A method of obtaining a carrier of catalysts for oil refining and petrochemical processes

 

(57) Abstract:

Describes how to obtain the carrier of catalysts for oil refining and petrochemical processes, including the formation of a mixture of compounds of aluminum and titanium, drying and calcination, wherein the precipitation of aluminium hydroxide lead from sodium aluminate and nitric acid and the salt of titanium, soluble in nitric acid, at a molar ratio of HNO3: Ti = 1 : (0,0001 - 0,006), pH 7.5 - 8,9, a temperature of 50 - 100oC, is subjected to the aging, and the resulting residue is mixed with aluminum hydroxide without titanium mass ratio of 1 : (0 - 1,25), washed, filtered, peptisers, molded, dried and calcined. The technical result is an increase in the activity of the catalyst. 2 C.p. f-crystals, 1 table.

The invention relates to the production of carrier catalysts for processes of refining and petrochemicals, and can be used in the refining and petrochemical industries.

A method of obtaining media (aluminum oxide) catalysts for processes of refining and petrochemicals (Ermolenko N. F., Efros, M. D. Regulation of the porous structure of the oxide adsorbents and catalysts. Minsk: Science and technology, 1971, S. 68-69) Potamia conditions for 100 hours, washing, filtering, shaping, drying and calcination.

The disadvantage of this medium is that obtained based catalysts have low activity.

For example, the catalyst for reforming of gasoline fractions composition, wt.%:

Platinum - 0,36

Rhenium - 0,36

Chloro - 1,2

Alumina - 98,08

at a temperature of 480oC, a pressure of 2.0 MPa shows when reforming a gasoline fraction 85-180oC the following indicators: octane number (O. H.) stable reformate by the motor method (m m) - 83 points (n), output stable reformate - 84 wt.%.

The closest in technical essence is the method of receiving media (U.S. patent N 4196101, B 01 J 21/04; 23/16, NCI 252/439, 1980), by stirring the aqueous suspension of aluminum oxide with a hydrolyzable titanium salt and ammonium hydroxide at a pH of 9.0 to 9.5, followed by drying the mixture at room temperature prior to molding, extruding and drying the extrudates at 121, 1millionoC for 16 hours and subsequent calcination in a stream of dry air at 537,8oC for 2 hours.

The disadvantage of this method is that the catalyst hydrodesulphurization unit, cooked on the media received this soderjashie of 0.42 wt.% sulfur at 350oC, a pressure of 4.0 MPa on the catalyst composition, wt.%:

Molybdenum - 8,42

Nickel - 2,78

Titan - of 4.38

Alumina - 84,42

the depth of the hydrodesulphurization unit is 90%.

Method for obtaining a carrier of catalysts for oil refining and petrochemical processes by precipitating aluminum hydroxide from sodium aluminate with nitric acid and titanium salt, soluble in nitric acid, at a molar ratio of HNO3: Ti= 1:(0,0001-0,006), pH 7.5 - 8,9, a temperature of 50 - 100oC for 15 -150 min and further mixed with aluminum hydroxide without titanium, precipitated from the sodium aluminate with the addition of nitric acid at pH of 8.9 to 9.2, temperature 10 - 25oC and subjected to aging at a pH of 9.2 and 9.6, the temperature of 90 - 102oC mass ratio of 1: (0 - 1,25), washing, filtration, peptization, forming, drying and calcination. As titanium salt use: nitrate titanium, or titanium sulfate or titanium chloride.

The proposed method of producing a carrier for catalysts for refining petrochemicals allows you to increase the activity of catalysts.

The proposed method of producing a carrier for catalysts for oil refining and petrochemistry carry out SL is. The titanium salt solution is prepared taking into account the molar ratio of HNO3: Ti= 1: (0,0001 - 0,006). The amount of titanium is taken in calculating the amount of titanium oxide in the finished carrier is 0.01 - 0.2 wt.%. The deposition is carried out at pH 7.5 - 8,9, a temperature of 50-100oC. the precipitate is subjected to aging in the mother solution for 15-150 min at pH 7.5-9.5 and a temperature of 50-100oC. the residue is mixed with aluminum hydroxide without titanium deposited nitric acid from sodium aluminate at a pH of 8.9 to 9.2, the temperature of 10-25oC, after aging last for 60-120 min at pH of 9.2-9.6 temperature 90-102oC mass ratio of 1: (0-1,25).

The mixture of oxides is subjected to washing, filtering, peptization nitric acid, forming, drying for 12 h at room temperature, 6 h at 120oC and calcination in air flow 4 h at 500 - 550oC.

Getting media and catalysts based on them is illustrated by the trail of examples.

Example 1

Taken 312,1 g of sodium aluminate solution and 148,87 g of the titanium salt solution in nitric acid, containing 0,72 g of titanium sulfate.

These solutions are simultaneously added to 200 ml of water placed in the flask, which is equipped with a stirrer. Adding solutions regulares residue is subjected to aging for 90 min at pH 8.0 and a temperature of 75oC. In other capacity is precipitated hydrate of aluminum oxide discharge solutions of nitric acid and sodium aluminate at a pH of 9.0, a temperature of 20oC. the Precipitated sludge is aged at a pH of 9.5, and a temperature of 100oC for 90 min Obtained precipitates are mixed in a mass ratio of 1:0.8, decantered, washed, filtered, peptizyde nitric acid are formed. The extrudates are dried for 12 h at room temperature, followed by 6 h at 120oC and prokalyvayutsya in a stream of dry air for 4 hours at 530oC.

From the received carrier is preparing a reforming catalyst by impregnation with a solution platinichloride and rhenium acids. The finished catalyst has the following composition, wt.%:

Platinum - 0,36

Rhenium - 0,36

Chloro - 1,2

Media - 98,08

The reformer was subjected to straight-run gasoline Fraction 85-180oC at 480oC, a pressure of 2.0 MPa, the space velocity of the feedstock 1.5 h, the ratio of circulating SIV 1500 nm3/m3of raw materials. The results are given in the table.

Example 2

Taken 312,1 g of sodium aluminate solution and 148,174 g of the solution of titanium sulfate in nitric acid, containing 0,024 g of salt, and cooked medium of example 1 without adding the WTO is ATA tests are given in the table.

Example 3

Taken 312,1 g of sodium aluminate solution, 149,56 g of the solution of titanium nitrate in nitric acid containing 1,41 g titanium salt. The media is prepared in the same conditions as in example 1, but the second precipitate is obtained by deposition conditions: pH of 9.2, the temperature of the 20oC; and the ageing conditions: pH of 9.6, temperature 100oC. the Mass ratio of precipitation 1:1,25.

On the basis of the received carrier is prepared and tested the catalyst of example 1. The test results presented in the table.

Example 4

Media prepared according to example 1 with the difference that comes 0,57 g of titanium tetrachloride, the pH during the precipitation of the first precipitate is equal to 7.5, and in the deposition of the second draft - 8,9, aging of the first precipitate is carried out at pH 7.5, and the second - 9,2.

On the basis of the received carrier is preparing a Hydrotreating catalyst by impregnation of the carrier with solutions of salts of molybdenum and cobalt. The finished catalyst had a composition, wt.%:

Molybdenum oxide - 8

The cobalt oxide - 4

Media - 88

The hydrodesulphurization unit exposed to diesel fraction, containing 0.42 wt.% sulfur, when 350oC pressure 4.0 MPa, the space velocity of the feedstock 1.5 h-1and the multiplicity of circulating SIV 1500 nm3what about the example 1 with the difference, what is taken 0.36 g of titanium trichloride, the pH during the precipitation of the first precipitate is 8,9; temperature deposition of the second draft - 10oC, and the aging of the first precipitate is carried out at pH of 9.5, the second at a temperature of 90oC for 120 minutes

On the basis of the received carrier is prepared and tested the catalyst according to example 4. The test results presented in the table.

Example 6

Media prepared according to example 1 with the difference that the temperature of deposition of the first sludge - 50oC, second draft - 25oC; aging first draft - 50oC, the second - 102oC, the ageing time of the first sludge - 150 min, second - 60 minutes

On the basis of the received carrier is prepared and tested the catalyst of example 1. The test results presented in the table.

Example 7

Media prepared according to example 1 with the difference that the temperature of deposition of the first sludge - 100oC, the aging is carried out at 100oC for 15 minutes

On the basis of the received carrier is prepared and tested the catalyst of example 1. The test results presented in the table.

Example 8 (comparative)

Media prepared according to example 1 with the difference that comes 0,012 g C 1.

The test results presented in the table.

Example 9 (comparative)

The catalyst carrier prepared according to example 1 with the difference that is taken of 1.93 g of titanium sulfate. On the basis of the received carrier is preparing a reforming catalyst and tested as in example 1.

The test results presented in the table.

Example 10 (comparative)

The catalyst carrier prepared according to example 1 with the difference that the deposition of the first precipitate is carried out at pH 7.0. On the basis of the received carrier is prepared and tested Hydrotreating catalyst as in example 4.

The test results presented in the table.

Example 11 (comparative)

The catalyst carrier prepared according to example 1 with the difference that the deposition of the first precipitate is carried out at a pH of 9.2. On the basis of the received carrier is prepared and tested Hydrotreating catalyst as in example 4.

The test results presented in the table.

Example 12 (comparative)

The catalyst carrier prepared according to example 1 with the difference that the temperature of deposition of the first draft is 45oC. On the basis of the received carrier is prepared and tested catalyst of reforming)

The catalyst carrier prepared according to example 1 with the difference that the mass ratio of the first and second precipitation is 1:1,5. On the basis of the obtained carrier was prepared and tested reforming catalyst of example 1.

The test results presented in the table.

Example 14 (comparative)

As the catalyst carrier is alumina. The catalyst had the same composition as that in example 1 and was tested under the conditions of example 1.

The test results presented in the table.

Example 15 (prototype)

The aluminum hydroxide obtained by precipitation from sodium aluminate and nitric acid under the conditions of deposition of the second precipitate of example 1. The precipitate is decanted from the syrup solution, washed, filtered, peptizer nitric acid, molded, dried and calcined. The resulting aluminum oxide grind and prepare a water suspension containing of 14.8 wt.% aluminum oxide.

675 g of aqueous slurry of aluminum oxide were mixed from 72.9 ml of a solution of titanium trichloride and this number is 14%-aqueous solution of NH4HE that the pH was equal to 9.0. The homogeneous mixture is then dried before molding condition and was extrudible. The extrudates were dried at 121ovale catalyst as in example 4. The test results presented in the table.

Thus, the proposed method of producing a carrier for catalysts for oil refining and petrochemistry allows you to get more active catalysts. However, this is only possible in the claimed limits of the molar relationship HNO3to Ti and conditions of deposition.

So, for example, increasing (9) and reducing (8) of the claimed ratio of HNO3: Ti activity of the reforming catalyst prepared on the received carrier, is reduced.

When reducing (10) and the increase (11) the pH of the solution and the temperature decrease (12) when the deposition of the first sludge catalytic activity of the reforming and Hydrotreating, prepared on the basis of the carrier obtained under these conditions falls.

The increase in the temperature of the solution during the precipitation of the first sediment leads to strong evaporation of the solution. The high content of the second residue in the media (13) entails a reduction in the activity of the reforming catalyst.

1. A method of obtaining a carrier of catalysts for oil refining and petrochemical processes, including the formation of a mixture of compounds of aluminum and titanium, drying and calcination, characterized in that ctnai acid, when the molar ratio of HNO3: Ti = 1 : (0,0001 - 0,006), pH 7.5 - 8,9, a temperature of 50 - 100oC, is subjected to the aging, and the resulting residue is mixed with aluminum hydroxide without titanium mass ratio of 1 : (0 - 1,25), washed, filtered, peptisers, molded, dried and calcined.

2. The method according to p. 1, characterized in that the aluminum hydroxide without titanium obtained by precipitation from sodium aluminate with the addition of nitric acid at pH of 8.9 to 9.2, temperature 10 - 25oC and subjected to aging at a temperature of 90 - 102oC and a pH of 9.2 - 9.6 V for 60 - 120 minutes

3. The method according to p. 1, characterized in that as salt use titanium nitrate, titanium, or titanium sulfate or titanium chloride.

4. The method according to p. 1, characterized in that the aging of the first precipitate is carried out at pH 7.5 to 9.5, at a temperature of 50 - 100oC for 15 to 150 minutes

 

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EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

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