RU1686748C - Method of preparing zeolite-containing catalyst of cracking - Google Patents

Abstract

The invention relates to catalytic chemistry, in particular the preparation of a zeolite-containing cracking catalyst for use in refining and petrochemicals. The goal is to increase the catalyst yield and eliminate environmentally harmful waste in the process. Erg are conducted by sequentially mixing a suspension of zeolite NaY (it is obtained by diluting the crystallization product of zeolite with water to a concentration of 110-140 g / l to zeolite) with sodium silicate solutions,. AlatSO 7 4. And A1 (OH) s. In this case, the ratio of equivalents H2S04 and AEDZSST support in the range of 1.45-1.55. Subsequent coagulation of the resulting ash is carried out in a layer of mineral oil with further dispersion, spray drying and calcination. Catalyst yield increased on May 9th. % in the absence of environmentally harmful effluents. 1 tab. ate with

Description

The invention relates to the production of zeolite containing cracking catalysts (CCC) and can be used in the refining and petrochemical industries.

The aim of the invention is to increase the yield of the catalyst and the elimination of environmentally harmful waste by using a suspension of zeolite NaY obtained by diluting the crystallization product of the zeolite with water to a concentration of 110-140 g / l of zeolite, and keeping the ratio of equivalents of sulfuric acid and aluminum sulfate in the range 1.45-1.55.

The invention is illustrated by the following examples.

Example 1. To prepare a reaction mass crystallizing in NaY zeolite, 14.5 m3 of a sodium silicate solution of 2.53 N concentration was mixed with continuous stirring. according to SI02 and a molar ratio of silicon oxides to sodium 2.8: 3.98 m3 of a solution of aluminum sulfate 4.4 n; 1.88 m3 of a solution of sodium aluminate with a concentration of 5 g / l; N320-257.3 g / l and 1 m of an amorphous alkaline seed composition 16 N320 AI203-15SI02 "320Н20.

The result is a reaction mass of the composition

2.4Na20 AG20z 6.75SI02 150.4N20.

The reaction mass is heated to 100 ° C and incubated for 16 hours. After crystallization

Os 00 Pts

2

00

zeolite crystals of the chemical composition NaaO AlaOs 4.8SI02 and mother liquor are formed. The calculated concentration of this suspension is 165.5 g / l by zeolite. The resulting crystallization product of a concentration of 165.5 g / l was diluted with water to a concentration of 110 g / l of zeolite and the resulting suspension was sent to molding the catalyst. “Preparation of the catalyst.

2.3 n sodium silicate solutions are fed to the mixer into the mixer column. (molar ratio of silicon oxides to sodium 2.85), acidified aluminum sulfate 1.2 N. in accordance with A12 (504) s with the ratio of equivalents of solutions of sulfuric acid and aluminum sulfate 1.5, a suspension of aluminum hydroxide (YEAR) with a concentration of 50 g / l; a suspension of NaY zeolite with a concentration of 110 g / l according to the zeolite.

The flow rate of solutions on the molding column, l / h:

Sodium Silicate 473

YEAR302

Zeolite suspension (110 g / l) 182 Acidified aluminum sulfate 288 Forming conditions; Temperature of working solutions, ° С 8.7 pH during molding 7.0

Coagulation time, s 5.2

Ash temperature, ° С 12.6

As a result, an alumina-silica sol is obtained, which coagulates into alumina-silica gel balls on a layer of mineral oil.

The obtained hydrogel balls (strength. 100 g / ball) are subjected to syneresis at 50 ° C for 12 hours in a solution of sodium sulfate without changing the solution and ion exchange in three stages,

In the first stage, the treatment is carried out with a solution of ammonium nitrate with a concentration of 16 g / l for 40 hours with a change of solution every 2 hours at 50 ° C.

At the second stage of ion exchange, hydrogel balls are treated with a solution of a mixture of salts of rare-earth elements (REE) with a concentration of 8 g / l with a pH of 5.5 at 50 ° C for 8 hours with a change of solution every 2 hours at 50 ° C.

At the second stage of ion exchange, the hydrogel beads are treated with a solution of a mixture of salts of rare-earth elements with a concentration of 8 g / l with a pH of 5.5 at 50 ° C for 8 hours with a change of solution every 4 hours.

. In the third stage, treatment with a solution of ammonium nitrate with a concentration of 16 g / l at 50 ° C for 20 hours is carried out with a change of solution every 2 hours.

0

5

5

After ion exchange, the hydrogel granules are washed with distilled water from ammonium salts, REE and sodium, and dispersed. The resulting mass was spray-dried in a spray dryer and a dry microspherical catalyst was obtained, which was calcined for an hour at 700 ° C and then stabilized in an atmosphere of 100% water vapor for 6 hours at 775 ° C.

The resulting catalyst has the following chemical composition, May,%: Na200,42

AlaOs. 19,3

5J278.21

Lu20a2.07

The catalytic properties of the zeolite-containing catalyst in the catalytic cracking reaction are evaluated according to the existing standard under flow conditions (research method). Test Conditions: Kerosene Gas Oil Raw Material

fraction

Cracking temperature, ° С500

Mass speed

Duration of cracking, min. 7 Stable activity is assessed by the yield of gasoline.

The resulting catalyst has a mechanical strength of 91.0%.

Stable activity,% 42.0.

The test results are presented in the table.

Example 2. Preparation of a zeolite suspension.

The zeolite was synthesized according to Example 1. A crystallization product of a concentration of 165.5 g / l by zeolite was diluted with water to a zeolite content of 135 g / l and sent to a molding column. Preparation of the catalyst. 2.3 N sodium silicate solutions are fed to the mixer. (molar ratio of silicon oxides to sodium 2.85), acidified aluminum sulfate 1.2 M according to AlafSO / Oa with a ratio of equivalents of solutions of sulfuric acid and aluminum sulfate 1.5, suspension with a concentration of 50 g / l, suspension of zeolite NaY with a concentration of 135 g / l zeolite at the following reagent consumption on the molding column, l / h:

Sodium Silicate 473

GOA302

Zeolite suspension (135 g / l) 148 Acidified aluminum sulfate 288 Forming conditions Temperature of working solutions, ° С 8.8 pH during molding 7.5

Coagulation time, s4

Ash temperature, ° С 12.2

5

0

5

0

5

An alumina-silica sol is obtained, which coagulates in a layer of oil into hydrogel balls. The strength of the obtained balls 120 g / ball.

Further syneresis, ion exchange, drying and calcining operations are carried out as in Example 1.

The composition of the obtained catalyst, May. %:

NaaO 0.47

A120z19.3

SIOz77.9

Lu20a2.33

The preparation conditions and properties of the resulting catalyst are shown in the table.

Example 3. Preparation of a zeolite suspension.

The zeolite synthesis was carried out as in Example 1.

A crystallization product of a concentration of 165.5 g / l on a zeolite is diluted with water to a zeolite content of 140 g / l and sent to a molding column.

Preparation of the catalyst.

2.3 N sodium silicate solutions are fed to the mixer. (molar ratio of silicon oxides to sodium 2.85), acidified aluminum sulfate 1.2 N. by (5Cm) s with the ratio of equivalents of solutions of sulfuric acid and aluminum sulfate 1.5; a suspension of GOA with a concentration of 50 g / l according to A120z, a suspension of zeolite NaY with a concentration of 140 g / l according to the zeolite with the following reagent consumption for the forming column, l / h:

Sodium Silicate 473

GOA302

Zeolite suspension (140-g / l) 143

Acidified Ammonium Sulfate 288

Forming conditions:

Temperature of working solutions, ° С 9.5

molding pH 8.3

Coagulation time, 3.2

Ash temperature, ° С, 13.0

Get alumina-silica sol, coagulating in a layer of mineral oil in hydrogel balls. The strength of the black-formed balls is 110 g / ball.

Further syneresis, ion exchange, drying and calcining operations are carried out as in Example 1.

The chemical composition of the obtained catalyst, May. %:

Na2O0.40

A 20z19.3

SI02 78.1

LU2032,2

The mechanical strength of the catalyst is 90.8%, the activity is stable at 41.8%.

Example 4. Preparation of a zeolite suspension.

A zeolite suspension is prepared according to Example 1. A crystallization product of a concentration of 165.5 g / l by zeolite is diluted with water to a zeolite content of 135 g / l and sent to a molding column.

Catalyst preparation

2.3 N sodium silicate solutions are fed to the mixer. (molar ratio of silicon oxides to sodium 2.85), acidified aluminum sulfate 1.2 N. according to (504) s with an equivalent ratio of solutions of sulfuric acid and aluminum sulfate of 1.45, a suspension of GOA with a concentration of 50 g / l according to A120z, a suspension of NaY zeolite with a concentration of 135 g / l according to zeolite with the following reagent flow to the molding column, l / h:

Sodium Silicate 473

GOA302

Zeolite suspension (135 g / l) 148 Acidified aluminum sulfate 288

Molding Conditions

Temperature of working solutions, ° С 8.8

molding pH 8.0

Coagulation time, s 4.8

Ash temperature, ° С 12.5

An alumina-silica sol is obtained, which coagulates in a layer of oil into hydrogel balls.

The strength of freshly formed syringes is 95 g / ball.

All subsequent operations of syneresis, ion exchange, drying, calcination are carried out as in Example 1.

The composition of the obtained catalyst, May. %: NazO0.47

A 20s19.0

Si0278.55

LU2031.98

Mechanical strength 89.5%, stable activity 41.6%.

Example 5. Preparation of a zeolite suspension.

The zeolite suspension was prepared according to Example 1 with a concentration of 135 g / l and sent to molding.

Preparation of the catalyst.

2.3 n sodium silicate solutions are mixed in the mold. (molar ratio of silicon oxides of silicon to sodium 2.85), acidified aluminum sulfate (1.2 N in accordance with (504) s with a ratio of equivalent solutions of sulfuric acid and aluminum sulfate 1.55, GOA suspension with a concentration of 50 g / L in suspension zeolite concentration of 135 g / l for zeolite with the following consumption of reagents on the molding, l / h:

Sodium Silicate 473

GOA302

Zeolite suspension (135 g / l) 148

Acidified Aluminum Sulphate 288 Conditions. molding: Temperature of working solutions, ° С 9.2 pH during molding 6.5

Coagulation time, s 5.0

Evil temperature, ° C. 12.0

The strength of the co-formed ball is 95 g / ball.

Further operations of ion exchange, drying and calcination are carried out as in Example 1.

The chemical composition of the obtained catalyst, May. %:

N3200,46

A 20s19.3

SI0278.24

ЦаОз2.0

The mechanical strength of the catalyst is 91.8%, the stable activity is 41.8%.

Example 6 (for comparison). Preparation of zeolite suspension.

The synthesis of zeolite is carried out according to example (.

The resulting zeolite suspension with a concentration of 165.5 g / l without dilution is sent to molding.

Preparation of the catalyst. Solutions of sodium silicate 2.3 N, (molar ratio of silicon oxides to sodium 2.85), acidified aluminum sulfate 1.2 N are mixed. with the ratio of equivalents of solutions of sulfuric acid and aluminum sulfate 1.5, a suspension of the YEAR concentration of 50 g / l in A (20h, suspension of NaY zeolite with a concentration of 165.5 g / l in zeolite with the following reagent flow to the molding column, l / h:

Sodium Silicate 473

YEAR302

Zeolite suspension (165.5 g / l) 121 Acidified aluminum sulfate 288 Forming conditions: Temperature of working solutions, ° С 9.2 pH during molding8.7

Coagulation time, s2.0

Ash temperature, ° С 12.0

Silica gel sol coagulates in the oil layer into hydrogel balls with a strength of 70 g / ball.

All subsequent operations of syneresis, ion exchange, drying and calcination are carried out as in Example 1.

The composition of the obtained catalyst, May.

%

N3200,43

A 20s19.0

SI0278.5

1igOz2.07

The properties of the resulting catalyst are shown in the table.

Example 7 (for comparison). Preparation of zeolite suspension.

The zeolite suspension is prepared according to Example 2 and sent to a molding with a concentration of 135 g / L.

Preparation of the catalyst.

2.3 n sodium silicate solutions are mixed in the mold. (molar ratio of silicon oxides to sodium 2.85), acidified aluminum sulfate 1.2 N. according to (504) s with the ratio of equivalents of sulfuric acid solutions to aluminum sulfate 1.2, a suspension of GOA with a concentration of 50 g / l;

Sodium Silicate 473

GOA302

Zeolite suspension (135 g / l) 148 Acidified aluminum sulfate 288

Forming conditions:

Temperature of working solutions, ° С 9.0

pH for sheep form 8.8

Coagulation time, s1.5

Ash temperature, ° С 12.8

Further operations of ion exchange, drying and calcination are carried out as in Example 1.

The composition of the obtained catalyst, May. %:,

NaaO0.45

A 20z19.8

S10277.85

LuaOs1.9

The properties of the obtained catalyst are shown in the table.

Example 8 (for comparison). The preparation of the zeolite suspension was carried out as in Example 2 and with a concentration of 135 g / L was sent to molding.

Preparation of the catalyst.

2.3 N sodium silicate solutions are mixed. (molar ratio of silicon oxides to sodium 2.85), acidified aluminum sulfate 1.2 N. according to (504) s with the ratio of equivalents of solutions of sulfuric acid and aluminum sulfate 1b, suspension of GOA with a concentration of 50 g / l; suspension of zeolite with a concentration of 135 g / l for zeolite at the following reagent consumption, l / h;

Sodium Silicate 473

GOA302

Zeolite suspension (135 g / l) 148

Acidified Aluminum Sulphate 288 Forming Mode:

The temperature of the working solutions, ° C 8.5

molding pH 6.0

coagulation time, s 7.4

Ash temperature, ° С 12.6

Further catalyst preparation operations are carried out as in Example 1.

The composition of the obtained catalyst, May.

%:

N3200,47

A 20s20,0

Si 0277.68

LU2031.85

The properties of the obtained catalyst are shown in the table.

Example 9 (for comparison). Preparation of zeolite suspension.

To prepare a reaction mass crystallizing in NaY zeolite, a 14.5 m 2.53 N sodium silicate solution is mixed in a crystallizer with continuous stirring. according to SI02. with a molar ratio of silicon oxides to sodium of 2.8.3.98 m3 of a solution of aluminum sulfate 4.4 N., 1.88 m3 of a solution of sodium aluminate with a concentration of 267.5 g / l, Na20 257.3 g / l and 1 m3 amorphous alkali seed composition

16Na20-15Si02 320H20. The result is a reaction mass of the composition

2.4Na20-6.75Si02-150.4H20. The reaction mass is heated to 100 ° C and incubated for 16 hours. After crystallization, zeolite crystals of the chemical composition Na20.-Al20j are formed. 4.8 Si02 and mother liquor. The calculated concentration of this suspension is 165.5 g / l by zeolite.

The resulting crystallization product by a concentration of 165.5 g / l was diluted with water to a concentration of 100 g / l by zeolite. The finished slurry is sent to molding the catalyst.

Preparation of the catalyst. 2.3 n sodium silicate solutions are fed to the mixer into the mixer column. (molar ratio of silicon oxides to sodium 2.85), acidified aluminum sulfate 1.2 N. according to Ai2 (S04) j with an equivalent ratio of solutions of sulfuric acid and aluminum sulfate 1.5, a suspension of GOA with a concentration of 50 g / l according to A120z, a suspension of zeolite NaY with a concentration of 100 g / l according to zeolite. The flow rate of solutions on the molding column, l / h:

Sodium Silicate 473

GOA302

Zeolite suspension (100 g / l) 200 Acidified aluminum sulfate 288 Forming conditions: Temperature of working solutions, ° C 8.5 pH during molding 6.8

Coagulation time, s 6.0

Ash temperature, ° С 12.5

The result is an alumina-silica gel sol coagulating into alumina-silica balls in a layer of mineral oil.

The resulting hydrogel beads

(ball strength 80 g / ball) is subjected to syneresis at 50 ° C for 12 hours in a solution of sodium sulfate without changing the solution and ion exchange in three stages. In the first stage, the treatment is carried out with a solution of ammonium nitrate with a concentration of 16 g / l for 40 hours with a change of solution every 2 hours at 50 ° C.

In the second stage of ion exchange, the hydrogel beads are treated with a solution of a mixture of REE salts with a concentration of 8 g / l with a pH of 5.5 at 50 ° C for 8 hours with a change of solution every 4 hours.

In the third stage, the solution is treated with a solution of ammonium nitrate with a concentration of 16 g / l at 50 ° C for 20 hours with a change of solution every 2 hours.

After ion exchange, the hydrogel granules are washed with distilled water of ammonium, REE and sodium salts, and dispersed. The resulting mass was spray dried in a spray dryer to obtain a dry microspherical catalyst, which was calcined for 6 hours at 700 ° C and then stabilized in an atmosphere of 100% water vapor for 6 hours at 775 ° C.

The resulting catalyst has the following chemical composition, May. %:

Na20 0.45

A 20s19.5

5J278.45

LU2031.6

The catalytic properties of the zeolite-containing catalyst in the catalytic cracking reaction are evaluated according to the existing standard under flowing conditions (research method). Test conditions: Raw materials of Kerosene-gas oil

fraction

Cracking temperature, ° С500

Mass speed, h

-1

twenty

Duration of cracking, min. 7 Stable activity is assessed by the yield of gasoline.

The preparation conditions and properties of the resulting catalyst are shown in the table.

As can be seen from the data given in the table, the quality of the catalyst obtained by the described method does not differ from the quality of the industrial catalyst of the KMTSR-ND brand. The proposed method for the preparation of the catalyst has significant advantages over the known:

the involvement of the mother liquor formed after crystallization of the zeolite in the molding of the catalyst makes it possible to abandon the construction of the mother liquor processing unit;

The loss of zeolite in the filtration and washing stages, which are in May, ceases. %;

the yield of the finished product increases on May 9th. %;

the return of valuable raw materials (silicon and sodium oxides) contained in the mother liquor reduces the consumption of raw materials (sodium silicate) by 300 kg / day;

there are no environmentally harmful effluents of zeolithic production;

The load on the treatment plant is reduced by eliminating the washing water of the zeolite plant.

Claims (1)

SUMMARY OF THE INVENTION A method for preparing a zeolite-containing cracking catalyst, comprising crystallizing an alkaline alumina gel into NaY zeolite, preparing a suspension of NaY zeolite, mixing the resulting suspension of NaY zeolite with solutions of sodium silicate, sulfuric acid, aluminum sulfate and aluminum hydroxide, coagulating the resulting zinc a layer of mineral oil, dispersion, spray drying and calcination, characterized in that, in order to increase the yield of the catalyst and eliminate environmentally harmful waste in the process In addition, a suspension of NaY zeolite is prepared by diluting the crystallization product with water to a concentration of 110-140 g / l by zeolite and, when mixed, the equivalent ratio of sulfuric acid and aluminum sulfate is kept in the range of 1.45-1.55.