RU2516847C1 - Catalytic additive for octane improvement in cat-cracked petrol and method of its manufacturing - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: catalytic additive includes zeolite ZSM-5 in a hydrogen form with silica modulus in the range from 25 up to 40 and the matrix which components include activated bentonite clay, aluminium hydroxide of pseudo-boehmitic modification treated by the nitric acid and amorphous alumosilicate with the following content of components, in wt %: zeolite ZSM-5 - 30-60; bentonite clay - 20-40; aluminium hydroxide - 10-40; amorphous alumosilicate - 10-20. The method of catalytic additive manufacturing includes ionic exchange of cations in zeolite ZSM-5 by ammonia cations, zeolite mixing with the matrix components which include boehmitic modification and amorphous alumosilicate, spray drying and ignition.

EFFECT: improving properties of catalytic additive.

2 cl, 3 tbl, 7 ex

Description

The present invention relates to the refining and petrochemical industries, in particular to the preparation of a catalytic additive to increase the octane number of catalytic cracking gasoline.

In recent years, many different catalytic additives to cracking catalysts have been used, which make it possible to vary the composition of the process products and increase the octane number of catalytic cracking gasoline without changing the design of the plants. The most common zeolite included in the additives is zeolite ZSM-5.

Known catalytic additive for cracking catalysts to increase the octane number of cracked gasoline (US patent No. 4309280, No. 4521298), in which zeolite ZSM-5 in hydrogen form was used as an additive to the cracking catalyst in an amount of 0.01-1.00 wt.% from the total mass of the catalyst. The disadvantage of this invention is the low octane number of cracked gasoline.

Known catalytic additive for cracking catalysts (US patent No. 4818738) containing zeolite ZSM-5 with a silica module of more than 12, and kaolin is used as a matrix component. The disadvantage of this invention is the low microactivity of the additive.

Known catalytic additive for cracking catalysts (US patent No. 5318696) containing zeolite ZSM-5 with a silica module of less than 30. The disadvantage of this invention is the low octane number of cracked gasoline.

Closest to the proposed catalytic additive is a catalytic additive for cracking catalysts containing from 30 to 85 wt.% Zeolite ZSM-5, 15-45 wt.% Kaolin, 3-15 wt.% Phosphorus in terms of P ₂ O ₅ (patent US 7547813, prototype). The disadvantage of this invention is the use of an inactive additive matrix, which, when used in a mixture with a cracking catalyst, leads to a decrease in the microactivity of the resulting mixture of a catalytic additive and a cracking catalyst. The disadvantage of this invention is the use in the preparation of the catalytic additives of large quantities of phosphoric acid to give the additive abrasion resistance during its operation.

The aim of the present invention is to provide an abrasion resistant catalytic additive based on zeolite ZSM-5 to increase the octane number of gasoline with high microactivity of the mixture of the catalytic additive and cracking catalyst without the use of phosphoric acid.

The proposed catalytic additive for increasing the octane number of cracked gasoline includes ZSM-5 zeolite in hydrogen form with a silica module in the range from 25 to 40 and a matrix, the components of which are activated bentonite clay, aluminum hydroxide of pseudoboehmite modification and amorphous aluminosilicate with the following components, wt.%: zeolite ZSM-5 30-60; bentonite clay 20-40; aluminum hydroxide 10-40 in terms of Al ₂ O ₃ ; amorphous aluminosilicate 10-20.

The proposed method for the preparation of a catalytic additive to increase the octane number of cracked gasoline includes conducting at the stage of preparation of the ZSM-5 zeolite an ion exchange of sodium cations for ammonium cations, mixing the ZSM-5 zeolite with matrix components, which use activated bentonite clay, pseudoboehmite aluminum hydroxide modification and amorphous aluminosilicate, spray drying the resulting composition from zeolite and matrix components, followed by calcination.

A method of preparing a catalytic additive is as follows. Pre-prepared zeolite ZSM-5 and matrix components.

At the stage of preparation of zeolite ZSM-5, an ion exchange of sodium cations of zeolite ZSM-5 to ammonium cations is carried out to ensure a residual content of sodium oxide of less than 0.1 wt.%.

Bentonite clay is activated with ammonium nitrate according to the ion exchange method to reduce the content of sodium oxide. After activation, the residual content of sodium oxide in the bentonite clay is less than 0.2 wt.%.

The pseudoboehmite modification of aluminum hydroxide suspension is treated with concentrated nitric acid. At this stage, part of the aluminum hydroxide is converted into basic nitric salts of aluminum, which ensures the strength of the resulting catalytic additives.

Amorphous aluminosilicate is obtained by precipitation of sodium aluminate with acidic aluminum sulfate followed by syneresis, activation with aluminum sulfate and washing. The content of alumina in the amorphous aluminosilicate is from 10 to 16 wt.%, The content of sodium oxide is 0.1-0.2 wt.%.

Suspensions of activated bentonite clay and pseudoboehmite modification of aluminum hydroxide treated with nitric acid are mixed in the required proportion. The main requirement for the implementation of this stage is the homogeneous mixing of the two suspensions. A suspension of zeolite ZSM-5 is added to the prepared suspension of a mixture of bentonite clay - aluminum hydroxide. The next step is to introduce amorphous aluminosilicate into the resulting suspension. A mixture of a composition of zeolite and matrix components is thoroughly mixed until a homogeneous suspension is obtained, formed by spray drying into microspherical particles with a particle size of about 70 microns. The resulting composition is calcined at a temperature of 700-740 ° C for 3-5 hours to obtain a catalytic additive.

To give the catalytic additive equilibrium properties before catalytic tests, it is subjected to processing at a temperature of 760 ° C in 100% water vapor for 5 hours.

Based on the obtained catalytic additives and an equilibrium cracking catalyst, mixtures are prepared from the calculation of the content of zeolite ZSM-5, equal to 2.5 wt.%, In the mixture.

The microactivity of mixtures of an equilibrium cracking catalyst and a catalytic additive is evaluated under the following conditions: temperature 527 ° C, catalyst / feed ratio 4.0, feed time 30 s. Test conditions are in accordance with ASTM D-5154. The properties of vacuum gas oil used as a cracking feed are given in table 1.

The wear resistance of catalytic additives is shown in table 2. The microactivity of mixtures of equilibrium cracking catalyst and catalytic additives in accordance with ASTM D-5154 are shown in table 3. The octane number is estimated by the research method based on the analysis of the chemical composition of gasoline by chromatography-mass spectroscopy, values are given in table 3.

The following examples are provided to illustrate the invention.

Example 1 (prototype)

309.0 g of a kaolin suspension (kaolin concentration in a suspension of 10.0 wt.%) Is treated with 6.0 g of concentrated phosphoric acid (in terms of P ₂ O ₅ ), mixed with 302 g of a suspension of ion-exchange zeolite ZSM-5 (zeolite concentration in suspensions of 10.0 wt.%). The resulting composition is formed into microspherical particles by spray drying and calcined at 720 ° C.

As a result, the obtained catalytic additive contains 40.0 wt.% Kaolin, 15.0 wt.% P ₂ O ₅ and 45.0 wt.% Zeolite ZSM-5.

The composition of the mixture for catalytic testing is as follows: 94.5 wt.% Equilibrium cracking catalyst and 5.5 wt.% Catalytic additives. The octane number of cracked gasoline according to the research method is 92.6.

Example 2

112.0 g of a suspension of zeolite ZSM-5 (concentration of zeolite in a suspension of 15.0 wt.%) Is subjected to ion exchange of sodium cations in a zeolite for ammonium cations at a ratio of 2 g-equivalent of ammonium per g-equivalent of sodium in zeolite. The residual content of sodium oxide in the zeolite is 0.1 wt.%.

84.0 g of a suspension of activated bentonite clay (concentration of bentonite clay in a suspension of 10.0 wt.%) Is mixed with 84.0 g of a suspension of pseudoboehmite modification of aluminum hydroxide treated with aluminum nitrate (concentration of 10.0 wt.% In terms of Al ₂ O ₃ ) Then, 112.0 g of a suspension of ion exchange zeolite ZSM-5 (zeolite concentration in suspension of 15.0 wt.%) Is added to the resulting suspension. In the next step, 90.3 g of amorphous aluminosilicate with a moisture content of 90.7 wt.% Are added to the resulting suspension. The resulting composition of zeolite and matrix components is formed into microspherical particles with a size of about 70 microns and calcined at 720 ° C.

As a result, the obtained catalytic additive contains 20.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide in terms of Al ₂ O ₃ , 20.0 wt.% Amorphous aluminosilicate and 40.0 wt.% Zeolite ZSM-5 .

The composition of the mixture for catalytic tests is as follows: 93.8 wt.% Equilibrium cracking catalyst and 6.2 wt.% Catalytic additives. The octane number of cracked gasoline according to the research method is 92.8.

Example 3

123.0 g of a suspension of zeolite type ZSM-5 (concentration of zeolite in a suspension of 15.0 wt.%) Is subjected to ion exchange of sodium cations in zeolite for ammonium cations at a ratio of 4 g equivalent of ammonium per g equivalent of sodium in zeolite. The residual content of sodium oxide in the zeolite is 0.05 wt.%.

73.8 g of a suspension of activated bentonite clay (concentration of bentonite clay in a suspension of 10 wt.%) Is mixed with 73.8 g of a suspension of pseudoboehmite modified aluminum hydroxide (concentration of 10.0 wt.% In terms of Al ₂ O ₃ ). Then, 123.0 g of a suspension of ion exchange zeolite ZSM-5 (concentration of zeolite in suspension 15.0 wt.%) Is added to the resulting suspension. In the next stage, 39.7 g of amorphous aluminosilicate with a moisture content of 90.7 wt.% Are added to the resulting suspension. The resulting composition from zeolite and matrix components is formed into microspherical particles with a size of 70 microns and calcined at 720 ° C.

As a result, the obtained additive contains 20.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide in terms of Al ₂ O ₃ , 10.0 wt.% Amorphous aluminosilicate and 50.0 wt.% Zeolite ZSM-5.

The composition of the mixture for catalytic tests is as follows: 95.0 wt.% Equilibrium cracking catalyst and 5.0 wt.% Catalytic additives. The octane number of cracked gasoline according to the research method is 93.1.

Example 4

Similar to example 3. The difference is that the obtained catalytic additive contains 20.0 wt.% Bentonite clay, 10.0 wt.% Aluminum hydroxide in terms of Al ₂ O ₃ , 10.0 wt.% Amorphous aluminosilicate and 60.0 wt.% zeolite ZSM-5.

The composition of the mixture for catalytic tests is as follows: 95.8 wt.% Equilibrium cracking catalyst and 4.2 wt.% Catalytic additives. The octane number of cracked gasoline according to the research method is 93.1.

Example 5

Similar to example 3. The difference is that the catalytic additive contains 40.0 wt.% Bentonite clay, 10.0 wt.% Aluminum hydroxide in terms of Al ₂ O ₃ , 20.0 wt.% Amorphous aluminosilicate and 30.0 wt. .% zeolite ZSM-5.

The composition of the mixture for catalytic tests is as follows: 91.7 wt.% Equilibrium cracking catalyst and 8.3 wt.% Catalytic additives. The octane number of cracked gasoline according to the research method is 92.8.

Example 6

Similar to example 3. The difference is that the catalytic additive contains 20.0 wt.% Bentonite clay, 40.0 wt.% Aluminum hydroxide in terms of Al ₂ O ₃ , 10.0 wt.% Amorphous aluminosilicate and 30.0 wt. .% zeolite ZSM-5.

The composition of the mixture for catalytic tests is as follows: 91.7 wt.% Equilibrium cracking catalyst and 8.3 wt.% Catalytic additives. The octane number of cracked gasoline according to the research method is 92.6.

Example 7

For comparison. For testing, only an equilibrium cracking catalyst was used without the use of a catalytic additive to increase the octane number of cracked gasoline.

The composition of the mixture for catalytic tests is as follows: 100 wt.% Equilibrium cracking catalyst and 0 wt.% Catalytic additives. The octane number of cracked gasoline according to the research method is 91.5.

Thus, as follows from table 2, catalytic additives containing zeolite ZSM-5 and a matrix based on activated bentonite clay, aluminum hydroxide pseudoboehmite modification and amorphous aluminosilicate, have higher wear resistance compared to the prototype. The proposed catalytic additive provides high microactivity in mixtures with an equilibrium cracking catalyst with a significant increase in the octane number of cracked gasoline, as follows from table 3.

Table 1 Characteristic of vacuum gas oil Options Vacuum gas oil Density at 20 ° С, kg / m ³ 986.4 Fractional composition, ° C: Boiling point 302.0 10% distilled at temperature 360.0 30% distilled at temperature 382.0 50% distilled at temperature 406.0 70% distilled at temperature 445.0 90% distilled at temperature 498.0 96% distilled at temperature 538.0 Boiling point 560.0 Characteristic factor 11.75 Sulfur content, wt.% 0.15 Coking ability, wt.% 0.12

Table 3 Catalytic properties of a mixture of a catalytic additive and an equilibrium cracking catalyst Example The content of the additive in the mixture, wt.% Microactivity, wt.% Octane number of cracked gasoline (research method) 1 (prototype) 5.5 76 92.6 2 6.2 79 92.8 3 5,0 81 93.1 four 4.2 83 93.1 5 8.3 78 92.8 6 8.3 77 92.6 7 0 78 91.5

Claims (2)

1. A catalytic additive for increasing the octane number of cracked gasoline, including ZSM-5 zeolite in hydrogen form with a silica module in the range from 25 to 40 and a matrix, characterized in that activated bentonite clay, nitric acid treated with pseudoboehmite aluminum hydroxide are used as matrix components modifications and amorphous aluminosilicate in the following components, wt.%: zeolite ZSM-5 30-60; bentonite clay 20-40; aluminum hydroxide 10-40; amorphous aluminosilicate 10-20. 2. A method of preparing a catalytic additive to increase the octane number of cracked gasoline, comprising mixing ZSM-5 zeolite with matrix components and preparing a composition, spray drying the resulting composition from zeolite and matrix components, followed by calcining and obtaining an additive, characterized in that at the zeolite preparation stage conduct ion exchange of sodium cations for ammonium cations on zeolite ZSM-5, and activated bentonite clay treated with nitric acid aluminum seed of pseudoboehmite modification and amorphous aluminosilicate in the following components, wt.%: zeolite ZSM-5 30-60; bentonite clay 20-40; aluminum hydroxide 10-40; amorphous aluminosilicate 10-20.