RU2393202C1 - Composition of gel-like concentrate extracted when processing hydrocarbon oil - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to oil refining. The invention pertains to a product of processing hydrocarbon oil, deposited on sorbing electrodes during combined effect of an electrostatic field with intensity less than 750 V/cm, a magnetic field with intensity of 400 A/m, pulse frequency of 50 Hz and pulse duration of 10 s and an ultrasonic field with frequency ranging from 18000 to 44000 Hz. The said product is a gel-like concentrate which contains clusters of chemical elements Au and/or V and/or Ni and/or Al and/or Ca and/or S and/or Si and/or P and/or Co.

EFFECT: extraction of chemical elements Au, V, Ni, Al, Ca, S, Si, P, Co from hydrocarbon oil for subsequent industrial processing.

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Description

The invention relates to industrial technology for the extraction of chemical elements from hydrocarbon oils Au, V, Ni, Al, Ca, S, Si, P, Co.

The term “heteroatomic cluster” is used in the present description and in the appended claims in the general sense and describes compounds containing atoms of two, three or more metals, coated externally with a dense layer of ligands that form a closed shell.

The composition of oil includes a huge number of organometallic, colloidal and other chemical and composite compounds containing a wide variety of elements [B. Tissot, D. Velte. The formation and distribution of oil, M .: Mir, 1981]. However, until the 70s of the XX century, many of them were not even determined in its composition by the methods of analytical chemistry, due to the fact that they are contained inside heteroatomic cluster formations 1-100 nm in size [I. Suzdalev. Physics and Chemistry of Nanoclusters, Nanostructures and Nanomaterials, KomKniga, M., 2005], which have the ability to sublimate with light fractions of oil, leaving no traces in the ashes of hydrocarbon feedstocks.

The emergence of a highly sensitive neutron activation analysis method made it possible to learn about the presence of many elements in oil, for example, metals, including noble ones [Determination of scattered elements in oil and oil fractions by neutron activation method. Berkutova I.D., Viunova E.S., Jalnina T.I., Ziotova I.M., Yakubson K.I., Dossage des elements-traces dans les petroles et leurs fractions par la methode d'activation aux neutrons, “J. Radional. Chem. ”, 1973, 18, No. 1-2, 119-132 (French)]. But this method also does not allow to obtain reliable quantitative results due to the high temperature in the reactor when samples are irradiated with thermal neutrons, as a result of which the metal content in the analysis results is greatly underestimated.

The prior art technology (methods and devices) for the processing of hydrocarbon oils by electrostatic, magnetic and ultrasonic fields.

A known method of processing liquid hydrocarbons using a magnetic field and installation for its implementation (patent RU 2121595 C1, publ. 10.11.1998), which consists in exposure to fuels and lubricants of a magnetic field, the frequency of which is increased from the beginning of processing to the end. A change in the frequency of the magnetic field during processing leads to a significant decrease in the surface tension forces in hydrocarbon liquids, active mixing of the flow. The installation comprises a spiral pipeline with inlet and outlet nozzles and a multipolar permanent magnet mounted on it, made in the form of two annular plates, each of which lies in a plane parallel to the spiral plane, and the other opposite. The execution of the pipeline in the form of a spiral with ring magnets located on both sides provides the processing of liquid hydrocarbons in a magnetic field constantly changing in frequency during the movement of the liquid through the pipeline.

A known method of processing liquid hydrocarbons by means of electromagnetic fields and installation for its implementation (patent RU 2098454 C1, publ. 10.12.1997), which consists in the fact that liquid hydrocarbons are exposed to a pulsed magnetic field with a strength of 0.8-2 MA / m with a pulse frequency of 700-800 Hz and a pulse duration of 0.02-0.009 s. The device consists of a tank for processing liquid hydrocarbons, a system for supplying and discharging liquid hydrocarbons, in each of which controlled chokes and shut-off valves are installed, as well as an electromagnetic field exciter made in the form of a solenoid, whose conductive winding covers a tank for processing liquid hydrocarbons. Using the known method and device, the macrostructure of the molecules of the processed hydrocarbons is changed, affecting their physicochemical properties, and slightly affect the atomic-molecular structure.

A known method of processing liquid hydrocarbons and installation for its implementation (patent RU 2179572 C1, publ. 02.20.2002), which consists in processing brought to a vapor state of liquid hydrocarbons by unipolar electromagnetic pulses with a power of more than 1 MW, a duration of less than 1 ns and a repetition rate not less than 1 kHz. The device includes a liquid hydrocarbon heater, a capacity in the form of coaxial cylinders for the electromagnetic treatment of hydrocarbon vapors, a unipolar electromagnetic pulse generator, and a condensation system for the processed products.

A known method of purification of liquid hydrocarbons from sulfur compounds (RF patent No. 2166530 C1, publ. 05/10/2001), including their oxidation by contacting the hydrocarbon feed with a working reagent containing transition metal ions in an oxidation state in excess of their minimum oxidation state, separation a mixture obtained by contacting a hydrocarbon feedstock with a working reagent to obtain purified hydrocarbon feedstock and spent working reagent, while the working reagent additionally contains ions at least one metal and / or the metal itself selected from the group of non-transition metals, including copper, lead, tin, gold, and / or their salts deposited on the surface of the sorbent. The prior art also known methods and devices for the acoustic excitation of liquids to solve various technological problems. These methods include the transfer of vibrational energy to a fluid using a source of mechanical vibrations interacting with the fluid, which can be used mechanical, electromechanical, magnetostrictive, piezoelectric, hydrodynamic, and other acoustic emitters well known in the art.

Closest to the claimed invention is a prototype method for processing heavy oil-containing fractions and an installation for its implementation (patent RU 2215775 C1, publ. 10.11.2003), including the supply of raw materials to the processing zone, processing of raw materials by wave action by forming a wide range of frequencies from acoustic to the light range in the medium to be processed, followed by thermal cracking of the products of exposure to which is carried out in the mode of primary oil refining, and obtaining from the vapor phase the final products, and installation for fractionation of hydrocarbon processing, including interconnected device for processing raw materials, made in the form of a working tank, generator and emitter of acoustic vibrations, which are made in the form of a generator and emitter of acoustic vibrations and in the form of an additional generator of electromagnetic waves associated electrically with a radiating antenna located in the working capacity, made in the form of two radiating circuits placed in a cylindrical housing, each of which consists of a series of transverse, parallel perforated metal plates rigidly fixed to the wall of the casing, with the contours made of metal with different electronegativity, and the plates of one of the circuits placed between the plates of another circuit, and the casing of the specified emitter is made of dielectric material with the property piezoelectric effect, the device for the selection of final products contains a cracking boiler for processed products associated with a reflux condenser-distiller, and storage tanks for the finished product and residual cracked products. The generator of electromagnetic waves can be made in the form of an electric spark gap. The generator of acoustic vibrations is an electric centrifugal pump installed on the pipeline at the inlet of the tank, and the emitter of acoustic vibrations is the pipeline for supplying raw materials to the tank and the walls of the tank.

The main disadvantage of this method and installation is that they do not allow commercial extraction of the chemical elements Au, V, Ni, Al, Ca, S, Si, P, Co from hydrocarbon oils in the form of organometallic clusters consisting of a metal core coated with outside with a layer of thiols, organic sulfides, creating a closed shell.

The objective of the invention is to obtain a product for the processing of hydrocarbon oils in the form of a gel-like concentrate containing heteroatomic clusters of chemical elements Au, and / or V, and / or Ni, and / or Al, and / or Ca, and / or S, and / or Si , and / or P, and / or Co as raw materials for subsequent industrial processing.

The technical result of the invention is a new product, which is obtained as a result of combined electrostatic, magnetic and ultrasonic effects on hydrocarbon oil, in which the clusters and organic compounds present in it are polarized, they are deposited on sorbing electrodes in the form of a gel-like concentrate containing Au chemical elements, and / or V, and / or Ni, and / or Al, and / or Ca, and / or S, and / or Si, and / or P, and / or Co. Technological production of a new product is as follows. Hydrocarbon oil is fed into a limited container, inside of which a combined electrostatic, magnetic and ultrasonic effect is produced. In this case, the electrostatic effect is produced by a voltage of at least 750 volts per centimeter, the magnetic pulse effect is produced by a voltage of 400 A / m with a frequency of 50 Hz and a pulse duration of 10 seconds, the ultrasonic effect is produced by a frequency of 18000 to 44000 Hz, due to which the total energy consumption for processing one tons of hydrocarbon oil do not exceed 1.5 kilowatt · hours. As a result of such exposure in hydrocarbon oil, the clusters and organic compounds present in it polarize, they are deposited on sorbing electrodes in the form of a gel-like concentrate containing chemical elements Au, and / or V, and / or Ni, and / or Al, and / or Ca, and / or S, and / or Si, and / or P, and / or Co. According to its physical and chemical characteristics, the concentrate corresponds to the following indicators:

- the structure has a heteroatomic cluster character, in the center of the core of which there is a metal core surrounded by heteroorganic ligands;

- the content of chemical elements is: Au, and / or V, and / or Ni, and / or Al, and / or Ca, and / or S, and / or Si, and / or P, and / or Co;

- the resulting yellow-brown concentrate has a viscosity of 8 MPa · s, a density of 1.15-1.28 g / cm ³ ;

- the duration of the combined exposure during processing takes about 30 s;

- the concentrate in tight conditions is stored for a long time at a temperature range from + 50 ° C to -50 ° C.

- industrially applicable.

Examples of specific applications of the claimed invention

Example 1

Hydrocarbon feed (0.8 cubic meters of Yamashneft Tatarstan trunk oil), passing through the reaction vessel at a speed of 100 l / h, was subjected to combined electrostatic field strength of at least 750 V / cm, magnetic pulse intensity of 400 A / m with pulse frequency 50 Hz and a duration of 10 s, ultrasonic - frequency from 18000 to 21000 Hz. The transit time of the combined impact oil did not exceed 30 s. Processing of raw materials carried out in 3 cycles. The cycles were completed as the electrodes were saturated with the concentrate; the saturation criterion was an increase in the current flowing through the electrodes 3-4 times with respect to the initial one. At the end of each cycle, the accumulated concentrate was washed with solvents with a low boiling point (benzene, hexane). The amount of solvent was chosen from the condition of the minimum necessary for flushing the concentrate from the electrodes. By weighing the spent solvent and the solution obtained after flushing, it was found that 22 g of concentrate was obtained as a result of exposure. Electron microscopic studies of concentrate samples taken directly from the electrodes before washing it off showed that it consists of various shapes, mostly close to spherical, and sizes from the first ten angstroms to the first thousand angstroms of cluster formations with a zonal-concentric structure, in which the metal core is surrounded by heteroorganic ligands in the form of a shell; there are both single and group formations with a single shell; the revealed formations are identical to the clusters identified in the black shales of the Bakyrchik gold ore deposits and others [“Clusters are the protoform of the presence of precious metals in ores and mineralized rocks”]. To determine the quality of the obtained concentrate as a raw material for subsequent processing in order to separate metals and other chemical elements, it was subjected to high-temperature evaporation for 2.5 hours to obtain a yellow powder, the mass of which was 0.67 g. A powder sample was subjected to chemical analysis by X-ray fluorescence method with using the Spectroscan Max-GV spectrometer. The percentage of extracted chemical elements was: Au - 90.2%, Al - 2.5%, Si - 0.4%, Ca - 0.2%, P - 0.1%.

Example 2

The volume and sequence of operations for processing oil of the same sample, as well as the duration and levels of exposure, with the exception of ultrasound, are identical to those shown in example 1. The frequency range of ultrasonic exposure was from 21000 to 33000 Hz. The resulting concentrate amount was 12 g, the content of chemical elements extracted from the concentrate in the dry residue (powder) was:

Au - 47.4%; V - 3.2%; Ni - 0.4%, Al - 2.2%, Ca - 1.0%, S - 3.1%, Si - 0.4%, P - 0.3%, Co - 0.1%.

Example 3

The volume and sequence of operations for processing oil of the same sample, as well as the duration and levels of exposure, with the exception of ultrasound, are identical to those shown in example 1. The frequency range of ultrasonic exposure was from 33,000 to 44,000 Hz. The resulting concentrate amount was 10 g, the content of the chemical elements recovered by evaporation from the concentrate in the dry residue (powder) was:

Au - 32.0%; V - 6.0%; Ni - 5.0%, Al - 2.0%, Ca - 1.0%, S - 0.6%, Si - 0.3%, P - 0.1%, Co - 0.1%.

Obtaining a product by the above method has a wide perspective of industrial application, namely, that it opens up the possibility of extracting a number of chemical elements from hydrocarbon materials at the stages of various technological redistribution from both crude oil and their oil products that have passed various stages of processing, fuel oil, and processing waste oil and gas hydrocarbon content, as well as in technological processes of processing industrial waste and household waste, in which there are fractions of hydrocarbon oil oils.

Claims (1)

The product of the processing of hydrocarbon oils deposited on sorbing electrodes during the combined exposure to an electrostatic field with a field strength of at least 750 V / cm, a magnetic field with a strength of 400 A / m with a pulse frequency of 50 Hz and a pulse duration of 10 s and an ultrasonic pulse with a frequency of 18000 to 44000 Hz, characterized in that it is a gel-like concentrate containing clusters of chemical elements Au, and / or V, and / or Ni, and / or Al, and / or Ca, and / or S, and / or Si, and / or P and / or Co.