Method of removal hydrocarbons, radioactive nuclides and heavy metals from soil and device to this end

FIELD: process engineering.

SUBSTANCE: invention relates to environmental protection, particularly, to reclamation of soils contaminated with hydrocarbons (oil products), radioactive nuclides and heavy metals with the help of electric osmosis. Proposed method consists in inducing nonuniform electric field between central and peripheral electrodes and applying magnetic field perpendicular to cleaning zone. Proposed device comprises central electrode. Said electrode is composed of a rod with cross-section of polygonal shape with concave sides. System of peripheral electrodes is composed by separate rods. The latter are interconnected by plates arranged in zigzag line so that its recess or ledge is aligned with those of central electrode surface. Besides, proposed device comprises two extra solenoids arranged one above the other. First solenoid is plunged in submerged zone soil while second electrode is fixed by crossbar at the post extending through central electrode axis.

EFFECT: higher quality of cleaning.

4 cl, 4 dwg

 

The invention relates to the protection of the environment, namely for the remediation of contaminated hydrocarbons (petroleum products) land disposal of soil from radionuclides and heavy metals by using the phenomenon of electroosmosis.

A known method of purification of capillary-porous media contaminated with oil and oil products, by introducing into the treatment zone of a solution of oil-oxidizing microorganisms, the introduction of a conductive liquid, passing electric current to create electroosmosis (EN 96115094 AND IPC VS 1/10, publ. 27.11.1998,).

There is a method of in-place restore contaminated with different composition and properties of (heterogeneous) soils, including the introduction of material for removing pollutants in the area of heterogeneous soil by passing a constant electric current within the contaminated heterogeneous soil between the electrodes, the application of a hydraulic gradient across the area of contamination (EN 2143954 C1 IPC VS 1/08, publ. 10.01.2000,).

The disadvantage of the above analogy is the complexity of their application and the insufficient degree of purification from soil pollution.

The closest analogue of the method adopted as a prototype, is a method of cleaning soil from hydrocarbons, including the establishment between the Central and peripheral electrodes in the treatment zone of the gradient of e is historical field, flow in the area of cleaning the cleaning liquid carrier, moving the carrier liquid under the influence of electroosmotic effect from the Central electrode to the peripheral displacement of the soil the carrier fluid hydrocarbons and removing them from the peripheral electrodes (RU 2132757 C1 IPC 6 VS 1/02, B01D 61/56 1/18, publ. 10.07.1999,).

The disadvantage of the prototype is insufficient purification of soil from hydrocarbons, as well as ineffective cleaning of radionuclides and heavy metals, as cleaning with the use of electroosmosis is conducted in a uniform electric field.

A device for application of the method of cleaning a capillary-porous medium, comprising a chamber for placing the cleaned environment with electrodes connected to a constant current source, the capacity of the treated liquid and the container for waste fluid (EN 2106432 C1 IPC 6 SS 1/22, publ. 10.03.1998,).

Famous line for cleaning contaminated soil and sludge containing hopper, a screw conveyor, the capacity of the overflow oil, vibrating screen, boot grill, washer (EN 2244686 C1 IPC C02F 1/40, publ. 20.01.2005,).

The disadvantage of the above devices analogues is also insufficient degree of purification from soil pollution.

Closest to the proposed device for implementing the method, adopted by the mu for the prototype, is a device that consists of a dip in the ground in a cleared area of the Central and peripheral electrodes, nozzles for water supply, the pump serving to remove from the peripheral electrodes of water with hydrocarbons, separator, used for separation of water and hydrocarbons capacity with a Venturi nozzle and heater, pump for water injection nozzle and the Venturi nozzle. The separator and the capacity of the piped water with non-return valve, the capacity is additionally connected to the nozzle high-pressure pipeline water supply (EN 2132757 C1 IPC 6 VS 1/02, B01D 61/56 1/18, publ. 10.07.1999,).

The disadvantage of the prototype is inefficient cleaning soil from hydrocarbons (oil) and insufficient cleaning of soils from heavy metals and radionuclides.

The objective of the proposed method and device for its implementation is to increase the efficiency of cleaning the soil from hydrocarbons (petroleum products), as well as from heavy metals and radionuclides.

The technical result is achieved due to the fact that the method of cleaning soil from hydrocarbons, radionuclides and heavy metals includes immersion in the soil on a cleared area of the Central and peripheral electrodes, creating between the Central and peripheral electrodes of the voltage gradient, the flow in the region adjacent to the Central electrode is, non-polluting liquid carrier, moving the carrier liquid under the influence of electroosmotic effect from the Central electrode to the peripheral displacement of the soil the carrier fluid hydrocarbons and removing them from the peripheral electrodes, but unlike the prototype to improve the level of cleaning soil from hydrocarbons, radionuclides and heavy metals between the Central and peripheral electrodes generate a nonuniform electric field and perpendicular to the surface of the site is additionally affected by the magnetic field. In addition, on the surface of the cleaned area of the soil is affected by the magnetic field of the opposite polarity.

The technical result of the use of the device for implementing the method is due to the fact that it contains immersed in the soil zone of clearing the Central electrode and the peripheral electrode, a nozzle for supplying a carrier fluid, a pump for forcing the liquid in the nozzle and remove the liquid containing impurities from the purification zone, but unlike the prototype to improve the degree of purification of the soil of the Central electrode is made in the form of a rod, the cross section of which is a polygon with concave sides, and the peripheral electrodes made of individual rods, interconnected plates, R is polozhennymi by a broken line so, opposite protrusions or depressions on the surface of the Central electrode is a depression or a protrusion broken line of the plate, the device further comprises two solenoid placed one above the other, the first of which is immersed in the soil zone cleaning, the second fixed with the help of the bar on the rack, passing through the axis of the Central electrode.

In addition, the surface of the Central electrode is made of a mesh with seals, and in the middle of each plate is rigidly fixed parabolic or needle spikes, and opposite the seal of the Central electrode are spikes plates.

In the invention a non-uniform electric field is created by passing a constant electric current between the projections or depressions (peak) of the Central electrode and the depressions or projections formed by the connecting plates of the peripheral electrodes, or by passing a constant electric current between the seals on the surface mesh of the Central electrode and the fixed parabolic or needle spiked plates.

It is known that the radionuclides and heavy metals sorbed by soils, formation of complexes on the surface of the clay particles, the value of the hydrogen ion exponent pH is reduced at the anode to pH=2, and the cathode increases up to pH=12 in the depending on the current strength (soil Pollution and latest technologies for their recovery. The Stupin DU St. Petersburg. - At the Deer. - 2009. - S). The transfer of substances in soils under the influence of an electric field occurs in the following areas: diffusion, electromigration, electroosmosis. Affected: mineral composition of the soil, the composition of the conducting medium with the carrier fluid, the conductivity of the carrier fluid, the electrochemical composition of the soil and its porosity. Electromigration is the main mechanism of transfer of substances in an electric field. Cations of radionuclides and heavy metals are attracted and are sorbed on the negative charges of the clay particles. Moreover, the mechanism sorbirovaniya includes education components on their surface (adsorption) or ion exchange. Aid in the Stripping (removal) of the cations of radionuclides and heavy metals from the soil renders the formation of hydrogen ions (H+at the anode during the electrolysis of water and transferred to the soil by diffusion, electromigration, electroosmosis. Heavy metals and radionuclides in the form complexes on the surface of clay particles, which is expressed by the reaction:

nH+-Meen+[pabouthinand]n-=Hnn+ [pabouthinand]n++Men+(1)

where Me+- cations of heavy metals or radionuclides, n is the number of the formed complexes.

Heavy metals and radionuclides have different absorption characteristics, which depend on the type of adsorbents, i.e. absorbents that absorb pollution of surface layer. The main difficulty in the removal of cations of heavy metals and radionuclides from the surface of the clay is their desorption from finely granular precipitation of clay, with a large cation capacity. Aid in the desorption of these cations have formed at the anode hydrogen ions (H+during the electrolysis of water (liquid carrier) and their movement in the soil under the effect of electroosmosis.

In the proposed method, the cations of radionuclides and heavy metals contaminated soil sorbed by the clay particles, are polarized in a non-uniform electric field under the influence of the moment of forces, seek to turn around the axis along the direction of the field action. A nonuniform electric field created by the electrodes, causes the migration of the cations of the clay sorbed radionuclide and heavy metals from the system peripheral electrodes to the Central electrode.

Under the action of the perpendicular directional contaminated site soil magnetic field created by the upper and lower solenoids, there is the Lorentz force. Under the action of this force, the cations of the clay with adsorbirovannymi radionuclides and heavy metals will begin to deviate from its straight-line path from the anode to the cathode and pull the carrier fluid, in which there is a circular flow around the Central electrode.

The circular motion of the carrier liquid around the Central electrode increases the cleaning path when the flow of the carrier liquid from the cathode to the anode, intensifies the process of cleaning the electromigration and electroosmosis cations of the clay with adsorbirovannymi them with radionuclides and heavy metals, which increases the efficiency of cleaning soil from pollution.

Figure 1 shows a diagram of an apparatus for implementing the method of cleaning soil from hydrocarbons, radionuclides, heavy metals;

figure 2 - scheme of the purification zone soil from the Central and peripheral electrodes are connected by plates by a broken line, top view;

figure 3 - zone cleaning solenoids;

figure 4 - scheme of the purification zone with the peripheral electrodes in the form of plates with parabolic or needle-like spines, top view.

In the diagram (figure 1) device is depicted: the purification zone 1, immersed in the soil the ones cleaning the Central electrode (anode) 2, the peripheral electrode (cathode) 3, a nozzle 4 for supplying a carrier fluid, a pump 5 for removal of the peripheral electrodes of the liquid containing petroleum products, radionuclides, heavy metals, pump 6 for the discharge of the carrier liquid in the nozzle 4, the protrusions and depressions of the surface of the Central electrode with a cross-section in the form of a polygon with concave sides 7 (2), the projections and depressions 8 formed by the connecting plates system peripheral electrodes arranged in a broken line, the upper solenoid 9 (3), the lower solenoid 10, the rack 11, the yoke 12, the perforated pipe 13(1), a pump 14 for pumping pollution with heavy metals and radionuclides, parabolic or needle spikes 15 (figure 4), net Central electrode 16.

The proposed method of cleaning soil is carried out by means of the device as follows.

The carrier fluid pump 6 is fed through the nozzle 4 in the region adjacent to the Central electrode 2 (Fig 1). Since the cross-section of the Central electrode has projections and depressions 7 and the connecting plate system peripheral electrodes are arranged in a broken line with depressions and protrusions 8, facing each other, enabling a constant current between them create an uneven electric field (figure 2). Uneven ELEH the electric field is also generated between the mesh seals Central electrode 16 and the studs 15, mounted on the plate system peripheral electrodes (figure 4).

The carrier fluid under the influence of electroosmotic effect flows from the Central electrode 2 to the peripheral electrodes 3 (Fig 1). The carrier fluid in the contamination of soil by oil emulsifies, which comes in the peripheral electrodes 3, whence it is removed by the pump 5.

On the negatively charged electrode (the cathode in the electrolysis of water, the formation of hydrogen ions (H+and the release of gaseous hydrogen. When cleaning soil from radionuclides and heavy metals hydrogen ions (H+razrezajut cations of radionuclides and heavy metals adsorbed on the clay particles. At the cathode are formed precipitation of radionuclides and heavy metals through the perforated pipe 13 are removed by the pump 14 (Fig 1).

Between the top 9 (3) a solenoid mounted on the rack 11 and the cross beam 12, and the bottom 10 of the solenoid creates a magnetic field. Under the action directed perpendicular magnetic field the Lorentz force occurs. Under the action of this force, the cations of the clay with sorbed radionuclides and heavy metals will begin to deviate from its straight-line path from the anode to the cathode and pull the carrier fluid, in which there is a circular flow (figure 3). Circular movement is giving liquid intensifies the electromigration and electroosmosis cations of the clay with sorbed radionuclides and heavy metals and ensures their removal from the soil, which increases the cleaning efficiency. If during a certain period of time to change the current direction on the opposite in the upper 9 and lower 10 solenoids, cyclically changing the direction of the magnetic field on the opposite, and after that there is a change of direction of the circular motion of the carrier liquid. This leads to a more intensive cleaning of contaminated site soil from radionuclides and heavy metals.

Example 1. Processing was exposed to the contaminated site soil size: 35 m, depth 11 m from the sandy heavy loam, containing a contaminant ions of heavy metals Cu, Zn, Pb, Cd.

As cathode electrodes are six graphite rods and one graphite rod anode diameter 220 mm, Rods wrapped in a shell, filled with iron filings and graphite in a ratio of 1/1. The device consists of six graphite rod cathode located on the perimeter of the purification zone at a distance of 1-1,2 m from each other and bonded plates with a width of 40-50 mm, and a graphite rod anode, located in the center of the zone of clearing the soil. The distance between the rods of the cathode and stud anode is of 2.2 m, the Voltage between the system of the terminals of the cathode and anode was maintained 100-150 V, the current density is 1 mA/cm2the stress gradient of 0.25 In/see handling Time: 20, 30, 50, 70, 225,450 hours. The magnetic field strength 250-370 E. processing of contaminated site soils speed of movement of the carrier liquid when electroosmosis of 0.3-0.45 cm/day.

After clearing soil and removal of specimens they cut into several pieces, and then processed by several extracts to remove forms of heavy metals in the movable and absorptive state. The concentration of heavy metal ions in aqueous solution was determined by absorption method using the apparatus "Zeiss" AAS-3. The concentration of heavy metal ions in the solid phase was determined by x-ray method. To separate the solid and liquid phases of the soil was used the method of successive ammonium acetate extracts. These forms along with a water-soluble form characterize the potential mobility of heavy metals. Changes in the concentration of heavy metal ions in samples of mineral loam before and after the impact of uneven electric field are presented in tables 1 and 2.

Table 1
The concentration of heavy metal ions in samples of mineral loam to the impact of uneven electric field
Heavy metal ions HumidityThe concentration of ions in the exchange complexThe concentration of ions in aqueous solution
%mEqmg/l
Cu+22938,162830
Zn+22973,576450
Pb+229139,9910370

/tr>
Table 2
The concentration of heavy metal ions in samples of mineral loam after exposure to nonuniform electric field
Heavy metal ionsWlasnosciAreaThe concentration of ions in the exchange complexThe concentration of ions in the pore solution of the soilThe concentration of ions in the pore solution of the soil
%mEqmg/lmEq
Cu+232The anode0,0180,040,009
Cu+228The cathode0,0680,960,267
Zn+232The anode0,0160,010,003
Zn+228The cathode0,1870,73rate 0.162
Pb+232The anode0,0120,070,017
Pb+228The cathode0,8473,890,944

The results in table 1 show that a significant portion of the ions Pb+2contained in absorbed form.

Under the influence of the nonuniform electric field concentration of adsorbed ions Cu+2changes from 38,16 mEq to 0,018 mg-EQ in the anode zone, Zn+2changes from 73,57 mEq up to 0.016 mEq in the anode zone, Pb+2changes from 139,99 mEq to 0.07 mEq in the anode zone (table 1 and 2). This is due to the influence of hydrogen ion exponent pH environment, because in the anode zone is formed acidic pH=3-5. In such conditions, the solubility of lead compounds with hydrated ions OH+Iand hydrocarbonate ions increases dramatically. Under the action of a nonuniform electric field and acidic part of the adsorbed ions is diverted from the solid phase of the soil in the liquid phase. The above studies have shown that the bulk of the heavy metals under the influence of the nonuniform electric field forms an anion pore solution soil complexes that are excreted by electroosmosis.

Cleanup of contaminated site soil radionuclides (cesium (CS-137), strontium (Sr 90), uranium, barium and phosphorus and organofluorine compounds) such soil purification from heavy metals (copper, lead, manganese, mercury, cobalt, cadmium, chromium, Nickel is). The degree of purification of the soil using a nonuniform electric field from heavy metals was 99%.

Example 2. In the study of clean soil loam from hydrocarbons using nonuniform electric field were accepted methodology, similar to that shown in example 1. The content of liquid hydrocarbons in soil was determined by thermal methods, as well as by chemical extraction with chloroform, oil and engine oil of the samples.

In the result, it was obtained the following results.

Oil and engine oil are removed from the cathode and anode zones.

Of the samples with an initial oil content of 5% is removed 50%of the initial oil content of 10% is removed 40%.

Similarly, of the samples with initial content engine oil 5% removed 60%, with the initial content engine oil 10% is removed 50%.

Cleanup of contaminated site soils from heavy metals (lead, manganese, mercury, cobalt, cadmium, chromium, Nickel) is similar to the cleanup of soil radionuclides (cesium (CS-137), strontium (Sr 90), uranium, barium and phosphorus and organofluorine compounds).

When processing contaminated site soils using the proposed device is substantially improved cleaning of soils from radionuclides (cesium (CS-137), strontium (Sr 90), uranium, barium, and fosfororganicheskim and organofluorine compounds).

In addition, when processing contaminated site soils using the proposed device, the content of heavy metals in the soil is reduced: for lead - up to 99%, manganese - 95%, mercury by up to 64%, cobalt up to 97%for cadmium - 96%, chromium up to 92%, iron up to 99%, Nickel up to 90%.

1. The method of cleaning soil from hydrocarbons, radionuclides and heavy metals, including immersion in the soil on a cleared area of the Central and peripheral electrodes, creating between the Central and peripheral electrodes of the voltage gradient, the flow in the region adjacent to the Central electrode, non-polluting liquid carrier, moving the carrier liquid under the influence of electroosmotic effect from the Central electrode to the peripheral displacement of the soil the carrier fluid hydrocarbons and removing them from the peripheral electrodes, characterized in that between the Central and peripheral electrodes generate a nonuniform electric field and perpendicular to the surface of the site is additionally affected by the magnetic field.

2. The method according to claim 1, characterized in that the surface of the cleaned area of the soil is affected by the magnetic field of the opposite polarity.

3. The device for implementing the method of cleaning soil from hydrocarbons, radionuclides and heavy metals according to claims 1, 2 containing p is loaded in the soil zone of clearing the Central electrode and the peripheral electrode, nozzle for supplying a carrier fluid, a pump for forcing the liquid in the nozzle and remove the liquid containing impurities from the purification zone, characterized in that the Central electrode is made in the form of a rod, the cross section of which is a polygon with concave sides, and the peripheral electrodes are made of individual rods, interconnected plates, placed in a broken line so that the protrusion or depression on the surface of the Central electrode is located depression or protrusion broken line of the plate, the device further comprises two solenoid placed one above the other, the first of which is immersed in the soil cleaning zones, the second fixed with the help of the bar on the rack, passing through the axis of the Central electrode.

4. The device according to claim 3, characterized in that the surface of the Central electrode is made of a mesh with seals, and in the middle of each plate is rigidly fixed parabolic or needle spikes, and opposite the seal of the Central electrode are spikes plates.



 

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6 ex

FIELD: disposal of solid waste.

SUBSTANCE: device comprises vehicle provided with the tank filled with coolant, collector that is used for supplying coolant and is connected with the tank though a T-shaped hose having detachable branch pipes connected with the appropriate cooling chambers. The cooling chamber is made of a box whose open section faces the surface to be frozen and receives the collector for spraying the coolant. The outer walls of the chamber are provided with face and side flanges that form a closed space for circulating coolant. The chamber walls are provided with means for interconnecting the chambers.

EFFECT: enhanced efficiency and reduced coolant consumption.

2 cl, 5 dwg

FIELD: restoration of soil contaminated with oil.

SUBSTANCE: at first stage, upper layer of oil sludge is collected and refuse is separated on vibrating screen; then oil sludge is subjected to centrifuging for separation of water, remaining refuse and mechanical admixtures. At second stage, middle layer of oil sludge is collected; this layer contains substratum water which is first cleaned from refuse by passing it through vibrating screen; then, water is subjected to centrifuging for separation of oil sludge, remaining refuse and mechanical admixtures from it; they are washed in surfactant solution. At third stage, bottom sediment is collected and is washed in surfactant solution for separation of oil sludge; then, refuse is separated from oil sludge in vibrating screen, after which oil sludge is subjected to centrifuging for separation of remaining water, refuse and mechanical admixtures.

EFFECT: increased degree of separation of oil sludge into cleaned oil sludge, water, refuse and mechanical admixtures.

3 dwg

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