RU2339678C2 - Method for modification of oil and oil products and system for modification of oil and oil products - Google Patents

Abstract

FIELD: oil and gas industry.

SUBSTANCE: oil and oil products are effected with modulated or not modulated structured or not structured magnetic fields, counter magnetic and radial electric fields , not modulated or modulated impulses with duration of the rising edge 2-20000 ns, duration of the trailing edge 2-25000 ns, impulses amplitude -1000 V - +1000 V, frequency 1-1×10⁶ Hz and/or closed magnetic fields of non-uniform structure along the pass of the medium and structured volume of medium pass cavities with magnetic induction of 1.5-12 T across the medium flow and/or crossing magnetic fields with magnetic induction of 0.1-1.2 T in stationary and/or flowing through condition of the medium. The system for modification of oil and oil products includes a device generating counter magnetic modulated or not modulated and radial electric modulated or not modulated fields along the medium flow, the device generating closed magnetic fields with periodical structure along the flow and structured volume of medium pass cavities; toroidal electromagnetic system generating crossing magnetic fields in the volume of medium present both in stationary and dynamic condition; a reservoir for modified medium; a pump for medium transportation; at that all devices are included into the system successively or successively-parallel.

EFFECT: upgraded quality and consumer characteristics of oil and oil products without employing additional chemical reagents.

5 cl, 4 tbl, 4 ex, 6 dwg

Description

The invention relates to the field of oil refining technology and can be used to modify the physico-chemical, as well as the operational characteristics of oils and petroleum products.

Known technologies (methods and devices) for processing products of oil and gas wells with a constant magnetic field, described in the guidance documents (Technology for restoration of well productivity based on the use of physical fields / RD 39-0147035 - 218. - M .: VNIIneft, 1987), based on placing several of the same type of permanent magnets placed by the same poles to each other along the central axis of the pipeline on a rod of non-magnetic material.

This technology allows you to increase the throughput of the pipeline by an average of 12%, however, when changing the characteristics of the medium, the effect of magnetic treatment is far from optimal due to the constant magnitude of the magnetic field.

A known method of processing a fluid flow in a pipeline, namely, oils and water-gas mixtures (RF patent 2168615, IPC ЕВВ 43/00, F15D 1/02, 2001), in which the medium passes through a pipe equipped with a turbulent nozzle type "confuser-diffuser "Made of a set of ring permanent magnets of different diameters and separated by inserts of non-magnetic material (aluminum). In this case, the turbulization of the flow provides a combination of pressure drops in the liquid ("baroprocessing") with an amplitude of up to 3 MPa and a magnetic field with an intensity of up to 40 thousand A / m. As a result, compared with the technology according to RD 39-0147035 - 218, the throughput of the pipeline is additionally increased by an average of 20%.

However, the method only changes the hydrodynamic characteristics of the medium flow in the pipeline and does not affect its quality characteristics.

A known method of processing liquid hydrocarbons and installation for its implementation, designed to process light petroleum products in order to improve their quality (RF patent 2179572, IPC C10G 32/02, 2000). The method consists in processing the liquid hydrocarbons brought to a vapor state by unipolar electromagnetic pulses with a power of more than 1 MW, a duration of less than 1 ns and a repetition rate of at least 1 kHz. The installation is a complex of devices consisting of a liquid hydrocarbon heater, a container in the form of coaxial cylinders for the electromagnetic treatment of hydrocarbon vapors, a generator of unipolar electromagnetic pulses, and a condensation system for the processing products. As a result, the tar and sulfur content in diesel fuel decreases by 16 and 2.5 times, respectively, and the sulfur content in gasoline decreases from 1.2 to 0.48%, while the octane number increases by 5 points, presumably due to an increase in the content of isooctane .

The method and device allows to achieve a known improvement in the quality of the target products, however, during the processing in the vapor phase, additional energy costs are required, and there is also a side process - the formation of resins, which are deposited on the surface of the gas path until it is completely clogged, since their continuous removal is not provided, which complicates the operation of the device for environmental reasons. The gasoline obtained as a result of processing does not meet the standards and cannot be used without further desulfurization, even as a technical liquid (gasoline-solvent).

A known method of purification of liquid hydrocarbons from sulfur and installation for its implementation (RF patent 2235114, IPC C10G 32/02, B03C 1/005, 2003), intended for the purification of oil from sulfur compounds by treating oil preheated to 50 ° C with unipolar electromagnetic pulses with a power of more than 1 MW, a duration of less than 1 ns and a repetition frequency of at least 1 kHz, followed by cooling. It is stated that, as a result of processing, “solvated electrons” are formed, initiating the radiolysis of hydrogen sulfide (with the formation of hydrogen and elemental sulfur), mercaptans and the gum formation of sulfur-containing compounds precipitated by sedimentation.

The achieved reduction in sulfur content in the claimed oil sample is “Bashkir oil” (Ural) from 3.82 to 2.78% wt. it does not allow to solve the problem of raising the quality of oil to the level of Brent, since this method and device provide a preferential break in the S-H (mercaptans) bond, rather than the C-S, which is part of most petroleum organo-sulfur compounds.

A known method of processing liquid hydrocarbons and a device for its implementation (RF patent 2098454, MKP C10G 32/02, B01J 19/12, 1997), intended for the production of liquid hydrocarbons of improved quality by exposure to them under static conditions of an electromagnetic field of intensity 0, 8-2 MA / m with a frequency of 700-800 Hz and a duration of 0.009-0.02 s. The device is a container with liquid hydrocarbons, made in the form of a solenoid, on the windings of which pulses from the voltage pulse generator are supplied. X-ray diffraction analysis methods established that the processing of model hydrocarbons (heptane and toluene) leads to a change in their spectral and physico-chemical characteristics (flash point and viscosity). It is shown that the consequences of processing motor gasolines have a pronounced relaxation character - 15 hours after processing the gasoline, X-ray analysis does not show changes in gasoline.

The main technical problem solved by the invention is to increase the technological parameters of the method of modification of physicochemical, as well as operational characteristics of oils and petroleum products.

The problem is achieved in that in the method of modifying oils and petroleum products by exposing them to modulated or non-modulated electric and / or structured magnetic fields, according to the proposed solution, the medium is affected by counter magnetic and radial electric fields with non-modulated and / or modulated pulses with a forward pulse duration edge from 2 ns to 20,000 ns, trailing edge duration from 2 ns to 25,000 ns, pulse amplitude from -1000 V to +1000 V, frequency from 1 to 1 × 10 ⁶ Hz, and / or closed magnetic fields of an inhomogeneous structure along the passage of the modified medium and a structured volume of the cavities of the passage of the medium with magnetic induction from 1.5 to 12 T across the duct of the modified medium and / or intersecting magnetic structured fields with an inductance of 0.1-1.2 T with magnetic field dispersion in various devices from 0.2 to 0.9 along and / or across the duct of the medium to be modified or in the stationary state of the medium to be modified.

Another objective of the invention is to develop a system for modifying oils and petroleum products to implement the method, and this system includes a device that generates counter magnetic modulated or non-modulated fields and radial electric modulated or non-modulated fields along the medium flow (VMRE) 1, the device creating closed magnetic fields with a periodic structure along the flow of the modified medium (ZMPS) 2, a toroidal electromagnetic system (TEMC) 3, the capacity for the modified medium 4, n pump for moving the modifiable medium 5, and all devices are included in the system sequentially (Fig. 1) or sequentially-in parallel and affect the modifiable medium pumped through them from the tank into it.

In another embodiment of a system for modifying media, the TEMS is connected to an additional pump 7 and immersed in another additional tank 6.

According to possible embodiments of the invention, the system may include various variants of series or parallel-parallel connection of system elements, which allows you to change the physical and chemical properties of the medium to be modified by implementing chemical reactions in it without the use of additional chemicals and / or catalysis.

In a system for modifying oil and oil products, counter magnetic fields and radial electric modulated or non-modulated fields along the flow are created in a pipe of non-magnetic material 13, on which coils or bifilar coil 14 are counter-wound, and an electrode 10 of non-magnetic material is located along the pipe axis. The coil (s) is supplied from a GMN-1 power source (Fig. 1), depending on the physicochemical properties of the medium being modified, or an unmodulated alternating voltage from 0.5 V to 50,000 V with a frequency from 0.5 Hz to 1,500,000 Hz, or additionally modulated by pulses with a leading edge duration from 2 ns to 20,000 ns, a falling edge duration from 10 ns to 25,000 ns, pulse amplitude from -1000 V to +1000 V, frequency from 1 to 1 × 10 ⁶ Hz, or on them from a GMN-1 power source, a pulse sequence of the above parameters or taking into account physico-chemical properties of the medium being modified pulse sequence, the phase of which is modulated by an alternating current with a frequency from 0.5 Hz to 1,500,000 Hz. Depending on the physicochemical properties of the medium being modified, an alternating voltage from 0.5 V to 50,000 V with a frequency from 0.5 Hz to 1,500,000 is supplied to the electrode located along the pipe axis from the GMN-2 power source of FIG. 1 Hz, or additionally modulated by pulses with a leading edge duration from 2 ns to 20,000 ns, a falling edge duration from 2 ns to 25,000 ns, pulse amplitude from -1000 V to +1000 V, frequency from 1 to 1 × 10 ⁶ Hz, or on them from a GMN-2 power source, a pulse sequence of the above parameters or with Chet physico-chemical properties of the medium being modified pulse sequence, the phase of which is modulated by an alternating current with a frequency from 0.5 Hz to 1,500,000 Hz.

Closed magnetic fields with a periodic structure along the medium flow are created in a device in which segments 17 (Fig. 5) are assembled from permanent magnets 16 (Fig. 4) in the housing along its longitudinal axis, the dimensions of which are width, height, length - 1 - 100 mm, oriented along the magnetic field in the same direction, with the given dimensions of the gap width between the magnets B1 (Fig. 4) and the width of the magnet B2 (Fig. 4) in a ratio determined by the physicochemical properties of the medium and changing within 1: 4-1: 150, with magnets located in the case so that in a section with a plane perpendicular to its axis, there are three or more petals, sets of “goose foot”, sets of parallelograms, sets of hexagons or a combination of the above sets that create a closed, constant but direction (left or right along the duct medium) a magnetic field with induction of 0.2-12 T (figure 5), and in the cavities between the segments of the sets of magnets along the axis of the housing are rods 18 (figure 5) of a non-magnetic material with a diameter of 0.12-6.5 mm, defined on the physicochemical properties of modifits sirovannoy environment.

Intersecting magnetic fields are created using a toroidal electromagnetic system 3, which includes from one to three toroidal electromagnets placed coaxially close to each other, through the inner cavity of which a pipe of non-magnetic material passes, which are connected in series to a stabilized direct current source with a voltage of 12-150 V providing current in electromagnets 10-280 A, designed to create a magnetic field with an induction of 0.1-1.2 T, and each of them contains from one to six sect ov winding 20 (Fig.6), each sector contains 5-60 turns connected in series, each of which is laid on the generatrix surface of the toroidal frame of non-magnetic material with radii R1 and R2 (Fig.6), the width of the sectors of the winding on the torus C1 ( 6) and the width of the zones free of winding, C2 (Fig.6).

It is advisable to place the sectors of the windings in the toroidal electromagnetic system on a toroidal frame, the radii of which R1 and R2 are related by the "golden ratio" (R1: R2 = 0.618: 0.382).

In addition, in TEMC, the width of the sectors of the C1 winding on the toroidal frame is related to the width of the zones free of the C2 winding by the "golden ratio" (C1: C2 = 0.382: 0.618).

Also in TEMS, in the case of an even number of sectors of electromagnet windings and using one or more of them in the device, then the first of them, in the direction of movement of the modified medium, half the winding sectors (even or odd numbers, or adjacent ones) are connected in series, in the second, in the direction of movement of the modified medium, the other half of the winding sectors is connected, respectively, and when using the third electromagnet, all sectors of its winding are connected in series.

Examples of specific performance.

Figure 1 presents a system for modifying oil and oil products, figure 2 - a system for modifying oil and oil products with immersed TEMS, figure 3 - a device for creating oncoming magnetic and radial electric fields with non-modulated and / or modulated pulses (VMRE ), in Fig. 4 - a line of permanent magnets, in Fig. 5 - variants of the arrangement of the rulers in the device case for creating closed magnetic fields, in Fig. 6 - a variant of the scheme of laying the sectors of the winding of the toroidal electromagnetic system and the cross section of the toroidal frame.

The system for modifying oil and petroleum products (Fig. 1) consists of a device for creating counter magnetic and radial electric fields with non-modulated and / or modulated pulses (VMEM), which is connected in series with a device for creating closed magnetic fields of an inhomogeneous structure (ZMPS), connected with a toroidal electromagnetic system 3. A power source GMN-1 and GMN-2 is connected to the VMER. The system for modification is equipped with a tank 4 and a pump 5. In FIG. 2, the TEMC is immersed in a tank 6 and connected to an additional pump 7.

The device VMRE (figure 3) is made in the form of a pipe 8 made of stainless steel with flanges with an inner diameter of 60 mm, a length of 900 mm, on which a bifilar coil 14 is wound with a copper bus bar with a cross section of 21 square meters. mm, containing 510 turns, inside the pipe 13, an electrode 10 of stainless steel with a diameter of 16 mm is installed along its axis. Using the electrode 10, in addition to counter magnetic fields, a modulated or non-modulated radial electric field is created in the cavity of the medium duct.

The ZMSS device is made in the form of a cylindrical body with flanges, in the cavity of which there are lines of 17 of five permanent magnets 16 with a width of 41.5 mm, a height of 41.5 mm, a gap width between them of 3 mm with a magnetic induction of 0.6 T, in each cavity between the rulers of the magnets along the axis of the housing are copper rods 18 in the amount of 8 pieces with a diameter of 1.2 mm and 6 pieces with a diameter of 0.8 mm (Fig. 5). Rulers 17 of magnets are located in the case so that in a section with a plane perpendicular to the axis of the case, they can have the following form (figure 5): three or more petals, sets of “goose foot”, sets of parallelograms, sets of hexagons or a combination of the above sets that create a closed magnetic field (left or right along the medium flow) of a constant magnetic field with induction from 1.5 to 12 T.

TEMC is made in the form of three toroidal electromagnets with the parameters of the toroidal cage R1 = 162 mm, R2 = 262 mm, each of which has a winding consisting of two sectors of 34 turns of a copper insulated bus bar with a cross section of 22 mm ² .

The TEMS device, unlike VMRE and ZMPS operating in the system in the mode of flow of the modified medium through them, can operate in the system both in the mode of flow of the modified medium through the pipe passing through the cavity of the toroidal frameworks of electromagnets and in the mode of immersion of electromagnets in the modified medium ( figure 2). In this case, the medium is circulated through a pipe passing through the cavity of the toroidal frames of the electromagnets.

Example 1

A-80 gasoline (from a city gas station) mixed with water in a ratio of 1: 1 was used as a modifiable medium. 50 l of A-80 gasoline (from a car column) and 50 l of water were taken, the water-gasoline emulsion was pumped for 30 minutes through a series-connected VMRE, ZMPS and TEMS pump 5 with a speed of 0.83 l / s from tank 4 into it (in front of the pump 5 there was a mixer of water and gasoline, into which water was supplied from the lower part of the tank 4, and gasoline from the upper one (not shown in the figures)).

Pulses with a leading edge duration of 15 μs, a leading edge duration of 10 μs, and an amplitude of 920 V were supplied to the bifilar coil 14 of the VMER through contacts 15 with a frequency of 50 Hz; a current providing a current of 100 A. In the central part of the toroidal frame, a fiberglass pipe with a diameter of 190 mm passes through which is connected at one end to the MPS device through transition joints ig. 1), and to others - to capacity 4.

After turning off the pump 5, the emulsion in the tank 4 was kept for 1 hour and a sample was taken from the upper part for analysis. The octane number was determined in an accredited Gosstandart laboratory. It was established that changes in the octane number are irreversible, that is, the relaxation effect is absent (the stability of the parameters remains for 60 days). Table 1 shows the changes in the octane number of marketable A-80 gasoline as a result of processing.

Table 1 Sample Name Research Octane Motor Octane Commodity gas A-80 74.1 76.9 Processed gasoline A-80 84.7 79.0

Example 2

A sample of native Talakan oil was processed.

The prepared oil-water emulsion (1: 1) at a temperature of 50 ° C was pumped through VMER, ZMPS at a speed of 5 m ³ / h at an overpressure of 0.05 MPa.

The parameters of the devices are similar to those in example 1.

After 5 cycles of pumping and sludge for 12 hours, a sample of oil was taken. Oil characteristics were determined in an accredited laboratory of Gosstandart. The results of the change in the characteristics of Talakan oil as a result of processing are presented in Table 2.

table 2 No. p.p. Name of indicator Source oil Refined oil one 2 3 four one Boiling point, ° С 26 26 2 Content,% wt. mercaptans 0.016 out chlorides (mg / dm ³ ) 80,4 2.09 sulfur 0.56 0.50 ash 0.006 0.003 water Ots. out 3 Pour point, ° C below -30 below -30 four Kinematic viscosity at 20 ° С, mm ² / s 15.45 14.20 5 Density at 20 ° С, kg / m ³ 842 840

As follows from the data presented, as a result of processing, the content of chloride salts is reduced by 40 times, mercaptans are completely removed, the ash content is reduced by 2 times. According to its characteristics, the prepared oil corresponds to the Brent brand.

Example 3

A sample of marketable South Yakut oil was processed in a system for the modification of oil and oil products, where the MPS is connected to the VMRE.

The parameters of the operation of devices: ZMSS analogously to example 1; The BMRE was powered by bifilar coils with a modulated alternating current voltage of 960 ± 40 V, a frequency of 50 Hz with additional pulse modulation with a leading edge duration of 300 ns, a trailing edge duration of 60 ns, a pulse amplitude of +500 V, and a frequency of 100 Hz.

Oil in an amount of 0.1 m ³ at a temperature of 50 ° C was pumped at a speed of 5 m ³ / h at an overpressure of 0.05 MPa by pump 5 from the initial tank to the sludge tank. Weathered for 12 hours. The fractional composition and properties of the fractions were determined in the accredited laboratory of Gosstandart. The change in the characteristics of oil fractions as a result of oil processing is given in table 3.

Table 3 Boiling range, ° С Value Refined oil Source oil one 2 3 four N.-k. - 150 (naphtha) Density at 20 ° С, kg / m ³ 680.3 670.7 Refractive Index, n _D ²⁰ 1,4030 1,4000 The content of mercaptan sulfur,% wt. out 0.010 Pour point, ° C -42 -47 Motor Octane 62 49 The beginning of the boil, ° C 26 26 Yield,% wt. 11.84 11.03 150-350 Density at 20 ° С, kg / m ³ 774.0 776.9 Refractive Index, n _D ²⁰ 1.4470 1.4510 The content of mercaptan sulfur,% wt. out 0.015 Temperature, ° С turbidity -26.7 -16.3 solidification -30.0 -26.0 Kinematic viscosity, mm ² / s at 20 ° С 2.81 3.47 Yield,% wt. 36.14 33.90 Over 350 Density at 20 ° С, kg / m ³ 970 973 The content of mercaptan sulfur,% wt. out 0.018 Pour point, ° C twenty twenty Kinematic viscosity, mm ² / s at 80 ° С 49.68 68.39 Ash content,% wt. 0,021 0,053 Yield,% wt. 52.02 55.07

As follows from the data presented, as a result of processing, the yield of light fractions increases, the mercaptans are completely removed, the cloud point and solidification temperature of the fraction 150-350 ° C decreases by 10.4 and 4 ° C, respectively. The octane number of naphtha increases by 13 points.

Example 4

A sample of marketable West Siberian oil, mixed with water 1: 1, was processed at the Bernsky Refinery’s oil treatment unit (capacity 50-60 tons / day) in a media modification system where the ZMPS is connected to VMRE and 4 with a volume of 1.2 m ³ . Water-oil emulsion at a temperature of 50 ° C was pumped at a speed of 16 m ³ / h at an overpressure of 0.05 MPa by pump 5 from tank 4 into it. Periodically, after 15-20 minutes with pump 7, 0.7-0.8 m ^{3 of} emulsion was pumped through the internal cavity of the TEMS, which is immersed into it, into the technological tank of a volume of 50 m ³ ;

The parameters of the devices: ZPSS parameters are similar to example 1; BMRE power of the bifilar coils was carried out by modulated alternating current with a voltage of 1200 ± 60 V, a frequency of 50 Hz with additional pulse modulation with a leading edge of 250 ns, a leading edge of 50 ns, a pulse amplitude of +500 V, a frequency of 100 Hz; TEMC is implemented in the form of three toroidal electromagnets placed coaxially close to each other, through the inner cavity of which a fiberglass pipe passes, which are connected in series to a source of stabilized direct current voltage of 120 V, providing a current in electromagnets of 100 A, with an induction of 0.1-0 , 2 T, and each of them contains two sectors of the winding, and each sector contains 34 turns connected in series, each of which is laid on the generatrix of the surface of the toroidal frame of textolite with p radius R1 = 162 mm and R2 = 262 mm.

1 hour after the start of the process, oil samples were taken from the upper zone of the process vessel for analysis. The fractional composition and properties of the fractions were determined in the accredited laboratory of Gosstandart. Changes in the characteristics of oil fractions as a result of oil processing are given in table 4.

Table 4 Options Before processing After processing Water,% (wt.) 0.51 no The amount of water soluble salts, mg / l 10.1 no Sulfur,% (wt.) 1,538 0.420 The yield of light fraction,% (wt.) 59 67

As can be seen from Table 4, the applied system for the modification of oil and oil products allowed us to transfer oil from the Ural class to the Brent class, while the demulsification time is reduced by an order of magnitude.

Claims (5)

1. A method of modifying oil and oil products, including exposure to oil and oil products, characterized in that they affect oil and oil products with modulated or non-modulated electric and / or structured magnetic fields, counter magnetic and radial electric fields, not modulated or modulated pulses with a duration of leading edge 2-20000 ns, trailing edge duration 2-25000 ns, pulse amplitude -1000 V - +1000 V, frequency 1-1.0 · 10 ⁶ Hz, and / or closed magnetic fields non-uniform structure along the passage of the medium and the structured volume of the cavities of the passage of the medium with magnetic induction of 1.5-12 T across the medium flow and / or intersecting magnetic fields with magnetic induction of 0.1-1.2 T, in a stationary and / or flowing state of the medium. 2. A system for modifying oil and oil products, including a device that generates counter magnetic modulated or non-modulated fields and radial electric modulated or non-modulated fields along the medium flow; a device that creates closed magnetic fields with a periodic structure along the flow of the medium and a structured volume of the cavities of the passage of the medium; a toroidal electromagnetic system that creates intersecting magnetic fields in the volume of the medium, which is both in a stationary and dynamic state; capacity for the modified environment; pump for moving the medium, and all devices are included in the system in series or in series-parallel. 3. The system for modifying oil and oil products according to claim 2, characterized in that the device that creates counter magnetic modulated or non-modulated fields and radial electric modulated or non-modulated fields along the medium flow and a device that creates closed magnetic fields with a periodic structure along the stream medium and structured volume of the cavities of the passage of the medium are included in series. 4. The system for modifying oil and oil products according to claim 2, characterized in that it includes a device that generates counter magnetic modulated or non-modulated fields and radial electric modulated or non-modulated fields along the medium flow. 5. The system for modifying media according to claim 2, characterized in that the device that creates counter magnetic modulated or non-modulated fields and radial electric modulated or non-modulated fields along the medium flow, and a device that creates closed magnetic fields with a periodic structure along the medium stream and a structured volume of the cavities of the passage of the medium are connected in series, and the toroidal electromagnetic system is immersed in another container for the medium to be modified.

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