JP2667986B2 - Method and apparatus for removing heavy metals contained in organisms - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for removing heavy metals contained in organisms such as marine products and agricultural products from the organisms. More specifically, the present invention relates to a method and apparatus suitable for removing heavy metals such as cadmium and arsenic contained in scallops.

[0002]

2. Description of the Related Art Up to now, it has been recognized that high concentrations of heavy metals such as cadmium and arsenic are accumulated in the midgut gland called uro of scallops and the kidney attached to the side of the scallop. Especially, the concentration of cadmium and arsenic in the midgut gland is several tens of pp
Since this value exceeds the guidance standard of the Ministry of Agriculture, Forestry and Fisheries, it is impossible to use the above-mentioned midgut glands and kidneys for feed fertilizer without any treatment. Or was incinerated. However, burying or burning the midgut gland and kidney has a problem that requires a lot of cost,
Reservation of buried land has reached its limit. Furthermore, heavy metals contained in the buried midgut glands and kidneys may infiltrate the groundwater and contaminate the groundwater.

[0003] In order to solve these problems, the Hokkaido Prefectural Industrial Research Institute has immersed the soft part of the scallop, such as the midgut gland , in a sulfuric acid solution and washed it three times with another water tank to remove cadmium from the midgut gland. The cadmium removal treatment was conducted, and the results were reported in the 1993 joint research (important) report, "R & D on Scallop By-product Processing and Utilization Technology" (Hokkaido Prefectural Central Fisheries Experimental Station, Industrial Experimental Station, Sanitary Research Institute, Central Agricultural Experiment Station and Takigawa Livestock Experiment Station). This treatment is carried out by immersing the soft body part such as the midgut gland in a sulfuric acid solution for 24 hours, and then washing the soft body part 3 times for 5 hours each time to remove 98% of cadmium from the soft body part. Can be.

[0004]

However, the above-mentioned conventional decadmium treatment has a problem that the treatment time is extremely long, 39 hours. Further, there is a problem that the apparatus becomes large-sized when processing a large amount of soft body parts such as the midgut gland at a time.
Further, there is a problem that a large amount of water is required at the time of washing with water and the subsequent wastewater treatment becomes large-scale.

[0005] An object of the present invention is to produce an organism in a relatively short time.
An object of the present invention is to provide a method and an apparatus for removing heavy metals contained in living organisms, which can remove heavy metals from living organisms without damaging them, have an extremely high removal rate, and can adjust the treatment time. Another object of the present invention is to provide a method and apparatus for removing heavy metals contained in living organisms, which can reduce the size of the apparatus, use relatively little water, and facilitate wastewater treatment. is there.

A configuration of the present invention for achieving the above object will be described with reference to FIGS. 1, 3 and 12 corresponding to the embodiment. As shown in FIGS. 1 and 3, the first method of the present invention is to dissolve an organism 11 containing a heavy metal in a living body and a heavy metal into an electrolytic cell 12 having an anode 13 and a cathode 14 to dissolve ions.
Sulfuric acid solution, hydrochloric acid solution, sodium hydroxide solution or
A step of supplying the electrolytic solution 15 consisting of sodium chloride solution
To stir the electrolytic solution 15 impregnated with the living body into the living body.
A step of eluting the Murrell heavy metals in the electrolytic solution 15 as the cation, applied to electrostatic DC voltage to the anode 13 and cathode 14
Depositing the heavy metal cations eluted in the solution 15 on the cathode 14. The second method of the present invention comprises the steps of:
Sulfuric acid having 3 and a cathode 14 to dissolve and ionize heavy metals
Solution, hydrochloric acid solution, sodium hydroxide solution or sodium chloride
A step of supplying the organism 11 electrolytic solution 15 consisting um solution contains heavy metals in the body in the electrolytic cell 12, which is stored
To stir the electrolytic solution 15 impregnated with the living body into the living body.
A step of eluting the Murrell heavy metals in the electrolytic solution 15 as the cation, applied to electrostatic DC voltage to the anode 13 and cathode 14
Depositing the heavy metal cations eluted in the solution 15 on the cathode 14. As shown in FIG. 12, the apparatus for removing heavy metals contained in living organisms according to the present invention dissolves the living organisms 11 containing heavy metals and the heavy metals in the living body by disposing an anode 73 and a cathode 74 at predetermined intervals. To be ionized
Acid solution, hydrochloric acid solution, sodium hydroxide solution or sodium chloride
Electrolyzer 7 capable of storing an electrolyte solution 15 composed of a lithium solution
2 and the electrolytic solution 15 in which the organism 11 in the electrolytic cell 72 is immersed.
To mix heavy metals contained in the living body into the electrolyte 15.
A cation of a heavy metal that is electrically connected to the agitating means 77 and the anode 73 and the cathode 74 , which are eluted as ions, and a voltage is applied between the anode 73 and the cathode 74 to elute into the electrolytic solution 15.
And a DC power supply 76 for depositing the

[0007]

In the device shown in FIGS. 1 and 3, the living body 11
By immersing the heavy metal contained in the electrolyte solution 15 in the stirred electrolyte solution 15, the heavy metal is gradually eluted into the electrolyte solution 15 and becomes a cation. When a DC voltage is applied to the anode 13 and the cathode 14, the heavy metal that has become positive ions is deposited on the cathode 14 and the organism 1
Since the ionization of the heavy metal contained in 1 into the electrolytic solution 15 is promoted, almost all of the heavy metal contained in the organism can be deposited on the cathode 14 in a relatively short time without damaging the organism 11. it can.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the present invention will be described in detail with reference to the drawings. <Example 1> As shown in Fig. 3, a midgut gland 11c called uro is located between a scallop 11a and a ligament 11b of a scallop 11, and a high concentration (several tens of ppm) is contained in the midgut gland 11c. ) Cadmium (Cd) is accumulated. 11d is a mantle called a string, and 11e is a kidney. As shown in FIGS. 1 and 2, the midgut gland 11 c and the electrolyte 15 are stored in an electrolytic cell 12 in which an anode 13 and a cathode 14 are arranged at a predetermined interval. Is connected to a DC power supply 16 electrically. Although not shown, the midgut gland 11c is immersed in the electrolytic solution 15 in the electrolytic cell 12 while being kept in a plastic basket. The electrolytic solution 15 in the electrolytic cell 12 is stirred by the stirring means 17. In this example, the anode 13 and the cathode 14 are made of graphite and stainless steel having a length of 65 mm and a width of 50 mm, respectively.
The distance between the cathode 3 and the cathode 14 is 70 mm. The electrolytic cell 12 is a 1-liter glass beaker in this example, and the electrolytic solution 15 is a sulfuric acid solution having a concentration of 5% by volume.

The stirring means 17 has stirring blades 17a located at the center of the bottom in the electrolytic cell 12, and driving means 17b for receiving the lower surface of the electrolytic cell 12. The stirring blade 17a is formed by a magnet, and the driving means 17b includes a magnet (not shown) rotatable by a motor. When the motor rotates, the magnet in the driving means 17b rotates,
The stirring blade 17a is rotated by being dragged by this rotation, whereby the electrolyte solution 15 is stirred. 800 ml of the electrolytic solution 15 is injected into the electrolytic cell 12, and 202.21 g of the midgut gland 11c is supplied into the electrolytic solution 15 in a plastic basket. This midgut gland 11
c contains 63.2 mg of cadmium per kg of dried midgut gland (hereinafter referred to as Cd content 63.2 mg / dry kg).

<Embodiment 2> As shown in FIGS. 4 and 5, the anode 13 and the cathode 14 are the same as the above-mentioned embodiment 1 except that they are respectively surrounded by a separator 28. The separator 28 is a filter formed of glass wool paper in this example, and is designed to allow the passage of heavy metal ions and prevent the passage of heavy metal deposited on the cathode 14. Midgut gland 1 in this example
Cadmium cations generated by elution of cadmium contained in 1c into the electrolytic solution 15 can pass through the separator 28, but cadmium deposited on the cathode 14 is separated by the separator 2.
8 can hardly be passed. 4 and 5
1 and 2 denote the same parts.

Example 3 As shown in FIGS. 6 and 7, the anode 3 formed in a cylindrical shape.
3 is inserted into the center of the electrolytic cell 12, and a cathode 34 formed of a cylindrical cadmium having a slightly smaller diameter than the inner diameter of the electrolytic cell 12 is inserted into the electrolytic cell 12 around the anode 33,
Further, it is the same as the first embodiment except that a cylindrical separator 38 having a diameter slightly smaller than that of the cathode 34 is inserted into the electrolytic cell 12 so as to be located inside the cathode 34 with the anode 33 as the center. . The midgut gland 11c is a separator 38
The cathode 34 is separated from the midgut gland 11c by the separator 38. 6 and FIG.
2 and FIG. 2 indicate the same parts.

<Comparative Test and Evaluation> A DC voltage of 5 V was applied between the anode and the cathode in Examples 1 to 3, and the current flowing through each electrolytic solution 15 was maintained at 0.8 to 1.0 A for 24 hours.
During this time, the electrolytic solution 15 is stirred by the stirring blade 17a of the stirring means 17.

[0013]

[Table 1]

The content of cadmium before and after the treatment was measured, and the results shown in Table 1 were obtained. As is evident from Table 1, Cadmium in hepatopancreas 11c becomes cations eluted in the electrolyte solution 15, the cations are deposited on the cathode 14 or 34, a relatively short time midgut gland 1
Almost all of the cadmium contained in 1c was converted to the cathode 14 or 3
4 is deposited. The reason why the cadmium removal rate of the second embodiment is higher than that of the first embodiment is that the cadmium deposited on the cathode 14 hardly adheres to the midgut gland 11c through the separator 28 in the second embodiment. It is believed that there is.
The reason why the cadmium removal rate of the third embodiment is higher than that of the second embodiment is that the cadmium once deposited on the cathode 34 does not separate from the cathode 34 because the cathode 34 is formed of cadmium in the third embodiment. Conceivable.

<Embodiment 4> As shown in FIG. 8, the electrolytic cell 42 is made of vinyl chloride resin in the shape of a rectangular parallelepiped box, and the anodes 43 and the cathodes 44 are alternately arranged at predetermined intervals. Electrolyzer 4
2 so as to be insertable. The anode 43 is formed of a gold-plated titanium plate which is an insoluble metal electrode in this example, and the cathode 44 is formed of a stainless steel plate. The upper ends of the anode 43 and the cathode 44 are a pair of electrode holders 4.
6, 47, respectively, and a pair of electrode holders 4
Reference numerals 6 and 47 are vertically movably held by a pair of support columns 48 and 48 which are erected outside the both ends of the electrolytic cell 42. The anode 43 and the cathode 44 are electrically connected to the DC power supply 16 via a pair of electrode holders 46 and 47. The same electrolytic solution 15 as that of the first embodiment is stored in the electrolytic cell 42. In the electrolytic cell 42, the gut and the kidney 11f other than the scallop and the mantle used for scallop are made of an insulating material (not shown). Supplied in a state. The electrolytic solution 15 in the electrolytic cell 42 is shown
Circulate or bubbling with agitating means
It is constituted so that it may be stirred by doing. 8, the same reference numerals as those in FIG. 1 indicate the same parts.

In the apparatus for removing heavy metals thus constructed, the anode 43 and the cathode 44 are connected to the electrolytic cell 4 along the columns.
2 and put into the electrolytic cell 42 with the scallop midgut gland and the kidney 11f remaining in a net (not shown). In this state, the anode 43 and the cathode 44 are lowered to remove the electrolytic cell 42. Insert Heavy metals such as cadmium and arsenic contained in the midgut glands of the scallop and the kidney 11f are
By stirring with a stirring means (not shown), it gradually elutes into the electrolytic solution 15 and becomes a cation. When the DC power supply 16 is turned on and a DC voltage is applied to the anode 43 and the cathode 44, the heavy metal that has become a cation precipitates on the cathode 44, and at the same time, the heavy metal contained in the midgut gland and the kidney 11 f flows into the electrolyte 15. Ionization is promoted. As a result, almost all of the heavy metals contained in the midgut gland and the kidney 11f can be deposited on the cathode 44 in a relatively short time. After a lapse of a predetermined time, the DC power supply 16 is turned off to raise the anode 43 and the cathode 44 along the support columns, and the net is pulled up to take out the midgut gland and the kidney 11f from the electrolytic bath 42 and wash them with water, if necessary. When the neutralization treatment is performed, the midgut gland and the kidney 11f that can be used as a fertilizer are obtained.

<Embodiment 5> As shown in FIGS.
The electrolytic cell 52 is formed of a vinyl chloride resin into a cylindrical box shape having an opening 52a. The anode 53 is formed of a gold-plated titanium rod, which is an insoluble metal electrode, and stands upright in the center of the electrolytic cell 52. The cathode 54 is formed of cylindrical stainless steel having a diameter slightly smaller than the inner diameter of the electrolytic cell 52 ( (FIG. 9). The electrolytic cell 52 is held by an agitating means 57 so as to be rotatable around the axis of the electrolytic cell 52.
7 is supported by a support 56 (FIGS. 9 to 11). The stirring means 57 includes a substantially U-shaped first holder 57a and a ring-shaped second holder 5 integrally formed with the holder 57a.
7b (FIGS. 10 and 11), a shaft 52b protruding from the center of the bottom surface of the electrolytic cell 52, and a first bearing 57c provided between the first holder 57a, and an opening 52 of the electrolytic cell 52.
a large-diameter second bearing 57d provided between the outer peripheral surface in the vicinity of a and the second holder 57b (FIG. 9), and the electrolytic bath 52 is rotatably held by these members. Electrolyzer 5
The ring gear 57e is fixed to the outer peripheral surface near the bottom surface of the second arm 57, and the arm 57 protrudes from the bottom surface of the first holder 57a.
An electric motor 57g is fixed to the end of f, and a pinion 57i that meshes with the gear 57e is fixed to an output shaft 57h of the motor 57g.

A shaft 57j projects from the center of the first holding member 57a, and is rotatably held at the upper end of the supporting member 56 (FIGS. 10 and 11). A worm wheel 58 is fixed to the shaft 57j, and a motor 59 with a speed reducer is fixed to a bracket 56a protruding from the support member 56. A worm 61 meshing with the wheel 58 is attached to an output shaft 59a of the motor 59. Is fixed. 62 is a slip ring electrically connected to the anode 53, and 63
Is a slip ring electrically connected to the cathode 54 (FIG. 9). These rings 62 and 63 are brushes 64 and 6
4 and is electrically connected to a DC power supply 16. 9, the same reference numerals as those in FIG. 8 indicate the same parts.

In the apparatus for removing heavy metals configured as described above, the motor 59 with a speed reducer is operated to operate the electrolytic cell 52.
With the opening 52a of the scallop facing upward (FIG. 11), the electrolyte solution 1 in which the midgut gland and the kidney 11f of the scallop are mixed in advance.
5 through the opening 52a, and then the motor 5
9 to tilt the opening 52a so as to face obliquely upward (FIG. 9). In this state, when the electric motor 57g is operated to rotate the electrolytic cell 52, the midgut gland and the kidney 11f
And the electrolyte solution 15 are stirred and uniformly mixed, and scallop
Such as cadmium and arsenic contained in the midgut gland and kidney 11f
Heavy metals are gradually eluted into the electrolyte solution 15 to form cations.
You. When turning on the DC power source 16 in this state, the positive ion
The heavy metal that has turned on is deposited on the cathode 54. When the processing is completed, the DC power supply 16 is turned off, the motor 59 with a speed reducer is turned on, the opening 52a of the electrolytic cell 52 is inclined so as to face obliquely downward, and the midgut gland, the kidney 11f, and the electrolytic solution 15 are discharged. (FIG. 10).

<Embodiment 6> As shown in FIGS. 12 to 14, the electrolytic cell 72 is formed in a rectangular tube shape extending horizontally by vinyl chloride resin. At one end of the electrolytic cell 72, the midgut gland and the kidney 11f of the scallop
And a supply port 72a for supplying the electrolytic solution 15 is formed, and a funnel 72b is connected to the supply port 72a (FIG. 1).
2). At the other end of the electrolytic cell 72, a discharge port 72c for discharging the midgut gland , the kidney 11f and the electrolytic solution 15 is formed, and a discharge tank 72d is connected to the discharge port 72c. An inclined conveyor 79 for discharging the treated midgut gland and kidney 11f is installed in the discharge tank 72d, and the midgut gland and kidney 1 conveyed by the inclined conveyor 79 are installed next to the discharge tank 72d.
A horizontal conveyor 81 that receives 1f and conveys it to a container 82 is provided. 83 is the midgut gland and kidney 1 on the horizontal conveyor 81
This is a tray for receiving the electrolytic solution 15 attached to 1f. Anode 7
Reference numeral 3 denotes a screw conveyor formed by an insoluble metal electrode, which in this example is gold-plated titanium. The anode 73 extends in the longitudinal direction of the electrolytic cell 72, is inserted horizontally, and is rotatably held via a pair of bearings 84, 84;
The supply port 72a of the portion inserted into the electrolytic cell 72 of FIG.
And a spiral blade 73b that is fixed to a portion other than the portion opposed to. A stirring blade, which is stirring means 77, is fixed to the portion of the shaft 73a facing the supply port 72a.

At the end of the shaft 73a protruding from the electrolytic cell 72, a motor 8 with a reducer is provided via a coupling 86.
7 is connected to the output shaft 87a, and a slip ring 88 is fixed to the shaft 73a near the coupling 86.
Spiral blade 73 of both side walls 72e, 72e of electrolytic cell 72
a pair of cathodes 74, 74 along the inner surface of the portion facing b
Is arranged. In this example, these cathodes 74, 74 are divided into three along the longitudinal direction of the electrolytic cell 72, and the supply port 72a
From the discharge port 72c toward the first cathode 74a and the second cathode 7
4b and the third cathode 74c. These cathodes 74, 7
4 is a pair of separators 78, 78 for the anode 73 and middle intestine
It is divided from the gland and the kidney 11f. Slip ring 88 and first cathode 74a are connected to DC power supply 76 via first current controller 91, and slip ring 88 and second cathode 74b are connected to DC power supply 76 via second current controller 92. The connection between the slip ring 88 and the third cathode 74c is connected to the DC power supply 76 via the third current controller 93.

The DC power supply 76 is a known power supply and is shown in FIG.
As shown in detail in FIG. 2, an AC having an input voltage of 100 _V to 200 _V can be converted to a DC of 0 _V to 150 _V by adjusting a variable resistor R _V in the phase control circuit. In FIG. 14, C _{1 to} C ₉ are capacitors, R _{1 to} R ₅ are resistors, TD is a trigger diode, SS is a bidirectional three-terminal thyristor, T ₁ is a transformer, F ₁ and F ₂ are fuses, and D ₁ to
D ₄ is diode, CH denotes a choke coil, respectively. The first to third current controllers 91 to 93 are configured so that currents flowing through the slip ring 88 and the first to third cathodes 74a to 74c can be controlled by a controller 94 described later (FIG. 12).

The electrolytic cell 72 has first to third sensors 101 to 101.
103 is inserted. The first sensor 101 has a supply port 72a.
Between the first cathode 74a and the second sensor 102
Is inserted between the first cathode 74a and the second cathode 74b,
The third sensor 103 is inserted between the second cathode 74b and the third cathode 74c. These sensors 101 to 103 are a temperature sensor for detecting the temperature of the electrolytic solution 15 in the electrolytic bath 72, a pH sensor for detecting the pH of the electrolytic solution 15 in the electrolytic bath 72, and an electrolytic solution 15 in the electrolytic bath 72, respectively. And a conductivity sensor for detecting the electrical conductivity of the sample. The detection outputs of the first to third sensors 101 to 103 are connected to the control input of the controller 94, and the control outputs of the controller 94 are the first to third
It is connected to the third current controllers 91 to 93.

The midgut gland and the kidney 11f of the scallop are stored in a biological tank 96, and the electrolyte 15 is stored in an electrolyte tank 97. A stirrer 99 is inserted into the mixing tank 98 into which the midgut gland or kidney 11f and the electrolytic solution 15 are charged at a predetermined ratio, and the stirrer 99 allows the midgut gland or kidney 11f and the electrolytic solution 15 to be uniform. It is stirred to become. One end of the supply pipe 98a connected to the lower portion of the mixing tank 98 has a funnel 7 at the other end.
Face 2b. Further, in the mixing tank 98, a pH sensor 116 for detecting the pH of the electrolytic solution 15 in this tank 98, and this tank 98
Conductivity sensor 1 for detecting the electric conductivity of the electrolyte 15 in the inside
17 are inserted. Reference numerals 104 and 106 are electric valves, 107 is an electromagnetic valve, and valves 104, 10 are provided.
6, 107 are controlled by the controller 94 based on the detection outputs of the sensors 116, 117.

Further, the overflow pipe 72f and the discharge pipe 72g of the discharge tank 72d and the discharge pipe 83a of the tray 83 are connected to a drainage treatment tank 108, and the electrolytic solution 15 purified in this drainage treatment tank 108 is electrolytic bath 72. Is returned to the supply port 72a side by the pump 109 via the return pipe 111. 112 is an electrolytic cell 72
Is a check valve for preventing the electrolyte 15 from flowing into the drainage treatment tank 108 via the return pipe 111.
Numerals 115 are electromagnetic valves. Further, as shown in detail in FIG. 13, a gas vent hole 72i is formed in the upper wall 72h of the electrolytic cell 72, and the bottom wall 72j between the side wall 72e of the electrolytic cell 72 and the cathode 74 is provided with the electrolytic solution 15 having a heavy metal concentration. Is connected to a discharge pipe 72k capable of discharging the water. In FIG.
The same reference numerals indicate the same parts.

In the thus configured apparatus for removing heavy metals, the mid-gut gland and kidney 11f of the scallop mixed in the mixing layer 98 and the electrolyte 15 are supplied to the supply pipe 98a and the funnel 7a.
After being charged into the supply port 72a of the electrolytic cell 72 via the 2b and stirred by the stirring means 77, it is slowly conveyed toward the discharge port 72c by the anode 73 also serving as a screw conveyor. When the electrolyte 15 mixed with the midgut gland and the kidney 11f reaches the position facing the first cathode 74, the pH sensor of the first sensor 101 detects the concentration of the electrolyte 15 close to 5% by volume. Is the first sensor 101
The first current controller 91 is controlled on the basis of the detection output of, and a predetermined voltage is applied between the slip ring 88 and the first cathode 74a to flow a predetermined current through the electrolyte 15.

The concentration of the electrolytic solution 15 arriving at a position facing the second cathode 74b is determined by the slip ring 88 and the first cathode 7
4a, the controller 94 controls the second current controller 92 based on the detection output of the second sensor 102, and the slip ring 88 and the second cathode 74b
A predetermined current is caused to flow through the electrolytic solution 15 by applying a voltage higher than the predetermined voltage in between. Further, the concentration of the electrolytic solution 15 that has reached the position facing the third cathode 74c becomes further thinner, and the controller 94 controls the third current controller 93 based on the detection output of the third sensor 103, and the slip ring 88 and the first A voltage higher than a predetermined voltage is applied between the three cathodes 74c to flow a predetermined current through the electrolytic solution 15. Heavy metals contained in the midgut gland and the kidney 11f are removed toward the outlet 72c of the electrolytic cell 72 and deposited on the first to third cathodes 74a to 74c,
The midgut gland and the kidney 11f reaching the discharge tank 72d hardly contain heavy metals, and can be used as a fertilizer. In this way, heavy metals can be automatically and continuously removed from the midgut gland and kidney 11f of the scallop.

Embodiment 7 As shown in FIGS. 15 and 16, the electrolytic cell 122 is formed in a horizontally elongated box shape, and the anode 123 is formed on a belt conveyor extending along the longitudinal direction of the electrolytic cell 122. The anode 123 is a belt 123 made of a conductive elastic material.
a and a large number of blades 123b projectingly provided on the outer peripheral surface of the belt 123a with a predetermined gap. Feather 123b
Is made of gold-plated titanium, which is an insoluble metal electrode, and transports the midgut glands and kidneys of scallops.
That Yusuke also function as a stirring means for stirring the electrolyte 15.
The cathode 124 is formed on both side walls 122 a, 122 a of the electrolytic cell 122.
Are provided along the inside, and are divided into three like the sixth embodiment. The belt 123a and the cathode 124 are electrically connected to the DC power supply 76 via first to third current controllers (not shown). 15, the same reference numerals as those in FIG. 12 indicate the same parts. The operation of the apparatus configured to remove heavy metals configured as described above is substantially the same as that of the sixth embodiment, and a description thereof will not be repeated.

In the above-mentioned Examples 1 to 7, scallops were mentioned as the organism containing heavy metals, but this is only an example, and organisms such as other marine products, animals, agricultural products or plants may be used as long as they contain heavy metals. In addition, in the above Examples 1 to 3, cadmium is cited as a heavy metal contained in living organisms, but the present invention is not limited to this, and heavy metals such as arsenic, mercury, copper, zinc, nickel, chromium, and manganese may be used. In Examples 1 to 7, the sulfuric acid solution was used as the electrolytic solution. However, as long as the electrolytic solution was used, a sodium hydroxide solution, a sodium chloride solution, a hydrochloric acid solution, or a nitric acid solution may be used. Further, in Examples 1 to 7, the sulfuric acid solution having a concentration of 5% by volume was used, but the concentration may be in the range of 0.5 to 20% by volume, preferably 2 to 10% by volume. The concentration of 0.5 to 20% by volume means that the concentration is 0.
If the concentration is less than 5% by volume, heavy metals contained in living organisms cannot be efficiently deposited on the cathode.
This is because the glands and kidneys are denatured and there is a problem that a lot of time is required for the subsequent neutralization treatment.

In the first, second and fourth to seventh embodiments, the cathode is formed of stainless steel. In the third embodiment, the cathode is formed of cadmium. However, the cathode is formed of copper, zinc, or an alloy thereof. Alternatively, it may be formed by plating copper or stainless steel with cadmium. In Examples 1 to 3 above, the anode was formed of graphite, and in Examples 4 to 7, the anode was formed of gold-plated titanium. However, conductive ferrite, platinum, gold, and platinum plating which are insoluble metal electrodes were used. It may be formed of titanium or graphite coated titanium. Further, although the electrolytic bath is formed of glass in Examples 1 to 3 and the electrolytic bath is formed of vinyl chloride resin in Examples 4 to 7, it may be formed of polystyrene resin, polyethylene resin, FRP or acrylic resin. . Although the separator is formed of glass wool paper, it may be formed of asbestos wool, unfired ceramics, a permeable membrane, or the like.

[0031] Also, although divided into three cathode In Embodiment 6, even without division, or may be even or 4 or more divisions divided into two parts. Further, the anode may be electrically divided corresponding to the cathode. In this case, the shaft and the spiral blade may be made of an insulating material and then coated with a conductive material for electrical division. Example 6
Although the slip ring is used to electrically connect the anode to the current controller in the above, the current controller may be connected to the shaft bearing without using the slip ring.

[0032]

As described above, according to the present invention, an organism containing a heavy metal in a living body and an electrolytic solution for ionizing the heavy metal are supplied to an electrolytic cell having an anode and a cathode ,
The heavy metal cations eluted in the electrolyte by stirring the electrolyte in which the organism is immersed to elute the heavy metals contained in the living body into the electrolyte, and further applying a DC voltage to the anode and the cathode. Since it was deposited on the cathode, it does not damage organisms in a relatively short time.
Ku can remove heavy metals from the organism, its removal rate is extremely high. Further, compared to the conventional decadmium treatment, it is possible to remove heavy metals with a low-concentration electrolytic solution, so that the organisms after treatment can be washed with water in a short time and the amount of water used can be small. It has an anode and a cathode and dissolves heavy metals
Supplying organism that contains a heavy metal in vivo to the electrolytic cell the electrolyte has been stored for reduction, stirring the electrolytic solution organism is immersed
To convert heavy metals contained in the living body into cations in the electrolyte.
In the electrolyte by applying a DC voltage to the anode and cathode.
Cations eluted heavy metals to precipitate on the cathode as well, the same effect can be obtained.

Further the electrolytic cell anode and cathode are arranged with a predetermined interval, organisms and heavy that contain heavy metals in the body
By dissolving the metal storing the electrolytic solution for ionizing electrolyzer
The stirring means stirs the electrolytic solution impregnated with the living organisms in the living organism.
The heavy metals contained in the electrolyte are eluted as cations in the electrolyte.
A direct current power supply electrically connected to the anode and cathode applies a voltage between the anode and cathode to remove heavy metals eluted into the electrolyte.
It is configured to so that precipitating cation cathode same effect as described above can be obtained. In addition, if organisms are placed in a basket or net and stored in an electrolytic cell and only the electrolyte is agitated, all organisms can be removed.
Ku it is possible to remove the heavy metals without causing damage. Also,
An electrolytic cell that separates the cathode from the organism by providing a separator that allows the passage of heavy metal ions generated by elution of the heavy metal contained in the living body of the organism into the electrolytic solution and prevents the passage of heavy metal deposited on the cathode. If it is inserted into, it is possible to prevent the heavy metal deposited on the cathode from reattaching to the organism.

[0034] Further, the detecting a temperature sensor for detecting the temperature of the electrolyte organism containing the heavy metal is mixed into the body, and a pH sensor for detecting the pH of the electrolyte solution, the electrical conductivity of the electrolyte If the controller is configured to control the DC power supply based on each detection output with the electric conductivity sensor,
By adjusting the electric current flowing through the electrolytic solution, the time for removing the heavy metal contained in the organism can be adjusted.

[Brief description of the drawings]

FIG. 1 is a vertical cross-sectional configuration diagram of an apparatus for removing heavy metals contained in a living organism according to a first embodiment of the present invention.

FIG. 2 is a sectional view taken along line AA of FIG.

FIG. 3 is an anatomical view of a scallop containing a heavy metal in a living body.

FIG. 4 is a longitudinal sectional view corresponding to FIG. 1, showing a second embodiment of the present invention.

FIG. 5 is a sectional view taken along line BB of FIG. 4;

FIG. 6 is a longitudinal sectional view corresponding to FIG. 1, showing a third embodiment of the present invention.

FIG. 7 is a sectional view taken along line CC of FIG. 6;

FIG. 8 is a longitudinal sectional view corresponding to FIG. 1, showing a fourth embodiment of the present invention.

FIG. 9 is a longitudinal sectional view corresponding to FIG. 1, showing a fifth embodiment of the present invention.

FIG. 10 is a side view of the device showing a state in which the midgut gland and the electrolyte of the scallop are discharged from the electrolytic cell.

FIG. 11 is a side view of the apparatus corresponding to FIG. 6, showing a state immediately before supplying an electrolytic solution mixed with the scallop midgut gland to the electrolytic cell.

FIG. 12 is a longitudinal sectional view corresponding to FIG. 1, showing a sixth embodiment of the present invention.

FIG. 13 is a sectional view taken along line DD of FIG. 12;

FIG. 14 is an electric circuit diagram showing a DC power source of the apparatus.

FIG. 15 is a vertical sectional view corresponding to FIG. 1, showing a seventh embodiment of the present invention.

16 is a cross-sectional view taken along the line EE of FIG.

[Explanation of symbols]

11 Scallop (organism) 11c Midgut gland of scallop 11f Midgut gland and kidney of scallop 12,42,52,72,122 Electrolyzer 13,33,43,53,73,123 Anode 14,34,44,54 , 74, 124 Cathode 15 Electrolyte 16 , 76 DC power supply 17 , 57 , 77 , 123 Stirring means 28 , 38 , 78 Separator 72a Electrolyte supply port 72c Electrolyte discharge 94 Controller 101 First sensor (temperature sensor, pH sensor, conductivity sensor 102 Second sensor (temperature sensor, pH sensor, conductivity sensor) 103 Third sensor (temperature sensor, pH sensor, conductivity sensor)

Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C25C 1/16 B09B 5/00 E (72) Inventor Katsumi Fujishima 11-1 Nishi, Kita-ku, Sapporo City (72) Inventor: Hideho Murakami, 6-14-11, Minami 14-jo Nishi, Chuo-ku, Sapporo City (72) Inventor: Hiroshi Saito 3-38-13, Asaya-minami, Suginami-ku, Tokyo (56) References JP-A-48-46147 (JP, A) JP-A-6-153863 (JP, A) JP-A-6-106155 (JP, A)

Claims (10)

(57) [Claims] An anode (13, 33, 43, 53, 73, 123) and a cathode (14, 3
An organism (11) containing a heavy metal in a living body and the heavy metal are dissolved in an electrolytic cell (12, 42, 52, 72, 122) having a 4,44,54,74,124).
Sulfuric acid solution, hydrochloric acid solution, sodium hydroxide
Beam solution or electrolyte solution consisting of sodium chloride solution (15) comprising the steps of supplying the organism is immersed electrolyte (15) within said living body stirring
The included a step of the heavy metals in the electrolyte (15) is <br/> eluted as cations are, the anode (13,33,43,53,73,123) to the cathode (14,34,44,5
4,74,124) by applying a DC voltage to dissolve it in the electrolyte solution (15).
Method for removing heavy metals contained in the organism and a step of precipitating the cations out heavy metal in the cathode (14,34,44,54,74,124). 2. An anode (13,33,43,53,73,123) and a cathode (14,3
4,44,54,74,124), which dissolves heavy metals and ionizes them
Sulfuric acid solution, hydrochloric acid solution, sodium hydroxide solution or sodium chloride
An electrolytic cell (1) containing an electrolytic solution (15) consisting of thorium solution
It is supplied to 2) organisms that contain the heavy metals in the body (11)
And a step of stirring the electrolyte solution (15) in which the organism is immersed in the living body.
A step of eluting the heavy metal contained in the electrolyte solution (15) as a cation , the anode (13,33,43,53,73,123) and the cathode (14,34,44,5).
4,74,124) by applying a DC voltage to dissolve it in the electrolyte solution (15).
Method for removing heavy metals contained in the organism and a step of precipitating the cations out heavy metal in the cathode (14,34,44,54,74,124). 3. An anode (13,33,43,53,73,123) and a cathode (14,3
4,44,54,74,124) are disposed at a predetermined interval and the living body (11) containing a heavy metal in the living body and the heavy metal are dissolved.
Sulfuric acid solution, hydrochloric acid solution, sodium hydroxide solution to be ionized
Solution or an electrolytic solution comprising a sodium chloride solution (15) and an electrolytic tank (12, 42, 52, 72, 122) capable of storing the biological cell (11) in the electrolytic tank (12, 42, 52, 72, 122). Is soaked
Stirring the electrolyte solution (15), the heavy metal contained in the living body
Agitation to elute the genus as a cation in the electrolyte (15)
Means (17,57,77,123b), the anode (13,33,43,53,73,123) and the cathode (14,34,44,5)
4,74,124) and the anode (13,33,43,53,7)
3,123) and the cathode (14, 34, 44, 54, 74, 124) to apply a voltage between the heavy metal cations eluted in the electrolyte (15).
DC power source (16, 7 ) deposited on the cathode (14, 34, 44, 54, 74, 124)
6) An apparatus for removing heavy metals contained in a living organism, comprising: 4. An organism (11) containing a heavy metal in a living body,
Sulfuric acid solution and hydrochloric acid solution that dissolve and ionize the heavy metals
Liquid, sodium hydroxide solution or sodium chloride solution
And an electrolytic bath (42) capable of storing an electrolytic solution (15), and formed between the electrolytic bath (42) so that it can be inserted into a predetermined space.
An anode (43) and a cathode (44), which are alternately arranged at an interval, and the anode (43) and the cathode which are erected outside the electrolytic cell (42).
A column (48, 48) for holding the pole (44) so as to be vertically movable, and circulating or bubbling the electrolyte (15) in the electrolytic cell (42).
A stirring means for further stirring, and the anode (43) and the cathode (44) electrically connected to the positive
Electrolyte by applying a voltage between the pole (43) and the cathode (44)
The heavy metal cations eluted in (15) are deposited on the cathode (44).
A device for removing heavy metals contained in living organisms, which is provided with a direct current power supply (16) . 5. A cylindrical shape having an opening (52a) at one end.
Organisms containing heavy metals in the living body (11) and the heavy metals
To dissolve and ionize sulfuric acid, hydrochloric acid solution, sodium hydroxide
Electrolyte consisting of thorium solution or sodium chloride solution (1
5) an electrolytic cell (52) capable of storing, an anode (53) standing upright in the center of the electrolytic cell (52), and a cathode provided along the inner peripheral surface of the electrolytic cell (52) (54)
The electrolytic cell (52) can be rotated around the axis of the electrolytic cell (52).
And the organism (11) in the electrolytic cell (52) is immersed.
Stirring the electrolyte solution (15), the heavy metals contained in the living body.
Stirrer that elutes as a cation into the electrolytic solution (15)
The step (57) and the stirring means (57) are connected via a shaft (57j) projecting in the horizontal direction.
Supporter (56) for rotatably supporting the positive electrode (53) and the positive electrode (53) and the negative electrode (54) that are electrically connected.
A voltage is applied between the electrode (53) and the cathode (54) to apply the electrolytic solution.
The heavy metal cations eluted in (15) were deposited on the cathode (54).
A device for removing heavy metals contained in living organisms, which is provided with a direct current power supply (16) . 6. A predetermined interval between the anode (73,123) and the cathode (74,124)
Biological organisms (1
1) and sulfuric acid solution that dissolves and ionizes the heavy metal, hydrochloric acid
Solution, sodium hydroxide solution or sodium chloride solution
An electrolytic cell (72, 122) capable of storing an electrolytic solution (15) made of the same, and the living organism (11) provided in the electrolytic cell (72, 122).
A supply port (72a) for supplying to the thawing tank (72, 122), and the living organism (11) provided in the electrolyzing tank (72, 122);
(72, 122), the outlet (72c), the anode (73, 123) and the cathode (74, 124).
A voltage is applied between the anode (73,123) and the cathode (74,124).
Heavy metals contained in living organisms with a direct current power supply (76)
A device for removing the anode (73, 123) the organism (11) the supply port (72a)
From the electrolytic cell (72, 122)
The electrolyte (15) in which the organism (11) of
The heavy metal contained in the living body is converted into a cation in the electrolytic solution (15).
The DC power supply (76) elutes in the electrolyte solution (15) when the DC power supply (76) is applied.
To deposit heavy metal cations on the cathode (74,124)
An apparatus for removing heavy metals contained in a living organism, wherein the apparatus is configured. 7. The apparatus for removing heavy metals contained in living organisms according to claim 3 , wherein the concentration of the sulfuric acid solution (15) is 0.5 to 20% by volume. 8. remove heavy metals at least the surface of the cathode (44,54,74,124) is contained in stainless steel, cadmium, copper, zinc or organisms of claims 3 formed by these alloys 6 wherein any Equipment to do. 9. A heavy metal contained in the living body of a living organism (11) is allowed to pass through a heavy metal ion produced by eluting into an electrolytic solution (15), and a heavy metal deposited on a cathode (74,124) is allowed to pass through. An apparatus for removing heavy metals contained in living organisms according to claim 3, wherein a blocking separator (78) is inserted into the electrolytic cell (72, 122) so as to partition the cathode (74, 124) from the living organism (11). 10. A temperature sensor (101, 102, 103) inserted into an electrolytic cell (72) and detecting a temperature of an electrolytic solution (15) mixed with a living body (11) containing a heavy metal in a living body; 72) pH sensor (101, 102, 103) inserted into the electrolytic solution (15) to detect the pH, and a conductivity sensor (101, 102, 103) inserted into the electrolytic cell (72) to detect the electrical conductivity of the electrolytic solution (15). ), The temperature sensor (101, 102, 103) and the pH sensor (101, 10
The apparatus for removing heavy metals contained in living organisms according to claim 3, comprising: a controller (94) for controlling a DC power supply (76) based on each detection output of the conductivity sensor (101, 102, 103).