WO2012002323A1

WO2012002323A1 - Magnesium hydroxide and production method for same

Info

Publication number: WO2012002323A1
Application number: PCT/JP2011/064682
Authority: WO
Inventors: 貴夫舩田
Original assignee: Funada Takao
Priority date: 2010-06-29
Filing date: 2011-06-27
Publication date: 2012-01-05
Also published as: JP4778111B1; JP2012031039A; KR20130038337A; CN102958842A

Abstract

The disclosed method repeats: a first reaction which forms a coating film containing magnesium hydroxide on the surface of magnesium metal by immersing the magnesium metal in an aqueous solution having magnesium salt as the main component thereof; and a second reaction wherein the coating film is dissolved by the aqueous solution, and the hydroxyl group ions and the magnesium ions in the aqueous solution combine. The resulting magnesium hydroxide precipitated in the aqueous solution is collected.

Description

Magnesium hydroxide and method for producing the same

Conventionally, as a method for producing magnesium hydroxide, an alkali source such as sodium hydroxide, calcium hydroxide or aqueous ammonia (ammonium hydroxide) is added to an aqueous solution containing magnesium chloride to precipitate magnesium hydroxide, and this is recovered. Was common. As a special method, a “method of spark discharge by applying a high voltage to magnesium metal in pure water” is used. In addition, as a method for directly producing magnesium oxide, which is a calcined product of magnesium hydroxide, a “method of dissolving magnesium metal to produce magnesium vapor and reacting it with oxygen in a gas phase” has been proposed (Patent Document 1). reference).

On the other hand, as a well-known fact, Non-Patent Document 1 indicates that “magnesium reacts with hot water to generate hydrogen to become a hydroxide”, and Non-Patent Document 2 states that “magnesium metal is a chloride. It reacts with water in an aqueous solution containing water to generate hydrogen to produce magnesium hydroxide. "

JP-A-2-307822

However, when calcium hydroxide (lime milk) is used as in the conventional manufacturing method described above, there is a problem that small magnesium crystals cannot be obtained, and the generation of impurities such as Ca, Si, and Fe is unavoidable. . In addition, when sodium hydroxide is used, there is a problem that it is necessary to use a large amount of pure water for removing sodium in a subsequent process unless the crystal is intentionally grown. When ammonia water was used, the above problem could be solved, but a sufficient amount of precipitate could not be obtained, so that it was unsuitable for industrial production.

Also, in the case of the method of producing magnesium hydroxide from magnesium metal, there is a problem that the burden of capital investment is large and a large amount of electric power is used. Furthermore, the method of producing magnesium oxide directly from magnesium metal has a safety problem, and the burden of capital investment is large, resulting in a cost problem.

Furthermore, as for the above-mentioned known facts, “in the case of hot water” reacts if it is a fine powder of magnesium, but it is very dangerous and difficult to put into practical use. In the case of an aqueous solution of chloride, for example, when magnesium metal for Grignard reagent is added to an aqueous solution of sodium chloride, it appears to form slightly at first, but magnesium hydroxide is formed on the surface of the magnesium metal. Becomes passive and the reaction stops. Further, hydrogen is only generated in the aqueous solution of aluminum chloride. In other words, the known fact that “magnesium hydroxide is produced when magnesium is immersed in an aqueous chloride solution” is actually “cannot be produced continuously, it can only be produced instantaneously. I think it is accurate to paraphrase.

The present invention has been made in view of such circumstances, and a main object thereof is to provide magnesium hydroxide and a method for producing the same that can solve the above-mentioned problems.

In order to solve the above problems, the magnesium hydroxide of the present invention is a first method in which a magnesium metal is immersed in an aqueous solution containing a magnesium salt as a main component to form a film containing magnesium hydroxide on the surface of the magnesium metal. The reaction and the coating are dissolved in the aqueous solution, and a second reaction in which magnesium ions and hydroxyl ions in the aqueous solution are combined is repeatedly caused. As a result, the coating is precipitated in the aqueous solution. The magnesium hydroxide obtained here may have a flake shape.

Further, in the method for producing magnesium hydroxide of the present invention, a first reaction for forming a film containing magnesium hydroxide on the surface of the magnesium metal by immersing magnesium metal in an aqueous solution containing a magnesium salt as a main component; The coating is dissolved by the aqueous solution, and a second reaction in which magnesium ions and hydroxyl ions in the aqueous solution are combined is repeatedly caused. As a result, magnesium hydroxide precipitated in the aqueous solution is recovered.

In the method for producing magnesium hydroxide according to the above invention, the magnesium salt is preferably magnesium chloride, magnesium sulfate, magnesium nitrate, or other water-soluble magnesium salt.

In the case of magnesium hydroxide according to the present invention, it can be easily produced with simple equipment. Moreover, according to the manufacturing method of magnesium hydroxide which concerns on this invention, it becomes possible to manufacture magnesium hydroxide simply, without providing special equipment and without using a lot of electric power.

FIG. 3 shows an X-ray diffraction pattern in Example 1. The figure which shows the electron microscope image of the magnesium hydroxide obtained by Example 1. FIG. The figure which shows the electron microscope image of the magnesium hydroxide obtained by Example 3. FIG. The figure which shows the electron microscope image of the magnesium hydroxide obtained by Example 4. FIG.

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

In the method for producing magnesium hydroxide according to the present embodiment, an aqueous solution containing a magnesium salt as a main component is prepared, and magnesium metal is immersed and reacted therewith, followed by filtration (solid-liquid separation), washing, drying and Disintegrate. The liquid after filtration can be concentrated and reused.

The mechanism of the reaction between magnesium and an aqueous magnesium salt solution will be described in detail below using magnesium chloride as an example. By using the magnesium salt, the magnesium hydroxide in which the acid in the magnesium salt aqueous solution is passivated is dissolved, and a new surface of the magnesium metal is formed, and new oxidation occurs. Therefore, it is thought that the reaction circulates and continues. In the aqueous solution of magnesium chloride, the following four types of equilibrium exist.
_{^{1. MgCl 2 ⇔ Mg 2+ + 2Cl}} -
_{^{2. H 2 O ⇔ H + +}} OH -
3. Mg ²⁺ ＋ 2OH ^- ⇔ Mg (OH) ₂
4. H ⁺ + Cl ^- ⇔ HCl
Putting these together,
MgCl ₂ + 2H ₂ O ⇔ Mg (OH) ₂ + 2HCl

Mg introduced into the aqueous solution first reacts with H ⁺ and OH ⁻ to generate hydrogen, and Mg (OH) ₂ is generated. This Mg (OH) ₂ forms a film on the surface of Mg, but HCl in the aqueous solution reacts with Mg (OH) ₂ of this film to become MgCl ₂ , dissolves in the aqueous solution and leaves the Mg. On the other hand, Mg ²⁺ released from 2Cl ⁻ binds to 2OH ⁻ and Mg (OH) ₂ in the aqueous solution increases. These reactions are repeated cyclically, so that Mg (OH) ₂ in the aqueous solution exceeds the saturation concentration and precipitates. This can be explained by the reaction formula as follows.
_{_{1. MgCl 2 + 2H 2 O ⇔}} Mg (OH) 2 + 2HCl ... Mg in aqueous solution (OH) ₂ is generated ^{^{2. Mg + 2H + + 2OH -}} → Mg (OH) 2 + H 2 ↑ ... metal Mg ( OH) ₂ film is formed 3. Mg (OH) ₂ + 2HCl → MgCl ₂ + 2H ₂ O… 1 HCl dissolves in the film formed by 2 The generated MgCl ₂ returns to 1 again, Mg (OH) ₂ will be generated.

Thus, the above reactions 1, 2, and 3 are repeated cyclically, so that Mg (OH) ₂ is saturated and precipitates. The same reaction occurs in an aqueous solution of magnesium sulfate, an aqueous solution of magnesium nitrate, or an aqueous solution of other magnesium salts. In the aqueous solution of magnesium sulfate, it is explained by replacing the chloride ion of magnesium chloride with sulfate ion. In the aqueous solution of magnesium nitrate, it is explained by replacing chlorine ions with nitrate ions. In other aqueous solutions of magnesium salts, it is explained by replacing chlorine ions with bromine ions, acetate ions, perchlorate ions, etc., respectively.

On the other hand, the following four types of equilibrium exist in an aqueous NaCl solution.
1. NaCl ⇔ Na ^{+ +} Cl ^-
_{^{2. H 2 O ⇔ H + +}} OH -
3. Na ⁺ + OH ^- ⇔ NaOH
4. H ⁺ + Cl ^- ⇔ HCl
When Mg introduced into the aqueous solution reacts with H ⁺ and OH ⁻ , hydrogen is generated, and a Mg (OH) ₂ film is formed on the surface of Mg to passivate. To advance the reaction, an acid that dissolves the film is required. However, in the aqueous NaCl solution, even if HCl is generated, NaOH is simultaneously generated. Therefore, this HCl reacts preferentially with NaOH rather than reacting with Mg (OH) ₂ and becomes NaCl again. Therefore, it is difficult to produce Mg (OH) ₂ continuously in an aqueous solution of NaCl.

Next, the following four types of equilibrium exist in the CaCl ₂ aqueous solution as well.
_{^{1. CaCl 2 ⇔ Ca 2+ + 2Cl}} -
_{^{2. H 2 O ⇔ H + +}} OH -
3. Ca ²⁺ ＋ 2OH ^- ⇔ Ca (OH) ₂
4. H ⁺ + Cl ^- ⇔ HCl
When Mg put into the aqueous solution reacts with H +, OH-, hydrogen is generated, and a film of Mg (OH) ₂ is formed on the surface of Mg. However, as with NaCl, the produced HCl reacts preferentially with Ca (OH) ₂ rather than with the coating Mg (OH) ₂ , so in the aqueous solution of CaCl ₂ Mg (OH) ) ₂ is difficult to produce.

The material of the container for storing the magnesium salt aqueous solution is not limited to a specific material, and any material that does not react with the aqueous solution may be used. For example, a container having a contact surface of the aqueous solution made of resin or glass can be used.

In the manufacturing method of the present embodiment, the temperature of the aqueous solution is not limited to a specific value. The concentration of the aqueous solution is not limited to a specific value, but a higher value is preferable because the reaction time tends to be faster near the saturated concentration.

As the magnesium salt used in the production method of the present embodiment, for example, magnesium chloride, magnesium sulfate, magnesium nitrate, or the like can be used. Here, when magnesium chloride or magnesium nitrate is used, anions (chlorine ions and nitrate ions) remaining in a small amount in the produced magnesium hydroxide can be decomposed and removed at 1,000 ° C. or less. It is really effective for manufacturing.

As described above, various magnesium salts can be used, but magnesium chloride is usually used for reasons such as easy availability. In this case, if calcium contained in the magnesium chloride is an undesirable component, it is preferably precipitated and removed beforehand with magnesium sulfate or the like.

The type of magnesium metal used in the manufacturing method of the present embodiment is not particularly limited, but it is preferably an ingot state. In the case of a cut piece of magnesium metal, the reaction is fast, but there is a disadvantage that the purity is low, and it is difficult to judge whether the reaction has been completed completely, and it is considered that there is a problem in quality.

Specifically, prepare a plastic box of a size that can hold a magnesium metal ingot sufficiently, inject an aqueous solution adjusted to a concentration of about 30% magnesium salt such as magnesium chloride into the box, and immerse the ingot there And react.

Here, it is preferable to set the weight ratio of the magnesium metal and the magnesium salt aqueous solution to about 1: 4. The concentration of the saturated aqueous solution of magnesium chloride is 35.3% at 20 ° C., but moisture is lost as the reaction proceeds, so it is preferable to set the concentration around 30%. If water is lost and the aqueous solution changes to a jelly state, water should be replenished.

After the reaction has progressed and the ingot has not become so small that it cannot be detected, the viscosity of the liquid can be increased by raising the ingot or allowing sufficient time to complete the reaction and then supplementing with a small amount of water as necessary. The magnesium chloride and magnesium hydroxide are separated by filtration. The magnesium hydroxide recovered in this manner is still adhered with a magnesium salt, so it is further thoroughly washed with water and dried at 100 ° C. or higher. As a result, the resulting dried product is agglomerated and is crushed. In addition, the method is not ask | required about crushing.

In the case of the manufacturing method of the present embodiment, it is possible to manufacture magnesium hydroxide from which alkali such as sodium and calcium is removed without using a very simple facility and without using a large amount of water or electricity. Therefore, a large amount of water and electricity can be saved, and no chemicals such as a precipitating agent are required, which is very effective in achieving energy saving.

Note that, as will be described later, the magnesium hydroxide produced according to the present embodiment has a flake shape. Focusing on this shape, the magnesium hydroxide is suitable for use as a coating material. In addition, when the flaky crystals are irregularly arranged, the surface area per unit area increases, so it can be said that it is suitable for use as an adsorbent.

The present invention will be described in detail with reference to examples. In addition, this invention is not limited to these Examples, unless it deviates from the summary.

Example 1
Three liters of a 24% strength magnesium chloride aqueous solution was placed in an 8 liter container made of polypropylene, and one side of a magnesium metal plate (purity 99.9% or more) having a width of 100 mm, a thickness of 5 mm, and a length of 300 mm was immersed therein. The liquid temperature was 13.5 ° C. After 25 hours, the magnesium metal plate was pulled up, and the cloudy liquid was filtered, washed, dried, and crushed. As a result, 23 g of powder was obtained. When this powder was subjected to X-ray diffraction, a beautiful peak of magnesium hydroxide was obtained (see FIG. 1). The results of ICP (Inductively Coupled Plasma) analysis were Fe: 15 ppm and Al: 24 ppm. Further, when observed with a field emission scanning electron microscope (SEM), the particle diameter was flaky magnesium hydroxide having a diameter of about 300 to 600 nm (see FIG. 2).

(Example 2)
In order to see the reaction rate with magnesium due to the difference in the concentration of magnesium chloride, the following experiment was conducted using reagents from Kanto Chemical Co., Inc.
Magnesium chloride hexahydrate was placed in 200 ml glass beakers of 0.3 mol, 0.25 mol and 0.2 mol, respectively, and pure water was poured and dissolved to prepare a 100 ml aqueous solution. Then, 0.5 gram of magnesium metal (in the form of a cutting piece for Grignard reaction) was added to this aqueous solution.
The results of this experiment are summarized as shown in Table 1 below.

As shown in Table 1, it was confirmed that the reaction time was faster when the concentration of the aqueous solution was higher than when the concentration was lower.

(Example 3)
0.25 mol of reagent-grade magnesium sulfate heptahydrate was taken and placed in a 200 ml beaker, and pure water was poured and dissolved to make an aqueous solution. Magnesium sulfate has a low solubility, so the liquid volume was 150 ml. In the same manner as in Example 2, 0.5 gram of cut piece of magnesium was added to this aqueous solution. The liquid temperature was 27.5 ° C.

After observation for 24 hours, a slight amount of unreacted material was observed, which was the same as the experimental result of 0.2 mol of magnesium chloride in Example 2. As observed by SEM, the shape of the particles was flaky (see FIG. 3).

Example 4
0.2 mol of reagent-grade magnesium nitrate hexahydrate was taken and placed in a 100 ml graduated cylinder, and pure water was poured and dissolved to make an aqueous solution. Magnesium nitrate has a high solubility, so the liquid volume was set to 65 ml in order to approach a saturated solution. In the same manner as in Example 2, 0.5 gram of cut piece of magnesium was added to this aqueous solution. The liquid temperature was 27.5 ° C.

Although observation was made after 24 hours had passed, a slightly larger amount of unreacted material was observed as compared with the experimental result of 0.2 mol of magnesium chloride in Example 2. As observed by SEM, the shape of the particles was flaky (see FIG. 4).

(Example 5)
0.25 mol of reagent grade 1 magnesium bromide hexahydrate was taken to prepare a 100 ml aqueous solution, and 0.5 g of cut piece of magnesium was added thereto. The liquid temperature was 20 ° C. When one week passed and observed, almost all was reacting.

(Example 6)
25 g of reagent-grade magnesium perchlorate was taken and dissolved in 50 g of pure water, and 0.5 g of cut piece of magnesium was added thereto. The liquid temperature was 20 ° C. When one week passed and observed, almost all was reacting.

Next, a magnesium salt in which the hydrogen atom of the carboxyl group of the carboxylic acid was replaced with a magnesium atom, magnesium citrate and an aqueous solution of magnesium acetate were prepared and tested.
(Example 7)
Cutting pieces of magnesium (3.0 g) were dissolved in the reagent citric acid monohydrate to prepare 70 ml of an aqueous solution of magnesium citrate. 0.5 g of cut piece of magnesium was added thereto. The liquid temperature was 20 ° C. When 21 hours passed, almost all were reacted.

(Example 8)
Using a reagent-grade magnesium acetate tetrahydrate, 100 ml of a 25 wt% aqueous solution was prepared. The liquid temperature was 16 ° C. When 0.5 g of cut piece of magnesium was added to this and observed 3 days later, the surface of magnesium became white due to adhesion of magnesium hydroxide, and the aqueous solution became cloudy due to the formation of magnesium hydroxide. . As described above, it was confirmed that magnesium hydroxide was produced, but hydrogen bubbles were still generated, and it was found that the reaction was continued.

Next, a comparative example in which magnesium metal is immersed and reacted in an aqueous solution other than magnesium salt will be described.

(Comparative Example 1)
The reagent sodium chloride (purity 99.98% or more) was used to prepare 100 ml of a 22 wt% aqueous solution. The liquid temperature was 25 ° C. When 0.3 g of cut piece of magnesium was added thereto, fine bubbles began to be generated after 1 hour. When observed after one week, the color of the surface of magnesium changed slightly due to the influence of magnesium hydroxide. However, when observed after another 12 days, the magnesium cracked and became smaller, but no other significant changes were observed.

(Comparative Example 2)
Using calcium chloride dihydrate for food additives, 100 ml of a 30% strength by weight aqueous solution was prepared. The liquid temperature was 25 ° C. When 0.3 g of cut piece of magnesium was added thereto, fine bubbles were generated. After one week, the surface of most magnesium changed whitish. However, no more magnesium hydroxide was observed after 12 days.

(Comparative Example 3)
A reagent-grade aluminum (III) chloride hexahydrate was placed in a 10 g beaker, and pure water was poured into it to prepare a 50 ml aqueous solution. The liquid temperature was 20 ° C. In this aqueous solution, 0.5 g of cut piece-like magnesium metal was added. Magnesium generated and dissolved hydrogen, but no magnesium hydroxide was produced.

The magnesium hydroxide and the production method thereof of the present invention are useful as magnesium hydroxide used in electronic materials, pharmaceuticals, refractory materials, coating materials, adsorbents, and the like, and production methods thereof.

Claims

By immersing magnesium metal in an aqueous solution containing a magnesium salt as a main component, a first reaction for forming a film containing magnesium hydroxide on the surface of the magnesium metal, the film is dissolved by the aqueous solution, Magnesium hydroxide obtained by repeatedly causing a second reaction in which magnesium ions and hydroxyl ions are bonded, and as a result, precipitated in an aqueous solution.
2. Magnesium hydroxide according to claim 1, which is in the form of flakes.
By immersing magnesium metal in an aqueous solution containing a magnesium salt as a main component, a first reaction for forming a film containing magnesium hydroxide on the surface of the magnesium metal, the film is dissolved by the aqueous solution, A method for producing magnesium hydroxide, wherein a second reaction in which magnesium ions and hydroxyl ions are combined is repeatedly caused, and as a result, magnesium hydroxide precipitated in an aqueous solution is recovered.
The method for producing magnesium hydroxide according to claim 3, wherein the magnesium salt is magnesium chloride.
The method for producing magnesium hydroxide according to claim 3, wherein the magnesium salt is magnesium sulfate.
The manufacturing method of the magnesium hydroxide of Claim 3 whose said magnesium salt is magnesium nitrate.