 2 - 1,1; metal component - 0.6, incl. Pt + - 0.3,
  • Pd + - 0.3, carrier (alumina) - the rest is up to 100.
  • the carrier corresponds to the general formula Al 20 O 29 (SnO 2 Cl 2 ) 0) 05 .
  • the preparation of the catalyst in the second stage is carried out according to example 2.
  • the biforming process is carried out under the conditions shown in the table. Water is continuously fed into the biforming reactor to maintain a Wash moisture content of 10 ppm and trichlorethylene to maintain a water / chlorine molar ratio of 15.
  • This example illustrates the possibility of obtaining the proposed method a high-octane component with an octane number of IOI more than 100 p.
  • Example 10 Use the catalyst of the following composition, wt.%: Acid component AlOSO 4 - 4.3; metal component - 0.6, incl. Pt + - 0.3,
  • Re is 0.3; the carrier is the rest up to 100, alumina 80, aluminosilicate clay (montmorillonite) 20.
  • the catalyst is prepared in two stages.
  • Aluminum oxysulfate is prepared in a known manner (RU 2050187, BOlJ 23/656, 12.20.1095).
  • aluminum hydroxide 80 g per aluminum oxide
  • montmorillonite in terms of calcined aluminosilicate
  • 3.0 g sulfuric acid at 20 ° C adding 8.2 ml of acetic acid.
  • the mass is formed into granules, dried and calcined at 580 ° C.
  • oxysulfate of the composition Al 1 C) Oa 7 (AlOSO 4 ) O132 with a sulfate ion content of 3.0 mass% is formed.
  • the second stage of preparation of the catalyst is carried out according to example 2.
  • the biforming process is carried out under the conditions given in the table.
  • the process provides obtaining BOK with an octane number of IOI 103 p. With the release of 98.8 wt.%.
  • Example 11 The process is carried out in a system of three reactors.
  • Example 12 The process is carried out as in example 11, but with the difference that it is carried out in reactors with a radial flow of the mixture through the catalyst bed in the direction from the center to the periphery of the reactor.
  • a decrease in temperature along the catalyst bed due to the endothermic effect of the reaction is compensated by a decrease in the space velocity (increase in contact time) as a result of an increase in the catalyst volume as the flow moves from the center of the reactor to the periphery.
  • the efficiency of the process increases (table). This is manifested in the achievement of high performance at even lower temperatures.

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Abstract

L'invention concerne un procédé pour produire des composants de carburant de moteur à indice d'octane élevé et de l'hydrogène à partir des fractions d'essence et de benzène et à partir des gaz d'hydrocarbures C1 - C4. Le procédé de l'invention consiste à transformer conjointement les gaz d'hydrocarbures C1 - C4 et les fractions d'essence dans un système de réacteurs à catalyseurs en des composants C5+ des carburants pour moteur, à séparer le gaz hydrogéné des produits liquides à indice d'octane élevé C5+ , à séparer le gaz contenant de l'eau en hydrogène et en gaz d'hydrocarbures C1 - C4 par la liaison de l'hydrogène au moyen d'une réaction d'hydruration catalytique des hydrocarbures aromatiques dans des hydrocarbures de l'ordre de cyclohexane et la recirculation des gaz d'hydrocarbures C1 - C4 séparés dans la zone de réaction de biforming pour la transformation en hydrocarbures liquides C5+ , l'extraction des produits liquides C5+ des gaz d'hydrocarbures dissous C3- C4 et leur recirculation dans la zone de réaction de biforming pour un traitement secondaire en hydrocarbures liquides C5+; on évacue du processus l'hydrogène excessif sous forme d'hydrocarbures de l'ordre de cyclohexane et/ou de mélange des gaz d'hydrocarbures C1 - C4 en excès; on ajoute dans les gaz d'hydrocarbures C1 - C4 circulant dans la zone de biforming les gaz obtenus à partir d'un gaz hydrogéné et les produits liquides C5+ à indice d'octane élevé et des gaz C3- C4 provenant d'une source externe. Le processus est réalisé en deux stades, le premier stade consistant à faire vieillir le catalyseur par le traitement avec des hydrocarbures C5+, à une température inférieure ou égale à 480°C, et le deuxième stade consistant à traiter le mélange des fractions d'essence et des gaz d'hydrocarbures C1-C4 des gaz d'hydrocarbures en composants C5+ des carburants pour moteur à indice d'octane élevé. Le processus est effectué sur la base d'un catalyseur contenant un composant acide en % en masse d'au moins 0,5 %, avec un composant métallique d'au moins 0,5, le solde étant constitué par un vecteur.
PCT/RU2006/000066 2006-02-09 2006-02-09 Procédé pour produire des carburants de moteur WO2007091912A1 (fr)

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