RU2365409C1 - Catalyst for deep oil fraction cracking and method of its preparation - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to field of oil-processing and oil-chemical industry, namely to preparation of catalysts of deep catalytic cracking of oil fractions for C₂-C₄ olefin and high-octane petroleum production. Claimed catalyst for deep oil fraction cracking contains ultrastable zeolite Y in cation-decationated form, zeolite HZSM-5, and as matrix components bentonite clay, aluminium hydroxide and amorphous alumosilicate are used with the following component content, wt %: zeolite Y 10-30; zeolite HZSM-5 - 10-30; bentonite clay - 15-40; aluminium hydroxide - 0-20; amorphous alumosilicate - 20-40. Claimed method of preparing catalysts for deep oil fraction cracking includes passing ionic exchanges of Na cations, contained in zeolite Y onto cations of rare earth metals and ammonium, ultrastabilisation of zeolite in water steam medium, mixing of zeolite Y with suspension of zeolite HZSM-5 and matrix components, dispersion drying of obtained composition with further burning and obtaining catalyst, as matrix components bentonite clay and amorphous alumosilicate or bentonite clay, aluminium hydroxide and amorphous alumosilicate being used.

EFFECT: obtaining catalyst ensuring high output of both C₂-C₄ olefins and petroleum.

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Description

The present invention relates to the field of oil refining and petrochemical industries, in particular to the preparation of catalysts for the deep catalytic cracking of oil fractions for the production of olefins

C ₂ -C ₄ and high octane gasoline.

The main methods for the production of C ₂ -C ₄ olefins are thermal cracking in a tube furnace of straight-run gasoline or light gas oil (pyrolysis), thermal cracking on a solid heat carrier of heavier hydrocarbon feedstocks.

In traditional catalytic cracking, in addition to high-octane gasoline and light gas oil, C ₂ -C ₄ olefins are formed, but their yield does not exceed 12.0 wt.% (Sadeghbeigi R., Fluid catalytic cracking handbook: Design, Operation and Troubleshooting of FCC. - Second ed. - Gulf. Professional Publ., 2000 .-- p. 155).

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

The most profitable process for producing olefins of the required composition from a variety of raw materials is the selective cracking of this raw material - deep catalytic cracking. Modern zeolite-containing catalysts are composite materials consisting of the active component — zeolite — and a matrix including binders and filler. Therefore, the proposed catalyst for deep catalytic cracking consists of an active component (zeolite Y and zeolite HZSM-5) and a matrix, the components of which are bentonite clay (the main mineral is montmorillonite Ca-form), aluminum hydroxide of pseudoboehmite modification and amorphous aluminosilicate.

A cracking catalyst is known (US Pat. No. 4,309,280), in which HZSM-5 zeolite was used as an additive to the cracking catalyst in an amount of 0.01-1.00 wt.% Of the total weight of the catalyst. The disadvantage of this invention is a slight increase in the yield of C ₂ -C ₄ olefins compared with the yield in conventional catalytic cracking.

Known cracking catalyst (US patent No. 3758403) containing zeolite ZSM-5 and broad-porous zeolite (e.g. zeolite X or zeolite Y) as active components, which manifested itself in a simultaneous increase in the octane number of gasoline and an increase in the yield of C ₃ -C ₄ olefins by 10 wt.% compared with the yield in traditional catalytic cracking.

A cracking catalyst is known (US patent No. 5380690) containing zeolite from the ZSM-5 family and zeolite Y as active components that have an effect on increasing the octane number of gasoline and the yield of C ₂ -C ₄ olefins, especially C ₃ -C ₄ olefins. The matrix of this catalyst was a mixture of halloysite and aluminum hydroxide. The disadvantage of this catalyst is the low yield of C ₂ -C ₄ olefins, which does not exceed 24.0 wt.%.

Closest to the proposed catalyst is a catalyst for cracking oil fractions and a method for its preparation (RF patent 2300420, prototype). The known catalyst contains ultrastable zeolite Y as an active component, and a mixture of bentonite clay, amorphous aluminosilicate and aluminum hydroxide as a matrix. The catalyst is prepared by conducting ion exchanges of Na cations contained in zeolite Y for cations of rare-earth elements and ammonium, ultra-stabilization of the zeolite in water vapor, mixing with matrix components, followed by spray drying and calcination of the resulting composition.

It is known that when the catalyst contains only zeolite Y, it is not possible to achieve high yields of C ₂ -C ₄ olefins (Cracking of oil fractions on zeolite-containing catalysts / Edited by S.N. Khadzhiev - M .: Chemistry, 1982, p. 55) .

The aim of the present invention is to obtain a catalyst for the deep cracking of oil fractions, providing a high yield of both C ₂ -C ₄ olefins and gasoline.

The proposed catalyst for deep cracking of oil fractions contains ultra-stable zeolite Y in cation-decationized form, HZSM-5 zeolite, and bentonite clay and amorphous aluminosilicate or bentonite clay, aluminum hydroxide and amorphous aluminosilicate are used as matrix components in the following components, wt.% : zeolite Y 10-30; zeolite HZSM-5 10-30; bentonite clay 15-40; aluminum hydroxide 0-20; amorphous aluminosilicate 20-40.

The proposed method for preparing a catalyst for deep cracking of oil fractions involves ion exchanges of Na cations contained in zeolite Y for cations of rare earth elements and ammonium, ultra stabilization of zeolite in water vapor, mixing of zeolite Y with a suspension of HZSM-5 zeolite and matrix components, spray drying the resulting composition, followed by calcining and obtaining a catalyst, moreover, bentonite clay and amorphous aluminosilicate or bentonite clay, gy aluminum hydroxide and amorphous aluminosilicate in the following components, wt.%: zeolite Y 10-30; zeolite HZSM-5 10-30; bentonite clay 15-40; aluminum hydroxide 0-20; amorphous aluminosilicate 20-40.

Zeolite Y is a white powder with a particle size of 0.2-0.8 microns. The lattice module of zeolite is from 6.0 to 12.0. Zeolite is used in REE-N form, the content of rare earth elements is from 4.0 to 11.0 wt.% In terms of oxides of rare earth elements, the content of sodium oxide should be less than 0.5 wt.%

Zeolite HZSM-5 is a white powder with a particle size of less than 2 microns. The content of sodium oxide should be less than 0.3 wt.%. Zeolite is used in the H-form.

The method of preparation of the catalyst is as follows. Bentonite clay is subjected to treatment with ammonium nitrate according to the ion exchange method to reduce the content of sodium oxide. After processing, the residual content of sodium oxide in clay is less than 0.2 wt.%. The aluminum hydroxide suspension is treated with concentrated nitric acid. Then mixed suspension of bentonite clay and aluminum hydroxide, and amorphous aluminosilicate. Suspensions of zeolite Y and zeolite HZSM-5 add bentonite clay - amorphous aluminosilicate or bentonite clay - aluminum hydroxide - amorphous aluminosilicate to the prepared composition. The mixture is filtered, molded into microspherical particles with a size of less than 0.25 mm. The resulting catalyst was dried and calcined.

The reaction conditions for evaluating the microactivity of catalyst samples are as follows: temperature 536 ° C, catalyst / feed ratio 7.0, weight feed rate 17.5 h ⁻¹ , feed time 30 s. Test conditions are in accordance with ASTM D-3907. The properties of vacuum gas oil used as raw material are shown in table 1.

The test results of the described catalysts in accordance with ASTM method D-3907 are shown in table 2. To illustrate the invention, the following examples are given.

Table 1
Characteristic of vacuum gas oil Indicator Value Density at 20 ° С, kg / m ³ 894.6 Fractional composition, ° C Boiling point 294.0 10% distilled at temperature 350,0 30% distilled at temperature 384.0 50% distilled at temperature 409.0 70% distilled at temperature 434.0 90% distilled at temperature 491.0 96% distilled at temperature 512.0 Boiling point 520.0 Volume average boiling point, ° С 400,0 Characteristic factor 11.15 Average molecular weight 347.0 Sulfur content, wt.% 0.36 Coking ability, wt.% 0.08

Example 1 (prototype).

88.0 g of a suspension of bentonite clay (the concentration of bentonite clay in a suspension of 10.0 wt.%) Is mixed with 80.0 g of a suspension of aluminum hydroxide pseudoboehmite modification with a concentration of 10.0 wt.% In terms of Al ₂ O ₃ and 171, 0 g of amorphous aluminosilicate with a moisture content of 88.9 wt.%. Then, 26.7 g of a zeolite Y suspension (concentration of zeolite in a suspension of 30.0 wt.%) Is added to the resulting suspension. The resulting suspension is filtered, formed into microspherical particles with a size of less than 0.25 mm The catalyst is dried at a temperature of 100 ° C and calcined at 550 ° C. As a result, the resulting catalyst contains 22.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide, 38.0 wt.% Amorphous aluminosilicate and 20.0 wt.% Zeolite Y.

Example 2

80.0 g of a suspension of bentonite clay (the concentration of bentonite clay in a suspension of 10.0 wt.%) Is mixed with 80.0 g of a suspension of aluminum hydroxide pseudoboehmite modification with a concentration of 10.0 wt.% In terms of Al ₂ O ₃ and from 90, 1 g of amorphous aluminosilicate with a moisture content of 88.9 wt.%. Then, 53.3 g of a suspension of zeolite HZSM-5 (concentration of zeolite in a suspension of 30.0 wt.%) Was added to the resulting suspension. The resulting suspension is filtered, formed into microspherical particles with a size of less than 0.25 mm The catalyst is dried at a temperature of 100 ° C and calcined at 550 ° C. As a result, the resulting catalyst contains 20.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide, 20.0 wt.% Amorphous aluminosilicate and 40.0 wt.% HZSM-5 zeolite.

Example 3

80.0 g of a suspension of bentonite clay (the concentration of bentonite clay in a suspension of 10 wt.%) Is mixed with 172.8 g of amorphous aluminosilicate with a moisture content of 92.6 wt.%. Then, 53.3 g of a suspension of zeolite HZSM-5 (concentration of zeolite in a suspension of 30.0 wt.%) Was added to the resulting suspension. The resulting suspension is filtered, formed into microspherical particles with a size of less than 0.25 mm The catalyst is dried at a temperature of 100 ° C and calcined at 550 ° C. As a result, the resulting catalyst contains 20.0 wt.% Bentonite clay, 40.0 wt.% Amorphous aluminosilicate and 40.0 wt.% Zeolite HZSM-5.

Example 4. Similar to example 3. The difference is that the resulting catalyst contains 30.0 wt.% Bentonite clay, 30.0 wt.% Amorphous aluminosilicate and 40.0 wt.% Zeolite HZSM-5.

Example 5. Similar to example 3. The difference is that the catalyst contains 40.0 wt.% Bentonite clay, 20.0 wt.% Amorphous aluminosilicate and 40.0 wt.% Zeolite HZSM-5.

Example 6

120.0 g of a suspension of bentonite clay (the concentration of bentonite clay in a suspension of 10.0 wt.%) Is mixed with 108.2 g of amorphous aluminosilicate with a moisture content of 88.9 wt.%. Then, 13.3 g of a suspension of zeolite Y (concentration of zeolite in a suspension of 30.0 wt.%) And 40.0 g of a suspension of zeolite HZSM-5 (concentration of zeolite in a suspension of 30.0 wt.%) Are added to the resulting suspension. The resulting suspension is filtered, formed into microspherical particles with a size of less than 0.25 mm The catalyst is dried at a temperature of 100 ° C and calcined at 550 ° C. As a result, the resulting catalyst contains 30.0 wt.% Bentonite clay, 30.0 wt.% Amorphous aluminosilicate, 10.0 wt.% Zeolite Y and 30.0 wt.% Zeolite HZSM-5.

Example 7

Similar to example 6. The difference is that the catalyst contains 30.0 wt.% Bentonite clay, 30.0 wt.% Amorphous aluminosilicate, 20.0 wt.% Zeolite Y and 20.0 wt.% Zeolite HZSM-5.

Example 8

Similar to example 6, but the catalyst contains 30.0 wt.% Bentonite clay, 30.0 wt.% Amorphous aluminosilicate and 40.0 wt.% Zeolite Y.

Example 9

80.0 g of a suspension of bentonite clay (the concentration of bentonite clay in a suspension of 10.0 wt.%) Is mixed with 80.0 g of a suspension of aluminum hydroxide pseudoboehmite modification with a concentration of 10.0 wt.% In terms of Al ₂ O ₃ and from 90, 1 g of amorphous aluminosilicate with a moisture content of 88.9 wt.%. Then, 26.7 g of a suspension of zeolite Y (concentration of zeolite in a suspension of 30.0 wt.%) And 26.7 g of a suspension of zeolite HZSM-5 (concentration of zeolite in a suspension of 30.0 wt.%) Are added to the resulting suspension. The resulting suspension is filtered, formed into microspherical particles with a size of less than 0.25 mm The catalyst was dried at a temperature of 100 ° C and calcined at 550 ° C. As a result, the resulting catalyst contains 20.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide, 20.0 wt.% Amorphous aluminosilicate, 20.0 wt.% Zeolite Y and 20.0 wt.% Zeolite HZSM- 5.

Example 10

Similar to example 9. The difference is that the catalyst contains 15.0 wt.% Bentonite clay, 15.0 wt.% Aluminum hydroxide, 30.0 wt.% Amorphous aluminosilicate, 20.0 wt.% Zeolite Y and 20.0 wt.% zeolite HZSM-5.

Example 11

Similar to example 9, but the catalyst contains 20.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide, 20.0 wt.% Amorphous aluminosilicate, 10.0 wt.% Zeolite Y and 30.0 wt.% Zeolite HZSM-5.

Example 12

Similar to example 9. The difference is that the catalyst contains 20.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide, 20.0 wt.% Amorphous aluminosilicate, 15.0 wt.% Zeolite Y and 25, 0 wt.% Zeolite ZSM-5.

Example 13

Similar to example 9. The difference is that the catalyst contains 20.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide, 20.0 wt.% Amorphous aluminosilicate, 25.0 wt.% Zeolite Y and 15.0 wt.% zeolite HZSM-5.

Example 14

Similar to example 9, but the catalyst contains 20.0 wt.% Bentonite clay, 20.0 wt.% Aluminum hydroxide, 20.0 wt.% Amorphous aluminosilicate, 30.0 wt.% Zeolite Y and 10.0 wt.% Zeolite HZSM-5.

Thus, as follows from the examples and table 2, samples containing only one zeolite show an increased formation of either gasoline, as for samples containing only zeolite Y, or C ₂ -C ₄ olefins, as for samples only with zeolite ZSM-5 . To achieve simultaneously high yields of gasoline and C ₂ -C ₄ olefins, it is necessary to balance the activity of zeolites Y and ZSM-5 in the structure of a biceolite catalyst.

Claims (2)

A catalyst for deep cracking of petroleum fractions, including ultra-stable zeolite Y in cation-decationized form and a matrix, characterized in that it further comprises HZSM-5 zeolite, and bentonite clay and amorphous aluminosilicate or bentonite clay, aluminum hydroxide and amorphous aluminosilicate are used as matrix components in the following components, wt.%: zeolite Y 10-30; zeolite HZSM-5 10-30; bentonite clay 15-40; aluminum hydroxide 0-20; amorphous aluminosilicate 20-40. 2. A method of preparing a catalyst for deep cracking of petroleum fractions, including conducting ion exchanges for cations of rare earth elements and ammonium on a NaY zeolite, ultra-stabilization of a zeolite in water vapor, mixing the zeolite with matrix components and preparing a composition, spray drying the resulting composition from zeolite and matrix components followed by calcining and obtaining a catalyst, characterized in that at the stage of mixing the zeolite with the matrix components, an additional suspension of zeolite HZSM-5 is added, and as the matrix components, bentonite clay and amorphous aluminosilicate or bentonite clay, aluminum hydroxide and amorphous aluminosilicate are used in the following components, wt.%: zeolite Y 10-30; zeolite HZSM-5 10-30; bentonite clay 15-40; aluminum hydroxide 0-20; amorphous aluminosilicate 20-40.