JP6960817B2 - Metal collecting material for valuable metal recovery, its manufacturing method and valuable metal recovery method - Google Patents

Description

The present invention is, for example, a metal collecting material capable of recovering valuable metals such as copper and cobalt dissolved in spouted water of hydrothermal deposits, hot springs, mineral springs, etc. as metal bodies at a high concentration, and a method for producing the same. And the method of recovering valuable metals.

As a resource-poor country, Japan relies on imports from overseas for most of its industrial resources, including metals. However, it is known that mineral resources such as submarine hydrothermal deposits and cobalt-rich manganese crusts are abundant in the territorial waters and exclusive economic zone (EEZ), which are 11 times larger than the land area.

Cobalt-rich manganese crust has the same origin and chemical composition as the manganese nodules found on the deep sea floor, and is produced so as to cover open rock areas such as seamounts and plateaus. This is the result of manganese, iron, cobalt, nickel, copper, platinum, rare earth elements, phosphorus, etc. dissolved in seawater settling at a very slow rate (about 2 to 7 mm per million years). It is believed that.

On the other hand, the seafloor hydrothermal deposit is formed by volcanic high-temperature (250 to 300 ° C) hot water ejected from a spout, also called a chimney, to the seafloor. Submarine hydrothermal deposits contain large amounts of valuable metals such as iron, zinc, copper, cobalt, lead, gold and silver, and form faster than cobalt-rich manganese crusts, making them promising resources for future use. It is being viewed.

As a method of digging resources from submarine hydrothermal deposits, for example, a method using a chemical reaction or an adsorbent such as an ion exchange resin or zeolite is being studied, but a collecting material for collecting valuable metals is used in the sea. The current situation is that there are many problems in terms of cost, as it is necessary to float on the surface, a mooring device and its collection device are required.

Patent Document 1 proposes a water treatment charcoal-metal composite containing metal particles coated with a water-soluble coating agent, charcoal particles, and a binder in order to remove harmful substances contained in wastewater and the like. .. It is conceivable that the wastewater treatment material described in Patent Document 1 can be diverted to the recovery of valuable metals, but the material of Patent Document 1 is one that removes heavy metals from wastewater by co-precipitating them with aluminum hydroxide. Therefore, the produced aluminum hydroxide flocs must be recovered, which entails great difficulty. Further, in order to use the recovered product as a metal resource, various post-treatments such as dehydration, separation, and concentration are required, which is a disadvantageous method in terms of cost.

Japanese Unexamined Patent Publication No. 2011-25160

Therefore, an object of the present invention is to provide a metal collecting material that can easily and at low cost recover and utilize valuable metal elements from water containing a large amount of valuable metals such as submarine hydrothermal deposits. Is.

In order to solve the above problems, the metal collecting material of the present invention is a metal collecting material which is a sintered body containing metal particles made of a metal having a potential lower than that of carbon and a carbonaceous substance.
The metal content per 100 parts by weight of the metal collecting material is in the range of 5 to 90 parts by weight.
The valuable metal element is precipitated as a metal body on the surface of the sintered body by a local battery action and recovered from water in which a valuable metal element having a higher potential than the metal particles is dissolved.

In the metal collecting material of the present invention, the metal constituting the metal particles may be one or more selected from aluminum and iron.

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

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

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

The method for producing a metal collecting material of the present invention is a method for producing any of the above metal collecting materials.
A process in which metal particles made of a metal having a lower potential than carbon and a carbonaceous precursor are mixed and granulated to obtain a granulated product.
as well as,
A step of sintering the granulated product at a temperature of 600 ° C. or higher in a reducing atmosphere to obtain a sintered body.
It is characterized by including.

The valuable metal recovery method of the present invention is a method for recovering valuable metals in water, in which any of the above metal collecting materials is brought into contact with water selected from hot water, hot springs or mineral spring water ejected from a hydrothermal deposit. It is characterized by including a step of collecting valuable metal elements dissolved in the water as a metal body.

In the metal collecting material of the present invention, metal particles having a lower potential than carbon are compounded with a carbonaceous substance. Therefore, by bringing this into contact with water, the potential is higher than that of the composited metal by the action of a local battery. Valuable metals in high water (for example, cobalt, zinc, copper, precious metals, etc.) can be deposited as a metal body on the surface of a metal collecting material to be recovered and recycled.
Therefore, although the metal collecting material of the present invention is a simple and inexpensive material composed of carbon and metal, the valuable metal in water can be recovered at low cost as a high-concentration metal body instead of in the state of hydroxide. , Easy to use as a resource. In the present invention, the "potential" is a corrosion potential (natural) indicating a potential difference between a reference electrode and carbon or various metals when, for example, a saturated copper sulfate electrode or a saturated silver chloride electrode is used as a reference electrode (reference electrode). Potential).

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

The metal collecting material of the present invention is a sintered body of metal particles and a carbonaceous material having a potential lower than that of carbon. The metal collecting material uses the local battery effect generated at the contact site between the metal particles and carbon to apply valuable metal elements such as zinc, cobalt, and copper dissolved in water to the surface of the metal collecting material. It is precipitated as a body and recovered at a high concentration. Therefore, as long as the metal particles are sintered and integrated with the carbonaceous material and a local battery can be formed, the form of the metal collecting material is not particularly limited, but the following < Two types, Form 1> and <Form 2>, can be exemplified.

<Form 1>
As the first form of the metal collecting material of the present invention, a form example shown in FIG. 1 or FIG. 2 can be mentioned.
FIG. 1 shows an example in which the metal particles 1 are granulated and sintered together with a precursor that becomes a solid carbon substance 2 by heat treatment, and the metal particles 1 and the solid carbon substance 2 are integrated.
Further, in FIG. 2, the metal particles 1 are granulated and sintered together with the precursor of the solid carbon substance 2 and the carbon aggregate 3, and the metal particles 1, the solid carbon substance 2 and the carbon aggregate 3 are integrated. This is an example of the form.
In the morphological example shown in FIG. 1, the solid carbonaceous material 2 corresponds to the carbonaceous material, and in the morphological example shown in FIG. 2, the solid carbonaceous material 2 and the carbon aggregate 3 correspond to the carbonaceous material.
As shown in FIGS. 1 and 2, the metal collecting material of the present embodiment exhibits the local battery effect by forming a network by binding the metal particles 1 and the solid carbon substance 2 to each other. The metal particles 1 are evenly present throughout the material.

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

In the metal collecting material of this embodiment, as shown in FIGS. 3 and 4, the metal particles 1 are unevenly distributed on the surface of the metal collecting material, and at least a part of the surface of the metal particles 1 is exposed from the carbonaceous material. Is what you are doing. In the embodiment shown in FIG. 4, the contact between the metal particles 1 and the carbon aggregate 3 is not essential, but it is preferable that they are in contact with each other.

(Metal particles)
The metal particles 1 contained in 100 parts by weight of the metal collecting 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. .. When 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 generated metal ions are small, so that the recovery efficiency of valuable metals is lowered. On the other hand, if the proportion of the metal particles 1 exceeds 90 parts by weight, the amount of carbonaceous material is too small, the number of battery-forming sites is reduced, and the amount of metal ions generated is reduced, which is not preferable.

The metal particles 1 used in the metal collecting material of the present invention are not particularly limited as long as they are made of a metal having a potential lower than that of carbon, and those having a potential lower than that of the metal element to be collected may be arbitrarily used. Can be done. Here, the electric potential refers to a natural potential measured using a saturated copper sulfate electrode or a saturated silver chloride electrode as a reference electrode, and as a guide, a metal below copper is preferable in terms of metal ionization tendency. However, in consideration of safety during production, reactivity with water, and influence on the environment, the metal forming the metal particles 1 is most preferably selected from, for example, aluminum, iron, and copper. The particle shape of the metal particles 1 is not particularly limited, and may be, for example, spherical, indefinite, or fibrous. The particle size of the metal particles 1 is preferably in the range of 10 μm to 5 mm, 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, for example, an alloy, and a reducing atmosphere for forming a sintered body as described later. Since it is fired in, a compound such as an oxide may be used at the raw material stage. However, when a compound is used as a metal raw material, sulfates and chlorides may generate corrosive gas and toxic gas in the manufacturing process, so use hydroxides and oxides. Is preferable. In particular, as the oxide of the metal particles 1, since powders and chips generated during iron making scale and processing can be used, it is possible to reduce the material cost in the metal collecting material, and it is possible to use a material that can be preferably used. It is one.

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

(Carbon aggregate)
In the metal collecting material of the present invention, the carbon aggregate 3 can be optionally added for the purpose of adjusting the surface area and the apparent specific gravity, improving the local battery effect, and the like. As the carbon aggregate 3, for example, it is preferable to use a pulverized product of graphite, needle coke, or pitch coke.

In the metal collecting material using the carbon aggregate 3, for example, the metal particles 1 and the pulverized material such as graphite, needle coke, and pitch coke which are the carbon aggregate 3 are mixed with the pitch which is the precursor of the solid carbon substance 2. Examples thereof include those obtained by granulating and then sintering, or those in which the metal particles 1 are sintered together with the solid carbon substance 2 on the surface of graphite, needle coke, pitch coke or the like which is the carbon aggregate 3.

When a pulverized product such as graphite, needle coke, or pitch coke is used as the carbon aggregate 3, the particle size thereof is preferably in the range of 10 μm to 10 mm, more preferably in the range of 50 μm to 5 mm. The mixing ratio of the solid carbonaceous 2 precursor to the precursor is preferably in the range of 3 to 50 parts by weight, preferably in the range of 5 to 25 parts by weight, based on 100 parts by weight of the pulverized product. Is more preferable.

(Arbitrary ingredient)
Further, the metal collecting material of the present invention can be blended with various additives in order to adjust the apparent specific gravity and give a secondary effect within a range that does not interfere with its performance. Examples of additives include ceramics such as silica, alumina, and bricks, as well as lumps of magnetic substances such as magnetite. The composition of the magnetic material is a metal collecting material that collects valuable metals. This is preferable because it enables magnetic recovery of silica.

(Appearance density)
Further, the apparent specific gravity of the metal collecting material is preferably 1.1 or more, more preferably 1.2 or more, for example. If the apparent density is 1.1 or more, it is less likely to be affected by currents such as ocean currents, it becomes easier to sprinkle and install the metal collecting material at the desired position, and it spreads over a wide area by the time of recovery. It is preferable because it becomes difficult.

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

A preferred method for producing a metal collecting material includes the following steps A to C.
Process A:
A step of mixing the metal particles 1 and the precursor of the solid carbonaceous material 2, and if necessary, the carbon aggregate 3 (which may further contain water, an organic solvent, and a binding aid, if necessary).
Process B:
A step of adhering and granulating a metal particle 1 and a precursor of a solid carbon substance 2 in a mixture to form a composite.
Process C:
A step of obtaining a metal collecting material by firing the complex obtained in step B at a temperature of 600 ° C. or higher in an inert or reducing atmosphere to form a sintered body.

In step A, the blending order of each raw material is not particularly limited, and a mixture of the metal particles 1 and the binding aid and the like may be first prepared, and then the precursor of the solid carbonaceous material 2 may be blended. , All ingredients may be blended at once. The same applies when other additives are blended.

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

Further, as an apparatus for granulating the mixture in step B, for example, it is preferable to use a press molding machine such as a briquette machine, a tableting machine, an extrusion machine, a pan pelletizer, or the like.
The mixture can be granulated at room temperature by using a granulation aid, but it is preferably heated. In order to heat the mixture to soften the precursor of solid carbon 2 and form a complex with the metal particles 1, a temperature equal to or higher than the softening point or melting point of the precursor of solid carbon 2 is secured. There is a need. Specifically, in step B, the solid carbonaceous 2 precursor has a temperature in the range of 70 ° C. to 300 ° C., preferably in the range of 30 to 150 ° C. from the softening point or melting point of the solid carbonaceous material 2 precursor. It is preferable to heat to a high temperature inside. For example, when the precursor of solid carbonaceous material 2 has a binder pitch of 90 ° C., the adhesiveness can be improved by heating the mixture to 100 ° C. or heating the surface of the aggregate to about 200 ° C. It gets higher. If the heating temperature is too low, the precursor of the solid carbonaceous material 2 does not soften or melt, the adhesiveness is low, and the metal particles 1 are likely to be missing. If the heating temperature is too high, the precursor of the solid carbon substance 2 becomes lumpy, and the composition of the complex becomes large unevenness, which is not preferable.

In step B, water, an organic solvent, or a granulation aid can also be used in order to improve productivity and workability. The granulation aid promotes the compounding of the precursor of the metal particles 1 and the solid carbon substance 2 due to its adhesiveness, is viscous at room temperature, and decomposes or carbonizes almost completely at 600 ° C. at the time of firing. The substance is preferred. For example, gelatin, starch paste, waste sugar honey, lignin sulfonate, konjak powder, sodium alginate, polyvinyl alcohol, dextrin, ethyl cellulose, carboxymethyl cellulose, acrylic resin, epoxy resin and the like are suitable as granulation aids and solid carbon. It is preferable that the weight blending ratio of the quality 2 with the precursor (the precursor of the solid carbon substance 2: the granulation aid) is in the range of 99: 1 to 30:70. By adjusting the blending ratio of the granulation aid and the precursor of the solid carbonaceous material 2 so as to be within the above range, the sinterability of the metal particle 1 and the precursor of the solid carbonaceous material 2 and the metal collecting material can be adjusted. It is possible to easily manufacture the metal collecting material without adversely affecting the performance of the metal collecting material.

When water or an organic solvent is used in step A, the complex prepared in step B is dried at 60 ° C. or higher, and then fired in step C under an inert or reducing atmosphere. The reducing atmosphere may be an inert atmosphere such as nitrogen or argon, or a non-oxidizing atmosphere such as a hypoxic atmosphere. For firing, for example, equipment such as a reed hammer furnace, a top charge furnace, a shuttle furnace, a tunnel furnace, a rotary kiln, a roller harskiln, or a microwave can be used, but the firing is not particularly limited to these, and a continuous type is used. Alternatively, it may be a batch type. The firing temperature is not particularly limited as long as the precursor of the solid carbon substance 2 is carbonized, but is preferably at least 600 ° C. or higher, and preferably equal to or lower than the boiling point of the metal particles 1 to be sintered with carbon. In particular, when a binder pitch is used as the organic binder, the firing temperature is preferably 700 ° C. or higher, more preferably 900 ° C. or higher, and more preferably 1000 ° C. in order to prevent aromatic compounds such as benzopyrene from remaining. The above is more preferable. Firing in a reducing atmosphere of 600 ° C. or higher can reliably carbonize the precursor of the solid carbon substance 2, and can also reduce the oxide film existing on the surface of the metal particles 1. Therefore, the metal collecting material of the present invention obtained by firing does not have an environmental load such as an increase in BOD and elution of harmful chemical substances and heavy metals, and when the metal particles 1 are ionized and eluted by the local battery effect. It is possible to deposit valuable metal ions having a higher potential than the metal particles 1 contained in water as a metal body on the surface of the metal collecting material by utilizing the electrons of.

The metal collecting material of the present invention is widely applied to, for example, industrial wastewater, mine wastewater, hot spring water, mineral spring water, spouted water from a submarine hydrothermal deposit, as long as it is water in which valuable metals to be recovered are dissolved. be able to. Among these, hot spring water, mineral spring water, and submarine hydrothermal deposit eruption water are preferable because they contain a high concentration of valuable metals, and in particular, submarine hydrothermal deposit eruption water is preferable as a target for recovering valuable metals because they are abundant. ..
Regarding the installation, for example, it was sprayed as it was in the vicinity of the hydrothermal vent of the submarine hydrothermal deposit, in the vicinity of the hydrothermal vent of hot springs and mineral springs, and its flow path, or the metal collecting material was stored in a holding member such as a net or a basket. It may be arranged by immersing an object.

The metal collecting material of the present invention deposits valuable metal ions dissolved in water as a metal body on the surface of the metal collecting material by ion exchange due to the local battery effect. For this reason, it is not co-precipitated with hydroxides or collected in the flocs of hydroxides, so the recovery of valuable metals is as simple as collecting the sprinkled metal or the installed metal collecting material, and dehydration after recovery. And the concentration work becomes simple, and the overall recovery cost can be suppressed.

Furthermore, since the metal collecting material of the present invention uses carbon for granulation and molding, it is stable in water for a long period of time and does not contain non-conductive substances such as cement, so that it collects metals. The efficiency of recovering valuable metals from the material collection 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, various measurements and evaluations are as follows unless otherwise specified.

<Appearance density>
It was measured by the Archimedes method using an electronic hydrometer (EW-300SG, AS ONE).

<Recovery amount of valuable metal>
After immersing the metal collecting material in a liquid (30 ml) containing valuable metal ions for a certain period of time, the concentration of the valuable metal in the liquid is measured. After soaking for a certain period of time, the metal collecting material is taken out and dried at 105 ° C. for a whole day and night. After crushing it, the adhered and recovered valuable metal was dissolved in nitric acid and analyzed by an inductively coupled plasma emission spectrophotometer (ICP) to determine the amount of the valuable metal recovered.

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

<Preparation of metal collecting material (form 1)>
After mixing and kneading a predetermined amount of raw materials (metal powder, solid carbon precursor, carbon aggregate, granulation aid) with a mixing stirrer, the mixture is mixed using a hand press under the condition of 10 MPa and a diameter of 20 mm. , A disk-shaped granulated product having a thickness of 2 to 6 mm was prepared.
The produced granulated product is heated at 100 ° C./hour using a reducing atmosphere firing furnace filled with coke powder, fired at 900 ° C. for 2 hours, and naturally allowed to cool in the furnace until it becomes 50 ° C. or lower. The sintered body was taken out.

<Preparation of metal collecting material (form 2)>
After mixing a predetermined amount of raw materials (metal powder, solid carbonaceous precursor) with a mixing stirrer, the mixture was put into a pan pelletizer (model 1237-S-3, Yoshida Seisakusho Co., Ltd.). In addition, carbon aggregate (pitch coke mass size 1 to 5 cm) that had been heat-treated in advance in an air atmosphere at 230 ° C. for 2 hours was put into a pan pelletizer containing 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 prepared.
The produced composite was heated at 100 ° C./hour using a reducing atmosphere firing furnace filled with coke powder, fired at 900 ° C. for 2 hours, and naturally allowed to cool in the furnace until the temperature became 50 ° C. or lower. The sintered body was taken out.

[Examples 1 to 3]
A metal collecting material of Form 1 was prepared by using aluminum powder as a metal powder, coal tar pitch as a precursor of solid carbonaceous material, pitch coke powder as a carbon aggregate, and an aqueous starch solution as a granulation aid.
The prepared metal collecting material was immersed in a sample bottle containing 30 ml of an aqueous solution in which zinc, cobalt, and copper were dissolved, and left at room 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 collecting material.

[Example 4]
Using the same raw materials as in Examples 1 to 3, the metal collecting material of Form 2 described in Example 4 of Table 1 was prepared.
The prepared metal collecting material was prepared by immersing the metal collecting material in a sample bottle containing 30 ml of an aqueous solution in which copper was dissolved, leaving the metal collecting material under normal temperature and pressure for 7 days, and then measuring the copper concentration.
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collecting material.

[Examples 5 and 6]
The metal collecting material of Form 1 shown in Examples 5 to 6 of Table 1 was prepared in the same manner as in Examples 1 to 3 except that iron powder was used as the metal powder.
The prepared metal collecting material was prepared by immersing the metal collecting material in a sample bottle containing 30 ml of an aqueous solution in which zinc, cobalt, and copper were dissolved, and allowing the metal collecting material to stand under normal temperature and pressure for 7 days, 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 collecting material.

[Example 7]
Using the same raw materials as in Examples 5 and 6, the metal collecting material of Form 2 shown in Example 7 of Table 1 was prepared.
The prepared metal collecting material was prepared by immersing the metal collecting material in a sample bottle containing 30 ml of an aqueous solution in which copper was dissolved, leaving the metal collecting material under normal temperature and pressure for 7 days, and then measuring the copper concentration.
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collecting material.

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

[Example 9]
A metal collecting material of Form 1 was prepared in the same manner as in Example 8 except that a mixture of iron powder and aluminum powder in a weight ratio of 1: 1 was used as the metal powder.
The prepared metal collecting material was prepared by immersing the metal collecting material in a sample bottle containing 30 ml of an aqueous solution in which copper was dissolved, leaving it at room temperature and pressure for 7 days, and then measuring the copper concentration.
Table 1 shows the results of the metal content, carbon content, immersion test, apparent specific gravity and valuable metal recovery amount of the metal collecting material.

[Examples 10-12, 14-16]
The metal collecting material of Form 1 prepared in the same manner as in Examples 5 and 6 was immersed in an aqueous solution in which cobalt and copper were dissolved, respectively, and the entire amount of the aqueous solution in which cobalt and copper were dissolved was 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 results of the 4-week immersion test of the metal collecting material.

[Examples 13 and 17]
The metal collecting material of Form 2 prepared in the same manner as in Example 4 is immersed in an aqueous solution in which cobalt and copper are dissolved, and an immersion test is performed while exchanging the entire amount of the aqueous solution in which cobalt and copper are dissolved every 7 days under normal temperature and pressure. Was carried out for 4 weeks.
Table 2 shows the metal content, carbon content, apparent specific gravity and the results of the 4-week immersion test of the metal collecting material.

[Example 18]
The metal collecting material of Form 1 prepared in the same manner as in Examples 5 and 6 was immersed in an aqueous solution in which cobalt and copper were dissolved, and the aqueous solution in which cobalt and copper were dissolved was completely exchanged every 7 days under normal temperature and pressure. The immersion test was performed for 4 weeks.
Table 2 shows the metal content, carbon content, apparent specific gravity and the results of the 4-week immersion test of the metal collecting material.

[Example 19]
The metal collecting material of Form 1 prepared 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 amount of the aqueous solution under normal temperature and pressure every 7 days.
Table 2 shows the metal content, carbon content, apparent specific gravity and the results of the 4-week immersion test of the metal collecting material.

[Comparative Examples 1 to 6]
1.00 g of iron powder or aluminum powder was immersed in an aqueous solution in which zinc, cobalt, and copper were dissolved, and left to stand in a normal temperature and pressure environment for 7 days, and then the concentrations of zinc, copper, and cobalt were measured.
In addition, the immersion test was carried out for 4 weeks while exchanging all the aqueous solutions in which zinc, cobalt and copper were dissolved every 7 days.
Table 3 shows the metal content, carbon content, true specific gravity, and the results of the immersion test for 4 weeks.

As shown in Tables 1 and 2, the metal collecting materials of Examples 1 to 19 which are sintered bodies of metal particles and carbon are compared with Comparative Examples 1 to 6 (see Table 3) which are metal powder alone. It is possible to collect valuable metals having a higher potential than the metals used for metal collecting materials from water with high efficiency by the action of a local battery.
In addition, it is not mainly collected by including valuable metal in the precipitate of hydroxide, but it is deposited as a metal body on the surface of the metal collecting material, so that it is easy to recover, and the immersion period is lengthened to increase the amount. It is also possible to deposit and recover valuable metals.
As described above, the metal collecting material of the present invention is suitable for recovering valuable metals at low cost from, for example, hot water ejected from a submarine hydrothermal deposit, hot springs, mineral springs, mine wastewater, and the like. 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 particles 2 ... Solid carbon 3 ... Carbon aggregate

Claims (5)

A sintered body containing a plurality of metal particles composed of one or more metal elements selected from aluminum and iron and a solid carbon substance, and the metal particles and the solid carbon substance are bound and integrated. It is a metal collecting material that is
The metal content per 100 parts by weight of the metal collecting material is in the range of 5 to 90 parts by weight.
It is characterized by precipitating and recovering the valuable metal element as a metal body on the surface of the sintered body by a local battery action from water in which one or more valuable metal elements selected from zinc, cobalt and copper are dissolved. Metal collecting material. The solid carbonaceous, petroleum and metal collecting material according to claim 1 pitch obtained from heavy oil of coal-based is a solid carbonaceous to the precursor. The invention according to claim 1 or 2 , further comprising a carbon aggregate composed of one or more pulverized products selected from graphite, needle coke, and pitch coke, and the solid carbon material being coated around the carbon aggregate. Metal collector. The method for producing a metal collecting material according to any one of claims 1 to 3.
A step of mixing the metal particles and the solid carbonaceous precursor and granulating to obtain a granulated product.
as well as,
A step of sintering the granulated product at a temperature of 600 ° C. or higher in a reducing atmosphere to obtain a sintered body.
A method for producing a metal collecting material, which comprises. It is a valuable metal recovery method for recovering valuable metals in water.
A metal collecting material according to any one of claims 1 to 3, hot water ejected from hydrothermal deposits, by contact with water selected from hot springs or mineral water, and the dissolved in the water A method for recovering a valuable metal, which comprises a step of collecting a valuable metal element as a metal body.

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