RU2445344C1 - Heavy oil stock processing method - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: invention refers to catalytic cracking method of heavy oil stock with high content of resins and asphaltenes in presence of nanodimensional nickel powder with average particle size of 10-20 nm, which has been taken in quantity of 0.5-1.0 wt % for original stock, at temperature of 430-450°C and pressure of 0.5-1.0 MPa in tight autoclave in inert gas environment.

EFFECT: high output of distillate fractions without coke formation.

7 ex, 2 tbl, 2 dwg

Description

The invention relates to the field of oil refining, in particular to processes for the processing of heavy oil, and can be used in catalytic and thermal cracking to obtain distillate fractions from heavy oil feedstocks.

The traditional methods for obtaining light fractions from heavy oil components are hydrocracking, thermal and catalytic cracking. With thermal cracking - the simplest and cheapest way to process heavy oil fractions - there is no significant formation of light and medium distillates, so the use of various activating additives is required. Hydrocracking processes are characterized by high flexibility and good quality of the products obtained, but they also have some disadvantages, including the high cost of equipment, the need for the presence of hydrogen-containing gas in the reaction zone, and increased pressure. Compared to hydrocracking, catalytic cracking is a relatively simple and cheap process; it does not require high pressure and the presence of hydrogen; the catalysts are characterized by a relatively low cost. However, the composition of the processed feedstock imposes certain restrictions on the catalytic systems, since catalytic systems with catalytically active elements supported on the carrier during the processing of heavy petroleum feedstocks with a high content of resins and asphaltenes are quickly carbonized and deactivated by catalytic poisons.

There is a method of producing distillate fractions from oil residues by mixing them with a catalyst crushed to a particle size of less than 1000 microns - waste from the processing of molybdenum, or cobalt, or nickel, or tungsten ores, and subsequent thermal cracking of the resulting mixture (RU 2182923, 2002).

The disadvantage of this method is the need for preliminary preparation of the catalyst (grinding), the subsequent homogenization of the catalyst with raw materials, a low yield of gasoline fractions and the binding of this method to the territorial location of the plants for the enrichment of the above ores (since the delivery of these catalysts over long distances and the inability to regenerate them reduce profitability this method).

A known method of producing liquid products from oil residues by thermocatalytic cracking at 350-500 ° C, a pressure of 0.1-10.0 MPa in the presence of catalysts - salts of Mo, V, Cr, W, Fe, Co and / or Ni, taken in an amount of 100-2500 ppm (FR 2555192, class C10G 47/00, 1985).

The disadvantage of this method is the need to use metal salts in the form of naphthenates, resins, or sulfides.

Closest to the proposed method is a method for catalytic cracking of heavy oils in the presence of nickel nanopowder (NP), taken in an amount of 1.0-5.0 wt.% On the feedstock (Modern techniques and technologies: proceedings of the XVI International scientific and practical conference of students , graduate students and young scientists. In 3 vol. T.3 / National Research Tomsk Polytechnic University.- Tomsk: Publishing House of Tomsk Polytechnic University, 2010. - p.353, signed for publication: May 2010).

The disadvantage of this method is the low yield of diesel fractions (180-350 ° C), not exceeding 25.0%.

The objective of the invention is to develop a method for the processing of heavy crude oil, characterized by a high yield of distillate fractions without coke formation.

The problem is achieved by using as a catalyst a nickel nanopowder with an average particle size of 10-20 nm, taken in an amount of 0.5-1.0 wt.% For heavy raw materials, at a temperature of 430-450 ° C and a pressure of 0.5-1, 0 MPa in a thermal autoclave in an inert gas environment.

The technical result of the invention is to increase the yield of diesel fraction (180-350 ° C) to 36.7 wt.% And light fractions (up to 350 ° C) - 79.6 wt.%.

The essence of the invention lies in the catalytic cracking of heavy crude oil with a high content of resins and asphaltenes in the presence of nanosized nickel powder with an average particle size of 10-20 nm, obtained by gas-phase synthesis, taken in an amount of 0.5-1.0 wt.% On feedstock, at a temperature of 430-450 ° C and a pressure of 0.5-1.0 MPa for 1 and 2 hours in a sealed autoclave in an inert gas environment.

The experiments were performed in a single inert gas medium, nitrogen, which was added to the reactor until the air was completely displaced from the autoclave.

The introduction of nanopowder of Nickel (as in the prototype) in the crude oil is carried out under the influence of ultrasound, which ensures uniform distribution of the nanocatalyst in the volume of crude oil.

According to the prototype, nickel nanopowder obtained by the method of electric explosion of a conductor, the average size of which, in accordance with the distribution curve, is 50 nm, was used as a catalyst (Fig. 1).

It is well known that the size of the reagent is a thermodynamic quantity equivalent to temperature, which, in turn, allows the interaction of the nanoreagent with the substrate at lower temperatures or the implementation of such chemical reactions that are impossible under similar conditions for coarser-dispersed reagents (Sergeev G .B. Nanochemistry. - Moscow: Publishing House of Moscow State University, 2003 .-- 288 p.).

In the present invention, a gas-phase nickel nanopowder with an average size of less than 10 nm was used as a catalyst (Fig. 2). So all the described effects, during the thermolysis of heavy oil feedstocks, related to an increase in the yield of light fractions, can be attributed to the chemical specificity of such nano-objects.

The quantitative assessment of the yield of oil fractions was determined by the thermogravimetric method (Derivatograf-S). The composition of the feedstock is shown in table 1. The results of catalytic cracking of heavy oil are presented in table 2.

Case Studies

Example 1. 1.0 wt.% Nickel nanopowder with an average particle size of 20 nm was added to the starting oil and subjected to ultrasound for 30 seconds to uniformly distribute the nanopowder in the oil. The process is carried out in a batch autoclave at a temperature of 430 ° C in an inert nitrogen gas atmosphere for 2 hours. The composition of the initial heavy oil feed is presented in table 1, the process indicators are shown in table 2.

Example 2. To the starting oil add 1.0 wt.% Nanopowder of Nickel with an average particle size of 10 nm. The process is carried out in a batch autoclave at a temperature of 450 ° C in an inert gas environment for 1 hour. The process indicators are shown in the table.

Example 3. To the starting oil add 1.0 wt.% Nanopowder of Nickel with an average particle size of 20 nm. The process is carried out in a batch autoclave at a temperature of 450 ° C in an inert gas atmosphere for 1 hour. The process indicators are shown in the table.

Example 4. To the starting oil add 1.0 wt.% Nanopowder of Nickel with an average particle size of 20 nm. The process is carried out in a batch autoclave at a temperature of 450 ° C in an inert gas environment for 2 hours. The process indicators are shown in the table.

Example 5. To the starting oil add 1.0 wt.% Nanopowder of Nickel with an average particle size of 10 nm. The process is carried out in a batch autoclave at a temperature of 450 ° C in an inert gas environment for 2 hours. The process indicators are shown in the table.

Example 6. To the starting oil add 0.5 wt.% Nanopowder of Nickel with an average particle size of 20 nm. The process is carried out in a batch autoclave at a temperature of 450 ° C in an inert gas atmosphere for 1 hour. The process indicators are shown in the table.

Example 7. To the initial oil add 1.0 wt.% Nickel nanopowder with an average particle size of 20 nm and is subjected to ultrasound for 30 seconds to evenly distribute the nanopowder in the oil. The process is carried out in a batch autoclave at a temperature of 430 ° C in an inert gas of argon for 2 hours. The composition of the initial heavy oil feed is presented in table 1, the process indicators are shown in table 2.

Thus, the proposed method allows to increase the yield of diesel fractions in comparison with the prototype by 1.5 times in the complete absence of coke formation.

Table 1 Fractional composition of the initial heavy oil feedstock (density - 966.7 kg / m ³ , at 20 ° С, kinematic viscosity - 3852.4 mm ² / s) Feedstock Content, wt.% The fraction boiling in the range of 180-350 ° C 28.1 The output of the light fraction, boiling up to 350 ° C 33.3 The remainder 66.7

table 2 Examples of the process of catalytic cracking of heavy oil in the presence of nickel nanopowder Example No. The content of nickel nanopowder in oil, wt.% Process temperature and duration The output of the fraction 180-350 ° C for oil raw materials, wt.% The yield of fractions up to 350 ° C for oil raw materials, wt.% one 1.0 (20 nm) 430 ° C, 2 h 41.2 71.3 2 1.0 (10 nm) 450 ° C, 1 h 36.7 79.6 3 1.0 (20 nm) 450 ° C, 1 h 34.8 74.5 four 1.0 (10 nm) 450 ° C, 2 h 32.6 77.0 5 1.0 (20 nm) 450 ° C, 2 h 35.5 76.3 6 0.5 (20 nm) 450 ° C, 1 h 29.3 74.9 7 1.0 (20 nm) 430 ° C, 2 h 41.2 71.3

Claims (1)

A method of processing heavy petroleum feedstock by catalytic cracking in the presence of nickel nanopowder as a catalyst, characterized in that nickel nanopowder with an average particle size of 10-20 nm, taken in an amount of 0.5-1.0 wt.%, Is used, the process is carried out at a temperature of 430 -450 ° C and a pressure of 0.5-1.0 MPa in a thermal autoclave in an inert gas environment.

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