JPH0899001A - Method for removing heavy metal included in living body and its device - Google Patents

Abstract

PURPOSE: To remove heavy metals from a living body in a relatively short time, to make the removing ratio extremely high, to make the processing time adjustable, to miniaturize the device to make the amt. of use of water relatively small and to perform easily water discharge processing. CONSTITUTION: An anode 13 and a cathode 14 are arranged at a specified interval in an electrolytic cell 12 wherein midgud glands 11c of scallops contg. heavy metals and an electrolyte 15 can be stored and a DC electric source 16 electrically connected with the anode 13 and the cathode 14 applies an electric voltage between the anode 13 and the cathode 14. The electrolyte is a sulfuric acid soln. with a concn. of 5vol.% and the cathode 14 is formed of a stainless steel. A stirring means 17 for stirring and mixing the midgut glands 11c and the electrolyte 15 is installed in an electrolytic cell 12.

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 line called uro of scallop and the kidney attached to the side of the scallop. Especially, the concentration of cadmium and arsenic in the midgut 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 line or kidney for feed fertilizer without any treatment. Or it was incinerated. However, there is a problem that it costs a lot of money to bury or incinerate the above-mentioned midgut line and kidneys,
Reservation of buried land has reached its limit. Further, there is a possibility that heavy metals contained in the buried midgut and kidney may infiltrate the groundwater and contaminate the groundwater.

In order to eliminate these points, the Hokkaido Industrial Research Institute immerses the soft body part such as the scallop midgut wire in a sulfuric acid solution and then rinses it with water 3 times in another water tank to remove cadmium from the midgut wire. The cadmium-free treatment was carried out, and the results are reported in the FY1993 joint research (priority) report, "Research and development on treatment and utilization technology of scallop by-products" (Hokkaido Central Fisheries Experimental Station, Industrial Testing Station, Sanitation Research Center, Central Research Institute). Agricultural Experiment Station and Takigawa Livestock Experiment Station). This treatment is carried out by immersing the soft body part such as the midgut line in a sulfuric acid solution for 24 hours, and then washing the soft body part with water 3 times for 5 hours each, whereby 98% of cadmium can be removed from the soft body part by the above treatment. it can.

[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 in size when it is attempted to process a large amount of soft body parts such as the midgut line at one 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.

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 in a relatively short time, have an extremely high removal rate, and can adjust the treatment time. To do. 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.

[0006]

The structure of the present invention for achieving the above object will be described with reference to FIGS. 1, 3 and 12 corresponding to the embodiments. The first method of the present invention is, as shown in FIGS. 1 and 3, in an electrolytic cell 12 having an anode 13 and a cathode 14, a living organism 11 containing a heavy metal in a living body and an electrolytic solution 1.
5 is supplied to dissolve the heavy metal into the electrolytic solution 15, and a DC voltage is applied to the anode 13 and the cathode 14 to remove the heavy metal from the cathode 1.
4 to deposit. The second method of the present invention is
A step of supplying a living body 11 containing a heavy metal in a living body and eluting the heavy metal into the electrolytic solution 15 into an electrolytic cell 12 having an anode 13 and a cathode 14 and storing an electrolytic solution 15;
And a step of applying a DC voltage to the cathode 14 to deposit a heavy metal on the cathode 14. As shown in FIG. 12, an apparatus for removing heavy metals contained in a living organism of the present invention has an anode 73 and a cathode 74 arranged at a predetermined interval and a living organism 11f containing a heavy metal in a living body and an electrolyte solution 15 And a DC power supply 76 that is electrically connected to the anode 73 and the cathode 74 and applies a voltage between the anode 73 and the cathode 74.

[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 electrolyte solution 15, the heavy metal is gradually eluted into the electrolyte solution 15 and becomes a cation. Anode 13
When a DC voltage is applied to the cathode 14 and the cathode 14, the heavy metal turned into cations is deposited on the cathode 14 and the ionization of the heavy metal contained in the organism 11 into the electrolyte solution 15 is promoted. Almost all heavy metals contained in living organisms are cathodes 1
4 can be deposited.

[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, the midgut line 1 called a uro is located between the scallop 11a and the ligament 11b of the scallop 11.
1c is located in this midgut line 11c and has a high concentration (tens of p
pm) cadmium (Cd) is accumulated. Again 1
1d is a mantle called a string, and 11e is a kidney. As shown in FIGS. 1 and 2, the midgut line 11c and the electrolytic solution 15 are stored in an electrolytic cell 12 in which an anode 13 and a cathode 14 are arranged at a predetermined interval, and the anode 13 and the cathode 14 are stored.
A DC power supply 16 is electrically connected to the. Midgut line 11c
Although not shown, it is immersed in the electrolytic solution 15 in the electrolytic cell 12 while being placed in a plastic basket. Further, the electrolytic solution 15 in the electrolytic bath 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, and the distance between the anode 13 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 a stirring blade 17a located in the center of the bottom of the electrolytic cell 12 and a 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 has 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 line 11c is supplied to the electrolytic solution 15 while being put in a plastic basket. This midgut line 11
c contains 63.2 mg of cadmium per 1 kg of dried midgut (hereinafter, referred to as Cd content of 63.2 mg / dry kg).

<Embodiment 2> As shown in FIGS. 4 and 5,
The same as Example 1 except that the anode 13 and the cathode 14 were surrounded by the separators 28, respectively. 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. In this example, the cadmium contained in the midgut 11c is eluted into the electrolytic solution 15 and the generated cadmium cations can pass through the separator 28, but the cadmium deposited on the cathode 14 can hardly pass through the separator 28. There is. 4 and 5, the same reference numerals as those in FIGS. 1 and 2 indicate the same parts.

<Embodiment 3> As shown in FIGS. 6 and 7,
A column-shaped anode 33 is inserted in the center of the electrolytic cell 12, and a cathode 34 made of cylindrical cadmium having a diameter slightly smaller than the inner diameter of the electrolytic cell 12 is inserted into the electrolytic cell 12 with the anode 33 as the center. Further, the same as Example 1 except that a separator 38 formed in a cylindrical shape 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 a center. is there. The midgut line 11c is supplied to the inside of the separator 38 and the cathode 34
Is separated from the midgut line 11c by the separator 38.
6 and 7, the same reference numerals as those in FIGS. 1 and 2 indicate the same parts.

<Comparison Test and Evaluation> A DC voltage of 5 V was applied between the anode and cathode of Examples 1 to 3, and the current flowing in each electrolyte 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 clear from Table 1, cadmium contained in the midgut line 11c is eluted into the electrolytic solution 15 to become a cation, and this cation is deposited on the cathode 14 or 34, and the midgut line 1 is relatively short.
Almost all of the cadmium contained in 1c was converted to the cathode 14 or 3
4 is deposited. The reason why the removal rate of cadmium in Example 2 is better than that in Example 1 is that in Example 2, cadmium deposited on the cathode 14 hardly passes through the separator 28 and reattaches to the midgut line 11c. it is conceivable that.
Further, the reason why the removal rate of cadmium is better in Example 3 than in Example 2 is that in Example 3, since the cathode 34 was formed of cadmium, the cadmium once deposited on the cathode 34 does not separate from the cathode 34. Conceivable.

<Embodiment 4> As shown in FIG.
2 is made of vinyl chloride resin in the shape of a rectangular box,
The anodes 43 and the cathodes 44 are alternately arranged at predetermined intervals and are formed so as to be inserted into the electrolytic cell 42.
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 held by a pair of electrode holders 46 and 47, respectively, and the pair of electrode holders 46 and 47 move up and down on a pair of columns 48 and 48 that are erected outside both ends of the electrolytic cell 42. Retained as possible. The anode 43 and the cathode 44 are a pair of electrode holders 4.
It is electrically connected to the DC power supply 16 via 6, 47.
In addition, the same electrolytic solution 15 as that of the first embodiment is stored in the electrolytic bath 42, and in this electrolytic bath 42, the midgut line other than the scallops and mantles used for scallops and the kidney 11f are formed into a net made of an insulating material (not shown). Supplied as supplied. 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.
In the state of being raised above 2, the scallop midgut line and the kidney 11f are put into the electrolytic bath 42 while being kept in the net (not shown), and in this state, the anode 43 and the cathode 44 are lowered to the electrolytic bath 42. insert. Heavy metals such as cadmium and arsenic contained in the midgut of the scallop and the kidney 11f are gradually dissolved in the electrolytic solution 15 by being immersed in the electrolytic solution 15 to become cations. The DC power source 16 is turned on to turn on the anode 43 and the cathode 44.
When a DC voltage is applied to the cathode, the heavy metal that has become positive ions is deposited on the cathode 44, and at the same time, the ionization of the heavy metal contained in the midgut line and the kidney 11f into the electrolytic solution 15 is promoted. As a result, almost all the heavy metals contained in the midgut 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, the anode 43 and the cathode 44 are raised along the support columns, the net is pulled up, the midgut line and the kidney 11f are taken out from the electrolytic bath 42, and washed with water. By the Japanese treatment, the midgut line and kidney 11f of the scallop, which 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.
It has 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 these members hold the electrolytic cell 52 rotatably. 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 is projectingly provided at the center of the first holder 57a, and the shaft 57j is rotatably held on the upper end of the support 56 (FIGS. 10 and 11). A worm wheel 58 is fixed to the shaft 57j, a motor 59 with a reduction gear is fixed to a bracket 56a protruding from the support tool 56, and 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, 63 are brushes 64, 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.
Electrolyte solution 1 in which the midgut line of the scallop and the kidney 11f were mixed in advance with the opening 52a of the shell facing upward (FIG. 11)
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 line and the kidney 11f
And the electrolyte solution 15 are agitated and uniformly mixed, and a direct current of 1
When 6 is turned on, the heavy metal of the midgut line and the kidney 11f becomes the cathode 5
4 is deposited. 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 line, 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 of a vinyl chloride resin in a horizontally extending rectangular tube shape. A supply port 72a for supplying the midgut line of the scallop, the kidney 11f and the electrolytic solution 15 is formed at one end of the electrolytic cell 72, and the funnel 7 is provided in the supply port 72a.
2b is connected (FIG. 12). At the other end of the electrolytic cell 72, there is a discharge port 72 for discharging the midgut line, the kidney 11f and the electrolytic solution 15.
c is formed, and a discharge tank 72d is provided at the discharge port 72c.
Are connected. An inclined conveyor 79 for discharging the treated midgut line and kidney 11f is installed in the discharge tank 72d, and next to the discharge tank 72d, the midgut line and kidney 11f conveyed by the inclined conveyor 79 are received and conveyed to the container 82. A horizontal conveyor 81 is provided. Reference numeral 83 is a pan for receiving the electrolytic solution 15 attached to the midgut line and the kidney 11f on the horizontal conveyor 81. The anode 73 is a screw conveyor formed by an insoluble metal electrode, which in this example is gold plated titanium. This anode 73
Is a shaft 73a which extends in the longitudinal direction of the electrolytic cell 72 and is inserted horizontally and is rotatably held via a pair of bearings 84, 84, and a supply port 72a of a portion of the shaft 73a inserted into the electrolytic cell 72. 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.
Of the side walls 72e, 72e of the electrolytic cell 72, the spiral blade 73
a pair of cathodes 74, 74 along the inner surface of the portion facing b
Is provided. 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 divided into the anode 73 and the midgut line or kidney 11f by a pair of separators 78,78. 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 the 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 line and kidney 11f of the scallop are stored in the organism tank 96, and the electrolytic solution 15 is stored in the electrolytic solution tank 97. A stirrer 99 is inserted into the mixing tank 98 in which the midgut line or kidney 11f and the electrolytic solution 15 are charged at a predetermined ratio, and the stirrer 99 makes the midgut line or kidney 11f and the electrolytic solution 15 uniform. Is stirred as. 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 electrical conductivity of the electrolyte solution 15 in
17 and 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. The pump 109 returns the gas to the supply port 72a side through the return pipe 111. 112 is the 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.
˜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. A discharge pipe 72k capable of discharging is connected. In FIG.
The same reference numerals denote the same parts.

In the device for removing heavy metals thus constructed, the midgut line 11f of the scallop and the kidney 11f and the electrolyte solution 15 mixed in the mixing layer 98 are supplied to the supply pipe 98a and the funnel 7.
After being charged into the supply port 72a of the electrolytic cell 72 via 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 electrolytic solution 15 mixed with the midgut or the kidney 11f arrives at the position facing the first cathode 74, the pH sensor of the first sensor 101 detects the concentration of the electrolytic solution 15 close to 5% by volume. First sensor 101
The first current controller 91 is controlled on the basis of the detection output of, and a predetermined current is applied to the electrolytic solution 15 by applying a predetermined voltage between the slip ring 88 and the first cathode 74a.

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
It becomes thin due to the electrolytic action between 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 voltage larger than a predetermined voltage is applied between them to flow a predetermined current through the electrolytic solution 15. 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 line and kidney 11f are removed as they go to the outlet 72c of the electrolytic cell 72 and are deposited on the first to third cathodes 74a to 74c,
The midgut line and the kidney 11f reaching the discharge tank 72d contain almost no heavy metals, and can be used as feed fertilizer. In this way, heavy metals can be automatically and continuously removed from the midgut of the scallop and the kidney 11f.

<Embodiment 7> As shown in FIGS. 15 and 16, the electrolytic cell 122 is formed in a horizontally long box shape, and the anode 123 is formed.
Is formed on a belt conveyor extending along the length of the electrolytic cell 122. The anode 123 includes a belt 123a formed of a conductive elastic body, and a large number of blades 123b protruding from the outer peripheral surface of the belt 123a with a predetermined gap.
Have and. The blade 123b is formed of gold-plated titanium which is an insoluble metal electrode. The cathode 124 is provided along the inside of both side walls 122a, 122a of the electrolytic cell 122, and is divided into three as in the sixth embodiment. Belt 1
23a and the cathode 124 are electrically connected to the DC power supply 76 via first to third current controllers (not shown). FIG.
12, 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. Further, although cadmium was mentioned as the heavy metal contained in the organism in the above-mentioned Examples 1 to 3, 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 it is less than 5% by volume, the heavy metals contained in the organism cannot be efficiently deposited on the cathode, and if the concentration exceeds 20% by volume, the midgut line and kidney will be deteriorated, and much time will be required for the subsequent neutralization treatment. This is because there is a defect.

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. Further, although the anode was formed of graphite in Examples 1 to 3 and the anode was formed of gold-plated titanium in Examples 4 to 7, conductive ferrite, platinum, gold, or a platinum-plated insoluble metal electrode was used. It may be formed of titanium, titanium coated with graphite, or the like. 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. . Further, although the separator is formed of glass wool paper, it may be formed of asbestos wool, unglazed ceramics, permeation film, or the like.

Further, the electrolytic solution in the electrolytic cell of Example 4 may be circulated or bubbled to stir. Further, although the cathode is divided into three in the sixth embodiment, it may be divided into two, divided into two, or divided into four or more. 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. Further, although the slip ring is used to electrically connect the anode to the current controller in the sixth embodiment, the current controller may be connected to the bearing of the shaft without using the slip ring.

[0032]

As described above, according to the present invention, an organism having a heavy metal contained in a living body and an electrolytic solution are supplied to an electrolytic cell having an anode and a cathode to elute the heavy metal into the electrolytic solution. Since a DC voltage is applied to the cathode to deposit the heavy metal on the cathode, the heavy metal can be removed from the organism in a relatively short time, and the 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. In addition, an organism containing heavy metals in the living body is supplied to an electrolytic cell having an anode and a cathode and an electrolyte is stored therein, and the heavy metals are eluted into the electrolyte, and a DC voltage is applied to the anode and the cathode to apply the heavy metals to the cathode. The same effect as described above can be obtained even if it is constituted so as to precipitate.

A direct current power source in which a living body containing a heavy metal and an electrolytic solution are stored in an electrolytic cell in which an anode and a cathode are arranged with a predetermined gap, and which is electrically connected to the anode and the cathode. Even if it is configured to apply a voltage between the anode and the cathode, the same effect as described above can be obtained. Further, if the organism is put in a cage, a net or the like and stored in the electrolytic cell and only the electrolytic solution is stirred, the heavy metal can be removed without damaging the organism. Further, when the stirring means is configured to stir and mix the organism stored in the electrolytic cell with the electrolytic solution, the deposition time of the heavy metal contained in the organism on the cathode can be further shortened. In addition, a heavy metal contained in the living body of a living body separates the cathode from the living body by a separator that allows the passage of heavy metal ions generated by elution in the electrolytic solution and prevents the passage of heavy metal deposited on the cathode. If it is inserted into the electrolytic cell, the heavy metal deposited on the cathode can be prevented from reattaching to the organism.

Further, the electrolytic cell is provided with a supply port for supplying a living body containing a heavy metal in the living body to the electrolytic cell and an outlet for discharging the biological body from the electrolytic cell, and an anode is provided for discharging the biological body from the supply port. By using a conveyor that conveys to, the heavy metal can be continuously removed from the organism, and the device can be downsized. Furthermore, a temperature sensor that detects the temperature of an electrolytic solution in which organisms containing heavy metals in the living body are detected, a pH sensor that detects the pH of the electrolytic solution, and an electrical conductivity sensor that detects the electrical conductivity of the electrolytic solution. If the controller is configured to control the DC power supply on the basis of each detection output of the above, the time for removing the heavy metal contained in the organism can be adjusted by adjusting the current flowing in the electrolytic solution.

[Brief description of 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 heavy metals in the living body.

FIG. 4 is a vertical cross-sectional configuration diagram 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 vertical cross-sectional configuration diagram corresponding to FIG. 1 showing a third embodiment of the present invention.

7 is a cross-sectional view taken along the line CC of FIG.

FIG. 8 is a vertical cross-sectional configuration diagram 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 apparatus showing a state in which scallop midgut lines and an electrolytic solution are being 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 in which the scallop midgut wire is mixed to the electrolytic cell.

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

13 is a cross-sectional view taken along line DD of FIG.

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 (living body) 11c Scallop midgut line 11f Scallop midgut line and kidney 12,42,52,72,122 Electrolyzer 13,33,43,53,73,123 Anode 14,34,44,54,74 , 124 cathode 15 electrolytic solution 16,76 direct current power supply 17, 57, 77 stirring means 28, 38, 78 separator 72a electrolytic cell supply port 72c electrolytic cell discharge port 94 controller 101 first sensor (temperature sensor, pH sensor, conduction) Temperature sensor) 102 second sensor (temperature sensor, pH sensor, conductivity sensor) 103 third sensor (temperature sensor, pH sensor, conductivity sensor)

[Procedure amendment]

[Submission date] October 18, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

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.
Of the side walls 72e, 72e of the electrolytic cell 72, the spiral blade 73
a pair of cathodes 74, 74 along the inner surface of the portion facing b
Is provided. 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 partitioned from the anode 73 and the midgut line and kidney 11f by a pair of separators 78,78. 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. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 10, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0002

[Correction method] Change

[Correction content]

[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 it 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. Further, heavy metals contained in the buried midgut glands and kidneys may infiltrate the groundwater and contaminate the groundwater.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction content]

[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.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[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.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

[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, the midgut gland 1 called a uro is located between the scallop 11a and the ligament 11b of the scallop 11.
1c is located in this midgut gland 11c and has a high concentration (tens of p
pm) cadmium (Cd) is accumulated. Again 1
1d is a mantle called a string, and 11e is a kidney. As shown in FIG. 1 and FIG. 2, the midgut gland 11c and the electrolytic solution 15 are stored in an electrolytic cell 12 in which an anode 13 and a cathode 14 are arranged at a predetermined interval, and the anode 13 and the cathode 14 are stored.
A DC power supply 16 is electrically connected to the. Midgut gland 11c
Although not shown, it is immersed in the electrolytic solution 15 in the electrolytic cell 12 while being placed in a plastic basket. Further, the electrolytic solution 15 in the electrolytic bath 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, and the distance between the anode 13 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.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

The stirring means 17 has a stirring blade 17a located in the center of the bottom of the electrolytic cell 12 and a 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 has 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).

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

<Embodiment 2> As shown in FIGS. 4 and 5,
The same as Example 1 except that the anode 13 and the cathode 14 were surrounded by the separators 28, respectively. 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. Cadmium contained in the midgut gland 11c in this example cadmium cations generated eluted into the electrolytic solution 15 can pass through the separator 28, cadmium deposited on the cathode 14 so as hardly pass through the separator 28 ing. 4 and 5, the same reference numerals as those in FIGS. 1 and 2 indicate the same parts.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

<Embodiment 3> As shown in FIGS. 6 and 7,
A column-shaped anode 33 is inserted in the center of the electrolytic cell 12, and a cathode 34 made of cylindrical cadmium having a diameter slightly smaller than the inner diameter of the electrolytic cell 12 is inserted into the electrolytic cell 12 with the anode 33 as the center. Further, the same as Example 1 except that a separator 38 formed in a cylindrical shape 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 a center. is there. Midgut
The gland 11c is supplied to the inside of the separator 38, and the cathode 34
Is separated from the midgut gland 11c by the separator 38.
6 and 7, the same reference numerals as those in FIGS. 1 and 2 indicate the same parts.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

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.
Further, the reason why the removal rate of cadmium is better in Example 3 than in Example 2 is that in Example 3, since the cathode 34 was formed of cadmium, the cadmium once deposited on the cathode 34 does not separate from the cathode 34. Conceivable.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

<Embodiment 4> As shown in FIG.
2 is made of vinyl chloride resin in the shape of a rectangular box,
The anodes 43 and the cathodes 44 are alternately arranged at predetermined intervals and are formed so as to be inserted into the electrolytic cell 42.
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 held by a pair of electrode holders 46 and 47, respectively, and the pair of electrode holders 46 and 47 move up and down on a pair of columns 48 and 48 that are erected outside both ends of the electrolytic cell 42. Retained as possible. The anode 43 and the cathode 44 are a pair of electrode holders 4.
It is electrically connected to the DC power supply 16 via 6, 47.
In addition, the same electrolytic solution 15 as that of the first embodiment is stored in the electrolytic bath 42, and in the electrolytic bath 42, the midgut glands other than the scallops and mantles used for scallops and the kidney 11f are made of a net made of an insulating material (not shown). Supplied in the state of being put in. 8, the same reference numerals as those in FIG. 1 indicate the same parts.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

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, the midgut gland and kidney 11f of the scallop are put into the electrolytic bath 42 while being kept in the net (not shown), and in this state, the anode 43 and the cathode 44 are lowered to drop the electrolytic bath 42. To insert. Heavy metals such as cadmium and arsenic contained in the midgut gland of the scallop and the kidney 11f are gradually dissolved in the electrolytic solution 15 by being immersed in the electrolytic solution 15 to become cations. The DC power source 16 is turned on to turn on the anode 43 and the cathode 44.
When a DC voltage is applied to the negative electrode, the heavy metal that has become positive ions is deposited on the cathode 44, and at the same time, the heavy metal contained in the midgut gland and the kidney 11f is promoted to be ionized into the electrolytic solution 15. As a result, almost all 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, the anode 43 and the cathode 44 are raised along the pillars, the net is pulled up, the midgut gland and the kidney 11f are taken out from the electrolytic bath 42, and washed with water. If necessary, a neutralization treatment is performed to obtain the midgut gland and kidney 11f of the scallop, which can be used as fertilizer.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

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.
Electrolyte solution 1 in which the midgut gland and kidney 11f of the scallop were mixed in advance with the opening 52a of the shell facing upward (FIG. 11).
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 agitated and uniformly mixed, and a direct current of 1
When 6 is turned on, the heavy metal of the midgut gland and the kidney 11f becomes the cathode 5
4 is deposited. 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).

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

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

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

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.
Of the side walls 72e, 72e of the electrolytic cell 72, the spiral blade 73
a pair of cathodes 74, 74 along the inner surface of the portion facing b
Is provided. 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.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

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 electrical conductivity of the electrolyte solution 15 in
17 and 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.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

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 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 electrolytic solution 15 in which the midgut gland and the kidney 11f are mixed arrives at the position facing the first cathode 74, the pH sensor of the first sensor 101 detects the concentration of the electrolytic solution 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 current is applied to the electrolytic solution 15 by applying a predetermined voltage between the slip ring 88 and the first cathode 74a.

[Procedure Amendment 16]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

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
It becomes thin due to the electrolytic action between 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 voltage larger than a predetermined voltage is applied between them to flow a predetermined current through the electrolytic solution 15. 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 kidney 11f are removed as they go to the outlet 72c of the electrolytic cell 72 and are deposited on the first to third cathodes 74a to 74c,
The midgut glands and the kidney 11f that have reached the discharge tank 72d contain almost no heavy metals and can be used as feed fertilizer. In this way, heavy metals can be automatically and continuously removed from the midgut gland and kidney 11f of the scallop.

[Procedure Amendment 17]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

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. Further, although cadmium was mentioned as the heavy metal contained in the organism in the above-mentioned Examples 1 to 3, 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 less than 5% by volume, heavy metals contained in organisms cannot be efficiently deposited on the cathode, and if the concentration exceeds 20% by volume, the midgut
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.

[Procedure 18]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of 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 heavy metals in the living body.

FIG. 4 is a vertical cross-sectional configuration diagram 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 vertical cross-sectional configuration diagram corresponding to FIG. 1 showing a third embodiment of the present invention.

7 is a cross-sectional view taken along the line CC of FIG.

FIG. 8 is a vertical cross-sectional configuration diagram 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.

13 is a cross-sectional view taken along line DD of FIG.

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 scallops (organisms) 11c intestinal gland and kidney in in the intestine glands 11f scallops scallop 12,42,52,72,122 electrolyzer 13,33,43,53,73,123 anode 14, 34,44,54,74,124 Cathode 15 Electrolyte solution 16,76 DC power supply 17,57,77 Stirring means 28,38,78 Separator 72a Electrolyte tank inlet 72c Electrolyzer outlet 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)

[Procedure Amendment 19]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 1

[Correction method] Change

[Correction content]

FIG.

[Procedure amendment 20]

[Document name to be corrected] Drawing

[Name of item to be corrected] Fig. 4

[Correction method] Change

[Correction content]

[Figure 4]

[Procedure correction 21]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 6

[Correction method] Change

[Correction content]

[Figure 6]

[Procedure correction 22]

[Document name to be corrected] Drawing

[Correction target item name] Figure 8

[Correction method] Change

[Correction content]

[Figure 8]

[Procedure amendment 23]

[Document name to be corrected] Drawing

[Correction target item name] Figure 9

[Correction method] Change

[Correction content]

[Figure 9]

[Procedure correction 24]

[Document name to be corrected] Drawing

[Name of item to be corrected] Fig. 12

[Correction method] Change

[Correction content]

[Fig. 12]

Continuation of the front page (71) Applicant 594161840 Katsumi Fujishima Kita-ku Kita-ku, Kita-ku, Kita-ku 11 West 11-chome, Hokkaido Industrial Research Institute (71) Applicant 594161851 Murakami Hideho, Chuo-ku, Chuo-ku, Sapporo 6-5-5 No. 11 (71) Applicant 591013355 Hiroshi Saito 3-38-13, Minami Asaya, Suginami-ku, Tokyo (72) Inventor Yoichi Sakuda 11-chome, Kita-ku, Kita-ku, Kita-ku, Sapporo 11 Hokkaido Industrial Research Institute (72) Inventor Keiichi Tomita 11-chome, Kita-ku, Kita-ku, Sapporo 11-chome, Hokkaido Industrial Test Station (72) Inventor Gosumi Wakasugi 11-chome, Kita-ku, Kita-ku, Kita-ku 11, Hokkaido (72) Invention Person Katsumi Fujishima 11-chome, Kita-ku, Kita-ku, Kita-ku, Sapporo 11 Hokkaido Industrial Test Station (72) Inventor Hideho Murakami 6-11-5, Minami 11-jo Nishi, Chuo-ku, Sapporo (72) Inventor Hiroshi Saito Tokyo No. 38-13-201, 3-38, Asaya Minami, Suginami-ku, Miyako

Claims (10)

[Claims] 1. An anode (13,33,43,53,73,123) and a cathode (14,3)
4,44,54,74,124) with an electrolytic cell (12,42,52,72,122) having a heavy metal in the living organism in the living body (11) and an electrolytic solution (15) and supplying the heavy metal to the electrolytic solution ( 15) elution step, the anode (13,33,43,53,73,123) and the cathode (14,34,44,5
A DC voltage is applied to the heavy metal to form the cathode (14,3,4,124).
4, 44, 54, 74, 124) and a step of removing heavy metals contained in an organism. 2. Anode (13,33,43,53,73,123) and cathode (14,3
4,44,54,74,124) and has an electrolytic solution (15)
Supplying an organism (11) containing a heavy metal in the living body (15) and eluting the heavy metal into the electrolytic solution (15), the anode (13,33,43,53,73,123) and the Cathode (14,34,44,5
A DC voltage is applied to the heavy metal to form the cathode (14,3,4,124).
4, 44, 54, 74, 124) and a step of removing heavy metals contained in an organism. 3. Anode (13,33,43,53,73,123) and cathode (14,3
4,44,54,74,124) is an electrolytic cell (12,42,52,) capable of storing an organism (11) and an electrolytic solution (15) in which a heavy metal is contained in a living body and arranged at predetermined intervals. 72,122), the anode (13,33,43,53,73,123) and the cathode (14,34,44,5
4,74,124) electrically connected to the anode (13,33,43,53,7
3,123) and a DC power supply (16,76) for applying a voltage between the cathodes (14,34,44,54,74,124) for removing heavy metals contained in living organisms. 4. An apparatus for removing heavy metals contained in a living organism according to claim 3, wherein the electrolytic solution (15) is a sulfuric acid solution, a hydrochloric acid solution, a sodium hydroxide solution or a sodium chloride solution. 5. An apparatus for removing heavy metals contained in an organism according to claim 4, wherein the sulfuric acid solution (15) has a concentration of 0.5 to 20% by volume. 6. The heavy metal contained in the organism according to claim 3, wherein at least the surface of the cathode (14, 34, 44, 54, 74, 124) is formed of stainless steel, cadmium, copper, zinc or alloys thereof. Device to do. 7. A stirring means (17,57,77) for stirring and mixing an organism (11) containing a heavy metal in a living body stored in an electrolytic cell (12,52,72) and an electrolyte solution (15). The apparatus for removing heavy metals contained in the organism according to claim 3, further comprising: 8. The heavy metal contained in the living body of the organism (11) is allowed to pass through the heavy metal ions produced by being eluted into the electrolytic solution (15) and is deposited on the cathode (14,34,74,124). The separator (28, 38, 78) that blocks the passage of heavy metals is the cathode (14, 3
4,74,124) to separate the organism (11) from the electrolyzer
The device for removing heavy metals contained in the organism according to claim 3, which is inserted into (12, 72, 122). 9. A supply port (72a) for supplying an organism (11) containing a heavy metal in a living body to an electrolytic cell (72,122) and the organism (1).
Discharge port (72c) for discharging 1) from the electrolytic cell (12, 42, 52, 72, 122)
4. The organism according to claim 3, wherein and are provided in the electrolytic cell (72, 122), and the anode (73, 123) is a conveyor that conveys the organism (11) from the supply port (72a) to the discharge port (72c). Equipment for removing contained heavy metals. 10. A temperature sensor (101, 102, 103) for detecting the temperature of an electrolytic solution (15), which is inserted into an electrolytic cell (72) and mixed with a living organism (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).