KR100401991B1 - METHOD FOR RECYCLING SPENT Zn CLECTROYTE - Google Patents
METHOD FOR RECYCLING SPENT Zn CLECTROYTE Download PDFInfo
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- KR100401991B1 KR100401991B1 KR10-1998-0056706A KR19980056706A KR100401991B1 KR 100401991 B1 KR100401991 B1 KR 100401991B1 KR 19980056706 A KR19980056706 A KR 19980056706A KR 100401991 B1 KR100401991 B1 KR 100401991B1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- C01D3/04—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
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- C01D3/16—Purification by precipitation or adsorption
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Abstract
본 발명은 아연도금폐액을 재활용하는 방법에 관한 것이며, 구체적으로는 Zn도금폐액에서 불순물을 정제한 후, 폐액중의 Zn을 ZnO로 회수하고, 또한, KCl을 회수하는 방법을 제공하는데 있다.The present invention relates to a method for recycling a zinc plating waste liquid, and more particularly, to purifying impurities in a Zn plating waste liquid, to recovering Zn in the waste liquid as ZnO, and also to a method for recovering KCl.
상기 목적을 달성하기 위한 본 발명은 Zn도금폐액에 폐액중 Zn몰수의 1/200-1/50에 해당하는 몰수의 KOH를 투여하고 이를 교반 숙성처리 하여 불순물이 흡착되도록 한후 이를 여과하는 단계; 여과하여 불순물이 제거된 Zn함유용액을 KOH용액에 투입하여 용액의 pH를 13이상으로 유지하면서 중화반응이 이루어지도록 혼합하고 1시간 이상 교반처리하여 ZnO를 얻는 단계; 상기 얻어진 산화물을 반복 여과 수세한 후 건조하는 단계를 포함하는 Zn도금폐액을 이용한 ZnO 제조방법에 관한 것을 그 요지로 하며, 또한, 본 발명은 상기 ZnO를 얻는 단계에서 남은 여액에 염산을 가하여 pH를 6-8로 조절한 후 농축과정을 거쳐 결정화하는 Zn도금폐액을 이용한 KCl 제조방법에 관한 것을 그 요지로 한다.The present invention for achieving the above object is a Zn plating waste liquid by administering a number of moles of KOH corresponding to 1 / 200-1 / 50 of the number of moles of Zn in the waste solution and stirring and aging it so that impurities are adsorbed and filtered therefrom; Filtering and adding Zn-containing solution from which impurities were removed to KOH solution to maintain neutralization reaction while maintaining the pH of the solution at 13 or more, and stirring for at least 1 hour to obtain ZnO; The present invention relates to a method for preparing ZnO using a Zn plating waste liquid comprising the step of repeating filtration and washing the obtained oxide, and the present invention further provides pH by adding hydrochloric acid to the remaining filtrate in the step of obtaining ZnO. The main point of the method is the preparation of KCl using Zn plating waste liquid which is crystallized by concentration after adjusting to 6-8.
Description
본 발명은 제철소 전기아연 도금공장 등에서 발생하는 폐액의 재활용방법에 관한 것으로, 보다 자세하게는 Zn도금폐액 중의 Zn성분을 ZnO형태로 회수하고, 이러한 ZnO회수 과정에서 발생하는 여액을 활용하여 KCl을 제조방법에 관한 것이다.The present invention relates to a method for recycling waste liquid generated in an electro-zinc plating plant, etc., and more particularly, to recovering Zn components in Zn plating waste liquid in the form of ZnO, and to producing KCl using the filtrate generated in the ZnO recovery process. It is about.
도금 공장에서는 Zn 도금시 부원료로서 전도 보조제를 사용한다. 즉, 전기도금시에는 도금액의 전도도와 도금 특성은 밀접한 관계를 가지므로 도금액의 전도도 확보를 위하여 KCl을 투입하여 일정농도로 유지하면서 도금 작업을 한다. 그러나 도금액은 일부의 불가피한 배출(고농도 폐액), 린스(Rinse), 드랙아우트(Drag Out)등으로 인하여 배출되며 또한 많은 물을 사용하므로 전도도 확보를 위하여 도금작업중에는 많은 양의 KCl과 같은 전도보조제가 사용된다. 이와 같은 도금용 전도보조제는 고순도를 요구하므로 고순도 제품을 사용하여야 한다는 엄격한 제한이 따른다.Plating plants use conduction aids as a subsidiary material for Zn plating. That is, during electroplating, the conductivity of the plating solution and the plating characteristics are closely related, so the plating operation is performed while maintaining the concentration by adding KCl to secure the conductivity of the plating solution. However, the plating liquid is discharged due to some unavoidable discharge (high concentration waste liquid), rinse, rinse and drag out, and also uses a lot of water. Used. Such conductive aids for plating require high purity, and therefore, there is a strict restriction that high purity products should be used.
한편, 종래의 대표적인 페라이트 분말을 제조하는 방법으로는 출발원료인 Fe2O3, ZnO 분말을 다른 조성 즉 NiO, CuO 등과 건식 또는 습식 혼합하여 700-1000℃에서 가소 공정을 거친 후 이를 미분쇄하는 것이었다. 그러나, 이 방법은 각각의 고순도 원료분말을 사용하여야 하므로 원료 구입비가 높은 단점이 있었다.On the other hand, the conventional representative method for producing a ferrite powder is dry or wet mixed with a starting material Fe 2 O 3 , ZnO powder and other compositions, such as NiO, CuO and the like to go through a calcination process at 700-1000 ℃ and finely pulverize it Was. However, this method has a disadvantage in that the raw material purchase cost is high because each high purity raw material powder must be used.
이 같은 단점을 해결하기 위하여 본 발명자들은 스러지를 중심으로 한 제철소 폐기물을 활용하여 아연-니켈-동 페라이트 분말을 제조하는 방법을 제시한 바 있다(한국특허 출원 97-69229, 97-70161). 특히 한국특허 출원 97-69229는 Fe가 다량 녹아 있는 폐산에 Ni 양극과 Zn 양극을 용해시키고 Cu 폐액을 혼합하여 페라이트 제조를 하는 방법에 관한 것이다. 이 방법은 소성온도를 낮춘다는 장점이 있으나 제조 부피가 큰 단점이 있어 Fe성분으로 폐액 대신 산화철을 사용하는 방법 (97-70161)이 제시되었다.In order to solve the above disadvantages, the present inventors have proposed a method of manufacturing zinc-nickel-copper ferrite powder using steel mill waste centered on sludge (Korean Patent Application 97-69229, 97-70161). In particular, Korean Patent Application 97-69229 relates to a method for producing ferrite by dissolving Ni anode and Zn anode in waste acid in which Fe is dissolved in a large amount and mixing Cu waste solution. This method has the advantage of lowering the firing temperature, but has a disadvantage in that the manufacturing volume is large, a method of using iron oxide instead of waste liquid (97-70161) has been proposed as Fe components.
제철소 도금공장에서 Zn 도금작업을 하면 불가피하게 폐도금액이 발생된다. 폐도금액내에는 Zn, KCl 성분이 함유되어 있어 이를 정제할 경우 페라이트의 원료인 ZnO 와 도금첨가제인 고순도 KCl로의 재활용이 가능해진다.Zn plating in steel mill plating factory inevitably generates waste plating solution. In the waste plating solution, Zn and KCl components are contained. When this is purified, it is possible to recycle ZnO, a raw material for ferrite, and high purity KCl, a plating additive.
이에 본 발명은 Zn도금폐액에서 불순물을 정제하여 재활용하는 방법을 제공하는데 그 목적이 있는 것으로, 구체적으로는 폐액중의 Zn을 ZnO로 회수하고, 또한, KCl을 회수하는 것이다.Accordingly, an object of the present invention is to provide a method for refining and recycling impurities in a Zn plating waste liquid, specifically, to recover Zn in waste liquid as ZnO and to recover KCl.
일반적으로 제철소 전기아연 도금공정 등에서 발생하는 Zn 폐액에는 Fe, Si, Al 등의 불순물을 다량포함하고 있어, 전자재료 원료인 페라이트의 원료로 사용함에 문제가 있었다. 또한, 수용액내에서 ZnO를 합성시 ZnO분말에 Cl이 혼입되는 문제가 있었다.In general, the Zn waste liquid generated in the electro-zinc plating process of a steel mill contains a large amount of impurities such as Fe, Si, and Al, and there is a problem in using it as a raw material for ferrite, which is a raw material for electronic materials. In addition, when synthesizing ZnO in an aqueous solution, there was a problem that Cl is mixed in the ZnO powder.
이에, 본 발명은 도금폐액을 정제하여 고순도 ZnO 및 KCl을 제조하는 새로운 방법을 제공하는 것이다. 또한, ZnO 제조공정에서 KOH로 중화 할 경우 고순도 KCl의 합성이 가능해진다.Accordingly, the present invention is to provide a new method for producing high purity ZnO and KCl by purifying the plating waste liquid. In addition, when neutralized with KOH in the ZnO manufacturing process, it is possible to synthesize high purity KCl.
이러한 관점으로 부터 출발하여, 상기 목적을 달성하기 위한 본 발명은 Zn도금폐액에 폐액중 Zn몰수의 1/200-1/50에 해당하는 몰수의 KOH를 투여하고 이를 교반 숙성처리 하여 불순물이 흡착되도록 한후 이를 여과하는 단계; 여과하여 불순물이 제거된 Zn함유용액을 KOH용액에 투입하여 용액의 pH를 13이상으로 유지하면서 중화반응이 이루어지도록 혼합하고 1시간 이상 교반처리하여 ZnO를 얻는 단계; 상기 얻어진 산화물을 반복 여과 수세한 후 건조하는 단계를 포함하는 Zn도금폐액을 이용한 ZnO 제조방법에 관한 것이며, 또한,Starting from this point of view, the present invention for achieving the above object is to administer the number of moles of KOH corresponding to 1 / 200-1 / 50 of the number of moles of Zn in the waste liquid to Zn plating waste liquid, and stirred and aged so that impurities are adsorbed. Then filtering it; Filtering and adding Zn-containing solution from which impurities were removed to KOH solution to maintain neutralization reaction while maintaining the pH of the solution at 13 or more, and stirring for at least 1 hour to obtain ZnO; The present invention relates to a ZnO manufacturing method using a Zn plating waste liquid comprising the step of repeating filtration and washing the obtained oxide.
본 발명은 Zn도금폐액에 폐액중 Zn몰수의 1/200-1/50에 해당하는 몰수의 KOH를 투여하고 이를 교반 숙성처리 하여 불순물이 흡착되도록 한후 이를 여과하는 단계; 여과하여 불순물이 제거된 Zn함유용액을 KOH용액에 투입하여 용액의 pH를 13이상으로 유지하면서 중화반응이 이루어지도록 혼합하고 1시간 이상 교반처리하여 ZnO를생성시키는 단계; 상기 생성된 산화물을 여과하여 제거하는 단계; 및 여과하여 산화물이 제거된 KCl용액에 염산을 가하여 pH를 6-8로 조절한 후 농축과정을 거쳐 결정화하는 단계를 포함하는 Zn도금폐액을 이용한 KCl 제조방법에 관한 것이다.The present invention comprises the steps of administering a number of moles of KOH corresponding to 1 / 200-1 / 50 of the number of moles of Zn in the Zn plating waste liquid and stirring and aging to allow impurities to be adsorbed and then filtering them; Filtering and adding Zn-containing solution from which impurities are removed to KOH solution to maintain neutralization reaction while maintaining the pH of the solution at 13 or above, followed by stirring for 1 hour to generate ZnO; Filtering the produced oxide to remove it; And it relates to a KCl manufacturing method using a Zn plating waste solution comprising the step of crystallization through the concentration process after adjusting the pH to 6-8 by adding hydrochloric acid to the KCl solution from which the oxide is removed by filtration.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 Zn도금폐액에 폐액중 Zn몰수의 1/200-1/50에 해당하는 몰수의 KOH를 투여하고 이를 교반 숙성처리 하여 불순물이 흡착되도록 한후 이를 여과하는 과정을 거친다.In the present invention, the Zn plating waste liquid is administered with KOH in the number of moles corresponding to 1 / 200-1 / 50 of the number of moles of Zn in the waste solution and subjected to stirring and aging so that impurities are adsorbed and then filtered.
상기 Zn도금폐액은 일반적으로 ZnCl2, KCl로 주로 구성되며 Si, Fe, Al과 같은 많은 불순물을 함유되어 있는데, 그 대표적인 조성의 일예를 들면 하기 표1과 같다.The Zn plating waste liquid is generally mainly composed of ZnCl 2 , KCl, and contains many impurities such as Si, Fe, and Al. For example, a representative composition thereof is shown in Table 1 below.
따라서, 상기 Zn도금폐액은 먼저 정제과정을 거치는데, 정제를 위해 폐액중 Zn몰수의 1/200-1/50에 해당하는 몰수의 KOH를 투여한다. 투여되는 KOH의 몰수가 Zn몰수의 1/200보다 작으면 완전하게 불순물이 제거되지 않고, 1/50보다 많으면 불순물의 제거는 없이 Zn의 손실을 가져오기 때문이다.Therefore, the Zn plating waste liquid is first subjected to a purification process, and for purification, an amount of molar KOH corresponding to 1 / 200-1 / 50 of the number of moles of Zn in the waste liquid is administered. This is because when the number of moles of KOH administered is less than 1/200 of the number of moles of Zn, impurities are not completely removed. If the number of moles of KOH is greater than 1/50, Zn is lost without removing impurities.
상기와 같은 몰수로 KOH를 투여하여 Zn이 함유된 스러지(ZnCl2·4Zn(OH)2)를 생성시킨다. 생성된 슬러지 ZnCl2·4Zn(OH)2이 존재하는 상황에서 교반 숙성 처리하면 이생성물에 불순이온이 흡착하여 불순물의 정제가 이루어지는데, 불순물 정제의 기구는 다음과 같이 예상된다.By administering KOH in the same mole number as described above, Zn-containing sludge (ZnCl 2 · 4Zn (OH) 2 ) is produced. In the presence of the produced sludge ZnCl 2 · 4Zn (OH) 2 , when stirring and aging treatment are carried out, impurities are adsorbed on the product to purify impurities. The mechanism for purifying impurities is expected as follows.
즉, 생성된 ZnCl2·4Zn(OH)2스러지를 교반함에 따라 도금액내의 불순물과 반응하여 하기식 1과 같이 (Zn,Fe,Si,Al)+x(OH)x라는 스러지로 변화하고 이를 여과하면 불순물이 제거된다.That is, as the resulting ZnCl 2 · 4Zn (OH) 2 sludge is agitated, it reacts with impurities in the plating solution to change into a sludge called (Zn, Fe, Si, Al) + x (OH) x as shown in Equation 1 below, and filter it. Impurities are removed.
또한, 본 발명에서는 여과하여 불순물이 제거된 Zn함유용액을 KOH용액에 투입하여 용액의 pH를 13이상으로 유지하면서 중화반응이 이루어지도록 혼합하고 1시간 이상 교반처리하여 ZnO를 얻는 과정을 거친다.In addition, in the present invention, the Zn-containing solution from which impurities are removed by filtration is added to KOH solution, mixed so that neutralization reaction is performed while maintaining the pH of the solution at 13 or more, and stirred for at least 1 hour to obtain ZnO.
상기 불순물이 제거된 폐용액을 KOH용액에 투입하는데, 혼합되는 용액은 항시 pH 13이상을 유지해야 하고, 30-80℃의 온도에서 1시간이상 교반처리를 행하는 것이 바람직하다. 그 이유는 다음과 같다.The waste solution from which the impurities have been removed is added to a KOH solution, and the mixed solution should always maintain pH 13 or more, and preferably agitate for at least 1 hour at a temperature of 30-80 ° C. The reason for this is as follows.
즉, KOH를 가함으로서, 하기식 2와 같은 반응을 일으켜 ZnO를 얻고자 하는 것이다.That is, by adding KOH, the reaction is carried out as in the following formula 2 to obtain ZnO.
이때, 알카리성 분위기를 유지하는 것이 ZnO 생성시의 Cl혼입 방지에 매우 중요한역할을 한다. 낮은 pH 조건 즉 pH 13을 넘지 않으면 ZnO 생성되는 대신 Zn(OH)2또는 ZnCl2·4Zn(OH)2라는 수산화물이 생성되므로 고알카리에서 중화함이 바람직하다. 또한, 알칼리와 ZnCl2용액의 혼합방법(투여 순서)은 매우 중요하다. 즉, ZnCl2용액에 KOH와 같은 알카리를 투여하는 방법(이하, "방법1")과 KOH 용액에 ZnCl2용액에을 투여하는 방법(이하, "방법 2")과는 매우 다른 생성물이 생긴다는 것이다.At this time, maintaining an alkaline atmosphere plays a very important role in preventing Cl mixing during ZnO formation. If the pH is not lower than pH 13, ZnO is formed instead of Zn (OH) 2 or ZnCl 2 .4Zn (OH) 2. Thus , neutralization in high alkali is preferable. In addition, the mixing method (dosing order) of alkali and ZnCl 2 solution is very important. That is, a very different product is produced from a method of administering an alkali such as KOH to a ZnCl 2 solution (hereinafter “Method 1”) and a method of administering a ZnCl 2 solution to a KOH solution (hereinafter “Method 2”). .
상기 방법 1로 합성할 경우 생성산물은 주로 ZnCl2·4Zn(OH)2가 얻어지며, 상기 방법 2를 사용할 경우 ZnO 이 수용액내에서 직접 생성한다. 이는 중화과정시 방법 1,2에 의한 최종 pH 는 동일하지만 중화과정중 생성되는 산물의 경우 방법 2는 항상 pH를 13이상으로 유지하는 반면, 방법 1은 산성에서 알카리성으로 변화하기 때문에 Cl의 흡착이 용이해지고 이에 따라 ZnCl2·4Zn(OH)2의 생성을 유발하기 때문이다.When synthesized by the method 1, the product is mainly ZnCl 2 · 4Zn (OH) 2 is obtained, when using the method 2 ZnO is produced directly in an aqueous solution. This means that the final pH of method 1 and 2 during neutralization is the same, but for products produced during neutralization, method 2 always maintains pH above 13, whereas method 1 changes from acidic to alkaline, so the adsorption of Cl This is because it facilitates the production of ZnCl 2 · 4Zn (OH) 2 .
또한, 본 발명에서는 상기 얻어진 산화물을 반복 여과 수세한 후 건조하는 과정을 거친다.In the present invention, the obtained oxide is repeatedly washed with filtration and then dried.
상기식 2의 반응에 의해 얻어진 산화물을 얻기 위해서 KCl을 제거하는데, 이는 통상적인 반복 여과, 수세를 통하여 행하며, 얻어진 ZnO를 건조하여 분말로 제조할 수 있다. 얻어진 ZnO분말은 고순도 페라이트용 출발원료로 적용할 수 있다.KCl is removed in order to obtain an oxide obtained by the reaction of Formula 2, which is carried out through conventional repeated filtration and washing with water, and the obtained ZnO may be dried to prepare a powder. The obtained ZnO powder can be applied as a starting material for high purity ferrite.
그러나, ZnCl2·4Zn(OH)2가 생성되면 수세공정으로 Cl 제거가 되지 않는 문제가 따른다. 따라서 ZnO 습식합성시 ZnCl2·4Zn(OH)2생성 방지는 ZnO 고순도화에 매우 중요하다.However, when ZnCl 2 · 4Zn (OH) 2 is generated, there is a problem that Cl is not removed by a washing process. Therefore, the prevention of ZnCl 2 · 4Zn (OH) 2 formation during ZnO wet synthesis is very important for ZnO high purity.
또한, 본 발명은 상기식 2에 의해 생성된 KCl를 회수하는 방법을 제공한다.The present invention also provides a method for recovering KCl produced by the above formula 2.
즉, 상기식 2에 의해 얻어진 산화물을 여과해 내고 나오는 여액내에는 KCl이 존재한다. 이 여액은 불순물이 거의 없는 고순도 KCl 용액이므로 KCl 함유용액의 pH를 6-8로 염산을 투여하여 조절한 후, 가열농축, 증발농축 등으로 농축 후 결정화를 통해 고순도 KCl의 회수가 가능하다.That is, KCl exists in the filtrate which filters out the oxide obtained by the said Formula 2. Since this filtrate is a high purity KCl solution with almost no impurities, the pH of the KCl-containing solution is adjusted to 6-8 by hydrochloric acid, and then concentrated by heating, evaporation, and the like to recover high purity KCl.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
실시예 1Example 1
상기표 1과 같은 조성의 Zn도금폐액에 Zn이온 몰수(1.54몰)의 1/400-1/25배에 해당하는 몰수의 KOH를 투여하거나 투여하지 않았다. 그후 초기 중화산물의 스러지를 여과 채취하여 XRD로 조사한 결과 생성산물은 ZnCl2·4Zn(OH)2로 확인되었다.Zn plating waste liquid having the composition shown in Table 1 was not administered or administered a number of moles of KOH corresponding to 1 / 400-1 / 25 times the number of moles of Zn ion (1.54 moles). Subsequently, the sludge of the initial neutralization product was filtered and examined by XRD, and the resultant product was identified as ZnCl 2 · 4Zn (OH) 2 .
이 생성물이 존재하는 상태에서 폐 Zn 도금액을 1시간 이상 교반흡착하여 불순물을 흡착시킨 후 여과하여 그 여액을 채취하였다. 그 여액을 분석한 결과를 하기표 2에 나타내었다.In the presence of this product, the waste Zn plating solution was stirred and adsorbed for at least 1 hour to adsorb impurities, followed by filtration to collect the filtrate. The results of analyzing the filtrate are shown in Table 2 below.
상기표 2에서 알 수 있는 바와같이, Zn 이온 몰수 (1.54몰)의 1/200-1/50의 몰수의 KOH를 투여하여 ZnCl2·4Zn(OH)2를 생성시킨 후 불순물을 흡착한 결과 불순물을 5ppm 이내로 감소시킬 수 있었으나, 1/400에서는 완전한 불순물 제거가 이루어지지 않았다. 1/25에서는 거의 완전한 불순물 제거가 이루어져 더 이상의 KOH 투여는 Zn 원료 손실을 가져오므로 ZnCl2·4Zn(OH)2생성량조건은 Zn 이온 몰수(1.54몰)의 1/200-1/50의 몰수의 KOH 투입이 바람직하였다.As can be seen in Table 2 above, ZnCl 2 · 4Zn (OH) 2 was formed by administering 1 / 200-1 / 50 moles of KOH to the number of moles of Zn ions (1.54 moles), and then the impurities were adsorbed. Was reduced to within 5 ppm, but at 1/400 no complete impurity was removed. Almost complete impurity removal at 1/25 results in more KOH dosing resulting in Zn raw material loss, resulting in ZnCl 2 · 4Zn (OH) 2 production conditions of 1 / 200-1 / 50 moles of Zn ion moles (1.54 moles) KOH injection of was preferred.
실시예 2Example 2
실시예 1에서 불순물이 제거된 Zn 용액에 알카리(KOH)를 가할 경우(방법1)와 알카리에 Zn 용액을 가하는 방법(방법2)으로, 중화방법을 달리하고 중화 후 최종 pH를 10-13으로 각각 달리 한 후 생성되는 중화산물을 XRD로 분석한 결과를 하기표 3에 나타내었다.In Example 1, when alkali (KOH) is added to the Zn solution from which impurities are removed (method 1) and the Zn solution is added to the alkali (method 2), the neutralization method is different and the final pH is 10-13 after neutralization. The results of analyzing the neutralized products produced after each different by XRD are shown in Table 3 below.
상기표 3에서 알 수 있는 바와같이, 용액의 pH를 항시 13이상으로 유지하면서 중화한 발명예 1을 제외하고는 ZnCl2·4Zn(OH)2상의 혼입이 이루어졌다. 따라서 ZnO 합성시 Cl 혼입을 최소화하기 위해서는 pH를 13이상으로 항시 유지하면서 중화반응함이 매우 중요함을 확인할 수 있었다.As can be seen in Table 3, except for Inventive Example 1 which was neutralized while maintaining the pH of the solution at all times 13 or more, the incorporation of ZnCl 2 · 4Zn (OH) 2 phase was made. Therefore, in order to minimize Cl incorporation during ZnO synthesis, it was confirmed that the neutralization reaction was very important while maintaining the pH at 13 or more at all times.
또한, 상기 발명예 a방법에 의해 ZnO를 제조시 여과하고 남은 여액에 염산을 가하여 pH를 7로 조절한 후, 가열농축을 하여 KCl을 얻었다. 얻어진 KCl은 고순도를 보였다.In addition, after preparing ZnO by the method of Inventive Example a, hydrochloric acid was added to the remaining filtrate to adjust pH to 7, and concentrated by heating to obtain KCl. The obtained KCl showed high purity.
상술한 바와같은 본 발명에 의하면, 제철소 전기아연 도금공정 등에서 발생하는 폐액을 이용하여 함유되어 있는 다량의 불순물을 제거한 후, ZnO 또는/및 KCl을 회수함으로서, 폐기물을 재활용하여 페리이트 등의 원료로 사용가능한 고순도의 ZnO 및 고순도의 KCl을 얻을 수 있는 효과가 제공된다.According to the present invention as described above, after removing a large amount of impurities contained in the waste liquid generated in the electro-galvanization process of steel mills, and recovering ZnO or / and KCl, the waste is recycled to raw materials such as ferrite The effect of obtaining high purity ZnO and high purity KCl usable is provided.
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| JPH04164816A (en) * | 1990-10-30 | 1992-06-10 | Mitsubishi Materials Corp | Production of acicular zinc oxide powder by submerged synthetic method |
| JPH04325414A (en) * | 1991-04-25 | 1992-11-13 | Sumitomo Chem Co Ltd | Production of zinc oxide-zinc hydroxide mixture |
| KR20010093909A (en) * | 2000-04-03 | 2001-10-31 | 김수태 | Process for simultaneously producing zinc oxide and calcium chloride dihydrate |
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| JPH04164816A (en) * | 1990-10-30 | 1992-06-10 | Mitsubishi Materials Corp | Production of acicular zinc oxide powder by submerged synthetic method |
| JPH04325414A (en) * | 1991-04-25 | 1992-11-13 | Sumitomo Chem Co Ltd | Production of zinc oxide-zinc hydroxide mixture |
| KR20010093909A (en) * | 2000-04-03 | 2001-10-31 | 김수태 | Process for simultaneously producing zinc oxide and calcium chloride dihydrate |
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