The method of obtaining the ball cracking catalyst

 

The catalyst was prepared by mixing the aqueous suspension of zeolite Y in ammonium or REE-ammonium cationic form with a water slurry of alumina content-Al2O3not more than 85 wt.% and-Al2O310-20 wt.%, a solution of sodium silicate and a solution of aluminum sulfate; formed into granules of catalyst in the column with mineral oil; make the activation solution of aluminum sulfate, are activated with a solution of a mixture of nitrates of rare-earth elements, washed catalyst salts, dried and calcined in the atmosphere of flue gases and water vapor. Get the catalyst with a bulk weight of more than 800 kg/m3, crushing strength above 15 kg/ball with high catalytic activity, low shrinkage and low shrinkage. table 1.

The invention relates to the refining, in particular to methods for ball zeolite catalysts (CSK) cracking.

A method of obtaining CSK (and.with. The USSR 389829, CL MKI 01 J 29/08, 1973) for the conversion of hydrocarbons by the introduction of a 15 wt.% zeolite NaY in 85% alumagrips in the forming process. The composition alumagrips 93% SIO, SIS2and 7% Al2About3. Smagulov is the target basic salt of aluminum sulfate with a concentration of 0.7 N on Al2About3and the respect HE/Al=0,7. Next, the hydrogel is washed with steam condensate, followed by a second activation solution mixture of nitrates of rare-earth elements concentration of 1.0-1.2 g/l in terms of REE oxides. After the second activation of the beads washed with steam condensate at a temperature of 50-52oC, dried at a temperature of 140-170oC and calcined at a temperature of 750oWith in 12 hours. The water vapor content in the flue gas 40-45%. The disadvantages of this method include the lack of durability of the catalyst and significant cracking of the balls during operation.

Known composition and production method of the catalyst for conversion of hydrocarbons (U.S. Pat. USA 3312615, CL 208-120, 1967) containing crystalline aluminosilicate (zeolite Y), aluminosilicate matrix and inert fillers, in which the rare earth zeolite in the cation form in the amount of 2-15 wt.% mixed with about 10-45. % pulverizedaluminum oxide (contents-aluminum oxide of more than 95 wt.%) with a particle size of 0.1 to 3.0 μm to 100%, and injected into the amorphous aluminosilicate matrix (50-75%) in the molding process of the balls in an oil bath. Hydrogel beads are subjected activos, then treated with 100% steam at a temperature of 700oC for 16 hours or at a temperature of 650o- Within 24 hours the Disadvantages of this method are the low bulk density is not more than 620-660 kg/m3and selectivity of the catalyst.

Closest to the technical essence and the achieved effect to the proposed technical solution is the method of obtaining aluminosilicate zeolite catalyst (U.S. Pat. RF 2167908, CL MKI With 10 G 11/05, 01 J 29/12, 2001), consisting of 5-20 wt.% zeolite Y with the module (molar ratio of silica/ alumina), equal to 4.5 to 9.5 and 80-95% of the aluminosilicate framework. The catalyst according to the method of preparing a mixture of aqueous solutions of aluminum sulfate acidified with sulfuric acid, sodium silicate and water suspensions of zeolite NaY with the formation of a Hydrosol, which then coagulates in the hydrogel pellet form in a layer of mineral oil. For afterburning of carbon monoxide (11) in gases oxidative regeneration in the course of its operation the catalyst is injected platinum by adding hexachloroplatinic acid, H2tl6in a solution of aluminum sulfate or aqueous suspension of the zeolite. The hydrogel is subjected to syneresis in a solution of sodium sulfate. the 5-60oC for 12-36 h and an aqueous solution of a mixture of nitrates of rare-earth elements concentrations of 1-5 kg/m3(calculated as oxides REE) within 24-36 h, or their mixture, washed with condensate water, dried at 110-190oC and calcined at 650-750oC for 12-24 h in a current of steam-air mixture with the water vapor content of 40 vol.%. The disadvantages of this method are low bulk density (550-680 kg/m3) and low mechanical strength, including low crushing strength.

The objective of the proposed technical solution is the improvement of the mechanical properties of the catalyst, including the increase of bulk density and crushing strength, reduced cracking and shrinkage, increasing its activity and selectivity.

The problem is solved by the proposed method of obtaining a ball of catalyst in the cracking of petroleum fractions, comprising mixing the aqueous suspension of zeolite Y in ammonium or REE-ammonium cationic form with a water slurry of alumina content-aluminium oxide is not more than 85 wt.% and 10-20%-aluminium oxide; sodium silicate solution and an aqueous solution of aluminum sulfate acidified with sulfuric acid; in sevrikova form in the layer of mineral oil. Next, the beads of hydrogel treated with an aqueous solution of aluminum sulfate, washed; treated with an aqueous solution of a mixture of nitrates of rare-earth elements; washed, dried and calcined. In the process of cleaning balls from salts in the catalyst composition is administered platinum in the form of hexachloroplatinic acid, preferably in a quantity of 2-3 ppm.

The resulting ball catalyst contains 7-15 wt.% zeolite has a composition, wt.%: Alumina - 30-55 Oxides of rare earth elements - 0,5-3,0 sodium Oxide is 0.01-0.5 silica - Rest of the Invention is illustrated in the examples that make up the essence of the proposed method of obtaining the ball cracking catalyst, but is not limited to them.

Example 1. Obtaining catalyst according to the present method.

1.1 Preparation of an aqueous suspension of zeolite Y in ammonium or rare earth ammonium cationic form. Prepare aqueous suspension of zeolite (WCC) with zeolite 100-260 kg/m3. To prevent adhesion of the crystallites of zeolite in the slurry, introducing the stabilizer.

1.2 Preparation of working solutions and suspensions.

a) a Solution of sodium silicate (liquid glass). Prepare sodium silicate concentration of NaOH of 4.1-4.5 kg-EQ/m3and silicate module, the d pressure, filtering and the introduction of a concentrated solution of caustic soda.

b) a Solution of aluminum sulphate. A solution prepared by dissolving aluminum hydroxide in sulphuric acid. The concentration of working solution on Al2(SO4)33.0 to 3.6 wt.%, the concentration of free H2SO450-60 kg/m3.

C) Suspension of alumina. Use the alumina powder with a content of-Al2O382 wt.% and-Al2O315 wt.%.

Fractional composition of powder particles less than 10 microns - more than 95%. Aqueous suspension of alumina is prepared by concentration on solid 200-350 kg/m3.

g) a Solution of a mixture of nitrates of rare-earth elements (REE) are the concentration of REE oxides 0,2-5,0 kg/m3. In the mixture of oxides REE content of cerium oxide is not more than 2.5 wt.% The content of ammonium nitrate is not more than 20 wt.% the amount of salts in solution.

1.3. Forming catalyst.

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

A suspension of alumina in sodium silicate (first thread) prepared by suspension of zeolite (second thread) and acidified with a solution of aluminum sulfate Sol serves to form in the oil column, filled with transformer oil.

The temperature of the mixture of sodium silicate with everything 6-8oC; the temperature of the acidic solution of aluminum sulfate 6-8oC; Temperature Zola after mixing 12-14oC; pH of the mixture prior to gelation of 8.0 to 8.3; the Temperature of the molding oil 20-22oC.

1.4. Thermochemical activation.

These granules are transported in the tank for conducting thermochemical activation (hereinafter - VAT) transport stream of water containing aluminium sulphate (SA) concentrations of 10-15 kg/m3and sodium sulfate in a concentration of not more than 6 kg/m3. After reformowania Chan it is connected to the first activation solution of aluminum sulfate is the last in a chain of 5 tanks so that the subsequent input VAT connected to the output of the previous one. The input of the first jar to submit a solution of aluminum sulfate concentration of 6-10 kg/m3specific consumption of 1.1-1.3 m3/m3wet balls per hour at a temperature of 15-25oC. after the first activation (20 h) switch the tank at the second activation.

The second activation is carried out with a solution of a mixture of nitrates REE concentrations of 0.2-2.0 kg/m3during 22-30 hours in a chain of 7 tanks. The solution flow rate of 1.1-1.3 m3/m3in the hour. The content of the oxide C the second activation connect the tub to wash out salts.

Washing of salts is carried out in a chain of 3 tanks steam condensate. The flow of wash water to 1.1-1.3 m3/m3per hour, the temperature of 15-25oC.

At the end of the second rinse added to the wash water solution of hexachloroplatinic acid based 2-5 ppm of metallic platinum on the dry catalyst.

1.5. Drying and calcination of the catalyst.

The catalyst is dried in a steam-belt drying apparatus with a gradual rise of temperature zones (7 zones) from 85-90 to 150-165oC for 4 h Residual moisture content in the dry granules is not more than 10 wt.%.

The catalyst is calcined at a temperature of 680-720oWith a mixture of flue gases and water vapor concentration pair 18-30% vol. within 72 hours

The catalyst containing 10 wt.% zeolite in REE-hydrogen cation form, 37% of aluminum oxide (including 30 wt.% aluminum oxide introduced as part of the alumina) and 2.2 wt.% REE in the calculation of their oxides.

1.6. Test methods of catalyst.

In the obtained sample to determine bulk density (kg/m3and catalytic activity in the cracking of hydrotreated diesel fuel (NC - 195oWith 10% of 223oC; 50% - 358oWith; up to 360oWith - 96,5%) after stabilization of the catalyst water PA the spine, the exit gas and coke. Determine the strength of balls crush strength (kg/balloon). Determine shrinkage after annealing and thermoprotei stabilization for changing the volume of the catalyst, about. %. Determine the stability of the granules of the catalyst to cracking by boiling in water, %, as the number of whole granules of the catalyst remaining after boiling in water for 10-15 minutes

Example 2. The catalyst is prepared analogously to example 1, using the alumina content-Al2O385 wt.% and-Al2O312 wt.%. The ratio of the sodium silicate solution to the volume of a suspension of alumina 1,0:0.45 and the content of alumina in the finished catalyst 30 wt.%
Example 3. The catalyst is prepared analogously to example 1, using alumina and alpha-alumina 80 wt.% and theta-alumina 17 wt.%. The ratio of the sodium silicate solution to the volume of a suspension of alumina 1,0:0.45 and the content of alumina in the finished catalyst 30 wt.%.

Example 4. The catalyst is prepared analogously to example 1. In use as a filler powder of alumina content-Al2O3more than 95 wt.%. The volume ratio of sodium silicate to the volume of WM the aqueous suspension of zeolite: flow solution of aluminum sulfate, acidified with sulfuric acid, = 1,0:0,15:0,9. The content of zeolite in the catalyst 10 wt.%; the alumina content of 30 wt.%.

Example 5 (prototype). Use the working solution of sodium silicate concentration of NaOH 1,68-1,72 kg-EQ/m3module 2,92, aqueous suspension of zeolite NaY without prior ion exchange, with the content of Na2O 12.0 wt. %; solution of aluminum sulfate acidified with sulfuric acid, the concentration of Al2About315 kg/m3and 60-70 kg/m3- sulfuric acid. After mixing the solution with a suspension of zeolite and molding the pellets into the oil column of the resulting ball hydrogel is incubated in a solution of sodium sulfate. Then hold the first activation solution of ammonium sulfate concentration of 10-15 kg/m3. Next, perform a second activation solution mixture of nitrates of rare-earth elements and ammonium nitrate concentrations of the REE oxides of 1.1-2.5 kg/m3; washed beads steam condensate at a temperature of 45-60oWith, dried and calcined at a temperature of 680-720oC for 12 hours the water vapor Content in the calcining zone 40% vol.

The test results of the catalysts shown in the table.

From examples 1-5 and table shows that the use of alumina content
Claims

The method of obtaining the ball zeolite catalyst cracking of oil fractions comprising a mixture of aqueous suspension of zeolite Y in ammonium or rare earth ammonium cationic form with a water suspension of the filler with a solution of sodium silicate and a solution of aluminium sulphate, forming granules of catalyst in the column with the mineral oil, the activation solution of aluminum sulfate, the activation solution of a mixture of nitrates of rare-earth elements, washing salts, drying and calcining in an atmosphere of flue gases and water vapor, characterized in that the filler IP is f">-Al2About310-20 wt.%, and the said alumina is used in the form of a suspension in a solution of sodium silicate.

 

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