JP2012122113A - Bismuth recovery cartridge, bismuth recovery device, and bismuth recovery method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bismuth recovery cartridge which has high operation efficiency and a low filling amount of MRT (molecule recognition technology) resin and with which replacement work of the MRT resin is easily performed, and to provide a recovery device and a recovery method using the same.SOLUTION: The cartridge A filled with the MRT resin 20 for bismuth recovery is detachably housed in a dual-partitioning housing. The cartridge A includes an outer case 1, an inner protector 10, a filter 15, and a strainer 16. The outer case 1 is a cylindrical member and includes a side wall on which a porous window 6W is formed, wherein the porous window 6W allows a processing liquid to flow in, and a bottom on which an opening section 5 for discharging a processed liquid is provided. The inner protector 10 is a cylindrical member to be inserted into the outer case and includes a side wall on which a porous window 11W is formed, wherein the porous window 11W allows the processing liquid to pass through. The filter 15 is inserted between the inner wall of the outer case 1 and the outer wall of the inner protector 10. The strainer 16 is fixed inside the opening section 5, preventing the MRT resin 20 from flowing out.

Description

  The present invention relates to a bismuth recovery cartridge, a bismuth recovery apparatus, and a bismuth recovery method. More specifically, the present invention relates to a technique for recovering bismuth which has a high possibility of adversely affecting the quality of electrolytically refined copper among metals that are impurities accumulated in a copper electrolyte by wet copper refining.

Generally, bismuth is contained in copper ore and recovered as a by-product in copper smelting.
A large amount of bismuth is produced in copper ore, and most of it is volatilized by high heat in the dry process of copper smelting, and is collected as smoky ash together with lead, arsenic, antimony, etc., but remains in the solution. Since bismuth has a small distribution ratio to slag, it remains in the crude copper produced in the dry process. Crude copper is used as an anode in the electrolysis process, but bismuth remaining in the crude copper is eluted in the electrolytic solution in the copper electrolytic purification process and accumulated in the electrolytic solution.
Since the precipitation potentials of bismuth and copper are substantially the same, when the concentration of bismuth in the electrolytic solution increases, bismuth eutectoids as impurities in the purified copper (electrolytic copper). When a certain amount or more of bismuth is taken into the electrolytic copper, the electrical characteristics of the electrolytic copper deteriorate and the product is not manufactured.

Therefore, the bismuth accumulated in the copper electrolyte is forcibly electrodeposited in the copper removal electrolysis process and removed from the copper electrolyte, and the copper electrolyte having a reduced bismuth concentration is returned to the electrolysis process. Since the electrodeposit is mainly composed of copper and contains a large amount of bismuth as an impurity, it is generally returned to the dry smelting process, which is the upper process.
Although the bismuth concentration in the copper electrolyte is temporarily reduced by the copper removal electrolysis process, the bismuth contained in the electrodeposit is returned to the dry smelting process, and remains in the crude copper again, in the electrolyte. It only moves repeatedly in the dry-wet process as it elutes. Therefore, the amount of bismuth circulated throughout the smelting process (hereinafter referred to as the circulation amount) is not reduced, and the risk of deterioration of the electrical characteristics is not reduced.

As a method for recovering bismuth in the smoke ash, a method using a lead smelting dry process is widely known, but it is a process mediated by lead, which is a harmful substance, and is not preferable in terms of the working environment. For this reason, for example, in Patent Document 1, MRT (Molecular is used without using a dry process of lead smelting.
Technology that collects bismuth using a resin (Recognition Technology, molecular recognition technology) has been developed (see Patent Document 1).

A method for recovering bismuth using MRT resin uses equipment in which a heater H, a filter F, and a column C are connected in series as shown in FIG. The heater H and the filter F are known. The column C varies depending on the amount of electrolytic solution and the concentration of bismuth, but for example, a cylindrical container having a capacity of about ³ to 4 m ³ is used. In this column C, MRT resin 211 is packed in the lower layer, and PP beads 212 are packed in the upper layer for the purpose of suppressing the drift of the processing starting solution and for suppressing the rise of the MRT resin. Yes. Reference numeral 213 denotes a strainer, which is inserted in the lowermost layer to prevent the MRT resin 211 from flowing out.
Normally, the column C is packed with about 600 kg (about 1.5 m ³ ) of the MRT resin 211, so the size thereof is very large.

A bismuth recovery method using the above equipment will be described with reference to FIG. This recovery method includes an adsorption step I and an elution step II.
In the adsorption step I, a copper electrolyte having an increased bismuth concentration (hereinafter sometimes referred to as a treatment starting solution) is passed through a heater H (201) to a temperature suitable for adsorption at about 50 to 60 ° C., Through a filter F having an opening of about 1 μm (202), suspended solid components such as anode slime are removed, and then passed through a column C filled with MRT resin 211 (203), whereby bismuth is converted into MRT. Adsorbed on resin 211.
Bismuth is removed from the liquid after adsorption (hereinafter sometimes referred to as post-adsorption liquid), returned to the electrolytic cell, and used again as the electrolytic solution.

If the adsorption capacity of the MRT resin becomes the limit and bismuth stops adsorbing even if it passes further, the electrolyte remaining on the column C is discharged, the electrolyte remaining on the resin surface is washed, and the elution step II To start. As the eluent, sulfuric acid of about 9 mol / liter is preferably used. Like the treatment start solution in the adsorption step I, heating with the heater H (204) and removal of suspended solid components with the filter F (205) And bismuth adsorption (206) in column C.
In this process, bismuth adsorbed on the MRT resin 211 is eluted from the resin and dissolved in the eluent, and as a result, a post-elution solution containing bismuth is obtained. And the liquid after elution is cooled, bismuth precipitates as bismuth sulfate, and bismuth is collect | recovered by carrying out solid-liquid separation.

However, in the above-described conventional recovery method, when the electrolyte containing bismuth that has passed through the column C in the adsorption step I passes through the MRT resin 211, as described above, the drift of the processing starting solution is suppressed. Therefore, although the PP beads 212 are packed, it is not sufficient and the column C has a wide cross section, and due to variations in flow resistance due to variations in the packing density of the MRT resin, the MRT resin 211 is evenly distributed. There is a problem that it is very difficult to pass through. Therefore, in many cases, a method is used in which the amount of MRT resin adsorption is maximized by setting the amount of liquid passage to be much larger than the adsorption capacity of the MRT resin 211.
However, when the liquid flow rate is increased as described above and the original adsorption capacity of the MRT resin is utilized to the maximum, the liquid flow time per batch becomes long, so that the operation efficiency decreases.

  In addition, since the copper electrolyte that requires removal of bismuth contains suspended matters such as electrolytic slime, the step (202) through which the filter F is passed is necessary. The risk that the electrolytic slime that cannot be removed by the filter F is mixed into the liquid after the filter is increased. When the suspended matter enters the column C, the risk of covering the resin surface and physically hindering the ability of the MRT resin 211 increases. For this reason, there is a problem that it is difficult to sufficiently use the adsorption capacity of the MRT resin 211, and in order to secure the planned adsorption amount, the MRT is more than the predetermined amount in consideration of the loss caused by the inhibition. The resin 211 needs to be packed into the column C, and the operation efficiency is reduced in terms of the packing amount.

  Further, when the adsorption and elution ability of the MRT resin 211 deteriorates, a resin replacement operation is performed. When replacing the resin, it is necessary to discharge a large amount of sandy resin (about 0.5 mm granular) out of the column C and to refill with a new MRT resin 211, so it takes a lot of work and stops the operation during the replacement. Since this is unavoidable, there is a problem that the operation efficiency is lowered.

JP 2003-213350 A

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a bismuth recovery cartridge that has high operational efficiency, requires only a small amount of MRT resin, and can easily replace MRT resin, and a bismuth recovery apparatus using the same. To do.
Moreover, it aims at providing the bismuth collection method with high operational efficiency.

The bismuth recovery cartridge of the first invention is a bismuth recovery cartridge filled with bismuth recovery MRT resin, and includes an outer case, an inner protector, a filter, and a strainer, and the outer case is closed at the top. The cylindrical member is formed with a porous window that allows inflow of the liquid to be processed on the side wall, and has a mouth for discharging the processing liquid at the bottom, and the inner protector It is a cylindrical member inserted into the outer case, and the side wall is formed with a porous window that allows the liquid to be treated to pass through, and the filter includes an inner wall of the outer case and an outer wall of the inner protector. The strainer is fixed to the inside of the mouth so as to prevent the MRT resin filled in the inner protector from flowing out. .
The bismuth recovery cartridge according to a second aspect of the present invention is characterized in that, in the first aspect, the filter is a filtration material having an opening of 0.5 to 2 μm.
The bismuth recovery cartridge of the third invention is characterized in that, in the first or second invention, the strainer is a porous material having an opening of 30 to 300 μm.
A bismuth recovery device according to a fourth aspect of the present invention comprises a single-mount housing and a single bismuth recovery cartridge according to claim 1, wherein the single-mount housing has a cartridge housing portion, an inlet, and an outlet. The cartridge housing part is composed of at least two members that can be separated and coupled, and the bismuth recovery cartridge can be attached and detached in the separated state, and the bismuth recovery cartridge can be fixed inside in the coupled state.
A bismuth recovery apparatus according to a fifth aspect of the present invention comprises a continuous housing and a plurality of bismuth recovery cartridges according to claim 1, wherein the continuous housing has a cartridge housing portion, an inlet, and an outlet. The cartridge housing portion is composed of at least two members that can be separated and coupled, and the bismuth recovery cartridge can be attached and detached in the separated state, and the bismuth recovery cartridge can be fixed inside in the coupled state.
The bismuth recovery method of the sixth invention is a method for recovering bismuth from a copper electrolyte having a high bismuth concentration by using a bismuth recovery cartridge surrounded by a filter and filled with MRT resin. In the adsorption step, the process starting solution is passed through the bismuth recovery cartridge, the suspended solid component is removed by a filter, and the bismuth is adsorbed on the MRT resin, whereby the bismuth is removed from the process starting solution. In the elution step, the eluent is passed through the bismuth recovery cartridge, and the suspended solid components are removed with a filter and the bismuth adsorbed on the MRT resin is eluted to evaporate the bismuth concentration. It is characterized by obtaining a higher post-elution solution.
The bismuth recovery method of the seventh invention is characterized in that the elution liquid obtained by the bismuth recovery method of claim 6 is cooled, bismuth is precipitated as bismuth sulfate, and then solid-liquid separation is performed to recover bismuth. To do.

Since the bismuth recovery cartridge of the first invention also incorporates a filter and MRT resin, it is possible to simultaneously perform the work of removing suspended solids with the filter and absorbing bismuth with the MRT resin.
According to the second invention, when a liquid to be treated such as a bismuth-containing electrolyte is passed, suspended solid components such as anode slime can be efficiently removed by a filtering material having an opening of 0.5 to 2 μm.
According to the third invention, the treatment target liquid after adsorbing bismuth on the MRT resin is discharged through the strainer, but the strainer of the porous material having an opening of 30 to 300 μm prevents the MRT resin from flowing out. There is no loss in the MRT resin.
According to the fourth invention, when the absorption capacity of the MRT resin reaches the limit, the bismuth recovery capacity can be recovered by exchanging the old cartridge and the new cartridge. This can be done and does not require much effort, improving operational efficiency. Further, by selecting the size of the cartridge, a bismuth recovery device having a capacity corresponding to the application can be configured.
According to the fifth invention, when the absorption capacity of the MRT resin reaches the limit, the bismuth recovery capacity can be recovered by exchanging the old cartridge and the new cartridge. This can be done and does not require much effort, improving operational efficiency. In addition, as the MRT resin is subdivided, the liquid can be uniformly passed through the MRT resin and can be brought close to an appropriate flow rate, so that the flow time per batch can be shortened. . Furthermore, by selecting the number of cartridges to be mounted, it is possible to configure a collecting device having a capacity corresponding to the application.
According to the sixth aspect of the present invention, if the cartridge of the present invention and the bismuth recovery apparatus using the cartridge are used, bismuth can be recovered from the copper electrolyte without passing through the filter step that has been conventionally required after the heating step. And operational efficiency can be improved.
According to the seventh invention, bismuth can be recovered by executing simple steps such as cooling and solid-liquid separation.

(A) is an external view of a bismuth recovery cartridge A according to an embodiment of the present invention, and (B) is a longitudinal sectional view of the bismuth recovery cartridge A. It is a partial section perspective view of single packaging type bismuth recovery device B concerning one embodiment of the present invention. It is the partial cross section front view which looked at the casing in the single package type bismuth collection | recovery apparatus B shown in FIG. FIG. 2 is an explanatory diagram of a use state of the single-mount bismuth recovery apparatus B shown in FIG. 1. FIG. 8 is a continuous bismuth recovery apparatus C according to another embodiment of the present invention, and is a vertical cross-sectional view taken along line VV in FIG. 6. FIG. 6 is a cross-sectional view taken along line VI-VI of the continuous bismuth recovery device C shown in FIG. 5. It is process drawing of the bismuth collection method of this invention. It is explanatory drawing of the conventional bismuth collection | recovery apparatus. It is process drawing of the conventional bismuth collection method.

Next, an embodiment of the present invention will be described with reference to the drawings.
(Overall configuration of bismuth recovery equipment)
In the present invention, a bismuth recovery cartridge is configured by detachably attaching a bismuth recovery cartridge filled with MRT resin to a housing, and the MRT resin can be easily replaced by replacing the bismuth recovery cartridge. There is a feature.

(Bismuth recovery cartridge)
First, a bismuth recovery cartridge A (hereinafter simply referred to as cartridge A) characterizing the present invention will be described with reference to FIG.
The cartridge A includes an outer case 1, an inner protector 10, a filter 15, and a strainer 16.

The outer case 1 has a cylindrical main body 2, a top 3 that closes the upper end of the main body 2, a bottom 4 at the lower end of the main body 2, and a mouth 5 formed below the bottom 4. It is the cylindrical member which consists of.
There are no special restrictions on the dimensions of the outer case 1, but for the convenience of handling such as replacement work, the height is preferably 100 to 800 mm and the diameter is 50 to 400 mm, particularly the height is 200 to 300 mm and the diameter is 80-120 mm is suitable.

A large number of holes 6 are formed in the side wall of the outer case 1, that is, in the main body portion 2 to allow inflow of the processing start liquid. In the present specification, such a large number of holes are collectively referred to as a porous window 6W.
The size of the hole 6 is not limited so long as the processing start liquid can pass through and the filter 15 inserted inside is not deformed by the pressure inside and outside, and the range of about 5 to 10 mm in length and about 7 to 13 mm in width is sufficient. Is preferred. The number of such holes 6 varies depending on the dimensions of the outer case 1, and for example, 14 to 24 holes in the circumferential direction and 15 to 30 steps in the vertical direction are provided.
The shape of the illustrated hole 6 is a horizontally long rectangle, but may be a vertically long rectangle, a regular square, or an arbitrary shape such as a circle, a triangle, or a pentagon.

The mouth 5 at the bottom of the outer case 1 is smaller in diameter than the main body 2. A packing groove 7a is formed on the outer periphery of the mouth portion 5 in the circumferential direction, and a packing 7 such as an O-ring is attached thereto.
On the other hand, a positioning plate 8 is provided on the top 3 of the outer case 1. The positioning plate 8 is a combination of two triangular plates 8a so as to be orthogonal in a plan view. For this reason, it looks like a triangle when viewed from the front or from the side, and there is a triangular pyramid gap between the plates 8a. A part of the hypotenuse of the triangular plate 8a can be brought into contact with the inner wall of the housing, which will be described later, to perform the positioning function.

The material of the outer case 1 is specified if the processing start solution, the cleaning solution, and the eluent for recovering bismuth are sulfuric acid acidity of about 2-9 mol / l, so that acid resistance can be obtained and the acid resistance is satisfied. It is not limited to the material.
However, it is preferable to use one or more materials selected from polypropylene, Teflon (registered trademark), polyester, and polyethylene in terms of weight, strength, price, and the like.

  The inner protector 10 is a cylindrical member having both an upper end and a lower end opened. The height may be a size that fits inside the outer case 1 and fits so as not to float. The diameter is smaller than the inner peripheral diameter of the outer case 1, and needs to be a dimension that can create a space for accommodating the filter 15 between the inner peripheral surface of the outer case 1 and the outer peripheral surface of the inner protector 10.

A large number of holes 11 are formed in the side wall of the inner protector 10 to form a porous window 11W. The dimensions, shape, and multi-stage multi-row arrangement may be substantially the same as the holes 6 of the outer case 1.
The material of the inner protector 10 can be the same as that of the outer case 1 without particular limitation.

The filter 15 is formed by folding a filter material made of a soft material into a bowl shape and molding the filter material into an annular shape as a whole. And it is inserted in the space between the outer case 1 and the inner protector 10. The filter 15 prevents inflow of solid components such as anode slime, which are impurities in the raw material liquid.
The filter 15 is made of a material that is not affected by the processing starting solution, and may be any filter material as long as it can supplement the anode slime. Typically, a filter paper made of PP (polypropylene) is used. It is done.

  Moreover, what is necessary is just to select the opening of the filtration raw material used for the filter 15 suitably according to the size of the filtration target object. When the copper electrolyte is passed, the object to be filtered is a floating solid component such as anode slime, and is preferably a filtration material having an opening of 0.5 to 2 μm. If the thickness is less than 0.5 μm, there is no problem in filtration itself, but pressure loss increases, and it takes time to pass the liquid and operation efficiency is lowered. If it exceeds 2 μm, filtration may be insufficient. Therefore, it is most preferable to use an opening having a nominal value of 1 μm because stable performance can be exhibited for sufficient filtration in terms of liquid passing time.

  A strainer 16 is provided inside the mouth portion 5. The strainer 16 is provided to prevent the MRT resin filled in the cartridge A from flowing out and to pass only the post-treatment liquid after adsorbing bismuth.

A strainer having any material and structure may be used as long as it is suitable for this purpose. Typically, porous materials such as glass fibers such as sintered glass and various resin fibers are used.
Moreover, it is preferable that the opening of the strainer 16 is 30 to 300 μm. If it is less than 30 μm, processing is difficult and the unit price of the member increases, which is not preferable. Moreover, it is because there exists a possibility that MRT resin 20 may leak when it exceeds 300 micrometers.

  The strainer 16 may have any size or shape as long as it does not interfere with the fitting to the mouth 5. However, in order to ensure the filling amount of the MRT resin 20, the size in the thickness direction of the lid is preferably thin, and for example, about 3 to 8 mm is preferable.

  The strainer 16 may be fixed in the mouth 5 as long as a necessary fixing strength can be obtained. For example, when the strainer 16 is made of glass fiber, polyvinyl chloride bonded with a molten resin is used. Welding or the like is used.

The MRT resin 20 is filled in the inner protector 10. The filling amount depends on the size of the cartridge A, but is usually 500 to 700 g.
The type of MRT resin 20 to be filled may be selected as appropriate depending on the purpose of use. Many MRT resins 20 have a particle size of 350 μm to 650 μm. However, when the above-described strainer 16 having an opening is used, no spillage occurs.
When filling the hollow portion of the cartridge A, that is, the inside of the inner protector 10, with the MRT resin 20, the tapping is sufficiently performed (powder is put in the container so that the container is vibrated so that the gap is reduced. Operation) is desirable.

(Bismuth recovery device)
The bismuth recovery apparatus of the present invention is configured by combining the above-described cartridge A and an appropriate housing. The housing accommodates the cartridge A, introduces a processing start solution (electrolyte), adsorbs bismuth with the MRT resin 20 in the cartridge A, discharges the processed liquid after removing bismuth, and replaces the cartridge A Any structure and shape may be used as long as it is possible.
A single-mount bismuth recovery device B using one cartridge A and a continuous bismuth recovery device C using a plurality of cartridges A will be described below.

(Single package bismuth recovery device B)
As shown in FIGS. 2 and 3, the single-mount bismuth recovery device B (hereinafter sometimes simply referred to as “bismuth recovery device B”) includes one cartridge A in a single-mount housing 30 (hereinafter simply referred to as the housing 30). Is detachably mounted.
The housing 30 includes an upper casing 31 and a lower casing 35 and a clamp 40 that detachably couples both.

The upper casing 31 is a cylindrical casing as a whole, and an inflow port 33 is formed at the upper portion of the main body portion 32, and a lower flange 34 that extends outward in the radial direction is formed at the lower end portion. The inside of the lower flange 34 is open.
The upper inflow port 33 has an upper flange 33a at the upper end, a small-diameter small-diameter portion 33b just below it, and an intermediate-diameter portion 33c with a medium diameter just below it, and the lower end of the medium-diameter portion 33c has a diameter at the bottom. It spreads in the direction and is connected to the main body 32.

  The lower casing 35 has a holding portion 36 and a discharge port 37 below the holding portion 36, an upper flange 38 is formed at the upper end of the holding portion 36, and a lower flange 39 is formed at the lower end of the discharge port 37. The holding portion 36 is a cylindrical member whose inner diameter is large enough to accommodate the bottom of the cartridge A, and the discharge port 37 is a cylindrical member whose inner diameter is large enough to insert the opening 5 of the cartridge A.

  The clamp 40 may have any structure as long as the upper casing 31 and the lower casing 35 can be arbitrarily coupled or separated. In the example shown in the figure, a pair of clamp pieces 41 and 42 formed of a semicircular annular body having a U-shaped cross section is used. Those that can be fixed by stoppers are used. In the screwing structure, a bolt 43 is attached to a protrusion 41a formed on one clamp piece 41 with a pin, a bolt 43 is passed through a grooved protrusion 42a formed on the other clamp piece 42, and screwed with a nut 44. It is what I did. This screwing structure is also an example, and any structure may be used as long as it can be detachably screwed.

FIG. 3 shows a state in which the cartridge A is fixed in the housing 30.
The opening 5 of the cartridge A is fitted into the discharge opening 37 of the lower casing 35 and is sealed in a liquid-tight manner by the packing 7 in this state. A packing 46 is interposed between the bottom end of the cartridge A and the upper end surface 37 a of the discharge port 37.
In this state, when the packing 47 is inserted between the lower flange 34 of the upper casing 31 and the upper flange 38 of the lower casing 35 and tightened with the clamp 40, the assembled state is obtained. Further, in this state, the positioning plate 8 at the upper end of the cartridge A hits the shoulder 33d of the middle diameter portion 33c of the upper casing 31 and is restrained from swinging in the lateral direction or moving upward.

Next, the flow point of the bismuth-containing electrolytic solution in the single-pack bismuth recovery apparatus B will be described with reference to FIG.
The processing start liquid (electrolyte solution in which bismuth is mixed) that has flowed in from the inlet 33 of the housing 30 flows downward in the upper casing 31 through the gaps in the positioning plate 8. During this time, it flows into the cartridge A from the porous window 6W of the outer case 1 of the cartridge A. The processing starting solution that has passed through the porous window 6W is filtered while passing through the filter 15 to be supplemented with impurities such as anode slime, and enters the inner protector 10 through the porous window 11W of the inner protector 10. Inside the inner protector 10, the processing start solution comes into contact with the MRT resin 20 filled and flows downward. At this time, the bismuth component in the processing start liquid is adsorbed by the MRT resin 20, and the processed liquid from which the bismuth component has been removed is discharged from the discharge port 37. At this time, the treated liquid passes through the strainer 16, but the strainer 16 has a sufficiently large opening to allow the treated liquid to pass therethrough, so that there is no problem in discharging. Further, since the MRT resin 20 has a particle size larger than the opening of the strainer 16, it does not flow out.

  In the bismuth recovery apparatus B described above, the electrolyte introduced from the inlet 33 passes through both the filter 15 and the MRT resin 20 in the process until it is discharged, which is necessary in the prior art shown in FIG. It is possible to simultaneously perform the two steps of the filter passing steps 202 and 205 and the column passing steps 203 and 206. This is an effect that can be achieved by combining the filter 15 and the MRT resin 20.

Next, a continuous bismuth recovery apparatus C (hereinafter, simply referred to as bismuth recovery apparatus C) will be described with reference to FIGS. 5 and 6.
The bismuth recovery apparatus C is configured such that a plurality of cartridges A are detachably mounted on a continuous housing 50 (hereinafter simply referred to as the housing 50).
The continuous housing used in the present invention is not limited to the number of cartridges A to be mounted, and any number of the two or more cartridges A may be used as long as it is two or more, but the illustrated example uses seven.

In the present embodiment, as shown in FIG. 6, one cartridge A is mounted at the center of the housing 50, and six cartridges A are arranged at equal intervals in the circumferential direction.
The structure of the housing 50 will be described with reference to FIG. The housing 50 is generally cylindrical and includes an upper casing 51 and a lower casing 55.

In the upper casing 51, an inflow port 53 is formed at the upper part of the main body part 52, and a lower flange 54 that extends outward in the radial direction is formed at the lower end part.
The lower casing 55 is formed with an upper flange 57 spreading outward in the radial direction at the upper portion of the main body portion 56 and a discharge port 58 at the lower end portion.

The upper casing 51 and the lower casing 55 are coupled by clamps with the respective flanges 54 and 57 combined, but any clamp 60 can be used as long as both flanges 54 and 57 can be fastened together and separated. It may be a thing.
The illustrated clamp 60 is an upper clamp piece 61 and a lower clamp piece 62 connected by bolts and nuts, but may be one using clamp pieces 61 and 62 divided in the circumferential direction, and a smaller clamp. A large number of pieces 61 and 62 may be used and arranged at equal intervals in the circumferential direction.
Further, the flanges 54 and 57 may be directly coupled with bolts and nuts, and the nuts may be removed as appropriate so that they can be separated.

A mounting plate 64 is fixed inside the main body 56 of the lower casing 55. The mounting plate 64 is a circular thick plate, and its periphery is fixed to the inner wall of the main body portion 56 by welding or the like and is liquid-tight.
In addition, seven mounting holes 65 are formed in the mounting plate 64, and the mouth portions 5 of the seven cartridges A are inserted into the mounting holes 65. The O-ring 7 fitted in the mouth portion 5 comes into contact with the inner wall of the mounting hole 65 so that liquid tightness can be secured.

The movement of the upper ends of the seven cartridges A mounted as described above is restricted by the anti-sway plate 66. Seven holes 67 are formed in the anti-sway plate 66, and these holes 67 are fitted in the positioning plates 8 of the seven cartridges A.
The position of the anti-sway plate 66 is fixed by screwing a bolt 68 passed between it and the lower mounting plate 64 with a nut or the like. The method for fixing the anti-sway plate 66 is arbitrary and is not limited to this method.

In order to incorporate the cartridge A into the bismuth recovery device C shown in FIG. Connected to the plate 64. In addition, the packing 63 is disposed between the upper flange 57 of the lower casing 55 and the lower flange 54 of the upper casing 51, and the upper and lower casings 61 and 65 are coupled to each other by the clamp 60.
The procedure for disassembling the housing 50 in order to take out the cartridge A may be reversed.

Also in this continuous bismuth recovery device C, if the processing start liquid is introduced from the inlet 53 and led into the upper casing 51, the processing start liquid enters each cartridge A, so that bismuth can be adsorbed on the MRT resin. The same as the single packaging type bismuth recovery apparatus B.
The treated liquid after bismuth is adsorbed on the MRT resin 20 is discharged from the discharge port 58 of the lower casing 55.
Also in the present embodiment, both the filter 15 and the MRT resin 20 are passed, and the two steps of the filter flow steps 202 and 205 and the column flow steps 203 and 206 required in the prior art shown in FIG. 9 are performed simultaneously. It becomes possible.

(Advantages of bismuth recovery devices B and C)
Next, advantages of the bismuth recovery apparatuses B and C will be described.
First, the size of the cartridge A of the present invention can be selected variously. For this reason, even if it is the single packaging type bismuth collection apparatus B, the collection | recovery apparatus of the capacity | capacitance according to a use can be comprised. Further, since the number of cartridges A mounted can be arbitrarily selected, the continuous bismuth recovery device C can also be configured with a recovery device having a capacity corresponding to the application.
Secondly, as the number of cartridges A is increased, that is, as the MRT resin 20 is subdivided, the liquid can be uniformly passed through the MRT resin 20 and can be close to an appropriate flow rate. Therefore, the liquid passing time per batch can be shortened.
Third, when the liquid flow rate is close to the appropriate amount as described above, the risk of suspended matter such as electrolytic slime physically hindering the ability of the MRT resin 20 is reduced, and an appropriate resin amount can be obtained. This eliminates the need to use extra MRT resin.
Fourthly, since replacement of each deteriorated MRT resin can be performed for each cartridge A, if a new cartridge A is prepared in advance, the housings 30 and 50 are separated vertically and the old cartridge A is removed and a new cartridge A is removed. The MRT resin can be exchanged by simply mounting the cartridge A and connecting the housings 30 and 50 again. That is, since it is not necessary to handle with a large amount of MRT resin in the form of powder, replacement of deteriorated MRT resin can be performed quickly. For this reason, it is not necessary to stop the operation.

Further, the description of the advantages of the bismuth recovery apparatuses B and C of the present invention will be continued.
In the present invention, the filtration area, size and material of the cartridge A can be arbitrarily selected according to the scale and purpose of the processing equipment. That is, by determining the volume of the hollow portion of the cartridge A, that is, the amount to be filled with the MRT resin 20, it is possible to adjust the number of cartridges A required for the processing equipment, and depending on the pH of the liquid to be processed. It is possible to select a material with low chemical resistance, and it is also possible to select a material with high pressure resistance when the liquid to be treated has a high viscosity and pressure inflow is required.

  The factors related to the life of the filtration function of the cartridge A, such as the filtration area and material, depend on the filling amount of the MRT resin 20, that is, the internal volume of the inner protector 10. It is desirable to choose one. For example, if the replacement frequency of the cartridge A and the replacement frequency of the MRT are made to coincide, the replacement operation only needs to be performed for all the cartridges A. This is preferable because the operation is simple and labor is reduced.

  Even if it is difficult to match the replacement frequency of each cartridge A due to economic demands, a new cartridge A should be prepared separately when the filter function life or MRT resin life is reached. Thus, if the operation is stopped and all the cartridges A are replaced, the operation can be resumed promptly. For this reason, the operation stop time of equipment can be minimized. If the MRT resin 20 that has reached the end of its life is taken out from the taken out cartridge A, discarded, and refilled with a new MRT resin, it can be prepared for the next use.

  In the present invention, the housings 30 and 50 of the bismuth recovery devices B and C are divided into two parts in the vertical direction. However, the cartridge A can be fixed and can be inserted and removed. It is possible to arbitrarily divide the structure into two parts, or to divide the structure into three or more members, or to open and close the structure. “Separable coupling is possible” in the scope of the claims means that it includes a split structure and an open / close structure.

(Bismuth recovery method)
A method of recovering bismuth from a copper electrolyte having a high bismuth concentration using the bismuth recovery apparatuses B and C of the present invention will be described with reference to the flowchart shown in FIG. This recovery method includes an adsorption step I and an elution step II.

In the adsorption step I, the heating step 101 and the adsorption step 102 are executed in that order.
In the heating step 101, a copper electrolyte having an increased bismuth concentration (hereinafter sometimes referred to as a treatment starting solution) is passed through the heater H to a temperature suitable for adsorption at about 50 to 60 ° C.
In the subsequent adsorption step 102, the processing start liquid is passed through the bismuth recovery apparatuses B and C of the present invention, and the solid substances such as anode slime are removed by the filter 15 in the cartridge A, and at the same time, the interior is filled. The bismuth is adsorbed on the MRT resin 20 thus prepared.

  The liquid after adsorption (liquid after adsorption) has bismuth removed, is returned to the electrolytic cell, and is used again as an electrolytic solution. In this adsorption step I, the amount of liquid flow is managed so as to maximize the adsorption ability of the MRT resin.

  At this time, the resin adsorption capacity can be fully utilized even when the liquid flow rate is about 10% smaller than that of the prior art described with reference to FIG. Can be operated without problems even if the amount is as small as about 5%, that is, without filling an extra resin. Details of this point will be described in Examples and Comparative Examples.

Next, the elution step II will be described.
If the adsorption ability of the MRT resin is limited and bismuth is not adsorbed even if liquid is passed further, elution step II is started. This elution step II is performed by executing the heating step 103 and the elution step 104 in that order. The heating step 103 is performed in the same manner as the adsorption step I.

In the elution step 104, about 9 mol / liter of sulfuric acid is suitably used as the eluent, and is passed through the bismuth recovery apparatuses B and C in the same manner as the adsorption step 102 in the adsorption step I.
In this process, bismuth adsorbed on the MRT resin is eluted from the MRT resin and dissolved in the eluent. As a result, a post-elution solution containing bismuth is obtained.

In addition, the liquid after elution is cooled, bismuth precipitates as bismuth sulfate, and finally bismuth as a metal is recovered by solid-liquid separation.
As described above, if the cartridge A of the present invention and the bismuth recovery apparatuses B and C using the cartridge A are used, bismuth can be extracted from the copper electrolyte without passing through the filter liquid passing process that has been conventionally required after the heating process. It can be recovered and operational efficiency can be improved.

Next, the performance of the bismuth recovery apparatus of the present invention will be described using examples.
In the bismuth recovery apparatus and method of the present invention, the filter 15 needs to be replaced if the filter capacity has a limited life, and if the MRT resin 20 has a limited life due to repeated adsorption and elution, the MRT resin 20 needs to be replaced. However, in the present invention, if the cartridge A is prepared in advance, even if the operation is stopped at the time of replacement, if all the cartridges A are replaced, the operation can be resumed promptly.
At this time, as compared with the prior art described in FIG. 8 and FIG. 9, the time required for the replacement work accompanied by the operation stop can be about 1/30. The details will be described below in comparison with the comparative example.

Conditions common to Example 1 and Comparative Example 1 are as follows.
In the adsorption step I, a copper electrolyte having a bismuth concentration of 0.6 g / liter and a temperature of 60 ° C. was used as a treatment starting solution. Bed volume of the starting solution B. V = 27.2.
In the washing step before entering the elution step II, sulfuric acid having a sulfuric acid concentration of 2 mol / liter and a temperature of 60 ° C. was used as a washing solution. Bed volume of cleaning liquid V = 1.7 and linear velocity LV = 1.2.
In the elution step II, sulfuric acid having a sulfuric acid concentration of 9 mol / liter and a temperature of 60 ° C. was used as an eluent. Bed volume of eluent V = 3.5 and linear velocity LV = 1.2.
The bismuth concentration in the electrolytic solution as the post-treatment solution was measured.
The bismuth concentration in the treatment starting solution and the treated solution was measured by ICP emission analysis.
The replacement work was carried out irrespective of the life of the filtration function of the cartridge A and the life of the MRT resin, and the required time was measured.

Example 1
The following cartridge A was prepared.
As the MRT resin, 0.75 L (0.3 kg) of a trade name: SuperLig # 83, manufactured by IBC of the United States, having a particle size of about 400 μm was used.
The filter 15 has a mesh size of 1.0 μm: TCP-1 type, manufactured by Advantech. The strainer 16 is made of Teflon (registered trademark) having an opening of 50 μm.
10 batches of the flow of the adsorption step I and the elution step II were performed according to the process diagram of FIG.
As a result, the amount of adsorbed bismuth was 31.0 (g-Bi / kg-MRT) on an average of 10 batches.
In addition, the amount of resin charged in the adsorption step I was 0.75 liters as described above, and the liquid flow rate was 20.4 liters.
The average time required for the replacement work performed three times by the same worker was 1 minute.

(Comparative Example 1)
Without using the cartridge A of the present invention, it was carried out under the same conditions as in Example 1 except that the conventional flow was carried out along the flow of FIG.
As a result, the amount of adsorbed bismuth was 30.0 (g-Bi / kg-MRT) on an average of 10 batches.
Further, the amount of resin filled in the adsorption step I required 0.82 liters in order to make use of a predetermined resin capacity. The flow rate was 22.4 liters.
And the average time required for the replacement | exchange operation | work implemented 3 times by the same worker as Example 1 was 30 minutes.

From the above Example 1 and Comparative Example 1, there is no significant difference in the amount of adsorbed bismuth, but in Example 1, both the liquid flow rate and the resin filling amount are reduced by about 10%, and the time required for the replacement work is It can be seen that it is 1/30.
The unit of adsorbed bismuth amount (g-Bi / kg-MRT) represents the amount of Bi adsorbed on 1 kg of MRT resin.

A Cartridge B Single-mount bismuth recovery device C Continuous-type bismuth recovery device 1 Outer case 6W Perforated window 10 Inner protector
11W Perforated window 15 Filter 16 Strainer 20 MRT resin 30 Single housing 40 Clamp 50 Continuous housing 60 Clamp

Claims (7)

A bismuth recovery cartridge filled with MRT resin for bismuth recovery,
It has an outer case, an inner protector, a filter, and a strainer.
The outer case is a cylindrical member whose top is closed, and a side wall is formed with a perforated window that allows inflow of the liquid to be processed, and a bottom is provided with a mouth for discharging the processing liquid. And
The inner protector is a cylindrical member inserted into the outer case, and a porous window is formed on the side wall to allow the liquid to be treated to pass through.
The filter is inserted between the inner wall of the outer case and the outer wall of the inner protector,
The bismuth recovery cartridge, wherein the strainer is fixed to the inside of the mouth so as to prevent the MRT resin filled in the inner protector from flowing out. The bismuth recovery cartridge according to claim 1, wherein the filter is a filtration material having an opening of 0.5 to 2 μm. 3. The bismuth recovery cartridge according to claim 1, wherein the strainer is a porous material having an opening of 30 to 300 [mu] m. A single housing and one bismuth recovery cartridge according to claim 1;
The single packaging housing has a cartridge housing portion, an inlet and an outlet,
The cartridge housing part is composed of at least two members that can be separated and coupled, the bismuth collection cartridge can be attached and detached in the separated state, and the bismuth collection cartridge can be fixed inside in the coupled state. apparatus.   It comprises a housing for connection and a plurality of bismuth recovery cartridges according to claim 1, wherein the housing for connection has a cartridge housing portion, an inlet and an outlet, and the cartridge housing portion is separated and coupled. A bismuth recovery apparatus comprising at least two possible members, wherein the bismuth recovery cartridge can be attached and detached in a separated state, and the bismuth recovery cartridge can be fixed inside in a connected state. A method of recovering bismuth from a copper electrolyte having a high bismuth concentration using a bismuth recovery cartridge filled with MRT resin inside a filter,
Including an adsorption step and an elution step;
In the adsorption step, the process starting solution is passed through the bismuth recovery cartridge, and the solid component is removed by a filter and the bismuth is removed from the process starting solution by adsorbing bismuth on the MRT resin. And
In the elution step, the eluent is passed through the bismuth recovery cartridge, the suspended solid component is removed by a filter, and the bismuth adsorbed on the MRT resin is eluted to obtain a post-elution liquid having a high bismuth concentration. A characteristic bismuth recovery method. A method for recovering bismuth, characterized in that the liquid after elution obtained by the method for recovering bismuth according to claim 6 is cooled, bismuth is precipitated as bismuth sulfate, and then bismuth is recovered by solid-liquid separation.