JP2005305411A - Device and method for separating/recovering metal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device and a method for separating/recovering industrial metals, which enables the separation and recovery of the metals from a solution, where the metals are dissolved, with high selectivity and high yield, and has a low treating cost. <P>SOLUTION: The metal separating/recovering device has a simulating moving bed separating means 1 provided with columns 11a to 11h filled with an ion-exchange resin or a chelating resin. The metal separating/recovering method enables the separation/recovery of the metals from the solution containing the metals by passing the solution containing the metals and an eluate through the column 11a to 11h using the separating means 1 provided with the columns filled with the ion-exchange resin or the chelating resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a metal separation and recovery apparatus and a metal separation and recovery method.

In refining and plating, a large amount of metal-containing waste liquid such as refining waste liquid and plating waste liquid is generated. However, if the metal-containing waste liquid flows out into the environment such as rivers, lakes and marshes, it may cause heavy metal contamination. is there. Therefore, it is required to separate and recover the metal from the metal-containing waste liquid, and further, it is desired from the viewpoint of effective use of resources that the metal is separated and recovered as a simple substance and recycled.
In particular, the amount of precious metals such as platinum, palladium, and rhodium, which are often used as catalysts for automobile exhaust gas treatment and chemical reaction, is extremely small, and the mining sites are limited. I'm waiting. Moreover, these noble metals are also contained in the high-level radioactive nitric acid waste liquid of spent nuclear fuel, and a technique for recovering from the high-level radioactive nitric acid waste liquid before solidification treatment with molten glass is required. Furthermore, in many cases, since the metal-containing solution contains a plurality of metals, it is desired to separate and recover each metal.

  In addition, reactions using homogeneous metal catalysts such as transesterification reactions with organotin catalysts and asymmetric hydrogenation reactions with rhodium complex catalysts have the advantage of clear reaction mechanism and high selectivity even at low reaction temperatures. On the other hand, it was difficult to separate the catalyst from the reaction solution. For this reason, those that can be industrialized are limited to those that can extract and separate the catalyst in an oil-water two-phase system, but there is a need for a method that can separate a metal-containing catalyst other than in an oil-water two-phase system. Further, since many homogeneous metal catalysts are expensive, establishment of a method for separating the reaction solution from the metal catalyst is awaited.

Examples of conventional metal recovery methods include a classic precipitation method in which precipitation and dissolution due to complex formation are repeated (for example, see Non-Patent Document 1), and an electrodeposition method for recovery by electrolytic deposition (for example, see Patent Document 1). In recent years, highly selective metal extractants have been developed, and many patents for solvent extraction methods using the metal extractants have been filed (see, for example, Patent Document 2). Also, in the adsorption method in which metal is adsorbed on an anion exchange resin, the method of incinerating the anion exchange resin after adsorption with the anion exchange resin (for example, refer to Non-Patent Document 2) and the method for elution after adsorption are selected. There have been proposed a method of performing a general elution (see, for example, Patent Document 3), a method of adsorbing and recovering with a chitosan derivative that is a chelate resin (for example, see Patent Document 4), and the like. Furthermore, a method of optically resolving an optically active platinum complex compound by a chromatographic method (see Patent Document 5), a method of applying a simulated moving bed method by size exclusion chromatography, specifically, using a halogen solution as an eluent, There has been proposed a method for separating and recovering a metal from a metal halogeno complex containing a noble metal or a base metal halide using a hydrophilic gel such as polysaccharide or polyacrylamide as a filler (see, for example, Patent Documents 6 to 8). Further, in the phenol resin production process, a method of separating and removing an acid catalyst and a metal cation that is a water-soluble impurity by a simulated moving bed method using a cation exchange resin as a filler (see Patent Document 9). ) Is disclosed.
Japanese Unexamined Patent Publication No. 01-83682 JP-A-10-265863 JP 07-310129 A Japanese Patent No. 3053102 Japanese Patent Laid-Open No. 06-287021 U.S. Pat. No. 4,885,143 Japanese Patent No. 3291203 Japanese National Patent Publication No. 2001-516808 JP 2001-226443 A R. Bee. Heslop (RB Heslop), Pea. El. Robinson, translated by Yoshihiko Saito, “Inorganic Chemistry (below)”, 3rd edition, published by Tokyo Chemical Doujin, p744 Ion Exchange Resin Division, “Diaion Ion Exchange Resin / Synthetic Adsorbent Manual [II] Application”, 15th edition, published by Mitsubishi Chemical Corporation, p87-92

In the precipitation method described in Non-Patent Document 1, it is necessary to repeat purification many times, and there are problems that the time required for separation is long and that the yield is low and the cost is high.
The electrodeposition method described in Patent Document 1 also has a problem that the selectivity is poor, the purification needs to be repeated many times, the time required for the separation is long, and the yield is low and the cost is high.
The solvent extraction method described in Patent Document 2 requires multi-stage extraction and back-extraction operations, and the extraction speed is slow, and the extractant tends to deteriorate, is expensive, and uses dangerous materials. It was.
The method described in Non-Patent Document 2 has poor adsorption selectivity, so it is not suitable for the separation and recovery of a plurality of noble metals, and the cost increases if the ion exchange resin is made disposable.
In the method described in Patent Document 3, it is difficult to achieve a large amount of processing because it is not highly purified by one elution and needs to be purified, and the adsorption capacity is limited.

In the method described in Patent Document 4, it has been proposed to use chitosan as an inexpensive chelating resin for adsorbing noble metals. However, since chitosan remains dissolved in most acids, it is insolubilized by crosslinking or derivatizing chitosan. It was necessary to process it, and it became expensive. In addition, there is a problem that elution selectivity and elution rate are lower than those of ion exchange resins.
In the method described in Patent Document 5, an excellent effect is exhibited for a small amount of analysis or the like, but when a large amount of metal-containing liquid is treated industrially, the efficiency is low and it cannot be applied.
Thus, when each metal is separated and recovered from a solution in which a plurality of metals are dissolved by a conventional metal recovery method, the selectivity and yield are low, and the time required for separation is long.

In addition, gel permeation chromatography as described in Patent Documents 6 to 8, as described in Patent Document 6, the separation mode is not sieving by molecular size, but molecular polarization or electrostatic This is considered to be separation utilizing hydrogen bonding with the gel due to attractive force. Therefore, the metal cations that do not form a complex by these methods have the disadvantage that they are uniformly eluted quickly and cannot be separated from each other, and the metal cations cannot be separated from each other even if a simulated moving bed is used. In addition, the material in the apparatus has to be made acid and corrosion resistant for separation in the halogen solution, and the apparatus cost is high, which is not industrial.
The method described in Patent Document 9 is not intended to recover metal from a metal-containing solution. In addition, a technique related to desalination of a sugar solution is also disclosed, but there is no description about separation and recovery of a homogeneous metal catalyst. That is, a technique for separating and recovering the homogeneous metal catalyst from the reaction liquid has not been established.
The present invention has been made in view of the above circumstances, and can separate and recover a metal from a solution in which the metal is dissolved with high selectivity and high yield. It is an object of the present invention to provide a recovery device and a metal separation and recovery method.

The metal separation and recovery device of the present invention is characterized by having a simulated moving bed type separation means including a column packed with an ion exchange resin or a chelate resin.
The method for separating and recovering a metal according to claim 2 of the present invention uses a simulated moving bed type separation means having a column packed with an ion exchange resin or a chelate resin, and passes the metal-containing solution and the eluent through the column, and the metal in the metal-containing solution. Is separated and recovered.
In the metal separation and recovery method of the present invention, when the metal-containing solution is a multiple-metal-containing solution containing a plurality of metals, the multiple-metal-containing solution is filled with an ion exchange resin before passing through the simulated moving bed type separation means. And passed through a pre-separation column.
In addition, the method for separating and recovering a metal according to claim 4 of the present invention uses a simulated moving bed type separation means, and from a metal-containing solution containing a homogeneous metal catalyst and a product obtained using the homogeneous metal catalyst, A system metal catalyst and a product are separated and recovered.

In the metal separation and recovery apparatus and the metal separation and recovery method of the present invention, each genus can be separated and recovered with high selectivity and high yield from a solution in which the metal is dissolved. In addition, since it is continuous and requires a short time for separation, the cost can be reduced and the apparatus may be non-corrosion resistant, which is industrial.
When the metal-containing solution is a multiple metal-containing solution, each metal can be separated and recovered with high selectivity and high yield. In particular, if the multiple metal-containing liquid is passed through a preliminary separation column packed with an ion exchange resin before passing through the simulated moving bed type separation means, the selectivity and yield can be further increased.
When the metal-containing solution is a reaction solution containing a homogeneous metal catalyst, the metal catalyst and the product can be separated and recovered with high selectivity, high yield, and low cost.

A first embodiment of the present invention will be described.
The first embodiment is an example of a multiple metal-containing solution in which the metal-containing solution contains a plurality of metals. That is, the metal separation and recovery method in the first embodiment uses a simulated moving bed type separation means having a column packed with a packing material, and passes the multiple metal-containing solution and the eluent through the column in the multiple metal-containing solution. This is a method for separating and recovering each metal.

(Multiple metal-containing solution)
The multiple metal-containing solution is a metal-containing solution containing a plurality of metals, and the metal-containing solution is a solution in which a metal is dissolved in water, an acid / alkali, an organic solvent or a mixed solution thereof. Here, the metal refers to B (boron), Si (silicon), As (arsenic), Te (tellurium), At among the 1 to 7 groups A, 8 and 1 to 7 groups B excluding hydrogen. (Astatine) is the element on the left.
Specific examples of the metal-containing solution include a transition metal-containing solution and a noble metal-containing solution, and the transition metal-containing solution is an element of the periodic table 3-7 group A, 8 group, 1-2 group B (transition metal) The noble metal-containing solution is a platinum group Ru (ruthenium), Rh (rhodium), Pd (palladium), Os (osmium), Ir of the periodic table group 8. It is a solution containing at least one of (iridium), Pt (platinum), Group 1 B Au (gold), Ag (silver) (previously, noble metal).

That is, transition metals and noble metals are added by adding an oxidant such as aqua regia, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid or the like, or chlorine gas (see Japanese Examined Patent Publication No. 62-2014) or hydrogen peroxide to the acid. Examples thereof include a solution dissolved as an ion or a metal complex, a solution dissolved as a cyano complex by a bluening method, and a solution obtained by dissolving a metal complex in water, an aqueous salt solution, an acid, an alkali, an organic solvent, or a mixed solution thereof. Furthermore, as a solution in which the metal complex is dissolved in water, an aqueous salt solution, an acid, an alkali, an organic solvent or a mixed solution thereof, for example, a thiocyanato complex salt solution in which a chloro complex salt is dissolved in an aqueous sodium thiocyanate solution or an aqueous potassium nitrite solution Examples thereof include a nitro complex salt solution, a phosphine complex solution dissolved in triphenylphosphine in an ethanol solvent, other ammine complexes, and various chelate complexes.
Among the complexes, halogeno complexes are obtained relatively easily and are stable, but there is a problem of apparatus corrosion due to halogen. In addition, halogen salts also have a problem of corrosion of equipment. Although cyano complexes are stable, there are safety issues due to the use of toxic cyanides. Therefore, the metal-containing solution is preferably a solution containing a complex other than a halogeno complex, a halogen salt and a cyano complex, that is, a solution containing a nitro complex, a thiocyanate complex, a phosphine complex, an ammine complex, or various chelate complexes.

The metal-containing liquid is, for example, a heterogeneous metal catalyst supported on a carrier, a substrate for electronic industry, jewelry, a solution in which metal is eluted from a dental metal-containing material, or a heterogeneous metal catalyst production waste liquid, metal refining Waste liquid, plating waste liquid, development waste liquid, nitric acid solution generated from a reprocessing plant for spent nuclear fuel in a light water reactor or fast reactor, a metal-containing waste liquid such as a radioactive process waste liquid, or a homogeneous metal catalyst-containing liquid.
When recovering the noble metal from the used heterogeneous metal catalyst, it is preferable to dissolve the noble metal after pulverizing the support in order to facilitate the dissolution of the noble metal. Moreover, when containing metals, such as iron and nickel, such as a used automobile catalyst and a metal support | carrier, these may also melt | dissolve. The same applies to substrates for electronic industries, jewelry, dental materials, and the like. It is preferable to filter after dissolution, and examples of the filtering method include a method of filtering the supernatant by centrifugation and a method of directly filtering. Although filtration depends on pH, it is an acid-resistant filter, and it is preferable to use a filter paper or a glass filter. In addition to filtration, the metal deposited by electrodeposition and deposited on the electrode may be redissolved or incinerated and redissolved.

(Metal separation and recovery equipment)
The metal separation and recovery apparatus has a simulated moving bed type separation means.
The simulated moving bed type separation means is a device in which a plurality of columns filled with a filler are connected in an endless manner in series, and liquid can be discharged from each column while liquid can be introduced into each column.
FIG. 1 shows an example of a simulated moving bed type separation means. This simulated moving bed type separation means 1 includes eight columns (packed beds) 11a to 11h filled with a filler and connected in series endlessly, and a plurality of metal-containing solution transfer pipes 21 for transferring a plurality of metal-containing solutions. An eluent transfer pipe 22 that transfers the eluent, an extract transfer pipe 23 that transfers the extract discharged from each column, a raffinate transfer pipe 24 that transfers raffinate discharged from each column, a column 11a and a column 11h, a recycling pipe 25 that guides the liquid discharged from the column 11h to the column 11a, connecting pipes 40a to 40g that connect adjacent columns, and a pump 50 provided in the recycling pipe 25. Configured. A flow path formed by the columns 11a to 11h, the recycle pipe 25, and the connection pipes 40a to 40g is referred to as a circulation flow path 70.
Here, the multiple metal-containing solution is a solution containing a plurality of metals, and the eluent is a multiple metal introduced into the circulation flow path 70 by moving the circulation flow path 70 by the pump 50. It is a mobile phase that causes the contained solution to flow, and the extract is a solution that contains a metal that is easily adsorbed on the filler, and the raffinate is a solution that contains a metal that is difficult to adsorb on the filler. It is.

  The multiple metal-containing solution transfer pipe 21 and the columns 11a to 11h are connected by multiple metal-containing solution introduction pipes 31a to 31h, respectively. The eluent transfer pipe 22 and the columns 11a to 11h are respectively connected to the eluent introduction pipe 32a. -32h, the extract transfer pipe 23 and the columns 11a-11h are connected by extract discharge pipes 33a-33h, respectively, and the raffinate transfer pipe 24 and the columns 11a-11h are respectively raffinate discharge pipes 34a-34h. Connected with. Further, the multiple metal-containing solution introduction pipes 31a to 31h, the eluent introduction pipes 32a to 32h, the extract discharge pipes 33a to 33h, and the raffinate discharge pipes 34a to 34h are set so as to be appropriately opened and closed by sequence control or the like. Solenoid valves 35a to 35h (solenoid valves for introducing a plurality of metal-containing solutions), 36a to 36h (solenoid valves for introducing an eluent), 37a to 37h (solenoid valves for discharging an extract), 38a to 38h (solenoid valves for discharging a raffinate) ) Is provided. The recycle pipe 25 is provided with a measuring device 60 for measuring ultraviolet (UV) absorption of the solution flowing through the recycle pipe 25.

[column]
The packing material filled in each of the columns 11a to 11h is an ion exchange resin or a chelate resin.
The ion exchange resin or chelate resin is obtained by crosslinking a functional monomer polymer with a crosslinkable monomer. Examples of the functional monomer include unsaturated carboxylic acid, (meth) acrylic acid ester, (meth) acrylamide derivative, styrene. Among the derivatives, vinyl esters, allyl alcohol derivatives, other vinyl compounds, chitosan derivatives, etc., those into which functional groups having ion exchange ability and chelate ability are introduced. Examples of the crosslinkable monomer include aliphatic or aromatic vinyl monomers such as ethylene glycol dimethyl acrylate, N, N′-methylenebisacrylamide, and divinylbenzene. Moreover, when a functional monomer is a chitosan derivative, what cross-linked by epichlorohydrin etc. and what introduce | transduced the functional group into this can be used.

  Commercially available ion exchange resins and chelate resins include Diaion WA20, Diaion SA10A, Diaion CR20 (manufactured by Mitsubishi Chemical Corporation), Sumichel CR-2 (manufactured by Sumitomo Chemical Co., Ltd.), Amberlite IRA400, Amberlite XAD4 Amberlyst A26 (Rohm & Haas, USA), Dowex Marathon A, Dowex Marathon C (Dow Chemical, USA), Chelate Chitopearl CS-03 (Fuji Boseki Co., Ltd.), and the like.

Examples of the shape of the filler include a granular shape and a monolithic shape, and a granular shape is preferable, and a spherical shape is preferable among the granular shapes. In that case, the particle size is preferably 1 to 2000 μm, and more preferably 100 to 600 μm.
The exchange capacity when the filler is an ion exchange resin does not need to be large for use as a chromatographic filler, but rather is preferably small, preferably 0.001 to 10 meq./g, more preferably 0.01. ~ 1 meq./g. Moreover, if a cation exchange resin and an anion exchange resin are mixed or each column is connected and used at the same time, both the cation and the anion can be separated from each other.

[Eluent]
The eluent is a fluid that can elute ions / complex ions adsorbed on the filler and is not limited unless it dissolves or swells the filler to increase pressure loss or does not dissolve ions / complex ions. Alternatively, a supercritical fluid may be used. For example, water, aqua regia, acidic aqueous solutions such as hydrochloric acid, nitric acid, sulfuric acid, various aqueous alkaline solutions such as aqueous ammonia, various aqueous salt solutions such as potassium chloride, sodium cyanide, sodium thiocyanate, alcohol, acetonitrile, n-hexane, etc. An organic solvent or a mixed solution thereof can be suitably used. In addition, halogen-based eluents containing halogen are not preferable because they cause a problem of apparatus corrosion due to halogen.

In separation of the chloro complex by anion exchange, it is preferable to use a 0.01 M or more hydrochloric acid aqueous solution or a sodium chloride aqueous solution as an eluent. The distribution coefficient of each element from hydrochloric acid aqueous solution to strong basic anion exchange resin has been reported (Ion Exchange Resin Division, “Diaion Ion Exchange Resin / Synthetic Adsorbent Manual [I] Fundamentals”, Section 16th edition, published by Mitsubishi Chemical Corporation, p89).
In the case of separation of chloro complexes by anion exchange, it is known that if perchlorate ions are present in the eluent, the competitive reaction with respect to the ion exchange site becomes more dominant than chloro complexes, and it becomes easier to elute (MD). Seymour, J.S. Fritz, “Analytical Chemistry”, Volume 45, (American Chemical Society), 1973, p1394, R. D. Rocklin. (RD Rocklin), “Analytical Chemistry”, Vol. 56, (American Chemical Society), 1984, p1959). Further, the eluent used for separation of the chloro complex by anion exchange may be perchlorate alone.
Furthermore, it is preferable to mix a buffer such as phosphate because the pH is stabilized. When the buffer is not mixed, it is preferable to monitor the pH of the eluent and adjust the pH with an acid or alkali.

  When the multiple metal-containing solution is a multiple metal-containing halogen solution, the halogen-free non-halogen eluent such as alkali cyanide or alkali thiocyanate, aqueous nitrite solution, triphenylphosphine solution, other chelate It is preferable to use an aqueous solution. In this way, by using a non-halogen-based eluent for a halogen solution containing a plurality of metals, a complex that is more stable than a halogeno complex can be formed and separated. This is because the ligand substitution reaction occurs instantaneously in the substitution active complex (The Chemical Society of Japan, “Experimental Chemistry Course 17”, 4th edition, published by Maruzen Co., Ltd., p2). Among non-halogen-based eluents, alkali thiocyanide, nitrite aqueous solution, and triphenylphosphine solution are preferable from the viewpoint of safety. The halogen may be discharged as an extract or raffinate, or may be discharged by exchanging the eluent.

  The temperature of the eluent may be within the temperature range in which the filler can be used, and is preferably 0 to 100 ° C, more preferably 20 to 40 ° C. In the eluent, a complexing agent such as citric acid or a reducing agent may be added. The flow direction of the eluent may be an upward flow or a downward flow with respect to the column.

  In the simulated moving bed type separation means 1, the liquid contact portion that comes into contact with the multiple metal-containing solution or the eluent is preferably made of a corrosion resistant material. Here, the corrosion resistant material is SUS316, SUS317, a metal selected from tantalum, hafnium, zirconium, niobium, titanium and / or an alloy thereof, or ceramic such as hastelloy or glass, silicone, polyolefin, polyetheretherketone. (PEEK resin), fluororesin, etc. are mentioned. In addition, a column is good also considering only the inner surface as a corrosion-resistant material, and making the outer surface which a liquid does not contact into a non-corrosion-resistant material.

(Metal separation and recovery method)
Next, an example of a method for separating and recovering a metal from a multiple metal-containing solution containing two kinds of metals using the above-described simulated moving bed type separation means will be described.
First, the pump 50 is operated to cause the eluent to flow into the circulation channel 70. Along the flow direction of the circulating fluid, (1) an eluent inlet, (2) an extract outlet for extracting a liquid (extract) containing metal that is easily adsorbed by the filler, (3 The electromagnetic valve is opened and closed so that the multiple metal-containing solution inlet and (4) the raffinate outlet for extracting the liquid (raffinate) containing the metal that is difficult to adsorb to the filler are arranged in this order. The electromagnetic valve opens and closes so that each of these inlets or outlets moves intermittently and sequentially in the direction of fluid flow in the columns 11a to 11h. For example, the solenoid valves 36a, 37a, 35b, and 38b are opened, and the multiple metal-containing solution is introduced into the column 11b from the multiple metal-containing solution transfer pipe 21 through the multiple metal-containing solution introduction pipe 31b. The introduced multiple metal-containing solution is introduced into the column 11b and flows in the column 11b. At that time, since the adsorptivity to the filler in 11b is different between the two types of metals, the solution (raffinate) containing a metal that is difficult to adsorb flows quickly in the column 11b, and a liquid containing an easily adsorbed metal (extract ) Flows slowly. By utilizing such a difference in adsorptivity, it can be separated into raffinate and extract.

  Next, the solenoid valves 36a, 37a, 35b, and 38b are closed, and the solenoid valves 36b, 37b, and 35c are passed through the vicinity of the outlet of the solenoid valve 35c in the connecting pipe 40b until the extract peak reaches after the raffinate peak passes. , 38c are opened. Then, the raffinate is discharged from the column 11c before the extract, and then is extracted to the raffinate transfer pipe 24 through the raffinate discharge pipe 34c. At the same time, the eluent is passed through the column 11b, and the extract is extracted to the extract transfer pipe 23 through the discharge pipe 33b. By such a series of steps, two kinds of metals can be separated and recovered.

  In this metal separation and recovery method, after the above-described steps are completed, the column for performing the metal separation and recovery is changed in order. That is, after the metal is separated and recovered by the column 11b, the metal is separated and recovered in the order of the column 11c, the column 11d,. Since the columns 11a to 11h are connected in series endlessly, after the metal is separated and recovered by the column 11h, the metal is separated and recovered by the column 11a. In addition, since the discharge | emission state of raffinate and an extract can be confirmed by the measurement of UV absorption etc., the timing which changes a column can be determined based on the result.

  After separating and recovering the extract and raffinate as described above, the metal is recovered from each of them. As a method for recovering the metal from the extract or raffinate, for example, an electrodeposition method in an electrolytic cell, a method of adding a reducing agent to precipitate as metal black, a combustion method, a method combining these, or the like can be applied. Among these, in the method of adding a reducing agent and precipitating, hydrazine, formaldehyde, formic acid, sodium borohydride, potassium and other metals, hydrogen, and the like can be used as the reducing agent. In the combustion method, firing may be performed at 300 ° C. or higher, preferably 350 to 700 ° C., and performed in a hydrogen stream.

  In this separation and recovery method, as a pre-process, a solution containing a plurality of metals is passed through a pre-separation column packed with a cation exchange resin or an anion exchange resin, so that the plurality of metals to be separated are only cations or anions. It is preferable to keep it. For example, it is preferable to remove a base metal cation through a preliminary separation column packed with a cation exchange resin in advance for mutual separation of noble metal complexes. Thus, when the multiple metal-containing solution is made only of cations or anions, the selectivity and yield of separation and recovery are further improved.

  In the first embodiment described above, a plurality of metals are separated from a plurality of metal-containing solutions using a simulated moving bed type separation means having a column filled with an ion exchange resin or a chelate resin as a filler. , Selectivity and yield are high. As a result, the purification process can be omitted. Moreover, the simulated moving bed type separation means is efficient because it separates and recovers metals continuously, and there is no need to use a halogen solution as a solution containing a plurality of metals. it can.

A second embodiment of the present invention will be described.
The second embodiment is an example of a reaction solution in which a metal-containing solution contains a homogeneous metal catalyst and a product obtained using the homogeneous metal catalyst. That is, the metal separation and recovery method in the second embodiment example uses the same metal separation and recovery apparatus as in the first embodiment example, and passes the reaction solution and the eluent through the column to pass the homogeneous metal catalyst and product. It is a method of separating and collecting.
In the second exemplary embodiment, the same filler and eluent can be used as in the first exemplary embodiment. However, as the filler, a homogeneous metal catalyst or one that easily adsorbs the product can be used, and in addition to the ion exchange resin and chelate resin, hydrophilic gels such as ODS, polysaccharide gel, and polyacrylamide gel are used. Can also be used. As the eluent, a homogeneous metal catalyst adsorbed on the filler or one that easily elutes the product is used.
Examples of the homogeneous metal catalyst include organic metals or metal complexes such as transesterification reaction using an organotin catalyst and asymmetric hydrogenation reaction using a rhodium complex catalyst.

By the separation and recovery method of the second embodiment, the reaction solution obtained using the homogeneous metal catalyst is separated into extract and raffinate, and the homogeneous metal catalyst is separated from one of them and the product is separated from the other. It can be recovered with high selectivity, high yield and low cost. Therefore, an expensive homogeneous metal catalyst can be industrially separated and recovered from the reaction solution.
The liquid containing the product separated and recovered by this method is purified by distillation or the like, and the homogeneous metal catalyst is reused or the metal is recovered by incineration.

In addition, this invention is not limited to the example mentioned above. In the example described above, the simulated moving bed type separation means has eight columns, but is not limited thereto, and preferably four or more columns are appropriately selected. As the simulated moving bed, for example, U.S. Pat. No. 2,985,589 which performs two-component separation, Japanese Patent Publication No. 42-15561, Japanese Patent No. 890042, Japanese Patent No. 2740780, which performs multi-component separation, and Japanese Patent No. 2,965,747. The publications described in Japanese Laid-Open Patent Publication No. 1954744, Japanese Patent Publication No. 200200292, and Japanese Patent No. 20000830 with four columns can be used.
Moreover, not only the separation and recovery of two types of metals, but also the separation and recovery of many types of metals is possible.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
(Example 1) Transition metal separation and recovery by simulated moving bed type separation means 30 ml of polyamine type chelate resin (Diaion CR20) is packed in a glass column (inner diameter 15 mm, length 300 mm), and as shown in FIG. Connected to provide a simulated moving bed type separation means. In addition, reagent-grade copper chloride (II) dihydrate and nickel chloride (II) hexahydrate (both manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 2N hydrochloric acid so as to be 10 g / l as a metal. A multiple metal containing solution was prepared.

First, in the simulated moving bed type separation means, the pump 50 (high pressure chemical pump SP-D-4602U (manufactured by Nippon Seimitsu Kagaku Co., Ltd.)) whose liquid contact part is a fluororesin (corrosion resistant material) is operated and circulated. The eluent was flowed into the flow path 70 at 1 ml / min. Next, the solenoid valves 36a, 37a, 35b, and 38b are opened, and an eluent is introduced into the column 11a from the eluent transfer pipe 22 through the eluent introduction pipe 32a at room temperature at 1 ml / min. The multiple metal-containing solution was introduced from the solution transfer tube 21 to the column 11b through the multiple metal-containing solution introduction tube 31b at 50 μl / min. Then, using the difference in the adsorptivity of copper and nickel to the polyamine type chelate resin, the column 11b was separated into a raffinate containing nickel chloride and an extract containing copper chloride.
Next, the solenoid valves 36a, 37a, 35b, and 38b are closed, and the solenoid valves 36b, 37b, 35c, and the like until the extract peak reaches after the raffinate peak passes near the outlet of the solenoid valve 35c in the connection pipe 40b. 38c was opened. Then, the raffinate was discharged from the column 11c before the extract, and extracted to the raffinate transfer pipe 24 through the raffinate discharge pipe 34c at 0.5 ml / min. At the same time, the eluent was passed through the column 11b, and the extract was extracted into the extract transfer pipe 23 through the discharge pipe 33b at 0.5 ml / min.

  Thereafter, the column for separating the metal was changed in the order of the column 11d,..., The column 11h, and the column 11a, and the metal was continuously separated and recovered. The timing for changing the order of the columns for separating the metal is determined based on the UV (225 nm) absorption of the liquid in the extract transfer tube 23 and raffinate transfer tube 24 and the result of the UV (225 nm) absorption measuring device 60 in the recycle tube 25. did.

  In this way, the multiple metal-containing solution is separated into extract and raffinate, and copper chloride can be recovered from the extract at a concentration of 0.95 g / l Cu (recovery rate 95%), and nickel chloride from the raffinate can be recovered at 0.90 g / Ni. It was recovered at a concentration of 1 (recovery rate 90%).

(Example 2) Separation and recovery of precious metals by simulated moving bed separation means Reagent-grade chloroplatinic acid hexahydrate, reagent-grade palladium chloride, calcium chloride (all manufactured by Wako Pure Chemical Industries, Ltd.) ) Was dissolved in 1N hydrochloric acid, and a solution having a metal concentration of 10 g / l was used. This multiple metal-containing solution was passed through a glass column (inner diameter: 15 mm, length: 300 mm), which was a preliminary separation column packed with 30 ml of a strongly acidic cation exchange resin Diaion SK1B in advance, and Ca ²⁺ was removed by adsorption.
The multiple metal-containing solution is 1N hydrochloric acid, and this is a simulated moving bed similar to that in Example 1 in which 30 ml of each column is packed with a quaternary ammonium salt type strongly basic anion exchange resin (Diaion SA10A). the separation means to separate into a raffinate containing ^2- [PtCl _6] extract and [PdCl _4], including ^2-.
[PtCl ₆ ] ²⁻ can be recovered from the extract at a concentration of Pt 0.98 g / l (recovery rate 98%), and [PdCl ₄ ] ²⁻ from the raffinate at a concentration of Pd 0.95 g / l (recovery rate 95%). I was able to recover.
Then, each 1000 ml of raffinate and extract was filled into a 250 ml magnetic crucible, concentrated and dried in small portions, and then incinerated at 700 ° C. to recover 0.98 g of solid Pt and 0.95 g of solid Pd, respectively. .

  In Example 1 and Example 2, metals are separated and recovered from a metal-containing liquid containing two types of metals using a simulated moving bed type separation means having a column packed with an ion exchange resin or a chelate resin as a packing material. Therefore, selectivity and yield were high and continuous. Therefore, it was low cost and industrial. In addition, as shown in Experimental Examples 1 to 5 below, when the separation of the metal by the filler can be confirmed, the same effect as in Examples 1 and 2 can be obtained by applying the conditions to the simulated moving bed type separation means. Is expected to be obtained.

(Experimental example 1) Example using ion exchange resin as filler and hydrochloric acid as eluent Quaternary ammonium salt using high-pressure inert pump PU-2080i (manufactured by JASCO Corporation) whose wetted part is a corrosion-resistant material The eluent was fed at a flow rate of 0.5 ml / min to a column (MCI GEL SCA04, Mitsubishi Electric PEEK column, inner diameter 4.6 mm, length 150 mm) packed with a strongly basic anion exchange resin. The eluent was 1N hydrochloric acid, and the eluent piping was made of PEEK (polyether ether ketone) resin.
Reagent-grade platinum chloride (IV) hexahydrate and reagent-grade (II) palladium chloride (both manufactured by Wako Pure Chemical Industries, Ltd.), sodium hexachlororhodium (III) dihydrate (Kanto Chemical ( Each) was dissolved in 1N hydrochloric acid and mixed in an equal amount with a noble metal concentration of 1 g / l, and 20 μl was injected into the eluent.
When the UV 215 nm absorption of the liquid discharged from the column was observed at an analysis time of 20 minutes, it was eluted in the order of [RhCl ₆ ] ³⁻ , [PdCl ₄ ] ²⁻ , [PtCl ₆ ] ²⁻ , and [RhCl ₆ ] ³⁻ And [PdCl ₄ ] ²⁻ were confirmed to have a resolution Rs = 3.0, and [RhCl ₆ ] ³⁻ and [PtCl ₆ ] ²⁻ were Rs = 3.8. The UV absorption was measured using UV-1570 manufactured by JASCO Corporation with PEEK resin and polytetrafluoroethylene in the liquid contact part, and made of quartz PEEK cell. Data processing system BORWIN manufactured by JASCO Corporation. We analyzed with.

<Separation degree: Rs>
_{Rs = 1.18 × (T A -T} B) / (W A + W B)
(T: retention time, W: half width, A, B: metal ion)

(Experimental example 2) Example using sodium chloride aqueous solution as eluent Separation was carried out in the same manner as in Experimental example 1 except that 1M NaCl aqueous solution was used as the eluent, and [RhCl ₆ ] ³⁻ , [PdCl ₄ ] ^2- and [PtCl ₆ ] ²⁻ are eluted in this order, and [RhCl ₆ ] ³⁻ and [PdCl ₄ ] ²⁻ have a resolution Rs = 1.7 and [RhCl ₆ ] ³⁻ and [PtCl ₆ ] ²⁻ Was confirmed to be Rs = 2.4.

(Experimental example 3) Example (1) using non-halogen aqueous solution as eluent
Separation was carried out in the same manner as in Experimental Example 1 except that a 0.1 M NaClO ₄ aqueous solution was used as an eluent and a chloro complex of platinum and rhodium was used, and [RhCl ₆ ] ³⁻ , [PtCl ₆ ] ²⁻ It was confirmed that [RhCl ₆ ] ³⁻ and [PtCl ₆ ] ²⁻ had a resolution Rs = 1.1.

(Experimental example 4) Example using non-halogen aqueous solution as eluent (2)
Separation was carried out in the same manner as in Experimental Example 1 except that 1M sodium thiocyanate aqueous solution was used as the eluent. As a result, the ligand of the chloro complex was substituted in the column. As a result, [Rh (SCN) ₆ ] ³⁻ , [Pd (SCN) ₄ ] ²⁻ , [Pt (SCN) ₆ ] ²⁻ are eluted in this order, and [Rh (SCN) ₆ ] ³⁻ and [Pd ( SCN) ₄ ] ²⁻ was confirmed to have Rs = 1.9 and [Rh (SCN) ₆ ] ³⁻ and [Pt (SCN) ₆ ] ^{2− to} be Rs = 2.6.

(Experimental example 5) Example using multiple metal-containing solution that is not a halogeno complex or halogen salt Potassium tetracyanonickel (II) monohydrate and potassium hexacyanoferrate (II) trihydrate (both are Wako Pure) Yakuhin Kogyo Co., Ltd.) 0.01M potassium cyanide aqueous solution with a metal concentration of 0.1 g / l as eluent 0.01M potassium cyanide, 0.15M potassium perchlorate, 0.02M water Separation was performed with the apparatus of Experimental Example 1 using a potassium oxide mixed aqueous solution. As a result, [Ni (CN) ₄ ] ²⁻ , [Fe (CN) ₆ ] ⁴⁻ were eluted in this order, and it was confirmed that the resolution Rs = 1.8.

It is a schematic diagram which shows the simulated moving bed type | mold separation means in one embodiment of the metal separation / recovery device according to the present invention.

Explanation of symbols

1 Simulated moving bed type separation means 11a-11h Column

Claims (4)

  A metal separation / recovery device comprising a simulated moving bed separation means comprising a column filled with an ion exchange resin or a chelate resin.   Separation and recovery of metals using a simulated moving bed separation means having a column filled with an ion exchange resin or a chelate resin, and separating and recovering the metal in the metal-containing solution through the metal-containing solution and the eluent. Collection method.   When the metal-containing solution is a multi-metal-containing solution containing a plurality of metals, the multi-metal-containing solution is passed through a preliminary separation column filled with an ion exchange resin before passing through the simulated moving bed type separation means. The metal separation and recovery method according to claim 2. Using the simulated moving bed type separation means, the homogeneous metal catalyst and the product are separated and recovered from the metal-containing solution containing the homogeneous metal catalyst and the product obtained using the homogeneous metal catalyst. A method for separating and recovering metals.

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