KR101464182B1 - method for producing aqueous mixed mineral and metallic lead from wastes containing iron, zinc, manganese, magnesium, calcium and cobalt - Google Patents

method for producing aqueous mixed mineral and metallic lead from wastes containing iron, zinc, manganese, magnesium, calcium and cobalt Download PDF

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KR101464182B1
KR101464182B1 KR1020120133928A KR20120133928A KR101464182B1 KR 101464182 B1 KR101464182 B1 KR 101464182B1 KR 1020120133928 A KR1020120133928 A KR 1020120133928A KR 20120133928 A KR20120133928 A KR 20120133928A KR 101464182 B1 KR101464182 B1 KR 101464182B1
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manganese
sulfate
water
iron
reaction
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KR20140066548A (en
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문상우
문기열
이영숙
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문상우
문기열
이영숙
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

본 발명은 제강전기로더스트(E,A,F,D), 페로망간전기로더스트(E,A,F,D), 탄산망간광석분쇄물, 이산화망간광석분쇄물, 철, 망간, 아연, 코발트가 혼합된 폐기물, 철, 아연, 망간, 코발트가 혼합된 수산화물의 필터케이크 폐기물, 알카리망간폐건전지분쇄물, 전기로더스트환원철과 고철분쇄물과 페로망간분쇄물과 폐알카리 망간전지외피분쇄물로부터 수용성 혼합 미네랄과 금속납을 제조하는 방법이다.
또한, 본 발명은 폐기물을 용해시키는 단계에서 발생한 폐수를 외부로 방류하지 않고 재사용하는 것을 포함하는 제조방법이다.The present invention relates to a method for producing a mixture of iron-making electric furnace dust (E, A, F, D), ferromanganese electric furnace dust (E, A, F, D), manganese carbonate ore crushed material, manganese ore crushed material, Filter cake wastes of hydroxide, iron, zinc, manganese and cobalt mixed wastes, alkaline manganese waste batteries crushed water, electric furnace dust reduced iron and scrap iron pulverized water, ferromanganese crushed water and waste alkaline manganese cell water soluble mixed minerals And metal lead.
Further, the present invention is a manufacturing method comprising reusing wastewater generated in the step of dissolving waste, without releasing it to the outside.

Description

철, 아연, 망간, 마그네슘, 칼슘, 코발트가 함유된 폐기물로부터 수용성 혼합 미네랄과 금속납을 제조하는 방법{method for producing aqueous mixed mineral and metallic lead from wastes containing iron, zinc, manganese, magnesium, calcium and cobalt}FIELD OF THE INVENTION The present invention relates to a method for producing water-soluble mixed minerals and metal lead from wastes containing iron, zinc, manganese, magnesium, calcium and cobalt }

본 발명은 제강전기로더스트(E,A,F,D), 페로망간전기로더스트(E,A,F,D), 탄산망간광석분쇄물, 이산화망간광석분쇄물, 철, 망간, 아연, 코발트가 혼합된 폐기물, 철, 아연, 망간, 코발트가 혼합된 수산화물의 필터케이크 폐기물, 알카리망간폐건전지분쇄물, 전기로더스트환원철과 고철분쇄물과 페로망간분쇄물과 폐알카리 망간전지외피분쇄물로부터 수용성 혼합 미네랄과 금속납을 제조하는 방법이다.The present invention relates to a method for producing a mixture of iron-making electric furnace dust (E, A, F, D), ferromanganese electric furnace dust (E, A, F, D), manganese carbonate ore crushed material, manganese ore crushed material, Filter cake wastes of hydroxide, iron, zinc, manganese and cobalt mixed wastes, alkaline manganese waste batteries crushed water, electric furnace dust reduced iron and scrap iron pulverized water, ferromanganese crushed water and waste alkaline manganese cell water soluble mixed minerals And metal lead.

또한, 본 발명은 폐기물을 용해시키는 단계에서 발생한 폐수를 외부로 방류하지 않고 재사용하는 것을 포함하는 제조방법이다.
Further, the present invention is a manufacturing method comprising reusing wastewater generated in the step of dissolving waste, without releasing it to the outside.

본원 출원인은 철강 공장 전기로더스트 또는 페로망간 공장 분진 또는 폐건전지외피분쇄물 또는 이들의 혼합물을 황산수에 투입하여 반응시키고 용액을 여과하고 얻은 액을 가열건조시키는 방법으로 황산제1철, 황산아연, 황산망간, 황산코발트가 혼합형태로 존재하는 혼합미네랄을 만드는 방법을 발명한바 있다.The applicant of the present application has proposed a process for producing iron sulfate, ferrous sulfate, zinc sulfate, zinc sulfide, zinc sulfide, zinc sulfide, zinc sulfide, Manganese sulfate, and cobalt sulfate in a mixed form.

그러나 상기 방법은 선택되는 폐기물의 범위가 제한적이라 황산마그네슘, 황산칼슘, 망초혼합물을 생산할 수 없는 불편이 있었고 반응이 끝난 찌꺼기에 포함된 수산화납을 버리기 때문에 경제성과 생산성이 낮은 불편이 있었으며 반응단계에서 수은, 납, 카드뮴 같은 중금속을 완벽하게 제거하지 못해 제품의 품질이 떨어지고 제품의 산화를 방지하는 장치가 없었으며 반응단계에서 발생한 폐수를 다시 사용하지 않고 외부로 배출함으로 막대한 시설비를 투자하여 폐수처리를 해야하는 불편이 있었다.
However, this method has a disadvantage that it is impossible to produce a mixture of magnesium sulfate, calcium sulfate and calcium sulfate due to limited range of selected wastes and disadvantages of economical efficiency and productivity because it discards lead hydroxide contained in the residue after the reaction, There is no device to prevent the oxidation of products because the heavy metals such as mercury, lead and cadmium can not be removed completely. There is no device to prevent the oxidation of the products and the waste water from the reaction stage is discharged to the outside without being used again. There was an inconvenience to do.

본 발명은 상기와 같은 종래의 방법을 개선하여 반응방법을 새롭게 개발함으로써 혼합 미네랄의 종류가 많이 형성되는 제조방법을 개발하고 반응물의 찌꺼기에 남아 있는 수산화납에서 금속납을 생산하여 경제성을 높이고 반응단계에서 발생되는 폐수를 재활용할 수 있도록 하여 시설비를 줄이며 중금속의 완벽한 제거가 이루어져 품질 좋은 혼합 미네랄이 만들어지고 변질이 없는 제품이 생산되도록 제조방법을 통해 질 좋은 수용성 미네랄 혼합물을 제조할 수 있도록 한 것이다.
The present invention has been made to overcome the above-described problems of the prior art by newly developing a reaction method, thereby developing a manufacturing method in which a large number of kinds of mixed minerals are formed, producing metal lead from the lead hydroxide remaining in the residue of reactants, The waste water generated from the waste water can be recycled to reduce the facility cost, and the heavy metal can be completely removed to produce a high quality mixed mineral and a high-quality water-soluble mineral mixture can be produced through the manufacturing method.

본 발명은 제강공장전기로더스트((E,A,F,D), 페로망간전기로더스트, 알카리망간폐건전지분쇄물, 이산화망간광석분쇄물, 철, 아연, 망간, 코발트 혼합폐기물, 철, 망간, 아연, 코발트혼합수산화물의 필터케이크 폐기물 중에서 선택한 폐기물을 을 황산수에 넣고 3∼4시간 가열교반하여 1차 반응시키고 1차 반응이 종료된 반응물에 페로망간분쇄물, 고철분쇄물, 폐알카리망간전지외피분쇄물, 전기로더스트환원철 중에서 선택한 금속철을 일정량 투입하고 가열교반하면서 2차 반응시켜 반응액이 pH4.0이 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시키면서 페로망간분쇄물을 계량 투입하여 30분간 가열교반하고 이어서 아연말을 계량 투입하여 1시간 가열교반하는 3차 반응을 실시하여 상기 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 pH를 3.5로 조성하여 진공농축하고 스프레이 건조기로 건조한 다음 가열건조기에 넣어 수분함량 1중량% 이하로 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하인 황산제1철과, 황산칼슘, 황산칼륨, 황산아연, 황산망간, 황산마그네슘, 황산코발트, 망초가 혼합형태로 존재하는 수용성의 혼합미네랄을 얻고 또한 1차 2차 반응이 끝난 반응물 찌꺼기에 일정량의 코크스를 계량 투입하고 400∼600℃로 가열하여 금속납을 용출시키는 금속납 제조단계를 포함하는 제조방법을 실시함으로써 경제성과 생산성이 양호하고 미네랄의 품질이 우수한 제품을 제조할 수 있고 동시에 폐기물의 반응단계에서 발생한 폐수를 다시 사용할 수 있게 설비함으로써 폐수가 외부로 배출되지 않도록 하여 폐수처리 설비를 하지 않는 방법으로 수용성 미네랄을 제조하는 방법이다.
The present invention relates to a process for producing iron oxide, which comprises the steps of (E, A, F, D) steelmaking mill electric furnace dust, ferromanganese electric furnace dust, alkali manganese waste battery crusher, manganese dioxide ore, iron, zinc, manganese, cobalt mixed waste, , Cobalt mixed hydroxide wastes were added to sulfuric acid water for 3 ~ 4 hours to perform primary reaction, and the reaction products after the first reaction were added with ferromanganese crushed material, scrap metal, waste alkaline manganese battery sheath A predetermined amount of the metal iron selected from the pulverized material and the electric furnace dust reduced iron is added and the mixture is subjected to a secondary reaction while heating and stirring. When the reaction liquid becomes pH 4.0, the reaction liquid is filtered with a filter and stored in a second reaction tank. And then washed with water to obtain a solution of pH 2. The solution was kept at 40 ° C while the pulverized ferromanganese was weighed and heated for 30 minutes with stirring. The reaction solution was filtered and stored in a vacuum concentrator. The pH of the filtrate was adjusted to 3.5 by addition of acidic water, and the filtrate was concentrated in vacuo, dried with a spray drier, By weight of calcium sulfate, zinc sulfate, manganese sulfate, magnesium sulfate, cobalt sulfate, and manganese in a mixed form in a mixed form of iron sulfate having a heavy metal content of 0.1 ppm or less and calcium sulfate, potassium sulfate, zinc sulfate, manganese sulfate, And a metal lead manufacturing step comprising the step of adding a predetermined amount of coke to the residue of the reactant after the first and second secondary reactions and heating the mixture to 400 to 600 캜 to elute metal lead It is possible to produce a product having good economy and productivity and excellent in mineral quality and at the same time, It not by equipment becomes available again be waste water is discharged to the outside by a method for producing a water-soluble minerals in a way that is the waste water treatment plant.

이와 같이 된 본 발명은 폐기물의 범위를 제강전기로더스트(E,A,F,D), 페로망간전기로더스(E,A,F,D), 알카리망간폐건전지분쇄물, 철, 아연, 망간, 코발트 혼합폐기물, 철, 아연, 망간, 코발트혼합 수산화물의 필터케이크폐기물, 탄산망간광석분쇄물을 이산화망간광석분쇄물, 페로망간분쇄물, 고철분쇄물, 폐알카리망간전지외피분쇄물, 전기로더스트환원철을 포함함으로써 원료 폐기물의 선택 범위가 넓어지고 상기 폐기물을 반응시킴에 있어는 물과 진한 황산을 2:1의 비율로 혼합한 황산수에 산업현장에서 수거한 폐황산수를 8∼9중량% 혼합하여 조성한 황산수에 1차로 제강전기로더스트, 페로망간전기로더스트, 알카리망간폐건전지분쇄물, 철, 아연, 망간, 코발트혼합 폐기물, 철, 아연, 망간, 코발트 혼합수산화물의 필터케이크 폐기물을 선택하여 계량투입하고 150℃의 스팀을 공급하면서 가열교반 반응시키고, 2차로 페로망간분쇄물, 고철분쇄물, 폐알카리망간전지외피분쇄물, 전기로더스트환원철 중에서 선택된 금속철을 계량 투입하여 97∼99℃에서 2∼3시간 가열교반시켜 pH4.0에서 반응물을 여과기로 여과하여 용액을 제2반응조에 저장하고 상기 여과기를 pH1이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척물을 제2반응조에 같이 넣어 pH2의 용액을 만들고 상기 용액을 40℃ 유지시킨 상태에서 페로망간분쇄물을 계량 투입하여 30분간 가열교반함으로써 수은을 고형화시키고 이어서 아연말을 얻어 1시간 가열교반하여 카드뮴과 납을 고형화시켜 반응액을 여과함으로써 중금속을 완전히 제거할 수 있게 되고 아연말의 사용량을 절약할 수 있으며 품질 좋은 미네랄을 생산할 수 있게 되고 진공농축기에 저장하고 상기 용액에 산성수를 가해 용액의 pH를 3.5로 조성함으로써 용액의 산화를 예방할 수 있는 효과를 얻게 된다.In the present invention as described above, the range of the waste can be selected from the group consisting of steelmaking electric dust dusts (E, A, F and D), ferromanganese electric rods (E, A, F and D), alkali manganese waste batteries, iron, Cobalt mixed waste, filter cake waste of iron, zinc, manganese, cobalt mixed hydroxide, manganese oxide ore crushed material, manganese oxide ore crushed material, ferromanganese crushed material, scrap metal crushed material, waste alkaline manganese cell crushed material, electric furnace dust reduced iron The selection range of the raw material wastes is widened. In reacting the wastes, 8 to 9% by weight of the aqueous sulfuric acid collected at the industrial site is mixed with the sulfuric acid water in which water and concentrated sulfuric acid are mixed at a ratio of 2: 1 We first select the filter cake waste from steelmaking electric furnace dust, ferromanganese electric dust dust, alkaline manganese waste battery crushed material, iron, zinc, manganese, cobalt mixed waste, iron, zinc, manganese and cobalt mixed hydroxide And the mixture is heated and stirred while being supplied with steam at 150 ° C. Secondarily, metal iron selected from pulverized ferromanganese crushed material, pulverized material of scrap iron, crushed waste alkaline manganese crushed material and electric furnace dust reduced iron is metered in at 97 to 99 ° C, The reaction solution was filtered with a filter at pH 4.0 by stirring for 3 hours, and the solution was stored in a second reaction tank. The filter was washed with acidic water having a pH of 1 or less, followed by washing with water, The solution was kept at 40 캜, and the ferromanganese pulverized material was metered in. The resulting solution was heated and stirred for 30 minutes to solidify the mercury, followed by heating and agitation for 1 hour to solidify the cadmium and lead, and filtrate the reaction solution It is possible to completely remove the heavy metals, to save the use amount of the end of the year, to produce high quality minerals, Groups are obtained in a number of storage and prevent the oxidation of by applying the acidic composition to the solution the pH of the solution to 3.5, the solution effect.

따라서 최종용액을 진공농축시키고 스프레이 건조기와 가열건조기를 통해 수분을 제거함으로써 제품의 수분함량 1%이하가 되게 건조시킬 수 있으며 목적하는 수용성 혼합미네랄을 얻을 수 있게 되는 장점을 얻는 것이다.Therefore, the final solution is concentrated in a vacuum, and the moisture is removed through a spray drier and a heat dryer to dry the product to a moisture content of 1% or less, thereby obtaining a desired water-soluble mixed mineral.

또 본 발명은 폐기물과 금속철 반응 단계에서 발생한 폐수를 저장조에 모아 반응조에 다시 투입하여 재활용함으로써 폐수가 외부로 배출되지 않아 폐수시설을 할 필요가 없으므로 시설비를 절약할 수 있는 이점이 있어서 경제적으로도 유용한 장점을 가지게 되는 효과가 있고 본 발며은 건조된 혼합미넬에 선택된 미네랄을 계량 보충하여 보다 정밀한 함량을 가지는 미네랄 제품을 제조할 수 있도록 되는 이점이 있다.
In addition, the present invention is advantageous in that the wastewater generated in the reaction step of waste and metal iron is collected in a storage tank and then recycled to the reaction tank so that waste water is not discharged to the outside, There is an advantage that it has a useful advantage, and the present invention has an advantage that a minerals product having a finer content can be produced by metering and replenishing the selected minerals in the dried minerals.

첨부된 도면은 본 발명의 공정도이다.The accompanying drawings are process drawings of the present invention.

본 발명은 제강공장전기로더스트(E,A,F,D), 알카리망간폐건전지분쇄물, 페로망간전기로더스트, 철, 망간, 아연, 코발트 혼합폐기물, 철, 망간, 아연, 코발트혼합수산화물 필터케이크 폐기물, 탄산망간광석분쇄물, 이산화망간광석분쇄물 중에서 선택한 폐기물과 물과 98% 농황산을 2:1의 중량%로 혼합한 것에 산업현장에서 수거한 폐황산수 8∼9중량%를 혼합하여 조성한 황산수(이하 황산수로 표시함)를 준비하여 황산수를 제1반응조(1)에 수용하고 황산수에 제강공장전기로더스트, 알카리망간폐건전지분쇄물, 페로망간전기로더스트, 철, 망간, 아연, 코발트 혼합폐기물, 철, 망간, 아연, 코발트 혼합 수산화물 필터케이크 폐기물, 탄산망간광석분쇄물, 이산화망간광석분쇄물 중에서 선택한 폐기물을 계량 투입하고 스팀관(2)으로 150℃되는 스팀을 가하면서 교반기(6)로 교반하면서 3∼4시간 가열교반하는 1차 반응단계와,The present invention relates to a filter cake of a steelmaking factory electric furnace dust (E, A, F, D), an alkaline manganese waste battery crusher, a ferromanganese electric furnace dust, iron, manganese, zinc, cobalt mixed waste, iron, manganese, zinc, cobalt mixed hydroxide A mixture of waste and water selected from wastes, manganese carbonate ore manganese ore, and manganese dioxide ore and 98% concentrated sulfuric acid in a weight ratio of 2: 1 was mixed with 8 to 9% by weight of waste sulfuric acid collected at the industrial site. (Hereinafter referred to as sulfuric acid water) is prepared, the sulfuric acid water is contained in the first reaction tank 1, and sulfuric acid water is added to the steelmaking factory electric furnace dust, alkali manganese waste battery pulverized material, ferromanganese electric furnace dust, iron, manganese, zinc, Cobalt mixed wastes, iron, manganese, zinc, cobalt mixed hydroxide filter cake wastes, manganese carbonate ore manganese ore manganese ore crushed, and stirred by adding steam at 150 ° C. to the steam pipe (2) A first reaction step in which the mixture is heated and agitated for 3 to 4 hours with stirring with a reactor (6)

1차 반응이 끝난 반응물에 폐알카리망간전지외피분쇄물, 페로망간분쇄물, 고철분쇄물, 전기로더스트환원철 중에서 선택된 금속철을 계량하여 첨가하고 95∼100℃에서 2∼3시간 교반하는 2차 반응단계와,A metal iron selected from pulverized alkaline manganese battery crushed material, ferromanganese crushed material, pulverized material of scrap iron and electric furnace dust reduced iron is weighed and added to the reaction product subjected to the first reaction, and secondary reaction is carried out at 95 to 100 ° C for 2 to 3 hours Step,

2차 반응에서 반응액이 pH4가 되면 반응액을 여과기(3)로 여과하여 용액을 제2반응조(4)에 저장하고 여과기를 pH1이하의 산성수(S1)로 세척하고 이어서 물(W)로 세척하여 발생한 세척물을 제2반응조에 같이 투입하여 pH2되는 용액을 얻고 제2반응조의 용액을 제2반응조에 장치된 히터(H)를 작동시켜 40℃로 가열하면서 페로망간분쇄물(5)을 계량 투입하여 30분간 반응시켜 수은을 고형화시키고 이어서 아연말(5a)을 계량 투입하여 1시간 가열교반하는 3차 반응을 실시하여 수은과 카드뮴과 납을 포함하는 중금속을 치환하여 고형화시키는 3차 반응단계와,When the reaction solution becomes pH 4 in the second reaction, the reaction solution is filtered with a filter 3 to store the solution in the second reaction tank 4, the filter is washed with acidic water (S1) having a pH of 1 or less, The washing solution generated by washing is put into the second reaction tank to obtain a solution having a pH of 2. The solution in the second reaction tank is heated to 40 DEG C by operating the heater (H) equipped in the second reaction tank, The third reaction step in which mercury is solidified by reacting for 30 minutes with weighing, followed by a third reaction in which mercury (5a) is metered in and stirred for 1 hour to solidify by substituting heavy metals including mercury, cadmium and lead Wow,

3차 반응이 끝난 반응액을 여과기(7)로 여과하여 진공농축기(8)에 이동시켜 저장하되 진공농축기에 저장된 용액에 산성수(S2)를 공급하여 용액을 pH3.5로 조정한 다음 수분함량 40∼45중량%가 되게 교반기(6)와 히터(H)를 작동시켜 농축시키고 상기 농축물을 스프레이 건조기(9)에 투입하여 수분함량 4∼5%되게 스프레이 건조시킨 다음 가열건조기(10)에 투입하여 수분함량 1중량%이하가 되게 건조시키는 건조단계를 통해 수용성의 황산제1철, 황산아연, 황산망간, 황산칼슘, 황산코발트와 황산마그네슘, 황산칼륨, 망초, 소금이 혼합된 수용성 혼합 미네랄제품(13)을 제조하는 미네랄 제조단계와,The reaction solution after the third reaction was filtered with a filter 7 and transferred to a vacuum concentrator 8 to store the solution. The solution was adjusted to pH 3.5 by supplying acidic water (S2) to the solution stored in a vacuum concentrator, The concentrate is put into a spray drier 9 to spray-dry the dispersion to a moisture content of 4 to 5%, and then the concentrate is applied to a heat dryer 10 Water soluble mixed minerals mixed with water-soluble ferrous sulfate, zinc sulfate, manganese sulfate, calcium sulfate, cobalt sulfate, magnesium sulfate, potassium sulfate, manganese and salt through a drying step in which the water content is 1 wt% A mineral production step for producing the product (13)

1차 2차 반응단계를 거처 반응물을 여과하고 남은 찌꺼기를 믹서기(14)와 가열기(15)로 구성된 찌꺼기처리장치의 믹서기에 넣고 찌꺼기 총량의 20∼35중량%에 해당하는 코크스(16)를 투입하고 가열기로 옮겨 가열기의 히터(15a)를 작동시켜 400∼600℃로 가열하여 찌꺼기 중에 함유된 수산화납을 금속납으로 용출시키는 금속납(17) 제조단계를 포함하여 이루어지는 제조방법이다.The reactants are filtered through a first secondary reaction step, and the remaining residue is put into a mixer of a residue treatment apparatus composed of a mixer (14) and a heater (15), and a coke (16) corresponding to 20 to 35 wt% And transferring the metal lead to a heater to operate the heater 15a of the heater to heat the metal lead at a temperature of 400 to 600 ° C to elute the lead hydroxide contained in the residue into a metal lead.

그리고 건조처리물을 믹서기(11)에 넣고 선택된 수용성 미네랄에 해당하는 황산동, 황산아연, 황산망간, 황산철, 황산마그네슘, 황산칼슘, 망초, 소금, 셀레늄, 요드중에서 선택한 미네랄류(12)를 필요량으로 계량보충하여 믹싱함으로써 수용성의 황산제1철, 황산아연, 황산망간, 황산칼슘, 황산코발트와 황산마그네슘, 황산칼륨, 망초, 소금이 혼합된 정밀도 높은 수용성 혼합미네랄을 제조하는 것이 포함된다.Then, the dried product is placed in a mixer (11), and a required amount of minerals (12) selected from among the selected water-soluble minerals selected from the group consisting of copper sulfate, zinc sulfate, manganese sulfate, iron sulfate, magnesium sulfate, calcium sulfate, Water mixing mixed minerals mixed with water soluble ferrous sulfate, zinc sulfate, manganese sulfate, calcium sulfate, cobalt sulfate, magnesium sulfate, potassium sulfate, manganese, and salt by mixing in a metering system.

상기에서 제강전기로더스트는 황산수량의 18∼25중량%, 알카리망간폐건전지분쇄물은 황산수량의 3∼24중량%, 철, 아연, 망간, 코발트 혼합폐기물 황산수량의 1∼3중량%, 철, 아연, 망간, 코발트 혼합수산화물 필터케이크 폐기물은 황산수량의 1∼12중량%, 탄산망간광석폐기물은 황산수량의 1∼2중량%, 폐로망간전기로더스트는 황산수량의 2∼3중량%범위로 사용되고In the above, the milling electric furnace dust contains 18 to 25% by weight of sulfuric acid, the alkaline manganese waste battery pulverized material contains 3 to 24% by weight of sulfuric acid, 1 to 3% by weight of iron, zinc, manganese and cobalt mixed waste sulfuric acid, , Zinc, manganese, cobalt mixed hydroxide filter cake waste is 1 ~ 12 wt% of sulfuric acid, manganese carbonate ore waste is 1 ~ 2 wt% of sulfuric acid water, and closed manganese electric furnace dust is 2 ~ 3 wt% Used

2차반응단계에서 투입되는 폐알카리망간전지외피분쇄물은 반응조에 남아 있는 황산수량의 6∼19중량%, 폐로망간분쇄물은 2∼7중량%, 고철분쇄물은 2∼7중량%, 전기로더스트환원철은 7∼13중량%가 투입되는 량으로 계량되어 사용이 되며 The pulverized alkaline manganese battery crush material to be charged in the second reaction step is 6 to 19 wt% of the amount of sulfuric acid remaining in the reaction tank, 2 to 7 wt% of pulverized manganese crushed material, 2 to 7 wt% Dust reduced iron is used in quantities of 7 ~ 13 wt%

3차 반응단계에서 투입되는 페로망간분쇄물을 아연말 사용량의 10∼20중량% 범위로 사용된다.
The ferro-manganese crushed material used in the third reaction step is used in a range of 10 to 20 wt% of the end-use amount.

한편, 본 발명은 1,2차 반응단계에서 발생되는 폐수를 집수조(18)에 모아서 정량공급기(RW)를 통해 제1반응조(1)에 다시 투입하는 장치와 1차 2차 반응단계에서 발생되는 분진과 이물질을 수집하여 집진처리하는 공해처리기(19)를 구성함으로써 폐수가 외부로 배출되지 않아 폐수처리시설을 할 필요가 없어 친환경적인 처리로 안전성 있는 제조가 달성되게 한 구성으로 이루어진다.The present invention also relates to an apparatus for collecting wastewater generated in the first and second reaction stages in a collecting tank 18 and returning the same to the first reaction tank 1 through a quantitative feeder RW, The pollution control unit 19 collects dust and foreign matter and collects the polluted water, thereby eliminating the waste water from being discharged to the outside, thereby eliminating the need for a wastewater treatment facility, thereby achieving safe production through environmentally friendly treatment.

Figure 112012097017517-pat00001

Figure 112012097017517-pat00001

실시예Example 1  One

제강전기로더스트(E,A,F,D)75g, 75g of steel-making electric furnace dust (E, A, F, D)

알카리망간폐건전지 15g, Alkaline manganese dry battery 15g,

철·아연·망간·코발트 산화폐기물 5g, Iron, zinc, manganese, cobalt oxide wastes 5g,

철·아연·망간·코발트 수산화물 필터케이크 폐기물 4g, Iron, zinc, manganese, cobalt hydroxide filter cake waste 4g,

탄산망간광석분쇄물 1g을 황산수400g에 투입하고 98℃로 교반반응 3시간 후에 폐알카리망간전지외피분쇄물 10g을 넣고 2시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액을 pH3.5로 조성하여 건조시킴으로써 산화가 방지되고 중금속이 0.1ppm이하 되는 황산아연 83g, 황산철 66g, 황산망간 24g, 황산마그네슘 6g, 황산칼슘 2g, 황산칼륨 6g, 황산알루미늄 0.6g, 황산코발트 0.2g, 망초(Na2So4) 9g, 수분 3g이 되는 수용성 혼합미네랄 199.8g을 얻었다.
1 g of the manganese carbonate ore crushed product was added to 400 g of sulfuric acid water and stirred at 98 ° C for 3 hours. 10 g of pulverized alkaline manganese battery crushed product was added to the reaction solution for 2 hours. When the pH reached 4, the reaction solution was filtered with a filter to be stored in the second reaction tank The filtrate was washed with acidic water having a pH of not more than 1, washed with water, and the resulting washing water was added to the second reaction tank to obtain a pH 2 solution. The solution was kept at 40 ° C, 2 g of ferromanganese powder was added and stirred for 30 minutes Subsequently, the mixture was heated and stirred for 1 hour, and the reaction solution was filtered and stored in a vacuum concentrator. The solution was adjusted to pH 3.5 by adding acidic water and dried to obtain 83 g of zinc sulfate having an oxidation inhibition of 0.1 ppm or less, iron 66g, 24g of manganese sulfate, magnesium sulfate and 6g, 2g calcium sulphate, potassium sulphate 6g, aluminum sulfate, 0.6g, 0.2g of cobalt sulfate, Glauber's salt (Na 2 So 4) 9g, the water-soluble mixed laminate that moisture 3g To give the 199.8g.

실시예Example 2  2

알카리망간폐건전지분쇄물 20g, 제강전기로더스트 80g을 농황산과 물이 1:2로 혼합되고 폐황산 10∼20%가 혼합된 황산수(이하 황산수로 표시함) 400g(물260g, 황산140g)에 투입하여 98℃로 교반반응 4시간 후에 전기로더스트환원철 5g, 폐알카리망간전지외피분쇄물을 5g 넣고 3시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 79g, 황산망간 19g, 황산철 76g, 황산마그네슘 5g, 황산칼슘 4g, 황산칼륨 6g, 수분 2g, 망초(Na2So4) 7g, 소금1g 되는 수용성 미네랄혼합물 199g을 얻었다.
20 g of crushed alkaline manganese dry battery and 80 g of steelmaking electric dust were mixed with 400 g of water (260 g of water and 140 g of sulfuric acid) mixed with 1: 2 of concentrated sulfuric acid and 10 to 20% of waste sulfuric acid (hereinafter referred to as sulfuric acid water) 5 g of electric furnace dust reduced iron and 5 g of pulverized alkaline manganese battery outer shell were added for 3 hours. After the reaction was completed at pH 4, the reaction solution was filtered with a filter and stored in a second reaction tank. And then washed with water and then rinsed with water to obtain a solution of pH 2, and 2 g of ferromanganese powder was added thereto while maintaining the solution at 40 ° C. The solution was heated and stirred for 30 minutes, then 4 g of phosphoric acid After stirring the mixture for 1 hour, the reaction solution was filtered and stored in a vacuum concentrator. The pH of the solution was adjusted to 3.5 by adding acidic water and dried to prevent oxidation, and zinc sulfate 79 having a heavy metal content of 0.1 ppm or less 19 g of manganese sulfate, 76 g of iron sulfate, 5 g of magnesium sulfate, 4 g of calcium sulfate, 6 g of potassium sulfate, 2 g of water, 7 g of Na 2 So 4 and 1 g of a salt were obtained.

실시예Example 3  3

알카리망간폐건전지분쇄물 20g, 제강전기로더스트 80g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 4시간 후에 페로망간광석분쇄물4g, 전기로더스트환원철5g, 폐알카리망간전지외피분쇄물5g을 넣고 3시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 80g, 황산망간 18g, 황산철 77g, 황산마그네슘 5g, 황산칼슘 4g, 황산칼륨 6g, 수분 2g, 망초(Na2So4) 7g되는 수용성 미네랄혼합물 199g을 얻었다.
20 g of crushed manganese waste batteries and 80 g of steelmaking electric dust were charged into 400 g of sulfuric acid water (including sulfuric acid). After stirring for 4 hours, 4 g of ferromanganese ore powder, 5 g of electric dust reduced iron, 5 g of waste alkaline manganese battery crushed material And the mixture was reacted for 3 hours. When the pH reached 4, the reaction solution was filtered with a filter, and the filter was washed with acidic water having a pH of 1 or less, followed by washing with water, and the resulting washing water was added to the second reaction tank to obtain a pH- 2 g of ferromanganese powder was added to 2 g of ferromanganese powder, and the mixture was heated and stirred for 30 minutes. Subsequently, the mixture was heated and stirred for 1 hour. The reaction mixture was filtered and stored in a vacuum concentrator. The pH of the solution was adjusted to 3.5 And dried by a spray drier dryer and a heat drier to thereby obtain 80 g of zinc sulfate having a heavy metal content of 0.1 ppm or less and 18 g of manganese sulfate, Sancheol 77g, 5g magnesium sulfate, calcium sulfate 4g, potassium persulfate 6g, water 2g, Glauber's salt (Na 2 So 4) to give 7g of a water-soluble mineral mixture 199g is.

실시예Example 4  4

알카리망간폐건전지분쇄물 20g, 제강전기로더스트 80g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 4시간 후에 고철분쇄물4g, 전기로더스트환원철5g, 폐알카리망간전지외피분쇄물5g을 넣고 3시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수에 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 상기 용액을 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 80g, 황산망간 18g, 황산철 77g, 황산마그네슘 5g, 황산칼슘 4g, 황산칼륨 6g, 수분 2g, 망초(Na2So4) 6g, 소금1g되는 수용성 미네랄혼합물 199g을 얻었다.
After 4 hours of stirring at 98 ° C, 4 g of scrap iron, 5 g of electric dust reduced iron and 5 g of pulverized alkaline manganese battery crushed material were added to a 400 g of sulfuric acid water (containing sulfuric acid), 20 g of pulverized alkaline manganese waste battery, The reaction solution was filtered with a filter and stored in a second reaction tank. The filter was washed with acidic water having a pH of 1 or less, followed by washing with water, and then added to the second reaction tank with the resulting washing water to obtain a solution having pH 2 2 g of ferromanganese powder was added to 2 g of ferromanganese powder, and the mixture was heated and stirred for 30 minutes. Subsequently, the mixture was heated and stirred for 1 hour. The reaction mixture was filtered and stored in a vacuum concentrator. The pH of the solution was adjusted to 3.5 80 g of zinc sulfate having a heavy metal content of 0.1 ppm or less and being oxidized by drying through a spray drier and a heat drier, Acid potassium manganese 18g, 77g of ferrous sulfate, magnesium sulfate 5g, calcium sulfate 4g, sulfate 6g, water 2g, Glauber's salt (Na 2 So 4) 6g, salt to obtain a water-soluble mineral mixture 1g 199g is.

실시예Example 5  5

알카리망간폐건전지분쇄물20g, 제강전기로더스트80g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 4시간 후에 전기로더스트환원철 5g, 폐알카리망간전지외피분쇄물 5g을 넣고 3시간 반응 pH4가 되면 반응액을 여과기로 여고하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 상기 용액을 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 80g, 황산망간 18g, 황산철 77g, 황산마그네슘 5g, 황산칼슘 4g, 황산칼 륨6g, 수분 2g, 망초(Na2So4) 7g되는 수용성 미네랄혼합물 199g을 얻었다.
20g of alkaline manganese waste battery pulverized powder and 80g of steelmaking electric dust dust are added to 400g of sulfuric acid water (including sulfuric acid). After 4 hours of stirring at 98 ° C, 5g of electric dust reduced iron and 5g of pulverized alkaline manganese battery crushed material are added. The reaction solution is filtered with a filter and stored in a second reaction tank. The filter is washed with acidic water having a pH of 1 or less, followed by washing with water, and the resulting washing water is put into a second reaction tank to obtain a pH 2 solution. 2 g of ferromanganese powder was added, and the mixture was heated and stirred for 30 minutes. Subsequently, 4 g of phosphoric acid was added and the mixture was heated and stirred for 1 hour. Then, the reaction solution was filtered and stored in a vacuum concentrator, acidic water was added thereto to adjust the pH of the solution to 3.5, 80 g of zinc sulfate having a heavy metal content of 0.1 ppm or less by oxidation, and 18 g of manganese sulfate, iron sulfate , 199 g of a water-soluble mineral mixture in which 5 g of magnesium sulfate, 4 g of calcium sulfate, 6 g of potassium sulfate, 2 g of water and 7 g of manganese (Na 2 So 4 ) were obtained.

실시예Example 6  6

제강전기로더스트로 100g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 4시간 후에 폐알카리망간전지외피분쇄물 5g, 전기로더스트환원철을 10g을 넣고 3시간 교반반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 91g, 황산망간 8g, 황산철 84g, 황산마그네슘 3g, 황산칼륨 5g, 황산칼슘 3g, 망초 5g, 수분 3g, 소금 1g 되는 수용성 미네랄혼합물 203g을 생산하였다.
(100 g) was added to 400 g of sulfuric acid water (including sulfuric acid). After 4 hours of stirring at 98 ° C, 5 g of pulverized alkaline manganese battery crushed material and 10 g of electric dust reduced iron were added and stirred for 3 hours. Was filtered with a filter and stored in a second reaction tank. The filter was washed with acidic water having a pH of 1 or less, followed by washing with water, and the resulting wash water was added to the second reaction tank to obtain a pH 2 solution. Ferromanganese powder was added, and the mixture was heated and stirred for 30 minutes. Subsequently, the mixture was heated and stirred for 1 hour. The reaction solution was filtered and stored in a vacuum concentrator. The pH of the solution was adjusted to 3.5 by addition of acidic water, 91 g of zinc sulfate with a heavy metal content of 0.1 ppm or less by drying through a drier, 8 g of manganese sulfate, 84 g of iron sulfate, 3 g of magnesium sulfate, 3 grams of calcium sulfate, 5 grams of gangue, 3 grams of water, and 1 gram of salt.

실시예Example 7  7

탄산망간광석분쇄물 5g, 알카리망간폐건전지분쇄물 95g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 3시간 후에 전기로더스트환원철 5g, 폐알카리망간전지외피분쇄물 5g, 페로망간광석분쇄물 5g, 고철분쇄물 5g을 넣고 3시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 57g, 황산망간 98g, 황산철 28g, 황산마그네슘 1g, 황산칼슘 1g, 황산칼륨 3g, 망초 3g, 황산코발트 0.1g 되는 수용서 미네랄혼합물 191.1g을 생산하였다.
5 g of manganese carbonate ore powder and 95 g of pulverized alkaline manganese waste batteries were charged into 400 g of sulfuric acid water (including sulfuric acid). After 3 hours of stirring at 98 캜, 5 g of electric furnace dust reduced iron, 5 g of pulverized alkaline manganese battery crushed material, 5 g of pulverized product and 5 g of scrap pulverized product were added and the mixture was reacted for 3 hours. When the pH reached 4, the reaction solution was filtered with a filter and stored in a second reaction tank. The filter was washed with acidic water having a pH of 1 or less, 2 g of ferromanganese powder was added thereto, and the mixture was heated and stirred for 30 minutes. Subsequently, the mixture was heated with stirring for 4 hours and then the reaction solution was filtered and stored in a vacuum concentrator The pH of the solution was adjusted to 3.5 by adding acidic water, and the solution was concentrated and dried through a spray drier and a heat drier to prevent oxidation and to have a heavy metal content of 0.1 ppm or less 57 g of zinc sulfate, 98 g of manganese sulfate, 28 g of iron sulfate, 1 g of magnesium sulfate, 1 g of calcium sulfate, 3 g of potassium sulfate, 3 g of manganese and 0.1 g of cobalt sulfate were produced.

실시예Example 8  8

탄산망간광석분쇄물 5g, 알카리망간폐건전지분쇄물 85g, 철, 아연, 망간, 코발트 혼합된 폐기물 10g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 3시간 후에 전기로더스트환원철 5g, 폐알카리망간전지외피분쇄물 10g을 넣고 3시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 상기 용액을 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 57g, 황산망간 98g, 황산철 28g, 황산마그네슘 1g, 황산칼슘 1g, 황산칼륨 3g, 망초 3g, 황산코발트 0.1g 되는 수용성 미네랄혼합물 191.1g을 생산하였다.
5 g of manganese carbonate ore crushed powder, 85 g of pulverized alkaline manganese waste batteries, and 10 g of mixed waste of iron, zinc, manganese and cobalt into 400 g of sulfuric acid water (including waste sulfuric acid) 10 g of the waste alkaline manganese battery crushed material was added and reacted for 3 hours. When the pH reached 4, the reaction solution was filtered with a filter and stored in a second reaction tank. The filter was washed with acidic water having a pH of not more than 1 and then washed with water, 2 g of ferromanganese powder was added thereto, and the mixture was heated and stirred for 30 minutes. Subsequently, the mixture was heated with stirring for 4 hours and then the reaction solution was filtered and stored in a vacuum concentrator The pH of the solution was adjusted to 3.5 by addition of acidic water, the solution was concentrated and dried through a spray dry dryer and a heat dryer to prevent oxidation and to remove heavy metal content To 0.1ppm or less which 57g of zinc sulfate, manganese sulfate 98g, 28g of ferrous sulfate, magnesium sulfate 1g, 1g calcium sulfate, potassium sulfate 3g, 3g Glauber's salt, water-soluble cobalt sulfate 0.1g 191.1g mineral mixture is produced.

실시예Example 9  9

탄산망간광석분쇄물 5g, 알카리망간폐건전지분쇄물 95g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 3시간 후에 페로망간광석분쇄물 15g을 넣고 3시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기로 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 상기 용액을 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 57g, 황산망간 98g, 황산철 28g, 황산마그네슘 1g, 황산칼슘 1g, 황산칼륨 3g, 망초 3g, 황산코발트 0.1g 되는 수용성 미네랄혼합물 191.1g을 생산하였다.
5 g of manganese carbonate ore pulverized product and 95 g of pulverized alkaline manganese waste battery were charged into 400 g of sulfuric acid water (including sulfuric acid) and stirred at 98 ° C. After 3 hours, 15 g of ferromanganese ore powder was added and the mixture was reacted for 3 hours. Was filtered with a filter and stored in a second reaction tank. The filtrate was washed with acidic water having a pH of not more than 1, washed with water and then washed with water to obtain a pH 2 solution. The solution was maintained at 40 캜 to give 2 g Ferromanganese powder was added, and the mixture was heated and stirred for 30 minutes. Subsequently, the mixture was heated and stirred for 1 hour. The reaction solution was filtered and stored in a vacuum concentrator. 57 g of zinc sulfate having a heavy metal content of 0.1 ppm or less, 98 g of manganese sulfate, 28 g of iron sulfate, 1 g of magnesium sulfate, 1 g of sulfur 1g of calcium, potassium sulfate 3g, 3g Glauber's salt, water-soluble cobalt sulfate 0.1g 191.1g mineral mixture is produced.

실시예Example 10  10

탄산망간광석분쇄물 5g, 알카리망간폐건전지분쇄물 95g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 3시간 후에 전기로더스트환원철 5g, 폐알카리망간전지외피분쇄물 5g, 고철분쇄물 5g을 넣고 3시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고에 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 상기 용액을 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 57g, 황산망간 98g, 황산철 28g, 황산마그네슘 1g, 황산칼슘 1g, 황산칼륨 3g, 망초 3g, 황산코발트 0.1g 되는 수용성 미네랄혼합물 191.1g을 생산하였다.
5 g of manganese carbonate ore powder and 95 g of pulverized alkaline manganese waste battery were charged into 400 g of sulfuric acid water (including sulfuric acid). After 3 hours of stirring at 98 캜, 5 g of electric dust reduced iron, 5 g of pulverized alkaline manganese battery crushed material, The reaction solution was filtered with a filter and stored in a second reaction tank. Then, the filter was washed with acidic water having a pH of 1 or less, followed by washing with water, and the resulting washing water was put in a second reaction tank to obtain a solution having a pH of 2 2 g of ferromanganese powder was added to the solution, and the mixture was heated and stirred for 30 minutes. Subsequently, 4 g of phosphoric acid was added and the mixture was heated and stirred for 1 hour. The reaction solution was filtered and stored in a vacuum concentrator. The pH was adjusted to 3.5 and the solution was concentrated and dried through a spray dry dryer and a heat drier to prevent oxidation and to remove zinc sulfate, which has a heavy metal content of 0.1 ppm or less , 98 g of manganese sulfate, 28 g of iron sulfate, 1 g of magnesium sulfate, 1 g of calcium sulfate, 3 g of potassium sulfate, 3 g of gangue and 0.1 g of cobalt sulfate.

실시예Example 11  11

탄산망간광석분쇄물 5g, 알카리망간폐건전지분쇄물 95g을 황산수(폐황산포함)400g에 투입 98℃로 교반반응 3시간 후에 전기로더스트환원철 15g을 넣고 3시간 반응하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 Ph를 3.5로 조성하여 상기 용액을 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 반응액을 여과 수세하여 용액을 얻고 상기 용액에 아연분말 4.5g을 투입 교반시간 50분(온도43℃) 치환반응 후 여과하여 얻은 용액을 진공농축하고 산성수를 가해 pH3.5로 조성한 후 스프레이 드라이기와 가열건조기로 건조하여 황산아연 57g, 황산망간 98g, 황산철 28g, 황산마그네슘 1g, 황산칼슘 1g, 황산칼륨 3g, 망초 3g, 황산코발트 0.1g 되는 수용성 미네랄혼합물 191.1g을 생산하였다.
5 g of crushed manganese carbonate ore and 95 g of pulverized alkaline manganese waste batteries were charged into 400 g of sulfuric acid water (including sulfuric acid) at 98 ° C. After 3 hours, 15 g of electric dust reduced iron was charged and reacted for 3 hours. And the filtrate was washed with acidic water having a pH of not more than 1 and then washed with water to obtain a solution having a pH of 2 by adding the resulting washing water into a second reaction tank and maintaining the solution at 40 캜 to obtain 2 g of ferromanganese The reaction solution was filtered and stored in a vacuum concentrator. Acidic water was added to the solution to adjust the pH of the solution to 3.5. The solution was concentrated, and the residue was dissolved in a spray-dried drier The reaction solution, which is prevented from oxidation by being dried through a heat drier and has a heavy metal content of 0.1 ppm or less, is washed with water to obtain a solution, The reaction mixture was filtered through a filtration apparatus. The filtrate was concentrated in vacuo. The filtrate was acidified to pH 3.5 and then dried with a spray dryer and a heat drier to obtain 57 g of zinc sulfate, 98 g of manganese sulfate, 28 g of iron sulfate, 1 g of magnesium sulfate, 1 g of calcium sulfate, 3 g of potassium sulfate, 3 g of manganese and 0.1 g of cobalt sulfate was produced.

실시예Example 12  12

알카리망간폐건전지분쇄물 50g, 철, 아연, 망간, 코발트혼합수산화물의 필터케이크폐기물 45g을 98℃ 황산수 400g에 넣고 교반 4시간 반응 후 폐알카리망간전지외피분쇄물 5g, 페로망간광석분쇄물 2g, 고철분쇄물 3g, 전기로더스트환원철 5g을 투입 3시간 교반하여 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 진공농축기에 저장하고 산성수를 가해 용액의 pH를 3.5로 조성하여 상기 용액을 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 58g, 황산망간 96g, 황산철 29g, 황산마그네슘 2g, 황산칼슘 2g, 황산칼륨 2g, 망초 3g, 황산코발트 0.2g, 수분 2.5g되는 수용성 미네랄혼합물 194.7g을 생산하였다.
Alkali manganese waste batteries 50g of pulverized water, 45g of filter cake waste of mixed iron, zinc, manganese and cobalt hydroxide were placed in 400g of 98 ℃ sulfuric acid, and after 4 hours of stirring, 5g of pulverized alkaline manganese battery crushed material, 2g of ferromanganese ore crushed material , 3 g of scrap metal pulp, and 5 g of electric furnace dust reduced iron were added and stirred for 3 hours. When the pH reached 4, the reaction solution was filtered with a filter and stored in a second reaction tank. The filter was washed with acidic water having a pH of 1 or less, 2 g of ferromanganese powder was added thereto, and the mixture was heated and stirred for 30 minutes. Subsequently, 4 g of phosphoric acid was added to the solution and the mixture was heated and stirred for 1 hour. Then, the reaction solution was filtered and concentrated in a vacuum concentrator The pH of the solution was adjusted to 3.5 by adding acidic water and the solution was concentrated and dried through a spray-dry dryer and a heat-dryer to prevent oxidation 58 g of zinc sulfate having a high metal content of 0.1 ppm or less, 96 g of manganese sulfate, 29 g of iron sulfate, 2 g of magnesium sulfate, 2 g of calcium sulfate, 2 g of potassium sulfate, 3 g of cobalt sulfate, 0.2 g of cobalt sulfate, Respectively.

실시예Example 13  13

페로망간전기로더스트 15g, 제강전기로더스트 75g, 폐알카리망간폐건전지분쇄물 10g을 황산수(폐황산포함)400g에 투입하여 98℃ 4시간 교반 반응 후 폐알카리망간전지외피분쇄물 5g, 페로망간분쇄물 5g, 제강전기로더스트환원철 5g을 투입 3시간 교반시켜 pH4가 되면 반응액을 여과기로 여과하여 제2반응조에 저장하고 상기 여과기를 pH1 이하의 산성수로 세척하고 이어서 물로 세척하여 발생한 세척수를 제2반응조에 같이 넣어 pH2의 용액을 얻고 상기 용액을 40℃로 유지시켜 2g의 페로망간분말을 넣어 30분간 가열교반하고 이어서 아연말 4g 넣어 1시간 가열교반한 다음 반응액을 여과하여 용액을 얻고 상기 용액에 산성수를 가하여 pH3.5로 만들어 농축하고 스프레이 드라이 건조기와 가열건조기를 통해 건조시킴으로써 산화가 방지되고 중금속 함량이 0.1ppm이하 되는 황산아연 70g, 황산망간 50g, 황산철 60g, 황산마그네슘 6g, 황산칼슘 3g, 황산칼륨 4g, 망초 5g, 소금 2g되는 수용성 미네랄혼합물 200g을 생산하였다.
15 g of ferro-manganese electric furnace dust, 75 g of steelmaking electric furnace dust, 10 g of pulverized alkaline manganese waste batteries were charged into 400 g of sulfuric acid water (including sulfuric acid), and the mixture was stirred at 98 ° C for 4 hours. Then, 5 g of waste alkaline manganese battery crushed material, 5 g of water and 5 g of dredged steel dust reduced iron were charged and stirred for 3 hours. When pH became 4, the reaction solution was filtered with a filter and stored in a second reaction tank. The filter was washed with acidic water having a pH of 1 or less, followed by washing with water, 2 g of ferromanganese powder was added thereto and the mixture was heated and stirred for 30 minutes. Subsequently, 4 g of phosphoric acid was added thereto and stirred for 1 hour. The reaction solution was filtered to obtain a solution, and the solution Acidic water was added to the mixture to adjust the pH to 3.5, and the mixture was concentrated to dryness through a spray dry dryer and a heat drier to prevent oxidation and to have a heavy metal content of 0.1 ppm or less Was produced zinc sulfate 70g, 50g of manganese sulfate, iron sulfate 60g, 6g of magnesium sulfate, calcium sulfate, 3g, 4g potassium sulfate, Glauber's salt 5g, water-soluble mineral salt mixture 2g 200g.

금속납제조방법 실시예Metal lead manufacturing method Example

① 수분이 포함된 1,2차 반응물 찌꺼기 80g에 코크스분쇄물 25g을 혼합하고 425∼550℃로 가열하여 금속납 11g 생산함.(1) First and second reactants containing water are mixed with 25 g of crushed coke to 80 g of residue, and heated to 425 to 550 ° C to produce 11 g of metal lead.

② 수분이 포함된 1,2차 반응물 찌꺼기 75g에 코크스 20g을 혼합하고 420∼500℃로 가열하여 금속납 9.5g 생산함.② First and second reactants containing water, 20g of coke is mixed with 75g of residue, heated to 420 ~ 500 ℃ to produce metal lead 9.5g.

③ 1,2차 반응물 찌꺼기 건조물 40g에 코크스 15g을 혼합하고 415∼500℃로 가열하여 금속납 9.8g 생산함.
③ 1st and 2nd reactants 15g of coke is mixed with 40g of dried residue and heated to 415 ~ 500 ℃ to produce 9.8g of lead metal.

1 : 제1반응조 2 : 스팀관
3 : 여과 기 4 : 제2반응조
5 : 페로망간분쇄물 5a : 아연말
6 : 교반기 7 : 여과기
8 : 진공농축기 9 : 건조기
10 : 가열건조기 11 : 믹서기
12 : 미네랄류 13 : 제품
14 : 믹서기 15 : 가열기
15a : 가열기의 히터 16 : 코크스
17 : 금속납 18 : 집수조
19 : 공해처리기 H : 히터
S1,S2 : 산성수 1: first reaction tank 2: steam tube
3: Filter 4: Second reaction tank
5: Ferromanganese ground product 5a:
6: Stirrer 7: Filter
8: Vacuum concentrator 9: Dryer
10: Heat dryer 11: Mixer
12: Minerals 13: Products
14: Mixer 15: Heater
15a: Heater heater 16: Coke
17: metal lead 18: water collecting tank
19: Air pollution processor H: Heater
S1, S2: acidic water

Claims (5)

제강공장전기로더스트(E,A,F,D), 알카리망간폐건전지분쇄물, 페로망간전기로더스트, 철, 망간, 아연, 코발트 혼합폐기물, 철, 망간, 아연, 코발트혼합수산화물 필터케이크 폐기물, 탄산망간광석분쇄물, 이산화망간광석분쇄물 중에서 선택한 폐기물준비단계와,
물과 순도98% 농황산을 2:1의 중량비로 혼합한 것에 산업현장에서 수거한 폐황산수 8∼9중량%를 혼합하여 조성하는 황산수(이하 황산수로 표시함)를 준비단계와,
황산수를 제1반응조(1)에 수용하고 황산수에 제강공장전기로더스트, 알카리망간폐건전지분쇄물, 페로망간전기로더스트, 철, 망간, 아연, 코발트 혼합폐기물, 철, 망간, 아연, 코발트 혼합 수산화물 필터케이크 폐기물, 탄산망간광석분쇄물, 이산화망간광석분쇄물 중에서 선택한 폐기물을 일정량 투입한 후, 스팀관(2)으로 150℃되는 스팀을 가하면서 교반기(6)로 작동시키면서 3∼4시간 가열교반하는 1차 반응단계와,
1차 반응이 끝난 반응물에 폐알카리망간전지외피분쇄물, 페로망간분쇄물, 고철분쇄물, 전기로더스트환원철 중에서 선택된 금속철을 일정량 첨가하고 95∼100℃에서 2∼3시간 교반하는 2차 반응단계와,
2차 반응에서 반응액이 pH4가 되면 반응액을 여과기(3)로 여과하여 여과된 용액을 제2반응조(4)에 저장하고 여과기를 pH1이하의 산성수(S1)로 세척하고 이어서 물(W)로 세척하여 발생한 세척물을 제2반응조에 같이 투입하여 pH2되는 용액을 얻고 제2반응조의 용액을 제2반응조에 장치된 히터(H)를 작동시켜 40℃로 가열하면서 페로망간분쇄물(5)을 투입하여 30분간 반응시켜 수은을 고형화시키고 이어서 아연말(5a)을 투입하여 1시간 가열교반하는 3차 반응을 실시하여 수은과 카드뮴과 납을 포함하는 중금속을 치환하여 고형화시키는 3차 반응단계와,
3차 반응이 끝난 반응액을 여과기(7)로 여과하여 진공농축기(8)에 이동시켜 저장하되 진공농축기에 저장된 용액에 산성수(S2)를 공급하여 용액을 pH3.5로 조정한 다음 수분함량 40∼45중량%가 되게 교반기(6)와 히터(H)를 작동시켜 농축시키고 농축물을 스프레이 건조기(9)에 투입하여 수분함량 4∼5중량%되게 스프레이 건조시킨 다음 가열건조기(10)에 투입하여 수분함량 1중량%이하가 되게 건조시키는 건조단계를 통해 수용성의 황산제1철, 황산아연, 황산망간, 황산칼슘, 황산코발트와 황산마그네슘, 황산칼륨, 망초, 소금이 혼합된 수용성 혼합 미네랄제품(13)을 제조하는 미네랄 제조단계와,
1차 2차 반응단계를 거처 반응물을 여과하고 남은 찌꺼기를 믹서기(14)와 가열기(15)로 구성된 찌꺼기처리장치의 믹서기에 넣고 찌꺼기 총량의 20∼35중량%에 해당하는 코크스(16)를 투입하고 가열기로 옮겨 가열기의 히터(15a)를 작동시켜 400∼600℃로 가열하여 찌꺼기 중에 함유된 수산화납을 금속납으로 용출시키는 금속납(17) 제조단계를 포함하여 이루어지는 철, 아연, 망간, 마그네슘, 칼슘, 코발트가 함유된 폐기물로부터 수용성 혼합 미네랄과 금속납을 제조하는 방법
Iron, manganese, zinc, cobalt mixed wastes, iron, manganese, zinc, cobalt mixed hydroxide filter cake wastes, carbonated waste, iron oxide manganese electric furnace dust, A manganese ore crushing product, a manganese ore crushing product,
Sulfuric acid water (hereinafter referred to as sulfuric acid water) constituted by mixing 8 to 9% by weight of waste sulfuric acid collected at the industrial site with water and 98% pure sulfuric acid at a weight ratio of 2: 1 was prepared,
The sulfuric acid water is contained in the first reaction tank 1 and the sulfuric acid water is mixed with the steelmaking electric furnace dust, the alkali manganese waste battery crushed material, the ferromanganese electric furnace dust, iron, manganese, zinc, cobalt mixed waste, iron, manganese, zinc, Hydroxide filter cake wastes, manganese carbonate ore manganese ore, and manganese dioxide ore, and then steamed at 150 ° C with a steam tube (2) while being operated with a stirrer (6) And a second reaction step
A second reaction step in which a predetermined amount of metal iron selected from pulverized alkaline manganese battery crushed material, ferromanganese crushed material, pulverized material of scrap iron and electric furnace dust reduced iron is added to the reactant after the first reaction and the mixture is stirred at 95 to 100 ° C for 2 to 3 hours Wow,
When the reaction solution becomes pH 4 in the second reaction, the reaction solution is filtered with a filter (3), the filtered solution is stored in a second reaction tank (4), the filter is washed with acidic water (S1) ), And the resulting washed product was put into a second reaction tank to obtain a solution having a pH of 2. The solution in the second reaction tank was heated to 40 ° C by operating a heater (H) equipped in the second reaction tank, ) Was added to the reaction mixture for 30 minutes to solidify the mercury. Subsequently, the reaction mixture was heated and stirred for 1 hour to add mercury to the mercury. The mercury, cadmium and lead heavy metals were substituted for the third step Wow,
The reaction solution after the third reaction was filtered with a filter 7 and transferred to a vacuum concentrator 8 to store the solution. The solution was adjusted to pH 3.5 by supplying acidic water (S2) to the solution stored in a vacuum concentrator, The mixture was concentrated by operating the stirrer 6 and the heater H to a concentration of 40 to 45 wt% and the concentrate was introduced into a spray drier 9 to spray-dry the dispersion to a moisture content of 4 to 5 wt% Water soluble mixed minerals mixed with water-soluble ferrous sulfate, zinc sulfate, manganese sulfate, calcium sulfate, cobalt sulfate, magnesium sulfate, potassium sulfate, manganese and salt through a drying step in which the water content is 1 wt% A mineral production step for producing the product (13)
The reactants are filtered through a first secondary reaction step, and the remaining residue is put into a mixer of a residue treatment apparatus composed of a mixer (14) and a heater (15), and a coke (16) corresponding to 20 to 35 wt% And a metal lead (17) which is transferred to a heater and heated by operating a heater (15a) of a heater to be heated to 400 to 600 DEG C to lead out the lead hydroxide contained in the residue to a metal lead, , A method for producing water-soluble mixed minerals and metal lead from wastes containing calcium and cobalt
청구항 제1항에서 ,
건조처리물을 믹서기(11)에 넣고 선택된 수용성 미네랄에 해당하는 황산동, 황산아연, 황산망간, 황산철, 황산마그네슘, 황산칼슘, 망초, 소금, 셀레늄, 요드중에서 선택한 미네랄류(12)를 필요량 보충하여 믹싱함으로써 수용성의 황산제1철, 황산아연, 황산망간, 황산칼슘, 황산코발트와 황산마그네슘, 황산칼륨, 망초, 소금이 혼합된 수용성 혼합미네랄을 제조하는 것이 포함되는 철, 아연, 망간, 마그네슘, 칼슘, 코발트가 함유된 폐기물로부터 수용성 혼합 미네랄과 금속납을 제조하는 방법.
The method according to claim 1,
The dried product is placed in a mixer 11 and supplemented with a required amount of mineral 12 selected from among the selected water-soluble minerals selected from among copper sulfate, zinc sulfate, manganese sulfate, iron sulfate, magnesium sulfate, calcium sulfate, The mixture is mixed to produce a water-soluble mixed mineral containing water-soluble ferrous sulfate, zinc sulfate, manganese sulfate, calcium sulfate, cobalt sulfate and magnesium sulfate, potassium sulfate, A method for producing water-soluble mixed minerals and metal lead from wastes containing calcium and cobalt.
청구항 제1항에서,
1차 반응단계에서 투입되는 첨가물은 황산수량에 대하여 제강전기로더스트 18∼25중량%, 알카리망간폐건전지분쇄물은 3∼24중량%, 철, 아연, 망간, 코발트 혼합폐기물 1∼3중량%, 철, 아연, 망간, 코발트 혼합수산화물 필터케이크 폐기물은 1∼12중량%, 탄산망간광석폐기물은 1∼2중량%, 폐로망간전기로더스트는 2∼3중량% 범위로 투입하는 것을 특징으로 하는 철, 아연, 망간, 마그네슘, 칼슘, 코발트가 함유된 폐기물로부터 수용성 혼합 미네랄과 금속납을 제조하는 방법.
The method according to claim 1,
In the first reaction step, the additive to be added in the first reaction step is 18 ~ 25 wt% of steel dust, 14 ~ 24 wt% of alkaline manganese waste battery pulverized product, 1 ~ 3 wt% of iron, zinc, manganese, cobalt mixed waste, Wherein the iron, zinc, manganese, cobalt mixed hydroxide filter cake waste is added in an amount of 1 to 12 wt%, the manganese carbonate ore waste is 1 to 2 wt%, and the closed manganese electric furnace dust is in an amount of 2 to 3 wt% A method for producing water-soluble mixed minerals and metal lead from wastes containing zinc, manganese, magnesium, calcium, and cobalt.
청구항 1항에서,
2차반응단계에서 투입되는 첨가물은 남아 있는 황산수량에 대하여 폐알카리망간전지외피분쇄물은 6∼19중량%, 폐로망간분쇄물은 2∼7중량%, 고철분쇄물은 2∼7중량%, 전기로더스트환원철은 7∼13중량% 범위로 투입되고
3차 반응단계에서 투입되는 페로망간분쇄물은 아연말 사용량의 10∼20중량% 범위로 투입하는 것을 특징으로 하는 철, 아연, 망간, 마그네슘, 칼슘, 코발트가 함유된 폐기물로부터 수용성 혼합 미네랄과 금속납을 제조하는 방법.
The method of claim 1,
The additive added in the second reaction step is 6 to 19 wt% of pulverized alkaline manganese battery crushed material, 2 to 7 wt% of pulverized manganese crushed material, 2 to 7 wt% of pulverized scrap material, The electric furnace dust reduced iron is charged in the range of 7 to 13 wt%
Wherein the ferromanganese crushed in the third reaction step is added in an amount ranging from 10 to 20% by weight based on the amount used in the end of the end of the year. The ferrous manganese crushed material is mixed with water-soluble mixed minerals and metals from wastes containing iron, zinc, manganese, magnesium, calcium and cobalt. ≪ / RTI >
청구항 1항에서,
1,2차 반응단계에서 발생되는 폐수는 집수조(18)에 모아서 정량공급기(RW)를 통해 제1반응조(1)에 다시 투입하는 장치와, 1차 2차 반응단계에서 발생되는 분진과 이물질을 수집하여 집진처리하는 공해처리기(19)를 더 구성함으로써 폐수가 외부로 배출되지 않아 폐수처리시설을 할 필요가 없어 친환경적인 처리로 안전성 있는 제조가 달성되게 하는 구성의 철, 아연, 망간, 마그네슘, 칼슘, 코발트가 함유된 폐기물로부터 수용성 혼합 미네랄과 금속납을 제조하는 방법.
The method of claim 1,
The wastewater generated in the first and second reaction stages is collected in the water collecting tank 18 and is supplied to the first reaction tank 1 through the quantitative feeder RW. Zinc, manganese, magnesium and the like, which are constituted so that the wastewater is not discharged to the outside and there is no need for a wastewater treatment facility so that safe production can be achieved through environmentally friendly treatment, A method for producing water-soluble mixed minerals and metal lead from wastes containing calcium and cobalt.
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