JP3980569B2 - Magnesium oxide - Google Patents

Magnesium oxide Download PDF

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JP3980569B2
JP3980569B2 JP2004122858A JP2004122858A JP3980569B2 JP 3980569 B2 JP3980569 B2 JP 3980569B2 JP 2004122858 A JP2004122858 A JP 2004122858A JP 2004122858 A JP2004122858 A JP 2004122858A JP 3980569 B2 JP3980569 B2 JP 3980569B2
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magnesium oxide
mol
magnesium hydroxide
lead
magnesium
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JP2004244313A (en
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洋 在田
彰 吉田
高行 渡辺
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Ube Material Industries Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide magnesium oxide useful for a fertilizer, a medicine raw material, or a cosmetic raw material. <P>SOLUTION: This magnesium oxide has a Pb content of 2&times;10<SP>-7</SP>mole/mole or lower and is yielded by firing magnesium hydroxide containing lead or a lead compound at 700-1,300&deg;C in the presence of a halogen source being a halide or a halogen gas. <P>COPYRIGHT: (C)2004,JPO&amp;NCIPI

Description

本発明は、鉛または鉛化合物の含有量の少ない酸化マグネシウムに関する。   The present invention relates to magnesium oxide having a low content of lead or a lead compound.

酸化マグネシウムの製造法には、炭酸マグネシウム(マグネサイトともいう)を焼成する方法と、海水あるいは塩化マグネシウム水溶液(苦汁またはかん水)に水酸化カルシウムを加えて水酸化マグネシウムを生成させ、これをろ過、乾燥した後、焼成する方法とがある。   Magnesium oxide is produced by baking magnesium carbonate (also called magnesite), adding calcium hydroxide to seawater or magnesium chloride aqueous solution (bitter or brine) to produce magnesium hydroxide, filtering this, There is a method of baking after drying.

上記の水酸化マグネシウムを焼成して製造される酸化マグネシウムは、その焼成温度でその性質や用途が異なる。水酸化マグネシウムを1500℃以上の高温で焼成したものは硬焼(重焼、死焼ともいう)マグネシアまたはマグネシアクリンカーと呼ばれる。本酸化マグネシウムは活性がほとんどなく、高温耐火性能を有し、耐火物材料として塩基性耐火れんがや不定形耐火物の原料などに利用されている。   Magnesium oxide produced by firing the above magnesium hydroxide has different properties and uses depending on the firing temperature. What calcined magnesium hydroxide at a high temperature of 1500 ° C. or higher is called hard-fired (also called heavy-fired or dead-fired) magnesia or magnesia clinker. This magnesium oxide has almost no activity, has high-temperature fire resistance, and is used as a raw material for basic refractory bricks and amorphous refractories as a refractory material.

また、水酸化マグネシウムを450〜1300℃で焼成して得られる酸化マグネシウム(軽焼または仮焼マグネシアともいう。以下、単に酸化マグネシウムという)は、活性が比較的大きく、マグネシアセメント材料、あるいはミネラルの供給源として肥料、食品等の添加剤、制酸剤や下剤などの医薬品の原料、化粧品原料などに利用されている。
この酸化マグネシウムは肥料、食品等の添加剤、医薬品原料として、人体に直接あるいは間接的に摂取され、あるいは化粧品原料として人体に接触するものであるため、重金属の混入量がより少ないものが望まれている。
In addition, magnesium oxide obtained by firing magnesium hydroxide at 450 to 1300 ° C. (also referred to as light calcined or calcined magnesia, hereinafter simply referred to as magnesium oxide) has a relatively large activity, and is a magnesia cement material or mineral. It is used as a supply source for fertilizers, food additives, pharmaceutical raw materials such as antacids and laxatives, and cosmetic raw materials.
This magnesium oxide is taken directly or indirectly by the human body as an additive for fertilizers, foods, etc., as a raw material for pharmaceuticals, or comes into contact with the human body as a cosmetic raw material. ing.

一般的に海水中には、重金属はほとんど存在しない(例えば、鉛については10-3〜10-6ppm程度)が、水酸化カルシウムの原料である石灰石(もしくは石灰岩)には、鉛または鉛化合物が鉛としておよそ0.2〜0.7ppm程度存在している。なお、鉛は、例えば酵素阻害剤として人体に有害な作用を示すことが知られている金属である。
また、海水と水酸化カルシウムから生成される水酸化マグネシウムは、重金属の吸着剤としても知られている(例えば、特許文献1には水酸化マグネシウムを用いた鉱山排水の処理方法が提案されている)。
Generally, there is almost no heavy metal in seawater (for example, about 10 -3 to 10 -6 ppm for lead), but limestone (or limestone), which is a raw material for calcium hydroxide, contains lead or lead compounds. About 0.2 to 0.7 ppm as lead. Lead is a metal that is known to have a harmful effect on the human body as an enzyme inhibitor, for example.
Magnesium hydroxide produced from seawater and calcium hydroxide is also known as a heavy metal adsorbent (for example, Patent Document 1 proposes a method for treating mine drainage using magnesium hydroxide. ).

上記の理由により、海水と水酸化カルシウムから水酸化マグネシウムを生成させた場合、石灰石に含まれている鉛または鉛化合物が水酸化マグネシウムに吸着され、水酸化マグネシウムのPb含有量(鉛含有量)が1.5ppm以上になることがある。
なお、水酸化マグネシウムに吸着された鉛も水酸化マグネシウムの乾燥、焼成に伴って、水酸化鉛あるいは酸化鉛等の鉛化合物となる。
上述した酸化マグネシウムは水酸化マグネシウムを1300℃以下で焼成して製造されるので、沸点が1300℃以上の鉛化合物が一旦水酸化マグネシウムに混入すると、この鉛化合物を除去することが難しいという問題がある。
For the above reasons, when magnesium hydroxide is produced from seawater and calcium hydroxide, lead or lead compounds contained in limestone are adsorbed by magnesium hydroxide, and the Pb content of magnesium hydroxide (lead content) May be 1.5 ppm or more.
Note that lead adsorbed on magnesium hydroxide also becomes a lead compound such as lead hydroxide or lead oxide as magnesium hydroxide is dried and fired.
Since the magnesium oxide described above is manufactured by firing magnesium hydroxide at 1300 ° C. or lower, once a lead compound having a boiling point of 1300 ° C. or higher is mixed into the magnesium hydroxide, it is difficult to remove the lead compound. is there.

水酸化マグネシウムに混入する鉛または鉛化合物の量を低減させる方法として、水酸化マグネシウムに吸着された鉛または鉛化合物を洗浄除去することが考えられるが、水酸化マグネシウムは上述したように鉛または鉛化合物を吸着しやすく洗い流すことは難しい。
また、水酸化マグネシウムに吸着される鉛または鉛化合物の量を低減させる方法としては、Pb含有量の少ない石灰石から生成された水酸化カルシウムを用いて、海水から水酸化マグネシウムを生成させる方法が考えられるが、石灰石の産出量や輸送コストなどから量産化は難しい。
特開昭60−22990号公報
As a method of reducing the amount of lead or lead compounds mixed in magnesium hydroxide, it is conceivable to wash away lead or lead compounds adsorbed on magnesium hydroxide. As described above, magnesium hydroxide is lead or lead. It is difficult to wash off the compound easily.
As a method of reducing the amount of lead or lead compound adsorbed on magnesium hydroxide, a method of generating magnesium hydroxide from seawater using calcium hydroxide generated from limestone having a low Pb content is considered. However, mass production is difficult due to limestone production and transportation costs.
JP 60-22990 A

本発明の目的は、肥料用、医薬品原料用又は化粧品原料用として有用なPb含有量の少ない酸化マグネシウムを提供することにある。   An object of the present invention is to provide magnesium oxide having a low Pb content that is useful as a fertilizer, a pharmaceutical raw material, or a cosmetic raw material.

本発明者は、鉛または鉛化合物を含有する水酸化マグネシウムを、ハロゲン化物もしくはハロゲンガスであるハロゲン源の存在下に焼成すると、酸化マグネシウム1モル中のPb含有量が2×10-7モル以下(好ましくは1×10-7モル以下、さらに好ましくは0.5×10-7モル以下)の酸化マグネシウムを得ることができることを見出した。 When the present inventors calcinate magnesium hydroxide containing lead or a lead compound in the presence of a halogen source which is a halide or a halogen gas, the Pb content in 1 mol of magnesium oxide is 2 × 10 −7 mol or less. It has been found that magnesium oxide can be obtained (preferably 1 × 10 −7 mol or less, more preferably 0.5 × 10 −7 mol or less).

従って、本発明は、Pb含有量が2×10-7モル/モル以下(質量基準に換算して1.0質量ppm以下に相当する)で、かつ1.9×10 -8 モル/モル以上である酸化マグネシウムにある。 Therefore, the present invention has a Pb content of 2 × 10 −7 mol / mol or less (corresponding to 1.0 ppm by mass or less in terms of mass) and 1.9 × 10 −8 mol / mol or more. in the magnesium oxide is.

本発明はまた、上記の酸化マグネシウムからなる肥料、医薬品原料又は化粧品原料にもある。 The present invention also resides in a fertilizer, a pharmaceutical raw material or a cosmetic raw material comprising the above magnesium oxide .

本発明の酸化マグネシウムの好ましい態様は、次の通りである。
(1)鉛または鉛化合物を含有する水酸化マグネシウムを、ハロゲン化物もしくはハロゲンガスであるハロゲン源の存在下に焼成して得たものである。
(2)Pb含有量が1×10-7モル/モル以下(質量基準に換算して0.5質量ppm以下に相当する)である。
(3)Pb含有量が0.5×10-7モル/モル以下(質量基準に換算して0.26質量ppm以下に相当する)である。
Preferred embodiments of the magnesium oxide of the present invention are as follows.
(1) It is obtained by firing magnesium hydroxide containing lead or a lead compound in the presence of a halogen source which is a halide or a halogen gas.
(2) The Pb content is 1 × 10 −7 mol / mol or less (corresponding to 0.5 mass ppm or less in terms of mass).
(3) Pb content is 0.5 × 10 −7 mol / mol or less (corresponding to 0.26 mass ppm or less in terms of mass standard).

本発明の酸化マグネシウムは、Pb含有量が少ないので肥料用、医薬品原料用又は化粧品原料用として有用である。また、本発明の酸化マグネシウムは、鉛または鉛化合物を含有する水酸化マグネシウムをハロゲン源の存在下にて焼成することによって製造することができる。従って、本発明の酸化マグネシウムは工業的に容易に製造することができる。   Since the magnesium oxide of the present invention has a low Pb content, it is useful for fertilizers, pharmaceutical raw materials, or cosmetic raw materials. The magnesium oxide of the present invention can be produced by firing magnesium hydroxide containing lead or a lead compound in the presence of a halogen source. Therefore, the magnesium oxide of the present invention can be easily produced industrially.

海水に水酸化カルシウムを加えて水酸化マグネシウムを生成させ、これをろ過、乾燥して、得られた水酸化マグネシウムには海水の主成分である塩化ナトリウムなどのハロゲン化物が存在する。
一般的に、ハロゲン化物が存在する水酸化マグネシウムを焼成すると、焼成炉が劣化しやすくなり、さらには得られた酸化マグネシウムはその純度が低くなったり、塩分が多くなりやすくなる。従って、通常水酸化マグネシウムを焼成して酸化マグネシウムを製造する場合、水酸化マグネシウムは重金属を含まない水で洗浄し、ハロゲン化物の存在量を低減した後焼成する。
Calcium hydroxide is added to seawater to produce magnesium hydroxide, which is filtered and dried. The resulting magnesium hydroxide contains halides such as sodium chloride, which is the main component of seawater.
In general, when magnesium hydroxide containing a halide is calcined, the calcining furnace tends to deteriorate, and the obtained magnesium oxide tends to have a low purity or a high salt content. Accordingly, when magnesium oxide is usually produced by firing magnesium hydroxide, the magnesium hydroxide is washed with water that does not contain heavy metals and fired after reducing the amount of halide present.

しかしながら、本発明者らは、水酸化マグネシウムを、ハロゲン化物もしくはハロゲンガスであるハロゲン源の存在下にて焼成することにより、酸化マグネシウムのPb含有量が低減することを見出した。酸化マグネシウムのPb含有量が低減する明確な理由は不明であるが、鉛化合物が沸点の低いハロゲン化鉛に変化して蒸発しやすくなる。あるいは、水酸化マグネシウムにハロゲン化物を存在させることにより鉛化合物自体の沸点が下がることなどが推定される。   However, the present inventors have found that the Pb content of magnesium oxide is reduced by firing magnesium hydroxide in the presence of a halide or a halogen source that is a halogen gas. The clear reason why the Pb content of magnesium oxide is reduced is unclear, but the lead compound is changed to lead halide having a low boiling point and easily evaporates. Alternatively, it is presumed that the boiling point of the lead compound itself is lowered by the presence of a halide in magnesium hydroxide.

本発明において、ハロゲン源は、ハロゲン化物である塩化物、臭化物が好ましく、その例としては、塩化ナトリウム、塩化マグネシウム、臭化ナトリウム、臭化マグネシウムなどが挙げられる。ハロゲン化物は有機物であっても良い。
ハロゲン源は、ハロゲン化物の気体あるいはハロゲンガスであっても良く、ハロゲン化物の気体の例としては、塩化水素ガス、臭化水素ガスなどが挙げられる。また、ハロゲンガスの例としては、塩素ガス、臭素ガスが挙げられる。
In the present invention, the halogen source is preferably a chloride or bromide which is a halide. Examples thereof include sodium chloride, magnesium chloride, sodium bromide and magnesium bromide. The halide may be organic.
The halogen source may be a halide gas or a halogen gas. Examples of the halide gas include hydrogen chloride gas and hydrogen bromide gas. Examples of the halogen gas include chlorine gas and bromine gas.

ハロゲン源の存在量は、ハロゲン源としてハロゲン化物を用いた場合には、水酸化マグネシウム1モルに対して、2×10-4〜4×10-2モルの範囲内の量で存在させることが好ましく、より好ましくは、6×10-4〜2×10-2モルの範囲内の量である。ハロゲン源の量が少なすぎると、鉛または鉛化合物の除去が不十分になり、またハロゲン源の量が多すぎると、上述したように、焼成炉が劣化しやすくなり、さらには得られた酸化マグネシウムの純度が低くなったり、塩分が多くなる。 When a halide is used as the halogen source, the halogen source may be present in an amount in the range of 2 × 10 −4 to 4 × 10 −2 mol with respect to 1 mol of magnesium hydroxide. The amount is preferably in the range of 6 × 10 −4 to 2 × 10 −2 mol. If the amount of the halogen source is too small, the removal of lead or lead compounds becomes insufficient, and if the amount of the halogen source is too large, the firing furnace tends to deteriorate as described above, and further the obtained oxidation Magnesium purity decreases and salt content increases.

本発明において、水酸化マグネシウムにハロゲン源を存在させる方法は、ハロゲン源としてハロゲン化物を用いた場合には、水酸化マグネシウムにハロゲン化物の固体を混合しても、互いに相対する量のハロゲン化物を含有する水酸化マグネシウムを混合しても、あるいは水酸化マグネシウムにハロゲン化物を含む溶液を混合しても良い。ハロゲン化物を含む溶液として、海水あるいは水酸化マグネシウムを生成させ、ろ過したときに発生するろ液を使用しても良い。   In the present invention, when a halide is used as the halogen source in the method of causing the halogen source to be present in the magnesium hydroxide, even if a halide solid is mixed with the magnesium hydroxide, the halides in an amount relative to each other are mixed. You may mix the magnesium hydroxide to contain, or you may mix the solution containing a halide in magnesium hydroxide. As a solution containing a halide, seawater or magnesium hydroxide may be produced and a filtrate generated when filtered may be used.

また、ハロゲン源としてハロゲン化物の気体あるいはハロゲンガスを用いる場合には、焼成炉中にハロゲン化物の気体あるいはハロゲンガスを循環させても、加熱することによりハロゲン化物の気体あるいはハロゲンガスを発生する化合物の液体あるいは固体を焼成炉中に供給して、水酸化マグネシウムの焼成中に気化させても良い。加熱することによりハロゲン化物の気体を発生する化合物として、臭化エチレンなどを使用することができる。   When a halide gas or halogen gas is used as the halogen source, a halide gas or halogen gas is generated by heating even if the halide gas or halogen gas is circulated in the firing furnace. The liquid or solid may be supplied into a firing furnace and vaporized during the firing of magnesium hydroxide. Ethylene bromide or the like can be used as a compound that generates a halide gas by heating.

(水酸化マグネシウムケ−クの製造)
海水1m3 に対し、水酸化カルシウムを3.5kg加えて、水酸化マグネシウムを生成させた後、これを水で洗浄した後、減圧ろ過して、含水率40%の水酸化マグネシウムケークを作成した。得られた水酸化マグネシウムケークに含まれているPb含有量を偏光ゼーマン型原子吸光分析法により定量したところ、Pb含有量は水酸化マグネシウム1モルに対して、2.8×10-7モルであった。なお、得られた水酸化マグネシウムケークに含まれているハロゲン化物の量は水酸化マグネシウム1モルに対して1.5×10-4モル以下であった。
(Manufacture of magnesium hydroxide cake)
After adding 3.5 kg of calcium hydroxide to 1 m 3 of seawater to form magnesium hydroxide, this was washed with water and then filtered under reduced pressure to prepare a magnesium hydroxide cake having a water content of 40%. . When the Pb content contained in the obtained magnesium hydroxide cake was quantified by polarized Zeeman atomic absorption spectrometry, the Pb content was 2.8 × 10 −7 mol per 1 mol of magnesium hydroxide. there were. The amount of halide contained in the obtained magnesium hydroxide cake was 1.5 × 10 −4 mol or less per 1 mol of magnesium hydroxide.

(実施例1)
上記の水酸化マグネシウムケークに粉末の塩化ナトリウムを、水酸化マグネシウム(固形分)1モルに対して、塩化ナトリウムが3.3×10-3モルになるように加えて、混合した後120℃で12時間乾燥して、次いで900℃で1時間焼成して、酸化マグネシウムを製造した。
Example 1
To the above magnesium hydroxide cake, powdered sodium chloride is added so that the sodium chloride is 3.3 × 10 −3 mol per 1 mol of magnesium hydroxide (solid content), and mixed at 120 ° C. It was dried for 12 hours and then calcined at 900 ° C. for 1 hour to produce magnesium oxide.

(実施例2)
実施例1において、塩化ナトリウムを水酸化マグネシウム1モルに対して、1.1×10-2モルになるように加えた以外は、実施例1と同一の条件で、酸化マグネシウムを製造した。
(Example 2)
In Example 1, magnesium oxide was produced under the same conditions as in Example 1 except that sodium chloride was added in an amount of 1.1 × 10 −2 mol per 1 mol of magnesium hydroxide.

(比較例1)
実施例1において、塩化ナトリウムを加えない以外は実施例1と同一の条件で、酸化マグネシウムを製造した。
(Comparative Example 1)
In Example 1, magnesium oxide was produced under the same conditions as in Example 1 except that sodium chloride was not added.

(比較例2)
実施例1において、焼成温度を550℃とした以外は実施例1と同一の条件で、酸化マグネシウムを製造した。
(Comparative Example 2)
In Example 1, magnesium oxide was produced under the same conditions as in Example 1 except that the firing temperature was 550 ° C.

(評価)
上記のようにして得た酸化マグネシウムのPb含有量を、偏光ゼーマン型原子吸光分析法により定量した。その結果を表1に示す。
(Evaluation)
The Pb content of magnesium oxide obtained as described above was quantified by polarized Zeeman atomic absorption spectrometry. The results are shown in Table 1.

表1
─────────────────────────────
酸化マグネシウム1モル
に対するPb含有量(モル)
─────────────────────────────
実施例1 7.4×10-8
実施例2 1.9×10-8
─────────────────────────────
比較例1 2.8×10-7
比較例2 2.8×10-7
─────────────────────────────
Table 1
─────────────────────────────
1 mole of magnesium oxide
Pb content in moles
─────────────────────────────
Example 1 7.4 × 10 −8
Example 2 1.9 × 10 −8
─────────────────────────────
Comparative Example 1 2.8 × 10 −7
Comparative Example 2 2.8 × 10 −7
─────────────────────────────

Claims (7)

Pb含有量が2×10-7モル/モル以下で、かつ1.9×10 -8 モル/モル以上である酸化マグネシウム。 Magnesium oxide having a Pb content of 2 × 10 −7 mol / mol or less and 1.9 × 10 −8 mol / mol or more . 鉛または鉛化合物を含有する水酸化マグネシウムを、ハロゲン化物もしくはハロゲンガスであるハロゲン源の存在下に700〜1300℃の温度で焼成して得たものである請求項1に記載の酸化マグネシウム。   Magnesium oxide according to claim 1, which is obtained by firing magnesium hydroxide containing lead or a lead compound at a temperature of 700 to 1300 ° C in the presence of a halogen source which is a halide or a halogen gas. Pb含有量が1×10-7モル/モル以下である請求項1もしくは2に記載の酸化マグネシウム。 The magnesium oxide according to claim 1 or 2, wherein the Pb content is 1 x 10 -7 mol / mol or less. Pb含有量が0.5×10-7モル/モル以下である請求項3に記載の酸化マグネシウム。 The magnesium oxide according to claim 3, wherein the Pb content is 0.5 × 10 −7 mol / mol or less. 請求項1乃至4のうちのいずれかの項に記載の酸化マグネシウムからなる肥料。A fertilizer comprising the magnesium oxide according to any one of claims 1 to 4. 請求項1乃至4のうちのいずれかの項に記載の酸化マグネシウムからなる医薬品原料。A pharmaceutical raw material comprising magnesium oxide according to any one of claims 1 to 4. 請求項1乃至4のうちのいずれかの項に記載の酸化マグネシウムからなる化粧品原料。Cosmetic raw material consisting of magnesium oxide according to any one of claims 1 to 4.
JP2004122858A 2004-04-19 2004-04-19 Magnesium oxide Expired - Fee Related JP3980569B2 (en)

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