JP6451973B1 - Soil purification system - Google Patents

Abstract

Provided is a simple and low-cost soil purification system capable of wet classification of soil into gravel, sand, and fine particles while removing harmful metals and the like adsorbed on the fine particles.
A soil purification system (S) is classified into gravel, sand and fine particles while washing soil with washing water by a mill breaker (3), a trommel (4), a hydrocyclone (5) and a thickener (8). The iron content removing device 12 adsorbs and removes iron-based fine particles from the sludge discharged from the thickener 8 by magnetic force, and reduces the content of harmful metals and the like in the sludge. The fine particle cleaning device 13 cleans sludge discharged from the iron content removing device 12 with a chelate cleaning liquid to remove harmful metals and the like from the fine particle content. The filtering device 14 filters the sludge discharged from the iron content removing device 12. The reverse osmosis membrane separation device 16 separates the filtrate of the filtration device 14 into permeated water and concentrated water. The chelating agent regenerator 17 removes harmful metals and the like from the concentrated water and supplies the fine particle cleaning device 13 as a chelate cleaning solution.
[Selection] Figure 1

Description

  The present invention relates to a soil purification system for purifying soil containing gravel, sand and fine particles and contaminated with harmful metals and / or compounds thereof.

  In recent years, sites of production facilities that use harmful metals such as chromium, lead, cadmium, selenium, mercury and / or their compounds (hereinafter collectively referred to as “hazardous metals”) as raw materials or materials, or the vicinity thereof In Japan, or soil pollution due to illegal dumping of industrial waste containing hazardous metals. Then, soil contaminated with toxic metals (hereinafter referred to as “toxic metal contaminated soil”) is present at the existing location (hereinafter referred to as “original location”), for example, insolubilization, containment or electrical restoration of toxic metals, etc. It is quite difficult to purify more effectively. For this reason, the toxic metal-contaminated soil is generally removed from the original position by excavation and purified at an external soil purification facility.

  As a method for purifying toxic metal-contaminated soil at such off-site soil purification facilities, conventionally, a cleaning method that removes toxic metal by washing toxic metal-contaminated soil with washing water or the like has been widely used. . When the toxic metal-contaminated soil is washed with washing water, most of the toxic metals once released from the soil into the water are adsorbed or adhered to the surface of the fine particles having a relatively small particle size. It is known that they are aggregated on the surface of the film (for example, see Non-Patent Document 1).

  Therefore, after washing the toxic metal contaminated soil with washing water and classifying it into gravel, sand and fine particles, by applying chemical treatment to remove toxic metals etc. on the fine particles, Gravel, sand, and fine particles that contain almost no harmful metals can be obtained. Thus, the applicant of the present application has already classified the gravel, the sand, and the fine particles while washing the toxic metal-contaminated soil with the washing water, and the chelate cleaning liquid containing the chelating agent and the water for the fine particles. Have proposed various soil remediation facilities (contaminated soil remediation devices) that remove harmful metals and the like from fine particles by performing a washing process (see, for example, Patent Documents 1 and 2).

Japanese Patent No. 5723054 Japanese Patent No. 5723055 Japanese Patent No. 4755159 Japanese Patent No. 6007144

Issued by the Ministry of the Environment, Water and Air Environment Bureau, Soil Environment Division, “Technical Considerations for Permitted Examination of Contaminated Soil Treatment Industry”, page 21, August 2013 Tetsuo Katsura “Wastewater Treatment by Iron Powder Method” flotation, vol. 23 (1976), no. 3, P190-198 (https://www.jstage.jst.go.jp/article/rpsj1954/23/3/23_3 — 190 / _pdf)

  By the way, in this type of soil purification facility by a contaminated soil treatment company, a large amount of contaminated soil is usually purified (for example, 2000 tons per day), so that a large amount of fine particles are generated (for example, on a dry basis). 500 to 600 tons per day). Therefore, when washing such a large amount of fine particles with, for example, a chelate washing solution, a large amount of a relatively expensive chelating agent is required, so that there is a problem that the cost for treating contaminated soil increases. The required or used amount of the chelating agent in such a soil purification facility increases as the content of harmful metals and the like in the fine particles increases. The same problem occurs when the fine particles are washed with a chemical other than the chelating agent to remove harmful metals and the like.

  The present invention was made in order to solve the above-mentioned conventional problems, and washes gravel and sand while washing soil containing gravel, sand and fine particles and contaminated with harmful metals with washing water. To provide a simple and low treatment cost soil purification system that can be classified into fine particles and that can remove harmful metals adsorbed or adhered to the separated fine particles. It is a problem to be solved.

  In order to solve the above-mentioned problems, the present invention is based on the present invention for purifying soil containing gravels, sand and fine particles and purifying soil contaminated with harmful metals or the like (toxic metals and / or compounds thereof) or these ions. The system includes a mixer, a wet crusher, a trommel, a hydrocyclone, a thickener, an iron content removal device, a fine particle washing device, a filtration device, a reverse osmosis membrane separation device, and a chelating agent regeneration device. And a permeate transfer means.

  Here, the mixer mixes the soil introduced into the soil purification system and the washing water. The wet crusher crushes gravel and / or sand in a mixture containing soil discharged from the mixer and washing water, thereby causing iron and / or scattered unevenly in the gravel and / or sand. Or iron oxides (hereinafter collectively referred to as “iron etc.”) produce iron-based fines exposed on the surface, and iron exposed on the surface of iron-based fines, etc. Is adsorbed (attached). Trommel separates gravel from a mixture of gravel, sand, fines and wash water discharged from a wet crusher. The hydrocyclone separates sand from a mixture containing sand, fines and wash water discharged from the trommel. The thickener separates a mixture containing fine particles discharged from the hydrocyclone and washing water into supernatant water and sludge containing fine particles and washing water by sedimentation separation.

  The iron content removing device reduces the content of harmful metals and the like in the sludge by adsorbing and removing the iron-based fine particles from the sludge discharged from the thickener by magnetic force. The iron-based fine particles contain iron or the like to such an extent that they can be adsorbed by magnetic force. The fine particle cleaning device mixes the sludge discharged from the iron content removal device with a chelate cleaning solution containing a chelating agent and water to generate a fine particle slurry, and the fine particle slurry is set in a preset residence time. In order to ensure that the toxic metal or the like adhering (adsorbing) to the fine particles is captured by the chelating agent. The filtration device filters the fine particle slurry discharged from the fine particle washing device to produce a filtrate and a filter cake.

  The reverse osmosis membrane separation device separates the filtrate discharged from the filtration device into concentrated water in which the chelating agent is concentrated and permeated water not containing the chelating agent by the reverse osmosis membrane. The chelating agent regeneration device accepts the concentrated water discharged from the reverse osmosis membrane separation device, and adsorbs harmful metals or the like ions in the concentrated water when it has a higher complexing power than the chelating agent and comes into contact with the concentrated water. Using a solid phase adsorbent, harmful metals and the like are removed from the chelating agent in the concentrated water, and the concentrated solution is supplied as a chelate cleaning solution to the fine particle cleaning device. The permeated water transfer means transfers (returns) the permeated water discharged from the reverse osmosis membrane separation device to the thickener.

  The iron removing device includes an iron-based fine particle adsorbing device, a screen device, a centrifuge, and a magnetic ball returning device. Here, in the iron-based fine particle adsorption device, a plurality of permanent magnets are mounted in the hollow portion of the hollow sphere so that the same magnetic pole (N pole or S pole) faces outward in the radial direction of the sphere. Accepts multiple (multiple) magnetic spheres and sludge discharged from thickener, and moves the fluid (mixture) in which magnetic spheres and sludge are mixed downward by a zigzag path by gravity. The iron-based fine particles are adsorbed on the magnetic sphere by magnetic force. The screen device receives the fluid (mixture) discharged from the iron-based fine particle adsorption device and separates (screens) it into magnetic spheres and sludge. The centrifugal separator intermittently receives the magnetic spheres adsorbing the iron-based fine particles discharged from the screen device in a batch system, and the iron-based fine particles are extracted from the magnetic spheres by centrifugal force. Let go. The magnetic sphere return device returns the magnetic sphere discharged from the centrifuge and hardly adsorbing the iron-based fine particles to the iron-based fine particle adsorption device.

In the soil purification system according to the present invention, the value obtained by dividing the mass of the magnetic sphere by the volume of the hollow sphere (that is, the apparent density or bulk density of the magnetic sphere) is in the range of 1.1 to 1.3 g / cm ³ . Is preferred.

  In the soil purification system according to the present invention, the magnetic ball return device preferably includes an upright belt conveyor, a magnetic ball conveying means, and a magnetic ball supply means. Here, the upright belt conveyor includes a driving roller disposed at a position lower than the lower end portion of the centrifuge, and a driven roller disposed at a position higher than the upper end portion of the iron-based fine particle adsorption device above the driving roller. And an endless metal belt made of a ferromagnetic metal wound around a driving roller and a driven roller, and attached to the outer surface of the endless metal belt and adsorbed to the endless metal belt when traveling above the endless metal belt. It is preferable to have a magnetic ball locking member that locks the descending of the magnetic ball. In this case, the magnetic sphere conveying means conveys the magnetic sphere discharged from the centrifugal separator to the lower end portion of the upright belt conveyor or in the vicinity thereof and causes the endless metal belt to adsorb it by magnetic force. The magnetic ball supply means separates the magnetic ball from the endless metal belt at the upper end of the upright belt conveyor or in the vicinity thereof and supplies (moves) the magnetic ball to the iron-based fine particle adsorption device.

  In general, in the process of cleaning and classification of contaminated soil using washing water, toxic metals and the like are hardly adsorbed (attached) to gravel and sand, but are aggregated and adsorbed (attached) to fine particles (for example, non-adhesive) Patent Document 1). The fine particles are divided into a relatively small amount of iron-based fine particles containing iron or the like that can be adsorbed by a magnetic force, and a relatively large amount of fine particles that cannot be adsorbed by a magnetic force other than the iron-based fine particles (hereinafter “ Non-ferrous fine particles ”). On the other hand, since iron and the like have the property of adsorbing harmful metals and the like (see, for example, Non-Patent Document 2), the amount of adsorption of harmful metals and the like of iron-based fine particles including iron exposed on the surface (attachment amount) ) Is considerably larger than the adsorption amount (adhesion amount) of toxic metals and the like for non-ferrous fine particles.

  And according to the soil purification system which concerns on this invention, although a gravel and / or sand are crushed with a wet crusher and a fine particle part is produced | generated, among these fine particle parts, it is unevenly distributed in a gravel or sand. The fine particles containing a large amount of fine particles such as iron that are scattered are iron-based fine particles, and the iron that is exposed on the surface of these iron-based fine particles is transferred from the wet crusher to the iron removal device. Adsorbs a relatively large amount of toxic metals in a series of distribution processes. Therefore, iron-based fine particles that existed before crushing and iron-based fine particles generated by crushing are introduced into the iron removal device, and both of these iron-based fine particles are considerably large (non-ferrous). (Compared with fine particles of the system)) Adsorbs harmful metals.

  Thus, in the iron content removal device, when the fluid (mixture) in which the magnetic spheres and sludge are mixed moves downward in the iron-based fine particle content adsorption device along a zigzag path, the amount of adsorption of harmful metals and the like is large The iron-based fine particles in the sludge are adsorbed magnetically by the magnetic spheres and removed from the sludge, so that the content rate or the retention rate of harmful metals and the like in the sludge can be greatly reduced. Therefore, the load of harmful metals, etc. on the fine particle washing device that purifies sludge discharged from the iron removal device with the chelate washing liquid, and the load of harmful metals, etc. on the chelating agent regenerator that removes the harmful metals, etc. from the chelating agent. It is possible to reduce the necessary amount or use amount of the chelating agent and the solid-phase adsorbent, and the soil treatment cost can be reduced. The wet crusher and the iron content removing device have a mechanical structure that performs physical treatment and do not use any special chemicals, so that the operation cost is very low.

  In each magnetic sphere, a plurality of permanent magnets are mounted in the hollow part of the hollow sphere so that the same magnetic pole (for example, N pole) is directed outward in the spherical body radial direction. Repel each other. Therefore, in the iron-based fine particle adsorption device, on the screen device, or in other magnetic sphere movement paths, the magnetic spheres are not attracted to each other to form a lump (grape bunch). Can move smoothly apart from each other while repelling each other.

It is a block diagram which shows schematic structure of the soil purification system which concerns on this invention. It is a typical elevational view of the iron content removal apparatus which comprises a soil purification system. It is a typical sectional view of a magnetic sphere. It is a typical partial cross section elevation of a centrifuge. (A) is a schematic side view of a part of a magnetic ball conveyor and an upright belt conveyor, (b) is a schematic side view of a part of an upright belt conveyor, and (c) is upright. It is a typical front view of a part of type | mold belt conveyor. (A) is a schematic plan view of the fine particle cleaning device, (b) is a cross-sectional view taken along line AA of the fine particle cleaning device shown in (a), and (c) is a fine particle cleaning device. FIG. 3 is an elevational cross-sectional view of one slurry passage of the apparatus. It is a typical elevation view of a chelating agent reproduction device.

  As shown in FIG. 1, in the soil purification system S according to the embodiment of the present invention, soil collected by excavation of ground contaminated with harmful metals or the like (harmful metals and / or their compounds) or these ions. (Contaminated soil) is received by the input hopper 1. Examples of harmful metals include chromium, lead, cadmium, selenium, mercury, and metal arsenic. Then, the soil in the charging hopper 1 is continuously or intermittently charged into the mixer 2 and mixed with the washing water continuously supplied to the mixer 2. Here, the soil includes gravel (for example, particle size 2 to 75 mm), sand (for example, particle size 0.075 to 2 mm), and fine particles (for example, particle size 0.075 mm or less). Some stones (for example, a particle size of 75 mm or more) are also included.

  A mixture (hereinafter referred to as “soil / water mixture”) containing soil and washing water generated by the mixer 2 is transferred to a mill breaker 3 which is a wet crusher. As the mill breaker 3, for example, a rod mill can be used. Although not shown in detail, the rod mill is a crushing device in which a plurality of rods (for example, ten 75 mmφ × 2 m steel rods) are arranged in a drum, and the rods rotate parallel to each other by the rotation of the drum. Moves and makes line contact, and can crush gravel and sand (and stone in some cases) by the impact force, shear force, friction force, etc. to generate small-diameter soil particles such as fine particles. . As the mill breaker 3, a ball mill or the like can be used in addition to the rod mill. The gravel and sand are partly fine and not all fine.

  Thus, the mill breaker 3 crushes the gravel and sand (and possibly stones) in the soil / water mixture discharged from the mixer 2 to generate small-sized soil particles such as fine particles. As a result, harmful metals adsorbed (attached) or contained in gravel and sand are released into the water. At this time, basically (aside from adsorption by iron, etc., which will be described later), harmful metals etc. released into the water are hardly adsorbed to gravel and sand, or do not adhere to them and are aggregated and adsorbed into fine particles. Or adhere (see, for example, Non-Patent Document 1).

  Furthermore, a large number of fine iron-based fine particles are produced in which minute masses of iron or the like (iron and / or iron oxide) that are unevenly distributed or scattered in the gravel and sand are exposed on the surface. On the other hand, iron and the like generally have a property of adsorbing harmful metals and the like. For this reason, noxious metals, etc. present in the washing water or a part of these ions are adsorbed or adhered to the exposed surface of the iron-based fine particles such as iron. As a result, the amount of adsorption (adhesion amount) of harmful metals and the like for iron-based fine particles is considerably larger than the amount of adsorption (adhesion amount) of harmful metals and the like for non-ferrous fine particles. In other words, the fine particles discharged from the mill breaker 3 are iron-based fine particles with a large amount of adsorption (adhesion amount) of toxic metals and non-ferrous fine particles with a small amount of adsorption (adhesion amount) of toxic metals. It consists of. Needless to say, iron-based fine particles existing before crushing also adsorb considerably more harmful metals and the like than non-ferrous fine particles.

  As described later, the iron-based fine particles adsorbing harmful metals and the like are removed by the iron content removing device 12. On the other hand, it is generally known that iron or the like (iron and / or iron oxide) has a property of adsorbing harmful metals and the like, and using this property, iron powder or iron oxide is added to sludge containing harmful metals and the like. Various “iron powder methods” have been proposed in which harmful metals and the like are removed from sludge by adding powder (see, for example, Patent Documents 3 to 4 and Non-Patent Document 2). However, as in the present invention, by crushing gravel and sand, fine iron-based fine particles with exposed fine lumps of iron (not yet adsorbing harmful metals, etc.) are generated on the surface. A method for treating harmful metals, etc., in which harmful metals, etc. are adsorbed on the exposed fine particles (iron-based fine particles) of iron, etc. has not yet been proposed by anyone other than the applicant or the inventor of the present application. .

  The soil / water mixture discharged from the mill breaker 3 is introduced into the trommel 4. Although not shown in detail, the trommel 4 is a sieving device having a receiving tank capable of storing water, and a substantially cylindrical drum screen arranged to be inclined with respect to a horizontal plane. Can be rotated around its central axis (cylindrical central axis) by a motor. Further, the washing water can be sprayed into the drum screen.

  When the soil / water mixture flows through the rotating drum screen of the trommel 4, the soil particles finer than the mesh of the drum screen pass through the mesh of the drum screen together with the washing water, and go out of the drum screen and into the receiving tank. to go into. On the other hand, the soil particles coarser than the mesh of the drum screen cannot pass through the mesh of the drum screen, and are discharged out of the drum screen via the lower open end of the drum screen.

  In the trommel 4, the classification diameter (opening) of the mesh of the drum screen is set so that soil particles having a particle diameter of less than 2 mm, that is, sand and fine particles, pass through the mesh of the drum screen. Therefore, in this trommel 4, gravel (soil in some cases) which is a soil particle having a particle size of 2 mm or more is separated from the soil / water mixture. As described above, harmful metals etc. that have separated into the water are hardly adsorbed or adhered to the gravel and sand, so the gravel separated by Trommel 4 is almost clean, for example, as aggregate for concrete Can be used. The mesh size (opening) of the drum screen of Trommel 4 is not limited to that described above, and can be arbitrarily set according to the particle size of the soil particles to be obtained. It is.

  A soil / water mixture containing soil particles having a particle size of less than 2 mm, that is, sand and fine particles, and washing water, contained in a receiving tank of the trommel 4 is introduced into a cyclone 5 (liquid cyclone). Although not shown in detail, the cyclone 5 pumps the soil / water mixture in a substantially conical cylinder that narrows downward to generate a swirling flow, and utilizes the centrifugal force generated thereby, A mixture of soil and water, a mixture of fine particles having a relatively small particle size (for example, a particle size of less than 0.075 mm) and water, sand having a relatively large particle size (for example, a particle size of 0.075 mm or more) and water Separated into a mixture of

  A mixture of fine particles and water (hereinafter referred to as “fine particle-containing water”) is discharged from the upper end of the cyclone 5, and a mixture of sand and water having a relatively large particle size is discharged from the lower end of the cyclone 5. Is done. Here, since the sand discharged from the lower end of the cyclone 5 does not contain any harmful metals or the like as described above, it is drained or dried and used as reclaimed sand. On the other hand, the water containing fine particles is transferred to the PH adjustment tank 6.

  In the pH adjustment tank 6, the pH (hydrogen index) of the water containing fine particles is made almost neutral using an acid solution (for example, sulfuric acid and hydrochloric acid) and an alkali solution (for example, an aqueous sodium hydroxide solution). Adjusted. Although not shown, in the pH adjustment tank 6, the pH of the water containing fine particles is automatically adjusted by a pH automatic control device equipped with a pH meter or the like.

  The fine particle-containing water whose pH has been adjusted in the pH adjusting tank 6 is introduced into the coagulating tank 7. In the agglomeration tank 7, a polyaluminum chloride (PAC) aqueous solution, a polymer flocculant, and a pH adjuster (an acidic liquid or an alkaline liquid) are added to the water containing fine particles. As a result, a large number of flocs in which the water-insoluble metal hydroxide and fine particles are mixed are generated in the aggregation tank 7.

  The water containing fine particles (including floc) in the coagulation tank 7 is introduced into a thickener 8 (gravity settling tank). Although the thickener 8 is not shown in detail, the water-insoluble floc or fine particle is settled by gravity in a state where the fine particle-containing water is almost stationary, and a sludge layer (for example, solid And 5% to 10%), and supernatant water (wash water) which is located in the upper part and hardly contains flocs or fine particles. When the floating oil is floating on the surface of the supernatant water, the floating oil is removed by overflowing a small amount of the supernatant water from the upper part of the thickener 8.

  The supernatant water in the thickener 8 is introduced into the washing water tank 10 and temporarily stored. When the washing water tank 10 is full, the auxiliary water tank 11 is used. The washing water stored in the washing water layer 10 or the auxiliary water tank 11 is supplied to the mixer 2 and the trommel 4 as circulating water. In addition, when the wash water stored in the wash water tank 10 decreases due to evaporation or the like, tap water is appropriately replenished. On the other hand, the sludge that has settled or stayed in the lower part of the thickener 8 is transferred to the intermediate tank 9 and temporarily stored.

  The sludge in the intermediate tank 9 is basically transferred to the iron removing device 12 continuously. The iron content removing device 12 reduces the content of harmful metals and the like in the sludge by adsorbing and removing the iron-based fine particles from the sludge with a magnetic force. The iron-based fine particles discharged from the iron removing device 12 are supplied to, for example, a steel manufacturer and used as a raw material for iron making. The sludge discharged from the iron removing device 12 is processed by the fine particle washing device 13, the filtering device 14, the clarification filter 15, the reverse osmosis membrane separation device 16, and the chelating agent regenerating device 17, and is used as a harmful metal. A substantially clean fine-grained portion containing almost no etc. and a chelate washing solution are produced. Note that specific configurations and functions of these processing devices 13 to 17 will be described in detail later.

Hereinafter, a specific configuration and function of the iron content removing device 12 will be described with reference to FIGS.
As shown in FIG. 2, the iron content removing device 12 has, as its main component, an iron-based fine particle adsorption that contacts a plurality (large number) of magnetic balls 20 and sludge discharged from the thickener 8 (see FIG. 1). The apparatus 18, a screen device 19 that separates the mixture discharged from the iron-based fine particle adsorption device 18 into magnetic spheres 20 and sludge, and iron-based fine particles are removed from the magnetic spheres 20 received from the screen device 19. A centrifuge 22 and a magnetic sphere return device 23 that returns the magnetic spheres 20 discharged from the centrifuge 22 to the iron-based fine particle adsorption device 18 are provided. Furthermore, the iron content removing device 12 stores first to third magnetic spheres that temporarily store the magnetic spheres 20 supplied to the iron-based fine particle adsorbing device 18, the centrifuge 22, or the magnetic sphere return device 23, respectively. The containers 24-26 and the sludge storage tank 27 which stores the sludge which flowed down from the screen apparatus 19 temporarily are provided.

  The iron-based fine particle adsorption device 18 receives a plurality (large number) of magnetic spheres 20 and sludge discharged from the thickener 8 (see FIG. 1), and a fluid (mixture) in which the magnetic spheres 20 and sludge are mixed. ) Is moved downward along a zigzag path by gravity, and the iron-based fine particles in the sludge are adsorbed to the magnetic sphere 20 by magnetic force during the movement. Specifically, the iron-based fine particle adsorption device 18 has a hollow cylindrical (cylindrical) or hollow quadrangular prism (duct) main body 21 (housing). An inclined plate 21a is attached. In these inclined plates 21a, the odd-numbered inclined plates 21a and the even-numbered inclined plates 21a are located on the opposite sides (opposite) from the upper side to the lower side (a part of the entire circumference). It is arrange | positioned so that it may descend | fall toward the center side from.

  For example, to explain the positional relationship in FIG. 2, the odd-numbered (left side) inclined plate 21a as viewed from above is descending from the left inner peripheral part (part of the entire circumference) toward the right side. The even-numbered (right side) inclined plate 21a extends while descending from the right inner peripheral part (a part of the entire circumference) toward the left side. Here, the odd-numbered inclined plates 21a and the even-numbered inclined plates 21a overlap each other at the central portion in plan view. For this reason, the magnetic ball 20 and sludge that have moved or flowed on a certain inclined plate 21a fall or flow down on the lower inclined plate 21a. As a result, the magnetic spheres 20 and sludge introduced into the upper part of the iron-based fine particle adsorption device 18 move or flow in the zigzag path in order on the upper surfaces of the plurality of inclined plates 21a arranged from the upper side to the lower side. To do. At that time, the iron-based fine particles adsorbing the harmful metal or the like in the sludge or adhering the harmful metal or the like are adsorbed to the outer peripheral surface of the magnetic sphere 20 by a magnetic force. Thereby, the content rate of the harmful metal etc. of sludge is reduced.

  The screen device 19 receives the fluid (mixture) discharged from the iron-based fine particle adsorption device 18 and separates (screens) it into magnetic balls 20 and sludge. Although not shown in detail, the screen device 19 has a mesh-like or lattice-like screen extending downward while inclining while descending from the lower position of the iron-based fine particle adsorption device 18. The opening (opening dimension) of the screen is such that the magnetic sphere 20 cannot pass through. When the fluid (mixture) in which the magnetic sphere 20 and sludge are mixed on the screen falls or flows down, the magnetic sphere 20 rolls on the inclined screen and falls into the second magnetic sphere storage container 25. . On the other hand, the sludge flows down through the mesh or opening of the screen and is stored in the sludge storage tank 27. The iron removing device 12 is provided with a sludge pump 34 for transporting the sludge in the sludge storage tank 27 to the fine particle cleaning device 13 (see FIG. 1).

  As shown in FIG. 3, the magnetic sphere 20 is schematically mounted with a plurality of permanent magnets 30 in the hollow part of the hollow sphere 29 so that each N pole faces outward in the spherical body radial direction. Is. In addition, the magnetic sphere 20 may be one in which each permanent magnet 30 is mounted such that each S pole faces outward in the spherical body radial direction. Specifically, each permanent magnet 30 is fitted into a magnet holding hole 32 formed in a hollow spherical magnet holding member 31. A magnet holding member 31 with a permanent magnet 30 is fitted in the hollow portion of the hollow spherical body 29. In other words, the hollow spherical body 29 is fitted on the circumferential surface of the magnet holding member 31, or the circumferential surface of the magnet holding member 31 is covered with the hollow spherical body 29.

  The magnet holding hole 32 formed in the magnet holding member 31 is a tapered hole whose cross-sectional area decreases toward the center of the magnetic sphere, and the permanent magnet 30 has a shape (complementary type) that fits or matches the magnet holding hole 32. ). For this reason, the permanent magnet 30 can be easily attached to the magnet holding member 31 by fitting or inserting the permanent magnet 30 into the magnet holding hole 32 from the outside of the magnet holding member 31. The shape of the end face of the permanent magnet 30 positioned on the radially outer side in the state of being mounted on the magnet holding member 31 is preferably a curved surface (part of a spherical surface) that matches the outer peripheral surface of the magnet holding member 31. In this way, the outer peripheral surface of the assembly of the permanent magnet 30 and the magnet holding member 31 is spherical, and the assembly and the hollow sphere 29 can be brought into close contact with each other.

The diameter of the magnetic sphere 20 (that is, the outer diameter of the hollow sphere 29) is practically 3 to 5 cm, for example, in order to facilitate the transportation or transportation of the magnetic sphere 20. Further, the apparent density (or bulk density) of the magnetic sphere 20, that is, the value obtained by dividing the mass of the magnetic sphere 20 by the volume thereof, is as light as possible without causing the magnetic sphere 20 to float in the sludge during flow. Therefore, it is practical to set it within the range of 1.1 to 1.3 g / cm ³ . The apparent density of the magnetic spheres 20 can be adjusted or increased or decreased by appropriately setting the size of the permanent magnets 20 and the number of the permanent magnets 20, the volume of the magnet holding member 31 or the hollow portion thereof, etc. It is easy to adjust the apparent density to 1.1 to 1.3 g / cm ³ .

  The material of the hollow sphere 29 is not particularly limited as long as it has corrosion resistance against sludge and appropriate mechanical strength, but it is practical to use stainless steel or aluminum (or an alloy thereof). The thickness of the hollow sphere 29 is preferably about 0.2 to 0.5 mm, for example. If the hollow sphere 29 is formed of a pair of hollow hemispheres that can be screwed together, the magnetic sphere 20 can be easily manufactured. In this case, the magnetic ball 20 can be easily assembled by inserting the magnet holding member 31 with the permanent magnet 30 into one hemisphere and screwing the other hemisphere into the hemisphere. If the match is canceled, the magnetic sphere 20 can be disassembled.

  The magnet holding member 31 can be manufactured, for example, by injection molding of a thermoplastic resin (for example, polyethylene, polypropylene, etc.). As the permanent magnet 20, a neodymium magnet having a tapered shape corresponding to the magnet holding hole 32, an end face on the large diameter side being an N pole, and an end face on the small diameter side being an S pole can be used. A neodymium magnet in which the end surface on the large diameter side is the S pole and the end surface on the small diameter side is the N pole may be used.

  As shown in FIG. 2 again, a first magnetic sphere storage container 24 is disposed above the iron-based fine particle adsorption device 18, and the opening of the first magnetic sphere storage container 24 is at its lower end (bottom). An opening / closing door 24a that can freely adjust the position is provided. By adjusting the opening degree of the opening / closing door 24a, the magnetic spheres 20 stored in the first magnetic sphere storage container 24 are continuously discharged downward with a desired passing amount (flow rate) to reduce the amount of iron-based fine particles. It can be supplied to the upper part of the particle adsorption device 18.

  A second magnetic sphere storage container 25 is disposed below the tip of the screen device 19 (the end far from the iron-based fine particle adsorption device 18), and the magnetic sphere 20 that has rolled on the screen of the screen device 19 is disposed. Is fallen by gravity from the tip of the screen device 19 and accommodated in the second magnetic sphere storage container 25. Since the magnetic spheres repel each other by a magnetic force (repulsive force), the magnetic spheres 20 can move smoothly and quickly without being aggregated or gathered into a bunch of grapes when moving (magnetic spheres 20). The same applies to the case of moving in a certain device or container, or moving to another device or container.)

  A centrifuge 22 is disposed below the second magnetic sphere storage container 25. The centrifugal separator 22 intermittently batches the magnetic spheres 20 discharged from the iron-based fine particle adsorption device 18 and temporarily stored in the second magnetic sphere storage container 25 via the screen device 19 (batch). The ferrous fine particles are separated from the magnetic sphere 20 by centrifugal force. At the lower end (bottom) of the second magnetic sphere storage container 25, an opening / closing door 25a for dropping the magnetic sphere 20 stored therein and supplying it to the centrifuge 22 at any time is attached.

  As shown in FIG. 4, the centrifuge 22 includes a housing 35 that is a substantially cylindrical container, and a bearing device 36 that is coaxially disposed in the housing 35 and fixed to the housing 35. And a rotating cylinder 37 supported rotatably around the axis. An upper opening / closing door 37a and a lower opening / closing door 37b, which can be opened and closed at any time, are attached to the upper end portion and the lower end portion of the rotating cylinder 37, respectively. The circumferential portion (side portion) of the rotating cylinder 37 is formed of a cylindrical net-like member or a lattice-like member having a large number of openings with openings that the magnetic ball 20 cannot pass through. The rotary cylinder 37 is rotationally driven by a motor 39 via a gear mechanism 38. Instead of the gear mechanism 38, a belt / pulley mechanism may be used. In addition, a hollow frustum-shaped baffle 40 (an umbrella-shaped baffle plate) that receives and drops particles of an iron-based fine particle flying in the horizontal direction by centrifugal force from a rotating cylinder 37 that rotates at a high speed is provided in the housing 35. Has been placed.

  As apparent from FIG. 2, the third magnetic ball storage container 26 is disposed below the centrifuge 22, and when the lower opening / closing door 37 b (see FIG. 4) is opened when the rotating cylinder 37 is stopped, the third magnetic ball storage container 26 rotates. The magnetic sphere 20 in the cylinder 37 falls by gravity and is stored in the third magnetic sphere storage container 26. An opening / closing door 26 a whose opening degree can be freely adjusted is attached to the lower end portion of the third magnetic ball storage container 26. By adjusting the opening degree of the opening / closing door 26a, the magnetic spheres 20 in the third magnetic sphere storage container 26 can be continuously discharged (dropped) downward at a desired passing amount (flow rate).

  Below the third magnetic ball storage container 26, the magnetic balls 20 continuously discharged from the third magnetic ball storage container 26 are received on a belt 41a (endless belt) and transported horizontally by the belt 41a. A horizontal belt conveyor 41 that is supplied to the upright belt conveyor 42 is provided. The horizontal belt conveyor 41 has one end (upstream end with respect to the magnetic ball transport direction) positioned near the lower end of the third magnetic ball storage container 26 and the other end (downstream end with respect to the magnetic ball transport direction). Are arranged in the vicinity of the lower end of the upright belt conveyor 42. The horizontal belt conveyor 41 and the upright belt conveyor 42 are components of the magnetic ball return device 23.

  The belt 41a is made of a flexible nonmagnetic material (for example, rubber). Further, side plates (not shown) are provided on both sides of the belt 41a so as to be close to the belt side portion and prevent the magnetic balls 20 on the belt from falling off the belt side portion. . In addition, the side plate may not be provided, and both sides of the belt 41a may have a moderate height (for example, 1 to 2 cm) and a bank-like or bank-like protrusion that extends in the belt extending direction may be integrally formed.

  The upright belt conveyor 42 is slightly higher than the upper end of the first magnetic ball storage container 24 immediately above the two driving rollers 43a and 43b and the driving rollers 43a and 43b disposed slightly above the horizontal belt conveyor 41. A ring-shaped (endless) made of a ferromagnetic material (for example, steel, stainless steel, etc.) wound around two driven rollers 44a, 44b, and driving rollers 43a, 43b and driven rollers 44a, 44b. A metal belt 45 and a plurality of idle rollers 46 are provided. Here, the drive rollers 43a and 43b are rotationally driven in a counterclockwise direction by a motor (not shown). Along with this, the metal belt 45 runs in a counterclockwise direction between the driving rollers 43a and 43b and the driven rollers 44a and 44b. Here, a plurality of permanent magnets 49 (see FIG. 5) are provided in the drive roller 43a to assist the movement / adsorption of the magnetic ball 20 on the belt 41a to the metal belt 45. It is mounted so that it faces outward. When the permanent magnet 30 is mounted on the magnetic sphere 20 so that the south pole faces outward in the spherical body radial direction, the permanent magnet 49 is mounted so that the north pole faces outward in the roller radial direction. The The idle roller 46 abuts on the inner surface (rear surface) of the ring-shaped metal belt 45 and regulates the position or travel path of the metal belt 45 so that the metal belt 45 travels on a predetermined travel path.

  Since the metal belt 45 is formed of a ferromagnetic material, the magnetic sphere 20 can adhere to the metal belt 45 by magnetic force. The magnetic characteristics or magnetic strength of the permanent magnet 30 (see FIG. 3) of the magnetic sphere 20 is such that when the metal belt 45 extends in the horizontal direction, the magnetic sphere 20 is positioned below the metal belt 45 at an appropriate interval (for example, 5 It is set so that the magnetic sphere 20 can move upward against gravity and adhere to the lower surface of the metal belt with a magnetic force when arranged with a gap of ~ 15 mm. The adhesion of the magnetic sphere 20 to the lower surface of the metal belt is assisted by a permanent magnet 49 (see FIG. 5).

  Further, the horizontal belt conveyor 41 has a magnetic force between the top of the magnetic ball 20 mounted on the belt 41a and the lower surface of the metal belt at the lower end of the upright belt conveyor 42. It arrange | positions so that the said moderate space | interval which can adhere can arise. Therefore, the magnetic balls 20 transported to the lower side of the upright belt conveyor 42 by the horizontal belt conveyor 41 are sequentially attached to the lower surface of the metal belt by magnetic force.

  As shown in FIGS. 5A to 5C, the outer surface of the metal belt 45 of the upright belt conveyor 42 is slightly longer than the diameter of the magnetic ball 20 in the direction in which the metal belt 45 extends (traveling direction). A plurality of (multiple) magnetic ball locking members 47 in the form of a prism or a rectangular bar extending linearly in the belt width direction are attached at intervals. The material of the magnetic ball locking member 47 is not particularly limited as long as it can be easily attached to and detached from the metal belt 45 (for example, screwed) and has durability against collision with the magnetic ball 20. For example, a synthetic resin or an aluminum alloy can be used.

  The magnetic ball locking member 47 is configured to move or move the magnetic ball 20 attached to the surface of the metal belt 45 by magnetic force downward when the metal belt 45 extends or moves upward in the vertical direction. Lock the rolling. The height or protrusion length of the magnetic ball locking member 47 from the metal belt surface is practically 1/8 to 1/4 of the diameter of the magnetic ball 20. Further, it is practical that the interval between the magnetic ball locking members 47 adjacent to each other in the extending direction (traveling direction) of the metal belt 45 is 1.2 to 1.5 times the diameter of the magnetic ball 20.

  Thus, the magnetic ball 20 transported by the horizontal belt conveyor 41 and attached to the metal belt 45 by the magnetic force at or near the lower end of the upright belt conveyor 42 is moved downward by the metal belt 45 traveling around counterclockwise. Are conveyed to the upper end of the upright belt conveyor 42 without moving or rolling.

  As is apparent from FIG. 2, in the vicinity of the upper end of the upright belt conveyor 42, the magnetic sphere 20 attached to the metal belt 45 by magnetic force is detached from the metal belt 45 and guided to the first magnetic sphere storage container 24. A guide member 48 is provided. The end of the guide member 48 on the upright belt conveyor side is positioned in the vicinity of the driven roller 44 a, while the end of the first magnetic ball storage container side is positioned in the vicinity of the upper end of the first magnetic ball storage container 24. . The guide member 48 is inclined downward from the upright belt conveyor side toward the first magnetic ball storage container side. The guide member 48 is made of a nonmagnetic material.

  In the positional relationship in FIG. 2, the magnetic ball 20 that is attached to and moves on the metal belt 45 that runs in the counterclockwise direction collides with or contacts the end of the guide member 48 in the vicinity of the driven roller 44a. As a result, the magnetic ball 20 is separated from the metal belt 45 by the guide member 48, rolls on the upper surface of the guide member 48 and falls into the first magnetic ball storage container 24. That is, the magnetic spheres 20 continuously discharged downward from the third magnetic sphere storage container 26 are first magnetic spheres by the magnetic sphere return device 23 (horizontal belt conveyor 41, upright belt conveyor 42, guide member 48). It is continuously returned to the storage container 24.

  As described above, the magnetic sphere 20 includes, in order, the first magnetic sphere storage container 24, the iron-based fine particle adsorption device 18, the screen device 19, the second magnetic sphere storage container 25, and the centrifuge 22. The third magnetic ball storage container 26 and the magnetic ball return device 23 (horizontal belt conveyor 41, upright belt conveyor 42, guide member 48) are circulated and moved. The seven broken arrows in FIG. 2 indicate the moving direction of such a magnetic sphere 20. The magnetic sphere 20 continuously moves from the first magnetic sphere storage container 24 to the second magnetic sphere storage container 25, and intermittently or batchwise from the second magnetic sphere storage container 25 to the third magnetic sphere storage container 26. , And continuously moves from the third magnetic sphere storage container 26 to the first magnetic sphere storage container 24.

  Hereinafter, an example of the operation method of the iron content removal apparatus 12 is demonstrated. A large number of magnetic spheres 20 substantially not adsorbing iron-based fine particles are continuously supplied from the first magnetic sphere storage container 24 to the upper part of the iron-based fine particle adsorption device 18, while the intermediate tank 9 (see FIG. 1), sludge consisting essentially of fine particles (iron-based fine particles and non-ferrous fine particles) and water is continuously supplied. In the iron-based fine particle adsorption device 18, the fluid or mixture obtained by mixing the magnetic sphere 20 and the sludge moves or moves downward along a zigzag path formed by the plurality of inclined plates 21a. To flow. At that time, iron-based fine particles in the sludge are adsorbed on the outer peripheral surface of the magnetic sphere 20 by magnetic force.

  The iron-based fine particles are produced by crushing gravel and sand with a mill breaker 3 (see FIG. 1), which is a wet crusher, or existing before crushing of gravel and sand. On the surface, a fine lump such as iron is exposed, and harmful metals and the like are adsorbed on the exposed fine lump such as iron. In general, small blocks such as iron are unevenly distributed or scattered in gravel and sand, and the ratio of such small blocks is about 2 to 7% by mass. For this reason, at least a part of the fine particles generated by crushing gravel and sand is an iron-based fine particle portion in which fresh iron (that is, no toxic metal or the like is adsorbed) is exposed on the surface.

Iron is a ferromagnetic material (soft magnetic material) and is adsorbed by a magnet. In addition, iron oxides present in the soil are substantially composed of triiron tetroxide (Fe ₃ O ₄ ), γ-type ferric trioxide (γ-Fe ₂ O ₃ ), and α-type diiron trioxide ( α-Fe ₂ O ₃ ), and triiron tetroxide and γ-type diiron trioxide are ferromagnetic materials (soft magnetic materials) and are adsorbed by a magnet. Note that α-type ferric trioxide is not magnetized and is not attracted to the magnet. For this reason, the iron-based fine particles having a surface exposed to a fine mass such as iron are permanent magnets in the magnetic sphere 20 due to ferromagnetism (soft magnetism) of iron, triiron tetroxide or γ-type diiron trioxide. 30 (see FIG. 3) and is attracted to the outer peripheral surface of the magnetic sphere 20 (hollow sphere 29) by magnetic force.

  Iron or other fine mass exposed on the surface of fine iron particles produced by crushing gravel and sand with a mill breaker 3 (see FIG. 1) is unevenly distributed or scattered in the gravel or sand. It originates from a small lump of fresh iron or the like that has not adsorbed the toxic metals that have been adsorbed, and is exposed to the surface after crushing and adsorbs toxic metals and / or these ions from the surrounding wash water. Thus, the fine particles discharged from the mill breaker 3 (see FIG. 1) and introduced into the iron-based fine particle adsorption device 18 are iron-based fine particles having a relatively large (or considerably) adsorption amount of harmful metals and the like. It is composed of non-ferrous fine particles with a relatively small (or considerably) amount of adsorption of harmful metals and the like.

  As described above, since the iron-based fine particles are removed from the sludge in the iron-based fine particle adsorption device 18, the fine particles contained in the sludge discharged from the iron-based fine particle adsorption device 18 are: Most of the non-ferrous fine particles are relatively (or considerably) less adsorbed with harmful metals. Therefore, a part or a substantial part of harmful metals and the like contained in the contaminated soil introduced into the soil purification system S is removed in the iron-based fine particle adsorption device 18.

  The mixture of magnetic spheres 20 and sludge discharged downward from the lower end of the iron-based fine particle adsorption device 18 is introduced into the screen device 19, and the magnetic spheres 20 adsorbing the iron-based fine particles and the iron-based fine particles It is separated into sludge from which the grain fraction has been removed. The magnetic sphere 20 is stored in the second magnetic sphere storage container 25, and the sludge is stored in the sludge storage tank 27.

  As will be described in detail later, the fine particle cleaning device 13 (see FIG. 1) uses the chelating agent for sludge discharged from the iron-based fine particle adsorption device 18 and separated by the screen device 19. And the chelating agent regeneration device 17 (see FIG. 1) regenerates the chelating agent with the solid-phase adsorbent. As described above, the iron-based fine particle adsorbing device 18 contains sludge in the sludge. Since harmful metals and the like are reduced, the burden of harmful metals and the like on chelate cleaning treatment of fine particles (sludge) and regeneration treatment of the chelating agent is reduced. For this reason, the required amount or usage-amount of the chelating agent and solid-phase adsorbent in the soil purification system S can be reduced, and the processing cost of soil can be reduced. That is, the iron-based fine particle adsorption device 18 (iron removal device 12) functions as a pretreatment device or pretreatment device that reduces the load of harmful metals or the like on the fine particle washing device 13 or chelating agent regeneration device 17. .

  The magnetic spheres 20 adsorbing the iron-based fine particles in the second magnetic sphere storage container 25 are appropriately supplied to the rotating cylinder 37 of the centrifuge 22. Specifically, the upper door 37a is opened, while the lower door 37b is closed, the door 25a is opened and processed once from the second magnetic ball storage container 25 into the rotary cylinder 37. Minute magnetic sphere 20 is supplied. For example, an amount of the magnetic sphere 20 that occupies 1/3 to 1/2 of the space in the rotary cylinder 37 is supplied.

  Thereafter, the upper opening / closing door 37a is closed, the motor 39 is started, and the rotating cylinder 37 is rotated at a high speed (for example, when the radius of the rotating cylinder 37 is 1 m, 100 to 500 rpm). As a result, the iron fine particles adsorbed or adhered to the outer peripheral surface of the magnetic sphere 20 are separated from the magnetic sphere 20 by a strong centrifugal force (for example, 10 to 100 G), and a large number of meshes on the peripheral wall of the rotating cylinder 37 Or jump out through the hole. Here, the rotational speed of the rotating cylinder 37 depends on the radius of the rotating cylinder 37, the magnetic force of the magnetic sphere 20, the magnetic characteristics of the iron-based fine particles, etc. It is preferably set to be separated.

  The iron-based fine particles separated from the magnetic sphere 20 and jumping out of the rotating cylinder 37 collide with the baffle 40 and then fall and accumulate at the bottom of the housing 35. The iron-based fine particles in the housing 35 are appropriately discharged to the outside by hand. The removed iron-based fine particles can be used, for example, as a raw material for iron making. Then, after the elapse of a predetermined time (for example, 2 to 5 minutes), the rotation of the motor 39 and thus the rotating cylinder 37 is stopped. Thereafter, the lower opening / closing door 37b is opened, and the magnetic sphere 20 from which the iron-based fine particles in the rotating cylinder 37 are almost removed falls into the third magnetic sphere storage container 26 by gravity.

  The magnetic spheres 20 in the third magnetic sphere storage container 26 are continuously supplied onto the belt 41a of the horizontal belt conveyor 41 and transported to the vicinity of the lower end of the upright belt conveyor 42 by the belt 41a. Thereafter, the magnetic sphere 20 on the belt 41 a is transported to the upper end portion thereof by the upright belt conveyor 42 and introduced into the first magnetic sphere storage container 24 by the guide member 48. The supply amount (supply speed) of the magnetic balls 20 from the third magnetic ball storage container 26 to the horizontal belt conveyor 41 is changed by changing the opening degree of the opening / closing door 26a. The conveyor 42 is adjusted to be equal to or less than the maximum transport amount.

  As shown in FIG. 1 again, the sludge discharged from the iron removing device 12 (sludge storage tank 27 in FIG. 2) is introduced into the fine particle cleaning device 13. The fine particle cleaning device 13 includes a sludge containing non-ferrous fine particles discharged from the iron content removing device 12 and cleaning water, and a chelating agent and water supplied from a chelating agent regenerating device 17 described later. Accept the chelate cleaning liquid, mix and agitate them to produce a fine-grained slurry, with a plug flow (plug flow) to ensure a preset residence time (eg 0.5-2 hours) By continuously flowing, the toxic metal or the like adhering (adsorbing) to the fine particles or these ions are captured by the chelating agent. Thereby, the harmful metal adsorbed (attached) on the surface of the fine particles in the fine particle slurry is removed. The ratio of the flow rate of the sludge supplied to the fine particle cleaning device 13 and the flow rate of the chelate cleaning solution is set to 1: 1, for example.

  Examples of the chelating agent used in the chelate cleaning solution include EDTA (ethylenediaminetetraacetic acid), HIDS (3-hydroxy-2,2′-iminodisuccinic acid), IDS (2,2′-iminodisuccinic acid), MGDA (methylglycine). Diacetic acid), EDDS (ethylenediaminediacetic acid) or sodium salt of GLDA (L-glutamic acid diacetic acid). Any of these chelating agents can effectively capture (chelate) the fine metal slurry or the harmful metals contained in the fine particle. Of course, a chelating agent suitable for the treatment is selected or a plurality of chelating agents are used depending on the type of harmful metal contained in the fine particles.

  Hereinafter, a specific configuration and function of the fine particle cleaning device 13 will be described with reference to FIGS. The fine grain cleaning device 13 has a storage tank 50 having five elongated rectangular parallelepiped or prismatic slurry passages 55 to 59 formed by partitioning with four flat partition walls 51 to 54 and extending in parallel to each other. doing. The storage tank 50 may be, for example, an iron rectangular parallelepiped square tank installed on the ground, or may be a concrete rectangular parallelepiped pit. Moreover, the partition walls 51-54 may be formed, for example, by connecting a plurality of iron plates or plastic plates in the direction in which the slurry passage extends.

  Two slurry passages adjacent to each other in the slurry passages 55 to 59 have four curved lines in the communicating portion (FIG. 6A) at one end in the longitudinal direction of the slurry passage (left and right in the positional relationship in FIGS. 6A and 6B). Are communicated with each other at the site indicated by the arrows. That is, partition walls 51 to 54 do not exist in these communicating portions, and adjacent slurry passages communicate with each other.

  Air discharge pipes 61 to 65 for discharging air into the fine particle slurry and stirring the fine particle slurry are arranged at the bottoms of the respective slurry passages 55 to 59. Each of the air discharge pipes 61 to 65 is a porous pipe extending in the slurry passage longitudinal direction and having a plurality of air discharge holes arranged in the slurry passage longitudinal direction at the bottom (lower side) of the peripheral wall. Although not shown, it is connected to a compressor or a blower that supplies compressed air. When pressurized air is supplied to the air discharge pipes 61 to 65, the air is bubbled from the air discharge holes and released into the fine particle slurry, and the fine particle slurry is stirred by the bubbles. Is done.

  FIG. 6C shows a cross section of the slurry passage 55 on the most upstream side in the flow direction of the fine particle slurry (the direction indicated by the curved arrow and the straight arrow in FIG. 6A). . As is clear from FIG. 6C, the air discharge pipe 61 is disposed near the bottom of the slurry passage in the vicinity of one side surface of the slurry passage 55. For this reason, the bubbles discharged from the air discharge pipe 61 rise in the vicinity of this side surface. As a result, a circulating flow that flows in the direction indicated by the arrow P in a plane perpendicular to the longitudinal direction of the slurry passage is formed in the slurry passage 55, and the fine particle slurry is stirred. The shape, size, capacity, and the like of the storage tank 50 and each of the slurry passages 55 to 59 and the amount of pressurized air supplied to the air discharge pipes 61 to 65 are set in advance in the fine particle washing device 13. The water content, flow rate, residence time, flow velocity, turbulence degree of flow (for example, Reynolds number) and the like are preferably set.

  As is clear from FIG. 1, the fine particle slurry discharged from the fine particle washing device 13 is transferred to the filtration device 14. The filtration device 14 filters the fine particle slurry to produce a filter cake and filtrate having a water content of 30 to 40 percent. In addition, as the filtration apparatus 14, a filter press, a vacuum filter, etc. can be used. Since the filter cake (fine particles) discharged from the filter device 14 does not contain any harmful metals or the like, it is used as, for example, agricultural soil or disposed of by landfill.

  The filtrate discharged from the filtration device 14, that is, the chelate washing solution is transferred to the reverse osmosis membrane separation device 16 after the suspended matter or suspended matter (SS) is removed by the clarification filter 15 (for example, sand filter). . Although not shown in detail, the reverse osmosis membrane separation device 16 receives the chelate washing liquid discharged from the clarification filter 15, pressurizes it with a high-pressure pump, and then concentrates the chelating agent concentrated by the reverse osmosis membrane. Separation into water and permeate without chelating agent. Then, the concentrated water is supplied to the chelating agent regeneration device 17, and the permeated water not containing the chelating agent is returned to the thickener 8 by the permeated water transfer means (for example, a pump and a pipe line).

  The reverse osmosis membrane of the reverse osmosis membrane separation device 16 is, for example, a three-layer structure in which a polysulfone support layer and a dense cross-linked aromatic polyamide layer are laminated on the surface of a polyester nonwoven fabric (thickness 100 to 120 μm). Can be used. The dense cross-linked aromatic polyamide layer has a large number of pores having a pore diameter of about 0.5 to 1.5 nm, and is very thin (for example, 0.2 to 0.25 μm) a semipermeable membrane. The polysulfone support layer is a relatively thick (for example, 40 to 50 μm) porous membrane for supporting or protecting a very thin crosslinked aromatic polyamide dense layer to prevent breakage thereof.

The reverse osmosis membrane separation device 16 is of a spiral type and has a plurality of reverse osmosis membrane elements in which a reverse osmosis membrane wound in a spiral shape is accommodated in a cylindrical container. It is practical that each reverse osmosis membrane element has, for example, a total length of about 1 to 2 m and an outer diameter of about 0.2 to 0.4 m. For example, the effective membrane area of a reverse osmosis membrane in a commercially available reverse osmosis membrane element of this type having a total length of about 1 m and an outer diameter of about 0.2 m (for example, manufactured by Authentec Co., Ltd., Nakatsugawa, Gifu Prefecture) is About 40 m ² . In the case of this reverse osmosis membrane element, when the chelate cleaning solution having a chelating agent concentration of about 1% by mass is supplied at a pressure of about 1 MPa, the treatment amount of the chelate cleaning solution is estimated to be about 1.5 m ³ / hr. Therefore, for example, when processing a chelate washing solution of 60 m ^{3 /} h, 40 reverse osmosis membrane elements may be connected in parallel.

  The reverse osmosis membrane separation device 16 is a continuous type, and the operating conditions such as the supply amount and supply pressure (operation pressure) of the chelate washing liquid, the discharge amount of concentrated water and permeate, the chelating agent concentration ratio of concentrated water are as follows. It is set appropriately according to the amount of chelate cleaning liquid to be supplied to the cleaning device 13 and the chelating agent concentration. For example, the ratio of the flow rate of the sludge supplied to the fine particle cleaning device 13 and the flow rate of the chelate cleaning solution is set to 1: 1, and the chelating agent concentration of the fine particle slurry in the fine particle cleaning device 13 is set to 1% by mass. In this case, the reverse osmosis membrane separation device 16 generates permeated water (chelating agent concentration 0) of about 50% of the supply amount of the chelate washing liquid and concentrated water (chelating agent concentration of about 2 mass%) of about 50%. Set to Therefore, in the fine particle cleaning device 13, the sludge not containing the chelating agent and the chelating cleaning solution having a chelating agent concentration of about 2% by mass are mixed at a ratio of 1: 1, and the chelating agent concentration in the fine particle cleaning device 13 is 1 mass. % Is maintained.

  The concentrated water, that is, the chelate washing liquid discharged from the reverse osmosis membrane separation device 16 is introduced into the chelating agent regeneration device 17 and regenerated. The chelating agent regenerating apparatus 17 has a complex forming power higher than that of the chelating agent, and a solid phase adsorbing material that adsorbs or extracts a harmful metal or the like in the chelating cleaning solution when it comes into contact with the chelating cleaning solution or a small piece on which the solid adsorbing material is fixed Or it has a granular material, removes a harmful metal etc. from the chelating agent in the chelating cleaning solution, and regenerates the chelating cleaning solution.

  The solid-phase adsorbent has a multipoint interaction by coordinating bonds and hydrogen bonds in which a cyclic molecule is supported on a carrier and a chelate ligand is modified on the cyclic molecule, and selectively incorporates ions such as harmful metals. is there. As a result, harmful metals and the like captured by the chelating agent are separated from the chelating agent and adsorbed or extracted by the solid phase adsorbent. As a result, harmful metals and the like are removed and collected from the chelate cleaning solution (chelating agent), and the chelate cleaning solution (chelating agent) is in a state where it can capture the harmful metals and the like again.

  A solid-phase adsorbent having a higher complexing power than a chelating agent is a solid material such as a gel, and is generally coordinated with a chelating agent when contacted with an aqueous solution containing a chelating agent capturing a metal. It has a strong binding force other than a covalent bond to such an extent that the metal ions can be detached from the chelating agent and transferred to the solid phase adsorbent. For example, when EDTA (ethylenediaminetetraacetic acid) is used as a chelating agent, such a solid-phase adsorbent has a strong binding force capable of recovering almost 100% of metal ions from an EDTA aqueous solution having a concentration of 10 mM / l. It is what you have.

  Examples of such a solid-phase adsorbent include a material in which a cyclic molecule is densely supported on a carrier such as silica gel or a resin and a chelate ligand is modified on the cyclic molecule. When such a solid-phase adsorbent is used, a plurality of various bonds and interactions such as coordination bonds and hydrogen bonds occur due to adjacent cyclic molecules and chelate ligands, resulting in multipoint interactions, and metal ions In contrast to this, a chemical bond stronger than that of a chelating agent is generated, and metal ions can be selectively taken in by the properties of the cyclic molecule.

  Hereinafter, a specific configuration and function of the chelating agent regeneration device 17 will be described with reference to FIG. The chelating agent regenerator 17 is provided with a packed tower 70 filled with solid phase adsorbent particles or a packing (packing) in which the solid phase adsorbent is fixed. The chelating agent regenerator 17 includes an intermediate storage tank 71 for storing a chelate cleaning liquid (concentrated water) to be regenerated, a cleaning liquid storage tank 72 for storing the regenerated chelate cleaning liquid, and an acid liquid storage tank 73 for storing an acid liquid. A water storage tank 74 for storing water is provided.

  In the intermediate storage tank 71, the concentrated water, that is, the chelate cleaning liquid discharged from the reverse osmosis membrane separation device 16 (see FIG. 1) is temporarily stored. When regenerating the chelate cleaning liquid, the chelate cleaning liquid stored in the intermediate storage tank 71 is transferred to the packed tower 70, while the chelate cleaning liquid regenerated in the packed tower 70 is transferred to the cleaning liquid storage tank 72 and a series. The pipe lines 77 to 80 are provided. In addition, a pump 81 and a pipe line 82 are provided for supplying the chelate cleaning liquid stored in the cleaning liquid storage tank 72 to the fine particle cleaning apparatus 13 (see FIG. 1).

  Further, when the solid phase adsorbent is regenerated, the chelating agent regenerator 17 transfers the acid solution stored in the acid solution storage tank 73 to the packed tower 70, while the acid solution discharged from the packed tower 70 is converted into an acid. A pump 83 and a plurality of pipes 84 and 85 for returning to the liquid storage tank 73 are provided. Further, when the solid phase adsorbent regenerated with the acid solution is washed with water, the chelating agent regenerator 17 transfers the water stored in the water storage tank 74 to the packed tower 70 while being discharged from the packed tower 70. A pump 86 and a plurality of pipes 87 and 88 for returning water to the water storage tank 74 are provided.

  Valves 91, 92, 93, 94 for opening and closing the corresponding pipe lines are interposed in the pipe lines 77, 78, 84, 87 for transferring the chelate cleaning solution, the acid solution or the water to the packed tower 70, respectively. Yes. On the other hand, valves 79, 80, 85, and 88 for discharging the chelate cleaning solution, acid solution, and water from the packed tower 70 are provided with valves 95, 96, 97, and 98 for opening and closing the corresponding channels, respectively. Has been. By switching the open / closed state of these valves 91 to 98, either the chelate cleaning liquid, the acid liquid or the water can be supplied to and discharged from the packed tower 70. Note that the opening and closing of these valves 91 to 98 are automatically controlled by a controller (not shown).

  Hereinafter, an example of the operation method of the chelating agent regeneration device 17 will be described. When regenerating the chelate cleaning liquid (chelating agent), the valves 91, 92, 95, 96 interposed in the pipe lines 77-80 are opened, while the other valves 93, 94, 97, 98 are closed, The pump 76 is operated. As a result, the chelate cleaning liquid in the intermediate storage tank 71 flows through the packed tower 70 and is transferred to the cleaning liquid storage tank 72.

  In the packed tower 70, a chelate cleaning liquid containing a chelating agent capturing toxic metals and the like is brought into contact with a solid phase adsorbent (solid phase adsorbent particles). As a result, harmful metals and the like captured by the chelating agent are separated from the chelating agent and adsorbed or extracted by the solid phase adsorbent. As a result, harmful metals and the like are removed and collected from the chelate cleaning solution, and the chelating agent becomes able to capture the harmful metals and the like again, and the chelate cleaning solution is regenerated.

  As the chelate cleaning solution is regenerated, the amount of adsorption of harmful metals and the like on the solid phase adsorbent increases with time, but there is an upper limit on the adsorption capacity of the solid phase adsorbent. For this reason, when the amount of adsorption of harmful metals or the like in the solid phase adsorbent reaches a saturated state or the vicinity thereof, the solid phase adsorbent is regenerated. That is, the acid solution is flowed into the packed tower 70 with the chelate cleaning solution removed, and harmful metals adsorbed on the solid phase adsorbent are removed by the acid solution to regenerate the solid phase adsorbent. Thus, while toxic metals and the like are recovered by the acid solution, the solid-phase adsorbent is regenerated so that the toxic metals and / or these ions can be adsorbed or extracted again.

  When the solid-phase adsorbent in the packed tower 70 is regenerated with an acid solution, the valves 93, 92, 95, 97 interposed in the pipes 84, 78, 79, 85 are opened, while the other valves 91 are opened. , 94, 96, 98 are closed, and the pump 83 is operated. As a result, the acid solution in the acid solution storage tank 73 flows through the packed tower 70 and returns to the acid solution storage tank 73. Whether or not the amount of harmful metal adsorption of the solid-phase adsorbent reaches a saturated state or the vicinity thereof can be determined by detecting the content of harmful metal or the like in the chelate cleaning liquid discharged from the packed tower 70. .

  When the solid-phase adsorbent is washed with water after the regeneration of the solid-phase adsorbent with the acid solution is completed, the valves 94, 92, 95, 98 provided in the pipes 87, 78, 79, 88 are opened. The other valves 91, 93, 96, 97 are closed and the pump 86 is operated. Thereby, the water in the water storage tank 74 flows through the packed tower 70 and returns to the water storage tank 74. Water circulates between the water storage tank 74 and the packed tower 70. At that time, the solid phase adsorbent in the packed tower 70 comes into contact with water, and the acid solution adhering to the solid phase adsorbent is washed. Thereafter, regeneration of the chelate cleaning solution is resumed.

  The chelate cleaning liquid regenerated in this way is temporarily stored in the cleaning liquid storage tank 72 and then supplied to the fine particle cleaning apparatus 13 (see FIG. 1). That is, the chelate cleaning liquid circulates while repeating purification of the fine particles and regeneration of the chelating agent. Note that the reduced amount of the chelating agent is appropriately supplemented.

  As described above, according to the soil purification system S according to the present invention, clean and reusable gravel, sand and fine particles can be obtained. Moreover, since the content rate of the toxic metal etc. of the sludge discharged | emitted from the iron content removal apparatus 12 can be reduced, the load of the toxic metal etc. with respect to the fine particle washing | cleaning apparatus 13, and the toxic metal etc. with respect to the chelating agent reproduction | regeneration apparatus 17 The load can be reduced, the necessary amount or amount of the chelating agent and the solid phase adsorbent can be reduced, and the treatment cost of the soil can be reduced.

  S soil purification system, 1 input hopper, 2 mixer, 3 mil breaker (wet crusher), 4 trommel, 5 cyclone, 6 PH adjustment tank, 7 coagulation tank, 8 thickener, 9 intermediate tank, 10 washing water tank, 11 spare Water tank, 12 Iron content removal device, 13 Fine particle washing device, 14 Filtration device, 15 Clarification filter, 16 Reverse osmosis membrane separation device, 17 Chelating agent regeneration device, 18 Iron-based fine particle adsorption device, 19 Screen device, 20 Magnetic sphere, 21 body part, 21a inclined plate, 22 centrifuge, 23 magnetic sphere return device, 24 first magnetic sphere storage container, 24a open / close door, 25 second magnetic sphere storage container, 25a open / close door, 26 third magnetic Sphere storage container, 26a Open / close door, 27 Sludge storage tank, 29 Hollow spherical body, 30 Permanent magnet, 31 Magnet holding member, 32 Magnet holding hole, 34 Wedge pump, 35 housing, 36 bearing device, 37 rotating cylinder, 37a upper door, 37b lower door, 38 gear mechanism, 39 motor, 40 baffle, 41 horizontal conveyor, 41a belt, 42 upright conveyor, 43a drive roller 43b Drive roller 44a Follower roller 44b Follower roller 45 Metal belt 46 Idle roller 47 Magnetic ball locking member 48 Guide member 50 Storage tank 51-54 Partition wall 55-59 Slurry passage 61-65 Air discharge pipe, 70 packed tower, 71 intermediate storage tank, 72 cleaning liquid storage tank, 73 acid storage tank, 74 water storage tank, 76 pump, 77-80 pipe, 81 pump, 82 pipe, 83 pump, 84 pipe, 85 pipe Line, 86 pump, 87 line, 88 line, 91-98 valve.

Claims (3)

A soil purification system for purifying soil containing gravel, sand and fine particles and contaminated with harmful metals or compounds thereof,
A mixer for mixing the soil introduced into the soil purification system and washing water;
Iron or iron oxide that is unevenly distributed or scattered in the gravel and sand is exposed to the surface by crushing gravel and sand in the mixture containing soil and washing water discharged from the mixer. A wet crusher that generates a system fine particle and adsorbs or adheres a harmful metal or its compound in the washing water to iron or iron oxide exposed on the surface of the iron system fine particle;
Trommel for separating gravel from a mixture containing gravel, sand, fine particles and washing water discharged from the wet crusher;
A liquid cyclone for separating sand from a mixture containing sand, fine particles and washing water discharged from the trommel;
A thickener that separates the mixture containing fine particles discharged from the hydrocyclone and washing water into supernatant water and sludge containing fine particles and washing water by sedimentation separation,
From the sludge discharged from the thickener, by removing the iron-based fine particles by magnetically adsorbing, an iron content removing device that reduces the content of harmful metals or compounds thereof in the sludge,
The sludge discharged from the iron content removal device is mixed with a chelate cleaning liquid containing a chelating agent and water to produce a fine particle slurry, and the fine particle slurry is flowed to ensure a preset residence time. A fine particle cleaning device that captures a toxic metal or a compound thereof adhering to the fine particle by a chelating agent,
A filtration device for filtering the fine particle slurry discharged from the fine particle washing device to produce a filtrate and a filter cake;
A reverse osmosis membrane separation device for separating the filtrate discharged from the filtration device into a concentrated water in which a chelating agent is concentrated and a permeated water not containing the chelating agent by a reverse osmosis membrane;
The concentrated water discharged from the reverse osmosis membrane separator is received and concentrated by a solid-phase adsorbent that adsorbs harmful metals or compounds thereof in the concentrated water when it has higher complexing power than a chelating agent and comes into contact with the concentrated water. A chelating agent regenerator that removes harmful metals or compounds thereof from the chelating agent in water and supplies the concentrated solution as a chelate cleaning solution to the fine particle cleaning device;
A permeated water transfer means for transferring the permeated water discharged from the reverse osmosis membrane separation device to the thickener,
The iron removing device is
A plurality of magnetic spheres in which a plurality of permanent magnets are mounted in a hollow portion of a hollow sphere so that magnetic poles of the same magnet face outward in the spherical body radial direction and sludge discharged from the thickener are received, and the magnetic sphere An iron-based fine particle adsorbing device that moves a fluid mixture of sludge and sludge downward by a zigzag path by gravity and adsorbs iron-based fine particles in the sludge to a magnetic sphere by magnetic force during movement,
A screen device that receives the fluid discharged from the iron-based fine particle adsorption device and separates it into magnetic spheres and sludge;
A centrifugal separator that intermittently receives the magnetic spheres adsorbing the iron-based fine particles discharged from the screen device, and separates the iron-based fine particles from the magnetic spheres by centrifugal force; and
A soil purification system, comprising: a magnetic sphere returning device that returns the magnetic sphere discharged from the centrifugal separator to the iron-based fine particle adsorption device. The soil purification system according to claim 1, wherein the value obtained by dividing the mass of the magnetic sphere by the volume of the hollow sphere is in the range of 1.1 to 1.3 g / cm ³ . The magnetic ball returning device is
A driving roller disposed at a position lower than a lower end portion of the centrifuge, a driven roller disposed at a position higher than the upper end portion of the iron-based fine particle adsorption device above the driving roller, and the driving roller; An endless metal belt made of a ferromagnetic metal wound around the driven roller, and a magnet that is attached to the outer surface of the endless metal belt and is attracted to the endless metal belt when traveling above the endless metal belt An upright belt conveyor having a magnetic ball locking member for locking the lowering of the ball;
Magnetic sphere conveying means for conveying the magnetic sphere discharged from the centrifuge to the lower end of the upright belt conveyor and attracting the endless metal belt with a magnetic force;
The magnetic sphere supply means for detaching the magnetic sphere from the endless metal belt at the upper end of the upright belt conveyor and supplying it to the iron-based fine particle adsorption device. 2. The soil purification system according to 2.

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