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INVENTION
Russian Federation Patent RU2129140

METHOD FOR PRODUCING CLEAN MOTOR FUELS

METHOD FOR PRODUCING CLEAN MOTOR FUELS

Name of the inventor: Demyanenko EA .; Caribbean AK .; Tverdohlebov VP .; Zlotnikov LY .; Kaminsky E.F .; Melik-Ahnazarov Talat Khosrow oglu; Kurganov VM .; Khavkin VA .; Tarhov VA .; Rabinovich GB
The name of the patentee: Limited Liability Company Scientific Production Firm "TSP"
Address for correspondence: 140004, Lyubertsy, Moscow Region. 1st Punk pr-d, 1, block 2, kv.75 Pavlova TV
Starting date of the patent: 1998.06.23

The invention relates to the field of oil refining, specifically to a method for producing environmentally friendly engine fuels. It describes a method for producing environmentally friendly engine fuels by catalytic hydrocracking of petroleum feedstock at elevated temperature and pressure with a degree of conversion of 50-85 wt. % With separation of a middle hydrogenation gasoline fraction boiling in the range of 130-360 o C and the residue followed by catalytic dearomatization 50-95 wt.% Of the product fraction and a middle dearomatization by mixing with the remaining 5-50 wt.% A middle fraction. The proposed method provides a motor fuel with improved environmental characteristics while substantially reducing the hydrogen pressure and flow rate as compared with known similar production techniques. This reduces capital and operating costs in the implementation of the method.

DESCRIPTION OF THE INVENTION

The present invention relates to the field of oil refining, specifically to a method for producing environmentally friendly engine fuels.

A method of producing motor fuels by hydrogenation of the various gas oil fractions, and including a catalytic cracking process. The process is carried out at a hydrogen pressure of 25 - 30 MPa, temperature of 340 - 380 o C, the volumetric hourly space velocity of 0.5 - 0.7 h -1, hydrogen / feedstock - 1500 Nm 3 / m 3 in the presence nikelvolframovyh sulfide catalysts. The obtained fuel comprises a middle less than 0.04 wt.% Sulfur and less than 10 wt. % Aromatic hydrocarbons and can be used as jet or diesel fuel (Arctic and winter) to meet modern environmental requirements (Babikov AF et al., "Production of diesel fuel with a low content of aromatic hydrocarbons", HTTM, N 3, 1993 p. 34).

A disadvantage of the method is the relatively low yield of the desired product, an increased hydrogen consumption, and very high pressure in the process, which greatly increases the capital and operating costs.

Known and a method for producing middle distillates by hydrogenating sulfur virgin gas oil at a hydrogen pressure of 5.1 MPa, a temperature of 316 - 329 o C. The process is carried out in two stages: first at seroustoychivom nickel-molybdenum catalyst, and then over a catalyst comprising platinum, palladium, and others.

The process reduces the content of aromatic hydrocarbons in the fuel with 32 -. 36% by weight to 5 -. 10% by weight (Cooper et al BH hydrogenation catalysts are aromatic hydrocarbons present in diesel fractions Neftegazonye technologies, N 3, 1994 g... , p. 42).

The disadvantage of this method is the ability to use it only for the relatively light distillate boiling end, no more than 381 o C, which drastically reduces the scope of its practical use.

The closest to the claimed one is a method for the production of motor fuels by catalytic hydrocracking of petroleum feedstock at a temperature of 350 - 450 o C and a pressure of 5 - 21 MPa, with the release of hydrogenation of the gasoline, a middle fraction and the residue, followed by catalytic dearomatization allocated a middle fraction at a temperature of 250 - 350 o C and a pressure of 3 - 7 MPa (Application N 95101036/04 published 27/10/96, the BI N 30.).

A disadvantage of the known method is the implementation of catalytic hydrocracking process at a relatively high hydrogen pressure that the metal-intensive and requires the use of expensive equipment and processing and involving considerable amount risayklovyh (unconverted) fractions, the latter significantly reduces the performance of the method.

The present invention is a method for producing environmentally friendly engine fuels, requiring lower capital and operating costs by reducing the hydrogen pressure, and reducing its flow rate.

To solve this problem a process for producing environmentally friendly engine fuels by catalytic hydrocracking of petroleum feedstock at elevated temperature and pressure with a degree of conversion of 50 - 85% with separation of the hydrogenator gasoline, a middle fraction boiled at temperatures of 130 - 360 o C, and the residue subsequent dearomatization catalyst 50 - 95% by weight of a middle fraction, and mixing with the remaining product dearomatization 5 -. 50% by weight of a middle fraction..

Moreover, as the petroleum feedstock in the present process, together with the use of straight-run distillates, distillates can be catalytic and / or thermal cracking.

The process of catalytic hydrocracking is carried out at a pressure of 8 - 12 MPa and temperature of 350 - 430 o C, and the dearomatization catalytic process at a pressure of 3 - 6 bar and a temperature of 250 - 370 o C.

Unlike the claimed method for producing environmentally friendly engine fuels it is that the process of catalytic hydrocracking is carried out with a degree of conversion of 50 - 85 wt.%; allocate a middle fraction boiling in the temperature range of 130 - 360 o C, 50 -. 95% by weight of this fraction was subjected to dearomatization catalyst dearomatization and then the product is mixed with the remaining 5 - 50% by weight of a middle fraction..

These differences make it possible to obtain motor fuels, corresponding to GOST and modern environmental requirements for jet fuel, "ECHDT". The pressure in the hydrocracking process is lower than in the known method, the hydrogen flow rate does not exceed 2.8 wt.%. The high degree of conversion eliminates the need for recycling "unconverted raw materials."

The following are specific examples of the inventive method.

example 1

Vacuum distillate West Siberian oil - a fraction of 350 - 500 o C:

  • . Sulfur content - 0.8 wt%;
  • nitrogen content - 0.1 wt.%;
  • . Coking - 0.14 wt%;
  • up to 360 o C boils - 12,0% vol..

Subjected to hydrocracking at a pressure of 8 MPa and a temperature of 350 o C, the volumetric feed rate - 0.6 h -1, the ratio of hydrogen gas / feed - 800/1 nm 3 / m 3 in the presence of nickel-molybdenum catalyst on a zeolite carrier. The conversion is 55 wt%, of which.:

  • . 15 wt% - gasoline distillate;
  • . 25 wt% - kerosene distillate;
  • . 15 wt% - diesel distillate.

Kerosene distillate (fraction of 130 - 260 o C) contains 25 wt% aromatics 0.01 wt.. % Sulfur, characterized by the onset of crystallization temperature below (-60 o C) and a density at 20 o C - 795 kg / m 3. This product meets the requirements of GOST fuel RT, except for the content of aromatic hydrocarbons (not more than 22 wt.%).

Diesel distillate (fraction of 260 - 360 o C) contains 29 wt% aromatics 0.03 wt% sulfur, characterized by a pour point (-10 o C) and a density at 20 o C -.. 845 kg / m3.

This product is a component of the low sulfur diesel fuel, summer.

The resulting gas can be used as a raw material a catalytic reforming process, the residue> 360 o C - as a raw material of a catalytic cracking process. 50% kerosene distillate (total number of which is 62.5% of a mixture of a middle fraction) was subjected to dearomatization at a pressure of 6 MPa, temperature 370 o C, the volumetric hourly space velocity of 5 hr -1, a ratio of hydrogen gas / feed - Nm 3 / m 3 in the presence of a palladium catalyst on aluminum oxide support. Dearomatization product containing 8 wt.% Aromatics, mixed with the remaining 50% kerosene distillate obtained in the hydrocracking stage. A product containing 17% of aromatic hydrocarbons, meeting the requirements of guests at the RT fuel.

The total hydrogen flow in both stages (dearomatization and hydrocracking) is 2.2 wt.% For the feedstock.

example 2

Vacuum distillate West Siberian oil - a fraction of 350 - 550 o C:

  • sulfur content -. 1.6 wt%
  • nitrogen content -. 0.2 wt%
  • coking -. 0.3%
  • up to 360 o C boils - 8.0% vol.

Subjected to hydrocracking at a pressure of 10 MPa, temperature 400 o C, the volumetric feed rate - 0.8 h -1, the ratio of hydrogen gas / feed = 1000 Nm 3 / m 3 in the presence of nickel-molybdenum catalyst on a zeolite carrier. The conversion of the raw material is 70 wt%, of which.:

20 wt.% - Petrol distillate

20 wt.% - Diesel distillate,

kerosene distillate is not isolated.

Diesel distillate - a fraction of 160 -.. 360 o C containing 30 wt% aromatics 0.01 wt% sulfur, characterized by a pour point (-18 o C) and a density at 20 o C - 850 kg / m 3. This product meets the requirements of State Standard for diesel fuel, saving, except for the content of aromatic hydrocarbons (up to 20 wt.%).

gasoline formed in the process is used as feedstock for catalytic reforming process.

The residue (> 360 o C) - as a low sulfur feedstock for catalytic cracking.

75% of the distillate is subjected to dearomatization of diesel at a pressure of 4.5 MPa, temperature 320 o C, the volumetric feed rate - 3 hr -1, a ratio of hydrogen gas / feed = 1000 nm 3 / m 3 in the presence of a palladium catalyst on aluminum oxide support. dearomatization product containing 12 wt.% aromatic hydrocarbons, mixed with 25 wt.% of the remaining diesel distillate obtained in the hydrocracking step to obtain a product containing 18 wt.% aromatics and satisfying the requirements of GOST DTL.

The total hydrogen flow in both steps does not exceed 2.5 wt.% For the feedstock.

example 3

A mixture comprising 80% by weight of vacuum distillate West Siberian oil -. Fr. 350 - 500 o C (condition shown in Example 1) and 20 wt% catalytic cracking of light gas oil:.

  • sulfur content - 1.4 wt.%;
  • nitrogen - 0.08 wt.%;
  • . Aromatic content - 55% by weight;
  • boiling limits - 180 - 360 o C.

Subjected to hydrocracking at a pressure of 12 MPa, temperature 430 o C, the volumetric feed rate - 1.1 hr -1, a ratio of hydrogen gas / feed - 1200 nm 3 / m 3 in the presence of nickel-molybdenum catalyst on a silica-alumina carrier. The conversion of raw materials is 90 wt%, of which.:

  • . 24 wt% - gasoline distillate;
  • . 38 wt% - kerosene distillate;
  • . 28 wt% - diesel distillate.

Kerosene distillate - 140 fraction -.. 260 o C comprises 27 wt% aromatics 0.01 wt% sulfur, characterized by the onset of crystallization temperature (below -60 o C) and a density at 20 o C - 797 kg / m 3.

This product meets the requirements of GOST fuel RT, except for the content of aromatic hydrocarbons (not more than 22 wt.%).

Diesel distillate - a fraction of 260 -.. 360 o C comprises 28 wt% aromatic hydrocarbons, sulfur 0.02 wt%, characterized by a pour point (-12 o C) and a density at 20 o C - 848 kg / m 3 and a low sulfur component summer diesel fuel.

gasoline formed in the process is used as feedstock for catalytic reforming process. The residue (> 360 o C) is a low sulfur feedstock for catalytic cracking.

. 95 wt% of the distillate is subjected to dearomatization of kerosene at a pressure of 3 MPa, temperature 250 o C, the volumetric hourly space velocity of 2.0 hr -1, a ratio of hydrogen gas / feed - 800 Nm 3 / m 3 in the presence of a platinum catalyst on aluminum oxide support . Dearomatization product containing 18 wt.% Aromatic hydrocarbons, mixed with 5 wt.% Of the remaining kerosene distillate obtained in the hydrocracking step to obtain a product containing 19 wt.% Aromatic hydrocarbons, and corresponding to the requirements of GOST RT fuel.

The total hydrogen flow in both steps does not exceed 2.8% on the feedstock.

Thus, the above examples show that the proposed method provides a motor fuel with improved environmental characteristics while substantially reducing the hydrogen pressure and flow rate as compared with known similar production techniques. This reduces capital and operating costs in the implementation of the method.

CLAIM

1. A method for producing environmentally friendly engine fuels by catalytic hydrocracking of petroleum feedstock at elevated temperature and pressure with release of hydrogenation of the gasoline, a middle fraction and the residue, followed by a middle fraction dearomatization catalyst at elevated temperature and pressure, characterized in that the catalytic hydrocracking process is carried out with a degree of conversion 50 -. 85%, allocate a middle fraction boiling in the temperature range of 130 - 360 o C, 50 - 95% which is subjected to dearomatization catalyst, and then the product is mixed with the remaining dearomatization 5 - 50% by weight of a middle fraction..

2. A method according to claim 1, characterized in that as a petroleum feedstock along with virgin distillates distillates using a catalytic and / or thermal cracking.

3. The method of claim 1 or 2, characterized in that the process of catalytic hydrocracking is carried out at a pressure of 8 - 12 MPa and temperature of 350 - 430 o C.

4. The method of claim. 1 - 3, characterized in that the dearomatization catalyst process is carried out at a pressure of 3 - 6 bar and a temperature of 250 - 370 o C.

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Publication date 07.04.2007gg