JP2001039713A - Production of zinc oxide - Google Patents
Production of zinc oxideInfo
- Publication number
- JP2001039713A JP2001039713A JP11210145A JP21014599A JP2001039713A JP 2001039713 A JP2001039713 A JP 2001039713A JP 11210145 A JP11210145 A JP 11210145A JP 21014599 A JP21014599 A JP 21014599A JP 2001039713 A JP2001039713 A JP 2001039713A
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- Japan
- Prior art keywords
- zinc
- purity
- precipitate
- zinc oxide
- acid
- Prior art date
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高純度の酸化亜鉛
の製造方法、更に詳細には光増幅器用高純度酸化物原料
の製造方法に関する。The present invention relates to a method for producing high-purity zinc oxide, and more particularly to a method for producing a high-purity oxide material for an optical amplifier.
【０００２】[0002]
【従来の技術】酸化亜鉛（ＺｎＯ）は、光増幅媒体と、
これを用いた光増幅器およびレーザ装置のもとになる二
酸化テルルを主成分とするテルライトガラスまたはテル
ライトガラスファイバの構成原料の一つである。2. Description of the Related Art Zinc oxide (ZnO) is composed of an optical amplifying medium,
It is one of the constituent materials of tellurite glass or tellurite glass fiber containing tellurium dioxide as a main component, which is the basis of optical amplifiers and laser devices using this.
【０００３】従来の酸化亜鉛の製造方法については、亜
鉛酸の水溶液に二酸化炭素を飽和した炭酸水素ナトリウ
ム溶液の作用で得る方法、具体的には、亜鉛塩の硫酸亜
鉛の水溶液に炭酸水素カリウム溶液を加えて炭酸亜鉛を
作製後、高温で焼成し製造する。A conventional method of producing zinc oxide is a method of obtaining an aqueous solution of zinc acid by the action of a sodium hydrogen carbonate solution saturated with carbon dioxide, specifically, a method of adding an aqueous solution of zinc sulfate of zinc salt to a solution of potassium hydrogen carbonate. Is added to produce zinc carbonate, and then calcined at a high temperature to produce.
【０００４】すなわち、さらに具体的には、従来法で
は、硫酸亜鉛のような亜鉛塩の水溶液、亜鉛酸の水溶液
を出発物質とし、該水溶液に炭酸ナトリウム、あるい
は、炭酸水素ナトリウムの溶液を加え、各々、塩基性の
炭酸亜鉛、中性の炭酸亜鉛を作製後、高温で焼成し、酸
化亜鉛を得るものである。[0004] More specifically, in the conventional method, an aqueous solution of a zinc salt such as zinc sulfate or an aqueous solution of zinc acid is used as a starting material, and a solution of sodium carbonate or sodium hydrogen carbonate is added to the aqueous solution. After preparing basic zinc carbonate and neutral zinc carbonate, they are fired at a high temperature to obtain zinc oxide.
【０００５】従来の酸化亜鉛の製造方法については、出
発物質として亜鉛塩あるいは亜鉛酸の水溶液を使用して
いる。亜鉛塩あるいは亜鉛酸の水溶液は、高純度の亜鉛
水溶液を使用していないので、製造した酸化亜鉛につい
ても高純度のものが得られていない点が欠点である。さ
らに、従来法においては、使用した硫酸亜鉛の硫酸の痕
跡が製造した酸化亜鉛中に不純物として残り、これを除
くために、８００℃以上で加熱し、硫酸の痕跡を除いた
酸化亜鉛としなければならない煩雑さがある。In the conventional method for producing zinc oxide, an aqueous solution of zinc salt or zinc acid is used as a starting material. Since an aqueous solution of zinc salt or zinc acid does not use a high-purity aqueous zinc solution, a disadvantage is that no high-purity zinc oxide is obtained from the produced zinc oxide. Furthermore, in the conventional method, traces of sulfuric acid of the used zinc sulfate remain as impurities in the produced zinc oxide, and in order to remove this, it is necessary to heat at 800 ° C. or more to form zinc oxide from which traces of sulfuric acid have been removed. There is some complexity.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、出発
物質にＦｅ，Ｃｕ，Ｎｉなどの遷移金属の不純物を除去
した高純度の金属亜鉛を使用することにより、亜鉛塩あ
るいは亜鉛酸などの不純物の多い水溶液を出発物質とす
る純度の低い酸化亜鉛の製造の欠点を解決した高純度の
酸化亜鉛を製造する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to use a high-purity metallic zinc from which impurities of transition metals such as Fe, Cu, and Ni have been removed as a starting material, so that a zinc salt or a zinc acid or the like can be obtained. It is an object of the present invention to provide a method for producing high-purity zinc oxide which has solved the disadvantages of producing low-purity zinc oxide using an aqueous solution containing many impurities as a starting material.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決するた
め、本発明による酸化亜鉛の製造方法は、高純度亜鉛を
出発物質として使用し、前記高純度亜鉛を酸溶液中で溶
解し、溶解後の亜鉛溶液に炭酸ナトリウムあるいは炭酸
水素ナトリウムを加え、炭酸亜鉛の沈殿物を作製し、該
沈殿物を脱水・乾燥し、焼成することを特徴とする。In order to solve the above-mentioned problems, a method for producing zinc oxide according to the present invention uses high-purity zinc as a starting material, dissolves the high-purity zinc in an acid solution, Sodium carbonate or sodium bicarbonate is added to the zinc solution to produce a zinc carbonate precipitate, and the precipitate is dehydrated, dried and calcined.
【０００８】すなわち、いかなる形状の高純度金属亜鉛
についても高純度金属亜鉛を塩酸、硝酸、硫酸などの酸
溶液内で溶解させた後、溶解後の水溶液に炭酸ナトリウ
ムあるいは炭酸水素ナトリウムを添加し、炭酸亜鉛の沈
殿物を作製し、該沈殿物を脱水・乾燥し、炭酸亜鉛と
し、これをさらに３００℃以上で焼成し、高純度の酸化
亜鉛とすることを特徴とする。That is, high-purity metallic zinc of any shape is dissolved in an acid solution such as hydrochloric acid, nitric acid or sulfuric acid, and then sodium carbonate or sodium hydrogen carbonate is added to the dissolved aqueous solution. A precipitate of zinc carbonate is prepared, and the precipitate is dehydrated and dried to obtain zinc carbonate, which is further calcined at 300 ° C. or higher to obtain high-purity zinc oxide.
【０００９】本発明は、従来技術の亜鉛酸あるいは亜鉛
塩の水溶液に炭酸ナトリウムもしくは炭酸水素ナトリウ
ム溶液を加え、塩基性あるいは中性の炭酸亜鉛から酸化
亜鉛を製造する方法などの問題点を解決するために、Ｆ
ｅ，Ｎｉ，Ｃｕなどの遷移金属不純物の少ない純度が９
９．９９９％以上の高純度の金属亜鉛について、粉末状
に限らず、ショット状、インゴット状のあらゆる形状の
金属亜鉛を出発物質に使用し、遷移金属不純物の少ない
酸化亜鉛、特に、高純度の酸化亜鉛を製造するものであ
る。The present invention solves the problems of the prior art method of adding zinc carbonate or sodium hydrogen carbonate solution to an aqueous solution of zinc acid or zinc salt to produce zinc oxide from basic or neutral zinc carbonate. For F
e, purity of transition metal impurities such as Ni, Cu, etc. is 9
Regarding high-purity metallic zinc of 9.999% or more, not only powdery metal but also shot-shaped and ingot-shaped metallic zinc is used as a starting material, and zinc oxide containing few transition metal impurities, particularly high-purity metallic zinc. This is to produce zinc oxide.
【００１０】[0010]
【発明の実施の形態】以下、本発明を具体的に説明す
る。本発明において出発物質として使用する金属亜鉛の
内、用途上、高純度の亜鉛が有用である。高純度の程度
は、９９．９９９％以上、すなわち、５Ｎ以上が好まし
い。また、金属亜鉛の形状には制限されるものではな
い。すなわち、粉末状、インゴット状、ショット状のど
の形状でも良い。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. Of the metal zinc used as a starting material in the present invention, high-purity zinc is useful for applications. The degree of high purity is preferably 99.999% or more, that is, 5N or more. Further, the shape of the metallic zinc is not limited. That is, any shape such as powder, ingot, and shot may be used.
【００１１】本発明において、上述のような高純度亜鉛
を酸によって溶解する。酸による溶解は特殊な条件を必
要とせず、該金属亜鉛を塩酸、硝酸、硫酸などの酸溶液
中に溶解できる条件であればよい。また、該金属亜鉛を
溶解した溶液の加熱溶解については、特殊な条件を必要
としない。前記酸としては前述のように塩酸、硝酸、硫
酸などを使用することができ、その純度は、高純度酸化
亜鉛を製造するためには９９．９９％以上が好ましい。In the present invention, high-purity zinc as described above is dissolved with an acid. Dissolution with an acid does not require special conditions, and any condition may be used as long as the metal zinc can be dissolved in an acid solution such as hydrochloric acid, nitric acid, and sulfuric acid. In addition, no special conditions are required for heating and dissolving the solution in which the zinc metal is dissolved. As the acid, hydrochloric acid, nitric acid, sulfuric acid and the like can be used as described above, and its purity is preferably 99.99% or more in order to produce high-purity zinc oxide.
【００１２】次に、この亜鉛溶液に炭酸ナトリウムある
いは炭酸水素ナトリウムを添加して炭酸亜鉛を沈殿さ
せ、洗浄、乾燥する。このような炭酸ナトリウムあるい
は炭酸水素ナトリウムも高純度酸化亜鉛を製造するため
には、純度が９９．９９％以上であるのが好ましい。Next, sodium carbonate or sodium hydrogen carbonate is added to the zinc solution to precipitate zinc carbonate, which is washed and dried. In order to produce high-purity zinc oxide, the purity of such sodium carbonate or sodium hydrogencarbonate is preferably 99.99% or more.
【００１３】炭酸亜鉛の水和物の洗浄操作も超純水を加
え、攪拌しながら洗浄を行えば良く、また、脱水も常用
の方法でよく、操作上、吸引ろ過又は遠心分離器が好適
である。最後に、乾燥および焼成についても常用の方法
でよく、操作上、真空乾燥又は酸素雰囲気での乾燥およ
び酸素雰囲気における電気炉における焼成が好適であ
る。焼成温度は３００℃以上であるのがよい。３００℃
未満であると、ＣＯ2が充分放散しない恐れがあるから
である。基本的に焼成温度の上限は限定されるものでは
ないが、あまり高温であると、エネルギーの損失が多
く、効率的ではなくなる。特に好ましくは４００〜６０
０℃である。[0013] The washing operation of the hydrate of zinc carbonate may be carried out by adding ultrapure water and washing with stirring, and the dehydration may be carried out by a conventional method. For the operation, a suction filtration or a centrifugal separator is preferable. is there. Lastly, drying and baking may be performed by a conventional method, and in operation, vacuum drying or drying in an oxygen atmosphere and baking in an electric furnace in an oxygen atmosphere are preferable. The firing temperature is preferably 300 ° C. or higher. 300 ℃
If it is less than this, there is a possibility that CO 2 may not be sufficiently emitted. Basically, the upper limit of the firing temperature is not limited. However, if the temperature is too high, energy loss is large and the efficiency is not high. Particularly preferably, 400 to 60
0 ° C.
【００１４】以上、具体的に説明したように、本発明方
法において、特に、高純度の酸化亜鉛を製造する方法の
場合には、従来技術の亜鉛塩あるいは亜鉛酸を出発物質
とし、酸に溶解し、炭酸ナトリウムあるいは炭酸水素ナ
トリウムを加え、炭酸亜鉛とし、これを高温で焼成して
酸化亜鉛とする方法とは、高純度金属亜鉛を出発物質と
し、高純度の酸に溶解する点、高純度の炭酸ナトリウム
あるいは炭酸水素ナトリウムを添加する点で異なる。As specifically described above, in the method of the present invention, particularly in the case of a method for producing high-purity zinc oxide, a zinc salt or zinc acid of the prior art is used as a starting material and dissolved in an acid. Then, sodium carbonate or sodium bicarbonate is added to form zinc carbonate, which is calcined at a high temperature to form zinc oxide. This method uses high-purity metallic zinc as a starting material and dissolves in high-purity acid. In that sodium carbonate or sodium hydrogen carbonate is added.
【００１５】[0015]
【実施例】以下、本発明を実施例により更に具体的に説
明するが、本発明はこれら実施例に限定されない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
【００１６】[0016]
【実施例１】純度：７Ｎ（９９．９９９９９％）の高純
度金属亜鉛を出発物質とする高純度酸化亜鉛の製造方法
について、図１に示す工程図によって説明する。形状が
ショット状の高純度亜鉛５０ｇを秤量し、１０００ｍｌ
のビーカに入れ、電子工業用の高純度の濃塩酸（塩化水
素含有量３６％）３００ｍｌに溶解する。溶解に要する
時間は３０分程度で、溶解後の水溶液は無色であり、無
色の溶液を孔径０．２μのメンブランフィルタを通し、
未溶解の亜鉛がある場合にはメンブランフィルタで未溶
解亜鉛を除去する。該水溶液に、純度が９９．９９％の
高純度炭酸ナトリウム（Ｎａ2ＣＯ3）１００ｇを少量づ
つ添加し、ＺｎＣＯ3沈殿物を得る。該沈殿物は、遠心
分離器で沈殿物と水溶液を分離する。分離後の沈殿物
は、再度、１０００ｍｌのビーカに入れ、超純水を８０
０ｍｌ添加し、洗浄を行う。洗浄操作は、３回繰り返
す。洗浄後のＺｎＣＯ3沈殿物は、遠心分離器で分離
し、分離後のＺｎＣＯ3沈殿物は、真空乾燥器で１００
℃で２４時間乾燥し、脱水を行い、高純度の炭酸亜鉛
（ＺｎＣＯ3）を製造後、清浄な酸素雰囲気の電気炉内
で４００℃において焼成し、酸化亜鉛とする。反応式
は、式１、式２、式３の反応で高純度酸化亜鉛が製造で
きる。Example 1 A method for producing high-purity zinc oxide starting from high-purity metallic zinc having a purity of 7N (99.999999%) will be described with reference to the process chart shown in FIG. Weigh 50g of shot-shaped high-purity zinc, 1000ml
And dissolved in 300 ml of high-purity concentrated hydrochloric acid for electronic industry (hydrogen chloride content: 36%). The time required for dissolution is about 30 minutes, the aqueous solution after dissolution is colorless, and the colorless solution is passed through a membrane filter having a pore size of 0.2 μ,
If there is undissolved zinc, remove the undissolved zinc using a membrane filter. 100 g of high purity sodium carbonate (Na 2 CO 3 ) having a purity of 99.99% is added little by little to the aqueous solution to obtain a ZnCO 3 precipitate. The precipitate is separated from the aqueous solution by a centrifuge. The sediment after separation is again put into a 1000 ml beaker,
Add 0 ml and wash. The washing operation is repeated three times. ZnCO 3 precipitate after washing, separated by centrifuge, ZnCO 3 precipitate after separation in a vacuum dryer 100
After drying at 24 ° C. for 24 hours to perform dehydration, high-purity zinc carbonate (ZnCO 3 ) is manufactured, and then calcined at 400 ° C. in an electric furnace in a clean oxygen atmosphere to obtain zinc oxide. With regard to the reaction formula, high-purity zinc oxide can be produced by the reactions of Formulas 1, 2, and 3.
【００１７】[0017]
【式１】Ｚｎ＋４ＨＣｌ → ＺｎＣｌ4 2-＋２Ｈ2 [Formula 1] Zn + 4HCl → ZnCl 4 2- + 2H 2
【００１８】[0018]
【式２】ＺｎＣｌ4 2-＋Ｎａ2ＣＯ3 → ＺｎＣＯ3＋２
ＮａＣｌ＋Ｃｌ2 [Formula 2] ZnCl 4 2- + Na 2 CO 3 → ZnCO 3 +2
NaCl + Cl 2
【００１９】[0019]
【式３】ＺｎＣＯ3 → ＺｎＯ＋ＣＯ2 [Formula 3] ZnCO 3 → ZnO + CO 2
【００２０】図２は、真空乾燥後の炭酸亜鉛のＴＧ（熱
重量分析）−ＤＴＡ（示差熱分析）曲線である。なお、
図２において、横軸は温度（℃）、左縦軸はＴＧにおけ
る重量減少率（％）、右縦軸はＤＴＡにおける熱容量
（μＶ）を意昧する。図２から、１５０℃〜３００℃付
近に炭酸亜鉛から二酸化炭素が放出され、酸化亜鉛（Ｚ
ｎＯ）となる吸熱ピークが観察された。すなわち、Ｘ線
回折（ＸＲＤ）及び熱分析（ＴＧ−ＤＴＡ）での解析結
果より、作製した物質は、無水の炭酸亜鉛（ＺｎＣ
Ｏ3）である。FIG. 2 is a TG (thermogravimetric analysis) -DTA (differential thermal analysis) curve of zinc carbonate after vacuum drying. In addition,
In FIG. 2, the horizontal axis represents temperature (° C.), the left vertical axis represents weight loss rate (%) in TG, and the right vertical axis represents heat capacity (μV) in DTA. 2, carbon dioxide is released from zinc carbonate around 150 ° C. to 300 ° C., and zinc oxide (Z
nO) was observed. That is, from the results of analysis by X-ray diffraction (XRD) and thermal analysis (TG-DTA), the produced substance was found to be anhydrous zinc carbonate (ZnC
O 3 ).
【００２１】また、作製した無水の炭酸亜鉛（ＺｎＣＯ
3）のＦｅ，Ｎｉ，Ｃｕの放射化分析を行い、Ｆｅ，Ｎ
ｉ，Ｃｕについて各元素とも不純物濃度は１ｐｐｂ以下
の分析結果が得られ、従来、製造されていた酸化亜鉛に
ついてのＦｅ，Ｎｉ，Ｃｕの不純物濃度の定量値よりも
３桁以上の高純度の無水の酸化亜鉛が作製できた。本実
施例における高純度の無水の酸化亜鉛の収率は９０％で
ある。The prepared anhydrous zinc carbonate (ZnCO 3)
3 ) Activation analysis of Fe, Ni, and Cu
As for i and Cu, the analysis result of each element has an impurity concentration of 1 ppb or less, which is higher than that of the conventionally manufactured zinc oxide by three orders of magnitude or more than the quantitative value of the impurity concentration of Fe, Ni and Cu. Was produced. The yield of high-purity anhydrous zinc oxide in this example is 90%.
【００２２】本実施例で作製した酸化亜鉛（ＺｎＯ）を
副成分とし、これに、主成分の二酸化テルル（Ｔｅ
Ｏ2）と他の副成分のＮａ2ＯとＢｉ2Ｏ3を添加したテル
ライトガラスファイバ（コアガラス組成：ＴｅＯ2−Ｚ
ｎＯ−Ｎａ2Ｏ−Ｂｉ2Ｏ3、クラッドガラス組成：Ｔｅ
Ｏ2−ＺｎＯ−Ｎａ2Ｏ）のシングルモードファイバを作
製したところ、波長が１．３μにおいて損失値１０ｄＢ
／ｋｍのファイバが作製できた。これは、従来品のテル
ライトガラスファイバが、市販のＺｎＯ原料を使用した
ために１．３μにおける損失値が１０００ｄＢ／ｋｍと
高い値を示したのに対し、大幅な損失値の低減が達成で
きた。The zinc oxide (ZnO) produced in this embodiment was used as a sub-component, and the main component was tellurium dioxide (Te).
Tellurite glass fiber (core glass composition: TeO 2 -Z) to which O 2 ) and other auxiliary components Na 2 O and Bi 2 O 3 are added.
nO-Na 2 O-Bi 2 O 3, the cladding glass composition: Te
When a single mode fiber of O 2 —ZnO—Na 2 O) was produced, the loss value was 10 dB at a wavelength of 1.3 μm.
/ Km fiber was produced. This is because the conventional tellurite glass fiber showed a high loss value of 1.3 dB / km at 1.3 μm due to the use of a commercially available ZnO raw material, whereas a significant reduction in the loss value could be achieved. .
【００２３】[0023]
【実施例２】純度：６Ｎ（９９．９９９９％）の高純度
金属亜鉛を出発物質とする高純度酸化亜鉛の製造方法に
ついて、図３に示す工程図によって説明する。形状がイ
ンゴット状の高純度金属亜鉛２５ｇを秤量し、１０００
ｍｌのビーカに入れ、電子工業用の高純度の濃硝酸（６
１％、比重＝１．４２ｇ／ｃｍ3）３００ｍｌに超純水
２００ｍｌを加えた希硝酸に溶解する。溶解に要する時
間は、約１時間である。溶解後の水溶液は無色であり、
無色の溶液を孔径０．２μのメンブランフィルタを通
し、未溶解の金属亜鉛があった場合にはメンプランフィ
ルタで除去する。溶解後の該水溶液に、純度が９９．９
９％の高純度炭酸ナトリウム（Ｎａ2ＣＯ3）１００ｇを
少量づつ添加し、ＺｎＣＯ3沈殿物を得る。該沈殿物
は、遠心分離器で沈殿物と水溶液を分離する。分離後の
沈殿物は、再度、１０００ｍｌのビーカに入れ、超純水
を８００ｍｌ添加し、洗浄を行う。洗浄操作は、３回繰
り返す。洗浄後のＺｎＣＯ3沈殿物は、遠心分離器で分
離し、分離後のＺｎＣＯ3沈殿物は、真空乾燥器で１７
０℃において２４時間乾燥し、脱水を行い、高純度の炭
酸亜鉛（ＺｎＣＯ3）を製造後、清浄な酸素雰囲気の電
気炉内で６００℃で焼成し、酸化亜鉛とする。Example 2 A method for producing high-purity zinc oxide starting from high-purity metallic zinc having a purity of 6N (99.9999%) will be described with reference to the process chart shown in FIG. Weigh 25 g of high-purity metallic zinc in the form of an ingot, and weigh 1000 g.
In a beaker of high purity, add concentrated nitric acid (6
(1%, specific gravity = 1.42 g / cm 3 ) Dissolve in 300 ml of dilute nitric acid by adding 200 ml of ultrapure water. The time required for dissolution is about 1 hour. The aqueous solution after dissolution is colorless,
The colorless solution is passed through a membrane filter having a pore size of 0.2 μm, and any undissolved metallic zinc is removed by a membrane filter. The aqueous solution after dissolution has a purity of 99.9.
100 g of 9% high purity sodium carbonate (Na 2 CO 3 ) is added in small portions to obtain a ZnCO 3 precipitate. The precipitate is separated from the aqueous solution by a centrifuge. The precipitate after separation is again put into a 1000 ml beaker, 800 ml of ultrapure water is added, and washing is performed. The washing operation is repeated three times. ZnCO 3 precipitate after washing, separated by centrifuge, ZnCO 3 precipitate after separation by a vacuum drier 17
After drying at 0 ° C. for 24 hours and dehydration to produce high-purity zinc carbonate (ZnCO 3 ), it is fired at 600 ° C. in an electric furnace in a clean oxygen atmosphere to obtain zinc oxide.
【００２４】反応式は、式４、式５に従い、炭酸亜鉛が
製造できる。さらに、炭酸亜鉛を６００℃で焼成すると
式６に従い、酸化亜鉛が作製できる。ＴＧ−ＤＴＡ分析
によるＤＴＡ曲線においても図２に示したＤＴＡ曲線と
同一のものが得られ、Ｘ線回折（ＸＲＤ）及び熱分析
（ＴＧ−ＤＴＡ）での解析結果より、作製した物質は、
酸化亜鉛である。また、作製した酸化亜鉛のＦｅ，Ｎ
ｉ，Ｃｕの放射化分析を行い、Ｆｅ，Ｎｉ，Ｃｕについ
て不純物濃度１ｐｐｂの分析結果が得られ、従来、行わ
れていた酸化亜鉛についてのＦｅ，Ｎｉ，Ｃｕ不純物濃
度の定量値よりも３桁以上の高純度の無水の酸化亜鉛が
９５％の収率で作製できた。According to the reaction formulas 4 and 5, zinc carbonate can be produced. Further, when zinc carbonate is fired at 600 ° C., zinc oxide can be produced according to the formula 6. The same DTA curve as that shown in FIG. 2 was obtained in the DTA curve by TG-DTA analysis. From the results of analysis by X-ray diffraction (XRD) and thermal analysis (TG-DTA), the prepared substance was
It is zinc oxide. In addition, Fe, N
Activation analysis of i and Cu was performed, and an analysis result of Fe, Ni, and Cu was obtained at an impurity concentration of 1 ppb, which was three orders of magnitude higher than the quantitative value of Fe, Ni, and Cu impurity concentrations for zinc oxide, which was conventionally performed. The high-purity anhydrous zinc oxide described above was produced with a yield of 95%.
【００２５】[0025]
【式４】Ｚｎ＋２ＨＮＯ3 → Ｚｎ2+＋２ＮＯ3 - [Formula 4] Zn + 2HNO 3 → Zn 2+ + 2NO 3 −
【００２６】[0026]
【式５】Ｚｎ2+＋Ｎａ2ＣＯ3＋Ｈ2Ｏ → ＺｎＣＯ3＋
２ＮａＯＨ[Formula 5] Zn 2+ + Na 2 CO 3 + H 2 O → ZnCO 3 +
2NaOH
【００２７】[0027]
【式６】ＺｎＣＯ3 → ＺｎＯ＋ＣＯ2 [Formula 6] ZnCO 3 → ZnO + CO 2
【００２８】本実施例で作製したＺｎＯを用い、これに
ＴｅＯ2を加えたテルライトガラスファイバ（コアガラ
ス組成：ＴｅＯ2−ＺｎＯ−Ｎａ2Ｏ−Ｂｉ2Ｏ3、クラッ
ドガラス組成：ＴｅＯ2−ＺｎＯ−Ｎａ2Ｏ）において、
１．３μの波長で損失値１０ｄＢ／ｋｍのシングルモー
ドファイバが作製できた。これは、従来のテルライトフ
ァイバ原料がＴｅＯ2に市販のＺｎＯの原料を用いて作
製したシングルモードファイバが、損失値１０００ｄＢ
／ｋｍであるのに対し、大幅な損失値の低減が達成でき
た。[0028] Using ZnO produced in this example, this TeO 2 tellurite glass fiber (core glass composition was added: TeO 2 -ZnO-Na 2 O -Bi 2 O 3, the cladding glass composition: TeO 2 - ZnO—Na 2 O)
A single mode fiber having a loss of 10 dB / km at a wavelength of 1.3 μm was produced. This is because a single-mode fiber manufactured by using a conventional tellurite fiber material and a commercially available ZnO material for TeO 2 has a loss value of 1000 dB.
/ Km, a significant reduction in loss value could be achieved.
【００２９】[0029]
【実施例３】純度：６Ｎ（９９．９９９９％）の高純度
の金属亜鉛を出発物質とする高純度酸化亜鉛の製造方法
について、図４に示す工程図によって説明する。形状が
チャンク状の高純度金属亜鉛５０ｇを秤量し、１０００
ｍｌのビーカに入れ、電子工業用の高純度の濃硫酸（９
６％）３００ｍｌに超純水２００ｍｌを加えた希硫酸水
溶液で溶解する。溶解と同時に白色の硫酸亜鉛の沈殿物
を得る。硫酸亜鉛の沈殿物をホットプレート上で加熱
し、溶解する。溶解後の亜鉛水溶液は無色であり、溶解
後の該水溶液に、純度が９９．９９％の高純度炭酸ナト
リウム（Ｎａ2ＣＯ3）１００ｇを３００ｍｌの超純水に
溶解した水溶液を少量づつ添加し、ＺｎＣＯ3沈殿物を
得る。該沈殿物は、遠心分離器で沈殿物と水溶液を分離
する。分離後の沈殿物は、再度、１０００ｍｌのピーカ
に入れ、超純水を８００ｍｌ添加し、洗浄を行う。洗浄
操作は、３回繰り返す。洗浄後のＺｎＣＯ3沈殿物は、
速心分離器で分離し、分離後のＺｎＣＯ3沈殿物は、真
空乾燥器で１３０℃で２４時間乾燥し、脱水を行い、高
純度の炭酸亜鉛（ＺｎＣＯ3）を製造後、清浄な酸素雰
囲気の電気炉内で６００℃で焼成し、酸化亜鉛とする。Embodiment 3 A method for producing high-purity zinc oxide using high-purity metallic zinc having a purity of 6N (99.9999%) as a starting material will be described with reference to the process chart shown in FIG. 50 g of high-purity metallic zinc in a chunk shape is weighed and 1000
in a beaker of high purity for the electronics industry (9
(6%) Dissolve in 300 ml of ultrapure water and 200 ml of diluted sulfuric acid aqueous solution. Upon dissolution, a white precipitate of zinc sulfate is obtained. The zinc sulfate precipitate is heated on a hot plate to dissolve. The aqueous zinc solution after dissolution is colorless, and an aqueous solution in which 100 g of high-purity sodium carbonate (Na 2 CO 3 ) having a purity of 99.99% is dissolved in 300 ml of ultrapure water is added little by little to the aqueous solution after dissolution. , To obtain a ZnCO 3 precipitate. The precipitate is separated from the aqueous solution by a centrifuge. The precipitate after separation is again put into a 1000 ml peaker, 800 ml of ultrapure water is added, and washing is performed. The washing operation is repeated three times. The ZnCO 3 precipitate after washing is
The ZnCO 3 precipitate is separated by a quick-core separator, and the separated ZnCO 3 precipitate is dried in a vacuum drier at 130 ° C. for 24 hours, dehydrated, and produced high-purity zinc carbonate (ZnCO 3 ). In an electric furnace at 600 ° C. to obtain zinc oxide.
【００３０】反応式は、式７、式８、式９、式１０に従
い、酸化亜鉛が製造できる。According to the reaction formula, zinc oxide can be produced according to the formulas 7, 8, 9, and 10.
【００３１】[0031]
【式７】Ｚｎ＋Ｈ2ＳＯ4 → ＺｎＳＯ4↓十Ｈ2 [Formula 7] Zn + H 2 SO 4 → ZnSO 4 ↓ 10 H 2
【００３２】[0032]
【式８】ＺｎＳＯ4 → Ｚｎ2+＋ＳＯ4 2- [Equation 8] ZnSO 4 → Zn 2+ + SO 4 2-
【００３３】[0033]
【式９】Ｚｎ2+＋ＣＯ3 2- → ＺｎＣＯ3 [Formula 9] Zn 2+ + CO 3 2- → ZnCO 3
【００３４】[0034]
【式１０】ＺｎＣＯ3 → ＺｎＯ＋ＣＯ2 [Formula 10] ZnCO 3 → ZnO + CO 2
【００３５】ＴＧ−ＤＴＡ分析は、図２に示した曲線と
同一のものが得られる。すなわち、Ｘ線回折（ＸＲＤ）
及び熱分析（ＴＧ−ＤＴＡ）での解析結果より、作製し
た物質は、無水の酸化亜鉛である。また、作製した無水
の酸化亜鉛のＦｅ，Ｎｉ，Ｃｕの放射化分析を行い、Ｆ
ｅ，Ｎｉ，Ｃｕについて不純物濃度が１ｐｐｂの分析結
果が得られ、従来、行われていた酸化亜鉛についてのＦ
ｅ，Ｎｉ，Ｃｕ不純物濃度の定量値よりも３桁ほど高純
度の無水の酸化亜鉛が９５％の収率で作製できた。TG-DTA analysis gives the same curve as shown in FIG. That is, X-ray diffraction (XRD)
From the results of analysis by thermal analysis (TG-DTA), the produced substance was anhydrous zinc oxide. Further, activation analysis of Fe, Ni, and Cu of the produced anhydrous zinc oxide was performed, and
As a result, an impurity concentration of 1 ppb was obtained for e, Ni, and Cu.
Anhydrous zinc oxide having a purity of approximately three orders of magnitude higher than the quantitative values of the impurity concentrations of e, Ni, and Cu could be produced at a yield of 95%.
【００３６】本実施例で作製したＺｎＯに主組成として
ＴｅＯ2を添加したテルライトガラスファイバ（コアガ
ラス組成：ＴｅＯ2−ＺｎＯ−Ｎａ2Ｏ−Ｂｉ2Ｏ3、クラ
ッドガラス組成：ＴｅＯ2−ＺｎＯ−Ｎａ2Ｏ）でシング
ルモードファイバを作製したところ、波長１．３μの損
失値１０ｄＢ／ｋｍが得られ、従来のテルライトガラス
原料が市販ＺｎＯの原料を用いたために、１．３μにお
いて、１０００ｄＢ／ｋｍの損失値しか得られなかった
のに対して、大幅な損失値の低減ができた。The tellurite glass fiber added to ZnO of manufacturing a TeO 2 as the main composition in the present embodiment (the core glass composition: TeO 2 -ZnO-Na 2 O -Bi 2 O 3, the cladding glass composition: TeO 2 -ZnO -Na 2 O), a loss value of 10 dB / km at a wavelength of 1.3 μm was obtained, and a conventional tellurite glass raw material was a commercial ZnO raw material. Although only a loss value of / km was obtained, the loss value was significantly reduced.
【００３７】[0037]
【発明の効果】以上説明したように、本発明の製造方法
によれば、高純度の金属亜鉛を出発物質とし、高純度の
酸に溶解後、炭酸ナトリウムあるいは炭酸水素ナトリウ
ムを加え、炭酸亜鉛の沈殿物を作製後、脱水・乾燥後、
焼成すれば、無水の高純度の酸化亜鉛が作製できる。特
に、従来の亜鉛酸あるいは亜鉛塩の水溶液に二酸化炭素
を飽和した炭酸水素ナトリウム溶液または炭酸ナトリウ
ム溶液の作用で得る方法に比べ、極めて簡便に無水の酸
化亜鉛を作製するものであるから、遷移金属を極低濃度
にした高純度の酸化亜鉛を製造することができるもので
ある。さらに、酸化亜鉛をテルライトガラスファイバを
用いた光増幅器の出発物質として用いることにより、増
幅度の高い光ファイバアンプを製造できる利点がある。As described above, according to the production method of the present invention, high-purity metallic zinc is used as a starting material, dissolved in a high-purity acid, and then sodium carbonate or sodium hydrogen carbonate is added. After preparing the precipitate, dehydrating and drying,
By firing, anhydrous high-purity zinc oxide can be produced. In particular, compared with the conventional method of obtaining an aqueous solution of zinc acid or a zinc salt by the action of a sodium hydrogen carbonate solution or a sodium carbonate solution saturated with carbon dioxide, anhydrous zinc oxide is extremely easily produced, and therefore, transition metal is used. It is possible to produce high-purity zinc oxide having an extremely low concentration. Further, by using zinc oxide as a starting material of an optical amplifier using tellurite glass fiber, there is an advantage that an optical fiber amplifier having a high amplification degree can be manufactured.
【図１】本発明の実施例１における高純度の酸化亜鉛の
製造方法を示す工程図。FIG. 1 is a process chart showing a method for producing high-purity zinc oxide in Example 1 of the present invention.
【図２】本発明の実施例１により作製した炭酸亜鉛のＴ
Ｇ−ＤＴＡ曲線を示す図。FIG. 2 shows the T of zinc carbonate produced according to Example 1 of the present invention.
The figure which shows a G-DTA curve.
【図３】本発明の実施例２における高純度の酸化亜鉛の
製造方法を示す工程図。FIG. 3 is a process chart showing a method for producing high-purity zinc oxide in Example 2 of the present invention.
【図４】本発明の実施例３における高純度の酸化亜鉛の
製造方法を示す工程図。FIG. 4 is a process chart showing a method for producing high-purity zinc oxide in Example 3 of the present invention.
Claims (3)
記高純度亜鉛を酸溶液中で溶解し、溶解後の亜鉛溶液に
炭酸ナトリウムあるいは炭酸水素ナトリウムを加え、炭
酸亜鉛の沈殿物を作製し、該沈殿物を脱水・乾燥し、焼
成することを特徴とする酸化亜鉛の製造方法。1. Using high-purity zinc as a starting material, dissolving the high-purity zinc in an acid solution, adding sodium carbonate or sodium bicarbonate to the dissolved zinc solution to prepare a zinc carbonate precipitate. A method for producing zinc oxide, comprising dehydrating, drying and calcining the precipitate.
高純度金属であり、炭酸ナトリウムあるいは炭酸水素ナ
トリウムも純度が９９．９９％以上の高純度の試薬であ
り、酸についても純度が９９．９９％以上の高純度の試
薬であることを特徴とする請求項１記載の酸化亜鉛の製
造方法。2. High-purity zinc is a high-purity metal having a purity of 99.999% or more, sodium carbonate or sodium hydrogencarbonate is also a high-purity reagent having a purity of 99.99% or more, and acid has a purity of 99.999% or more. 2. The method for producing zinc oxide according to claim 1, wherein the reagent is a highly pure reagent of not less than .99%.
を特徴とする請求項１又は２記載の酸化亜鉛の製造方
法。3. The method for producing zinc oxide according to claim 1, wherein the firing temperature is 300 ° C. or higher.
Priority Applications (1)
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|---|---|---|---|
| JP11210145A JP2001039713A (en) | 1999-07-26 | 1999-07-26 | Production of zinc oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11210145A JP2001039713A (en) | 1999-07-26 | 1999-07-26 | Production of zinc oxide |
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| Publication Number | Publication Date |
|---|---|
| JP2001039713A true JP2001039713A (en) | 2001-02-13 |
Family
ID=16584525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11210145A Pending JP2001039713A (en) | 1999-07-26 | 1999-07-26 | Production of zinc oxide |
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| Country | Link |
|---|---|
| JP (1) | JP2001039713A (en) |
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| WO2005033355A1 (en) * | 2003-09-30 | 2005-04-14 | Nikko Materials Co., Ltd. | High purity zinc oxide powder and method for production thereof, and high purity zinc oxide target and thin film of high purity zinc oxide |
| KR100725444B1 (en) | 2006-09-11 | 2007-06-07 | 한양대학교 산학협력단 | A method for preparing zinc oxide nanoparticles |
| JP2008230915A (en) * | 2007-03-20 | 2008-10-02 | Mitsui Mining & Smelting Co Ltd | Electrically conductive zinc oxide particle and method for manufacturing the same |
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| JP2008230915A (en) * | 2007-03-20 | 2008-10-02 | Mitsui Mining & Smelting Co Ltd | Electrically conductive zinc oxide particle and method for manufacturing the same |
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| KR101186170B1 (en) | 2012-04-13 | 2012-10-08 | 주식회사 황조 | The method of withdrawing zinc oxide from waste powder of steel making |
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