JP2021038113A - Manufacturing method of metallic compound - Google Patents

Abstract

To provide a manufacturing method of a metallic compound, specifically of hydroxide exhibiting high reactivity via mechanochemical reaction by a simple and inexpensive method.SOLUTION: A manufacturing method of a metallic compound according to the present invention comprises a step of mixing (A) metal particles, (B) a solvent, and (C) a crusher to manufacture (D) a metallic compound via mechanochemical reaction. Accordingly, it is possible to easily manufacture the metallic compound at low cost at normal temperature via the mechanochemical reaction. Specifically, metal hydroxide having high reactivity and poor stability can be easily synthesized.SELECTED DRAWING: Figure 3

Description

The present invention relates to a method for producing a metal compound using a mechanochemical reaction.

Conventionally, methods for producing various metal compounds have been developed. _{For example, silicon oxide (silica: SiO 2} ), which is a compound of silicon, can be prepared by reacting tetrachlorosilane with hydrogen and oxygen, or by reacting sodium silicate (water glass) with an acid, as shown below. Synthesized (Non-Patent Document 1).
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl
Na ₂ O-mSiO ₂ + HCl → SiO ₂ · nH ₂ O + NaCl

Further, silicon hydroxide is produced by the following formula. That is, silicon hydroxide (silanol group (Si—OH) -containing silane) is produced by hydrolyzing organochlorosilane and organoalkoxysilane.
R ₂ SiCl ₂ + 2H ₂ O → R ₂ Si (OH) ₂ + 2HCl
R ¹ ₂ Si (OR ² ) ₂ + 2H ₂ O → R ¹ ₂ Si (OH) ₂ + 2R ² OH

Alkoxysilane is produced by reacting organochlorosilane with an alcohol to synthesize organoalkoxysilane, as shown below.
R ¹ _4-n SiCl _n + nR ² OH → R ¹ _4-n Si (OR ² ) _n + nHCl
(N = 1-3)

Kunio Ito, "Silicone Handbook", Nikkan Kogyo Shimbun, September 1990, p32,49,288-290

In the conventional method for producing a metal compound, such as the silicon compound described above, the synthesis step is long, complicated, and the production efficiency is low. Further, it is difficult to obtain a metal compound having excellent reactivity, particularly a hydroxide, by a conventional method for producing a metal compound.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a metal compound, particularly a highly reactive hydroxide, by a simple and inexpensive method by a mechanochemical reaction.

In order to achieve the above object, in the method for producing a metal compound according to the present invention,
(A) metal particles and (B) solvent
(C) Mix using a crusher and
The metal compound (D) is produced by a mechanochemical reaction.

In addition, the metal particles (A) are
At least one selected from the group consisting of silicon (Si), titanium (Ti), aluminum (Al), chromium (Cr), manganese (Mn), iron (Fe), germanium (Ge) and tin (Sn). ,
It may be that.

In addition, the solvent (B) is
Selected from water, alcohol or mixed solvent of water / alcohol,
It may be that.

The solvent (B) is an alkaline solution.
It may be that.

The concentration of the alkaline solution is
0.01-6M,
It may be that.

Further, the (C) crusher is
Select from ball mill, bead mill, rod mill, jet mill, SAG mill, ROM mill, rotary millstone,
It may be that.

Further, using the (A) metal particles, (E) a metal compound represented by the general formula (1) is produced.
It may be that.
(XO) _a MO _{(ba) / 2} (1)
(In the formula, M is a metal, X is hydrogen, sodium (Na), potassium (K), at least one atom or organic group selected from an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and a is 0. An integer of ~ 4, b is an integer of 3 (when a = 0 to 3) or 4 (when a = 0 to 4).

Further, the metal particles (A) are silicon (Si), and (E) a silicon compound represented by the general formula (2) is produced.
It may be that.
(XO) _a SiO _{(4-a) / 2} (2)
(In the formula, X is at least one atom or organic group selected from hydrogen, sodium (Na), potassium (K), and aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and a is an integer of 0 to 4. Is.)

Further, the metal particles (A) are titanium (Ti), and (E) a titanium compound represented by the general formula (3) is produced.
It may be that.
(XO) _a TiO _{(4-a) / 2} (3)
(In the formula, X is at least one atom or organic group selected from hydrogen, sodium (Na), potassium (K), and aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and a is an integer of 0 to 4. Is.)

Further, the metal compound represented by the general formulas (1) to (3) in (E) is a metal compound selected from a metal oxide, a metal hydroxide, and a metal alkoxide.
It may be that.

Further, together with the (A) metal particles and the (B) solvent, an additive (F) that promotes a mechanochemical reaction is added.
Mixing using the (C) crusher.
It may be that.

The additive (F) is copper (Cu).
It may be that.

According to the present invention, a metal compound can be easily and inexpensively produced at room temperature by a mechanochemical reaction. In particular, a metal hydroxide having high reactivity and lacking stability can be easily synthesized.

It is a conceptual diagram which shows the structure of the planetary ball mill apparatus. It is a conceptual diagram which shows the state of milling by the rotation of a container. It is a flowchart which shows the flow of the metal compound manufacturing process which concerns on Embodiment 1 of this invention. It is a graph which shows the example of NMR of the milled solution. (A) is a graph showing an example of NMR when an additive is added, and (b) is a graph showing an example of NMR when no additive is added.

Hereinafter, the method for producing a metal compound according to the embodiment of the present invention, that is, (A) metal particles and (B) solvent are mixed using (C) a pulverizer, and (D) metal compound is subjected to a mechanochemical reaction. The method of manufacturing the above will be described in detail with reference to the drawings.

(Embodiment 1)
<(A) Metal particles>
The metal particles (A) are metals that are raw materials for producing a target metal compound by a mechanochemical reaction, and are group 13 (boron group element), group 14 (carbon group element), titanium (Ti), and the like. Chromium (Cr), manganese (Mn), iron (Fe), vanadium (V), magnesium (Mg), zirconium (Zr), tungsten (W) and the like. The metal particles (A) are composed of, for example, silicon (Si), titanium (Ti), aluminum (Al), chromium (Cr), manganese (Mn), iron (Fe), germanium (Ge) and tin (Sn). At least one metal selected from the group. The metal particles (A) are preferably silicon, titanium or aluminum, and more preferably silicon or titanium.

<(B) Solvent>
(B) The solvent is, for example, water, alcohol or a mixed solvent of water / alcohol. The mixing ratio of water / alcohol when a mixed solvent of water / alcohol is used is not particularly limited, and the type of (A) metal particles to be selected, (A) the amount of metal particles charged, and (B) the amount of solvent charged are selected. It is appropriately set depending on the relationship with the above, the type of the (D) metal compound to be produced, and the like.

As the water, for example, distilled water, seawater or the like can be used, and the pH of the water is preferably 5 or more. The term "seawater" refers to water containing 3% or more of salt, and in the present invention, particularly refers to an aqueous solution containing 3% or more of sodium chloride.

The alcohol is selected from the following group of aliphatic hydrocarbon-based alcohols having 1 to 10 carbon atoms. Alcohol can be used alone or in combination of a plurality of alcohols. Typical examples of the alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropanol, butyl alcohol, hexyl alcohol, and octyl alcohol, which are compatible with water, reactive with metals, and contain an alkoxy group. Alcohols having a small number of carbon atoms are preferable from the viewpoint of hydrolysis and reactivity of metal compounds, and methyl alcohols and ethyl alcohols are more preferable.

Further, in order to control the amount of metal alkoxide produced by the mechanochemical reaction in the water / alcohol mixed system, the water content of the alcohol used is preferably 50 ppm or less. More specifically, when a commercially available alcohol is usually used, it is preferable to dehydrate the alcohol in advance with a molecular sieve or the like.

Further, an alkaline solution may be used as the solvent (B). Examples of the alkaline solution include a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a mixed aqueous solution of sodium hydroxide and potassium hydroxide, a sodium carbonate aqueous solution, an ammonia aqueous solution, and a sodium chloride aqueous solution. Of these, it is preferable to use an aqueous sodium hydroxide solution because it suppresses the formation of a passivation film on the surface of the metal particles and improves the efficiency of the metal compound formation reaction.

The alkaline solution concentration is preferably 0.01 to 6M. The solvent (B) having an alkaline solution concentration in this range _{increases the solubility of the oxide (for example, SiO 2} ) of the metal particles forming the oxide film by the compound ions, and thus improves the production rate of the metal compound. Conceivable.

<(C) Crusher>
The (C) crusher crushes (A) metal particles and enhances the activity of (A) metal particles and (B) solvent by the mechanical energy applied to (A) metal particles and (B) solvent. , Anything that causes a mechanochemical reaction is sufficient, and the type of operation principle, scale, etc. is not particularly limited. The crusher (C) is, for example, a ball mill, a bead mill, a rod mill, a jet mill, a SAG (Semi-Autogenous Grinding) mill, a ROM (Run Of Mine) mill, a rotary millstone, or the like. In particular, a planetary ball mill is preferable for producing a metal compound because of its high efficiency of mechanochemical reaction.

<(D) Metal compound>
The metal compound produced (D) can synthesize metal oxides, metal hydroxides, and metal alkoxides, depending on the metal particles (A) and the solvent (B). For example, when (A) the metal particles are silicon (Si) and (B) the solvent is water alone, silicon oxide (silica: SiO ₂ ), silicon hydroxide (Si _n (OH) _4-n ) and hydroxide are used. Silicon oligomers are produced.

(B) When an alkaline solution, for example, an aqueous sodium hydroxide solution is used as the solvent, a silicic acid compound similar to a Na-containing water glass compound is produced. Further, for example, when the solvent (B) is a methyl alcohol alone system, tetramethoxysilane (Si (OCH ₃ ) ₄ ) is produced. When the solvent (B) is a water / alcohol (for example, methyl alcohol) mixed system, a mixture of silicon oxide, tetramethoxysilane, trimethoxysilanolsilane, dimethoxydisylanolsilane, and trisilanolmethoxysilane, two amounts thereof. Polymers such as body and trimer (for example, tetramethoxysilane of the same type) and dimer consisting of two or more kinds, polymer such as trimer (for example, dimer from tetramethoxysilane and dimethoxysilane), A trimer and a complex thereof) are produced.

(A) The metal particles are metal particles other than silicon (Si), for example, titanium (Ti), aluminum (Al), chromium (Cr), manganese (Mn), iron (Fe), germanium (Ge) and tin (Sn). ), Similarly, metal oxides, metal hydroxides, and metal alkoxides corresponding to the metal particles (A) used are produced.

For example, as metal oxides, titanium oxide (TiO ₂ , TiO, Ti ₂ O, Ti ₃ O, Ti ₂ O ₃ ), aluminum oxide (Al ₂ O _3, Al ₂ O, AlO), chromium oxide (III) ( Cr ₂ O ₃ ), chromium oxide (II) (CrO), chromium oxide (IV) (CrO ₂ ), chromium oxide (VI) (CrO ₅ , CrO ₃ ), manganese oxide (IV) (MnO ₂ ), manganese oxide (II) (MnO), Manganese Oxide (III) (Mn ₂ O ₃ ), Manganese Oxide (VI) (MnO ₃ ), Manganese Oxide (VII) (Mn ₂ O ₇ ), Manganese Oxide (II, III) (Mn) ₃ O ₄ ), iron oxide (III) ( _{α, β, γ, ε type in Fe 2} O ₃ ), iron oxide (II) (FeO), iron oxide (II, III) (Fe ₃ O ₄ ), oxidation Germanium (GeO ₂ ) and tin oxide (SnO ₂ ) are produced. Further, for example, as metal hydroxide, Ti (OH) ₂ , Al (OH) ₃ , Mn (OH) ₂ , Fe (OH) ₃ , Fe (OH) ₂ , FeOOH (α, β, γ, δ type) (Iron oxyhydroxide), Ge (OH) ₂ , Sn (OH) ₂ are produced. The hydroxide of Cr _{becomes chromic acid (H 2} CrO ₄ ).

Metal alkoxides include Ti (OCH ₃ ) ₄ , Ti (Ot-C ₄ H ₉ ) ₄ , Ge (OC ₂ H ₅ ) ₄ , Sn (On-C ₄ H ₉ ) ₄ , Sn (Ot-C ₄ H). ₉ ) ₄ is produced, but (A) the reactivity is lower than when silicon is used as the metal particles, and oxide synthesis is easier.

Further, generated by the selected (A) the metal particles, as the polyacid _"M x _{O y"} (M is, Si, Ti, Al, W , Mo, V, Nb, Zr , etc.), (D) a metal compound Will be done. These (D) metal compounds are used in catalysts, magnetic materials, pharmaceuticals and the like. Further, in this reaction, the above-mentioned metals such as Si, Ti, W and Zr may be used for the container 12 and the pulverizing medium 21, and two or more kinds of metals may be used. That is, during the operation of the planetary ball mill device 1, polyacid may be produced as a (D) metal compound based on the metal scraped from the container 12 and the pulverizing medium 21. Further, by using magnesium (Mg) as the metal particles (A), an organometallic compound such as _{Grignard reagent or W (CH 3} ) _{6 may be produced.}

<Manufacturing method of metal compounds>
Subsequently, a method for producing a metal compound will be described. In the present embodiment, a method using the planetary ball mill device 1 as the (C) crusher will be described as an example. As shown in the conceptual diagram of FIG. 1, the planetary ball mill device 1 includes a central shaft 11 that is rotationally driven, a table 13 that rotates integrally with the central shaft 11, and a plurality of containers 12 that are rotatably supported by the table 13. To be equipped.

As shown in FIGS. 1 and 2, the container 12 revolves around the central axis 11 in the direction of the arrow a in the drawing, and around the central axis 12a of the container 12 in the direction of the arrow b in the drawing. Rotate. As a result, the metal particles (A) are pulverized by the pulverizing medium 21 in each container 12. At this time, the mechanical energy applied to the (A) metal particles and the (B) solvent increases the activity of the (A) metal particles and the (B) solvent, causing a mechanochemical reaction to generate a metal compound. ..

In the metal compound production process according to the present embodiment, first, the pulverizing medium 21 is charged into the container 12 as shown in the flowchart of FIG. 3 (step S11).

The container 12 contains (A) metal particles, (B) solvent, and the like to be crushed, and is, for example, a cylindrical container with a lid. As described above, the container 12 is set in the planetary ball mill device 1 and is rotated by the operation of the planetary ball mill device 1. As a result, a mechanochemical reaction occurs between the metal particles (A) and the solvent (B) inside the container 12.

The material of the container 12 is not particularly limited, and is, for example, tungsten carbide (WC), stainless steel, zirconia (ZrO ₂ ), etc., but it is preferable to use a material having a hardness higher than that of the metal particles (A). The material of the container 12 according to this embodiment is tungsten carbide (WC). The capacity of the container 12 is not particularly limited, and may be appropriately selected depending on the amount of metal oxide to be produced, the allowable temperature at the time of reaction, and the like.

The crushing medium 21 is a medium that is housed in a container 12 together with (A) metal particles and (B) a solvent, and crushes (A) metal particles by rotation of a planetary ball mill device 1. The shape of the crushing medium 21 is not particularly limited, such as a ball shape or a rod shape, and its size is not particularly limited. However, since (A) metal particles are crushed by applying sufficient mechanical energy, (A) metal. It is preferably larger than the particles. The material of the crushing medium 21 is generally the same as that of the container 12. More specifically, the material of the pulverizing medium 21 is generally the same as the material inside the container 12 in which (A) metal particles, (B) solvent and the like are in contact with each other. The pulverizing medium 21 according to the present embodiment is a tungsten carbide ball having a diameter of about 1.6 mm. The weight of the crushing medium 21 charged into the container 12 is about 100 g.

Subsequently, the metal particles (A) are charged into the container 12 (step S12). The metal particles (A) are metal materials that are crushed in the container 12 and cause a mechanochemical reaction. (A) The shape, size, etc. of the metal particles are not particularly limited. The metal particles (A) according to the present embodiment are silicon (Si) powder (manufactured by Sigma-Aldrich), and the particle size is approximately 20 μm to 60 μm. The amount of the metal particles (A) charged into the container 12 is not particularly limited, but is 0.1 g in the present embodiment.

Subsequently, the solvent (B) is charged into the container 12 (step S13). As described above, the solvent (B) is water, alcohol, a mixed solvent of water / alcohol, or the like. In this embodiment, methyl alcohol dehydrated by methanol (stationary method) is used as the solvent (B). The amount of the solvent (B) charged into the container 12 is 10 ml. The metal particles (A) and the solvent (B) may be mixed in advance before being charged into the container 12.

After the metal particles (A) and the solvent (B) are charged, the container 12 is closed with the lid closed. In the present embodiment, the inside of the container 12 is adjusted to an argon gas atmosphere before sealing. As a result, it is possible to prevent the gas existing in the container 12 from affecting the mechanochemical reaction.

The sealed container 12 is set in the planetary ball mill device 1 as shown in FIG. 1 (step S14). The planetary ball mill device 1 used in the present embodiment is a planetary ball mill (trade name: Premium Line P-7) manufactured by Fritsch, Germany.

After setting the container 12 in the planetary ball mill device 1, the operation of the planetary ball mill device 1 is started (step S15). By changing the rotation speed of the planetary ball mill, that is, the rotation speed of the container 12, the acceleration applied to the contents of the container 12 changes. Therefore, the magnitude of the mechanical energy applied to the (A) metal particles is adjusted by the mass of the pulverizing medium 21 and the rotation speed of the container 12, and the production rate of the (D) metal compound by the mechanochemical reaction is controlled. Can be done.

Specifically, using the radius of gyration R (mm) of the planetary ball mill device 1 and the rotation speed N (rpm) of the container 12, the relative centrifugal acceleration G (G) applied to the contents of the container 12 is calculated by the following equation. Desired.
G = 1.118 × R × N ² × ^10-6

The radius of gyration of the planetary ball mill device 1 according to the present embodiment (distance between the central axis 11 of the planetary ball mill device 1 and the central axis 12a of the container 12) is 70 mm. Therefore, for example, when the rotation speed N = 500 rpm, The relative centrifugal acceleration G is about 19.6 G. When the rotation speed N = 300 rpm, the relative centrifugal acceleration G is about 7.04 G. The rotation speed of the container 12 of the planetary ball mill device 1 according to the present embodiment is preferably 100 to 700 rpm. Further, the rotation speed of the specific container 12 in the present embodiment is 200 rpm.

As the container 12 rotates, the metal particles (A) are milled (crushed). At this time, mechanical energy is applied to the (A) metal particles and the (B) solvent, the activities of the (A) metal particles and the (B) solvent are increased, and a mechanochemical reaction occurs. As a result, the metal compound represented by the following (E) general formula (1) is produced (step S16).
(XO) _a MO _{(ba) / 2} (1)
(In the formula, M is a metal, X is hydrogen, sodium (Na), potassium (K), at least one atom or organic group selected from an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and a is 0. An integer of ~ 4, b is an integer of 3 (when a = 0 to 3) or 4 (when a = 0 to 4).

FIG. 4 shows the results of analysis of the components of the solution milled by the above method using Nuclear Magnetic Resonance (NMR). The solution analyzed by NMR is obtained by centrifuging the milled solution at 15,000 rpm for 30 minutes and then extracting the supernatant. This supernatant solution was analyzed by ^{29 Si NMR.} The conditions for NMR measurement are resonance frequency: 119.24 MHz, pulse: 45 deg / 5.5 μs, pulse interval: 2 s, number of integrations: 1000 times, sample tube: Teflon (registered trademark) tube (5 mmφ).

As shown in FIG. 4, peaks of metal compounds formed in the range of -30 to -90 ppm have been detected. The metal particles (A) of the present embodiment are silicon (Si), and the metal compound produced is represented by the following general formula (2).
(XO) _a SiO _{(4-a) / 2} (2)
(In the formula, X is at least one atom or organic group selected from hydrogen, sodium (Na), potassium (K), and aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and a is an integer of 0 to 4. Is.)

The silicon compound of the general formula (2) is produced with silicon oxide (silica: SiO ₂ ) as a main component. Further, in a water / alcohol (for example, methyl alcohol) mixed system, a mixture of silicon oxide, tetramethoxysilane, trimethoxysilanolsilane, dimethoxydisylanolsilane, and trisilanolmethoxysilane is produced. Typically, Tetramethoxysilane (Si (OCH ₃ ) ₄ ) is produced. The peak due to the metal compound shown in FIG. 4 corresponds to the chemical shift of the metal compound, and it is considered that these metal compounds are produced.

As described in detail above, in the present embodiment, (A) metal particles and (B) solvent are mixed using (C) a pulverizer, and (D) a metal compound is produced by a mechanochemical reaction. Therefore, it is possible to easily and inexpensively produce a metal compound at room temperature. In particular, a metal hydroxide having high reactivity and lacking stability can be easily synthesized.

In the present embodiment, the metal particles (A) are silicon, but the metal particles are not limited to silicon, and as described above, titanium (Ti), aluminum (Al), chromium (Cr), manganese (Mn), and iron. (Fe), germanium (Ge), tin (Sn) and the like may be used, and a plurality of these metals may be contained.

For example, when titanium is used as the metal particles (A), the metal compound produced is a titanium compound represented by the following general formula (3).
(XO) _a TiO _{(4-a) / 2} (3)
(In the formula, X is at least one atom or organic group selected from hydrogen, sodium (Na), potassium (K), and aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and a is an integer of 0 to 4. Is.)

The titanium compound represented by the general formula (3) is, for example, tetramethoxytitanium (Ti (OCH ₃ ) ₄ ). (A) When titanium is used as the metal particles, it is considered that an oxidation reaction and a reduction reaction are carried out by a mechanochemical reaction, and the metal compound according to the present invention is efficiently produced.

(Embodiment 2)
The method for producing a metal compound according to the present embodiment is different from the first embodiment in that the additive (F) is charged into the container 12 together with the metal particles (A) and the solvent (B). Since other configurations are the same as those in the first embodiment, the same reference numerals are given.

The flow of the metal compound production process according to the present embodiment is the same as the flowchart of FIG. 3 according to the first embodiment.

The materials, sizes, and the like of the container 12 and the crushing medium 21 are the same as those in the first embodiment. Specifically, the material of the container 12 and the pulverizing medium 21 is tungsten carbide (WC). The size of the crushing medium 21 is about 1.6 mm in diameter, and the input amount is about 100 g.

The crushing medium 21 is put into the container 12 together with the metal particles (A). The metal particles (A) according to the present embodiment are silicon (Si) powders, and the particle size is approximately 20 μm to 60 μm. The amount of the metal particles (A) charged into the container 12 is not particularly limited, but is 0.5 g in the present embodiment.

In the present embodiment, the additive (F) is charged into the container 12 together with the metal particles (A). The (F) additive is a substance that transfers a charge to and from the (A) metal particles and promotes the formation of a metal compound. For example, gold (Au), silver (Ag), platinum (Pt), and nickel. (Ni), palladium (Pd), chromium (Cr), molybdenum (Mo), niobium (Nb), technetium (Tc), cobalt (Co) and the like. The additive (F) according to the present embodiment is a powder of copper (Cu) and has a particle size of approximately 200 μm to 500 μm. The amount of the additive (F) charged into the container 12 is not particularly limited, but is 0.05 g in the present embodiment.

Subsequently, the solvent (B) is charged into the container 12. The solvent (B) is a methyl alcohol dehydrated by methanol as in the first embodiment. The amount of the solvent (B) charged into the container 12 is 10 ml. The metal particles (A), the additives (F) and the solvent (B) may be mixed in advance before being charged into the container 12.

After the metal particles (A), the solvent (B) and the additive (F) are charged, the container 12 is closed with the lid closed and set in the planetary ball mill device 1. After setting the container 12 in the planetary ball mill device 1, the operation of the planetary ball mill device 1 is started. In the present embodiment, the rotation speed of the planetary ball mill, that is, the rotation speed of the container 12, is 300 rpm, and the milling time is 2 hours.

As the container 12 rotates, the metal particles (A) are milled (crushed). At this time, mechanical energy is applied to the (A) metal particles and the (B) solvent, the activities of the (A) metal particles and the (B) solvent are increased, and a mechanochemical reaction occurs. As a result, the metal compound represented by the following (E) general formula (2) is produced.
(XO) _a SiO _{(4-a) / 2} (2)
(In the formula, X is at least one atom or organic group selected from hydrogen, sodium (Na), potassium (K), and aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and a is an integer of 0 to 4. Is.)

FIG. 5A is an example of NMR in the case where copper as an additive (F) is added and milled. The sample to be subjected to NMR is a sample obtained by collecting the supernatant solution after centrifugation (15000 rpm for 30 minutes) in the same manner as in the first embodiment. The NMR conditions are also the same as in the first embodiment. It can be seen that many metal compounds are produced as compared with the NMR results when the additive (F) shown in FIG. 5 (b) is not added.

As described in detail above, in the present embodiment, the (F) additive is mixed with the (A) metal particles and the (B) solvent to produce the (D) metal compound by a mechanochemical reaction. It is possible to produce a metal compound more efficiently.

The present invention allows for various embodiments and modifications without departing from the broad spirit and scope of the invention. Moreover, the above-described embodiment is for explaining the present invention, and does not limit the scope of the present invention. That is, the scope of the present invention is indicated not by the embodiment but by the claims. Then, various modifications made within the scope of the claims and the equivalent meaning of the invention are considered to be within the scope of the present invention.

The present invention is suitable for a metal compound manufacturing process for producing various metal compounds. In particular, it is suitable for a manufacturing process of a metal compound having excellent reactivity such as hydroxide.

1 Planetary ball mill device, 11 central shaft, 12 container, 12a central shaft, 13 table, 21 crushing medium

Claims (12)

(A) metal particles and (B) solvent
(C) Mix using a crusher and
(D) A metal compound is produced by a mechanochemical reaction.
A method for producing a metal compound. The metal particles (A) are
At least one selected from the group consisting of silicon (Si), titanium (Ti), aluminum (Al), chromium (Cr), manganese (Mn), iron (Fe), germanium (Ge) and tin (Sn). ,
The method for producing a metal compound according to claim 1. The solvent (B) is
Selected from water, alcohol or mixed solvent of water / alcohol,
The method for producing a metal compound according to claim 1 or 2, wherein the metal compound is produced. The solvent (B) is an alkaline solution.
The method for producing a metal compound according to claim 1 or 2, wherein the metal compound is produced. The concentration of the alkaline solution is
0.01-6M,
The method for producing a metal compound according to claim 4, wherein the metal compound is produced. The (C) crusher is
Select from ball mill, bead mill, rod mill, jet mill, SAG mill, ROM mill, rotary millstone,
The method for producing a metal compound according to any one of claims 1 to 5, wherein the metal compound is produced. Using the (A) metal particles, (E) a metal compound represented by the general formula (1) is produced.
The method for producing a metal compound according to any one of claims 1 to 6, wherein the metal compound is produced.
(XO) _a MO _{(ba) / 2} (1)
(In the formula, M is a metal, X is hydrogen, sodium (Na), potassium (K), at least one atom or organic group selected from an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and a is 0. An integer of ~ 4, b is an integer of 3 (when a = 0 to 3) or 4 (when a = 0 to 4). The metal particles (A) are silicon (Si), and (E) a silicon compound represented by the general formula (2) is produced.
The method for producing a metal compound according to any one of claims 1 to 6, wherein the metal compound is produced.
(XO) _a SiO _{(4-a) / 2} (2)
(In the formula, X is at least one atom or organic group selected from hydrogen, sodium (Na), potassium (K), and aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and a is an integer of 0 to 4. Is.) The metal particles (A) are titanium (Ti), and (E) a titanium compound represented by the general formula (3) is produced.
The method for producing a metal compound according to any one of claims 1 to 6, wherein the metal compound is produced.
(XO) _a TiO _{(4-a) / 2} (3)
(In the formula, X is at least one atom or organic group selected from hydrogen, sodium (Na), potassium (K), and aliphatic hydrocarbon groups having 1 to 6 carbon atoms, and a is an integer of 0 to 4. Is.) The metal compound represented by the general formulas (1) to (3) in (E) is a metal compound selected from metal oxides, metal hydroxides, and metal alkoxides.
The method for producing a metal compound according to any one of claims 7 to 9, wherein the metal compound is produced. Along with the (A) metal particles and the (B) solvent, an additive (F) that promotes a mechanochemical reaction is added.
Mixing using the (C) crusher.
The method for producing a metal compound according to any one of claims 1 to 10, wherein the metal compound is produced. The additive (F) is copper (Cu).
The method for producing a metal compound according to claim 11, wherein the metal compound is produced.