RU2485168C1 - Method for processing of hydrocarbon-containing raw material - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: invention refers to oil-processing and petrochemical industries. The invention refers to the method for processing of hydrocarbon-containing raw material, and namely heavy and/or residual raw material, in which to raw material there additionally added is metal organic salt having the following formula: M(OOC-R)_n, or M(SOC-R)_n or M(SSC-R)_n, where R means alkyl, aryl, isoalkyl, tert-alkyl, alkylaryl, which possibly includes hydroxylic, keto-, amino-, carboxyl, thiocarbamic group, where n - 1-3, and M means transition metal from elements of the Periodic system, at decomposition of which there obtained are metal nanoparticles, or nanoparticles of those metals, based on 0.001-0.1 wt % of metal per mass of raw material; at that, as hydrocarbon additive, there used are paraffin hydrocarbons, or olefinic hydrocarbons, or fraction of shale tar, or their mixture in the quantity of 2.0-20.0 wt %.

EFFECT: increasing conversion degree of hydrocarbon-containing raw material; increasing the yield of distillate fractions.

3 cl, 22 tbl, 16 ex

Description

The invention relates to the refining and petrochemical industries and can be used to increase the depth of processing of hydrocarbon-containing raw materials.

A known method of producing boiler fuel (SU 1675318, publ. 07.09.1991). Heavy oil residues are preheated and then visbreaked in a tube furnace in the presence of an olefinic hydrocarbon concentrate in order to achieve a better degree of conversion of the feed mixture.

A known method of producing a component of heating oil (RU 1617948, publ. 10/30/1994) by visbreaking oil residues in the presence of a highly aromatic additive, in order to reduce the viscosity of the target product, an additive for the selective purification of oils or catalytic cracking residues boiling in the range 420 ° C are used as additives - c.k. taken in an amount of 2-8% wt.

However, the known method is aimed at achieving a decrease in the structural viscosity of the visbreaking residue.

A known method of processing residual oil products (RU 2021994, publ. 30.10.1994). Residual oil is visbreaked to the presence of an aromatic fraction or a polar compound. The feedstock is preliminarily subjected to cavitation treatment. As an aromatic fraction, an extract of selective purification of oils or gas oil of catalytic cracking is used in an amount of 2.0-8.0% by weight. As a polar compound, acetone is used in an amount of 0.001-0.05% wt.

The disadvantage of this method is the additional processing of residual petroleum products through cavitation treatment, which is not economically feasible.

The objective of the present invention is to increase the degree of conversion of hydrocarbon-containing raw materials, including heavy and residual raw materials, increasing the yield of distillate fractions.

The problem is solved due to the fact that the method of processing a hydrocarbon-containing raw material involves thermal conversion of the raw material with the introduction of a hydrocarbon additive, which is used as paraffin hydrocarbons or olefinic hydrocarbons, or a fraction of shale resin, or a mixture thereof in an amount of 2.0-20.0% by weight ., wherein an organometallic salt of the formula M (OOC-R) _n , or M (SOC-R) _n , or M (SSC-R) _n , where R is alkyl, aryl, isoalkyl, tert- alkyl, alkylaryl, possibly including hydroxyl, keto, amino, carboxyl thiocarbamine group, where n = 1-3, and M denotes a transition metal from elements of the Periodic system of elements, upon decomposition of which receive metal nanoparticles, or nanoparticles of these metals, from the calculation of 0.001-0.1% wt. metal to the mass of raw materials.

The term "thermal conversion" as used in the present invention involves atmospheric distillation and / or vacuum distillation, or a single evaporation, or distillation, or distillation with distillation, as well as thermal cracking (deep thermal cracking), or visbreaking (light thermal cracking), or their combinations.

As hydrocarbon-containing raw materials, mainly heavy and / or residual raw materials with a density of more than 850 g / cm ^{3 are used} : heavy oils, vacuum gas oils, straight-run fuel oils, tars, semi-tars, cracked residues, oil sludges individually or in mixture, as well as mixtures thereof with fossil fuels (oil shale, tar sands).

Example 1. In samples with black oil of West Siberian oil with a density of 0.89 g / cm ³ with and without the addition of solid paraffin hydrocarbons (n.a. 405 ° C) in a mass ratio of 4: 1, respectively, cobalt 2-ethylhexanoate is introduced at a rate of 0.1 % wt. cobalt to the mass of the feedstock and subjected to distillation according to Engler. The results of the distillation are presented in table. 1 and 2.

Table 1 Fraction yield without the addition of solid paraffin hydrocarbons Temperature ° C 219 240 271 285 294 295 301 307 312 321 333 334 The volume of distillate, ml 5 10 fifteen twenty 25 thirty 35 40 45 fifty 55 60

table 2 The yield of fractions with the addition of solid paraffin hydrocarbons Temperature ° C 219 252 277 296 294 317 334 342 347 350 354 360 The volume of distillate, ml 5 10 fifteen twenty 25 thirty 35 40 45 fifty 60 85

In the table. Figures 4 and 3 show the material balances of Angler distillation of West Siberian oil fuel oil with and without the addition of solid paraffin hydrocarbons.

Table 3 Material balance of Angler distillation of West Siberian oil fuel oil without the addition of solid paraffin hydrocarbons Product name Download, g % Received Mass fraction, g % to raw materials Fuel oil without the addition of solid paraffin hydrocarbons 146.3 one hundred 1. Fraction (up to 352ºС) 80.6 55.1 2. Fraction (360ºС and higher) 58.8 40,2 3. Losses (gas) 6.9 4.7 Total 146.3 one hundred

Table 4 The material balance of the Angler distillation of a mixture of fuel oil of West Siberian oil and solid paraffin hydrocarbons in a mass ratio of 4: 1 Product name Download, g % Received Mass fraction, g % to raw materials Solid paraffin added fuel oil 118.1 one hundred 1. Fraction (up to 360ºС) 72.9 61.7 2. Fraction (360ºС and higher 39.0 33.0 3. Losses (gas) 6.2 5.3 Total 118.1 one hundred

Samples of the intermediate feedstock are examined on a NT-MDT Solver Pro-M scanning probe microscope. The measurement results show that the weight average size of cobalt nanoparticles is 27 nm.

Example 2. The distillation of a mixture of fuel oil with solid paraffin hydrocarbons according to Engler is carried out as in example 1, only with the difference that nickel nanoparticles (weight average particle size of 34 nm) and tungsten (weight average particle size of 54 nm) are taken in the amount of 0.001 % wt. (with a mass ratio of nickel and tungsten 1: 1) by weight of fuel oil. The results of the distillation are presented in table. 5.

Table 5 The yield of fractions with the addition of solid paraffin hydrocarbons Temperature ° C 219 250 267 286 290 307 315 331 338 342 349 350 The volume of distillate, ml 5 10 fifteen twenty 25 thirty 35 40 45 fifty 60 85

Example 3. In the distillate, boiling within 300-360 C, obtained by distillation of fuel oil according to Engler as in example 1, add molybdenum nanoparticles (weight average particle size of 61 nm) in an amount of 0.001% wt. and solid paraffin hydrocarbons in an amount of 10.0% wt. and refluxed for 15 minutes. The resulting mixture was subjected to Angler distillation. The results of the distillation are presented in table. 6.

Table 6 The yield of fractions with the addition of solid paraffin hydrocarbons Temperature ° C 83 154 168 184 187 189 201 237 262 276 304 333 The volume of distillate, ml 5 10 fifteen twenty 25 thirty 40 fifty 60 70 80 95

Example 4. In the fraction with a temperature of NK 360 ° C, obtained by distillation of fuel oil in Example 1, in the presence of molybdenum nanoparticles in an amount of 0.1% wt. (weight average particle size of 61 nm) add solid paraffin hydrocarbons in an amount of 10.0% wt. and subjected to acceleration according to Engler. The results of the distillation are presented in table.7.

Table 7 The yield of fractions with the addition of solid paraffin hydrocarbons Temperature ° C 227 254 268 294 310 316 329 337 341 344 349 361 The volume of distillate, ml 5 10 fifteen twenty 25 thirty 35 40 45 fifty 55 73

Example 5. Tar with a density of 1.08 g / cm ³ obtained from West Siberian oil, with the addition of diethyldithiocarbamate iron at the rate of 0.01% wt. iron per mass of feedstock and the addition of liquid paraffin hydrocarbons in an amount of 20.0% wt. subjected to the process of visbreaking at t = 400ºC and P = 0.5 MPa. The results are presented in table. 8.

Table 8 Fractions Yield,% wt. With the addition of 0.01% wt. iron and 20.0% wt. paraffin hydrocarbons Fractions n.k. and up to 360ºС 84 Fraction N.K. 360ºС and higher 10

The cracked residue is examined for the content of nanoparticles by AFM microscopy using a NT-MDT Solver Pro-M scanning probe microscope. The measurement results show that the size of 93% of iron nanoparticles is 5-45 nm.

Example 6. Analogously to example 5, except that instead of iron diethyldithiocarbamate, a cobalt salt of diethylthiocarbamic acid is added. The results are presented in table.9.

Table 9 Fractions Yield,% wt. With the addition of 0.01% wt. cobalt and 20.0% wt. liquid paraffin hydrocarbons Fractions n.k. and up to 360ºС 87 Fraction N.K. 360ºС and higher eleven

The cracked residue is examined for the content of nanoparticles by AFM microscopy using a NT-MDT Solver Pro-M scanning probe microscope. The measurement results show that the size of 82% of cobalt nanoparticles is 1-20 nm.

Example 7. Vacuum gas oil with a density of 0.870 g / cm ³ with the addition of the vanadium salt of aminohexanoic acid at the rate of 0.001% wt. vanadium on the mass of raw materials and the addition of 2.0% wt. solid paraffin hydrocarbons are sent to the stage of thermal cracking, carried out at a temperature of 450 ° C and a pressure of 0.8 MPa. The results are presented in table. 10.

Table 10 Fractions Yield,% wt. With the addition of 0.001% wt. vanadium and 2.0% wt. solid paraffin hydrocarbons Fractions n.k. and up to 360ºС 87 Fraction N.K. 360ºС and higher 12

The cracked residue is examined for the content of nanoparticles by AFM microscopy using a NT-MDT Solver Pro-M scanning probe microscope. The measurement results of the samples show that the size of 83% of the vanadium nanoparticles is 10-50 nm.

Example 8. In the tar with a density of 1.08 g / cm ³ obtained from West Siberian oil, add cobalt salt of diethylthiocarbamic acid at the rate of 0.1% wt. cobalt on the mass of raw materials and 20.0% wt. mixtures of olefinic hydrocarbons C ₅ -C ₁₁ and subjected to the process of visbreaking at t = 400 ° C and P = 1.5 MPa, and then fractionation by atmospheric distillation. The distillation results are presented in table.11.

Table 11 Product name Download, g % Received Mass fraction, g % to raw materials Tar Visbreaking Product 1116.3 one hundred 1. Fraction (up to 360 ° С) 989.0 88.6 2. Fraction (above 360 ° C) 72.5 6.5 3. Losses (gas) 54.8 4.9 Total 1116.3 one hundred

Samples of the intermediate feedstock are examined on a NT-MDT Solver Pro-M scanning probe microscope. The measurement results show that the weight average size of cobalt nanoparticles is 57 nm.

Example 9. The distillation of fuel oil according to Engler is carried out as in example 2, only with the difference that 20.0% wt. mixtures of liquid paraffin hydrocarbons obtained from distillates of high-paraffin oils boiling in the range of 240-360 ° C, and palladium 2-oxohexonoate is used as a catalyst at the rate of 0.01% wt. palladium on a mass of raw materials. The results of the distillation are presented in tables 12 and 13.

Table 12 The yield of fractions with the addition of liquid paraffin hydrocarbons Temperature ° C 215 231 253 275 291 308 319 333 344 348 356 358 The volume of distillate, ml 5 10 fifteen twenty 25 thirty 35 40 45 fifty 60 85

Table 13 The material balance of the Angler distillation of a mixture of fuel oil of West Siberian oil and liquid paraffin hydrocarbons Product name Download, g % Received Mass fraction, g % to raw materials Liquid paraffin oil 106,2 one hundred 1. Fraction (up to 360 ° С) 84.1 79.2 2. Fraction (360 ° C and above) 16.6 15.6 hydrocarbons 3. Losses (gas) 6.5 5.2 Total 106,2 one hundred

Samples of a fraction of 360 ° C and higher are studied on a NT-MDT Solver Pro-M scanning probe microscope. The measurement results show that the average weight size of palladium nanoparticles is 63 nm.

Example 10. The distillation of fuel oil according to Engler is carried out as in example 9, only with the difference that manganese 6-amiohexanoate is used as a catalyst. The result of the distillation are presented in tables 14 and 15.

Table 14 The yield of fractions with the addition of solid paraffin hydrocarbons Temperature ° C 221 241 256 275 285 312 325 344 350 353 358 362 The volume of distillate, ml 5 10 fifteen twenty 25 thirty 35 40 45 fifty 60 85

Table 15 The material balance of the Angler distillation of a mixture of fuel oil of West Siberian oil and liquid paraffin hydrocarbons Product name Download, g % Received Mass fraction, g % to raw materials Solid paraffin added fuel oil 102.6 one hundred 1. Fraction (up to 360ºС) 80.8 78.7 2. Fraction (360ºС and higher 16.9 16.5 3. Losses (gas) 5.2 4.8 Total 102.6 one hundred

Samples of fractions above 362 ° C are examined on a NT-MDT Solver Pro-M scanning probe microscope. The measurement results show that the average weight size of manganese nanoparticles is 106 nm.

Example 11. The distillation of fuel oil according to Engler is carried out as in example 9, with the difference that molybdenum 6-oxyhexanoate is used as a catalyst. The results of the distillation are presented in table. 16 and 17.

Table 16 The yield of fractions with the addition of solid paraffin hydrocarbons Temperature, ºC 224 243 258 275 284 310 323 344 351 354 358 362 The volume of distillate, ml 5 10 fifteen twenty 25 thirty 35 40 45 fifty 60 85

Table 17 The material balance of the Angler distillation of a mixture of fuel oil of West Siberian oil and liquid paraffin hydrocarbons Product name Download, g % Received Mass fraction, g % to raw materials Solid paraffin added fuel oil 114.3 one hundred 1. Fraction (up to 360ºС) 87.9 76.9 2. Fraction (360ºС and higher 19.8 17.3 3. Losses (gas) 6.6 5.8 Total 114.3 one hundred

Samples of fractions above 362 ° C are examined on a NT-MDT Solver Pro-M scanning probe microscope. The measurement results show that the average weight size of the molybdenum nanoparticles is 66 nm.

Example 12. The process is carried out under the conditions of example 7, except that as a hydrocarbon additive, shale resin is used in an amount of 2.0% by weight, having the following characteristics: density - 0.991 g / cm ³ , viscosity at 80 ° C - 2.54ºVU, kinematic viscosity at 80ºС - 17.0 cSt, pour point - minus 20ºС, content, wt.%: Water - 0.5; no mechanical impurities, elemental composition, wt.%: С - 79.96, Н - 9.86; O - 9.46; S - 0.68, and as an organometallic salt, chromium naphthenate is used at the rate of 0.1% wt. chromium per mass of feedstock. The results are presented in table 18.

Table 18 Fractions Yield,% wt. With the addition of 0.1% wt. chromium and 2.0% wt. shale fractions Gas 4,5 Fractions n.k. 360 ° C 69.5 Fraction N.K. 360 ° C and above fifteen

The size of 91% of chromium nanoparticles is 30-50 nm.

Example 13. As a raw material, a mixture of tar with a density of 1.002 g / cm ³ and oil of the Shugurovskoye field is used, which has the following indicators: density - 0.914 g / cm ³ , kinematic viscosity at 20 ° C - 220.23 cSt, conditional viscosity at 20 ° C - 29.73 ° W, pour point minus 20 ° C, in a mass ratio of 1: 1. The visbreaking process is carried out under the conditions of example 8, while manganese 4-oxopentanoate is used as the salt, and a mixture of olefinic hydrocarbons is used in an amount of 2.0% by weight. The results are presented in table.19.

Table 19 Fractions Yield,% wt. With the addition of 0.1% wt. manganese and 2.0% wt. olefinic hydrocarbons Gas 4.4 Fractions n.k. 360 ° C 67.3 Fraction N.K. 360 ° C and above 15,2

The size of 89% of manganese nanoparticles is 65 nm.

Example 14. The process is carried out under the conditions of example 12, except that the fraction of shale resin is used in an amount of 20.0% by weight. The results are presented in table 20.

Table 20 Fractions Yield,% wt. With the addition of 0.01% wt. chromium and 20.0% wt. shale fractions Gas 3,5 Fractions n.k. 360ºС 74.5 Fraction N.K. 360ºС and higher eleven

The size of 88% of chromium nanoparticles is 60-90 nm.

Example 15. The process is carried out under the conditions of example 7, except that as a hydrocarbon additive, a mixture of liquid paraffin hydrocarbons, olefinic hydrocarbons and a fraction of shale resin (mass ratio 1: 1: 1) in an amount of 20.0% wt. The results are presented in table. 21.

Table 21 Fractions Yield,% wt. With the addition of 0.001% wt. vanadium and 20.0% wt. mixtures of liquid paraffin hydrocarbons, olefinic hydrocarbons and a fraction of shale resin in a ratio of 1: 1: 1 Fractions n.k. and up to 360ºС 85 Fraction N.K. 360ºС and higher 9

The size of 82% of vanadium nanoparticles is 40-75 nm.

Example 16. Analogously to example 7, except that instead of vacuum gas oil take crude oil with a density of 0.7488 g / cm ³ . The results of the distillation are presented in table. 22.

Table 22 Fractions Yield,% wt. With the addition of 0.001% wt. vanadium and 2.0% wt. solid paraffin hydrocarbons Fractions n.k. and up to 360ºС 88 Fraction N.K. 360ºС and higher 7

As the results show, the claimed method for the joint processing of hydrocarbon-containing raw materials with a hydrocarbon additive using the proposed catalyst allows to obtain additional distillate fractions.

Claims (3)

1. A method of processing hydrocarbon-containing raw materials, which is mainly used heavy and / or residual raw materials selected from the group: heavy oils, vacuum gas oils, straight-run fuel oils, tars, half tars, cracked residues individually or in mixtures, including thermal conversion of raw materials with the introduction of a hydrocarbon additive characterized in that an organometallic salt of the formula M (OOC-R) _n or M (SOC-R) _n or M (SSC-R) _n , where R is alkyl, aryl, isoalkyl, tert, is additionally added to the feedstock -alkyl, alkylaryl, possibly including idroxyl, keto, amino, carboxyl, thiocarbamine group, where n = 1-3, M denotes a transition metal from elements of the Periodic system of elements, upon decomposition of which receive metal nanoparticles or nanoparticles of these metals, at the rate of 0.001-0.1% metal on the mass of raw materials, while paraffin hydrocarbons, or olefinic hydrocarbons, or a fraction of shale resin, or mixtures thereof in an amount of 2.0-20.0 wt.% are used as a hydrocarbon additive. 2. The method according to claim 1, characterized in that the hydrocarbon-containing raw materials use oil sludge individually or mixed with heavy oils, vacuum gas oils, straight-run fuel oils, tars, semi-tars, cracking residues, as well as mixtures of oil sludges, heavy oils, vacuum gas oils, straight-run fuel oils, tars, half tars of cracked residues with fossil fuels from the group: oil shales, tar sands. 3. The method according to claim 1, characterized in that as the hydrocarbon-containing raw materials use raw materials with a density of more than 0.850 g / cm ³ .