Method of producing high octane gasoline

 

(57) Abstract:

The invention relates to systems for producing high-octane gasoline low-octane reforming of gasoline fractions. Low-octane gasoline fraction is subjected to reforming in the presence of the oxide aluminoborosilicate catalyst treated with a solution of aluminosiloxane and/or alyumomolibdyenovykh. 3 table.

The invention relates to processes of oil refining industry, namely, to a method of production of high-octane gasoline of low octane gasoline straight-run type of catalytic reforming.

Known methods of production of high-octane gasoline of low octane gasoline catalytic reforming in the presence of a platinum-rhenium and other polymetallic catalysts [1,2,3].

In such ways when reforming of low-octane gasoline in the presence of polymetallic catalysts must be used hanging hydrogen pressure (1.5 to 5.5 MPa), high temperature (763-788 K) and elevated amounts of circulating hydrogen in the system that leads to increased energy consumption.

Developed ways of producing vysokooktanovoe vysokooktanovogo gasoline in the presence of the catalyst [4]. The process is carried out at a temperature of 320-440oC, a pressure of 0.2 to 4.0 MPa and space velocity of the liquid raw material 2.0 hours-1.

The Zeoforming typical low pressure of the reaction mixture, low temperature and high velocity flow of the liquid raw material.

The disadvantage of this method is the increased kokoulina and gas.

Closest to the proposed method is a method of producing high-octane gasoline low-octane reforming of gasoline fractions in the presence of the oxide catalyst, which used a ball silicate treated with a solution of modifier-complexes derived siloxane with metals, namely a solution of Nickel or aluminiumsilicon in acetone or toluene (5). The mixture is stirred and maintained at room temperature for 24 h Then the modified catalyst is separated from the liquid, dried and heated at a temperature 723-773oin a stream of air for 6 hours

The method allows to obtain gasoline with an octane rating of 85.5 p by the motor method.

The disadvantage of this method is the relatively low output you get gasoline.

The technical result ol CLASS="ptx2">

This result is achieved in the proposed method of producing high-octane gasoline low-octane reforming of gasoline fractions in the presence of the oxide aluminoborosilicate catalyst treated aluminosiloxane and/or alyumomolibdyenovykh.

The used catalyst was prepared as follows. Selected free of defects pills industrial aluminoborosilicate catalyst is loaded into a quartz or a metal reactor in the zone of constant temperature. Top and bottom layer of catalyst is placed inert porcelain beads or grains of quartz. The top layer of balls is designed for pre-substance introduced into the reactor, and the bottom layer to dekolirovaniya substances. The catalyst is heated to a temperature of 723 - 773 K in air flow for 6 hours Then the catalyst was cooled down to 60 - 80oC and through the layer of catalyst flow solution of the modifier with a bulk velocity of 0.3 - 1.6 m3/m3h within 1 to 3 hours

As a modifier use aluminometasilicate, aluminosilica or mixtures thereof, preferably in a weight ratio of from 30:70 to 50:50. The modifier is dissolved in benzene, tolowercase catalyst may be implemented in any capacity, including, in the reactor, a barrel in the absence of flow of the solution of the modifier.

In this case, the calcined catalyst is loaded into the container, pour a solution of the modifier and maintain the system within 24-48 h at room temperature. Then the solution is drained, overload the catalyst used in the reactor.

After the above processing, the catalyst is rinsed with an inert gas (N2, CO2within 30-60 min to separate the organic solvent, raising the temperature in the catalyst bed to 473 K.

Upon completion of flushing of the catalyst from the organic solvent include air supply, raise the temperature in the catalyst bed at a rate of 100 - 150oC/h and warm up the modified catalyst at a temperature of 723 - 773 K for 3 to 9 hours, preferably 6 hours

Example 1. Use industrial preformed alumina-cobalt-molybdenum (Al - Co - Mo) catalyst, composition, %: CoO - 4,2, MoO3to 18.6,Al2O3- 76,2, the rest of the mixture. Use modifier-aluminometasilicate having a molecular weight of M = 717; aluminometasilicate is a solid powder, soluble in these solvents.

Catalysate is defecator.

After annealing the obtained catalyst spend reforming a gasoline fraction having an octane number 58 p by the motor method (limits boiling NC - 160oC, density 204= 710 kg/m3the refractive index n2d02400 . The process is carried out for 4 h at a temperature of 440oC and space velocities of 0.6 and 1.25 h-1. The results of the experiments are given in table. 1.

Example 2. Used Al - Co - Mo catalyst according to example 2 is treated with a solution of a modifier, which is used as alumalite phenylsilanes (AMPS). The latter is a powder (M = 4860), soluble in aromatic liquid hydrocarbons and acetone. In this example, use a solution of AMPS in toluene.

The catalyst modified by the method described above. The used catalyst contains, wt%: of 0.25, 1.0 and 2.0 modifier.

After calcination of the catalyst to carry out the reforming of a gasoline fraction having an octane number 58 p by the motor method in the conditions of example 1. The results of the experiments are given in table. 2.

Example 3. The original Al - Co - Vo catalyst according to example 2 is treated with a solution of a modifier, which is used as the mixture was almocabar Katara in toluene.

The catalyst modified by the method described above. The resulting catalyst contains, wt%: of 0.25, 1,0, 2,0 modifier.

After calcination of the catalyst to carry out the reforming of a gasoline fraction having an octane number 58 p by the motor method in the conditions of example 1.

The results of the experiments are shown in table.3.

As can be seen from these tables, the described method allows to obtain high octane gasoline with access to 92.3 wt.%.

The sources of information.

1. Chemistry and technology of fuels and oils, 1981, No. 1, S. 37 - 39.

2. Pat. USA N 3871996.

3. Sulimov, A. D. Catalytic reforming of gasolines. - M.: Chemistry, 1972.

4. Refining and petrochemicals, M. TSNIITENEFTEHIM, 1992, No. 10, S. 14

5. RF patent N 2054027, class C 10 G 35/095, B 01 J 29/06, 1996.

Method of producing high-octane gasoline low-octane reforming of gasoline fractions in the presence of the oxide catalyst, treated with a solution of modifier-complexes derived siloxane with metals, characterized in that the catalyst used allocability the catalyst was treated with a solution of aluminosiloxane and/or alyumomolibdyenovykh.

 

Same patents:

The invention relates to the refining catalysts, in particular catalysts for Hydrotreating of crude oil

The invention relates to catalysts for Hydrotreating and hydrogenation of oil and coke raw material and method of its use

The invention relates to the field of oil refining, in particular to a method of preparation of the catalyst intended for use in the hydrogenation processes for Hydrotreating petroleum fractions

The invention relates to the refining and petrochemical industry, in particular to methods for catalyst conversion (Hydrotreating, hydrogenation and t

FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

FIELD: petroleum processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention provides catalyst for hydrofining of petroleum fractions, which catalyst shows elevated strength and stability upon regeneration. This is achieved supplementing alumina-based carrier with texturing additives selected from alumina and gibbsite thermochemical activation product in amount 5 to 30 wt %. Alumina additive is used with particle size not larger than 15 μm and gibbsite thermochemical activation product with that not larger than 45 μm. As binding agent in catalyst, nitric acid is used at molar ratio to alumina (0.01-0.03):1 and/or aluminum nitrate/ aluminum metal reaction product in amounts 1 to 5% based on alumina. Prior to be impregnated, catalyst is steamed at elevated temperature and impregnation is carried out from aqueous solution of nickel-cobalt-molybdenum-containing complex at pH 1-3.

EFFECT: improved performance characteristics of catalyst.

2 cl, 3 tbl, 10 ex

FIELD: petroleum chemistry.

SUBSTANCE: claimed method includes purification of naphthalene-containing cuts from unsaturated compounds by catalytic polymerization followed by isolation of high purity naphthalene. Polymerization is carried out in presence of aluminum-cobalt-molybdenum catalyst, containing (mass %): cobalt oxide (CoO) 2.0-6.0 and molybdenum trioxide (MoO3) on carrier: Y-Al2O3 under pressure up to 0.6 MPa, at temperature of 180-200°C for 1-10 hours.

EFFECT: increased naphthalene yield.

2 tbl, 5 ex

FIELD: petroleum processing.

SUBSTANCE: object of invention is production of low-sulfur diesel fuels from high sulfur-level hydrocarbon feedstock. Proposed process consists in conversion of straight-run diesel fuel having high sulfur level in presence of preliminarily sulfidized heterogeneous catalyst containing group VIII metal and group VIB metal deposited on alumina characterized by pore volume 0.3-0.7 mL/g, specific surface area 200-350 m2/g, and average pore diameter 9-13 nm. Prior to be sulfidized, catalyst has following components: cobalt compounds in concentration 2.5-7.5% calculated as CoO; molybdenum compounds, 12-25% as MoO3; citric acid derivatives, 15-35% as citric acid; boron compounds, 0.5-3% as B2O3; and alumina, the balance. Process is conducted at 320-370°C, pressure 0.5-10 MPa, feedstock weight rate 0.5-5 h-1, and hydrogen-to-feedstock volume ratio 100-1000.

EFFECT: reduced sulfur level in diesel fuel to less than 50 ppm.

3 cl, 1 tbl, 8 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.

EFFECT: intensified diesel fraction desulfurization.

7 cl, 2 tbl, 13 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for production of low-sulfur motor fuels and methods for preparing such catalysts. Hydrodesulfurization catalyst according to invention is characterized by pore volume 0.3-0.7 mL/g, specific surface 200-350 m2/g, and average pore diameter 9-13 nm and containing following components, wt %: cobalt compounds (calculated as CoO) 2.5-7.5, molybdenum compounds (as MoO3), citric acid 15-35, boron compounds (as B2O3) 0.5-3.0, aluminum oxide - the rest, cobalt, molybdenum, citric acid, and boron optionally being part of complex compound having different stoichiometry. Catalyst is prepared by impregnating catalyst support with impregnation solution obtained by dissolving, in water or aqueous solution, following compounds: citric acid, ammonium paramolybdate (NH4)6Mo7O24·4H2O, at least one cobalt compound, and at least boron compound, addition order and component dissolution conditions being such as to provide formation of complex compounds, whereas concentration of components in solution is selected such that catalyst obtained after drying would contain components in above-indicated concentrations.

EFFECT: maximized activity of desired reactions ensuring production of diesel fuels with sulfur level below 50 ppm.

9 cl, 8 ex

FIELD: chemical industry; other industries; production of the magnetic materials and the catalysts on the basis of ferrites- chromites of cobalt (II).

SUBSTANCE: the invention is pertaining to the method of production of the solid solutions of CoFe2-xCrxO4 composition with the spinel structure and may be used in chemical industry for production of the magnetic materials and the catalysts on the basis of ferrites- chromites of cobalt (II). The method of production of the solid solutions of CoFe2-xCrxO4 composition includes homogenization of the source oxides of cobalt (II), iron (III), chromium(chrome) (III), briquetting and the thermal treatment at the temperature of 800-1000°С. The homogenization is conducted in the presence of the mineralizer, in the capacity of which use the mixture of 0.3-0.5 mass % of potassium chloride and 0.3-0.5 mass % of sodium chloride. The technical result of the invention is reduction of the time of the production process, the decreased power input and the production price.

EFFECT: the invention ensures reduction of the time of the production process, the decreased power input and the production price.

2 ex, 2 tbl

FIELD: petroleum processing catalysts.

SUBSTANCE: invention relates to catalysts for deep processing of hydrocarbon stock and can be employed in petroleum processing and petrochemical industries. Particularly, invention provides catalyst for diesel fraction hydrodesulfurization process, which contains, as active component, oxygen-containing molybdenum and cobalt and/or nickel complex compound at Mo/(Co+Ni) atomic ratio 1.5-2.5 and is characterized by specific surface 100-190 m2/g, pore volume 0.3-0.5 cm3/g, prevailing pore radius 80-120 Å. Catalyst support is constituted by alumina or alumina supplemented with silica or montmorillonite. Described are also catalyst preparation procedure and diesel fraction hydrodesulfurization process.

EFFECT: increased catalytic activity and resistance of catalyst against deactivation in presence of diesel fuel hydrocarbon components and sulfur compound of thiophene and its derivatives series.

8 cl, 1 tbl, 7 ex

FIELD: oil and gas industry.

SUBSTANCE: catalytic reforming system described below includes the following: raw material stream including naphtha and at least one compound containing manganese, which is chosen from the group consisting of manganese cyclopentadienyl tricarbonyl, manganese methylcyclopentadienyl tricarbonyl, manganese dimethylcyclopentadienyl tricarbonyl, manganese trimethylcyclopentadienyl tricarbonyl, manganese tetramethylcyclopentadienyl tricarbonyl, manganese pentamethylcyclopentadienyl tricarbonyl, manganese ethylcyclopentadienyl tricarbonyl, manganese diethylcyclopentadienyl tricarbonyl, manganese propylcyclopentadienyl tricarbonyl, manganese isopropylcyclopentadienyl tricarbonyl, manganese tert- butylcyclopentadienyl tricarbonyl, manganese octylcyclopentadienyl tricarbonyl, manganese dodecyclopentadienyl tricarbonyl, manganese ethylmethylcyclopentadienyl tricarbonyl and manganese indenyl tricarbonyl; and catalyst; at that, catalyst of reforming plant includes the following: substrate; precious metal on substrate; and deposit of free particles of manganese on catalyst, which are formed during decomposition at least of one manganese containing compound which is described above. Method for increasing octane number of mixture of reforming product produced with catalytic reforming plant at oil refinery having the stream of raw product of reforming plant is described; the above method includes the following: addition of catalyst to raw product stream of reforming plant; the above catalyst contains oxidised manganese; as a result, octane number of mixture of the produced reforming product increases relative to octane number of mixture of produced reforming product obtained at oil refinery without any addition of catalyst containing the oxidised manganese; at that, oxidised manganese catalyst is obtained from group of manganese tricarbonyls which are specified above.

EFFECT: increasing catalyst service life or increasing octane number of reforming product stream.

19 cl

FIELD: oil and gas industry.

SUBSTANCE: as an additive to increase the processing depth of hydrocarbon-containing raw materials, in thermocatalytic processes there used is organic salt having the following formula: M(OOC-R)n, or M(SOC-R)n, or M(SSC-R)n, where R means alkyl, aryl, isoalkyl, tert-alkyl, alkylaryl, possibly containing hydroxylic, keto-, amino-, carboxylic, thiocarbamic groups, n 1-3, and M means transition metal from the elements of the Mendeleyev's Classification Table. Also, invention refers to the method for increasing the processing depth of hydrocarbon-containing raw materials, in which the above additive is used.

EFFECT: use of the described invention allows increasing the processing depth of hydrocarbon-containing raw materials in thermocatalytic processes.

14 cl, 8 ex, 12 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining engine fuel in interval of petrol boiling by benzole alkylation. Invention deals with method of obtaining hydrocarbon product in interval of petrol boiling, which has concentration of benzole not more than 1 vol.% and regulated temperature of evaporation, from raw material, which consists of reforming product, with concentration of benzole at least 20 wt %, which includes reforming product alkylation in reactor of alkylation in presence of zeolite catalyst MWW at least in two immobile catalytic layers in mode of single passing in liquid phase by alkylation agent.

EFFECT: high level of benzole and olefin conversion.

10 cl, 10 dwg, 15 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a fluidised-bed reactor and a method of catalytic hydrogenation in the reactor. The fluidised-bed reactor comprises a reactor shell, vertical to the ground, a phase separator located within the top part of the shell, an internal circulation zone, located under the phase separator. The internal circulation zone comprises a cylinder, a tapered diffusion section and a guide support. Both the cylinder and the tapered diffusion section at the bottom of the cylinder are located inside the reactor shell, the guide support is fitted on the shell inner wall at the bottom of the tapered diffusion section. The guide support is an annular protrusion of the reactor inner wall.

EFFECT: invention provides effective hydrogenation resulting in a high quality product, and stable operation of the reactor.

26 cl, 2 dwg, 4 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a Sn(Zr)-γ-Al2O3 support for a gasoline fraction reforming catalyst, wherein the support is prepared by precipitating aluminium nitrate solution with aqueous ammonia solution, with subsequent steps of filtering the suspension and washing the precipitate, peptising the precipitate with an acid and simultaneously adding a modifying additive of Sn(Zr) by liquid-phase formation of a pseudo-sol in the form of spherical granules, followed by washing the spherical granules, drying and heat treatment, wherein a spherical support with a diameter of 1.7±0.1 mm is obtained, which is characterised by monomodal pore size distribution with specific surface area of (265-326) m2/g, pore volume of (0.6-0.68) cm3/g, average pore diameter of (8.0-9.6) nm, bulk density of (0.53-0.59) g/cm3 and mechanical bearing strength (148-205) kg/cm2. The invention also relates to a method of preparing a reforming catalyst by saturating a Sn-γ-Al2O3 support with a solution containing 0.24-0.26 wt % chloroplatinic acid with respect to Pt, or saturating a Zr-γ-Al2O3 support with a solution containing 0.28-0.29 wt % perrhenic acid with respect to Re and 0.24-0.26 wt % chloroplatinic acid with respect to Pt. The invention also relates to a method of reforming gasoline fractions in the presence of catalysts prepared using methods described above.

EFFECT: high activity and selectivity of catalysts when reforming gasoline fractions.

13 cl, 2 tbl, 25 ex

Up!