EA025338B1 - Method for production of light petroleum products from heavy petroleum residues - Google Patents

Abstract

The invention is related to the field of high conversion of petroleum, in particular, to production of light petroleum products from heavy petroleum residues. The objective of the invention consists in production of light petroleum products with a high yield by hydrocracking of heavy petroleum residues using nano-size natural zeolites. At a temperature interval of 430-440°C and a pressure of 0.5-1.0 MPa as proposed by the invention, and in the presence of a suspended catalyst in an amount of 1-2.5% by mass of the raw material, an oil-tar hydrocracking process was conducted, and an increase in the yield of high-quality light petroleum products (petrol and diesel fraction) from 53.5 to 61.4% by mass was achieved.

Description

The invention relates to the field of deep oil refining, in particular to the production of light petroleum products from heavy oil residues.

The essence of the invention lies in the fact that tar, which is a heavy oil residue, does not undergo preliminary preparation processes (deasphalting, desulfurization, demetallization, etc.), is subjected to direct thermal hydrocracking at a low pressure of 0.5-6 MPa and a temperature of 430-450 ° С using kaolinite as a solid additive - catalyst in the amount of 1-2.5% by weight of tar and as a liquid additive of light catalytic cracking gas oil boiling within the temperature range of 200-350 ° С in the amount of 2.5% of tar weight .

The invention relates to the field of deep oil refining, is to obtain light oil products through the deep processing of heavy oil residues with the process of thermal hydrocracking.

In the known process [1], using fuel oil as a heavy oil residue, nickel on kieselguhr in the amount of 2.5-7% as a solid additive and light catalytic cracking gas oil (200-350 ° C) in an amount of 2, 5% at a temperature of 420-450 ° C and a pressure of 5-7 MPa, hydrocracking of fuel oil was carried out, up to 65% of light oil products were obtained. As a disadvantage of the process, relatively high energy costs can be shown.

Recently, thermal hydrocracking of heavy oil products, in particular oil residues (fuel oil, tar), has been carried out using solvent donor processes.

In the known process [2], a fraction of 250-450 ° C isolated from the aromatized oil fraction of oil shale and containing up to 10% atomic hydrogen is added to the tar. The resulting mixture is activated by acoustic exposure with a frequency of 0.5-50 kg-s, with an intensity of at least 0.2 W / cm ² , with a force of at least 5 kW, is subjected to thermal hydrocracking at a temperature of 390-450 ° C, a pressure of 5-15 MPa , a space velocity of 0.5-5.0 h ^-1 , while 49.2% of light petroleum products are obtained.

The disadvantages of the known invention are:

to provide acoustic effects on the mixture requires additional equipment and high energy costs;

to involve in the process fractions of 250-450 ° C, extracted from the hydrogenated oil fraction and shale, additional energy and technological process are needed;

the low yield of light petroleum products and the multi-stage method for their preparation indicate the disadvantage of this process from an economic point of view.

In another source [3], upon receipt of light petroleum products, the used raw materials (tar, semi-tar, fuel oil) as a process activator recycle (2-10 wt.%) Solid additives from coal, including sapropelite (sulfur shale, sapromixide), and as a liquid additive (2-10 wt.%) of the fraction boiling at 220-240 ° C obtained by gasification of oil shale, 10-20% of the fraction boiling in the range of 200-370 ° C obtained from the hydrocracking process is also recycled and, in addition, 20-40% of the fraction boiling above 370 ° C of the hydrocracking process is recycled.

The hydrocracking process was carried out in a rotating autoclave with a volume of 2 l at a temperature of 390440 ° C, a pressure of 5-20 MPa for 20-90 min, with a hydrogen to fuel oil ratio of 500: 2000. The yield of the fraction up to 200 ° C is 16-30.8%, and the yield of the fraction 200-370 ° C is 46-68.6%.

A disadvantage of the known invention is that the process is carried out under high pressure, in addition, the addition of more than 60 wt.% Liquid activator to the processed heavy raw material residue causes low productivity of the heavy oil residue, and the multi-stage process reduces its economic benefit.

In another source [4], close to the present invention, to obtain light petroleum products, a heavy oil product (tar) is added 8-25 wt.% Crushed up to 500 microns oil shale and thermocatalytic cracking is carried out at a temperature of 400-440 ° C at a pressure of 3 -8 MPa in continuous mode and a pressure of 6-13 MPa in periodic mode for 0.5-12 hours

The disadvantage of the invention is the use for the process of a large amount of solid additives and the process under high pressure, which reduces the rationality of the process from an economic point of view.

In a source still closer to the invention [5], heavy oil residues were thermocracked using ore wastes containing molybdenum, either cobalt or nickel (1.2–2.8 wt.% Iron and 3.8–58, 0 wt.% Silicon) at a temperature of 390-450 ° C, a pressure of 0.2-5.0 MPa, the amount of solid additives 1-10 wt.%. The catalyst particles, crushed to 1000 μm, were added to the tar.

Under optimal conditions - a temperature of 450 ° C, a pressure of 5 MPa, a taken catalyst in an amount of 10% - 16 wt.% Gasoline, 42 wt.% Diesel, residual fraction and coke were obtained.

The disadvantage of this invention is the large consumption of catalyst, as well as the large particle size of the catalyst, which, due to the small specific surface area does not provide the possibility of obtaining light oil products with a high yield and, thus, is disadvantageous from an economic point of view.

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The objective of the invention is to obtain light petroleum products with a high yield during hydrocracking of heavy oil residues, using nanoscale natural zeolites.

The object of the invention is solved in that the method for producing light oil products from heavy oil residues consists in the process of hydrocracking of heavy oil residues using a suspended catalyst at a temperature of 430-440 ° C and a pressure of 0.5-1.0 MPa, where the hydrocracking process is carried out with the use of a catalyst of natural zeolite-kaolinite with a nanoscale size of 50-500 nm, taken in an amount of 1-2.5 wt.% on the tar used as raw material.

Nanoscale sizes of 50-500 nm and a large specific surface area of the catalyst used in the process, i.e. the ability to increase the degree of dispersion increases the number of catalyst particles in the feedstock, thus facilitating the contacting of the catalyst with the molecules of the feedstock and, by reducing their resistance to the catalyst surface, hydrocracking with high conversion is achieved, as a result of which the yield of light oil products is 53-61.4 wt.% .

In the present invention in table. 1, using X-ray fluorescence microscopy and a laser-induction spectrum, the metal composition of the tar used in the hydrocracking process is presented in the form of a suspension of natural zeolite - kaolinite, the main components of which are δί and A1 (65.21% δί and 15.21% A1).

Table 1

Sample Elements, mg / kg Kaolinite TO Sa Τί SG Mp Re With ΝΪ Si Ζη Ag ky 5g Ζγ Mo ΡΙ Wa 10986 580 2378 - 10049 174 - - 17 - fifteen 285 133 - - 235

As a raw material in the process, a tar mix of Baku oil was used. Physico-chemical properties of the tar are given in table. 2. The process of hydrocracking tar in the presence of nanosized kaolinite was carried out as follows.

table 2

Indicators quantity Density at 20 ° С, kg / m ³ 959.0 Viscosity, 20 ° С, mm ² / s 61.70 Flash point, ° С 200 Fractional composition,% of May .: 450 ° C 5 475 ^b C 19,4 500 ° C thirty Chemical group composition,% May. Paraffin-naphthenic hydrocarbons 29.7 Light aromatic hydrocarbons 9.5 Medium Aromatic Hydrocarbons 4.8 Resin: I 8.0 II * 9.5 Asphaltenes 3.4 Sulfur, mg / kg 0.8

Hydrocracking of the tar taken as a raw material was carried out at a high temperature and low hydrogen pressure in a 1 liter rotating autoclave using a solid additive used in the form of a kaolinite suspension (50-500 nm) taken in an amount of 1-2.5 wt.% To the raw material in within 30 minutes The hydrogenate obtained in the process, undergoing atmospheric vacuum distillation, was divided into gasoline, diesel and residual fractions.

Experience 1. In an autoclave with a capacity of 1 liter of taken 300 g of tar, 3 g (1 wt.%) Of solid catalyst — kaolinite — is added, after which, with stirring, until a homogeneous mass is formed, a suspension is prepared and a hydrocracking process is carried out at a temperature of 440 ° C and a pressure of 0.5 MPa The hydrogenate obtained in the process is divided into gasoline (NK - 180 ° C), diesel (180-360 ° C) and residual (fra.> 360 ° C) fractions in an atmospheric-vacuum unit (ί'ΌΌδ Ό2892). The material balance of experience is given in table. 3.

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Table 3

The yield of products,% wt. P _H2 = 0.5 MPa, T = 440 ° C, Cat. one% Gases C1-C4 10 Gasoline N.C. - 180 ° C 43 Fraction 180-360 ° C eighteen Σ fractions <360 ’C,% May. 61 Residue> 360 ° C 21 Coke 8

The physicochemical properties of the gasoline and diesel fractions obtained in the process were determined by standard methods, the individual and group compositions of gasoline fractions were determined by the method ΡΙΟΝΑ on a Chromatograph уιιΙο §у81ет ХЬ from Regkt Е1teg and are respectively presented in Table. 4.

Table 4

Indicators GOST number Gasoline fraction Density, at 20 ° С, kg / m ³ 0.690-0.700 3900-85 Hydrocarbon Composition: 13379-67 Paraffins 43.16 ί-paraffins 32.00 Olefins 2.01 Naphthenes 15.10 Aromatic 7.37 Octane number 70-71 511-82 Sulfur,% of May. 0.1087 19121-73 Iodine number, g Y ₂ / 100t 17 2070-82 Diesel fraction Density, at 20 ° С, kg / m ³ 0.845-0.849 3900-85 Viscosity, 20 ° С, mm ² / s 2.2 33-82 Actual pitches, mg / 100ml 33 8489-58 Sulfur,% of May. 0.10-0.15 19121-73 Iodine number, g J ₂ / 100g 7.4 2070-82 Cetane number 46 3122-67

Experience 2. In an autoclave with a volume of 1 liter of taken 300 g of tar, 3 g (1 wt.%) Of solid catalyst — kaolinite — is added, after which a suspension is prepared with stirring until a homogeneous mass is formed and a hydrocracking process is carried out at a temperature of 440 ° C and a pressure of 1 MPa.

Experience 3. In an autoclave with a volume of 1 liter of taken 300 g of tar, 7.5 g (2.5 wt.%) Of solid catalyst - kaolinite are added, after which, with stirring until a homogeneous mass is formed, a suspension is prepared and a hydrocracking process is carried out at a temperature of 440 ° C. pressure of 1 MPa.

Experience 4. In an autoclave with a volume of 1 liter of taken 300 g of tar, 7.5 g (2.5 wt.%) Of solid catalyst - kaolinite are added, after which, with stirring until a homogeneous mass is formed, a suspension is prepared and a hydrocracking process is carried out at a temperature of 430 ° C. pressure of 0.5 MPa.

Experiments 5-10 were carried out similarly to experiments 1-4 with a change in temperature, pressure and amount of catalyst, the effect of a change in operating parameters in the process of tar hydrocracking on the yield of light oil products is shown in table. 5.

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Table 5

No. Temperature the process hydrocracking ° C Pressure the process hydrocracking MRA The amount of catalyst,% May. The yield of light oil products,% wt. one 440 0.5 1,0 61,4 2 430 0.5 1,0 53.5 3 440 one 2,5 58.0 4 430 0.5 2,5 55.0 5 440 0.5 1,5 59.2 6 450 0.5 1,0 50,0 7 410 0.5 1,5 31,4 8 440 2 1,0 60.1 nine 410 2 2,5 35.0 10 440 0.5 3,5 61.5

As can be seen from the table. 5, in experiments 1-5 under optimal conditions - a temperature of 430-440 ° C, a pressure of 0.5-1 MPa, a catalyst amount of 1-2.5% to raw materials, the yield of light oil products increases from 53.5 to 61.4 wt. %

As can be seen from experiment 6, when the temperature rises to 450 ° C, the yield of light oil products decreases from 61.4 to 50 wt.%, The amount of gases and coke increases, i.e. the deepening of the cracking process is increasing. As can be seen from experiments 7 and 9, at low temperatures of -410 ° C, the yield of light oil products, decreasing, reaches 31.4 wt.%, I.e. the hydrocracking process is very weak.

As follows from experiment 8, despite the fact that when the temperature rises to 440 ° C, pressure up to 2 MPa, the yield of the target products is 60.1 wt.%, A pressure indicator above the optimal value reduces the rationality of the process from an economic point of view.

As can be seen from experiment 10, the increase in the amount of catalyst to 3.5% compared with the optimal value, i.e. in terms of catalyst consumption (1.0%), has a slight effect on the yield of light oil products: 61.5 versus 61.4 wt. economically disadvantageous.

Thus, in the present invention, the tar hydrocracking process was carried out at a temperature of 430-440 ° C, a pressure of 0.5-1 MPa using a suspended catalyst - kaolinite in an amount of 1-2.5 wt.% To the feedstock and an increase in the yield of high-quality light oil products was achieved (gasoline and diesel fraction) from 53.5 to 61.4 wt.%.

Bibliography

1. Patent Αζ I 20100016, 2010

2. Patent KI, 2292378, 2007

3. Patent KP, 2009166, 1994

4. Patent KI, 2024578, 1994.

5. Patent KI, 2182923, 2002

Claims (1)

CLAIM A method of obtaining light oil products from heavy oil residues, which consists in the process of hydrocracking of heavy oil residues using a suspended catalyst, carried out at a temperature of 430-440 ° C and a pressure of 0.5-1.0 MPa, characterized in that the hydrocracking process is carried out using as a catalyst of natural zeolite-kaolinite with a nanoscale size of 50-500 nm, taken in an amount of 1-2.5 wt.% in relation to the tar used as raw material.