RU2166529C1 - Motor fuel production process - Google Patents

Abstract

FIELD: gasoline production. SUBSTANCE: oil fractions are subjected to catalytic cracking in presence of catalyst consisting of 5 to 29% of zeolite Y with silica-alumina molar ratio 4.5-9.5 and 80 to 95% of aluminosilicate base containing, wt %: aluminum oxide 5.5- 9.5, rare-earth element oxides 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, and silica - the balance. EFFECT: increased yield of gasoline, increased octane number of gasoline, and reduced atmospheric emission of sulfur oxides in catalyst regeneration process. 2 tbl

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 petroleum fractions using a zeolite-containing aluminosilicate catalyst in ball and microspherical forms. In ball form, the catalyst contains 10 to 12 wt.% Zeolite Y and has a chemical composition, wt.%:
Alumina - 9 - 10
Rare earth oxides - 2.0 - 2.5
Sodium oxide - 0.2 - 0.6
Silica - Else
(Cracking of oil fractions on zeolite-containing catalysts. Edited by S. N. Khadzhiev. M .: Chemistry. 1982)
In microspherical form, the catalyst contains 16 to 18 wt.% Zeolite Y and has the following chemical composition, wt.%:
Alumina - 10 - 12
Rare earth oxides - 2.5 - 3.0
Sodium oxide - 0.2 - 0.6
Silica - Else
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 4429053, class B01J 29/12; patent of France 2500326, class B01J 29/12; Yandieva L.A., Zakarina N.A. Cracking catalysts and zeolites. Collection of scientific works of GrozNII, M., TsNIITENEFTECHIM, 1984, 38, p. 76 - 80).

Closest to the proposed method in terms of technical nature and the achieved result is a method for 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 zeolite content of the salt-treated metal II-VIII gr. accounts for 12-60%; the catalyst also contains possibly ≅ 75% clay 20-50% α-Al ₂ O ₃ trihydrate and an inorganic binder of the oxide type.

 The disadvantage of this method of producing motor fuels by cracking petroleum fractions is the insufficiently high yield of the gasoline fraction.

 The objective of the present invention is to increase the yield of the gasoline fraction by increasing the activity and selectivity of the aluminosilicate 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 to 20 wt.% Zeolite Y with a molar ratio of silicon oxide: aluminum oxide of 4.5 to 9 is used , 5 and 80 - 95 wt.% Aluminosilicate base, and having a chemical composition, wt.%:
Alumina - 5.5 - 9.5
Rare earth oxides - 0.5 - 3.0
Platinum - 0.0001 - 0.1
Iron oxide - 0.01-0.4
Calcium oxide - 0.01 - 0.5
Sodium oxide - 0.01 - 0.5
Silica - Else
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 - 480 ^o C, a volumetric feed rate of 1.0 to 2.5 h ^-1 , a catalyst circulation of 1.5 to 2 5 kg / kg; on microspherical catalysts, cracking is carried out at 470 - 510 ^o C, a volumetric feed rate of 4.8 h ^-1 , a circulation ratio of 6.9 kg / kg.

 The catalyst is prepared according to the following procedure.

Aqueous solutions of aluminum sulfate, acidified with sulfuric acid, containing 15 - 25 kg / m ³ of aluminum oxide and 50 - 80 kg / m ^{3 of} sulfuric acid, sodium silicate (water glass) with a NaOH concentration of 1.4 - 1.8 kg equiv. / m ³ and a suspension of NaY zeolite containing 30 - 110 kg / s ³ zeolite is mixed in a mixer to form an aluminosilicate zeolite-containing hydrosol, which is then coagulated at 5 - 20 ^° C and a pH of 7.5 - 8.5 into a ball hydrogel in a layer of mineral oil. Then, the hydrogel may undergo syneresis at 35 - 60 ^o C for 6 - 24 hours. Next, the hydrogel is treated with an aqueous solution of nitrate or ammonium sulfate concentration of 5 - 20 kg / m ³ at 35-60 ^o C for 12-36 hours and the aqueous rare earth nitrates of a concentration of 1-5 kg / m ³ (calculated on rare earth oxides) for 24 to 36 hours or a mixture thereof, washed with condensate water containing iron cations of 0.01 - 0.4 kg / m ³ , calcium 0 , 01 - 0.5 kg / m ³ (calculated as metal oxides) at 35 - 60 ^o С for 8 - 24 hours, washed with condensate water at 35 - 60 ^o С 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.

Platinum is removed to the catalyst by adding platinum hydrochloric acid, H ₂ PtCl ₆ 6H ₂ O, to a solution of aluminum sulfate in an amount of 0.0002 - 0.04 kg / m ³ (calculated on platinum) or in an amount of 0.0006 - 0.085 kg / m ³ (calculated on platinum) in an aqueous suspension of zeolite.

Upon receipt of the catalyst in microspherical form, the hydrogel beads after washing are dispersed in water at 20-60 ^° C, spray-dried at a temperature of inlet of flue gases of 400-650 ^° C and an exit of 160-190 ^° C for 12-24 hours in a stream of steam-air mixture .

 The microspherical catalyst is also obtained by screen separation of the catalyst in a ball form after the drying and / or calcination step, taking a fraction of balls with a diameter of less than 2 mm and subsequent grinding to a fraction of 20-140 microns.

 The following are examples of the preparation of a catalyst and a method for producing motor fuels by cracking petroleum 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 70 kg / m ³ H ₂ SO ₄ , an aqueous solution of sodium silicate (water glass) with a NaOH concentration of 1.6 kg equiv / m ³ and a zeolite suspension containing 80 kg / m ³ NaY with a molar ratio of silica: alumina of 4.5 and platinum chloride acid at a concentration of 0.008 kg / m ³ (calculated on platinum), mixed in a mixer with the formation of a hydrosol, coagulated at 5 ^o C and pH 8.3 in a ball-type hydrogel in a layer of mineral oil. Then the hydrogel is treated with an aqueous solution of ammonium sulfate at a concentration of 10 kg / m ³ at 50 ^o C for 12 h and an aqueous solution of nitrates of rare-earth elements with a concentration of 1.5 kg / m ³ (calculated on the oxides of rare-earth elements - ORZE) at 50 ^o C in for 36 hours, washed with condensate water containing iron cations of 0.01 kg / m ³ , calcium cations of 0.001 kg / m ³ , at 50 ^o C for 24 h, dried at 150 ^o C and calcined at 750 ^o C for 12 h in a stream of vapor-air mixture.

The resulting ball catalyst contains 10 wt. % zeolite and has a composition, wt.%:
Alumina - 8.5
Rare earth oxides - 2.5
Platinum - 0.0001
Iron oxide - 0.01
Calcium Oxide - 0.01
Sodium oxide - 0.2
Silica - Else
Example 2. An aqueous solution of aluminum sulfate containing 25 kg / m ³ Al ₂ O ₃ and 80 kg / m ³ H ₂ SO ₄ , an aqueous solution of sodium silicate (water glass) with a NaOH concentration of 1.8 kg equiv / m ³ and a zeolite suspension containing 30 kg / m ³ NaY with a molar ratio of silicon oxide: alumina of 9.5 and platinum chloride acid concentration of 0.015 kg / m ³ (calculated on platinum), mixed in a mixer with the formation of a hydrosol, coagulated at 5 ^o C and pH 8.5 in a ball-type hydrogel in a layer of mineral oil. Then the hydrogel is treated with an aqueous solution of ammonium sulfate concentration of 5 kg / m ³ at 35 ^o C for 36 h and an aqueous solution of nitrates of rare-earth elements with a concentration of 5 kg / m ³ (calculated on the oxides of rare-earth elements - ORZE) at 35 ^o C for 24 h, washed with condensate water containing iron cations of 0.4 kg / m ³ , calcium cations of 0.5 kg / m ³ , at 35 ^o C for 24 h, dried at 110 ^o C and calcined at 750 ^o C for 12 h in a stream of vapor-air mixture.

The resulting ball catalyst contains 20 wt.% Zeolite and has a composition, wt.%:
Alumina - 9.5
Rare earth oxides - 3.0
Platinum - 0.01
Iron oxide - 0.4
Calcium Oxide - 0.5
Sodium oxide - 0.5
Silica - Else
Example 3. An aqueous solution of aluminum sulfate containing 15 kg / m ³ Al ₂ O ₃ and 50 kg / m ³ H ₂ SO ₄ , an aqueous solution of sodium silicate (water glass) with a NaOH concentration of 1.4 kg equiv / m ³ and a zeolite suspension containing 110 kg / m ³ NaY with a molar ratio of silica: alumina of 6.2 and platinum chloride acid concentration of 0.085 kg / m ³ (calculated on platinum), mixed in a mixer with the formation of a hydrosol, coagulated at 20 ^o C and pH 7.5 in a hydrogel ball form in a layer of mineral oil. Then the hydrogel is treated with an aqueous solution of ammonium sulfate concentration of 20 kg / m ³ at 60 ^o C for 18 h and an aqueous solution of nitrates of rare-earth elements with a concentration of 1 kg / m ³ (calculated on the oxides of rare-earth elements - ORZE) at 60 ^o C for 36 h, washed with condensate water containing iron cations of 0.1 kg / m ³ , calcium cations of 0.15 kg / m ³ at 60 ^o C for 24 h, dried at 150 ^o C and calcined at 750 ^o C for 12 h in a stream of vapor-air mixture.

The resulting ball catalyst contains 5 wt.% Zeolite and has a composition, wt.%:
Alumina - 5.5
Rare earth oxides - 0.5
Platinum - 0.004
Iron oxide - 0.1
Calcium Oxide - 0.15
Sodium oxide - 0.01
Silica - Else
Example 4. An aqueous solution of aluminum sulfate containing 20 kg / m ³ Al ₂ O ₃ and 70 kg / m ³ H ₂ SO ₄ , an aqueous solution of sodium silicate (water glass) with a NaOH concentration of 1.6 kg equiv / m ³ and a zeolite suspension containing 80 kg / m ³ NaY with a molar ratio of silica: alumina of 5.8 and platinum chloride acid concentration of 0.0002 kg / m ³ (calculated on platinum) is mixed in a mixer with the formation of a hydrosol, coagulate at 10 ^o C and pH 8.3 in a ball-shaped hydrogel in a layer of mineral oil. Then the hydrogel is treated with an aqueous solution of ammonium sulfate at a concentration of 10 kg / m ³ at 50 ^o C for 12 h and an aqueous solution of nitrates of rare-earth elements with a concentration of 1.5 kg / m ³ (calculated on the oxides of rare-earth elements - ORZE) at 50 ^o C in for 36 hours, washed with condensate water containing iron cations of 0.02 kg / m ³ , calcium cations of 0.02 kg / m ³ , at 50 ^o C for 24 h, dried at 150 ^o C and calcined at 750 ^o C for 12 hours in a stream of vapor-air mixture.

The obtained ball catalyst contains 10 wt.%: Zeolite and has a composition, wt.%:
Alumina - 8.5
Rare earth oxides - 1.5
Platinum - 0.0001
Iron oxide - 0.2
Calcium Oxide - 0.2
Sodium oxide - 0.15
Silica - Else
Example 5. An aqueous solution of aluminum sulfate containing 20 kg / m ³ Al ₂ O ₃ , 0.04 kg / m ³ platinum hydrochloric acid (calculated on platinum) and 70 kg / m ³ H ₂ SO ₄ , an aqueous solution of sodium silicate ( water glass) of 1.6 kg equiv / m ³ NaOH concentration and a zeolite suspension containing 80 kg / m ³ NaY with a silica: alumina molar ratio of 5.8, mixed in a mixer to form a hydrosol, coagulated at 10 ^o C and pH 8.3 in a ball-shaped hydrogel in a layer of mineral oil. Then the hydrogel is treated with an aqueous solution of ammonium sulfate at a concentration of 10 kg / m ³ at 50 ^o C for 12 h and an aqueous solution of nitrates of rare-earth elements with a concentration of 1.5 kg / m ³ (calculated on the oxides of rare-earth elements - ORZE) at 50 ^o C in for 36 hours, washed with condensate water containing iron cations of 0.01 kg / m ³ , calcium cations of 0.01 kg / m ³ , at 50 ^{° C.} for 24 hours, washed with condensate water at 50 ^° C. for 24 hours, dried at 150 ^o C and calcined at 750 ^o C for 12 hours in a stream of vapor-air mixture.

The resulting ball catalyst contains 12 wt.% Zeolite and has a composition, wt.%:
Alumina - 8.5
Rare earth oxides - 1.5
Platinum - 0.01
Iron oxide - 0.01
Calcium Oxide - 0.01
Sodium oxide - 0.2
Silica - Else
Example 6. The catalyst is prepared analogously to example 5. Next, after washing, the hydrogel balls are dispersed in water at 50 ^° C, spray-dried at a temperature of inlet of flue gases of 650 ^° C and an 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 5.

Example 7. The catalyst is prepared analogously to example 5. Next, after washing, the hydrogel balls are dispersed in water at 35 ^° 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 5.

Example 8. The catalyst is prepared analogously to example 5. 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 5.

 Example 9. The catalyst is prepared analogously to example 5. Next, after calcining the catalyst, it is subjected to sieve separation and the fraction of balls with a diameter of less than 2 mm is subjected to grinding to obtain a microspherical catalyst.

 The resulting catalyst has a composition as in example 5.

Example 10. The catalyst obtained in example 4 is used in the process of cracking a vacuum gas oil of West Siberian oil. The process is carried out in a pilot installation with a moving catalyst bed at a cracking reaction temperature of 450 ^° C., a feed volumetric flow rate of 1.0 h ⁻¹ and a catalyst circulation of 1.5 kg / kg.

Example 11. The catalyst obtained in example 4 is used in the process of cracking a vacuum gas oil of West Siberian oil. The process is carried out on a pilot installation with a moving catalyst bed at a cracking reaction temperature of 480 ^o C, a volumetric feed rate of 2.5 h ^-1 and a catalyst circulation of 2.5 kg / kg.

Example 12. The microspherical catalyst obtained in example 6 is used in the process of cracking a vacuum gas oil of West Siberian oil. The process is carried out on a pilot installation with a "fluidized" catalyst bed at a cracking reaction temperature of 470 ^{° C.} , a feed volumetric feed rate of 4.0 h ^-1 and a catalyst circulation of 6.0 kg / kg.

Example 13. The microspherical catalyst obtained in example 6 is used in the process of cracking a vacuum gas oil of West Siberian oil. The process is carried out on a pilot installation with a "fluidized" catalyst bed at a cracking reaction temperature of 510 ^{° C.} , a feed space velocity of 8.0 h ^−1, and a catalyst circulation of 9.0 kg / kg.

The obtained catalysts before laboratory tests are treated with 100% steam at 750 ^o C for 6 hours. Testing of ball catalysts is carried out according to OST 38.01176-79 at a temperature of 460 ^o C and a volumetric 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 ^o С 862 kg / m ³ , boiling point 203 ^o С, boiling point temperature 360 ^o С). Microspherical catalysts are tested according to OST 38.01161-78 at 480 ^o C and a weight feed rate of 7.0 h ^-1 . The results of laboratory tests are presented in table. 1.

Ball catalysts obtained in examples 1-5 are used in the process of cracking a vacuum gas oil of West Siberian oil (density 916 kg / m ³ , boiling point 512 ^o C, sulfur content 1.6 wt.%). The process is carried out on a pilot installation with a moving catalyst bed at a temperature of 460 ^o C, a volumetric feed rate of 1.5 h ^-1 , a catalyst circulation of 2 kg / kg.

Microspherical catalysts obtained in examples 6 to 9 are used in the process of cracking a vacuum gas oil of West Siberian oil. The process is carried out on a pilot installation with a "fluidized" catalyst bed at a temperature of 480 ^o C, a mass feed rate of 5 h ^-1 , a catalyst circulation of 7 kg / kg.

 The results of pilot tests of ball and microspherical catalysts are presented in table. 2.

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 to 20 wt.% Zeolite Y with a molar ratio of silicon oxide: aluminum oxide of 4.5 to 9.5 and 80 to 95 wt.% aluminosilicate base, and having a chemical composition, wt.%:
Alumina - 5.5 - 9.5
Rare earth oxides - 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 - Else

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