RU2252242C1 - Method of engine fuels production - Google Patents

Abstract

FIELD: petroleum refining industry; production of engine fuels.

SUBSTANCE: the invention is pertaining to the field of petroleum refining industry, in particular, to production of engine fuels. Substance: the method provides for carrying out a catalytic cracking of petroleum fractions in presence of platinumzeolite-bearing rare-earth aluminum-silicate catalyst. The used catalyst consists of 5-20 mass % of "Y" zeolite with a molar ratio of silicon oxide to aluminum oxide within 4.5-9.5 and 80-95 mass % of the silica-alumina base in turn consisting of 40-95 mass % of amorphous aluminosilicate and 5-60 mass % of clay, and having a chemical composition, in mass %: aluminum oxide - 4.5-40.0, oxides of rare earths - 0.5-4.0, platinum - 0.0001-0.01, sodium oxide - 0.01-0.5, silicon oxide - the rest. The technical result: increased output of a gasoline fraction.

EFFECT: the invention ensures increased output of a gasoline fraction.

2 tbl, 8 ex

Description

The invention relates to the production of motor fuels and can be used in the process of catalytic cracking in the oil refining industry.

A known method of producing motor fuels by cracking oil fractions using a zeolite-containing aluminosilicate catalyst in ball and microspherical forms. In ball form, the catalyst contains 10-12 wt.% Zeolite Y and has a chemical composition, wt.%:

alumina 9-10

rare earth oxides (ORZE) 2.0-2.5

sodium oxide 0.2-0.6

silica rest

(Cracking of oil fractions on zeolite-containing catalysts. Edited by S.N. Khadzhiev. M., Chemistry, 1982).

In microspherical form, the catalyst contains 16-18 wt.% Zeolite Y and has the following chemical composition, wt.%:

alumina 10-12

rare earth oxides (ORZE) 2.5-3.0

sodium oxide 0.2-0.6

silica rest

There is also known a method of cracking oil fractions in the presence of zeolite-containing aluminosilicate catalysts with the addition of trace amounts of platinum 0.0001-0.1 wt.% (US Patent No. 4429053, Cl. B 01 J 29/12; French Patent No. 2,500326, Cl. B 01 J 29/12; Yandieva LA, Zakarina NA Cracking catalysts and zeolites. Collection of scientific works of the GrozNII, M., TsNIITENEFTEKHIM, 1984, No. 38, p. 76-80).

A known method of producing ball zeolite-containing catalysts (and.with. SSSR No. 389.829, CL MKI B 01 J 29/08, 1973) for the conversion of hydrocarbons by introducing 15% wt. zeolite NaY in 85% aluminosilicon during molding. The composition of aluminosilicon is 93% SiO ₂ and 7% Al ₂ O ₃ . After keeping the zeolite-containing hydrogel in the sodium sulfate solution (syneresis), it is treated with a solution of the basic salt of aluminum sulfate with a concentration of 0.7 N in Al ₂ O ₃ and the ratio OH ^- / Al = 0.7. Next, the hydrogel is washed with steam condensate, after which a second activation is carried out with a solution of a mixture of rare-earth nitrates with a concentration of 1.0-1.2 g / l in terms of freeze-drying. After the second activation, the balls are washed with steam condensate, dried and calcined. The disadvantages of this method include: a low yield of gasoline fraction in the cracking of hydrocarbons, increased consumption of the catalyst due to the low strength of the catalyst and not enough high bulk density.

Also known is a method of producing motor fuels by cracking petroleum fractions in the presence of a platinum zeolite-containing rare-earth aluminosilicate catalyst with a platinum content of 0.00001-0.002% (patent FR 2407745, 1979). The content of zeolite treated with a metal salt of II-VIII gr. Is 12-60%; the catalyst also contains possibly <75% clay, 20-50% α-Al ₂ O ₃ and an inorganic binder of the oxide type. The disadvantages of this method are: low gasoline yield, as well as increased catalyst consumption.

Closest to the proposed method in technical essence and the achieved result is a method for producing motor fuels in the presence of a platinum zeolite-containing aluminosilicate catalyst, consisting of 5-20 wt.% Zeolite Y with a module (molar ratio of silicon oxide: alumina) of 4.5-9.5 and 80-95 wt.% aluminosilicate base and having a chemical composition, wt.%:

alumina 5.5-9.5

ORZE 0.5-3.0

platinum 0.0001-0.01

iron oxide 0.01-0.4

calcium oxide 0.01-0.5

sodium oxide 0.01-0.5

silica rest

(RF patent No. 21656529 dated September 1, 1999, issued May 10, 011, class C 10 G 11/05, B 01 J 29/12).

The disadvantage of the method of producing motor fuels by cracking oil fractions on this catalyst is the insufficiently high yield of the gasoline fraction, as well as the insufficiently high bulk density, which does not allow it to be used in cracking processes with increased circulation rate.

The objective of the present invention is to increase the yield of the gasoline fraction by increasing the activity and selectivity of the used platinum zeolite-containing rare-earth aluminosilicate catalyst and increasing the bulk density of the catalyst.

The problem is solved by the proposed method for producing motor fuels by catalytic cracking of oil fractions in the presence of a platinum zeolite-containing rare-earth aluminosilicate catalyst, in which a catalyst consisting of 5-20 wt.% Zeolite Y with a molar ratio of silicon oxide: aluminum oxide of 4.5-9 is used , 5, and 80-95 wt.% Aluminosilicate base, consisting of 40-95 wt.% Amorphous aluminosilicate and 5-60 wt.% Clay such as kaolinite, montmorillonite (bentonite) and having a chemical composition, wt.%:

alumina 4.5-40.0

ORZE 0.5-4.0

platinum 0.0001-0.01

sodium oxide 0.01-0.5

silica rest

The process of producing motor fuels by cracking oil fractions is carried out as follows: on ball catalysts, vacuum gas oil cracking is carried out at a temperature of 450-510 ° C, a volumetric feed rate of 1.0-4.0 h ^-1 , a catalyst circulation of 1.5-7 5 kg / kg; on microspherical catalysts, cracking is carried out at 470-520 ° C, a volumetric feed rate of 3-10 h ^-1 , a circulation ratio of 3-12 kg / kg.

The catalyst is prepared according to the following procedure.

Aqueous solutions of aluminum sulfate, acidified with sulfuric acid, containing 3-25 kg / m ³ of aluminum oxide and 40-80 kg / m ^{3 of} sulfuric acid, and sodium silicate (water glass) with a SiO ₂ content _of 140-180 kg / m ³ and Na ₂ O 55-75 kg / m ³ in which zeolite Y powders are suspended in Н-, NH ₄ , REE or NH ₄ - REE forms with a module equal to 4.5-9.5, in an amount of 20-140 kg / m ³ and clay 20-250 kg / m ³ are mixed in a mixer with the formation of aluminosilicate zeolite-containing hydrosol, which is then coagulated at 5-20 ° C and pH 7.5-8.5 in a ball-shaped hydrogel in a layer of mineral oil. Then the hydrogel is subjected to syneresis in water or in an aqueous solution of ammonium sulfate concentration of 2-20 kg / m ³ or in an aqueous solution of aluminum sulfate concentration of Al ₂ O ₃ 1-30 kg / m ³ at 5-50 ° C for 6-36 hours. Next, the hydrogel is treated with an aqueous solution of ammonium nitrate or sulfate concentration of 5-20 kg / m ³ , or aluminum sulfate concentration of 5-20 kg / m ³ calculated on Al ₂ About ₃ - at 15-50 ° C for 12-36 h - and an aqueous solution of nitrates of rare-earth elements with a concentration of 1-5 kg / m ³ (calculated on the basis of the free-flowing element) for 24-48 hours at 15-50 ° C, washed with steam condensate at 15-50 ° C for 8-24 hours, dried at 110-190 ° C and calcined at 650-750 ° C for 12-24 hours in a stream of steam-air mixture.

The catalyst is also prepared by mixing in a mixer an aqueous solution of aluminum sulfate, acidified with sulfuric acid, with the characteristics described above, and an aqueous solution of sodium silicate containing 150-350 kg / m ³ SiO ₂ and 60-165 kg / m ³ Na ₂ O, in which powders of zeolite Y 15-60 kg / m ³ and clay 15-200 kg / m ^{3 are} suspended, with the formation of a hydrosol and hydrogel under the conditions indicated above, as well as with subsequent processing of the hydrogel under the conditions described above.

Platinum is introduced into the catalyst by adding platinum chloride, H ₂ PtCl ₆ · 6H ₂ O, in an aluminum sulfate solution in an amount of 0.0002-0.04 kg / m ³ (calculated on platinum) or in an amount of 0.0003-0.055 kg / m ³ (calculated on platinum) - in an aqueous suspension of zeolite.

Surfactants can be added to the suspension of zeolite Y and clay suspensions, as well as to stabilize the process of ash formation and the transition of the hydrosol to hydrogel, in a suspension of zeolite Y and clay powders.

Upon receipt of the catalyst in microspherical form, the hydrogel beads after washing are dispersed in water at 15-60 ° C, spray-dried at a temperature of inlet of flue gases of 400-650 ° C and an exit of 160-190 ° C and calcined at 600-750 ° C for 12-24 hours in a steam-air mixture.

The following are examples of the preparation of a catalyst and a method for producing motor fuels by cracking oil fractions in the presence of this catalyst.

Example 1. An aqueous solution of aluminum sulfate containing 20 kg / m ³ Al ₂ O ₃ and 60 kg / m ³ H ₂ SO ₄ and an aqueous solution of sodium silicate with a content of silicon oxide 180 kg / m ³ and sodium oxide 75 kg / m ³ in which zeolite Y is suspended in a rare-earth form (REE form) with a module of 4.5, with platinum chloride hydrochloric acid at a concentration of 0.003 kg / m ³ (calculated on platinum) in an amount of 60 kg / m ³ and kaolinite clay 20 kg / m ³ - is mixed in a mixer with the formation of a hydrosol and coagulated at 5 ° C and pH 8.2 in a ball-shaped hydrogel in a layer of mineral oil. The hydrogel is subjected to syneresis in water for 6 hours. Then, the hydrogel is treated with an aqueous solution of ammonium sulfate at a concentration of 5 kg / m ³ at 5 ° C for 24 hours and an aqueous solution of aluminum sulfate at a concentration of 1 kg / m ³ at Al ₂ O ₃ at 5 ° C for 12 hours, and then with an aqueous solution of rare-earth nitrates of a concentration of 1.0 kg / m ³ (calculated as ORES) at 50 ° C for 36 hours and washed with steam condensate at 15 ° C for 24 hours; dried at 150 ° C and calcined at 750 ° C for 12 hours in a stream of vapor-air mixture.

The resulting ball catalyst contains 20 wt.% Zeolite and has a composition, wt.%:

alumina 15.5

rare earth oxides 2.5

platinum 0.001

sodium oxide 0.2

silica rest

Example 2. An aqueous solution of aluminum sulfate containing 5 kg / m ³ Al ₂ O ₃ and 40 kg / m ³ H ₂ SO ₄ and an aqueous solution of sodium silicate with a silica content of 160 kg / m ³ and sodium oxide 65 kg / m ³ in which zeolite Y in the N-form is suspended with a module equal to 9.5, with a concentration of 0.002 kg / m ³ platinum chloride hydrochloride (calculated on platinum), in an amount of 22 kg / m ³ , and kaolinite clay 250 kg / m ³ , mixed in a mixer with the formation of a hydrosol, coagulated at 10 ° C and pH 8.5 in a ball-shaped hydrogel in a layer of mineral oil. The hydrogel is subjected to syneresis in a solution of ammonium sulfate concentration of 15 kg / m ³ for 20 hours. Then the hydrogel is treated with: an aqueous solution of ammonium sulfate concentration of 15 kg / m ³ at 20 ° C for 6 h, an aqueous solution of aluminum sulfate concentration of 15 kg / m ³ - at 20 ° С for 12 h - and with an aqueous solution of rare-earth nitrates of a concentration of 5 kg / m ³ (calculated on the basis of freeze-drying) - at 20 ° С for 36 h, - washed with steam condensate at 20 ° С for 12 h, dried at 110 ° C and calcined at 750 ° C for 12 h in a stream of steam-air mixture.

The obtained ball catalyst contains 5 wt.% Zeolite and has a composition,% wt .:

alumina 40.0

ORZE 0.7

platinum 0.01

sodium oxide 0.01

silica rest

Example 3. An aqueous solution of aluminum sulfate containing 15 kg / m ³ Al ₂ O ₃ and 60 kg / m ³ H ₂ SO ₄ , and an aqueous solution of sodium silicate with a content of silica 160 kg / m ³ and sodium oxide 65 kg / m ³ , in which zeolite Y is suspended in an NH ₄ form with a module of 6.2, with platinum chloride hydrochloric acid at a concentration of 0.018 kg / m ³ (calculated on platinum), in an amount of 40 kg / m ³ , and montmorillonite clay 150 kg / m ³ - is mixed in a mixer with the formation of a hydrosol and coagulated at 5 ° C and pH 8.0 in a ball-shaped hydrogel in a layer of mineral oil. The hydrogel is subjected to syneresis in a solution of ammonium sulfate concentration of 20 kg / m ³ for 8 hours. Then the hydrogel is treated with: an aqueous solution of ammonium sulfate concentration of 20 kg / m ³ at 20 ° C for 6 h, an aqueous solution of aluminum sulfate concentration of 30 kg / m ³ at 20 ° C for 6 hours and with an aqueous solution of rare-earth nitrates of a concentration of 3 kg / m ³ (calculated as ORES) at 50 ° C for 36 hours, washed with steam condensate at 50 ° C for 8 hours, dried at 150 ° C and calcined at 750 ° C for 12 hours in a stream of steam-air mixture.

The resulting ball catalyst contains 11 wt.% Zeolite and has a composition,% mass:

alumina 29.8

ORZE 0.5

platinum 0.005

sodium oxide 0.07

silica rest

Example 4. An aqueous solution of aluminum sulfate containing 5 kg / m ³ Al ₂ O ₃ and 80 kg / m ³ H ₂ SO ₄ and an aqueous solution of sodium silicate with a content of silicon oxide of 140 kg / m ³ and sodium oxide 55 kg / m ³ in which zeolite Y is suspended in REE form with a module equal to 5.8, with platinum chloride acid concentration of 0.018 kg / m ³ (calculated on platinum), in an amount of 40 kg / m ³ -, and kaolinite clay 100 kg / m ³ - is mixed in a mixer with the formation of a hydrosol and coagulated at 10 ° C and pH 8.1 in a ball-shaped hydrogel in a layer of mineral oil.

The hydrogel is subjected to syneresis in a solution of ammonium sulfate concentration of 10 kg / m ³ for 36 hours. Then the hydrogel is treated with: an aqueous solution of ammonium sulfate concentration of 10 kg / m ³ at 50 ° C for 12 hours, an aqueous solution of aluminum sulfate concentration of 2 kg / m ³ at 50 ° C for 6 h and an aqueous solution of rare-earth nitrates of a concentration of 1.5 kg / m ³ (calculated on the freeze-drying element) at 50 ° C for 18 h, washed with steam condensate at 50 ° C for 24 h, dried at 150 ° C and calcined at 750 ° C for 12 hours in a stream of vapor-air mixture.

The resulting ball catalyst contains 14 wt.% Zeolite and has a composition, wt.%:

alumina 21.8

ORZE 1.0

platinum 0.0001

sodium oxide 0.02

silica rest

Example 5. An aqueous solution of aluminum sulfate containing 2.5 kg / m ³ Al ₂ O ₃ and 60 kg / m ³ H ₂ SO ₄ , and an aqueous solution of sodium silicate with a content of silicon oxide 180 kg / m ³ and sodium oxide 75 kg / m ³ in which zeolite Y is suspended in REE form with a module of 5.2 with platinum chloride acid at a concentration of 0.002 kg / m ³ (calculated on platinum), in an amount of 15 kg / m ³ and montmorillonite clay 10 kg / m ³ - mixed in a mixer with the formation of a hydrosol and coagulated at 20 ° C and pH 7.5 in a ball-shaped hydrogel in a layer of mineral oil. The hydrogel is subjected to syneresis in a solution of aluminum sulfate at a concentration of 10 kg / m ³ for 8 hours. Then, the hydrogel is treated with an aqueous solution of aluminum sulfate at a concentration of 10 kg / m ³ at 20 ° C for 12 hours, an aqueous solution of nitrates of rare-earth elements with a concentration of 5 kg / m ³ (based on ORZE) - at 25 ° С for 36 h - and an aqueous solution of ammonium sulfate concentration of 15 kg / m ³ at 25 ° С for 24 h, washed with steam condensate at 25 ° С for 24 h, dried at 150 ° C and calcined at 750 ° C for 12 hours in a stream of vapor-air mixture.

The resulting ball catalyst contains 7.5 wt.% Zeolite and has a composition, wt.%:

aluminum oxide 4.5

ORZE 4.0

platinum 0.001

sodium oxide 0.15

silica rest

Example 6. The catalyst is prepared analogously to example 4. Next, after washing, the hydrogel balls are dispersed in water at 25 ° C, spray dried at a temperature of inlet of flue gases of 650 ° C and exit of flue gases of 190 ° C and calcined in a fluidized bed at 750 ° C for 12 hours in a stream of vapor-air mixture. The resulting catalyst has a composition as in example 4.

Example 7. The catalyst is prepared analogously to example 4. Next, after washing, the hydrogel balls are dispersed in water at 15 ° C, spray dried at a temperature of inlet of flue gases of 400 ° C and exit of flue gases of 160 ° C and calcined in a fluidized bed at 600 ° C 24 hours in a stream of vapor-air mixture.

The resulting catalyst has a composition as in example 4.

Example 8. The catalyst is prepared analogously to example 4. Next, after washing, the hydrogel balls are dispersed in water at 60 ° C, spray dried at a temperature of inlet of flue gases of 500 ° C and exit of flue gases of 175 ° C and calcined in a fluidized bed at 750 ° C 24 hours in a stream of vapor-air mixture.

The resulting catalyst has a composition as in example 4.

The obtained catalysts are treated with 100% water vapor at 750 ° C for 6 hours before laboratory tests. Ball catalyst tests are carried out according to OST 38.01176-79 at a temperature of 460 ° C and a bulk feed rate of 1.5 h ^-1 . The raw materials used are standard raw materials - the kerosene-gas oil fraction of Krasnodar oils (density at 20 ° С 862 kg / m ³ , boiling point 203 ° С, boiling point temperature 360 ° С). Microspherical catalysts are tested according to OST 38.01161-78 at 480 ° C and a weight feed rate of 7.0 h ^-1 . The results of laboratory tests are presented in tables 1 and 2.

Ball and microspherical catalysts obtained according to examples 1-8 were tested in the process of cracking a vacuum gas oil of West Siberian oil (density 916 kg / m ³ , sulfur content 1.6 wt.%). The process using ball catalysts was tested at a temperature of 480 ° C, a volumetric feed rate of 1.8 h ^-1 , and microspherical catalysts during cracking of vacuum gas oil of West Siberian oil at a temperature of 500 ° C, a bulk feed rate of 10.0 h ^-1 .

List of references

1. Cracking of oil fractions on zeolite-containing catalysts. Ed. S.N. Khadzhieva. M., Chemistry. 1982 g.

2. US Patent No. 4429053, cl. B 01 J 29/12.

3. Auth. USSR certificate No. 389829, cl. At 01 J 29/08.

4. French patent No. 2500326, cl. B 01 J 29/12.

5. Yandieva L.A., Zakarina N.A. Cracking catalysts and zeolites. Collection of scientific works of the GrozNII, M., TsNIITENEFTEKHIM, 1984, No. 38, p.76-80.

6. RF patent No. 2166529, Cl. C 10 G 11/05, B 01 J 29/12.

Table 1
Test results of ball and microspherical catalysts during cracking of a kerosene-gas oil fraction Indicator Ball catalysts according to examples 1 2 3 4 5 prototype 1. The yield of cracking products, wt.%: gasoline (FR. ₅ -200 ° C) 57.7 53,4 59.9 60.3 57.8 52,5 -gas 16,0 11.2 12,4 12.1 11.7 12.9 -coke 1.8 1,6 1.7 1.7 1.8 1.9 2. The bulk density of the catalyst, kg / m ³ 895 870 840 790 820 705

Continuation of table 1 Indicator Microspherical catalysts according to examples 6 7 8 prototype 1. The yield of cracking products, wt.%: gasoline (FR. ₅ -200 ° C) 60.6 60.5 61.2 52.9 -gas 16,0 15.7 15.6 16.9 -coke 2.0 2.1 1.9 2.7 2. The bulk density of the catalyst, kg / m ³ 805 820 790 720

table 2
Test results for ball and microspherical catalysts in vacuum gas oil cracking Indicator Ball catalysts according to examples 1 2 3 4 5 Prototype 1. The yield of cracking products, wt.% gasoline (FR. ₅ -200 ° C) 43,4 39.6 45.5 45.8 42.9 38.1 diesel fuel (fr. 200-350 ° С) 30,2 31.8 31.6 31.7 31.5 30.1 -gas 16,0 15,2 15.8 16.1 15.9 16,2 -coke 4.8 4.7 4.8 4.9 4.8 5.1

Continuation of table 2 Indicator Microspherical catalysts according to examples 6 7 8 Prototype 1. Product Output cracking, wt.% gasoline (FR. ₅ -200 ° C) 44.5 44,4 44.9 39.5 diesel fuel (fr. 200-350 ° С) 31.7 32.1 31.5 30,2 -gas 15.7 15,5 15.3 15.7 -coke 4.8 4.9 4.8 5,0

Claims (1)

A method of producing motor fuels by catalytic cracking of petroleum fractions in the presence of a platinum zeolite-containing rare-earth aluminosilicate catalyst, characterized in that they use a catalyst consisting of 5-20 wt.% Zeolite U with a molar ratio of silicon oxide: aluminum oxide of 4.5 to 9.5 and 80 -95 wt.% Aluminosilicate base, consisting of 40-95 wt.% Amorphous aluminosilicate and 5-60 wt.% Clay, and having a chemical composition, wt.%: alumina 4.5-40.0 rare earth oxides 0.5-4.0 platinum 0.0001-0.01 sodium oxide 0.01-0.5 silica rest