JP5478240B2 - Metal recovery method and metal separation recovery device - Google Patents

Description

The present invention relates to a beauty metals separation and recovery device Oyo method metals recovery.

  Although the main component of magnetic alloys used in magnetic recording devices and the like is iron, a small amount of rare earth metals such as neodymium, dysprosium, and praseodymium are added to increase the coercive force. In recent years, when resources are depleted, the movement to isolate and reuse them is accelerating.

  Conventionally, as a general method for recovering rare earth metals, a magnetic alloy is dissolved in a strong acid such as nitric acid, and oxalic acid is added to the magnetic alloy, and the rare earth oxalate insoluble in the strong acid is collected by filtration. Thereafter, the oxalate is roasted and recovered in the form of an oxide.

  In addition, the magnetic alloy is crushed, contacted with chlorine gas, converted into chloride, and then heated to volatilize iron chloride with a low boiling point to obtain a high-concentration rare earth residue in the form of chloride ( Patent document 1) is also mentioned.

JP 2000-144275 A

  Among these, the method using oxalic acid requires an operation such as filtration of a strong acid solution, and the apparatus also requires measures corresponding to the strong acid. When using chlorine gas, it is necessary to take measures against corrosion of the equipment.

  Furthermore, since both methods roast or iron chloride is volatilized at a high temperature, the amount of energy used becomes enormous. In the case of roasting, it is heated at approximately 1000 ° C. for several hours to decompose and remove oxalic acid, which is an organic substance. Further, since the boiling point of iron chloride is about 350 ° C., it is considered necessary that the temperature of the heating furnace is about 400 ° C.

As described above, in the prior art, countermeasures against corrosion of the apparatus against strong acid and chlorine gas and further enormous energy consumption have been problems. In addition, processing in one batch requires several hours to several tens of hours.
An object of the present invention is to recover a rare earth in a short time without using a high temperature treatment using an apparatus that does not require a high countermeasure against corrosion. In addition, a transition metal having a large ionic radius other than the rare earth is also recovered.

  In order to solve the above-mentioned problems, the present invention is characterized in that a metal recovery agent that makes a metal an aggregate by coordination bond, a water-soluble polymer having an amino group, a water-soluble polymer having an acidic group, and The water-soluble polymer having an amino group has an amino group bonded to the main chain composed of a straight chain hydrocarbon, and the water-soluble polymer having an acidic group is an acid group on the main chain composed of a straight chain hydrocarbon. A metal recovery agent, wherein a part of an amino group of a water-soluble polymer having an amino group or a part of an acid group of a water-soluble polymer having an acid group is a salt, and This is a metal separation and recovery device using the same.

  A feature of the present invention is a metal recovery agent that makes a metal an agglomerate by coordination bond, having a water-soluble polymer having an amino group and a water-soluble polymer having an acidic group, The water-soluble polymer having a chain is a copolymer composed of a polymer in which an amino group is bonded to a main chain composed of a straight chain hydrocarbon and a polymer not having an amino group in the main chain composed of a straight chain hydrocarbon. There are provided a metal recovery agent and a metal separation / recovery device using the same.

  A feature of the present invention is a metal recovery agent that makes a metal an agglomerate by coordination bond, having a water-soluble polymer having an amino group and a water-soluble polymer having an acidic group, The water-soluble polymer having a polymer is a copolymer composed of a polymer in which an acidic group is bonded to a main chain composed of straight chain hydrocarbons and a polymer not having an acid group in the main chain composed of linear hydrocarbons. There are provided a metal recovery agent and a metal separation / recovery device using the same.

  In addition, a feature of the present invention is a metal recovery method for recovering a metal as an agglomerate by coordination bond, which is an aqueous solution having an amino group that is partially a carboxylic acid ammonium salt in an aqueous solution in which the metal is dissolved. This is a metal recovery method comprising a step of adding a functional polymer and a step of adding a water-soluble polymer having an acidic group, part of which is an alkali metal salt, to an aqueous solution in which the metal is dissolved.

  According to the present invention, a large amount of metals such as rare earth having a large ionic radius can be recovered at high speed.

2 is an agglomerate formation scheme of one embodiment of the present invention. 2 is a metal recovery scheme of one embodiment of the present invention. 2 is a metal recovery scheme of one embodiment of the present invention. It is a schematic diagram of the coordination bond of a water-soluble polymer having a metal having a large ionic radius and an amino group. It is a schematic diagram of the coordinate bond of the water-soluble polymer which has a small ionic radius metal and an amino group. It is a mimetic diagram of a metal separation recovery device of one embodiment of the present invention. It is a mimetic diagram of a metal separation recovery device of one embodiment of the present invention. It is a mimetic diagram of a metal separation recovery device of one embodiment of the present invention. It is a mimetic diagram of a metal separation recovery device of one embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

<Principle of the present invention>
The principle of metal recovery from the metal-containing water of the present invention will be described with reference to FIG. In the present invention, the metal recovery agent has a water-soluble polymer having an amino group and a water-soluble polymer having an acidic group. In the present invention, the transition metal having a large ionic radius refers to those having an ionic radius of 0.8 angstrom or more. Specifically, monovalent silver (ion radius: 1.37 angstrom), divalent cadmium (ion radius: 0.97 angstrom), trivalent gold (ion radius: 0.85 angstrom), lanthanide-based praseodymium (Trivalent, ionic radius: 1.01 angstrom), neodymium (trivalent, ionic radius: 1.00 angstrom), europium (trivalent, ionic radius: 0.95 angstrom), dysprosium (trivalent, ionic radius) : 0.91 angstrom).

  First, the water-soluble polymer 2 having an amino group is added to metal-containing water in which the transition metal ions 1 are dissolved. Then, the amino group is coordinated to the metal ion. In addition, although the transition metal has shown the thing of 6 coordination, in the case of metals other than 6 coordination, the amino group for the number of coordinations coordinate-bonds with respect to one metal ion. Thereby, the coupling | bonding material 3 which consists of a water-soluble polymer which has a metal ion and an amino group produces | generates. In this way, metal ions in the metal-containing water are trapped in the water-soluble polymer 2 having an amino group.

  Next, a solution of the water-soluble polymer 4 having a carboxyl group is added. In addition, although the case where it has a carboxyl group as an acidic group is illustrated here, it is the same also in the case of a sulfone group.

  By adding the water-soluble polymer 4 having a carboxyl group, an ionic bond 5 composed of an amino group of the water-soluble polymer 2 having an amino group and an acidic group of the water-soluble polymer 4 having a carboxyl group is formed. By the formation of the ionic bond 5, the water-soluble polymer 4 having a carboxyl group and the water-soluble polymer 2 having an amino group are cross-linked. Then, this cross-linked product cannot be dissolved in water, and precipitates as an aggregate 6 in which metal ions are trapped. This agglomerate can be separated by passing through a filtration tank, and as a result, the metal can be recovered.

  Here, if the number of substituents that can be coordinated with the drug is greater than the product of the number of metal ions in the metal-containing water and the coordination number, metal ions that cannot be coordinated in the metal-containing water are generated. Metal recovery efficiency is not improved. Moreover, the acidic group of the water-soluble polymer 4 having a carboxyl group also functions as a ligand. Therefore, in FIG. 1, the water-soluble polymer 2 having an amino group is first added, but the water-soluble polymer 4 having a carboxyl group may be added first. The aggregate 6 formed in the present invention is instantly formed when the water-soluble polymer 4 having a carboxyl group is added. Therefore, metal recovery can be performed at high speed. Further, since the amount of addition of the water-soluble polymer 2 having an amino group and the amount of addition of the water-soluble polymer 4 having a carboxyl group is agglomerated, the amount of these polymers remains in the waste water. Is extremely small. This is because even if polymers slightly crosslink, they become insoluble in water. Therefore, the water-soluble polymer 2 having an amino group and the water-soluble polymer 4 having a carboxyl group are so small that the waste water is contaminated by the flocculant.

  Next, the principle of metal recovery according to the present invention will be described with reference to FIGS.

First, a method for adding an acid will be described with reference to FIG. The agglomerate 6 formed by the above method is transferred to a container and acid 7 (H ⁺ Y ⁻ ) is added. Then, the aggregate is dissolved and the metal ion forms an ion-bonded form (M ⁺ Y ⁻ ) with the added acid anion. In the water-soluble polymer 4 having a carboxyl group, the carboxyl group had an anion structure (CO ₂ ⁻ ) during the formation of the aggregate, and an ionic bond was formed. However, when an acid is added, it changes to a carboxyl group (CO ₂ H), and the ionic bond with the water-soluble polymer 2 having an amino group is eliminated. Since the ionic bond between the polymers is eliminated, the aggregate becomes water-soluble and dissolves. Further, the amino group of the water-soluble polymer 2 having an amino group is changed to a polymer 8 having an acid anion and an ammonium salt structure. Here, the acid 7 has a monovalent structure for both the cation and the anion, but it can be used in the divalent or trivalent form, and there is no particular limitation on the valence.

  In the solution in which the aggregate is dissolved, the water-soluble polymer 2 having a high molecular weight amino group and the water-soluble polymer 4 having a carboxyl group are separated from the metal salt by a dialysis membrane or the like and recovered as a metal salt. Can do.

Next, a method for adding a base such as a strong base will be described with reference to FIG. The agglomerate 6 formed by the above method is transferred to a container, and an aqueous solution of base 9 (N ⁺ OH ⁻ ) is added. Then, the aggregate is dissolved, and the metal ions are ion-bonded to the added base anion (M ⁺ OH ⁻ ). Further, in the water-soluble polymer 2 having an amino group, the amino group became a cation structure (NH ₃ ⁺ ) and formed an ionic bond when the aggregate was formed. However, by adding an aqueous solution of a base, it changes to an amino group (NH ₂ ), and the ionic bond with the water-soluble polymer 4 having a carboxyl group is eliminated. Since the ionic bond between the polymers is eliminated, the aggregate becomes water-soluble and dissolves. Furthermore, the carboxyl group of the water-soluble polymer 4 having a carboxyl group becomes a polymer 10 having a cation of the added base and a carboxylate structure. Here, the base 9 has a monovalent structure for both the cation and the anion, but it can be used in the divalent or trivalent form, and there is no particular limitation on the valence. In the solution in which the aggregates are dissolved, the metal changes to a hydroxide. Since transition metal hydroxides are sparingly soluble in water, they can be recovered by filtration.

  Next, the principle of selectively recovering a transition metal having a large ion radius such as rare earth according to the present invention will be described with reference to FIGS.

  FIG. 4 shows a state in which the amino group of the water-soluble polymer 13 having an amino group in which a part of the amino group is a carboxylate structure 12 is coordinated to the transition metal ion 11 having a large ionic radius. is there. Here, the transition metal ion 11 has a coordination number of six, but the transition metal ion 11 having a different coordination number has the same idea.

  In FIG. 4, since the transition metal ion 11 has a large ionic radius, six amino groups are coordinated. However, as shown in FIG. 5, in the case of the transition metal ion 11 having a small ionic radius, the carboxylate structure 12 sterically interferes with the coordination of other amino groups or the flexibility of the polymer chain. In other words, there are limits to the number of amino groups that are bonded. Therefore, when a water-soluble polymer having an acidic group is added and agglomerated, it is not taken in by the agglomerate and is not recovered as a result. In this way, the metal having a large ionic radius is selectively agglomerated and finally recovered.

  By the way, acidic groups such as carboxyl groups and sulfonic acid groups can also be ligands. Therefore, the water-soluble polymer 13 having an amino group in FIGS. 4 and 5 may be replaced with a water-soluble polymer having an acidic group.

<Water-soluble polymer having an acidic group>
In the present invention, a part of the acidic group of the polymer having an acidic group is used in the form of a salt structure, particularly an alkali metal salt. Acidic groups (carboxyl groups, sulfonic acid groups, etc.) function as transition metal ligands. However, when converted to alkali metal salts of acidic groups, the functions as ligands are considerably weakened. Thereby, the distance between acidic groups which function as a ligand can be extended. In addition, a transition metal having a large ionic radius can be selectively aggregated by inserting an alkali metal salt of an acidic group having a weak function as a ligand between them.

  When a divalent metal such as an alkaline earth metal is used, the carboxyl groups in the polymer are cross-linked and become hardly soluble in water. Therefore, an alkali metal which is a monovalent metal is desirable. Also, amines are conceivable, but they themselves bind to transition metals as ligands, and it has been found that metals with small ionic radii also aggregate. Therefore, when an acidic group is made into a salt structure, alkali metals, specifically lithium, sodium, potassium, rubidium, cesium and the like are used. In the introduction, an alkali metal hydroxide aqueous solution is added to an aqueous solution of a water-soluble polymer having an acidic group and stirred. The addition ratio at that time is controlled so that the number of moles of alkali metal is smaller than the number of moles of acidic groups of the water-soluble polymer having acidic groups. If it is too much, the transition metal may be precipitated as a hydroxide. Therefore, it is desirable that 50% or more and 90% or less of the acidic group of the water-soluble polymer having an acidic group is an alkali metal salt.

  The water-soluble polymer having an acidic group will be specifically described as candidates. The water-soluble polymer having an acidic group includes a carboxyl group or a sulfonic acid group as the acidic group. Among these, as the water-soluble polymer having a carboxyl group, polyacrylic acid is preferable because it is inexpensive and easily forms an ionic bond with an amino group. In addition, copolymers of polymethacrylic acid, polyacrylic acid, and polymethacrylic acid are also included. These are polymers in which an acidic group is bonded to a main chain composed of a straight chain hydrocarbon. It is not restricted to these materials, and two or more of these materials may be used in combination.

  Examples of the water-soluble polymer having a sulfonic acid group include polyvinyl sulfonic acid and polystyrene sulfonic acid. Since these sulfonic acid groups have a higher acidity than the carboxyl group, the ratio of forming an ionic bond with an amino group is high, which is preferable in that a stable aggregate can be obtained.

  By the way, even if it does not convert into a salt structure, the distance between carboxyl groups can be separated. For example, a copolymer composed of a polymer in which an acidic group is bonded to a main chain composed of a linear hydrocarbon and a polymer not having an acidic group is applicable. Specific examples include a copolymer made of polyacrylic acid and polymethyl acrylate, a copolymer made of polyacrylic acid and polystyrene, and the like.

  Examples of the polymer having an acidic group include polyacrylic acid and polymethacrylic acid. Polymers that do not have acidic groups include poly (methyl acrylate), poly (ethyl acrylate), poly (propyl acrylate), poly (butyl acrylate), poly (hexyl acrylate), poly (octyl acrylate), poly (decyl acrylate), poly (acrylic acid) Examples include dodecyl, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyhexyl methacrylate, polyoctyl methacrylate, polydecyl methacrylate, polydodecyl methacrylate, and polystyrene. It is not restricted to these materials, and two or more of these materials may be used in combination. The above materials are synthesized by appropriately mixing and polymerizing the monomers to be used, and a desired copolymer is obtained. The mixing ratio is preferably 30% or more of polymers having acidic groups in terms of moles. This is because when it is less than 30%, it becomes difficult to dissolve in water. Further, considering that it is easy to agglomerate and collect a metal having a large ionic radius such as rare earth, it is desirable that the polymer having an acidic group is 90% or less.

  Next, the average molecular weight (number average molecular weight) of the water-soluble polymer having an acidic group will be described. If the average molecular weight of the water-soluble polymer having an acidic group is too low, the number of cross-linked sites of the aggregate decreases, and the stability of the aggregate decreases. In addition, the agglomerates tend to become liquids with high viscosity. In this case, it becomes difficult to collect the aggregate by filtration. Therefore, the average molecular weight of the water-soluble polymer having an acidic group is desirably 2000 or more.

  In addition, when the temperature of the water containing a metal will be 40 degreeC or more, when an average molecular weight is 2000, an aggregate will come to have adhesiveness. In the case of industrial wastewater, the temperature may increase to about 60 ° C. In this case, the aggregate can be solidified even at a high temperature by further increasing the average molecular weight. Specifically, by setting the average molecular weight to 5000 or more, the aggregate can be solidified even when the temperature of the wastewater is 40 ° C. Therefore, the average molecular weight of the water-soluble polymer having an acidic group is more preferably 5000 or more. Furthermore, by setting the average molecular weight to 10,000 or more, the aggregate can be solidified even when the temperature of the waste water is 60 ° C. Therefore, the average molecular weight of the water-soluble polymer having an acidic group is more preferably 10,000 or more.

  On the other hand, if the molecular weight is too large, the solubility in water tends to decrease and precipitate during the formation of coordination bonds with metal ions. This is remarkable when the metal valence is 2 or more.

  The cause of the above is as follows. In the case of a metal having a valence of 2 or more, one metal ion forms a plurality of cross-linked structures in one polymer and is hardly soluble in water. As the molecular weight of the polymer increases, this tendency becomes stronger, so that the solubility decreases before the addition of the water-soluble polymer having an amino group, and the metal-containing water being treated becomes cloudy. If it becomes like this, the ratio by which a metal ion will not make a coordinate bond with the water-soluble polymer which has an acidic group, but will remain in metal-containing water will increase, and metal recovery will fall as a result.

  Therefore, the average molecular weight of the water-soluble polymer having an acidic group is desirably 200,000 or less. Thereby, even if it coordinates-bonds with bivalent ions, such as copper or cadmium, the combined substance will not precipitate in water. However, with trivalent ions such as aluminum or iron, some precipitation is still observed. Therefore, the average molecular weight of the water-soluble polymer having an acidic group is more preferably 100,000 or less. Thereby, even if it ion-bonds with trivalent ions, such as aluminum or iron, the combined substance will not precipitate in water. The number average molecular weight is measured by gel permeation chromatography (GPC).

<Water-soluble polymer having amino group>
In the present invention, a part of the amino group of the polymer having an amino group is used in the form of a salt structure such as a carboxylate. The amino group functions as a transition metal ligand, but when converted to a carboxylate of an amino group, the function as a ligand is considerably weakened. As a result, the distance between amino groups that function as ligands is increased, and a carboxylate of an amino group that weakly functions as a ligand is inserted between them to selectively agglomerate transition metals having a large ionic radius. Can be made.

  Examples of the carboxylic acid to be used include those having a hydrocarbon group such as a methyl group or an ethyl group bonded thereto. However, in order to selectively recover rare earths with large ionic radii, instead of carboxylic acids having a simple linear alkyl chain between amino groups, aliphatic carboxylic acids having residues with large steric hindrance are introduced. Is preferred. As the residue having a large steric hindrance, a cyclic hydrocarbon group or a branched alkyl group can be considered. Specific examples of the carboxylic acid having such a residue include cyclobutane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, cyclodecane carboxylic acid, cyclododecane carboxylic acid, t-butyl carboxylic acid, t-amyl carboxylic acid and the like. Is mentioned. Note that the cyclic hydrocarbon group or the branched alkyl group preferably has 12 or less carbon atoms. This is because when the number of carbon atoms is 12 or more, the water solubility of the polymer having an amino group decreases. Moreover, it is desirable that 50% or more and 90% or less of the amino of the water-soluble polymer having an amino group is a carboxylate.

  When introducing into a water-soluble polymer having an amino group, it is obtained by adding an aqueous solution of a carboxylic acid to an aqueous solution of a water-soluble polymer having an amino group and stirring. The addition ratio in that case is controlled so that the number of moles of carboxylic acid is less than the number of moles of amino groups of the water-soluble polymer having amino groups. If it is more than this, the carboxylic acid is coordinated to the transition metal, the metal having a small ionic radius is likely to aggregate, and the selectivity when recovering the metal having a large ionic radius is lowered.

  The water-soluble polymer having an amino group will be specifically described. As the water-soluble polymer having an amino group, polyethyleneimine is preferable in that the amino group ratio is the largest in the same molecular weight. A type having an amino group in a linear hydrocarbon such as polyvinylamine or polyallylamine is also preferable because it is relatively inexpensive and easily dissolved in water.

  By the way, even if it does not convert into a salt structure, the distance between amino groups can be separated. For example, a copolymer composed of a polymer in which an amino group is bonded to a main chain composed of linear hydrocarbons and a polymer not having an amino group is applicable. Specific examples include a copolymer composed of polyallylamine and polymethyl acrylate.

  Examples of the polymer having an amino group include polyallylamine. Polymers that do not have an amino group include polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polybutyl acrylate, hexyl acrylate, octyl polyacrylate, decyl polyacrylate, dodecyl polyacrylate , Polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyhexyl methacrylate, polyoctyl methacrylate, polydecyl methacrylate, polydodecyl methacrylate, and the like. It is not restricted to these materials, and two or more of these materials may be used in combination. The above materials are synthesized by appropriately mixing and polymerizing the monomers to be used, and a desired copolymer is obtained. The mixing ratio is preferably 30% or more of the polymer having amino groups in terms of moles. This is because when it is less than 30%, it becomes difficult to dissolve in water. Further, considering that it is easy to agglomerate and collect a metal having a large ionic radius such as rare earth, it is desirable that the water-soluble polymer having an amino group is 90% or less.

  Moreover, the polymer which amidated some amino groups, such as polyallylamine and polyethyleneimine, is also mentioned. The amidation can be obtained by adding a carboxylic acid to an aqueous solution of the water-soluble polymer having an amino group and condensing it. Examples of the carboxylic acid include acetic acid, propionic acid, valeric acid and the like as the compound having an alkyl chain. Examples of the compound having a cycloalkyl chain include cyclobutane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, cyclodecane carboxylic acid, and cyclododecane carboxylic acid. It can be synthesized by using a condensation reagent such as water-soluble carbodiimide in the condensation reaction.

  A water-soluble polymer having an amino group generates an amine-specific odor even at room temperature when the average molecular weight is small. Specifically, it becomes prominent when the average molecular weight is less than 200. Therefore, the average molecular weight of the water-soluble polymer having an amino group is preferably 200 or more. Further, the average molecular weight is preferably 500 or more, if possible, so that the odor is hardly felt.

  On the other hand, when the average molecular weight is increased, the viscosity of the aqueous solution is high, and it becomes difficult to manage the input amount and perform the operation for charging the metal-containing water. Specifically, when the average molecular weight exceeds 1,000,000, the viscosity becomes 3000 mPa · s or more even with a 10% by weight aqueous solution. Therefore, the average molecular weight of the water-soluble polymer having an amino group is preferably 1000000 or less. Moreover, even if it is a 10% by weight aqueous solution, the viscosity becomes 1000 mPa · s or less, and in order to simplify the handling at the time of charging control or charging operation into metal-containing water, the average of water-soluble polymers having amino groups The molecular weight is preferably 200,000 or less.

<Addition ratio of flocculant, etc.>
Next, the addition ratio of the flocculant and the like will be specifically described. Here, MB is the product of the number of moles and coordination number of metal ions in the metal-containing water, PA is the number of acidic groups of the water-soluble polymer having acidic groups to be added, and the water-soluble polymer having amino groups to be added. Let the number of amino groups in PB be PB. In the case of selectively recovering a transition metal having a large ionic radius such as rare earth, PA + PB does not need to be larger than MC, and the product of the number of moles and the coordination number of transition metal ions having a large ionic radius contained in the metal-containing water. It should be smaller than MB. That is, the conditions of the following formula are preferable.

PA + PB <MB Formula (1)
By adding under the condition of formula (1), metal ions having a large ion radius in the metal-containing water can be selectively recovered with high efficiency. If too much of each water-soluble polymer is added, the organic component in the aggregate after metal recovery increases, and the metal content in the aggregate decreases. Moreover, since the amount of acid or base used to dissolve the aggregate for metal recovery increases, it is preferable to control PA + PB so that it is not larger than MB.

  It should be noted that a polymer having an acidic group bonded to a main chain composed of linear hydrocarbons and a copolymer composed of a polymer not having an acidic group and an amino group bonded to the main chain composed of linear hydrocarbons. The effect of the present invention can be achieved by a single polymer and a copolymer composed of a polymer not having an amino group, but by having both, a metal having a large ionic radius is more selected. Can be recovered.

  The application of magnetic separation will be described. By containing magnetic powder or iron powder in the aggregate during the formation of the aggregate, the aggregate can be recovered by magnetic separation. However, since it is desirable to add at the time of aggregation, if it is dispersed in an aqueous solution to be added later among water-soluble polymers having amino groups and water-soluble polymers having acidic groups, Easy to mix evenly. By mixing uniformly, the fraction of aggregates that are not recovered during magnetic separation becomes very small. Therefore, it is important to uniformly disperse the magnetic powder or iron powder with respect to the aggregate.

(1) Invention 1 of a metal separation and recovery apparatus
Next, the metal separation / recovery device of the present invention will be described. A basic configuration of a metal separation and recovery apparatus of a type having two mixing tanks will be described with reference to FIG.

  First, a water-soluble polymer aqueous solution having an acidic group is introduced into the first mixing tank 17 from the first tank 14 by the pump 15 through the pipe 16.

  Next, an alkali metal hydroxide aqueous solution is introduced into the first mixing tank 17 from the second tank 18 through the pipe 20 by the pump 19. The second tank 18, the pump 19, and the pipe 20 serve as a mechanism for introducing an alkali metal hydroxide aqueous solution into the first mixing tank 17. These liquids are stirred by an overhead stirrer 21. Thereby, a part of the acidic group of the water-soluble polymer having an acidic group in the first mixing tank 17 changes to an alkali metal salt structure. Alkali metal hydroxides include sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and the like. In addition, if a part of the acidic group of the water-soluble polymer having an acidic group is changed into an alkali metal salt structure in advance in the first tank 14, the second tank 18 becomes unnecessary. .

  Next, metal-containing water containing a transition metal having a large ionic radius such as rare earth is introduced into the first mixing tank 17 through the pipe 23 by the pump 22. The pump 22 and the pipe 23 serve as a mechanism for introducing the metal-containing water into the first mixing tank 17. The liquid in the first mixing tank 17 is stirred by an overhead stirrer 21. The overhead stirrer 21 serves as a mechanism for mixing the liquid in the first mixing tank 17 by stirring. Thus, the transition metal having a large ionic radius contained in the metal-containing water mainly forms a coordinate bond with the acidic group of the water-soluble polymer having an acidic group.

  Next, the liquid in the first mixing tank 17 is introduced into the second mixing tank 26 through the pipe 25 by the pump 24. An aqueous solution of a water-soluble polymer having an amino group is introduced into the second mixing tank 26 from the third tank 27 by a pump 28 through a pipe 29. Then, the acidic group of the water-soluble polymer having an acidic group and the amino group of the water-soluble polymer having an amino group form an ionic bond, thereby forming an aggregate 30 that is insoluble in water. The first tank 14, the pump 15, the pipe 16, the third tank 27, the pump 28, and the pipe 29 are mixed with an aqueous solution of a water-soluble polymer having an acidic group and an aqueous solution of a water-soluble polymer having an amino group. It becomes the mechanism to throw in.

  Subsequently, when the shutter 31 is opened, the liquid other than the aggregate 30 is discharged from the second mixing tank 26 through the filter 32. The filter 32 serves as a mechanism for collecting the aggregate 30 generated by the second mixing tank 26 by filtration. Since the aggregate 30 is blocked by the filter 32, it is not discharged from the second mixing tank 26. After the liquid component in the second mixing tank 26 is discharged, the shutter 31 is closed.

  Next, when the hydrochloric acid aqueous solution is introduced into the second mixing tank 26 from the fourth tank 33 through the pipe 35 by the pump 34, the aggregate 30 is dissolved. The fourth tank 33, the pump 34 and the pipe 35 serve as a mechanism for adding hydrochloric acid to the aggregate 30. An aqueous nitric acid solution may be used instead of the aqueous hydrochloric acid solution.

  When the shutter 31 is opened again, the liquid in which the aggregate 30 is dissolved is discharged from the second mixing tank 26 through the filter 32 and enters the metal recovery tank 36. The valve 37 controls whether or not the metal recovery tank 36 is charged.

  Subsequently, a sodium hydroxide aqueous solution, which is an alkali metal hydroxide aqueous solution, is supplied from the fifth tank 38 through the pipe 40 to the metal recovery tank 36 by the pump 39. The fifth tank 38, the pump 39, and the pipe 40 serve as a mechanism for introducing an alkali metal hydroxide aqueous solution. Then, transition metal ions are precipitated as transition metal hydroxide 41 which is hardly soluble in water. When the shutter 42 at the lower part of the metal recovery tank 36 is opened, the liquid enters the drug recovery tank 44 from the metal recovery tank 36 through the filter 43. The metal recovery is completed by removing the transition metal hydroxide remaining in the metal recovery tank 36. The metal recovery tank 36 serves as a mechanism for recovering the solid produced after charging the alkali metal hydroxide aqueous solution. Although not shown here, when these operations are finished, the second mixing tank 26 can be washed with purified water or the like to remove hydrochloric acid adhering to the wall surface or the like.

  Here, the order of the water-soluble polymer having an acidic group and the water-soluble polymer having an amino group may be reversed. That is, an aqueous solution of a water-soluble polymer having an amino group is placed in the first tank 14, and an aqueous solution of a water-soluble polymer having an acidic group is placed in the third tank 27. However, not the aqueous solution of alkali metal hydroxide but the aqueous solution of carboxylic acid is put in the second tank 18.

(2) Embodiment 2 of the metal separation and recovery apparatus
Of the metal separation and recovery apparatus of the present invention, a configuration having one mixing tank will be described with reference to FIG.

  The first mixing tank 17 is provided with the shutter 31, the filter 32, the pipe 29 from the third tank 27, and the pipe 35 from the fourth tank 33 provided in the second mixing tank 26 of (1). . Thereby, even if it does not provide the 2nd mixing tank 26, the metal separation collection | recovery apparatus of this invention can be comprised, and since a mixing tank can be reduced by one, an apparatus can be made compact.

(3) Form 3 of the invention of the metal separation and recovery device
Of the metal separation and recovery apparatus of the present invention, a configuration for performing metal separation and metal recovery using a magnetic separation method will be described with reference to FIGS.

  First, the magnetic powder is mixed with the water-soluble polymer aqueous solution having amino groups in the third tank 27. When the magnetic powder is put into the first mixing tank 17 together with the water-soluble polymer aqueous solution having amino groups from the third tank 27, an aggregate 30 is formed, and the magnetic powder is contained in the aggregate 30. Is done.

  The apparatus of the present embodiment has a magnetic powder-containing aggregate transport mechanism including a first roller 45, a second roller 46, a third roller 47, a fourth roller 48, and a belt 49. Since the belt surface between the fourth roller 48, the first roller 45, and the second roller 46 has a magnetic force, the magnetic powder-containing aggregates in the first mixing tank 17 are adhered to the belt surface. Can do. Since there is no magnetic force from the second roller 46 to the fourth roller 48, the aggregate 30 comes off from the third roller 47 and falls into the aggregate recovery tank 50. In this way, the aggregate 30 trapping the metal ions is collected in the aggregate recovery tank 50.

  Next, the process of recovering the metal from the aggregate in which the metal ions are trapped will be described with reference to FIG.

  First, an aqueous hydrochloric acid solution is introduced from the fourth tank 33 into the agglomerate collection tank 50 through the pipe 35 by the pump 34. Then, the aggregate 30 is dissolved. When the shutter 51 is opened, the liquid in which the aggregate 30 is dissolved is put into the metal recovery tank 36 through the filter 52.

  Subsequently, an aqueous sodium hydroxide solution is introduced into the metal recovery tank 36 from the fifth tank 38 through the pipe 40 by the pump 39. Then, the dissolved metal becomes a hydroxide and precipitates. Here, when the shutter 42 is opened, the water-soluble polymer having an acidic group and the water-soluble polymer having an amino group that are dissolved enter the chemical recovery tank 44 through the filter 43. The deposited metal hydroxide remains on the filter 43. Thus, the metal can be recovered also by using the magnetic separation method.

  The present invention will be described in more detail with reference to specific examples. The following examples show specific examples of the contents of the present invention, and the present invention is not limited to these examples, but by those skilled in the art within the scope of the technical idea disclosed in this specification. Various changes and modifications are possible. Moreover, all the following examples are performed at room temperature (15 degreeC or more and 20 degrees C or less).

Fe ₃₀ Nd ₃ PrDy is prepared as a magnet alloy containing a rare earth. In this alloy, three types of neodymium (Nd), praseodymium (Pr), and dysprosium (Dy) are added as rare earth metals to iron (Fe).

  Concentrated hydrochloric acid was added to 1 kg of this alloy and dissolved. Thereafter, 1N sodium hydroxide solution was added as an alkali metal hydroxide in order to control the pH to about 2. Thereafter, purified water was added to prepare a 1000 kg magnetic alloy aqueous solution as a whole. When components of this aqueous solution were analyzed by ion chromatography, Fe was 727 ppm, Nd was 160.4 ppm, Pr was 52.2 ppm, and Dy was 60.4 ppm. The total amount of metals was 1000 ppm.

  The trivalent ionic radii of these metals were 0.64 angstrom for Fe, 1.00 angstrom for Nd, 1.01 angstrom for Pr, and 0.91 angstrom for Dy.

  As a water-soluble polymer having an acidic group, 500 g of a 14.4% by weight polyacrylic acid aqueous solution was prepared. The repeating unit of polyacrylic acid has a molecular weight of about 72. Therefore, polyacrylic acid equivalent to 1 mol is dissolved in the repeating unit. To this, 500 g of 1N aqueous sodium hydroxide solution was added and stirred well. Thus, an aqueous solution in which 50% of the carboxyl groups of polyacrylic acid had a sodium salt structure was obtained. Let this aqueous solution be the aqueous solution A.

  1 kg of the magnetic alloy aqueous solution was put in a glass container, and 44 g of the aqueous solution A was dropped while stirring. While continuing the stirring, 30 g of a 4.3% by weight aqueous solution of polyethyleneimine was added dropwise. Then, an aggregate was formed. The liquid in the glass container was removed by filtration to collect aggregates. When hydrochloric acid was added to the aggregate, the aggregate was dissolved. While stirring the liquid in which the aggregate was dissolved, 1N sodium hydroxide was added dropwise to precipitate a solid. The liquid was filtered to recover the solid.

  The solid was dissolved in hydrochloric acid and purified water was added to make 1 kg. When the metal content in the liquid was measured by ion chromatography, Fe was 36 ppm, Nd was 152 ppm, Pr was 50 ppm, and Dy was 57 ppm. Fe became less than 5% by the said process. However, about 95% of the rare earth Nd, Pr, and Dy were all recovered, and the rare earth having a large ionic radius could be selectively recovered.

  As a water-soluble polymer having an acidic group, 500 g of a 14.4% by weight polyacrylic acid aqueous solution was prepared. To this, 450 g of 2N aqueous sodium hydroxide solution and 50 g of purified water were added and stirred well. Thus, an aqueous solution in which 90% of the carboxyl groups of the polyacrylic acid had a sodium salt structure was obtained. This aqueous solution is designated as aqueous solution B.

  Moreover, the sodium hydroxide aqueous solution to be added was reduced, and purified water was added correspondingly to prepare an aqueous solution in which 40% of the carboxyl groups of polyacrylic acid had a sodium salt structure and an aqueous solution in which 30% became a sodium salt structure. Let these aqueous solutions be the aqueous solution C and the aqueous solution D, respectively.

  An experiment was conducted in the same manner as in Example 1 except that 44 g of the aqueous solution B was used instead of 44 g of the aqueous solution A. As a result of ion chromatography, Fe was 30 ppm, Nd was 155 ppm, Pr was 51 ppm, and Dy was 58 ppm. Fe became less than 5% by the said process. However, about 95% of the rare earth Nd, Pr, and Dy were all recovered, and the rare earth having a large ionic radius could be selectively recovered.

  When an experiment was conducted in the same manner as in Example 1 except that 44 g of the aqueous solution C was used instead of 44 g of the aqueous solution A, the results of ion chromatography were 145 ppm for Fe, 147 ppm for Nd, 47 ppm for Pr, and 54 ppm for Dy. About 20% of Fe and about 90% of rare earth Nd, Pr and Dy were recovered by the above treatment. Although it was found that a rare earth having a large ionic radius can be selectively recovered, the selectivity is lower than when the aqueous solution A and the aqueous solution B are used.

  An experiment was performed in the same manner as in Example 1 except that the aqueous solution D44g was used instead of the aqueous solution A44g. As a result of ion chromatography, Fe was 295 ppm, Nd was 147 ppm, Pr was 47 ppm, and Dy was 54 ppm. About 40% of Fe and about 90% of rare earth Nd, Pr, and Dy were recovered by the above treatment. Although it was found that a rare earth having a large ionic radius could be selectively recovered, the selectivity was lower than when the aqueous solution A, the aqueous solution B and the aqueous solution C were used.

  From the above, the rare earth was selectively recovered when 50% or more of the carboxyl groups which are acidic groups have a sodium salt structure. Therefore, a rare earth metal having a large ionic radius could be selectively recovered by making 50% or more of the acidic groups into an alkali metal salt structure.

  1 kg of an aqueous solution in which 1.63 g of cadmium chloride and 2.91 g of ferric chloride were dissolved was prepared. This is a cadmium aqueous solution. Analysis of the components of this aqueous solution by ion chromatography revealed that 1000 ppm of cadmium (Cd) and 1000 ppm of Fe were dissolved. The ionic radii of these metals are 0.64 angstroms for Fe (trivalent) and 0.97 angstroms for Cd (divalent).

  While agitating 1 kg of the cadmium aqueous solution in a glass container, 72 g of the aqueous solution A was dropped. While continuing to stir, 48 g of a 4.3 wt% aqueous solution of polyethyleneimine was added dropwise. Then, an aggregate was formed. The liquid in the glass container was removed by filtration to collect aggregates. When hydrochloric acid was added to the aggregate, the aggregate was dissolved. While stirring the liquid in which the aggregate was dissolved, 1N sodium hydroxide was added dropwise to precipitate a solid. The liquid was filtered to recover the solid.

  The solid was dissolved in hydrochloric acid and purified water was added to make 1 kg. When the metal content in the liquid was measured by ion chromatography, Fe was 50 ppm and Cd was 952 ppm. Fe became about 5% by the said process. However, 95% of Cd was recovered, and Cd having a large ionic radius could be selectively recovered in addition to rare earths.

  500 g of an 8.6% by weight aqueous solution of polyethyleneimine was prepared. The repeating unit of ethyleneimine has a molecular weight of about 43. Therefore, polyacrylic acid equivalent to 1 mol is dissolved in the repeating unit. To this, 58 g of cyclohexanecarboxylic acid (molecular weight is about 116) which is a carboxylic acid having a cycloalkane ring and 442 g of purified water were added and stirred well. In this way, an aqueous solution in which 50% of the amino groups of polyethyleneimine had a carboxylate structure of cyclohexanecarboxylic acid was obtained. This aqueous solution is designated as aqueous solution E.

  Example 1 except that 44 g of a 7.2% by weight aqueous solution of polyacrylic acid was used as the water-soluble polymer having an acidic group instead of the aqueous solution A, and the aqueous solution E was used instead of 30% of a 4.3% by weight aqueous solution of polyethyleneimine. The same experiment was conducted. As a result of ion chromatography, Fe was 32 ppm, Nd was 150 ppm, Pr was 50 ppm, and Dy was 57 ppm. Fe became less than 5% by the said process. However, about 95% of the rare earth Nd, Pr, and Dy were recovered. Therefore, when the amino group of the water-soluble polymer having an amino group is 50% of a cyclic amine salt structure, a rare earth having a large ionic radius can be selectively recovered.

  50% of the amino group of polyethyleneimine is 2,2-dimethyl in the same manner as in Example 4 except that 51 g of 2,2-dimethylpropanoic acid, which is a carboxylic acid having a branched alkyl chain, is used instead of 58 g of cyclohexanecarboxylic acid. An aqueous solution having a propanoic acid carboxylate structure was prepared. This aqueous solution is designated as an aqueous solution F.

  An experiment was conducted in the same manner as in Example 4 except that 30 g of the aqueous solution F was used instead of 30 g of the aqueous solution E. As a result of ion chromatography, Fe was 35 ppm, Nd was 152 ppm, Pr was 50 ppm, and Dy was 58 ppm. Fe became less than 5% by the said process. However, about 95% of the rare earth Nd, Pr, and Dy were recovered. Therefore, when the amino group of the water-soluble polymer having an amino group has a 50% amino group and a salt structure of an amine having a branched alkyl chain, a rare earth having a large ionic radius can be selectively recovered.

  Further, by controlling the amount of 2,2-dimethylpropanoic acid added and the amount of purified water added, an aqueous solution in which 90% of the amino groups of polyethyleneimine have a carboxylate structure, A 30% aqueous solution was also prepared. Let these aqueous solutions be the aqueous solution G, the aqueous solution H, and the aqueous solution I, respectively.

  An experiment was performed in the same manner as in Example 4 except that 30 g of the aqueous solution G was used instead of 30 g of the aqueous solution E. As a result of ion chromatography, Fe was 32 ppm, Nd was 152 ppm, Pr was 50 ppm, and Dy was 57 ppm. Fe became less than 5% by the said process. However, about 95% of the rare earth Nd, Pr, and Dy were all recovered, and the rare earth having a large ionic radius could be selectively recovered.

  An experiment was conducted in the same manner as in Example 4 except that 30 g of the aqueous solution H was used instead of 30 g of the aqueous solution E. As a result of ion chromatography, Fe was 150 ppm, Nd was 147 ppm, Pr was 47 ppm, and Dy was 54 ppm. About 20% of Fe was recovered by the above treatment, and about 90% of all rare earth Nd, Pr, and Dy were recovered. Although a rare earth having a large ionic radius could be selectively recovered, the selectivity was lower than when the aqueous solution E and the aqueous solution F were used.

  An experiment was conducted in the same manner as in Example 1 except that 30 g of the aqueous solution I was used instead of 30 g of the aqueous solution E. As a result of ion chromatography, Fe was 300 ppm, Nd was 145 ppm, Pr was 46 ppm, and Dy was 52 ppm. About 40% of Fe was recovered by the above treatment, and about 90% of all rare earth Nd, Pr, and Dy were recovered. Although a rare earth having a large ionic radius could be selectively recovered, the selectivity was lower than when the aqueous solution E, the aqueous solution F, the aqueous solution G and the aqueous solution H were used.

  As described above, the rare earth was selectively recovered when 50% or more of the amino groups of the water-soluble polymer having an amino group have a carboxylate structure. Therefore, a rare earth metal having a large ionic radius could be selectively recovered by making 50% or more of amino groups into a carboxylate structure.

  An experiment was conducted in the same manner as in Example 1 except that 30 g of the aqueous solution F was used instead of 30 g of the 4.3% by weight aqueous solution of polyethyleneimine. As a result of the ion chromatography, Fe was 22 ppm, Nd was 151 ppm, and Pr was 50 ppm. , Dy was 57 ppm. Fe was about 3% by the above treatment. However, about 95% of the rare earth Nd, Pr, and Dy were recovered.

  As a result, even when both the water-soluble polymer having an acidic group and the water-soluble polymer having an amino group were partially salted, a rare earth having a large ionic radius could be selectively recovered.

  As a water-soluble polymer having an acidic group, 500 g of a 36.8% by weight aqueous solution of polystyrene sulfonic acid was prepared. The repeating unit of polystyrene sulfonic acid has a molecular weight of about 184. Therefore, polystyrene sulfonic acid equivalent to 1 mol is dissolved in the repeating unit. To this, 500 g of 1N aqueous sodium hydroxide solution was added and stirred well. Thus, an aqueous solution in which 50% of the sulfonic acid groups of polystyrene sulfonic acid had a sodium salt structure was obtained. This aqueous solution is designated as aqueous solution J.

  An experiment was conducted in the same manner as in Example 1 except that 44 g of the aqueous solution A was used instead of 44 g of the aqueous solution A. As a result of ion chromatography, Fe was 36 ppm, Nd was 155 ppm, Pr was 50 ppm, and Dy was 58 ppm. It was. Fe became less than 5% by the said process. However, about 95% of the rare earth Nd, Pr, and Dy were recovered.

  Therefore, even when the acidic group of the water-soluble polymer having an acidic group is not a carboxylic acid but a sulfonic acid, a rare earth having a large ionic radius can be selectively recovered.

  A copolymer composed of polyacrylic acid and polymethyl methacrylate was synthesized by suspension polymerization of acrylic acid (molecular weight of about 72) and methyl methacrylate (molecular weight of about 100). Three types of monomer ratios in the polymerization were synthesized: acrylic acid: methyl methacrylate = 30: 70, 50:50, 70:30. These are referred to as acrylic acid-30, acrylic acid-50, and acrylic acid-70, respectively.

  Next, a 9.16 wt% aqueous solution of acrylic acid-30, an 8.6 wt% aqueous solution of acrylic acid-50, and an 8.04 wt% aqueous solution of acrylic acid-70 are prepared.

  Instead of using 44 g of aqueous solution A, 44 g of 9.16 wt% aqueous solution of acrylic acid-30, 44 g of 8.6 wt% aqueous solution of acrylic acid-50, and 44 g of 8.04 wt% aqueous solution of acrylic acid-70, respectively The same experiment as in Example 1 was performed.

  As a result, when acrylic acid-70 was used, Fe was 36 ppm, Nd was 152 ppm, Pr was 50 ppm, and Dy was 57 ppm. Fe became less than 5% by the said process. However, about 95% of the rare earth Nd, Pr, and Dy were all recovered, and the rare earth having a large ionic radius could be selectively recovered.

  When acrylic acid-50 was used, Fe was 20 ppm, Nd was 130 ppm, Pr was 48 ppm, and Dy was 48 ppm. Fe became less than 3% by the said process. However, about 80% of the rare earth Nd, Pr, and Dy were recovered, and the rare earth having a large ionic radius could be selectively recovered.

  When acrylic acid-30 was used, Fe was 14 ppm, Nd was 120 ppm, Pr was 44 ppm, and Dy was 45 ppm. Fe became less than 2% by the said process. However, about 75% of the rare earth Nd, Pr, and Dy were recovered, and the rare earth having a large ionic radius could be selectively recovered.

  As described above, as the proportion of acrylic acid, that is, the proportion of acidic groups in the molecule decreases, Fe having a small ionic radius is hardly recovered. In addition, Pr, which has a particularly large ionic radius, shows less reduction in the recovery rate than Nd and Dy, indicating that the smaller the proportion of acidic groups in the molecule, the more selectively a metal with a larger ionic radius can be recovered. It was.

  Water-soluble DCC was added as a condensing agent to a part of the amino group of polyallylamine (the molecular weight of the repeating unit was about 57), and acetic acid was crosslinked with an amide bond. Two ratios of 50:50 and 70:30 were synthesized for the ratio of the non-amidated amino group and the amidated amino group, respectively. These are designated as polyallylamine-50 and polyallylamine-70, respectively.

  Next, an aqueous solution of 6.4% by weight of polyallylamine-50 and 5.56% by weight of polyallylamine-70 was prepared. Example 1 except that 30 g of a 6.4 wt% polyallylamine-50 aqueous solution and 30 g of a 5.56 wt% polyallylamine-70 aqueous solution were used instead of using 30 g of a 4.3 wt% polyallylamine aqueous solution. A similar experiment was conducted.

  As a result, when polyallylamine-50 was used, Fe was 20 ppm, Nd was 130 ppm, Pr was 48 ppm, and Dy was 48 ppm. Fe became less than 3% by the said process. However, about 80% of the rare earth Nd, Pr, and Dy were recovered, and the rare earth having a large ionic radius could be selectively recovered.

  When polyallylamine-70 was used, Fe was 36 ppm, Nd was 152 ppm, Pr was 50 ppm, and Dy was 57 ppm. Fe became less than 5% by the said process. However, about 95% of the rare earth Nd, Pr, and Dy were all recovered, and the rare earth having a large ionic radius could be selectively recovered.

  As described above, as the proportion of polyallylamine, that is, the proportion of amino groups in the molecule decreases, Fe having a small ionic radius is hardly recovered. In the case of this example, with respect to the mixing molar ratio of the copolymer, the ratio of the polymer in which the acidic group is bonded to the main chain composed of linear hydrocarbon is adjusted to 30% or more and 70% or less. The metal was selectively recovered. In addition, Pr with a particularly large ionic radius has a lower recovery rate than Nd and Dy, so that the metal with a larger ionic radius could be selectively recovered as the proportion of the amino group in the molecule decreased.

  The same experiment as in Example 1 was performed except that acrylic acid-50 prepared in Example 8 was used in the same manner as in Example 8, and polyallylamine-50 prepared in Example 9 was used in the same manner as in Example 9. As a result, Fe was 5 ppm, Nd was 120 ppm, Pr was 44 ppm, and Dy was 45 ppm. Fe became less than 1% by the said process. However, about 75% of the rare earth Nd, Pr, and Dy were all recovered, and the rare earth having a large ionic radius could be selectively recovered.

  As described above, the amino group is bonded to the main chain consisting of a polymer composed of a polymer having an acidic group bonded to the main chain composed of linear hydrocarbons and a polymer not containing an acidic group, and the main chain composed of linear hydrocarbons. In comparison with Example 8 and Example 9 used alone, the polymer and the copolymer composed of a polymer having no amino group are used as in this example, so that The metal of ionic radius could be collected more selectively.

DESCRIPTION OF SYMBOLS 1 Transition metal ion 2,13 Water-soluble polymer having amino group 3 Bonded product composed of metal ion and water-soluble polymer having amino group 4 Water-soluble polymer having carboxyl group 5 Ion bond 6,30 Aggregate 7 Acid 8 Ammonium salt polymer 9 Base 10 Carboxylate polymer 11 Transition metal ion 12 Carboxylate structure 14 First tank 15, 19, 22, 24, 28, 34, 39 Pump 16, 20 , 23, 25, 29, 35, 40 Piping 17 First mixing tank 18 Second tank 21 Overhead stirrer 26 Second mixing tank 27 Third tank 31, 42, 51 Shutter 32, 43, 52 Filter 33 First 4 tank 36 metal recovery tank 37 valve 38 fifth tank 41 transition metal hydroxide 44 drug recovery tank 45 first roller 46 second Ra 47 third roller 48 the fourth roller 49 the belt 50 aggregates recovery tank

Claims (10)

A metal recovery method for recovering a metal as an aggregate by coordination bond,
Adding a water-soluble polymer having an amino group, part of which is an ammonium carboxylate, to an aqueous solution in which either rare earth metal or cadmium and iron are dissolved;
Adding a water-soluble polymer having an acidic group, part of which is an alkali metal salt, to form an aggregate containing either the rare earth metal or cadmium;
A metal recovery method including a step of recovering the aggregate. The metal recovery method according to claim 1,
The product of the number of moles and the coordination number of the metal in the aqueous solution is MB, the number of acidic groups of the water-soluble polymer having acidic groups is PA, and the number of amino groups of the water-soluble polymer having amino groups is Metal recovery method that adjusts so that PA + PB <MB when PB is satisfied. The metal recovery method according to claim 1 or 2,
A metal recovery method comprising a step of adding magnetic powder or iron powder to the water-soluble polymer having an amino group or the water-soluble polymer having an acidic group. In the metal recovery method according to any one of claims 1 to 3,
Adding an aqueous solution of a strong acid to the aggregate to dissolve the aggregate;
A step of Ru to precipitate a hydroxide by adding a strong base aqueous solution to the liquid in which the agglomerate has dissolved,
And a step of recovering the hydroxide . A first tank comprising an aqueous solution of a water-soluble polymer having an acidic group;
A second tank comprising an alkali metal hydroxide aqueous solution;
A first mixing tank in which an aqueous solution of the water-soluble polymer having an acidic group, the alkali metal hydroxide aqueous solution, a rare earth metal or an aqueous solution in which cadmium is dissolved and iron is mixed;
A third tank comprising an aqueous solution of a water-soluble polymer having an amino group;
A second mixing tank in which the aqueous solution of the water-soluble polymer having an amino group and the liquid mixed in the first mixing tank are mixed;
A metal separation and recovery device comprising: a mechanism for recovering an aggregate containing either the rare earth metal or cadmium generated in the second mixing tank from the liquid component of the second mixing tank. The metal separation and recovery apparatus according to claim 5,
The first tank includes an aqueous solution of a water-soluble polymer having an amino group instead of the aqueous solution of the water-soluble polymer having an acidic group,
The third tank is a metal separation / recovery device comprising an aqueous solution of a water-soluble polymer having an acidic group instead of an aqueous solution of a water-soluble polymer having an amino group. In the metal separation / recovery device according to claim 5 or 6,
The third tank is a metal separation and recovery device further comprising magnetic powder or iron powder. In the metal separation / recovery device according to any one of claims 5 to 7,
A metal separation and recovery device having a mechanism for adding hydrochloric acid or nitric acid to the aggregate. The metal separation and recovery device according to claim 8,
A metal separation and recovery device having a mechanism for adding a second alkali metal hydroxide aqueous solution after adding hydrochloric acid or nitric acid. The metal separation and recovery apparatus according to claim 9,
A metal separation and recovery device having a mechanism for recovering a solid produced after charging the second alkali metal hydroxide aqueous solution.

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