RU2560161C1 - Support, method of preparing same (versions), method of preparing reforming catalyst (versions) and method of reforming gasoline fractions - Google Patents

Abstract

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

Description

The invention relates to a method for producing a carrier and, on its basis, gasoline reforming catalysts and aromatic compounds production. The process of catalytic reforming of gasoline fractions is one of the basic processes of oil refining, providing efficient production of motor fuels.

The catalytic reforming process is carried out in the presence of bifunctional catalysts combining the hydrogenation / dehydrogenation function with the isomerizing one. As catalysts for this process, heterogeneous systems are used containing platinum, which is usually deposited on alumina; accordingly, platinum provides a hydrogenating / dehydrogenating function, and alumina provides isomerization of naphthenic rings, hydrocracking of paraffins and partial isomerization of low molecular weight paraffins and olefins.

The level of process technology, its technical and economic efficiency, largely determine the efficiency of oil refining as a whole. Therefore, the development of highly efficient catalysts used in the reforming process with a moving catalyst bed - RDS, is given increased attention; however, for the RDS process, it is necessary to use a catalyst, and hence a carrier in the form of spherical granules with a certain mechanical strength.

Analysis of Patent Sources [US 4,588,495, 1986; US 4,722,780, 1988; RU 2155792, 2000; RU 2161638, 2001; US2003136708, 2003; CN 1393513, 2003; CN 1393514, 2003; CN 1611575, 2005; RU 2280663, 2006; US 7456130, 2008] shows that alumina predominantly in the form of γ-Al ₂ O ₃ or a mixture of γ and η-Al ₂ O _{3 is} widely used as a carrier of reforming catalysts. In some cases, the initial precursor is aluminum hydroxide, which is mixed with an acid (nitric, acetic, citric), taken in a certain ratio, with subsequent stages of molding, drying and calcination to obtain γ-Al ₂ O ₃ [CN 1160747, 1997]. Particular attention is paid to the specific surface area of aluminum oxide and the pore size distribution: it is shown [CN 101293208, 2008] that when using aluminum oxide as a carrier, the specific surface of which is 210-250 m ² / g, the pore volume is 0.50- 0.55 cm ³ / g, and the proportion of pores with a radius of less than 2 nm is 2-5%, the proportion of pores with a radius of 2 to 5 nm is 90-94%, the proportion of pores with a radius of 5 to 10 nm is 3 -6% and the proportion of pores with a radius of more than 10 nm - 0.1-1% of the total pore volume, get an active and selective catalyst for the reforming of naphtha.

It is known that special requirements are imposed on the chemical composition of alumina intended for the synthesis of reforming catalysts, while the sodium content is of great importance, which affects not only thermal stability, but also surface acidity, in addition, it is a “poison” for noble metals deposited on the surface of alumina in the preparation of reforming catalysts.

Aluminum oxides produced by Russian manufacturers using the “aluminate” or “sulfate” technology contain a significant amount of impurities, mainly sodium and sulfate ions, the presence of which significantly reduces the activity of most reforming catalysts obtained on its basis. Therefore, a new modification of high-purity alumina is needed, the production of which is absent in Russia.

Active alumina in the form of a γ-form is obtained, as a rule, by thermal decomposition of aluminum hydroxide of a pseudoboehmite structure (AlOOH × nH ₂ O) at a temperature of 500-600 ° C, characterized by a high specific surface area (250-380) m ² / g, relative to a large pore volume (0.6-0.9) cm ³ / g and high thermal stability.

It is known [SU 852798, C01F 7/34; CN 101332997, С01В 3/08], that high-purity alumina is obtained by the sol-gel method using aluminum alcoholates as initial precursors; The synthesis of aluminum hydroxide involves the following stages: hydrolysis of aluminum alcoholate, condensation and the formation of monomers, dimers and oligomers. The properties of the precipitate can be controlled by the ratio of water to alkoxide [Gonzalez RD, Lopez T., Gomez R. Sol-Gel preparation of supported metal catalysts. // Catalysis Today, 1997. V. 35, No. 3, P.293; CN 1419961, B01J 19/30, 2003; CN 1807246, B01J 21/04, 2006], changing the specific surface area from 250 to 500 m ² / g while reducing the pore diameter from 15 to 9 nm, forming a monomodal pore size distribution. The disadvantages of the method based on the hydrolysis of alkoxides include the specificity of the feedstock, the need to prevent contact with the environment and the need to strictly comply with the water / alkoxide ratio and the use of special equipment; in addition, the resulting hydroxide and alumina has a higher cost compared to the precipitation of solutions of aluminum salts {Al (NO ₃ ) ₃ , AlCl ₃ , Al (SO ₄ ), NaAlO ₂ } with an aqueous solution of the precipitator {NH ₄ OH, NaOH, KOH , HNO ₃ }. Shown [Dzisko VL., Ivanova A.S. The main methods for producing active alumina. // Izv. SB USSR Academy of Sciences, Ser. Chem. sciences. 1985. No.15, no. 5, p. 110], that by changing the pH, the deposition temperature, and the duration of “aging” (keeping the suspension under given conditions), one can vary the phase composition and texture characteristics of the obtained hydroxide and aluminum oxide.

The chemical purity of the obtained hydroxide and alumina depends on the nature of the initial precursors, and the most suitable are aluminum nitrate and aqueous ammonia, namely: Al (NO ₃ ) ₃ + 3NH ₄ OH → AlOOH ↓ + 3NH ₄ NO ₃ . Depending on the deposition conditions, the resulting precipitate may be pure pseudoboehmite - AlOOH × nH ₂ O, the thermal treatment of which at a temperature of 500-600 ° C promotes the formation of γ-Al ₂ O ₃ .

Alumina is used mainly in the form of extrudates of different sizes, however, in [SU 1594874, C01F 7/02] it is shown that aluminum hydroxide obtained by aluminate technology and stabilized at a pH of 8.5-8.9 can be formed by the hydrocarbon-ammonia method in the form of granules of a spherical shape, but there is no information about the presence of impurities, in particular sodium, and texture characteristics. According to [SU 1653294, C01F 7/02], alumina in the form of spherical granules is obtained by peptization of aluminum hydroxide with a moisture content of 78-83 wt. % acid with an acid module M _k = 0.06-0.09 mol of acid per 1 mol of Al ₂ O ₃ in the presence of 10-40% triethylene glycol; the resulting pseudo sol is formed by the hydrocarbon-ammonia method with subsequent stages of drying and calcination. However, in this case, there are no data on the texture and strength characteristics of the oxide; in addition, taking into account the fact that the carrier is intended for a moving layer, and the presence of 10-40% triethylene glycol at the synthesis stage can lead to the formation of large pores, the presence of which can adversely affect the strength of the obtained granules.

In turn, according to [V. B. Maryshev, B.V. Krasius. Modern domestic reforming catalysts for gasoline fractions. // Petrochemicals, 2007, T. 47, No. 4, P. 289-295], alumina obtained by the alcoholate technology and molded in the form of a ball with a diameter of 1.6-1.8 mm, in which the total content of impurities (Na, Ca, Fe, S, C) does not exceed 0.01 wt. %, and the specific surface area is 180-220 m ² / g, the pore volume is ≥0.55 cm ³ / g, with a predominant pore diameter of 7.6-11.0 nm, it turned out to be a suitable carrier for the preparation of a platinum-rhenium reforming catalyst with a fixed catalyst bed: the use of such a carrier has improved the strength, activity, selectivity and stability of the catalyst.

Recent generations of reforming catalysts are distinguished by the fact that, along with platinum, compounds of other metals, such as rhenium, iridium, gallium, germanium, tin, as well as chlorine or fluorine additives, are introduced into the system to modify its catalytic properties. Such catalysts are characterized by high stability and high selectivity of the aromatization process of paraffin hydrocarbons.

One approach to modifying the tin-alumina is treated support stannous salt with a mixture of hydrochloric and acetic acids, to obtain the surface atsetatohlorida tin composition: Al ₂₀ O _30-x (SnA _qn Cl _m) p where Ac - acetate ion, x = 1 -2, n = 1-3, m = 1-3, p = 0.01-0.05 [SU 1785124, B01J 23/62; C10G 35/085, 01/20/1995]. Modification of alumina, for example, with zirconium, is carried out by mixing pseudoboehmite structured aluminum hydroxide washed from impurities of iron and sodium (up to 0.02 wt.%) With an aqueous solution of monosulfatozirconic acid HZrO (SO ₄ ) OH containing organic components (formic, acetic, oxalic and citric acid), followed by drying, molding and calcining; the obtained reforming catalyst support is a dehydrated aluminum monosulfate zirconate with the general formula Al ₂ O ₃ · [ZrO (SO ₄ )] x with a stoichiometric coefficient x from 0.45 · 10 ^-2 to 9.7 · 10 ^-2 and a true density of less than 3.3 ± 0 , 01 g / cm ³ [RU 2289475, B01J 23/656; C10G 35/09, 12.20.2006].

Closest to the proposed technical solution and taken as a prototype is a method of obtaining a carrier of a reforming catalyst Pt / Sn-Al ₂ O ₃ [US 5665223, B01J 23/63; Cl0G 35/09; 09/09/1997] containing 0.38 wt. % Pt and 0.30 wt. % Sn, based on the production of spherical granules by drop-drop coagulation ("oil drop") molding of an aluminum hydrosol synthesized by the interaction of aluminum hydroxide prepared by the alcoholate technology with hydrochloric acid (HCl) and containing the required amount of tin. The hydrosol is dosed in an oil bath at a certain temperature, from which spherical granules enter an aqueous solution of ammonia, then they are washed and dried at a temperature of 120-150 ° C for 18-20 hours. The prepared granules are treated with steam with a humidity of 10% at a temperature of 650 ° C for 3-5 hours. The resulting carrier is γ-Al ₂ O ₃ , characterized by a specific surface of 185-235 m ² / g; pore volume 0.3-0.8 cm ³ / g; bulk density of 0.6-1.0 g / cm ³ .

The Pt / Sn-Al ₂ O ₃ reforming catalyst is prepared by impregnating a spherical support with a solution of platinum chloride in HCl, followed by drying and oxychlorination at 525 ° C with 2M HCl in air and reducing with pure hydrogen at 565 ° C. The resulting catalyst has a composition, wt. %: 0.38% Pt, 0.30 Sn, alumina - the rest.

The activity and selectivity of the catalyst was determined in naphtha reforming under the following conditions: pressure - 0.8 MPa, bulk feed rate - 3 h ^-1 , H ₂ / feed ratio = 8; naphtha conversion was determined at temperatures of 502, 512, 522 and 532 ° C; selectivity - according to the yield of stable C ₅₊ reformate depending on the aromatic content. According to the data obtained, the indicated naphtha reforming catalyst is characterized by the following catalytic properties:

The disadvantage of this method of obtaining a reforming catalyst carrier is that, firstly, its synthesis based on hydrolysis of alkoxides is expensive, and secondly, in the synthesis of aluminum hydroxide, it is necessary to prevent contact with the environment and strictly observe the water / alkoxide ratio. Therefore, the synthesis of aluminum hydroxide is more promising, based on the precipitation of a solution of aluminum nitrate with an aqueous solution of ammonia, i.e. on nitrate-ammonia technology.

The objective of the invention is to develop a granular spherical carrier based on alumina, characterized by high chemical purity, a certain texture and mechanical strength, and a reforming catalyst based on it, which is platinum (platinum-rhenium) deposited on a spherical carrier, providing:

- on model raw materials (n-heptane) at a pressure in the reactor of 1.0 ± 0.2 MPa: reformate yield 82-86 wt. %, hydrogen yield 1.6-2.0 wt. %, RTI of reformate 67-70;

- on real raw materials at a pressure in the reactor of 1.0 (1.5) MPa: reformate yield 86-92 wt. %, hydrogen yield 3-4 wt. %, RTI of the reformate 100-102 (96-100).

To solve this problem, a method for producing a spherical aluminum-containing support Sn (Zr) -Al ₂ O ₃ containing 0.16 ÷ 0.18 wt. % Sn or 0.45 ÷ 0.55 wt. % Zr, the reforming catalyst, which is prepared by precipitation of aluminum nitrate solution with an aqueous ammonia solution under certain pH and temperature with subsequent filtration steps suspension and washing the precipitate, its acid peptization by acid module (M _k), equal to 0.085 ÷ 0.12, the liquid phase forming pseudo-sol in the form of spherical granules by dosing it into a layer of kerosene, using a layer of an aqueous solution of ammonia as a “hardener”, followed by washing of the spherical granules and drying first in air and then dried cabinet at 120 ± 20 ° C for 14 ± 2 hours and heat treatment at 600 ± 20 ° C for 4.5 ± 0.5 hours in a stream of dried air, in this case receive a spherical carrier with a diameter of 1.6-1, 7 mm, which is γ-Al ₂ O ₃ , characterized by high chemical purity (the content of Na ₂ O and Fe ₂ O ₃ does not exceed 0.003 wt.%), A monomodal pore size distribution, with a specific surface area equal to (265 ÷ 326) m ² / g, pore volume - (0.60 ÷ 0.88) cm ³ / g, average pore diameter - (8.0 ÷ 9.6) nm, bulk density - (0.53 ÷ 0.59 ) g / cm ³ and mechanical crushing strength - (148 ÷ 205) kg / cm ² .

The problem is also solved by the method of forming a pseudo-sol of aluminum hydroxide obtained by peptization of aluminum hydroxide in the presence of acetic or nitric acid with MK - [HNO ₃ ] / [Al ₂ O ₃ ] or [CH ₃ COOH] / [Al ₂ O ₃ ] equal to 0.085 ÷ 0.12.

The problem is also solved by the method of introducing modifying additives (tin or zirconium) at the stage of peptization of aluminum hydroxide in the form of salts, which are either tin acetate (zirconyl) or tin chloride (zirconyl). The resulting carrier is γ-Al ₂ O ₃ and is characterized by a monomodal pore size distribution with a specific surface area of (295 ÷ 309) m ² / g, a pore volume of (0.68 ÷ 0.88) cm ³ / g, and an average diameter then - (8.8 ÷ 11.4) nm, bulk density - (0.28 ÷ 0.53) g / cm ³ and mechanical crushing strength - (40 ÷ 161) kg / cm ² .

The problem is also solved by the method of introducing modifying additives (tin or zirconium) by impregnating the dried spherical granules of aluminum hydroxide with a solution of salts containing either tin acetate (zirconyl) or tin chloride (zirconyl). The resulting carrier is a γ-Al ₂ O _3, characterized by a monomodal pore size distribution with a specific surface area equal to (265 ÷ 326) m ² / g, a pore volume - (0,60 ÷ 0,66) cm ³ / g, the average pore diameter is (8.0 ÷ 9.6) nm, bulk density is (0.54 ÷ 0.59) g / cm ³ and the mechanical crushing strength is (169 ÷ 205) kg / cm ² .

The problem is also solved by the method of applying the active component (platinum or platinum and rhenium) by impregnating a carrier modified with either tin or zirconium, followed by drying stages at 120 ° C and heat treatment at 500 ° C for 2-3 hours. Catalyst samples, modified with tin, then were reduced in a stream of hydrogen at 500 ° C, and catalyst samples modified with zirconium were additionally sulphurized.

The problem is also solved by the method of reforming model raw materials (n-heptane), carried out in the presence of the catalyst described above at a pressure of 1.0 ± 0.2 MPa, in the temperature range 460-520 ° C, a volumetric feed rate of raw materials (ISPS) equal to 8- 14 h ^-1, against h ₂ / n-heptane = 5 mol / mol.

The problem is also solved by the method of reforming real raw materials, carried out in the presence of the tin-containing (zirconium-containing) catalyst described above at a pressure of 1.0-1.5 MPa, in the temperature range 460-520 ° C, a volumetric feed rate of raw materials (ISPS) equal to 1.3 -1.5 h ^-1 , and the multiplicity of circulation of the WASH = 1000-1400 nl / l of raw material.

Distinctive features of the proposed carrier, a catalyst based on it and the method of their preparation are:

1. The method of obtaining media Sn (Zr) -Al ₂ O ₃ containing 0.16 ÷ 0.18 wt. % Sn or 0.45 ÷ 0.55 wt. % Zr, including the precipitation of a solution of aluminum nitrate with an aqueous solution of ammonia at pH 7 ± 0.2 and a temperature of (70 ± 2) ° C with subsequent stages of filtering the suspension and washing the precipitate, peptizing it with acid, liquid-phase molding of a pseudo-sol in the form of spherical granules, drying them and heat treatment.

2. A method of obtaining a carrier, including liquid-phase molding of spherical granules by a hydrocarbon-ammonia method with subsequent stages of drying and calcination.

3. The method of introducing modifying additives (tin or zirconium) by impregnating the dried spherical granules of aluminum hydroxide with a solution of salts containing either tin acetate (zirconium) or tin chloride (zirconyl).

4. The method of heat treatment of the carrier at a temperature of 600 ± 20 ° C for 4.5 ± 0.5 hours in a stream of dried air.

5. The method of applying the active component (platinum or platinum and rhenium) by circulating the impregnation of a carrier modified with either tin or zirconium, followed by drying and heat treatment at 500 ° C for 2-3 hours, followed by reduction in a stream of hydrogen at 500 ° C, and catalyst samples modified with zirconium, additional sulfurization.

6. The method of reforming n-heptane at a pressure of 1.0 ± 0.2 MPa, in the temperature range 460-520 ° C, a volumetric feed rate (ISPS) of 8-14 h ^-1 , and the ratio of H ₂ / n- heptane = 5 mol / mol.

7. The method of reforming real raw materials, carried out in the presence of a tin-containing (zirconium-containing) catalyst at a pressure of 1.0-1.5 MPa, in the temperature range 460-520 ° C, a volumetric feed rate (OSPS) of 1.3-1, 5 h ^-1 , and the multiplicity of circulation of the VSG = 1000-1400 nl / l of raw material.

The main characteristics of the resulting carrier based on alumina determine:

- chemical composition by inductively coupled plasma atomic emission spectroscopy (ICP AES) [1] on an ISP spectrometer. The method is based on the atomization processes of the molecules of the analyte in a high-temperature plasma, the excitation of the formed atoms and the emission of light by the excited atoms. The amount of light emitted is proportional to the concentration of the element being determined, which allows quantitative analysis of the substance;

- precipitation moisture was calculated according to the loss during calcination, which was determined by the ratio of the mass difference between the initial precipitate and the sample calcined at 800 ° C for 4 hours to the initial sample;

- phase composition on a HZG-4C diffractometer (Germany) in monochromatic radiation CuK _α (λ = 1.5418 Å) in the range of angles from 10 to 75 ° (in 2θ) with a scan step of τ = 0.05 degree 2θ and an accumulation time of 5 s in every point. Phase analysis is carried out according to the PCW.2.4 program by comparing experimental diffraction patterns and theoretically calculated on the basis of known structures taken from the ICDS structural database taking into account the profile of diffraction lines;

- textural characteristics (size S _ud, a pore volume - V _n, the average pore diameter - d _thresh and pore size distribution) by low-temperature (-196 ° C) nitrogen adsorption at installation ASAP-2400 Micromeritics; preliminarily, the samples are trained in vacuum at 150 ° C;

- bulk weight of the samples by determining the mass of the catalyst layer, occupying a certain volume. A test sample of a fraction of 0.25-0.50 mm is poured into a cylinder with a known mass to a certain volume and the densest packing is achieved. Bulk weight - ρ (g / cm ³ ) is calculated by the formula: ρ = m / v, where m is the mass of the sample, g; v is the sample volume, cm ³ . The arithmetic average of two parallel determinations, the discrepancy of which does not exceed 1.5% of the arithmetic average, was taken as the test result; the measurement error is ± 3%;

- the mechanical strength of the samples of the carrier for crushing was determined on the device brand MP-9C. The essence of the method for determining the mechanical strength of samples is to measure the force exerted to break a granule placed between two parallel planes. The mechanical strength of the samples was estimated by the value of the breaking force applied to crush the ball (kgf), referred to the unit surface of the granule (cm ² ). Strength (kgf / cm ² ) was calculated by the formula: P = (N × a) / S, where N is the indicator reading, kgf; a is a calibration coefficient, S is the cross-sectional area of the granule, cm ² .

Testing of the catalysts in the reforming reaction on model raw materials (n-heptane) is carried out by the flow method with a microcatalytic integrated reactor. The activity criterion for the gasoline variant is the dependence of the reformate octane (MI, research method) on the process temperature; The selectivity criterion is the dependence of the yield of stable reformate on the octane number. An additional criterion characterizing the activity and selectivity of the catalyst is the yield of hydrogen. Test samples of the catalyst are loaded into a tubular reactor; the volume of the catalyst is 1 to 3 cm ³ depending on the bulk density; fractions 0.2-0.4 mm. Testing is carried out at a pressure of 1.0 ± 0.2 MPa, in the temperature range 460-520 ° C, a volumetric feed rate (ISPS) of 8-14 h ^-1 , and the ratio of H ₂ / n-heptane = 5 mol / the mole.

Testing of the catalysts in the reforming reaction on real raw materials (hydrogenated fr. 100-180 ° С OAO Gazpromneft-Omsk Oil Refinery) is carried out on a mini-pilot installation that provides testing of the catalysts at a pressure of up to 3.0 MPa with recirculation of hydrogen-containing gas (VGS) under conditions as close as possible to industrial tests (conditions). The criterion for the activity of the catalysts is the temperature at which the required process stiffness is achieved (the target process with a moving catalyst bed is the octane number of the reformate 100-102 according to the research method, and the process with periodic regeneration is 96-100). The selectivity criterion is the yield of stable reformate (wt.% For raw materials) at a given process rigidity; an additional criterion for selectivity is the yield of hydrogen.

The essence of the invention is illustrated by the following examples, showing a change in the chemical composition, texture characteristics, bulk density and mechanical strength of the carrier depending on the alumina content in the pseudozole, on the acid module, on the nature, composition and method of introducing the modifying additive into alumina. The main characteristics of the media are shown in table 1.

The essence of the invention is illustrated by the following examples, showing the change in activity and selectivity (octane according to the research method; yield of stable reformate and hydrogen) depending on the composition of the catalysts, the method of their preparation, the method of reforming on model and real raw materials. The main characteristics of the catalysts and their catalytic properties are shown in table 2.

Examples 1-12 illustrate a method for the preparation of carriers, the nature of the modifying additive and its precursor, the method of its introduction into alumina.

Examples 13-22 illustrate the catalytic properties of catalysts that differ in the nature of the modifying additive and its precursor, the method of its introduction into alumina, in the reforming reaction of model raw materials (n-heptane), which is carried out at a pressure of 1.0 MPa, in the temperature range 460-520 ° C, a volumetric feed rate (ISPS) of 8-14 h ^-1 and a ratio of H ₂ / n-heptane = 5 mol / mol.

Examples 23-24 illustrate the catalytic properties of the catalysts, differing in the nature of the modifying additive, in the reforming reaction of real raw materials (hydrogenated fr. 100-180 ° C), which is carried out at a pressure of 1.0 MPa, in the temperature range 460-520 ° C, space velocity supply of raw materials (ISPS), equal to 1.5 h ^-1 , and the circulation rate of the WASH = 1000 nl / l of raw material.

Example 25 illustrates the catalytic properties of the catalyst in the reforming reaction of real raw materials (hydrogenated fr. 100-180 ° C), which is carried out at a pressure of 1.5 MPa, in the temperature range 460-520 ° C, the volumetric feed rate of raw materials (ISPS) equal to 1 , 3 h ^-1 , and the multiplicity of circulation of the WASH = 1400 nl / l of raw material.

Example 1

200 ml of distilled water are poured into the reactor, placed in a thermostat, a pH meter is installed and heating of the reactor and stirrer are turned on; when the temperature reaches 70 ° C, a solution of aluminum nitrate containing 40 g of Al ₂ O _{3 is} metered into the reactor at a rate of 25 ml / min, while 360 ml of an aqueous solution of NH ₄ OH is added to maintain the precipitation pH of 7.0 ± 0.2. The resulting suspension is filtered and washed with distilled water. The washed precipitate is peptized in the presence of acetic acid at MK = 0.12, adding 0.044 g of Sn in the form of a tin acetate solution, followed by molding of the obtained pseudo-sol by the liquid-phase method in the form of spherical granules by dosing it into a layer of kerosene, using an aqueous solution layer as a “hardener” ammonia, followed by washing the spherical granules and drying first in air and then in an oven at 120 ± 20 ° C for 14 ± 2 hours and heat treatment at 600 ± 20 ° C for 4.5 ± 0.5 hours in flow of dried air, while receiving spherical carrier Sn-Al ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm.

Example 2

Similar to example 1, the difference is that the washed precipitate is peptized in the presence of nitric acid at MK = 0.09, adding 0.06 g of Sn in the form of 0.11 g of SnCl ₂ * 2H ₂ O salt, whereby a spherical support Sn -Al ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm.

Example 3

200 ml of distilled water are poured into the reactor, placed in a thermostat, a pH meter is installed and heating of the reactor and stirrer are turned on; when the temperature reaches 70 ° C, a solution of aluminum nitrate containing 40 g of Al ₂ O _{3 is} metered into the reactor at a rate of 25 ml / min, while 360 ml of an aqueous solution of NH ₄ OH is added to maintain the precipitation pH of 7.0 ± 0.2. The resulting suspension is filtered and washed with distilled water. The washed precipitate is peptized in the presence of nitric acid at MK = 0.09, followed by molding of the obtained pseudo sol by the liquid-phase method in the form of spherical granules by dosing it into a kerosene layer, using a layer of an aqueous ammonia solution as a “hardener”, followed by washing of the spherical granules and drying first in air and then in an oven at 120 ± 20 ° C for 14 ± 2 hours

A portion of the dried spherical granules of aluminum hydroxide - AlOOH * nH ₂ O, equal to 10 g, is soaked in moisture capacity with a solution of tin acetate containing 0.0159 g of Sn (CH ₃ COO) ₂ , dried at 120 ± 20 ° C for 14 ± 2 h and calcined at 600 ± 20 ° C for 4.5 ± 0.5 hours in a stream of dried air, thereby obtaining a spherical carrier Sn-Al ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm

Example 4

Similar to example 3, the difference is that the washed precipitate is peptized in the presence of nitric acid at MK = 0.10, and a spherical support Sn-Al ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm is obtained.

Example 5

Similar to example 3, the difference is that the washed precipitate is peptized in the presence of nitric acid at MK = 0.085.

A portion of the dried spherical granules of aluminum hydroxide - AlOOH * nH ₂ O, equal to 10 g, is impregnated by moisture capacity with a solution of tin chloride containing 0.028 g of SnCl ₂ * 2H ₂ O, whereby a spherical support Sn-Al ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm

Example 6

Similar to example 3, the difference is that the washed precipitate is peptized in the presence of nitric acid at MK = 0.085.

A portion of the dried spherical granules of aluminum hydroxide - AlOOH * nH ₂ O, equal to 10 g, is impregnated by moisture capacity with a solution of tin chloride containing 0.032 g of SnCl ₂ * 2H ₂ O, whereby a spherical support S11-Al ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm

Example 7

200 ml of distilled water are poured into the reactor, placed in a thermostat, a pH meter is installed and heating of the reactor and stirrer are turned on; when the temperature reaches 70 ° C, a solution of aluminum nitrate containing 40 g of Al ₂ O _{3 is} metered into the reactor at a rate of 25 ml / min, while 360 ml of an aqueous solution of NH ₄ OH are added to maintain the precipitation pH of 7. ± 00.2. The resulting suspension is filtered and washed with distilled water. The washed precipitate is peptized in the presence of acetic acid at MK = 0.12, adding 0.128 g of Zr in the form of a solution of zirconium acetate; the resulting pseudo-sol is molded by liquid-phase method in the form of spherical granules by dosing it into a kerosene layer, using a layer of an aqueous solution of ammonia as a “hardener”, followed by washing the spherical granules and drying first in air and then in an oven at 120 ± 20 ° C in for 14 ± 2 hours and heat treatment at 600 ± 20 ° C for 4.5 ± 0.5 hours in a stream of dried air, whereby a spherical carrier Zr-Al ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm is obtained.

Example 8

Similar to example 7, the difference is that the washed precipitate is peptized in the presence of nitric acid at MK = 0.09, adding 0.169 g of Zr in the form of 0.60 g of ZrOCl ₂ * 8H ₂ O salt, whereby a spherical Zr-Al carrier is obtained ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm.

Example 9

200 ml of distilled water are poured into the reactor, placed in a thermostat, a pH meter is installed and heating of the reactor and stirrer are turned on; when the temperature reaches 70 ° C, a solution of aluminum nitrate containing 40 g of Al ₂ O _{3 is} metered into the reactor at a rate of 25 ml / min, while 360 ml of an aqueous solution of NH ₄ OH is added to maintain the precipitation pH of 7.0 ± 0.2. The resulting suspension is filtered and washed with distilled water. The washed precipitate is peptized in the presence of nitric acid at MK = 0.09; the resulting pseudo-sol is molded by liquid-phase method in the form of spherical granules by dosing it into a kerosene layer, using a layer of an aqueous solution of ammonia as a “hardener”, followed by washing the spherical granules and drying first in air and then in an oven at 120 ± 20 ° C in within 14 ± 2 hours

A portion of the dried pellets aluminum hydroxide - AlOOH * nH ₂ O, of 10 g, was impregnated by incipient wetness with a solution of zirconium acetate containing 0.133 g of ZrO (CH ₃ COO) _2, dried at 120 ± 20 ° C for 14 ± 2 hours and calcined at 600 ± 20 ° C for 4.5 ± 0.5 hours in a stream of dried air, whereby a spherical support Zr-Al ₂ O _{3 with a} diameter of 1.7 ± 0.1 mm is obtained.

Example 10

Similar to example 9, the difference is that the washed precipitate is peptized in the presence of nitric acid at MK = 0.10.

A portion of the dried spherical granules of aluminum hydroxide - AlOOH * nH ₂ O, equal to 10 g, is impregnated by moisture capacity with a solution of zirconium acetate containing 0.114 g of ZrO (CH ₃ COO) ₂ , whereby a spherical support Zr-Al ₂ O _{3 with a} diameter of 1.7 is obtained ± 0.1 mm.

Example 11

Similar to example 9, the difference is that the washed precipitate is peptized in the presence of nitric acid at MK = 0.085.

A portion of the dried spherical granules of aluminum hydroxide - AlOOH * nH ₂ O, equal to 10 g, is impregnated by moisture capacity with a solution of zirconyl chloride containing 0.16 g of ZrOCl ₂ * 8H ₂ O, whereby a spherical support Zr-Al ₂ O _{3 with a} diameter of 1 is obtained, 7 ± 0.1 mm.

Example 12

Similar to example 9, the difference is that the washed precipitate is peptized in the presence of nitric acid at MK = 0.10.

A portion of the dried spherical granules of aluminum hydroxide - AlOOH * nH ₂ O, equal to 10 g, is impregnated by moisture capacity with a solution of zirconyl chloride containing 0.16 g of ZrOCl ₂ * 8H ₂ O, whereby a spherical support Zr-Al ₂ O _{3 with a} diameter of 1 is obtained, 7 ± 0.1 mm.

The characteristics of the obtained aluminum-containing supports Sn-Al ₂ O ₃ and Zr-Al ₂ O ₃ are shown in table 1.

Example 13

On a weighed support of the Sn-Al ₂ O ₃ support obtained in Example 2, equal to 10 g, 0.25 g of Pt from platinum hydrochloric acid solution is applied by impregnation, followed by drying and heat treatment at 500 ± 20 ° C for 2-3 hours followed by reduction in a stream of hydrogen at 500 ± 20 ° C ° C, while receiving a catalyst RDS-1 composition: 0.25 wt. % Pt / Sn-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 14

Similar to example 13, the difference is that as the carrier use the composition Sn-Al ₂ O ₃ obtained in example 3. Get the catalyst RDS-2 composition: 0.25 wt. % Pt / Sn-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 15

Similar to example 13, the difference is that as the carrier use the composition Sn-Al ₂ O ₃ obtained in example 4. Get the catalyst RDS-3 composition: 0.25 wt. % Pt / Sn-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 16

Similar to example 13, the difference is that as the carrier use the composition Sn-Al ₂ O ₃ obtained in example 5. Get the catalyst RDS-4 composition: 0.24 wt. % Pt / Sn-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 17

Similar to example 13, the difference is that the composition used is Sn-Al ₂ O ₃ , obtained according to example 6. Get RDS-5 catalyst composition: 0.25 wt. % Pt / Sn-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 18

On a sample of carrier Zr-Al ₂ O ₃ obtained in Example 8, equal to 10 g, are applied by impregnation circulation Re 0.29 g of perrhenic acid solution and 0.26 g of Pt solution of chloroplatinic acid followed by drying steps and heat treatment at 500 ± 20 ° C for 2-3 hours, followed by reduction in a stream of hydrogen at 500 ± 20 ° C ° C and sulphurization, whereby an RDS-6 catalyst of the composition is obtained: (0.29 wt.% Re - 0.26 wt. .% Pt) Zr-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 19

Similar to example 18, the difference is that the Zr-Al ₂ O ₃ composition obtained in example 9 is used as the carrier. The RDS-7 catalyst is obtained with the composition: (0.29 wt.% Re - 0.26 wt.% Pt ) Zr-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 20

Similar to example 18, the difference is that the composition used is the Zr-Al ₂ O ₃ composition obtained in example 10. A RDS-8 catalyst is obtained with the composition: (0.28 wt.% Re - 0.26 wt.% Pt ) Zr-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 21

Similar to example 18, the difference is that the Zr-Al ₂ O ₃ composition obtained in example 11 is used as the carrier. The RDS-9 catalyst is obtained with the composition: (0.28 wt.% Re - 0.25 wt.% Pt ) Zr-Al ₂ O ₃ , the catalytic properties of which in the reforming of n-heptane are shown in table 2.

Example 22

Similar to example 18, the difference is that the composition used is the Zr-Al ₂ O ₃ composition obtained in example 12. A RDS-10 catalyst is obtained with the composition: (0.29 wt.% Re - 0.25 wt.% Pt ) / Zr-Al ₂ O ₃ , the catalytic properties of which in n-heptane reforming are shown in Table 2.

Example 23

Similar to example 15, the difference lies in the fact that testing the catalyst RDS-3 in the reforming reaction of hydrogenation of FR. 100-180 ° C OAO Gazpromneft - Omsk Oil Refinery is carried out at a pressure of 1.0 MPa, a volumetric feed rate (ISPS) of 1.5 h ^-1 , and a circulation rate of Wash = 1000 nl / l of feedstock. The catalytic properties of the catalyst RDS-3 are shown in table 2.

Example 24

Similar to example 23, the difference is that they test the catalyst RDS-5 in the reforming reaction of hydrogenation of FR. 100-180 ° C. The catalytic properties of the catalyst RDS-5 are shown in table 2.

Example 25

Similar to example 20, the difference is that testing the catalyst RDS-8 in the reforming reaction of hydrogenation of FR. 100-180 ° C is carried out at a pressure of 1.5 MPa, a volumetric feed rate (ISPS) of 1.3 h ^-1 , and a circulation rate of VSG = 1400 nl / l of raw material. The catalytic properties of the catalyst RDS-3 are shown in table 2.

As can be seen from the above examples No. 1 ÷ 12 (table 1), the proposed media provide high chemical purity, phase composition and texture characteristics. It should be noted that the proposed media are primarily intended for reforming catalysts with a moving bed (RDS) of the catalyst, which are subject to increased requirements regarding their mechanical strength. An analysis of the data in Table 1 shows that the aluminum-containing carriers obtained by peptization of aluminum hydroxide in the presence of acetic acid are characterized by low mechanical strength and a rather low bulk density (table 1, examples No. 1, 7), therefore, they cannot be used for the synthesis of reforming catalysts RDS. All other proposed carriers are characterized by bulk density equal to (0.53 ÷ 0.59) g / cm ³ and high mechanical strength - (148 ÷ 205) kg / cm ² , respectively, they can be used for the preparation of reforming catalysts.

According to the examples No. 13 ÷ 22 (table 2), the proposed catalysts RDS-1 ÷ RDS-10, obtained using the above-mentioned carriers based on modified alumina, provide efficient reforming of n-heptane: with an IOC equal to 67.2 ÷ 70 , 1, the yield of stable C ₅₊ reformate and hydrogen is 88.8 ÷ 90.0 wt. % and 1.6 ÷ 1.7 wt. % respectively on catalysts Pt / Sn-Al ₂ O ₃ and 76.0 ÷ 80.0 wt. % and 1.5 ÷ 1.6 wt. % respectively on Pt-Re / Zr-Al ₂ O ₃ catalysts, i.e. in the severe mode of the reforming process (IOC = 67.2 ÷ 70.1), reflecting the actual industrial conditions, high activity and selectivity of the catalysts is ensured.

Testing reforming catalysts on real raw materials (hydrogenated FR. 100-180 ° C) also confirmed their high activity and selectivity. It should be noted that the Pt / Sn-Al ₂ O ₃ catalysts designed for reforming with a moving catalyst bed provide an IOC equal to 100 ÷ 103, while the yield of stable C ₅₊ reformate and hydrogen is 89.0 ÷ 89.7 wt. % and 3.5 ÷ 3.6 wt. %, respectively. Catalysts Pt-Re / Zr-Al ₂ O ₃ , designed for reforming with a stationary catalyst bed, are VOC = 96 ÷ 100, the yield of stable reformate C ₅₊ and hydrogen is 85.0 ÷ 86.7 wt. % and 2.9 ÷ 3.2 wt. % respectively.

Thus, the proposed reforming catalysts Pt / Sn-Al ₂ O ₃ and Pt-Re / Zr-Al ₂ O ₃ are effective both in the reforming of model raw materials (n-heptane) and real - hydrogenated fr. 100-180 ° C.

Claims (13)

1. A method of preparing a Sn (Zr) -γ-Al ₂ O ₃ support for a catalyst for reforming gasoline fractions, characterized in that the support is prepared by precipitating an aluminum nitrate solution with an aqueous ammonia solution, followed by filtering the suspension and washing the precipitate, peptizing it with acid and simultaneously introducing it with acid modifying additives Sn (Zr) by liquid-phase molding of a pseudo-sol in the form of spherical granules, followed by washing of the spherical granules, drying and heat treatment, and a spherical support with a diameter of 1.7 is obtained 0.1 mm, characterized by a monomodal pore size distribution with a specific surface area equal to (265 ÷ 326) m ² / g, a pore volume - (0,6 ÷ 0,68) cm ³ / g, average pore diameter - (8 ., 0 ÷ 9.6) nm, bulk density - (0.53 ÷ 0.59) g / cm ³ and mechanical crushing strength - (148 ÷ 205) kg / cm ² . 2. The method according to p. 1, characterized in that the liquid-phase molding of the pseudo-sol in the form of spherical granules is carried out by dosing it into a layer of kerosene, using a layer of aqueous ammonia as a hardener. 3. The method according to p. 1, characterized in that the modifying additive - tin or zirconium - is introduced at the stage of peptization of aluminum hydroxide in the presence of nitric acid in the form of tin chloride (zirconyl) 4. The method according to p. 1, characterized in that the drying is carried out first in air and then in an oven at 120 ± 10 ° C for 14 ± 2 hours and heat treatment at 600 ÷ 20 ° C for 4.5 ÷ 0.5 h in a stream of dried air. 5. The method of claim. 1, characterized in that psevdozol aluminum hydroxide produced in the presence of nitric acid at an acidic module Mk ÷ 0.085 = 0.10 moles [HNO _3], per mole of [Al ₂ O _3]. 6. A method of preparing a Sn (Zr) -γ-Al ₂ O ₃ support for a catalyst for reforming gasoline fractions, characterized in that the modifying additive (tin or zirconium) is introduced by impregnating spherical granules of dried aluminum hydroxide with a solution of salts containing either tin (zirconyl acetate) ), or tin chloride (zirconyl), in this case a spherical support with a diameter of 1.7 ± 0.1 mm is obtained, characterized by a monomodal pore size distribution, with a specific surface area equal to (265 ÷ 326) m ² / g, pore volume - (0,6 ÷ 0,68) cm ³ / g, a mean diameter n p - (8,0 ÷ 9,6) nm, a bulk density of - (0,53 ÷ 0,59) g / cm ³ and a compressive crushing strength - (148 ÷ 205) kg / cm ^2. 7. A method of preparing a catalyst for reforming gasoline fractions containing a noble metal of a platinum group deposited on an oxide support, followed by stages of drying, calcination, reduction, characterized in that the catalyst is prepared by impregnating the support of Sn-γ-Al ₂ O ₃ with a solution containing platinum chloride acid in terms of Pt 0.24 ÷ 0.26 wt. % 8. The method of preparation of the catalyst according to p. 7, characterized in that the carrier is used as a carrier, the tin content of which is 0.15 ÷ 0.17 wt. %, the rest is γ-Al ₂ O ₃ , the carrier has the shape of spherical granules with a diameter of 1.7 ± 0.1 mm, a unimodal pore size distribution, specific surface area equal to (265 ÷ 326) m ² / g, pore volume - (0 , 60 ÷ 0.68) cm ³ / g, average pore diameter - (8.0 ÷ 9.6) nm, bulk density - (0.53 ÷ 0.59) g / cm ³ and mechanical crushing strength - ( 148 ÷ 205) kg / cm ² . 9. A method of preparing a catalyst for reforming gasoline fractions containing a noble metal of the platinum group deposited on an oxide support, followed by stages of drying, calcination, reduction and sulphurization, characterized in that the catalyst is prepared by impregnating the support of Zr-γ-Al ₂ O ₃ with a solution containing rhenium acid in terms of Re 0.28-0.29 wt. % and platinum chloride acid in terms of Pt 0.24 ÷ 0.26 wt. % 10. The method of preparation of the catalyst according to p. 9, characterized in that the carrier is used as a carrier, the content of zirconium in which is 0.42 ÷ 0.54 wt. %, the rest is γ-Al ₂ O ₃ , the carrier has the shape of spherical granules with a diameter of 1.7 ± 0.1 mm, a unimodal pore size distribution, specific surface area equal to (265 ÷ 326) m ² / g, pore volume - (0 , 60 ÷ 0.68) cm ³ / g, average pore diameter - (8.0 ÷ 9.6) nm, bulk density - (0.53 ÷ 0.59) g / cm ³ and mechanical crushing strength - ( 148 ÷ 205) kg / cm ² . 11. The method of reforming gasoline fractions in the presence of a catalyst, characterized in that it is carried out in the presence of a catalyst obtained by any of the methods according to PP. 7-10. 12. The reforming method according to p. 11, characterized in that it is carried out at a pressure of 1.0 ± 0.2 MPa, a volumetric feed rate of n-heptane equal to 8-14 h ^-1 , and the ratio of H ₂ / n-heptane = 5 mol / mol. 13. The reforming method according to p. 11, characterized in that it is carried out at a pressure of 1.0-1.5 MPa, a volumetric feed rate of 1.3-1.5 h ^-1 , and a multiplicity of hydrogen-containing gas circulation = 1000 -1400 nl / l of raw materials.