KR20010093909A - Process for simultaneously producing zinc oxide and calcium chloride dihydrate - Google Patents
Process for simultaneously producing zinc oxide and calcium chloride dihydrate Download PDFInfo
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- KR20010093909A KR20010093909A KR1020000017229A KR20000017229A KR20010093909A KR 20010093909 A KR20010093909 A KR 20010093909A KR 1020000017229 A KR1020000017229 A KR 1020000017229A KR 20000017229 A KR20000017229 A KR 20000017229A KR 20010093909 A KR20010093909 A KR 20010093909A
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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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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
Description
본 발명은 염화아연을 탄산칼슘과 반응시켜 산화아연과 염화칼슘을 제조하는 방법을 제공하는 것이다.The present invention provides a method for producing zinc oxide and calcium chloride by reacting zinc chloride with calcium carbonate.
산화아연은 공업, 의약분야에서는 아연화, 아연백으로 불리며 백색안료, 페인트, 그림물감, 고무충진제, 시멘트, 경질수지 에나멜, 유탁글래스의 제조, 의약품, 화장품 등에 널리 사용되며, 다른 아연염, 예를 들면 염화아연 등에 비해 상당히 고가이다.Zinc oxide is called zinc or zinc bag in industrial and pharmaceutical fields. It is widely used in white pigments, paints, colorings, rubber fillers, cement, hard resin enamels, emulsion glass, pharmaceuticals, cosmetics, and other zinc salts. For example, it is considerably more expensive than zinc chloride.
이러한 산화아연의 제조방법은 예로부터 건식법과 습식법이 알려져 있으며, 건식법으로는 직접법과 간접법으로 나뉘며, 직접법은 아메리카산의 프랑크리아니트 (Zn, Mn)FeO4, 스미소나이트 (ZnCO3)와 같은 휘발성이 적은 아연광석을 석탄, 코크스와 같은 환원제화 함께 배소시키면 환원된 아연이 기화하고, 이를 산화시켜 산화아연으로 제조한다. 이 방법은 미국에서 발달하여 현재에도 미국에서 사용되고 있으나, 원료면의 제약상 우리실정에는 적합하지 않다. 또한, 간접법은 아연광석에서 일단 금속아연을 만들고, 이를 산화하여 산화아연을 제조하는 방법이다. 금속아연을 로중에서 1000℃로 가열하여 나오는 아연증기를 예열공기로 산화하고, 공냉관을 통해 냉각하여 산화아연을 얻는 것으로 원료는 전기아연, 드로스 등은 불순물을 함유한 제품의 불순 착색의 원인이 된다. 유황을 가하여 배소하면 백색으로 된다. 이 방법은 미국을 제외한 국가에서 널리 사용되고 있다.Such a method of producing zinc oxide is known from the dry method and wet method from the past, and the dry method is divided into direct method and indirect method, the direct method is the Francianitite (Zn, Mn) FeO 4 of the American, such as Smithsonite (ZnCO 3 ) When the low volatility zinc ore is roasted together with a reducing agent such as coal and coke, the reduced zinc is vaporized and oxidized to produce zinc oxide. This method was developed in the United States and is still used in the United States, but it is not suitable for our situation due to the constraint of raw materials. In addition, the indirect method is a method of producing zinc oxide by first forming a metal zinc from zinc ore and oxidizing it. Zinc zinc from metal furnace is heated to 1000 ℃ in the furnace to oxidize with preheated air, and cooled through air cooling tube to obtain zinc oxide.The raw material is electro zinc, dross, etc. Becomes When sulfur is added and roasted, it turns white. This method is widely used in countries other than the United States.
상기와 같은 건식법은 아연광이나, 금속아연을 사용하고, 전기로 등의 고비용을 에너지가 요구되는 등 공업적으로 문제점이 많다. 이러한 건식법의 문제점을 해결하기 위하여 습식법이 제안되어 있다. 즉, 염화아연 용액에 소다회(탄산나트륨) 용액을 가하여 염기성 탄산염을 침전시키고, 수제 건조후 배소하여 제조하는 방법이다. 그러나, 이 방법은 소다회의 값이 비싸서 경제적으로 불리하며, 반응생성물인 염화나트륨은 식용으로 사용할 수 없어 이를 3%이하로 희석하여 배출하여야 하기 때문에 폐기 비용이 높은 등 여러 가지 문제점이 있다. 이를 해결하기 위하여 소다회 대신에 소석회를 사용하여 본 결과, 생성되는 수산화아연이 겔상으로 되어 염화칼슘과 분리하는 것이 거의 불가능하였다.The dry method as described above has many industrial problems, such as using zinc ore or metal zinc and requiring high energy costs such as an electric furnace. In order to solve this problem of the dry method, a wet method has been proposed. In other words, a soda ash (sodium carbonate) solution is added to the zinc chloride solution to precipitate basic carbonate, which is produced by drying after roasting. However, this method is economically disadvantageous because the cost of soda ash is expensive, and the reaction product sodium chloride cannot be used for food, so it has to be discharged by diluting it below 3%. In order to solve this problem, as a result of using slaked lime instead of soda ash, the resulting zinc hydroxide became gel and it was almost impossible to separate from calcium chloride.
본 발명자는 산업계에서 요구되는 산화아연의 양 및 품질을 조사한 바, 산화아연의 수요가 대단히 많아서 그의 공급이 부족한데도 불구하고, 전술한 공지의 방법은 산화아연의 제조비용이 지나치게 높아 공업적으로 유리하지 않고, 아연재나 아연드로스 등의 폐기물을 이용하기에는 적합하지 않았다. 본 발명자는 상기 문제점을 해결하기 위하여 지난 20년간 염화아연과 탄산칼슘의 수용액을 사용하는 방법을 개발하기 위하여 꾸준히 노력하여 왔으나, 염화아연과 탄산칼슘의 반응진행율이약 50%, 조건을 변경하여도 70%를 넘지 못하여 거의 포기 단계로 간주하였으나, 최근 반응조건중, 압력을 2 Kg/㎤ 이상으로 올리고, 온도를 120℃이상으로 하여 반응시켜본 결과, 의외로 반응 진행율이 100%로 되어 산화아연과 염화칼슘을 고순도로 제조할 수 있음을 발견하고, 본 발명을 완성하게 되었다.The present inventors have investigated the amount and quality of zinc oxide required in the industry, and although the demand for zinc oxide is so great that there is a shortage of supply thereof, the above-mentioned known method is industrially advantageous because the production cost of zinc oxide is too high. In addition, it was not suitable to use waste materials such as zinc material and zinc dross. The present inventors have steadily tried to develop a method of using an aqueous solution of zinc chloride and calcium carbonate for the past 20 years to solve the above problems, the reaction progress rate of zinc chloride and calcium carbonate is about 50%, even if the conditions are changed Although not more than 70%, it was regarded as almost abandonment stage. However, in recent reaction conditions, the pressure was raised to 2 Kg / cm 3 or more and the reaction was carried out at a temperature of 120 ° C. or higher. It has been found that calcium chloride can be produced in high purity, and the present invention has been completed.
즉, 본 발명의 목적은 염화아연과 탄산칼슘 수용액을 반응시켜 고순도의 산화아연 및 염화칼슘을 제조하는 방법을 제공하는 것이다.That is, an object of the present invention is to provide a method for producing zinc oxide and calcium chloride of high purity by reacting zinc chloride and calcium carbonate aqueous solution.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
아연 자원으로는 연간 수만톤씩 발생하는 아연 도금 및 다이케스팅 등에서 부생하는 아연재, 아연 드로스로부터 염화아연을 제조하여 사용하거나, 또는 상대적으로 값싼 염화아연을 사용할 수 있다. 또한, 고순도의 탄산칼슘은 시중에서 값싸게 구입할 수 있다.As a zinc resource, zinc chloride produced from zinc plating and die casting, which are produced in tens of thousands of tons per year, and zinc chloride are produced from zinc dross or relatively cheap zinc chloride may be used. In addition, high purity calcium carbonate can be purchased cheaply on the market.
본 발명은 염화아연 수용액을 당량비의 탄산칼슘, 바람직하기로는 입도가 200∼300메쉬의 탄산칼슘을 충분히 교반하고, 이를 120℃이상, 바람직하기로는 130℃ ∼160℃에서, 반응기 내압이 2 kg/㎤이상, 바람직하기로는 3∼5kg/㎤에서 반응시킨다. 이 때의 반응은 하기 화학식으로 나타낼 수 있다.In the present invention, an aqueous zinc chloride solution is sufficiently stirred in an equivalent ratio of calcium carbonate, preferably calcium carbonate having a particle size of 200 to 300 mesh, and the mixture is at least 120 ° C, preferably at 130 ° C to 160 ° C, and the reactor internal pressure is 2 kg /. Reaction is carried out at 3 cm <3> or more, Preferably it is 3-5 kg / cm <3>. The reaction at this time can be represented by the following formula.
ZnCl2+ CaCO3→ ZnCO3·Zn(OH)2+ CaCl2 ZnCl 2 + CaCO 3 → ZnCO 3 · Zn (OH) 2 + CaCl 2
상기 반응을 130℃, 3 kg/㎤의 조건에서 반응시켰을 때, 30∼40분에서 반응 진행이 99% 이상이었다.When the reaction was reacted at 130 ° C. and 3 kg / cm 3, the progress of the reaction was 99% or more in 30 to 40 minutes.
상기 반응에서 중화염으로 사용된 탄산칼슘은 염화칼슘을 생성하므로 소다회를 사용하여 반응시키는 것에 비하여 생성물 자체가 제설용, 냉매 등으로 사용되므로 경제적이고, 폐기물의 발생이 없다. 또한, 상기 반응에서 발생되는 탄산가스의 압력이 유지되므로 ZnCO3·Zn(OH)2중, ZnCO3의 염이 Zn(OH)2의 염에 비해 다량 합성되고, 여과성 및 수세성이 우수한 장점을 갖는다. 상기 반응에서 얻어진 ZnCO3·Zn(OH)2과 염화칼슘을 수세하면, 염화칼슘은 물에 용해되고, ZnCO3·Zn(OH)2은 수불용성으로 남게 된다. 이 조작을 수회 반복하여 ZnCO3·Zn(OH)2염중의 염화칼슘을 씻어내고, 이 세정액을 농축하여 염화칼슘 2수염으로 얻고, ZnCO3·Zn(OH)2는 350∼450℃로 가열하면, 이산화탄소가 분리되어 나가고, 산화아연만 남게 된다.Calcium carbonate used as the neutralizing salt in the reaction produces calcium chloride, so the product itself is used as a snow removal, a refrigerant, etc., compared to the reaction using soda ash, economical, there is no generation of waste. Further, the since the holding pressure of the carbon dioxide gas generated ZnCO 3 · Zn (OH) 2 salts of, ZnCO 3 large quantity synthesized than the salts of Zn (OH) 2, filterability and can washout superior advantages in the reaction Have When ZnCO 3 · Zn (OH) 2 and calcium chloride obtained in the reaction are washed with water, calcium chloride is dissolved in water, and ZnCO 3 · Zn (OH) 2 remains water insoluble. Repeat this operation several times to wash out the calcium chloride in ZnCO 3 · Zn (OH) 2 salt, concentrate this washing solution to get calcium chloride dihydrate, and heat ZnCO 3 · Zn (OH) 2 to 350 ~ 450 ° C. Is separated and only zinc oxide remains.
이하, 실시예를 들어 본 발명을 구체적으로 설명한다. 그러나, 본 발명이 이들 실시예에 의해 제한되는 것은 아니다.Hereinafter, an Example is given and this invention is demonstrated concretely. However, the present invention is not limited by these examples.
실시예 1Example 1
5리터의 스텐레스 압력용기에 1 kg의 염화아연과 물 3 리터를 넣고, 교반하여 용해시킨다. 시약용 탄산칼슘 735 g을 넣고 교반하면서, 반응기 내압을 3 kg/㎠, 온도 120∼130℃를 유지하면서, 40분간 가열하였다. 얻어진 반응생성물을 진공 여과하여 고액 분리하고, 얻어진 ZnCO3·Zn(OH)2을 수세, 건조하고, 약 350℃에서 가열하여 산화아연 590 g을 얻었다. 또한, 수세 용액을 건조하여 염화칼슘 2수염 1000 g을 얻었다.1 kg of zinc chloride and 3 liters of water are added to a 5 liter stainless steel pressure vessel and stirred to dissolve. 735 g of calcium carbonate for reagent was added thereto, followed by stirring for 40 minutes while maintaining the reactor internal pressure at 3 kg / cm 2 and the temperature of 120 to 130 ° C. Filtering the resultant reaction product was vacuum to a solid-liquid separation, and the obtained ZnCO 3 · Zn (OH) 2 washed with water, dried and heated at about 350 ℃ to give the 590 g of zinc oxide. Furthermore, the water washing solution was dried to obtain 1000 g of calcium chloride dihydrate.
얻어진 산화아연과 염화칼슘을 분석한 결과, 각각, 99.8% 및 99%이었다.The obtained zinc oxide and calcium chloride were analyzed and found to be 99.8% and 99%, respectively.
비교예 1Comparative Example 1
실시예 1에서 반응온도를 95∼100℃로 하고, 상압에서 1시간 반응시킨 것을 제외하고는 실시예 1과 동일하게 하였다.In Example 1, the reaction temperature was set to 95 to 100 ° C, and the same procedure as in Example 1 was carried out except that the reaction was carried out at atmospheric pressure for 1 hour.
반응후의 생성물을 분석한 결과, 탄산칼슘의 미반응 물질이 약 18%이었고, 또한, 생성된 ZnCO3·Zn(OH)2중 ZnCO3의 생성율이 Zn(OH)2에 비하여 지나치게 적어 여과하는 것이 대단히 곤란했다.As a result of analyzing the product after the reaction, the unreacted substance of calcium carbonate was about 18%, and the production rate of ZnCO 3 in the produced ZnCO 3 · Zn (OH) 2 was too small compared to Zn (OH) 2 , It was very difficult.
실시예 2Example 2
5리터의 스텐레스 압력용기에 1 kg의 염화아연과 물 3 리터를 넣고, 교반하여 용해시킨다. 탄산칼슘(200∼300메쉬) 735 g을 넣고 교반하면서, 반응기 내압을 5 kg/㎠, 온도 130∼150℃를 유지하면서, 20분간 가열하였다. 얻어진 반응생성물을 진공 여과하여 고액 분리하고, 얻어진 ZnCO3·Zn(OH)2을 수세, 건조하고, 약 400℃에서 가열하여 산화아연 591 g을 얻었다. 또한, 수세 용액을 건조하여 염화칼슘 2수염 1050 g을 얻었다.1 kg of zinc chloride and 3 liters of water are added to a 5 liter stainless steel pressure vessel and stirred to dissolve. 735 g of calcium carbonate (200 to 300 mesh) was added thereto, followed by stirring for 20 minutes while maintaining the reactor internal pressure at 5 kg / cm 2 and the temperature of 130 to 150 ° C. The obtained reaction product was subjected to vacuum filtration to solid-liquid separation. The obtained ZnCO 3 · Zn (OH) 2 was washed with water, dried, and heated at about 400 ° C. to obtain 591 g of zinc oxide. Furthermore, the water washing solution was dried to obtain 1050 g of calcium chloride dihydrate.
얻어진 산화아연과 염화칼슘을 분석한 결과, 각각, 99.7% 및 99%이었다.The obtained zinc oxide and calcium chloride were analyzed and found to be 99.7% and 99%, respectively.
이 실시예로부터 온도와 압력이 증가하면 반응온도가 단축됨을 확인하였다.It was confirmed from this example that the reaction temperature was shortened when the temperature and pressure were increased.
이상에서와 같이 지금까지 전기로 다스트, 아연재, 아연 드로스로부터 염화아연을 주로 회수하여왔으나, 본 발명에 의하여 이러한 염화아연과 탄산칼슘을 사용하여 고가의 산화아연과 염화칼슘을 고순도로, 또한 경제적으로 얻을 수 있을 뿐만 아니라, 폐기물도 발생하지 않는 등의 유용한 발명을 제공한다.As mentioned above, zinc chloride has been mainly recovered from the dust, zinc material, and zinc dross by electricity. However, according to the present invention, zinc zinc and calcium carbonate can be used in high purity and Not only can it be economically obtained, it also provides useful inventions such as no waste.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100401991B1 (en) * | 1998-12-21 | 2003-12-18 | 주식회사 포스코 | METHOD FOR RECYCLING SPENT Zn CLECTROYTE |
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|---|---|---|---|---|
| JPS57118023A (en) * | 1981-01-16 | 1982-07-22 | Shiro Sakuma | Manufacture of zinc oxide using zinc ash as starting material |
| US5876688A (en) * | 1993-08-06 | 1999-03-02 | Elementis Uk Limited | Zinc oxide and a process of making it |
| KR20000040809A (en) * | 1998-12-19 | 2000-07-05 | 이구택 | Preparation method of zinc oxide powder using zn-ni plating waste solution |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57118023A (en) * | 1981-01-16 | 1982-07-22 | Shiro Sakuma | Manufacture of zinc oxide using zinc ash as starting material |
| US5876688A (en) * | 1993-08-06 | 1999-03-02 | Elementis Uk Limited | Zinc oxide and a process of making it |
| KR20000040809A (en) * | 1998-12-19 | 2000-07-05 | 이구택 | Preparation method of zinc oxide powder using zn-ni plating waste solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100401991B1 (en) * | 1998-12-21 | 2003-12-18 | 주식회사 포스코 | METHOD FOR RECYCLING SPENT Zn CLECTROYTE |
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