KR100355155B1 - Method for isolating and recovering of iron and nickel - Google Patents
Method for isolating and recovering of iron and nickel Download PDFInfo
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- KR100355155B1 KR100355155B1 KR1019990058662A KR19990058662A KR100355155B1 KR 100355155 B1 KR100355155 B1 KR 100355155B1 KR 1019990058662 A KR1019990058662 A KR 1019990058662A KR 19990058662 A KR19990058662 A KR 19990058662A KR 100355155 B1 KR100355155 B1 KR 100355155B1
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
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Abstract
본 발명은 철 및 니켈을 포함하는 슬러지, 합금계 주괴 등을 염산 수용액 또는 혼산 수용액에 용해시킨 다음 용매 추출법의 적용에 의해 수용액 중의 철 이온 및 니켈 이온을 각각 고순도로 분리, 회수하는 방법에 관한 것이다.The present invention relates to a method of dissolving iron and nickel ingots and alloy ingots in an aqueous hydrochloric acid solution or a mixed acid solution and then separating and recovering the iron and nickel ions in the aqueous solution with high purity, respectively, by applying a solvent extraction method. .
본 발명은 염화철 및 염화니켈 혼합물을 염산 또는 염산 함량이 70몰% 이상이고 잔액으로서 질산 또는 황산을 혼합한 혼산에 용해시켜 철 및 니켈 염을 20∼60중량% 함유하는 혼산 수용액을 제조하는 단계, 상기 제조된 혼산 수용액에 염소(Cl2) 기체를 불어 넣어 상기 혼산 수용액 중의 2가 철 이온을 3가 철 이온으로 산화시키는 단계, 상기 산화 처리된 혼산 수용액에 탄소수 5∼20의 알코올을 체적비 5.0:1 ∼1.0:1로 첨가하여 상기 3가 철 이온의 염을 추출하는 단계 및 상기 3가 철 이온의 염을 추출한 알코올에 물을 체적비 3.0:1∼0.5:1로 첨가하여 상기 3가 철 이온의 염을 역추출하는 단계로 이루어진다.The present invention is to prepare a mixed acid aqueous solution containing 20 to 60% by weight of iron and nickel salts by dissolving a mixture of iron chloride and nickel chloride in a hydrochloric acid or hydrochloric acid content of more than 70 mol% and mixed with nitric acid or sulfuric acid as a balance, Chlorine (Cl 2 ) gas is blown into the prepared mixed acid solution to oxidize divalent iron ions in the mixed acid solution to trivalent iron ions, and an alcohol having 5 to 20 carbon atoms is added to the mixed acid solution. Extracting the salt of the trivalent iron ions by adding 1 to 1.0: 1, and adding water to the alcohol from which the salt of the trivalent iron ions are extracted in a volume ratio of 3.0: 1 to 0.5: 1 Back extraction of the salt.
본 발명은 철 및 니켈의 분리, 회수 공정이 단순하고 폐수 처리 비용도 훨씬 적게 드는 경제적인 방법이다.The present invention is an economical method that simplifies the separation and recovery of iron and nickel and costs much less wastewater treatment.
Description
본 발명은 철 및 니켈을 포함하는 분말, 매트, 산성 수용액, 슬러지, 합금계 주괴 등을 염산 수용액 또는 혼산 수용액에 용해시킨 다음 용매 추출법의 적용에 의해 수용액 중의 철 이온 및 니켈 이온을 각각 고순도로 분리, 회수하는 방법에 관한 것이다.The present invention dissolves iron and nickel ions in aqueous solution by dissolving powders, mats, acidic aqueous solutions, sludges, alloy ingots, etc., containing iron and nickel in aqueous hydrochloric acid or mixed acid, and then applying solvent extraction. It is about a method of collecting.
일반적으로 염화물 수용액 내에 함유되어 있는 철 및 니켈 등의 금속 이온을 분리, 회수하는 방법으로서는 pH 조정에 의한 방법, 용매 추출에 의한 방법 등이 있다.Generally, as a method of separating and recovering metal ions such as iron and nickel contained in an aqueous chloride solution, there is a method by pH adjustment, a method by solvent extraction, and the like.
상기 전자의 방법은 염화물 수용액 내에 알칼리 용액을 첨가하여 용액의 pH를 4∼5로 조정하여 용액 내의 3가의 철을 수산화철로 침전, 분리하는 방식이다. 이 방식은 수산화철의 침전시 니켈 염화물도 일부 수산화철에응집되어 침전함에 따라 고순도의 수산화철을 제조하기 어렵다는 단점이 있다.In the former method, an alkali solution is added to an aqueous chloride solution to adjust the pH of the solution to 4 to 5 to precipitate and separate trivalent iron in the solution with iron hydroxide. This method has a disadvantage in that it is difficult to produce high-purity iron hydroxide as nickel chloride is also agglomerated with some iron hydroxide during precipitation of iron hydroxide.
한편, 상기 후자의 방법은 상호 혼합되지 않는 2종의 용매가 접촉할 때 특정 용질이 양쪽의 상에 녹아 평형 상태가 되는 현상을 이용한 것으로, 특정 용질의 분리, 회수율이 우수한 방법이다. 이 방식은 추출 용매가 고가이고, 이것이 수용액에 일부 용해됨으로써 폐수 처리시 비용이 많이 든다는 단점이 있다.On the other hand, the latter method utilizes a phenomenon in which a specific solute melts in both phases and becomes in an equilibrium state when two solvents which are not mixed with each other come into contact with each other, and are excellent in separation and recovery of the specific solute. This method is disadvantageous in that the extraction solvent is expensive, and it is expensive in treating wastewater by dissolving it in an aqueous solution.
본 발명은 철 이온 및 니켈 이온의 분리, 회수 방법으로서 공정이 단순하면서 고순도로 분리할 수 있으며 폐수 처리 비용이 적게 드는 방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a method for separating and recovering iron ions and nickel ions, in which the process is simple and can be separated with high purity and the waste water treatment cost is low.
도 1은 본 발명의 실시예에 따른 용매 추출 장치의 개략도를 도시한 것이다.1 shows a schematic diagram of a solvent extraction apparatus according to an embodiment of the present invention.
상기 목적을 달성하기 위하여 본 발명은 염화철 및 염화니켈 혼합물을 염산 또는 염산 함량이 70몰% 이상이고 잔액으로서 질산 또는 황산을 혼합한 혼산에 용해시켜 철 및 니켈 염을 20∼60중량% 함유하는 혼산 수용액을 제조하는 단계, 상기 제조된 혼산 수용액에 염소(Cl2) 기체를 불어 넣어 상기 혼산 수용액 중의 2가 철 이온을 3가 철 이온으로 산화시키는 단계, 상기 산화 처리된 혼산 수용액에 탄소수 5∼20의 알코올을 체적비 5.0:1∼1.0:1로 첨가하여 상기 3가 철 이온의 염을 추출하는 단계 및 상기 3가 철 이온의 염을 추출한 알코올에 물을 체적비 3.0:1∼0.5:1로 첨가하여 상기 3가 철 이온의 염을 역추출하는 단계로 이루어진다.In order to achieve the above object, the present invention is a mixed acid containing 20 to 60% by weight of iron and nickel salts by dissolving a mixture of iron chloride and nickel chloride in a mixed acid of hydrochloric acid or hydrochloric acid content of 70 mol% or more and nitric acid or sulfuric acid as a balance. Preparing an aqueous solution, oxidizing divalent iron ions in the mixed acid solution to trivalent iron ions by blowing chlorine (Cl 2 ) gas into the prepared mixed acid solution, and having 5 to 20 carbon atoms in the mixed acid solution. Adding alcohol in a volume ratio of 5.0: 1 to 1.0: 1 to extract the salt of trivalent iron ions, and adding water to the alcohol from which the salt of trivalent iron ions were extracted in a volume ratio of 3.0: 1 to 0.5: 1. Back extracting the salt of the trivalent iron ion.
또한, 상기 목적을 달성하기 위하여 본 발명은 철-니켈 합금계 주괴를 염산과 질산의 몰비가 2.5:1∼4.5:1인 혼산에 용해시켜 철 및 니켈 염을 20∼60중량% 함유하는 혼산 수용액을 제조하는 단계, 상기 제조된 혼산 수용액에 염소(Cl2) 기체를 불어 넣어 상기 혼산 수용액 중의 2가 철 이온을 3가 철 이온으로 산화시키는 단계, 상기 산화 처리된 혼산 수용액에 탄소수 5∼20의 알코올을 체적비 5.0:1∼1.0:1로 첨가하여 상기 3가 철 이온의 염을 추출하는 단계 및 상기 3가 철 이온의 염을 추출한 알코올에 물을 체적비 3.0:1∼0.5:1로 첨가하여 상기 3가 철 이온의 염을 역추출하는 단계로 이루어진다.In addition, in order to achieve the above object, the present invention is a mixed acid aqueous solution containing 20 to 60% by weight of iron and nickel salts by dissolving the iron-nickel alloy ingot in a mixed acid having a molar ratio of hydrochloric acid and nitric acid of 2.5: 1 to 4.5: 1. Step of preparing, blowing chlorine (Cl 2 ) gas in the prepared mixed acid solution to oxidize the divalent iron ions in the mixed acid solution to trivalent iron ions, the carbonic acid solution of 5 to 20 Adding an alcohol in a volume ratio of 5.0: 1 to 1.0: 1 to extract the salt of the trivalent iron ions, and adding water in a volume ratio of 3.0: 1 to 0.5: 1 to the alcohol from which the salt of the trivalent iron ions were extracted. Back extracting the salt of trivalent iron ions.
본 발명 중 제 1 발명은 망간, 구리, 알루미늄, 아연, 규소, 인, 칼슘, 나트륨 등의 불순물이 극미량 함유된 철 및 니켈 염화물을 염산 또는 혼산에 용해시킨 후, 염산 또는 혼산 수용액 중의 2가 철 이온을 염소 기체 산화법에 의해 3가 철 이온으로 산화시킨다. 이 후 용매 추출법을 적용하여 3가 철 이온 및 니켈 이온을 고순도로 분리, 회수하게 된다.In the first aspect of the present invention, after dissolving iron and nickel chloride containing trace amounts of impurities such as manganese, copper, aluminum, zinc, silicon, phosphorus, calcium, and sodium in hydrochloric acid or mixed acid, divalent iron in an aqueous solution of hydrochloric acid or mixed acid Ions are oxidized to trivalent iron ions by chlorine gas oxidation. After that, the solvent extraction method is applied to separate and recover trivalent iron ions and nickel ions in high purity.
용매 추출은 추출 및 역추출의 두 개의 공정으로 구성된다. 용매 추출시의 용매는 탄소수 5∼20의 알코올이 사용될 수 있는데, 특히 1-옥탄올(1-octanol)이 적절하다.Solvent extraction consists of two processes: extraction and back extraction. The solvent for solvent extraction may be an alcohol having 5 to 20 carbon atoms, in particular 1-octanol.
추출 조건은 추출 용매와 산 수용액의 체적비가 5.0:1∼1.0:1, 추출 회수가 2∼7회, 교반 속도가 400rpm 이상으로 한다.As for extraction conditions, the volume ratio of an extraction solvent and an acid aqueous solution is 5.0: 1-1.0: 1, the number of times of extraction is 2-7 times, and the stirring speed is 400 rpm or more.
추출 후에 추출 용매에 대해 순수를 이용하여 역추출이 실시되며, 역추출 조건은 추출 용매와 순수의 체적비가 3.0:1∼0.5:1, 추출 회수가 1∼3회, 교반 속도가 400rpm 이상이 된다.After extraction, back extraction is carried out using pure water to the extraction solvent, and the reverse extraction conditions are such that the volume ratio of the extraction solvent and pure water is 3.0: 1 to 0.5: 1, the number of extraction is 1 to 3 times, and the stirring speed is 400 rpm or more. .
본 발명 중 제 2 발명은 철-니켈 합금계 주괴를 염산을 함유하는 혼산에 용해시킨 후, 혼산 수용액에 염소 기체를 불어 넣어 철 이온을 산화시킨다. 이 후 용매 추출법을 적용하여 3가 철 이온 및 니켈 이온을 고순도로 분리, 회수하게 된다. 이 후의 공정은 전술한 철 및 니켈 염화물의 경우와 동일하다.According to a second aspect of the present invention, after the iron-nickel alloy ingot is dissolved in a mixed acid containing hydrochloric acid, chlorine gas is blown into the mixed acid aqueous solution to oxidize iron ions. After that, the solvent extraction method is applied to separate and recover trivalent iron ions and nickel ions in high purity. The subsequent process is the same as for iron and nickel chlorides described above.
이하, 도면을 참조하여 본 발명의 실시예를 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
도 1은 본 발명의 실시예에 따른 용매 추출 장치의 개략도를 도시한 것이다.1 shows a schematic diagram of a solvent extraction apparatus according to an embodiment of the present invention.
본 장치는 추출(Extraction)부와 역추출(Stripping)부로 구성되어 있다. 추출부는 7회까지 추출이 가능하도록 7개의 반응관이 설치되어 있고, 각 반응관마다 산 수용액 및 추출 용매가 적정 속도로 유입 및 교반되도록 펌프와 교반기가 하나씩 설치되어 있다.The apparatus is composed of an extraction section and a stripping section. The extraction unit is provided with seven reaction tubes to extract up to seven times, and a pump and a stirrer are installed in each reaction tube so that the acid aqueous solution and the extraction solvent are introduced and stirred at an appropriate rate.
추출부를 통과하여 3가 철 이온을 다량 함유한 용매는 역추출부로 넘어간다. 역추출부는 3회까지 역추출이 가능하도록 3개의 반응관이 설치되어 있고, 기타 장치 구성은 추출부와 동일하다.After passing through the extraction section, the solvent containing a large amount of trivalent iron ions is passed to the back extraction section. The back extraction section is provided with three reaction tubes for back extraction up to three times, and the other device configuration is the same as the extraction section.
본 발명 중 제 1 발명에 사용된 철-니켈 염화물 수용액은 철-니켈 염화물 슬러지 등을 염산 또는 염산을 70몰% 이상 함유하는 혼산에 녹인다. 혼산의 경우 염산이 70몰% 미만으로 되면 용매 추출시 철 성분의 추출이 용이하지 않게 된다.The iron-nickel chloride aqueous solution used in the first invention of the present invention dissolves iron-nickel chloride sludge and the like in a mixed acid containing 70 mol% or more of hydrochloric acid or hydrochloric acid. In the case of mixed acid, when the hydrochloric acid is less than 70 mol%, extraction of the iron component during solvent extraction is not easy.
사용되는 염산 또는 혼산의 농도는 5∼60중량%이다.The concentration of hydrochloric acid or mixed acid used is 5 to 60% by weight.
염화물의 염산 또는 혼산 수용액 중 철 및 니켈 염의 함량은 20∼60중량%가 요구되며, 가장 바람직한 범위는 30∼50중량%이다. 20중량% 미만에서는 추출성이 좋지 않으며, 60중량% 이상에서는 철 및 니켈 염이 침전되어 수용액 조성의 불균일을 초래한다.The content of iron and nickel salts in the hydrochloric acid or mixed acid aqueous solution of chloride is required 20 to 60% by weight, the most preferred range is 30 to 50% by weight. At less than 20% by weight, the extractability is poor, and at 60% by weight or more, iron and nickel salts precipitate, resulting in nonuniformity of the aqueous solution composition.
추출 용매는 3가 철 이온에 대해 친화력이 강하다. 산 수용액에 녹아 있는 철은 주로 2가로 되어 있으므로 용매 추출을 하기 위해서는 3가로 산화시켜야 한다. 이를 위해서는 기존에 알려진 방법으로서 염소(Cl2) 기체를 산 수용액에 불어 넣어 산화시키는 방법을 적용한다.The extraction solvent has a strong affinity for trivalent iron ions. The iron dissolved in the acid solution is mainly divalent, so it must be oxidized to trivalent in order to extract the solvent. To this end, as a known method, a method of blowing chlorine (Cl 2 ) gas into an aqueous acid solution is applied.
염화물 수용액에서 염화제이철(FeCl3)의 추출을 위한 용매로서 종래에는 중성 추출제인 MIBK(Methyl iso-butyl ketone)나 TBP(Tributyl phosphate)가 사용되었다. 이들은 추출성은 양호하나, 물에 대한 용해도가 3중량% 이상으로 높아서 폐수 처리 비용이 많이 든다는 점이 문제가 되었다. 이러한 문제점을 해결하기 위해서 본 발명에서는 물에 대한 용해도가 0.5중량% 이하인 1-옥탄올을 용매로 사용하였다.As a solvent for the extraction of ferric chloride (FeCl 3 ) in the aqueous solution of chloride, a neutral extractant, MIBK (Methyl iso-butyl ketone) or TBP (Tributyl phosphate) was conventionally used. They have good extractability, but have a high solubility in water of 3% by weight or more, resulting in high waste water treatment costs. In order to solve this problem, in the present invention, 1-octanol having a solubility in water of 0.5 wt% or less was used as a solvent.
추출시의 온도는 상온에서 90℃까지 가능하나, 바람직한 온도는 50℃이하이다. 90℃ 이상의 온도가 되면 용매가 미량 휘발될 수 있으므로 좋지 않다.The temperature at the time of extraction can be up to 90 ℃ at room temperature, the preferred temperature is 50 ℃ or less. If the temperature is above 90 ° C., the solvent may be volatilized, which is not good.
추출시의 용매와 수용액의 체적비는 5.0:1∼1.0:1이 요구되며, 바람직한 범위는 3.0:1∼1.0:1이다. 1.0 미만이 되면 3가 철 이온의 추출량이 너무 작아져서 추출 회수가 늘어나야 하며, 5.0을 초과하면 최종 추출시의 용매에 녹아 있는 3가 철 이온의 농도가 너무 낮게 된다.The volume ratio of the solvent and aqueous solution at the time of extraction requires 5.0: 1-1.0: 1, and the preferable ranges are 3.0: 1-1.0: 1. If it is less than 1.0, the extraction amount of trivalent iron ions is too small to increase the number of extractions. If it is greater than 5.0, the concentration of trivalent iron ions dissolved in the solvent during final extraction is too low.
추출 회수는 2∼7회가 적당하며, 가장 바람직한 회수는 3∼6회이다. 2회 미만이 되면, 3가 철 이온의 추출량이 너무 낮으며, 7회를 초과하면 공정 비용 및 설비 비용이 많이 들게 된다.The number of extraction is appropriate 2 to 7 times, the most preferred is 3 to 6 times. If it is less than two times, the extraction amount of trivalent iron ions is too low, and if it exceeds seven times, the process cost and equipment cost are high.
추출시에 용매와 수용액과의 반응성을 높이기 위해서 반드시 교반이 필요하며, 교반의 정도는 장치의 크기와 체적에 따라 달라지지만 수용액과 용매가 충분히 혼합될 정도의 교반이 요구된다. 도 1의 장치에서는 400rpm 이상이 요구된다.Agitation is necessary to increase the reactivity of the solvent and the aqueous solution during extraction, and the degree of agitation depends on the size and volume of the apparatus, but it is required that the stirring is sufficient to mix the aqueous solution and the solvent. In the apparatus of FIG. 1, 400 rpm or more is required.
최종 추출 용매로부터 3가 철 이온의 회수 및 용매의 재순환을 위해 역추출 공정으로 넘어 간다.The back extraction process is passed to recover trivalent iron ions from the final extraction solvent and to recycle the solvent.
본 발명에서 역추출 공정에서 사용되는 역추출액으로서 순수가 사용된다. 역추출시의 추출 용매와 순수의 체적비는 3.0:1∼0.5:1이 요구되며, 바람직한 범위는 2.0:1∼0.5:1이다. 역추출 회수는 1∼3회가 요구되며, 바람직한 회수는 2∼3회이다.In the present invention, pure water is used as the back extraction liquid used in the back extraction process. The volume ratio of the extraction solvent and the pure water at the time of back extraction is required 3.0: 1 to 0.5: 1, and the preferred range is 2.0: 1 to 0.5: 1. The number of back extractions is required 1 to 3 times, and the preferred number of times is 2-3 times.
역추출시에도 추출 용매와 순수와의 반응성을 높이기 위해서 교반이 반드시 필요하며, 교반은 상호 혼합이 될 정도가 요구된다.In the case of back extraction, stirring is necessary to increase the reactivity between the extraction solvent and the pure water, and stirring is required to be mutually mixed.
본 발명 중 제 2 발명에 사용된 철-니켈 합금계 주괴는 염산을 함유하는 혼산으로 녹이게 된다. 혼산은 염산과 질산으로 이루어지며, 농도가 5∼60중량%인 혼산이 사용되며, 이때 염산과 질산의 몰비는 2.5:1∼4.5:1인 것이 바람직하다. 염산이 2.5 미만으로 되면 용매 추출시 철 성분의 추출이 용이하지 않게 된다.The iron-nickel alloy ingot used in the second invention of the present invention is dissolved with a mixed acid containing hydrochloric acid. The mixed acid is composed of hydrochloric acid and nitric acid, and a mixed acid having a concentration of 5 to 60% by weight is used, wherein the molar ratio of hydrochloric acid and nitric acid is preferably 2.5: 1 to 4.5: 1. If the hydrochloric acid is less than 2.5 it is not easy to extract the iron component during solvent extraction.
철-니켈 합금계 주괴를 녹인 혼산 수용액 중 철 및 니켈 염의 조성은 20∼60중량%가 요구되며, 가장 바람직한 범위는 30∼50중량%이다. 20중량% 미만에서는 추출성이 좋지 않으며, 60중량% 이상에서는 침전이 생성되어 수용액 조성의 불균일을 초래한다.The composition of the iron and nickel salts in the mixed acid aqueous solution in which the iron-nickel alloy ingot is dissolved is required to be 20 to 60% by weight, and the most preferable range is 30 to 50% by weight. If it is less than 20% by weight, the extractability is not good, and if it is more than 60% by weight, precipitates are generated, resulting in nonuniformity of the aqueous solution composition.
추출 용매는 전술한 제 1 발명의 경우와 동일하며, 이 후의 공정도 전술한 제 1 발명의 경우와 동일하다.The extraction solvent is the same as in the first invention described above, and the subsequent steps are also the same as in the first invention described above.
본 발명으로 분리, 회수된 철 및 니켈 이온을 배소하거나 환원 처리하여 최고급의 소프트 페라이트 및 기계 구조용 소재로 적용할 수 있다.The present invention can be applied to the highest quality soft ferrite and mechanical structural materials by roasting or reducing iron and nickel ions separated and recovered.
이하에서, 본 발명을 실시예를 들어 좀 더 상세히 설명하지만, 본 발명은 이에 한정되지 않는다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
실시예 1Example 1
철 43중량%, 니켈 12중량%를 함유한 염화물 슬러지를 9중량% 염산 에 녹여 33중량% 염화물(NiCl2, FeCl2, FeCl3) 수용액을 제조한 다음, 염소(Cl2) 기체를 수용액에 불어 넣어 수용액 중의 염화제일철(FeCl2)을 염화제이철(FeCl3)로 산화시켰다. 도 1의 추출 장치를 이용하여 각 반응관에 200cc의 염화물 수용액을 채운 다음, 제 1 반응관 하부로부터 교반하면서 용매(1-옥탄올)를 일정 유량 속도로 투입하였다. 투입 용매량이 200cc가 되었을 때 제 1 반응관 상부에서 용매 투입시의 유량 속도와 동일하게 제 1 추출된 용매만을 제 2 반응관 하부로 투입하였다. 동일 조건으로 7차 반응관까지 용매 추출을 연속적으로 실시한 다음 ICP(Inductively Coupled Plasma)에 의한 성분 분석을 행하였다. 7차 반응관까지 처리한 후의 추출 용매 및 잔류수에 있어서의 성분 분석 결과를 표 1에 나타내었다.Chloride sludge containing 43% by weight of iron and 12% by weight of nickel was dissolved in 9% by hydrochloric acid to prepare a 33% by weight aqueous solution of chloride (NiCl 2 , FeCl 2 , FeCl 3 ), and then chlorine (Cl 2 ) gas was added to the aqueous solution. The ferrous chloride (FeCl 2 ) in the aqueous solution was blown to oxidize with ferric chloride (FeCl 3 ). After filling 200 cc of aqueous chloride solution in each reaction tube by using the extracting apparatus of FIG. 1, the solvent (1-octanol) was introduced at a constant flow rate while stirring from the bottom of the first reaction tube. When the amount of the added solvent was 200 cc, only the first extracted solvent was added to the lower portion of the second reaction tube in the same manner as the flow rate of the solvent in the upper portion of the first reaction tube. Solvent extraction was continuously performed to the 7th reaction tube under the same conditions, and the component analysis was performed by ICP (Inductively Coupled Plasma). Table 1 shows the results of component analysis in the extraction solvent and the residual water after treatment up to the seventh reaction tube.
실시예 2Example 2
실시예 1에서 각 반응관에 염화물 수용액을 100cc로 채워 6차 반응관까지 연속적으로 용매 추출을 실시하는 것 이외에는 실시예 1과 동일하게 실시했다. 표 1에 추출 용매 및 잔류수에 있어서의 성분 분석 결과를 나타내었다.In Example 1, it carried out similarly to Example 1 except having filled the aqueous solution of the chloride with 100 cc of each reaction tube, and performing solvent extraction continuously to the 6th reaction tube. Table 1 shows the component analysis results in the extraction solvent and the residual water.
실시예 3Example 3
실시예 1에서 각 반응관에 염화물 수용액을 70cc로 투입하는 것 이외에는 실시예 1과 동일한 방법으로 4차 반응관까지 실시하였다. 표 1에 추출 용매 및 잔류수에 있어서의 성분 분석 결과를 나타내었다.In Example 1, the reaction was carried out up to the fourth reaction tube in the same manner as in Example 1 except adding 70 cc of an aqueous chloride solution to each reaction tube. Table 1 shows the component analysis results in the extraction solvent and the residual water.
실시예 4Example 4
실시예 1에서 각 반응관에 염화물 수용액을 50cc로 투입하는 것 이외에는 실시예 1과 동일한 방법으로 3차 반응관까지 실시하였다. 표 1에 추출 용매 및 잔류수에 있어서의 성분 분석 결과를 나타내었다.In Example 1, except that 50 cc of an aqueous chloride solution was added to each reaction tube, the same procedure as in Example 1 was carried out to the third reaction tube. Table 1 shows the component analysis results in the extraction solvent and the residual water.
실시예 5Example 5
실시예 3에서 각 반응관에 염화물 수용액을 50중량%로 조정하는 것 이외에는 실시예 3과 동일한 방법으로 4차 반응관까지 실시하였다. 표 1에 추출 용매 및 잔류수에 있어서의 성분 분석 결과를 나타내었다.Except for adjusting the aqueous chloride solution to 50% by weight in each reaction tube in Example 3 to the fourth reaction tube in the same manner as in Example 3. Table 1 shows the component analysis results in the extraction solvent and the residual water.
실시예 6Example 6
철-40중량%니켈 합금계 주괴를 10중량%의 왕수(HCl:HNO3의 몰비=3:1)에 녹여 제조한 35중량% 염화물 및 질산화물 혼합 용액에 염소(Cl2) 기체를 불어 넣어 수용액중 Fe2+를 Fe3+로 산화시켜 혼합 용액을 제조하는 것 이외에는 실시예 3과 동일하게 실시했다. 표 2에 추출 용매 및 잔류수에 있어서의 성분 분석 결과를 나타내었다.An aqueous solution of chlorine (Cl 2 ) was blown into a 35 wt% chloride and nitrate mixture solution prepared by dissolving an iron-40 wt% nickel alloy ingot in a 10 wt% aqua regia (molar ratio of HCl: HNO 3 = 3: 1). It carried out similarly to Example 3 except having oxidized Fe2 + in Fe3 + and preparing a mixed solution. Table 2 shows the component analysis results in the extraction solvent and the residual water.
실시예 7Example 7
철-40중량%니켈 합금계 주괴를 HCl:HNO3의 몰비=4:1로 혼합한 혼산 용액에 녹이는 것 이외에는 실시예 6과 동일하게 실시했다. 표 2에 추출 용매 및 잔류수에 있어서의 성분 분석 결과를 나타내었다.-40% by weight of an iron nickel alloy based ingot HCl: 4 molar ratio of HNO 3: except that dissolve in a mixed acid solution was mixed in a 1 was conducted in the same manner as in Example 6. Table 2 shows the component analysis results in the extraction solvent and the residual water.
실시예 8Example 8
도 1의 역추출 장치를 이용하여 각 반응관에 순수를 200cc씩 채운 다음, 실시예 3에서 4회까지 추출된 추출 용매를 제 1 반응관 하부로부터 교반하면서 일정 유량 속도로 투입하였다. 투입 용매량이 200cc가 되었을 때 용매 투입시의 유량 속도와 동일하게 1회 역추출된 용매를 제 1 반응관상부로부터 제 2 반응관 하부로 투입하였다. 동일 조건으로 제 2 반응관까지 역추출을 연속적으로 실시한 다음 ICP에 의한 성분 분석을 행하였다. 표 3에 잔류 추출 용매 및 역추출수에 있어서의 성분 분석 결과를 나타내었다.200 cc of pure water was charged to each reaction tube by using the back extraction apparatus of FIG. 1, and the extraction solvent extracted up to 4 times in Example 3 was added at a constant flow rate while stirring from the bottom of the first reaction tube. When the amount of the added solvent was 200 cc, the solvent extracted back once was added from the first reaction tube portion to the lower portion of the second reaction tube in the same manner as the flow rate at the time of solvent addition. Back extraction was continuously performed to the second reaction tube under the same conditions, and then component analysis was performed by ICP. Table 3 shows the results of component analysis in the residual extraction solvent and back extraction water.
실시예 9Example 9
실시예 8에서 각 반응관에 순수를 100cc로 채우는 것 이외에는 실시예 8과 동일하게 실시했다. 표 3에 잔류 추출 용매 및 역추출 수에 있어서의 성분 분석 결과를 나타내었다.In Example 8, it carried out similarly to Example 8 except having filled each reaction tube with 100 cc of pure water. Table 3 shows the results of component analysis in the residual extraction solvent and back extraction water.
실시예 10Example 10
실시예 8에서 각 반응관에 추출 용매를 100cc로 투입하는 것 이외에는 실시예 8과 동일하게 실시했다. 표 3에 잔류 추출 용매 및 역추출수에 있어서의 성분 분석 결과를 나타내었다.In Example 8, it carried out similarly to Example 8 except adding 100 cc of extraction solvents to each reaction tube. Table 3 shows the results of component analysis in the residual extraction solvent and back extraction water.
비교예 1Comparative Example 1
실시예 1에서 각 반응관에 투입 용매량을 100cc로 하는 것 이외에는 실시예 1과 동일하게 실시했다. 추출 용매 및 잔류수에 있어서의 성분 분석 결과를 표 1에 나타내었다.In Example 1, it carried out similarly to Example 1 except having set the solvent amount into 100 cc of each reaction tube. Table 1 shows the results of component analysis in the extraction solvent and residual water.
비교예 2Comparative Example 2
실시예 7에서 HCl:HNO3의 몰비=2:1로 혼합한 혼산 용액을 사용하는 것 이외에는 실시예 7과 동일하게 실시했다. 표 2에 추출 용매 및 잔류수에있어서의 성분 분석 결과를 나타내었다.Example 7 in HCl: HNO 3 molar ratio of 2: except that the mixed acid solution was mixed in a 1 was conducted in the same manner as in Example 7. Table 2 shows the results of component analysis in the extraction solvent and residual water.
비교예 3Comparative Example 3
실시예 8에서 각 반응관에 순수를 50cc 투입하는 것 이외에는 실시예 8과 동일하게 실시했다. 표 3에 잔류 추출 용매 및 역추출 수에 있어서의 성분 분석 결과를 나타내었다.In Example 8, it carried out similarly to Example 8 except adding 50 cc of pure water to each reaction tube. Table 3 shows the results of component analysis in the residual extraction solvent and back extraction water.
표 1Table 1
본 발명에서 추출 용매:수용액의 체적비는 5.0:1∼1.0:1이나, 비교예 1의 경우 체적비가 0.5:1이므로 잔류수에 철 이온이 실시예들에 비해 많이 남아 있다. 즉, 본 발명의 체적비를 벗어나면 추출 용매의 추출 효율이 떨어진다.In the present invention, the volume ratio of the extraction solvent: aqueous solution is 5.0: 1 to 1.0: 1, but in Comparative Example 1, since the volume ratio is 0.5: 1, more iron ions remain in the residual water than the examples. That is, the extraction efficiency of the extraction solvent is lowered out of the volume ratio of the present invention.
표 2TABLE 2
본 발명에서는 철-니켈 합금계 주괴를 용해시키기 위해서 염산과 질산의 몰비가 2.5:1∼4.5:1인 혼산 수용액을 사용해야 하나, 비교예 2의 경우 염산과 질산의 몰비가 2:1인 혼산 수용액을 사용했으므로 잔류수에 철 이온이 실시예들에 비해 많이 남아 있다. 즉, 본 발명의 몰비를 벗어나면 추출 용매의 추출 효율이 떨어진다.In the present invention, in order to dissolve the iron-nickel alloy ingot, a mixed acid solution having a molar ratio of hydrochloric acid and nitric acid of 2.5: 1 to 4.5: 1 should be used. In Comparative Example 2, a mixed acid solution having a molar ratio of hydrochloric acid and nitric acid is 2: 1. Since much iron ions remain in the residual water compared to the embodiments. In other words, the extraction efficiency of the extraction solvent is lowered outside the molar ratio of the present invention.
표 3TABLE 3
본 발명에서 추출 용매:물의 체적비는 3.0:1∼0.5:1이나, 비교예 3의 경우 체적비가 4.0:1이므로 잔류 추출 용매에 철 이온이 실시예들에 비해 많이 남아 있다. 즉, 본 발명의 체적비를 벗어나면 추출 수의 역추출 효율이 떨어진다.In the present invention, the volume ratio of the extraction solvent: water is 3.0: 1 to 0.5: 1, but in Comparative Example 3, since the volume ratio is 4.0: 1, more iron ions remain in the residual extraction solvent than in the examples. That is, if the volume ratio of the present invention is out of the back extraction efficiency of the extraction water is lowered.
본 발명은 철 및 니켈이 주성분으로 다량 녹아 있는 산 수용액에 철과 니켈을 고순도로 분리, 회수할 수 있으며, 종전의 상용화되고 있는 pH 조정법 및 용매 추출법에 비해 분리, 회수 공정이 단순하고 폐수 처리 비용도 훨씬 적게 드는 경제적인 방법이다.The present invention is capable of separating and recovering iron and nickel with high purity in an acid solution in which iron and nickel are dissolved in a large amount as a main component, and the separation and recovery process is simpler than the conventional pH adjustment method and solvent extraction method, and wastewater treatment cost It is an economical way that costs much less.
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| KR1019990058662A KR100355155B1 (en) | 1999-12-17 | 1999-12-17 | Method for isolating and recovering of iron and nickel |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101645012B1 (en) | 2015-01-30 | 2016-08-03 | 삼봉기업(주) | The nickel collecting method from industrial waste |
| KR20200087525A (en) | 2019-01-11 | 2020-07-21 | 타운마이닝리소스주식회사 | A method for producing a nickel sulfate solution which can be used as material to prepare a precursor by using nickel briquettes |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101461733B1 (en) * | 2012-12-21 | 2014-11-19 | 주식회사 포스코 | The method for recovering of value metals efficiently from Ni-Fe compound |
| KR101510532B1 (en) * | 2013-09-12 | 2015-04-10 | 주식회사 포스코 | The method for recovering Fe from Iron chloride solution acquired during hydrometallurgical process |
| KR20180059601A (en) * | 2016-11-25 | 2018-06-05 | (주) 케이엠씨 | Recycling method of waste etching solution for producing highly concentrated iron chloride |
| KR102006249B1 (en) * | 2016-11-25 | 2019-08-02 | (주)케이엠씨 | Circulation concentrating method for producing highly concentrated iron chloride recycling waste etching solution |
| KR20180059599A (en) * | 2016-11-25 | 2018-06-05 | (주) 케이엠씨 | Recycling method of waste etching solution for collecting highly concentrated nickel |
| KR102143162B1 (en) * | 2019-07-12 | 2020-08-12 | 전북대학교산학협력단 | Recovery method of residual metals via hydrometallurgical treatment of electroplating solution |
| KR20230122362A (en) | 2022-02-14 | 2023-08-22 | 주식회사 이브이링크 | Method for recovering nickel from spent electrolyte solution |
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| JPS51149117A (en) * | 1975-06-17 | 1976-12-21 | Katsutoshi Ono | Treatment of ni ores |
| JPS54107801A (en) * | 1978-02-14 | 1979-08-24 | Chiyoda Chem Eng & Constr Co Ltd | Separating and recovering mehtod for metal from waste catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101645012B1 (en) | 2015-01-30 | 2016-08-03 | 삼봉기업(주) | The nickel collecting method from industrial waste |
| KR20200087525A (en) | 2019-01-11 | 2020-07-21 | 타운마이닝리소스주식회사 | A method for producing a nickel sulfate solution which can be used as material to prepare a precursor by using nickel briquettes |
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