JP2019063732A - Metal trapping material for recovering valuable metals, method for producing the same and method for recovering valuable metals - Google Patents

Abstract

To provide a metal trapping material that can easily and inexpensively recover and use valuable metal elements from water containing a large amount of valuable metals such as submarine hydrothermal deposits, etc. as resources.SOLUTION: In a metal trapping material, metal particles 1 are granulated and sintered together with a precursor of a solid carbonaceous matter 2 so that the metal particles 1 and the solid carbonaceous matter 2 are integrated. The metal particles 1 contained in 100 parts by weight of the metal trapping material are in a range of 5 to 90 parts by weight, and the metal forming the metal particles 1 is preferably selected from, for example, aluminum, iron and copper. The solid carbonaceous matter 2 may be any solid, conductive carbon which can form a local cell in water in contact with metal, and a precursor of the solid carbonaceous matter 2 may be a substance which is carbonized by sintering at 600°C or higher in a non-oxidizing atmosphere.SELECTED DRAWING: Figure 1

Description

  The present invention relates to, for example, a metal capturing material capable of recovering, as a metal body, valuable metals such as copper and cobalt dissolved in a spout water of a hydrothermal deposit, a hot spring, a spring, etc. And a method of recovering valuable metals.

  As a small resource country, Japan relies on imports from abroad for most of industrial resources including metals. However, it is known that mineral resources such as a seafloor hydrothermal deposit and cobalt-rich / manganese crust are abundantly present in 11 times territorial waters and exclusive economic zones (EEZ) of land areas.

  Cobalt-rich manganese crusts have the same origin and chemical composition as manganese nodules found on the deep-sea floor and are produced to cover open rock areas such as seamounts and plateaus. It is made of manganese, iron, cobalt, nickel, copper, platinum, rare earth elements, phosphorus, etc. that were dissolved in seawater and precipitated at a very slow speed (about 2 to 7 mm in 1,000,000 years) It is believed that.

  On the other hand, the submarine hydrothermal deposit is formed by high temperature (250 to 300 ° C.) hydrothermal water that is ejected from the spout, which is also called a chimney, to the seabed surface. The submarine hydrothermal deposit contains a large amount of valuable metals such as iron, zinc, copper, cobalt, lead, gold, silver and so on, and has a faster formation rate than cobalt-rich manganese crust, so it is promising as a resource available in the future It is viewed.

  As a resource mining method from the seafloor hydrothermal deposit, for example, although a method using an adsorbent such as a chemical reaction, an ion exchange resin, or a zeolite has been considered, the collecting material for collecting valuable metals is underwater. In the current situation, there is a need for a mooring device and its collection device, and there are many problems in cost as well.

  Patent Document 1 proposes a carbon-metal complex for water treatment containing metal particles coated with a water-soluble coating agent, carbon particles, and a binder in order to remove harmful substances contained in waste water and the like. . Although it is conceivable to divert the waste water treatment material described in Patent Document 1 to recovery of valuable metals, the material of Patent Document 1 removes heavy metals from waste water by coprecipitation with aluminum hydroxide. As a result, the aluminum hydroxide floc formed must be recovered, with great difficulty. In addition, in order to use the recovered material as a metal resource, various post-treatments such as dehydration, separation, concentration and the like are required, which is a cost disadvantage.

JP, 2011-25160, A

  Therefore, an object of the present invention is to provide a metal collecting material capable of easily and inexpensively recovering valuable metal elements as resources from water containing a large amount of valuable metals such as a seafloor hydrothermal deposit or the like. It is.

In order to solve the above-mentioned subject, the metal collection material of the present invention is a metal collection material which is a sintered compact containing metal particles which consist of a metal whose electric potential is lower than carbon, and a carbonaceous material,
The metal content per 100 parts by weight of the metal collecting material is in the range of 5 to 90 parts by weight,
From the water in which the valuable metal element having a potential higher than that of the metal particles is dissolved, the valuable metal element is precipitated as a metal on the surface of the sintered body by a local cell action and recovered.

  In the metal collection material of the present invention, the metal constituting the metal particles may be at least one selected from aluminum and iron.

  In the metal-trapping material of the present invention, the carbonaceous material may be a carbonaceous material having a pitch obtained from petroleum-based and coal-based heavy oils as a precursor.

  In the metal-trapping material of the present invention, the carbonaceous material may further contain one or more pulverized materials selected from graphite, needle coke, and pitch coke.

  In the metal collection material of the present invention, the sintered body may further contain a substance having paramagnetism.

The method for producing a metal collection material of the present invention is a method for producing any of the metal collection materials described above,
Mixing a metal particle composed of a metal having a potential lower than that of carbon and a carbonaceous precursor and granulating to obtain a granulated product;
as well as,
Sintering the granulated material at a temperature of 600 ° C. or higher under a reducing atmosphere to obtain a sintered body,
It is characterized by including.

  The method for recovering valuable metals according to the present invention is a method for recovering valuable metals in water, wherein any one of the above metal trapping agents is contacted with water selected from hot water, hot spring or spring water spouted from a hot water deposit. And collecting the valuable metal element dissolved in the water as a metal body.

In the metal capturing material of the present invention, since metal particles having a potential lower than that of carbon are complexed with a carbonaceous material, by bringing this into contact with water, the electric potential is higher than that of a complexed metal by local cell action. Valuable metals (for example, cobalt, zinc, copper, precious metals, etc.) in water having a high water content can be deposited as a metal body on the surface of the metal collection material to recover and recycle.
Therefore, although the metal collection material of the present invention is a simple and inexpensive material consisting of carbon and metal, valuable metals in water can be recovered at low cost as a high concentration metal body instead of a hydroxide state. It is easy to use as a resource. In the present invention, “potential” refers to, for example, a corrosion potential (naturally occurring potential difference between carbon and various metals and a reference electrode when a saturated copper sulfate electrode or a saturated silver chloride electrode is used as a reference electrode). Means potential).

It is a schematic diagram which shows the external appearance structure of the metal collection material which concerns on 1st embodiment of this invention. It is a schematic diagram which shows the external appearance structure of another metal collection material which concerns on 1st embodiment of this invention. It is a schematic diagram which shows the external appearance structure of the metal collection material which concerns on 2nd embodiment of this invention. It is a schematic diagram which shows the external appearance structure of another metal collection material which concerns on 2nd embodiment of this invention.

  The metal collection material of the present invention is a sintered body of metal particles and carbonaceous material having a potential lower than that of carbon. The metal collection material uses the local battery effect generated at the contact site between metal particles and carbon to deposit valuable metal elements such as zinc, cobalt and copper dissolved in water on the surface of the metal collection material. It is deposited as a body and recovered in high concentration. For this reason, the metal particles are sintered to be integrated with the carbonaceous material, and the form of the metal collection material is not particularly limited as long as it can form a local battery, but the form below is preferred as a preferred state. Two types of form 1> and <form 2> can be illustrated.

<Form 1>
As a first embodiment of the metal collection material of the present invention, the embodiment shown in FIG. 1 or 2 can be mentioned.
FIG. 1 shows an embodiment in which a metal particle 1 is granulated and sintered together with a precursor that becomes a solid carbonaceous matter 2 by heat treatment, and the metal particle 1 and the solid carbonaceous matter 2 are integrated.
Further, in FIG. 2, the metal particles 1 are granulated and sintered together with the precursor of the solid carbonaceous matter 2 and the carbon aggregate 3 so that the metal particles 1, the solid carbonaceous matter 2 and the carbon aggregate 3 are integrated. An example of the embodiment is shown.
In the embodiment shown in FIG. 1, the solid carbonaceous matter 2 corresponds to the carbonaceous matter, and in the embodiment shown in FIG. 2, the solid carbonaceous matter 2 and the carbon aggregate 3 correspond to the carbonaceous matter.
As shown in FIG. 1 and FIG. 2, the metal collection material of this embodiment exhibits a local cell effect by the metal particles 1 and the solid carbonaceous matter 2 being mutually bound to form a network, The metal particles 1 are present uniformly throughout the material.

<Form 2>
As a 2nd form of the metal collection material of this invention, the form example shown in FIG. 3 or FIG. 4 can be mentioned.
FIG. 3 shows an example of the embodiment in which the metal particles 1 are granulated and sintered together with the precursor of the solid carbonaceous matter 2 and the metal particles 1 and the massive solid carbonaceous matter 2 are integrated.
Further, FIG. 4 shows solid carbon in a state in which the metal particle 1 is granulated and sintered together with the precursor of the solid carbonaceous substance 2 and the carbon aggregate 3 and coated around the metal particle 1 and the carbon aggregate 3. It is integrated with quality 2. In the example shown in FIG. 3 and FIG. 4, the solid carbonaceous matter 2 and the carbon aggregate 3 correspond to the carbonaceous matter.

  In the metal-trapping material of this embodiment, as shown in FIGS. 3 and 4, the metal particles 1 are unevenly distributed on the surface of the metal-trapping material, and at least a part of the surface of the metal particles 1 is exposed from the carbonaceous material It is In the embodiment shown in FIG. 4, although the contact between the metal particles 1 and the carbon aggregate 3 is not essential, it is preferable that the two be in contact with each other.

(Metal particles)
The metal particles 1 contained in 100 parts by weight of the metal collection material are in the range of 5 to 90 parts by weight, preferably in the range of 25 to 90 parts by weight, and more preferably in the range of 50 to 90 parts by weight . If the proportion of the metal particles 1 is less than 5 parts by weight, the area of the metal particles 1 in contact with water is small, and the amount of metal ions generated is small, so the recovery efficiency of valuable metals decreases. On the other hand, if the proportion of the metal particles 1 exceeds 90 parts by weight, it is not preferable because the amount of carbonaceous material is too small, the battery formation site is reduced, and the generated metal ions are reduced.

  The metal particle 1 used for the metal collection material of the present invention is not particularly limited as long as it is made of a metal having a potential lower than that of carbon, and one having a potential lower than the metal element to be collected is optionally used. Can. Here, the potential refers to a natural potential measured using a saturated copper sulfate electrode or a saturated silver chloride electrode as a reference electrode, but as a standard, metals less than copper are preferable in terms of metal ionization tendency. However, in consideration of safety during production, reactivity with water, and environmental impact, the metal forming the metal particles 1 is most preferably selected from, for example, aluminum, iron, and copper. The particle shape of the metal particle 1 is not particularly limited, and may be, for example, spherical, indeterminate or fibrous. The particle diameter of the metal particles 1 is preferably in the range of 10 μm to 5 mm, and more preferably in the range of 100 μm to 3 mm.

  The metal particles 1 are preferably composed of a single metal element, but may contain other metal elements, and may be, for example, an alloy, or a reducing atmosphere to form a sintered body as described later. Since the firing is performed at the raw material stage, a compound such as an oxide may be used. However, in the case of using a compound as a metal source, sulfates and chlorides, etc. have a risk of generating corrosive gas and toxic gas in the manufacturing process, so use hydroxide or oxide form. Is preferred. In particular, since the oxide of the metal particles 1 can be used for iron-making scale or powder or chips generated at the time of processing, it is possible to reduce the material cost of the metal collection material, and a material that can be preferably used It is one.

(Solid carbon and its precursor)
The solid carbonaceous matter 2 is a solid, and any conductive carbon can be used as long as it is conductive carbon that can form a local battery in water in contact with a metal. The precursor of solid carbonaceous matter 2 to be sintered together with the metal particles 1 is not limited as long as it is a material which is carbonized by firing at 600 ° C. or higher in a non-oxidizing atmosphere. As the solid carbonaceous substance 2 precursor, for example, starch paste, starch syrup, natural organic matter such as lignin, epoxy resin, organic synthetic resin such as phenol resin, etc. can be used, but the residual carbon ratio is 50% or more It is preferable to use, as a precursor, a pitch produced from a heavy oil obtained from a petroleum-based or coal-based carbon that has high carbon yield and high conductivity carbon. In particular, since a pitch having a softening point of 70 ° C. or more can be used as a powder, it is easy to granulate by mixing it with the metal particles 1 and heating it, and a large amount of solid carbonaceous matter 2 is obtained after sintering. It is a preferable material as a precursor.

(Carbon aggregate)
In the metal-trapping material of the present invention, it is also possible to optionally optionally add a carbon aggregate 3 for the purpose of adjusting the surface area and the apparent specific gravity, and improving the local battery effect. As the carbon aggregate 3, for example, it is preferable to use a pulverized material of graphite, needle coke, or pitch coke.

  The metal collection material using the carbon aggregate 3 is obtained by, for example, mixing metal particles 1 and carbon aggregate 3 such as graphite, needle coke, pitch coke and the like with a pitch which is a solid carbonaceous matter 2 precursor. After being granulated, they are sintered, or those obtained by sintering metal particles 1 together with solid carbonaceous matter 2 on the surface of carbon aggregate 3 such as graphite, needle coke, pitch coke and the like.

  When a pulverized material such as graphite, needle coke, pitch coke or the like is used as the carbon aggregate 3, the particle diameter thereof is preferably in the range of 10 μm to 10 mm, and more preferably in the range of 50 μm to 5 mm. Moreover, about the compounding ratio with the precursor of solid carbonaceous substance 2, the inside of the range of 3-50 weight part of solid carbonaceous substance 2 is preferable with respect to 100 weight part of ground materials, and the range of 5-25 weight part The inside is more preferable.

(Optional ingredient)
Furthermore, the metal collection material of this invention can also mix | blend various additives in order to give adjustment of an apparent specific gravity and a secondary effect within the range which does not prevent the performance. Examples of the additives include ceramics such as silica, alumina and bricks, and lumps of substances exhibiting magnetism such as magnetite, but the composition of the magnetic substance is a metal collector that has collected valuable metals. It is preferable because it enables the magnetic recovery of

(Apparent specific gravity)
In addition, the apparent specific gravity of the metal collection material is, for example, preferably 1.1 or more, and more preferably 1.2 or more. If the apparent specific gravity is 1.1 or more, it becomes less susceptible to the influence of the current such as the ocean current, and it becomes easy to spread and install the metal trapping material at the desired position, and it is diffused widely by the time of recovery. It is preferable because it becomes difficult.

<Manufacturing method>
In the metal collection material of the present embodiment, if the metal particles 1 made of a metal having a lower potential than carbon are sintered with carbon and integrated, and a local battery can be formed, the manufacturing method is It is not particularly limited.

The preferable manufacturing method of a metal collection material includes the following process A-the process C.
Process A:
A step of mixing the metal particle 1 and the solid carbonaceous matter 2 precursor, and optionally, the carbon aggregate 3 (in addition, it may contain water, an organic solvent, and a binding aid as required).
Process B:
Attaching and granulating the metal particles 1 in the mixture and the precursor of the solid carbonaceous matter 2 to form a complex.
Process C:
A step of firing the composite obtained in step B at a temperature of 600 ° C. or higher in an inert or reducing atmosphere to obtain a sintered body to obtain a metal collection material.

  In addition, in the step A, the order of blending of the respective raw materials is not particularly limited, and a mixture of the metal particles 1 and the binding aid may be prepared first, and then the solid carbonaceous matter 2 precursor may be blended. , You may mix all the ingredients at once. The same applies to the case of blending other additives.

  As a blending method, general mixers such as various blenders and mixers can be used.

Further, as an apparatus for granulating the mixture in step B, it is preferable to use, for example, a briquette machine, a tableting machine, a press molding machine such as an extruder, a pan pelletizer, or the like.
In addition, although granulation of a mixture can be performed also at normal temperature by use of a granulation auxiliary agent, it is preferable that it is heated. In order to heat the mixture to soften the solid carbonaceous matter 2 precursor to form a complex with the metal particles 1, a temperature above the softening point or melting point of the solid carbonaceous matter 2 precursor is secured There is a need. Specifically, in step B, the solid carbonaceous 2 precursor is used at a temperature in the range of 70 ° C. to 300 ° C., preferably in the range of 30 to 150 ° C. than the softening point or melting point of the solid carbonaceous 2 precursor. It is preferred to heat to a high temperature within. For example, in the case where the precursor of solid carbonaceous matter 2 is a binder pitch having a softening point of 90 ° C., adhesion is obtained if the mixture is heated to 100 ° C. or the surface of the aggregate is heated to about 200 ° C. Get higher. If the heating temperature is too low, the solid carbonaceous matter 2 precursor does not soften or melt, the adhesion is low, and the metal particles 1 are likely to be missing. When the heating temperature is too high, the precursor of solid carbonaceous matter 2 becomes lumpy, and a large unevenness occurs in the composition of the composite, which is not preferable.

  In the step B, water, an organic solvent and a granulating aid can also be used to improve productivity and workability. The granulation aid promotes the complexation of the metal particle 1 and the precursor of the solid carbonaceous matter 2 by its adhesiveness, is viscous at normal temperature, and almost completely decomposes or carbonizes at 600 ° C. at the time of firing. Substances are preferred. For example, gelatin, starch paste, waste molasses, lignin sulfonate, konjac powder, sodium alginate, polyvinyl alcohol, dextrin, ethylcellulose, carboxymethylcellulose, acrylic resin, epoxy resin, etc. are suitable as granulation aids, and solid carbon It is preferable that the weight 2 blending ratio with the quality 2 precursor (solid carbon 2 precursor: granulation aid) be in the range of 99: 1 to 30:70 and used. Sinterability of metal particle 1 and precursor of solid carbonaceous matter 2 and metal trapping material by adjusting the blending ratio so that the granulation aid and the precursor of solid carbonaceous matter 2 fall within the above range It is possible to enable easy manufacture of the metal collection material without adversely affecting the performance as

  The composite prepared in step B is dried at 60 ° C. or higher when water or an organic solvent is used in step A, and then fired in step C under an inert or reducing atmosphere. Note that the reducing atmosphere may be a non-oxidizing atmosphere such as an inert atmosphere such as nitrogen or argon, or a low oxygen atmosphere. For example, equipment such as a lead hammer furnace, a top charge furnace, a shuttle furnace, a tunnel furnace, a rotary kiln, a roller hearth kiln or a microwave can be used for firing, but it is not particularly limited thereto and a continuous type Or it may be either of batch type. The firing temperature is not particularly limited as long as the precursor of solid carbonaceous matter 2 is carbonized, but is preferably at least 600 ° C. or more and preferably not more than the boiling point of metal particles 1 to be sintered with carbon. In particular, when a binder pitch is used as an organic binder, the firing temperature is preferably 700 ° C. or higher, more preferably 900 ° C. or higher, and 1000 ° C. in order to prevent residual aromatic compounds such as benzopyrene. It is more preferable that it is more than. Baking can certainly carbonize the precursor of solid carbonaceous matter 2 in a reducing atmosphere of 600 ° C. or higher, and can also reduce the oxide film present on the surface of the metal particle 1. For this reason, the metal collection material of the present invention obtained by firing has no environmental load such as increase of BOD or elution of harmful chemical substances and heavy metals, and when metal particles 1 are ionized and eluted by the local cell effect. Valuable metal ions having a potential higher than that of the metal particles 1 contained in water can be deposited on the surface of the metal collection material as a metal body by using the electrons of the above.

The metal collection material of the present invention is widely applied to industrial waste water, mine waste water, hot spring water, mineral water, spouted water from a seafloor hydrothermal deposit, for example, as long as it is water in which valuable metals to be recovered are dissolved. be able to. Among these, spouted water from hot spring water, mineral spring water, and submarine hydrothermal deposit is preferable because it contains valuable metals in high concentration, and in particular, spouted water from the submarine hydrothermal deposit is abundant and preferable as a recovery target of valuable metals. .
Regarding the installation, for example, it was distributed as it is in the vicinity of the hydrothermal vents of the submarine hydrothermal deposit, in the vicinity of the spout of hot spring or spa and its flow path, or the metal collecting material was stored in a holding member such as a net or basket. You may arrange by immersing things etc.

  The metal collection material of the present invention is a material that causes valuable metal ions dissolved in water to be deposited as a metal body on the surface of the metal collection material by ion exchange due to the local battery effect. For this reason, it is not something which is coprecipitated with hydroxide or collected in flocs of hydroxide, so recovery of valuable metals only needs to recover spread and installed metal collection material, and dehydration after recovery And concentration operations are simplified, and overall recovery costs can be reduced.

  Furthermore, since the metal-trapping material of the present invention utilizes carbon at the time of granulation and molding, it is stable in water for a long period of time, and it does not contain non-conductive substances such as cement. The valuable metal recovery efficiency from the collecting material is also good.

  Hereinafter, the contents of the present invention will be specifically described based on examples, but the present invention is not limited to the scope of these examples. In the following examples, unless otherwise specified, various measurements and evaluations are as follows.

<Apparent specific gravity>
It measured by the Archimedes method using an electronic densimeter (EW-300SG, Asone).

<Valuable Metal Recovery>
After immersing the metal collection material in a liquid (30 ml) containing valuable metal ions for a fixed period, the concentration of valuable metal in the liquid is measured. After being immersed for a certain period, the metal collecting material is taken out and dried at 105 ° C. for one day. The pulverized valuable metals were dissolved in nitric acid and analyzed by inductively coupled plasma emission spectroscopy (ICP) to determine the amount of valuable metals recovered.

<Raw materials>
Metal powder ・ Iron powder (made by Takeuchi Kogyo Co., Ltd. Cast iron powder 28 mesh under product Carbon: 2 to 4 wt%, Si: 4 wt% or less, Mn: 0.5 to 1.5 wt%, P: 0.03 wt % Or less, S: 0.03% by weight or less)
・ Aluminum powder (Kanto Chemical Co., Ltd., particle size: 45 μm)
Solid carbonaceous precursor-Coal tar pitch (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Softening point: 85 ° C, fixed carbon content: 58% by weight, 50 mesh under)
Carbon aggregate ・ Pitch coke powder (made by Nippon Steel & Sumikin Chemical Co., Ltd. 200 mesh under, 50-200 mesh, 6-9 mesh)
・ Pitch coke lump (2 to 5 g manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
Granulating aid ・ Starch (Numada Powder Co., Ltd. Rye binder Main component: about 80% starch bulk specific gravity about 0.5)

<Preparation of a metal collection material (form 1)>
After mixing and kneading predetermined amounts of raw materials (metal powder, solid carbonaceous precursor, carbon aggregate, granulation aid) with a mixing stirrer, using a hand press, the mixture has a diameter of 20 mm under the condition of 10 MPa. , 2 to 6 mm thick disc-like granules were produced.
The manufactured granulated product is heated at 100 ° C./hour using a reducing atmosphere baking furnace filled with coke powder, baked at 900 ° C. for 2 hours, and naturally cooled in the furnace until it becomes 50 ° C. or less The sintered body was taken out.

<Preparation of a metal collection material (form 2)>
After mixing predetermined amounts of raw materials (metal powder, solid carbonaceous precursor) with a mixing stirrer, the mixture was introduced into a pan pelletizer (type 1237-S-3, Yoshida Seisakusho Co., Ltd.). In addition, carbon aggregate (pitch coke block size 1 to 5 cm) heat treated at 230 ° C for 2 hours in an air atmosphere in advance is introduced into the pan pelletizer charged with the mixture while rotating at 30 rpm, and rotated for 3 minutes. Then, a composite in which metal particles were attached to the surface of the carbon aggregate was produced.
The prepared composite is heated at a rate of 100 ° C./hour using a reducing atmosphere firing furnace filled with coke powder, fired at 900 ° C. for 2 hours, and naturally cooled in the furnace until it becomes 50 ° C. or less The sintered body was taken out.

[Examples 1 to 3]
An aluminum powder as the metal powder, a coal tar pitch as a solid carbonaceous precursor, and a starch aqueous solution as a granulation aid for a pitch coke powder as a carbon aggregate were used to produce a metal collector of form 1.
The prepared metal collecting material was immersed in a sample bottle containing 30 ml of an aqueous solution in which each of zinc, cobalt and copper was dissolved, allowed to stand at normal temperature and pressure for 7 days, and then the concentrations of zinc, cobalt and copper were measured.
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collection material.

Example 4
The metal trapping material of form 2 described in Example 4 of Table 1 was produced using the same raw materials as in Examples 1 to 3.
The prepared metal collecting material was immersed in a sample bottle containing 30 ml of an aqueous solution in which copper was dissolved, allowed to stand at normal temperature and normal pressure for 7 days, and then the concentration of copper was measured.
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collection material.

[Examples 5, 6]
Except having used iron powder for metal powder, it carried out similarly to Examples 1-3, and produced the metal collection material of the form 1 described in Examples 5-6 of Table 1.
The prepared metal collecting material is immersed in a sample bottle containing 30 ml of an aqueous solution in which each of zinc, cobalt and copper is dissolved, and left for 7 days under normal temperature and normal pressure, and then the concentration of zinc, cobalt and copper Was measured.
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collection material.

[Example 7]
Using the same raw materials as in Examples 5 and 6, a metal collection material of Form 2 described in Example 7 of Table 1 was produced.
The prepared metal collecting material was immersed in a sample bottle containing 30 ml of an aqueous solution in which copper was dissolved, allowed to stand at normal temperature and normal pressure for 7 days, and then the concentration of copper was measured.
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collection material.

[Example 8]
Using the same raw materials as in Examples 5 and 6, the metal collection material of Form 1 described in Example 8 in Table 1 was produced.
The metal trapping material was prepared by immersing the metal trapping material in a sample bottle containing 30 ml of an aqueous solution in which cobalt and copper were dissolved, and allowed to stand at normal temperature and pressure for 7 days, after which the concentrations of cobalt and copper were measured. .
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collection material.

[Example 9]
A metal capturing material of Form 1 was produced in the same manner as in Example 8 except that iron powder and aluminum powder were used as metal powder in a weight ratio of 1: 1.
The prepared metal collecting material was immersed in a sample bottle containing 30 ml of an aqueous solution in which copper was dissolved, and left for 7 days under normal temperature and normal pressure, and then the concentration of copper was measured.
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collection material.

[Examples 10 to 12 and 14 to 16]
The metal-capturing material of form 1 prepared in the same manner as in Examples 5 and 6 is immersed in an aqueous solution in which cobalt and copper are dissolved, and the entire aqueous solution in which cobalt and copper are dissolved is exchanged every 7 days under normal temperature and pressure. The immersion test was conducted for 4 weeks.
Table 2 shows the metal content, carbon content, apparent specific gravity and the result of the 4-week immersion test of the metal collection material.

[Examples 13 and 17]
Immersion test was carried out while immersing the metal collection material of form 2 prepared in the same manner as in Example 4 in an aqueous solution in which cobalt and copper are dissolved, and exchanging the entire aqueous solution in which cobalt and copper were dissolved every 7 days under normal temperature and pressure. For 4 weeks.
Table 2 shows the metal content, carbon content, apparent specific gravity and the result of the 4-week immersion test of the metal collection material.

[Example 18]
The metal-capturing material of embodiment 1 produced in the same manner as in Examples 5 and 6 is immersed in an aqueous solution in which cobalt and copper are dissolved, and the entire aqueous solution in which cobalt and copper are dissolved is exchanged every 7 days under normal temperature and pressure. The immersion test was carried out for 4 weeks.
Table 2 shows the metal content, carbon content, apparent specific gravity and the result of the 4-week immersion test of the metal collection material.

[Example 19]
The metal-trapped material of embodiment 1 produced in the same manner as in Example 9 was immersed in an aqueous solution in which copper was dissolved, and left for 4 weeks while exchanging the entire aqueous solution every 7 days under normal temperature and normal pressure.
Table 2 shows the metal content, carbon content, apparent specific gravity and the result of the 4-week immersion test of the metal collection material.

Comparative Examples 1 to 6
After immersing iron powder or aluminum powder 1.00 g in an aqueous solution in which zinc, cobalt and copper were dissolved respectively, and left for 7 days in a normal temperature and pressure environment, the concentration of zinc, copper and cobalt was measured.
In addition, the immersion test was conducted for 4 weeks while exchanging all the aqueous solution in which zinc, cobalt and copper were dissolved every 7 days.
Table 3 shows the results of metal content, carbon content, true specific gravity, and 4-week immersion test.

As shown in Tables 1-2, the metal collection material of Examples 1-19 which is a sintered compact of a metal particle and carbon is compared with comparative examples 1-6 (refer Table 3) which is metal powder independent. Valuable metals having a higher potential than metals used for metal trapping materials by local cell action can be collected from water with high efficiency.
In addition, since the collection of valuable metals is not mainly included in the precipitation of hydroxides, they are deposited as metal bodies on the surface of the metal collection material, so recovery is easy, and the immersion period is extended to increase the amount of It is also possible to precipitate and recover valuable metals.
Thus, the metal-trapping material of the present invention is a material suitable for recovering valuable metals at low cost, for example, from hot water, hot springs, mineral springs, mine wastewater, etc., which are ejected from a seafloor hydrothermal deposit. Was confirmed.

  Although the embodiments of the present invention have been described in detail for the purpose of illustration, the present invention is not limited to the above embodiments.

1 ... metal particle 2 ... solid carbon 3 ... carbon aggregate

Claims (7)

It is a metal collection material which is a sintered compact containing metal particles which consist of a metal whose electric potential is lower than carbon, and carbonaceous matter,
The metal content per 100 parts by weight of the metal collecting material is in the range of 5 to 90 parts by weight,
A metal trap characterized in that the valuable metal element is deposited as a metal body on the surface of the sintered body by the action of a local battery from water in which a valuable metal element having a higher potential than the metal particles is dissolved. Gathering material.   The metal collecting material according to claim 1, wherein the metal constituting the metal particles is at least one selected from aluminum and iron.   The metal trap according to claim 1 or 2, wherein the carbonaceous matter is a pitched precursor obtained from petroleum-based and coal-based heavy oils.   The metal trapping material according to any one of claims 1 to 3, wherein the carbonaceous material further contains at least one pulverized material selected from graphite, needle coke, and pitch coke.   The metal collection material according to any one of claims 1 to 4, wherein the sintered body further contains a substance having paramagnetism. It is a method of manufacturing the metal collection material according to any one of claims 1 to 5,
Mixing a metal particle composed of a metal having a potential lower than that of carbon and a carbonaceous precursor and granulating to obtain a granulated product;
as well as,
Sintering the granulated material at a temperature of 600 ° C. or higher under a reducing atmosphere to obtain a sintered body,
A method of producing a metal collection material comprising: A valuable metal recovery method for recovering valuable metals in water, comprising
The metal collection material according to any one of claims 1 to 5 is dissolved in the water by bringing the metal collection material into contact with water selected from hot water, hot spring or mineral water spouted from a hydrothermal deposit. A valuable metal recovery method comprising the step of collecting a metal element as a metal body.

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