RU2287370C1 - Method of production of globular catalyst of cracking - Google Patents

Abstract

FIELD: oil refining; methods of production of cracking globular catalysts.

SUBSTANCE: proposed method includes mixing aqueous suspension of zeolite Y in cation-exchange form with alumina suspension in aqueous solution of sodium silicate and aluminum sulfate solution, introducing platinum into aluminum sulfate solution or into aqueous suspension of zeolite fed for molding, forming catalyst granules in column filled with mineral oil, successive activation with solutions of aluminum sulfate and mixture of nitrates of rare-earth elements, washing-off with condensate water containing cations of iron, calcium and magnesium for removal of salts and calcination of granules in atmosphere of flue gases and water steam. For obtaining catalyst possessing enhanced activity, mechanical strength and bulk density, type Y zeolite is added into catalyst in hydrogen or hydrogen-rare-earth form; alumina is also added in the amount of 3-65 mass-%: with size of particles lesser than 10 mcm, 95-100 mass-%; lesser than 5 mcm, 40-80 mass-%. Catalyst has following composition in terms of oxides, mass-%: aluminum, 10.0-67.0; rare-earth elements, 0.5-3.5; platinum, 0.0001-0.01; iron, 0.01-0.2; calcium, 0.01-0.2; magnesium, 0.01-0.2; sodium, 0.01-0.3; the remainder being silicon. Catalyst has mechanic crushing strength of 22-40 kg/ball, wear resistance 900-1400 s, bulk density, 720-11000 kg/m³ and catalytic activity by gasoline yield, mass-%: 62.0-64.9 in cracking of kerosene-gas oil fraction and 41.5-45.7 in cracking of vacuum gas oil.

EFFECT: enhanced efficiency.

Description

The invention relates to oil refining, in particular to methods for producing ball zeolite-containing catalysts (CSK) cracking.

A known method of producing CSK (AS USSR 389829, class IPC B 01 J 29/08, 1973) for the conversion of hydrocarbons by introducing 15 wt.% Zeolite NaY into 85 wt.% Aluminosilica in the molding process. The composition of aluminosilicon: wt.% SiO ₂ - 93, Al ₂ O ₃ - 7. Zeolite-containing hydrogel after keeping in sodium sulfate solution (syneresis) is treated with a solution of the basic salt of aluminum sulfate with a concentration of 0.7 N in Al ₂ O ₃ and the ratio of OH ^- / Al = 0.7. Next, the hydrogel is washed with condensate, followed by a second activation with a solution of a mixture of rare earth nitrates (REE) with a concentration of 1.0-1.2 kg / m ³ in terms of REE oxides. Treated balls are washed with condensate at 50-52 ° C, dried at 140-170 ° C and calcined at 750 ° C for 12 hours. The content of water vapor in flue gases is 40-45 vol.%.

The disadvantages of this method include the lack of strength of the catalyst and significant cracking of the balls during production and operation.

A known composition and method of producing a catalyst for the conversion of hydrocarbons (US Pat. US 3312615, CL 208-120, 1967) containing crystalline aluminosilicate (zeolite Y), aluminosilicate matrix and inert fillers in which zeolite in rare earth cationic form in an amount of 2-15 wt.% mixed with 10-45 vol.% finely ground α-alumina (content of α-alumina more than 95 wt.%) with a particle size of 0.1-3.0 μm - 100% and introduced into an amorphous aluminosilicate matrix (50 -75 vol.%) In the process of forming balls in an oil bath. The hydrogel beads are activated with a solution of ammonium sulfate, washed from salts, dried in air at 135 ° C for 6 hours, and then treated with 100% steam at 700 ° C for 16 hours or at 650 ° C for 24 hours .

The disadvantages of this method are the low bulk density is not more than 620-660 kg / m ^{3 the} strength and activity of the catalyst.

A known method of producing a zeolite-containing aluminosilicate catalyst (US Pat. RF 2167908, class IPC With 10 G 11/05, 01 J 29/12, 2001), consisting of 5-20 wt.% Zeolite Y with a module (molar ratio of silicon oxide / aluminum oxide), equal to 4.5-9.5 and 80-95% aluminosilicate base. The catalyst according to this method is prepared by mixing aqueous solutions of aluminum sulfate, acidified with sulfuric acid, sodium silicate and an aqueous suspension of zeolite NaY with the formation of a hydrosol, which then coagulates into a ball-shaped hydrogel in a layer of mineral oil. To burn carbon monoxide in oxidative regeneration gases during its operation, platinum is introduced into the catalyst by adding platinum chloride hydrochloric acid (H ₂ PtCl ₆ ) to an aluminum sulfate solution or to an aqueous zeolite suspension. The hydrogel is subjected to syneresis in a solution of sodium sulfate. Next, the hydrogel is treated with an aqueous solution of ammonium nitrate or sulfate concentration of 5-20 kg / m ³ at 35-60 ° C for 12-36 hours and an aqueous solution of a mixture of REE nitrates of a concentration of 1-5 kg / m ³ (calculated on REE oxides) for 24-36 hours or a mixture thereof, washed with condensate water, dried at 110-190 ° C and calcined at 650-750 ° C for 12-24 hours in a stream of steam-air mixture with a water vapor content of 40 vol.%.

The disadvantages of the known method of producing the catalyst are its low bulk density (550-680 kg / m ³ ) and low mechanical crushing and abrasion strength.

A known method of producing ball cracking catalyst (US Pat. RF 2221644, class IPC 01 J 37/04, 01 J 29/12, 01 J 29/06, C 10 G 11/05, 2002) of oil fractions, comprising mixing aqueous solutions of sodium silicate, aluminum sulfate, a suspension of high modulus zeolite NaY and a suspension of alumina (particle size: less than 20 microns - 100 wt.%; less than 10 microns - 95 wt.%; less than 4 microns - 40 wt.%) introduced into the solution sodium silicate in a mixer with the formation of an aluminosilicate zeolite-containing hydrosol, which then coagulates into a ball-shaped hydrogel in a layer of mineral oil. The hydrogel balls are sequentially treated with an aqueous solution of ammonium sulfate or ammonium nitrate, an aqueous solution of REE nitrates, containing: ammonium nitrate not more than 20 wt.% And cerium oxide not more than 2.5 wt.% (Total REE oxides), and washed. In the process of washing the balls, platinum is introduced into the composition of the catalyst in the form of platinum chloride hydrochloric acid (PCVC), preferably based on 5-7 g of platinum (12-14 g PCVC) per 2.0-2.5 tons of dry catalyst: the catalyst is dried and calcined at 680- 720 ° C for 68-75 hours with a water vapor content of flue gases of 18-30 vol.%.

The obtained ball catalyst contains 7-15 wt.% Zeolite and has a chemical composition, wt.%:

Aluminium oxide 15-55 Rare Earth Oxides 0.5-3.0 Iron oxide 0.01-0.4 Sodium oxide 0.01-0.5 Silica Rest

The disadvantages of the known method of producing the catalyst are the low yield of the gasoline fraction in the cracking process on this catalyst; low mechanical crushing strength and resistance to cracking, as well as low bulk density of the catalyst.

A known method of producing motor fuels (US Pat. RF 2233309, class IPC C 10 G 11/05, 01 S 29/12, 2003), according to which the process of producing motor fuels by cracking oil fractions is carried out on a ball cracking catalyst, which is prepared by following technique.

Aqueous solutions of aluminum sulfate, acidified with sulfuric acid, containing 5-25 kg / m ³ of aluminum oxide and 40-80 kg / m ^{3 of} sulfuric acid, and sodium silicate (water glass) containing zeolite Y in cation exchange forms in an amount of 20-140 kg / m ³ , alumina 20-250 kg / m ³ , SiO ₂ 140-180 kg / m ³ and Na ₂ O 55-75 kg / m ³ are mixed in a mixer with the formation of aluminosilicate zeolite-containing hydrosol, which is then coagulated at 5- 20 ° C and pH 7.5-8.5 in a ball-type hydrogel in a layer of mineral oil. Then the hydrogel in the mother liquor or in an aqueous solution of aluminum sulfate, Al ₂ O ₃ concentration of 1-30 kg / m ^{3 is} subjected to syneresis at 5-50 ° C for 6-36 hours. Next, the hydrogel is treated with an aqueous solution of concentration 5 ammonium nitrate or ammonium sulfate -20 kg / m ³ at 15-50 ° C for 12-36 h and / or an aqueous solution of REE nitrates of a concentration of 1-5 kg / m ³ (calculated on REE oxides) for 24-48 hours at 15-50 ° C, washed with condensate water at 15-50 ° C for 8-24 hours, dried at 110-190 ° C and calcined at 650-750 ° C for 12-24 hours in a stream of steam-air mixture. Platinum is introduced into the catalyst by adding platinum chloride in an amount of 0.0002-0.04 kg / m ³ (calculated on platinum) or in the amount of 0.0003-0.055 kg / m ³ (calculated on platinum) in aqueous suspension of zeolite. Surfactants can be added to stabilize the suspension of zeolite Y and Al ₂ O ₃ , as well as to stabilize the process of ash formation and the transition of the hydrosol to hydrogel in a suspension of zeolite Y and Al ₂ O ₃ .

The catalyst contains 5-20 wt.% Zeolite Y with a molar ratio of silica: alumina 4.5-9.5 and 80-95 wt.% Aluminosilicate base, consisting of 40-95 wt.% Amorphous aluminosilicate and 5-60 wt. .% alumina containing aluminum oxide in the form of α - Al ₂ O ₃ not more than 85 wt.% and alumina in low temperature forms of 10-20 wt.%.

The catalyst has a chemical composition, wt.%:

Aluminium oxide 15,5-62,5 Rare Earth Oxides 0.5-4.0 Platinum 0.0001-0.01 Iron oxide 0.01-0.4 Calcium oxide 0.01-0.5 Sodium oxide 0.01-0.5 Silica Rest

The disadvantages of this method are the low bulk density and mechanical strength of the catalyst.

The closest in technical essence and the achieved result to the alleged invention is the "Method of producing ball cracking catalyst" (US Pat. RF 2221645, class IPC 01 J 37/04, C 10 G 11/05, 2002), which is chosen as the prototype . According to the prototype, a method for producing a ball catalyst for cracking oil fractions involves mixing an aqueous suspension of zeolite Y (in ammonium or REE-ammonium cationic form) with an aqueous suspension of alumina (with an α-alumina content of not more than 85 wt.% And 10-20 wt.% Θ -alumina), sodium silicate solution and an aqueous solution of aluminum sulfate, acidified with sulfuric acid, in a mixer with the formation of aluminosilicate zeolite-containing hydrosol, which then coagulates into a ball-shaped hydrogel in a layer of mineral oil. Next, the hydrogel beads are treated with an aqueous solution of aluminum sulfate, washed, treated with an aqueous solution of a mixture of rare earth nitrates; washed, dried and calcined. In the process of washing the balls from salts, platinum is introduced into the catalyst composition in the form of platinum chloride hydrochloric acid, preferably in an amount of 2-3 ppm.

The obtained ball catalyst contains 7-15 wt.% Zeolite and has a chemical composition, wt.%:

Aluminium oxide 30-55 Rare Earth Oxides 0.5-3.0 Sodium oxide 0.01-0.5 Silica Rest

The disadvantages of the known method of producing the catalyst are the low yield of the gasoline fraction in the cracking process on this catalyst, low mechanical crush strength and abrasion of the catalyst. The impossibility of obtaining a wide range of catalysts with predetermined values of bulk density and strength.

The aim of the invention is to increase the activity (yield of gasoline fraction in the cracking process) of a ball cracking catalyst while increasing its mechanical strength and making it possible to obtain catalysts having a wide range of required (including increased) bulk density.

The goal is achieved by the proposed method for producing ball cracking catalyst by introducing type Y zeolite in the hydrogen or hydrogen-rare-earth form and 3-65 wt.% Alumina with a particle size of less than 10 microns, 95-100 wt.%, Less than 5 microns 40-80 wt.%. The ball catalyst used in the cracking process has a chemical composition, wt.%:

Aluminium oxide 10.0-67.0 Rare Earth Oxides 0.5-3.5 Platinum 0.0001-0.01 Iron oxide 0.01-0.2 Calcium oxide 0.01-0.2 Magnesium oxide 0.01-0.2 Sodium oxide 0.01-0.3 Silica Rest

A comparative analysis of the proposed method with the prototype allows us to conclude that the claimed method differs from the known introduction of type Y zeolite in H ⁺ or H ⁺ REE cation exchange forms into the catalyst composition and the amount of alumina (3-65 wt.%) Introduced into the catalyst particles less than 10 microns 95-100 wt.%, less than 5 microns 40-80 wt.%, as well as the chemical composition resulting from the catalyst. These features of the proposed technical solution allow us to conclude that it meets the criterion of "novelty."

An analysis of the known methods for producing ball cracking catalysts showed that the tendency to introduce finely divided alumina into the composition of the cracking catalyst to increase the bulk density and mechanical strength of the catalyst is known. However, only the fact of the simultaneous introduction of type Y zeolite into the catalyst in H ⁺ or H ⁺ REE cation exchange forms and 3-65 wt.% Alumina with a particle size of less than 10 microns 95-100 wt.%, Less than 5 microns 40-80 wt. %, and the use in the cracking process of the obtained catalyst having a chemical composition, wt.%:

Aluminium oxide 10.0-67.0 Rare Earth Oxides 0.5-3.5 Platinum 0.0001-0.01 Iron oxide 0.01-0.2 Calcium oxide 0.01-0.2 Magnesium oxide 0.01-0.2 Sodium oxide 0.01-0.3 Silica Rest

allows to achieve a high yield of gasoline fraction. The inventive catalyst has increased mechanical strength for crushing and abrasion and may have, depending on the synthesis conditions, a wide range of values (including increased) bulk density. These differences make it possible to obtain and use in the cracking process (with any multiplicity of catalyst circulation) a new, optimal catalyst that meets the requirements of a particular installation without increasing its consumption per ton of processed raw materials.

The essence of the invention is as follows. An aqueous suspension of alumina containing α-Al ₂ O ₃ not more than 85 wt.% And Θ-Al ₂ O ₃ 10-20 wt.% And having a particle size: less than 10 microns 95-100 wt.%, Less than 5 microns 40- 80 wt.%, With a dry alumina concentration of 200-350 kg / m ³ , is mixed with a solution of sodium silicate (NaOH 4.1-4.5 kg-equiv / m ³ , 2.2-3.0 modulus) in volume the ratio of 0.45: 1.0 and stirred for 2 hours. The specified mixture, an aqueous suspension of type Y zeolite in H ⁺ or H ⁺ REE cation exchange form (100-260 kg / m ³ zeolite), an acidified solution of aluminum sulfate (Al ₂ (SO ₄ ) ₃ 3.0-3.6 wt.%, H ₂ SO ₄ 50-60 kg / m ³ ) are cooled and mixed in a three-stream mixture itel in a volume ratio of 1.0: 0.1: 0.9. After the mixer, the sol is fed for molding into a column filled with transformer oil.

The temperature of the mixture of sodium silicate with VSG 6-8 ° C;

the temperature of the acidic solution of aluminum sulfate 6-8 ° C;

Sol temperature after mixing 12-14 ° C;

the pH of the mixture before gelation is 8.0-8.3;

molding oil temperature 20-22 ° C.

The formed granules are transported to a container for thermochemical activation by a stream of water containing 10-15 kg / m ^{3 of} aluminum sulfate and not more than 6 kg / m ^{3 of} sodium sulfate. Then, the first activation of the catalyst is carried out with an aluminum sulfate solution of a concentration of 6-10 kg / m ³ at a specific solution flow rate of 1.1-1.3 m ³ / m ^{3 of} wet balls per hour and a temperature of 15-25 ° C for 20 hours. Second activation spend a solution of a mixture of REE nitrates (0.2-2.0 kg / m ³ ) for 22-30 hours. The hourly flow rate of the solution is 1.1-1.3 m ³ / m ³ . The content of cerium oxide in the solution used is not more than 2.5 wt.% For the sum of REE oxides; the content of ammonium nitrate is 18 wt.%. Then, the catalyst is washed from salts with condensate water containing cations of iron 0.01-0.04 kg / m ³ , calcium 0.01-0.05 kg / m ³ and magnesium 0.001-0.04 kg / m ³ (calculated on oxides). The flow rate of washing water is 1.1-1.3 m ³ / m ³ per hour, temperature is 15-25 ° C. Platinum is introduced into the catalyst by adding platinum chloride hydrochloric acid (PCVC) to a solution of aluminum sulfate in an amount of 0.0002-0.04 kg / m ³ or in the WCC in an amount of 0.0006-0.035 kg / m ³ (based on platinum) supplied on the formation of the catalyst. The catalyst is dried in a vapor-air medium with a gradual increase in temperature from 85-90 to 150-165 ° C for 4 hours. The residual moisture content in the dry granules is not more than 10 wt.%. The catalyst is calcined at 680-720 ° C in a mixture of flue gases and water vapor (18-30 vol.%) For 72 hours

The resulting catalyst contains 5-20 wt.% Type Y zeolite in REE - hydrogen cationic form, 10.0-67.0 wt.% Alumina, including 3-65 wt.% Alumina introduced with alumina.

The catalyst has a chemical composition, wt.%:

Aluminium oxide 10.0-67.0 Rare Earth Oxides 0.5-3.5 Platinum 0.0001-0.01 Iron oxide 0.01-0.2 Calcium oxide 0.01-0.2 Magnesium oxide 0.01-0.2 Sodium oxide 0.01-0.3 Silica Rest

and has a mechanical crushing strength of 22-40 kg / ball, wear resistance according to the "Rental" method of 900-1400 s, bulk density of 720-1100 kg / m ³ and catalytic activity for gasoline yield, wt.%:

in cracking of kerosene-gas oil fraction 62.0-64.9;

in cracking of vacuum gas oil 41.5-45.7.

The present invention is illustrated by examples that make up the essence of the proposed method for producing ball cracking catalyst.

An example is a prototype.

Preparation of an aqueous suspension of zeolite Y in ammonium or rare-earth-ammonium cationic form. Prepare an aqueous suspension of zeolite (WCC) with a zeolite content of 100-260 kg / m ³ . To prevent the zeolite crystallites from sticking together, a stabilizer is introduced into the suspension.

Preparation of working solutions and suspensions.

a) A solution of sodium silicate (water glass). Prepare sodium silicate with a concentration of NaOH 4.1-4.5 kg-equiv / m ³ with a silicate module (molar ratio of SiO ₂ / Na ₂ O) equal to 2.2-2.5 - by dissolving the silicate block in industrial water under pressure, filtering and adding a solution of sodium alkali.

b) A solution of aluminum sulfate. The solution is prepared by dissolving aluminum hydroxide in sulfuric acid. The concentration of the working solution in Al ₂ (SO ₄ ) ₃ 3.0-3.6 wt.%, The content of free H ₂ SO ₄ 50-60 kg / m ³ .

c) A suspension of alumina. Use alumina powder with a content of α-Al ₂ O ₃ 82 wt.% And Θ-Al ₂ O ₃ 15 wt.%. Fractional composition of the powder: particles less than 10 microns - 95%. An aqueous suspension of alumina is prepared with a dry concentration of 200-350 kg / m ³ .

g) A solution of a mixture of rare earth nitrates (REE) is prepared with a concentration of REE oxides of 0.2-5.0 kg / m ³ . In a mixture of REE oxides, the content of cerium oxide is not more than 2.5 wt.%, The content of ammonium nitrate is not more than 20 wt.% Per total salt in the solution.

The formation of the catalyst.

An aqueous suspension of alumina (WASH) is mixed with a solution of sodium silicate in a volume ratio of 0.45: 1.0 and stirred for at least 2 hours

A suspension of alumina in sodium silicate (first stream), a prepared suspension of zeolite (second stream) and an acidified solution of aluminum sulfate (third stream) are cooled and mixed in a three-stream mixer in a volume ratio of 1.0: 0.1: 0.9. After the mixer, the sol is fed for molding into a column filled with transformer oil.

The temperature of the mixture of sodium silicate with VSG 6-8 ° C;

the temperature of the acidic solution of aluminum sulfate 6-8 ° C;

Sol temperature after mixing 12-14 ° C;

the pH of the mixture before gelation is 8.0-8.3;

molding oil temperature 20-22 ° C.

Thermochemical activation.

The formed granules are transported to a container for thermochemical activation (hereinafter referred to as “chan”) by a stream of transport water containing aluminum sulfate (CA) of a concentration of 10-15 kg / m ³ and sodium sulfate with a concentration of not more than 6 kg / m ³ . After forming the vat, it is connected to the first activation with aluminum sulfate solution last in a chain of 5 vats so that the input of the subsequent vat is connected to the output of the previous one. At the inlet of the first tub, a solution of aluminum sulfate with a concentration of 6-10 kg / m ³ at a specific flow rate of 1.1-1.3 m ³ / m ³ wet balls per hour and a temperature of 15-25 ° C is fed. After the first activation (20 hours), the vat is switched to the second activation. The second activation is carried out with a solution of a mixture of REE nitrates of a concentration of 0.2-2.0 kg / m ³ for 22-30 hours in a chain of 7 tanks. The flow rate of the solution is 1.1-1.3 m ³ / m ³ per hour. The cerium oxide content in the solution is not more than 2.5 wt.% For the sum of REE oxides; the content of ammonium nitrate is 18 wt.%. After the second activation, the vat is connected to the washing from salts. Washing from salts is carried out in a chain of 3 tanks with steam condensate. Condensate flow rate 1.1-1.3 m ³ / m ³ per hour, temperature 15-25 ° C. At the end of the second washing, a solution of platinum chloride hydrochloric acid is added to the condensate at the rate of 2-5 ppm metallic platinum per dry catalyst.

Drying and calcining the catalyst.

The catalyst is dried in a steam-air belt dryer with a gradual increase in temperature in the zones (7 zones) from 85-90 to 150-165 ° C for 4 hours. The residual moisture content in the dry granules is not more than 10 wt.%. The catalyst is calcined at 680-720 ° C in a mixture of flue gases and water vapor (18-30 vol.%) For 72 hours

The resulting catalyst contains 10 wt.% Zeolite in REE - hydrogen cationic form, 37% alumina (including 30 wt.% Alumina introduced with alumina) and 2.2 wt.% REE based on oxides.

Catalyst Test Methods

Bulk density (kg / m ³ ) and catalytic activity in cracking of the kerosene-gas oil fraction (NK - 195 ° C; 10% - 223 ° C; 50% - 358 ° C; up to 360 ° C - 96.5%) are determined in the obtained sample. at a temperature of 460 ° C and a volumetric feed rate of 1.5 h ^-1 after stabilization of the catalyst with steam at 750 ° C, 6 hours; 100% steam The yield of gasoline, wt.% On the supplied raw materials, the yield of gas and coke are determined. The crush strength of the balls (kg / ball) and the resistance of the catalyst granules to cracking by boiling in water,%, are determined as the number of whole catalyst granules preserved after boiling in water for 10-15 minutes.

Example 1

1.1. Preparation of an aqueous suspension of zeolite Y in hydrogen cationic form. Prepare an aqueous suspension of zeolite (WCC) with a zeolite content of 100-260 kg / m ³ . To prevent the zeolite crystallites from sticking together, a stabilizer is introduced into the suspension.

1.2. Preparation of working solutions and suspensions.

a) A solution of sodium silicate (water glass). Prepare sodium silicate concentration of NaOH 4.1-4.5 kg-equiv / m ³ with a silicate module (molar ratio of SiO ₂ / Na ₂ O) equal to 2.2-3.0, by dissolving the silicate block in industrial water under pressure and filtering.

b) A solution of aluminum sulfate. The solution is prepared by dissolving aluminum hydroxide in sulfuric acid. The concentration of the working solution in Al ₂ (SO ₄ ) ₃ 3.0-3.6 wt.%, The content of free H ₂ SO ₄ 50-60 kg / m ³ .

c) A suspension of alumina. Use alumina powder with a content of α-Al ₂ O ₃ 82 wt.% And Θ-Al ₂ O ₃ 15 wt.%. The fractional composition of the powder: particles less than 10 microns - 100 wt.%, Less than 5 microns - 60 wt.%. An aqueous suspension of alumina is prepared with a dry concentration of 200-350 kg / m ³ .

g) A solution of a mixture of rare earth nitrates (REE) is prepared with a concentration of REE oxides of 0.2-5.0 kg / m ³ . In a mixture of REE oxides, the content of cerium oxide is not more than 2.5 wt.%, The content of ammonium nitrate is not more than 20 wt.% Per total salt in the solution.

1.3. Formation of the catalyst.

An aqueous suspension of alumina (WASH) is mixed with a solution of sodium silicate in a volume ratio of 0.45: 1.0 and stirred for at least 2 hours

A suspension of alumina in sodium silicate (first stream), a prepared suspension of zeolite (second stream) and an acidified solution of aluminum sulfate (third stream) are cooled and mixed in a three-stream mixer in a volume ratio of 1.0: 0.1: 0.9. After the mixer, the sol is fed for molding into a column filled with transformer oil.

The temperature of the mixture of sodium silicate with VSG 6-8 ° C;

the temperature of the acidic solution of aluminum sulfate 6-8 ° C;

Sol temperature after mixing 12-14 ° C;

the pH of the mixture before gelation is 8.0-8.3;

molding oil temperature 20-22 ° C.

1.4. Thermochemical activation.

The formed granules are transported to a container for thermochemical activation by a stream of transport water containing aluminum sulfate (CA) with a concentration of 10-15 kg / m ³ and sodium sulfate with a concentration of not more than 6 kg / m ³ . After forming the vat, it is connected to the first activation with aluminum sulfate solution last in a chain of 5 vats so that the input of the subsequent vat is connected to the output of the previous one. At the inlet of the first tub, a solution of aluminum sulfate of a concentration of 6-10 kg / m ^{3 is} supplied, with a specific flow rate of 1.1-1.3 m ³ / m ^{3 of} wet balls per hour, a temperature of 15-25 ° C. After the first activation (20 hours), the vat is switched to the second activation. The second activation is carried out with a solution of a mixture of REE nitrates of a concentration of 0.2-2.0 kg / m ³ for 22-30 hours in a chain of 7 tanks. The flow rate of the solution is 1.1-1.3 m ³ / m ³ per hour. The cerium oxide content in the solution is not more than 2.5 wt.% For the sum of REE oxides; the content of ammonium nitrate is 18 wt.%. After the second activation, the vat is connected to the washing from salts. Washing from salts is carried out in a chain of 3 tanks with condensate water containing cations of iron 0.01-0.04 kg / m ³ , calcium 0.001-0.05 kg / m ³ and magnesium 0.001-0.04 kg / m ³ (in based on oxides). The flow rate of washing water is 1.1-1.3 m ³ / m ³ per hour, temperature is 15-25 ° C.

Platinum is introduced into the catalyst by adding platinum chloride hydrochloric acid (PCVC) to solutions of aluminum sulfate in an amount of 0.0002-0.04 kg / m ³ or in the WCC in an amount of 0.0006-0.035 kg / m ³ (based on platinum) supplied on the formation of the catalyst.

1.5. Drying and calcining the catalyst.

The catalyst is dried in a steam-air belt dryer with a gradual increase in temperature in the zones (7 zones) from 85-90 to 150-165 ° C for 4 hours. The residual moisture content in the dry granules is not more than 10 wt.%. The catalyst is calcined at 680-720 ° C in a mixture of flue gases and water vapor (18-30 vol.%) For 72 hours

The resulting catalyst contains 10 wt.% Zeolite in REE - hydrogen cationic form, 37% alumina (including 30 wt.% Alumina introduced with alumina) and 2.3 wt.% REE based on their oxides.

1.6. Catalyst Test Methods

Bulk density (kg / m ³ ) and catalytic activity in cracking of the kerosene-gas oil fraction (NK - 195 ° C; 10% - 223 ° C; 50% - 358 ° C; up to 360 ° C - 96, are determined in the obtained catalyst sample) 5%) at a temperature of 460 ° C and a volumetric feed rate of 1.5 h ^-1 after stabilization of the catalyst with steam at 750 ° C, 6 h; 100% steam In addition, the catalytic activity is determined in the cracking of vacuum gas oil of West Siberian oil (density 916 kg / m ³ , sulfur content 1.6 wt.%) At 480 ° C and a bulk feed rate of 1.8 h ^-1 . Determine the strength of the balls for crushing (kg / ball), abrasion according to the method of "Rental", as abrasion of 50 wt.% Granules for a certain time (s), and the resistance of the catalyst granules to cracking by boiling in water,%, as the number of whole granules catalyst, preserved after boiling in water for 10-15 minutes

Data on the properties of the catalyst in example 1 are shown in tables 1, 2.

Data on the conditions of preparation of the catalyst, its physico-mechanical, chemical and catalytic properties of the prototype and examples 2-8 are presented in tables 1, 2.

The introduction into the composition of the catalyst more coarse alumina (example 6 is comparative) leads to an increase in cracking of the catalyst during drying and operation, reducing its mechanical strength for crushing and abrasion.

Introduction to the composition of the catalyst more finely divided alumina is desirable, but not feasible, finely dispersed alumina is not produced in our country due to the complexity of the fine grinding of the initial alumina.

The introduction of more than 65 wt.% Alumina into the composition of the catalyst (comparative example 7) leads to an increase in cracking of the catalyst during drying and operation and to a decrease in its catalytic activity.

The preparation of the catalyst without introducing alumina into its composition (comparative example 8) causes an increase in cracking of the catalyst during drying and operation and a decrease in its crush and abrasion strength.

Table 1
Preparation conditions and physicomechanical properties of ball cracking catalyst. Preparation conditions and physicomechanical properties of the catalyst Examples Prototype one 2 3 four 5 6 * 7 * 8* Cooking conditions: - cation exchange form of zeolite NH ₄ ⁺ ; (NH ₄ ⁺ REE) H ⁺ H ⁺ H ⁺ N ⁺ REE N ⁺ REE H ⁺ H ⁺ H ⁺ - alumina content, wt.% thirty thirty 65 3 thirty thirty thirty 70 - - particle size of alumina, wt.% less than 10 microns 95 one hundred one hundred one hundred 95 one hundred 80 one hundred - less than 5 microns - 60 60 60 40 80 thirty 60 - Physico-mechanical properties of the catalyst: - bulk density, kg / m ³ : dry 822-830 850 1005 690 830 865 820 1090 690 calcined 848-872 880 1100 720 870 900 865 1190 710 - cracking during drying, wt.% 14-22 10 6 16 13 8 eighteen 28 thirty Physicomechanical Properties of calcined catalyst: - crushing strength, kg / ball, 16.7-18.5 32 40 22 26 33 21 42 eighteen - abrasion resistance "Rental", 50 wt.% abrasion, s 1000 1200 1400 900 1150 1350 1050 1460 700 - resistance to cracking,% 92-96 96 98 94 95 97 93 80 92 - specific surface, m ² / g 157-187 172 158 222 164 168 184 142 242

Note: * Examples 6, 7, 8 are comparative.

table 2
Chemical composition and catalytic properties of ball cracking catalyst. The chemical composition and catalytic properties of the catalyst Examples Prototype one 2 3 four 5 6 * 7 * 8* Chemical composition, wt.%: - aluminium oxide 37.0 37.0 67.0 10.0 37.0 37.0 37.0 72.0 7.0 - rare earth oxides 2.2 2,3 2,4 3,5 0.5 2,4 2.2 2.0 3,5 - platinum 0,0005 0,0005 0.001 0.01 0,0005 0.01 0,0005 0.001 0.01 - iron oxide 0.02 0.01 0.01 0.2 0.01 0.01 0.01 0.01 0.2 - calcium oxide 0,03 0.02 0.01 0.2 0.02 0.01 0.02 0.01 0.2 - magnesium oxide no 0.02 0.01 0.2 0.02 0.01 0.02 0.01 0.2 - sodium oxide 0.2 0.2 0.02 0.3 0.2 0.01 0.2 0.2 0.3 - silicon oxide rest Catalytic activity, yield, wt.%:
cracking of a kerosene-gas oil fraction: - gasoline C ₅ - 200 ° C 59.1-61.7 62,2 62.0 64.9 62.0 62.5 61.9 59,4 59.1 - gas 13.4-17.3 15.8 16,0 16.8 16.5 16.5 17.1 15.6 17,2 - coke 0.5-1.8 1,1 1.3 1.7 1,2 1.3 1,5 1.7 1.8 - cracking of vacuum gas oil: - gasoline C ₅ - 200 ° C 39.8-41.2 42.1 41.5 45.7 42.1 42.5 41.8 40.8 41.8 - gas 15.9-16.3 15.8 15.7 16.1 15.9 15.9 16,2 16,2 16.5 - coke 4.8-5.1 4.9 4.9 5,0 4.9 4.9 5,0 5.1 5.2

Note: * examples 6, 7, 8 - comparative

Claims (1)

A method of obtaining a ball catalyst for cracking oil fractions, comprising mixing an aqueous suspension of zeolite Y in cation exchange form with a suspension of alumina containing α-Al ₂ O ₃ not more than 85 wt.% And Θ-Al ₂ O ₃ 10-20 wt.%, In aqueous a solution of sodium silicate and a solution of aluminum sulfate, moreover, platinum is introduced by adding platinum hydrochloric acid to a solution of aluminum sulfate or into an aqueous suspension of zeolite fed to the molding, the formation of catalyst granules in a column with mineral oil, successive activation solutions aluminum sulfate and a mixture of rare earth nitrates, washing from salts with condensate water containing cations of iron, calcium and magnesium, drying and calcining the granules in an atmosphere of flue gases and water vapor, characterized in that they use type Y zeolite in hydrogen or hydrogen-rare earth form, alumina is introduced in an amount of 3-65 wt.% (based on the calcined catalyst) with a particle size of: less than 10 microns 95-100 wt.%, less than 5 microns 40-80 wt.%, and the catalyst has a chemical composition, wt.%: Aluminium oxide 10.0-67.0 Rare Earth Oxides 0.5-3.5 Platinum 0.0001-0.01 Iron oxide 0.01-0.2 Calcium oxide 0.01-0.2 Magnesium oxide 0.01-0.2 Sodium oxide 0.01-0.3 Silica Rest