KR100406367B1 - RECYCLING METHOD OF SLUDGE INCLUDING FeNi GENERATED FROM RECYCLING PROCESS OF Ni CONTAINED SPENT ETCHING SOLUTION - Google Patents
RECYCLING METHOD OF SLUDGE INCLUDING FeNi GENERATED FROM RECYCLING PROCESS OF Ni CONTAINED SPENT ETCHING SOLUTION Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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Abstract
본 발명은 Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 함유 슬러지의 재활용 방법에 관한 것으로,The present invention relates to a method for recycling FeNi-containing sludge generated in the Ni-containing etching waste recycling process,
Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 함유 슬러지를 염산에 pH 3∼4가 되도록 용해시켜 철염화물 및 니켈염화물 함유 수용액을 제조하고, 상기 염화물 함유 수용액에 공기를 취입하여 산화시킴으로써 FeCl2를 FeCl3로 산화시킨 다음, 생성된 FeCl3를 pH 3∼5에서 물과 반응시켜 주황색의 수산화철(FeOOH)핵을 형성하며, 나아가 산화분위기하에서 용액중의 Fe 몰수의 최대 2배의 몰수로 그리고 pH 3∼5로 유지되도록 알칼리를 첨가하면서 온도를 40∼70℃로 조절하여 수산화철 슬러지를 형성한 다음, 여과하여 수산화철 슬러지와 니켈 염화물 함유 여액을 분리하고 수산화철 슬러지를 수세하여 수산화철을 수득하고, 여과시 분리된 여액에는 pH 10이상이 되도록 알칼리를 첨가하여 수산화니켈의 침전물을 형성하며, 여과 및 수세하여 수산화니켈을 수득한다. 상기한 바에 따르면, Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 슬러지에서 별도의 폐기물을 생성하지 않으면서 수산화철, 산화철 및 산화니켈을 수득할 수 있다.FeNi-containing sludge from the Ni-containing etching waste recycling process was dissolved in hydrochloric acid to pH 3-4 to prepare an aqueous solution containing iron chloride and nickel chloride, and air was blown into the chloride-containing aqueous solution to oxidize FeCl 2 to FeCl 3. The resulting FeCl 3 is then reacted with water at pH 3 to 5 to form an orange iron hydroxide (FeOOH) nucleus, and further at a maximum molar number of twice the number of moles of Fe in the solution under an oxidation atmosphere and at pH 3 to The temperature was adjusted to 40-70 DEG C while adding alkali to maintain 5 to form iron hydroxide sludge, followed by filtration to separate the iron hydroxide sludge and the nickel chloride-containing filtrate, washing with iron hydroxide sludge to obtain iron hydroxide, which was separated during filtration. An alkali is added to the filtrate to pH 10 or more to form a precipitate of nickel hydroxide, which is filtered and washed with water to obtain nickel hydroxide. The. According to the above, it is possible to obtain iron hydroxide, iron oxide and nickel oxide in FeNi sludge generated in the Ni-containing etching waste recycling process without generating a separate waste.
Description
본 발명은 Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 함유 슬러지를 재활용하는 방법에 관한 것으로, 보다 상세하게는 샤도우마스크 제조 공정에서 발생하는 Ni-함유 에칭 폐액을 재활용하는 공정에서 발생하는 2차 폐기물인 Fe-Ni 폐기물 슬러지로부터 수산화철, 산화철 및 산화니켈을 수득하게 되는 Fe,Ni 슬러지의 재활용 방법에 관한 것이다.The present invention relates to a method for recycling the FeNi-containing sludge generated in the Ni-containing etching waste recycling process, more specifically, the secondary waste generated in the process of recycling the Ni-containing etching waste generated in the shadow mask manufacturing process The present invention relates to a method for recycling Fe, Ni sludge, which obtains iron hydroxide, iron oxide and nickel oxide from Fe-Ni waste sludge.
텔레비젼 브라운관에 원형 또는 사각형의 홈을 일컫는 샤도우마스크는 Ni을 함유한 Fe 합금, 즉 인바(Invar) 합금을 FeCl3에칭액으로 국부에칭하는 공정을 통하여 제조된다. 연속적으로 에칭 작업을 하면 다음과 같은 반응에 의하여 인바 합금 모재는 용해되고 용액내에는 FeCl2와 NiCl2가 발생한다.A shadow mask, which refers to a circular or rectangular groove in a television CRT, is manufactured through a localization process of a Ni-containing Fe alloy, that is, an Invar alloy, with a FeCl 3 etching solution. In the continuous etching operation, the Invar alloy base material is dissolved and FeCl 2 and NiCl 2 are generated in the solution by the following reaction.
따라서 어느 정도 작업이 진행되면 FeCl2와 NiCl2함유량이 많아져 에칭 능력이 떨어진다. 이를 용액의 피로도가 증가하였다고 말한다. 따라서 피로도 관리를 위하여 특정 농도 이상 FeCl2와 NiCl2혼입량이 늘어나면 용액은 폐기되고 새로운 FeCl3용액을 사용하여야 한다.Therefore, if the work is progressed to some extent, the content of FeCl 2 and NiCl 2 increases, which reduces the etching ability. This is said to increase the fatigue of the solution. Therefore, if the FeCl 2 and NiCl 2 incorporation increases above a certain concentration for fatigue control, the solution should be discarded and a new FeCl 3 solution should be used.
이와 같이 발생한 에칭폐액은 Fe 분말 처리를 하여 Ni을 Fe 분말에 치환시켜 제거한 후 그 용액을 염소산화하여 FeCl3로 재활용하는 방법(일본 특허 제95-87474)이 주로 이용되고 있다. 이는 상기식 1의 반응에 의해 생성된 Ni 이온을 전기화학적으로 치환석출시키는 방법에 관한 것으로 그 반응식은 다음과 같다.The etching waste solution thus produced is mainly subjected to Fe powder treatment by replacing Ni with Fe powder to remove the solution, and then chlorination of the solution to recycle into FeCl 3 (Japanese Patent No. 95-87474). This relates to a method of electrochemically replacing and depositing Ni ions produced by the reaction of Equation 1 as follows.
상기식 3의 반응으로 생성된 FeCl2는 Cl2로 산화하여 FeCl3로 재활용된다. 그러나 식 3의 반응으로 생성된 슬러지는 재활용시 다음과 같은 문제가 있다. 즉, FeNi 슬러지는 산용해후 용매추출등으로 분리하여 NiCl2, FeCl3등으로 분리가 가능하지만 경제적이지 못하고, 이 공정에서 역시 3차 폐기물이 생성되는 단점이 있다.FeCl 2 produced by the reaction of Formula 3 is oxidized to Cl 2 and recycled to FeCl 3 . However, sludge produced by the reaction of Equation 3 has the following problems in recycling. In other words, FeNi sludge can be separated by acid extraction, solvent extraction and the like can be separated into NiCl 2 , FeCl 3, etc., but it is not economical, there is also a disadvantage that the third waste is generated in this process.
이에 본 발명의 목적은 Fe-Ni이 함유된 폐기 슬러지에서 별도의 폐기물을 생성하지 않는 FeNi 슬러지 재활용 방법을 제공하는 것이다.Therefore, an object of the present invention is to provide a FeNi sludge recycling method does not generate a separate waste from the waste sludge containing Fe-Ni.
본 발명의 다른 목적은 수산화철, 산화철 및 산화니켈을 수득하는 FeNi 함유 슬러지 재활용 방법을 제공하는 것이다.Another object of the present invention is to provide a FeNi-containing sludge recycling method for obtaining iron hydroxide, iron oxide and nickel oxide.
본 발명에 의하면,According to the invention,
(a)Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 함유 슬러지를 염산에 pH 3∼4가 되도록 용해시켜 철염화물 및 니켈염화물 함유 수용액을 제조하는 단계;(a) dissolving the FeNi-containing sludge from the Ni-containing etching waste recycling process to pH 3-4 in hydrochloric acid to prepare an aqueous solution containing iron chloride and nickel chloride;
(b)상기 염화물 함유 수용액에 공기를 취입하여 산화시킴으로써 FeCl2를 FeCl3로 산화시킨 다음, 생성된 FeCl3를 pH 3∼5에서 물과 반응시켜 주황색의 수산화철(FeOOH)핵을 형성하는 단계;(b) oxidizing FeCl 2 to FeCl 3 by blowing air into the chloride-containing aqueous solution and oxidizing it, and then reacting the resulting FeCl 3 with water at pH 3 to 5 to form orange iron hydroxide (FeOOH) cores;
(c)산화분위기하에서 용액중의 Fe 몰수의 최대 2배의 몰수로 그리고 pH 3∼5로 유지되도록 알칼리를 첨가하면서 온도를 40∼70℃로 조절하여 수산화철 슬러지를 형성하는 단계;(c) forming iron hydroxide sludge by adjusting the temperature to 40-70 ° C. while adding alkali to maintain a maximum number of moles of the number of moles of Fe in the solution and a pH of 3 to 5 under an oxidation atmosphere;
(d)그후 여과하여 수산화철 슬러지와 니켈 염화물 함유 여액을 분리하고 수산화철 슬러지를 수세하여 수산화철을 수득하는 단계; 및(d) thereafter filtering to separate the iron hydroxide sludge and the nickel chloride-containing filtrate and washing the iron hydroxide sludge to obtain iron hydroxide; And
(e)상기 여과시 분리된 니켈 염화물 함유 여액에 pH 10이상이 되도록 알칼리를 첨가하여 수산화니켈의 침전물을 형성하며, 여과 및 수세하여 수산화니켈을 수득하는 단계;로 이루어지는 Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 함유 폐기 슬러지 재활용 방법이 제공된다.(e) adding an alkali to a pH of 10 or more to the separated nickel chloride-containing filtrate during the filtration to form a precipitate of nickel hydroxide, and filtering and washing to obtain nickel hydroxide; in the Ni-containing etching waste recycling process consisting of A method of recycling FeNi-containing waste sludge generated is provided.
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명에서는 Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 함유 슬러지를 사용하여 별도의 폐기물을 발생하지 않으면서 수산화철, 산화철 및 수산화니켈을 수득하게 된다.In the present invention, iron hydroxide, iron oxide and nickel hydroxide are obtained using FeNi-containing sludge generated in the Ni-containing etching waste recycling process without generating any waste.
본 발명의 단계(a)에서는 FeNi 슬러지를 염산에 용해하면 철 염화물 및 니켈 염화물이 동시에 혼합된 혼합 수용액이 얻어진다.In step (a) of the present invention, when FeNi sludge is dissolved in hydrochloric acid, a mixed aqueous solution in which iron chloride and nickel chloride are simultaneously mixed is obtained.
즉, 산용해반응시 pH가 증가하여 pH 3∼4에 이르면 철염화물과 니켈염화물이 동시에 용해된 혼합 수용액이 제조된다. pH가 3∼4에 이르면 더 이상 반응이 진행되지 않으므로 pH는 3∼4로 조절하는 것이 바람직하다.That is, a mixed aqueous solution in which iron chloride and nickel chloride are dissolved at the same time is produced when the pH is increased and the pH is 3 to 4 during the acid dissolution reaction. When the pH reaches 3 to 4, the reaction does not proceed anymore, so the pH is preferably adjusted to 3 to 4.
단계(b)에서는 상기 염화물 함유 수용액에 공기를 취입하여 FeCl2를 FeCl3로 산화시킨다.In step (b), air is blown into the chloride-containing aqueous solution to oxidize FeCl 2 to FeCl 3 .
이때 생성된 FeCl3는 pH 3∼5의 조건하에 물과 반응하여 주황색의 수산화철(FeOOH)핵을 형성한다. 그 반응식은 다음과 같다:The produced FeCl 3 reacts with water under the condition of pH 3 to 5 to form an orange iron hydroxide (FeOOH) nucleus. The scheme is as follows:
단계(c)에서는 산화분위기하에서 용액중 Fe 몰수의 최대 2배의 몰수로 그리고 용액의 pH가 3∼5로 유지되도록 수산화철 핵이 형성된 용액에 알칼리를 첨가하고 온도를 40∼70℃로 조절함으로써 하기 반응식 5와 같이 수산화철을 형성한다.In step (c), an alkali is added to a solution in which the iron hydroxide nucleus is formed at a maximum of twice the number of moles of Fe in the solution under an oxidation atmosphere and the pH of the solution is maintained at 3 to 5, and the temperature is adjusted to Iron hydroxide is formed as in Scheme 5.
이때 상기식 4와 같이 HCl이 계속 생성됨으로 인하여 pH가 저하되게 되면 Fe가 더 이상 FeOOH로 산화침전되지 않게 되므로 pH는 3∼5가 되도록 알칼리를 계속 공급하여 HCl을 제거하여야만 반응이 지속적으로 일어날 수 있다.At this time, when the pH is lowered due to the continued generation of HCl as in Formula 4, Fe is no longer oxidized and precipitated with FeOOH. Therefore, the pH can be continuously generated only by continuously supplying alkali so that the pH is 3 to 5 and HCl is removed. have.
이때 알칼리로는 KOH 및 NaOH를 사용하는 것이 바람직하며, 그 투여량은 Fe, Ni등의 혼합 수용액에서의 Fe 몰수의 2배가 될 때까지만 투여함으로써 하기식 6에서와같이 Ni이 함께 침전되지 않도록 하는 것이 중요하다.In this case, it is preferable to use KOH and NaOH as the alkali, and the dosage is to be administered until the molar number of Fe in the mixed aqueous solution such as Fe and Ni is twice, so that Ni does not precipitate together as shown in Equation 6 below. It is important.
예를 들어 알칼리로서 NaOH를 Fe몰수의 3배가 되는 양으로 투입하게 되면, 하기식 6과 같이 반응하여 니켈 침전물이 형성된다.For example, when NaOH is added as an alkali in an amount of three times the number of Fe moles, it reacts as shown in Equation 6 below to form a nickel precipitate.
따라서 Ni이 Fe와 함께 침전되지 않도록 알칼리는 Fe 몰수의 최대 2배까지만 첨가하여야 한다.Therefore, alkali should be added only up to twice the number of moles of Fe so that Ni does not precipitate with Fe.
이때 반응온도도 또한 중요한데, 온도를 40℃이상으로 유지하면 미려한 황색의 수산화철이 얻어지게 되어 바람직하다. 그러나 반응 온도가 이보다 낮으면 미세한 입자가 생성되면서 초기 수산화철 핵과 동일한 주황색을 유지하게 되는 반면,온도가 70℃를 초과하게 되면 황색의 FeOOH를 생성하는 대신에 NiFe2O4라는 Ni이 혼입된 흑색의 산화물이 형성되므로 바람직하지 않다. 따라서 온도를 40∼70℃로 유지하는 것이 바람직하다.At this time, the reaction temperature is also important. If the temperature is maintained above 40 ° C, a beautiful yellow iron hydroxide is obtained. However, when the reaction temperature is lower than this, fine particles are formed and maintain the same orange color as the initial iron hydroxide nucleus, whereas when the temperature exceeds 70 ° C, instead of generating yellow FeOOH, NiFe 2 O 4 is mixed with Ni. It is not preferable because an oxide is formed. Therefore, it is preferable to keep the temperature at 40 to 70 ° C.
이와 같이 수산화철이 형성된 다음, 단계(d)에서는 수용액을 여과 및 수세하여 수산화철을 수득한다.After iron hydroxide is formed as described above, in step (d), the aqueous solution is filtered and washed with water to obtain iron hydroxide.
즉, 수산화철이 형성된 수용액을 여과하여 수산화철 슬러지와 니켈 염화물을 함유하는 여액을 분리하고, 수산화철 슬러지를 수세하여 KCl 혹은 NaCl등의 불순물을 제거하게 된다. 또한 상기 공정도중에는 원래 FeNi 폐기물내에 존재하던 불순물이 함께 제거되게 된다. 이에 따라 수산화철을 수득하게 되며, 이는 전자재료 원료로 사용된다.That is, the aqueous solution formed with iron hydroxide is filtered to separate the filtrate containing iron hydroxide sludge and nickel chloride, and the iron hydroxide sludge is washed with water to remove impurities such as KCl or NaCl. In addition, during the process, impurities that originally existed in the FeNi waste are removed together. As a result, iron hydroxide is obtained, which is used as an electronic material raw material.
보다 바람직하게는 이와 같이 제조된 수산화철을 600∼1000℃의 온도로 열처리함으로써 Fe2O3를 얻을 수 있으며, 이는 적색 안료 및 전자재료 원료로 사용된다. 600℃이하의 온도에서 열처리하게 되면 비표면적(BET)값이 나빠지게 되어 색상이 불량하게 되며, 1000℃이상의 온도에서 열처리하게 되면 입자가 소결 반응에 의해 입자 크기가 증가되게 되어 안료로 사용하기에 적절하지 않다.More preferably, Fe 2 O 3 can be obtained by heat-treating the iron hydroxide thus prepared at a temperature of 600 to 1000 ° C., which is used as a red pigment and an electronic material raw material. If the heat treatment at the temperature below 600 ℃, the specific surface area (BET) value will be bad and the color will be poor.If the heat treatment at the temperature above 1000 ℃, the particle size will increase due to the sintering reaction. Not appropriate
단계(e)에서는 상기 여과시 분리된 니켈 염화물을 함유하는 여액에 pH 10이상이 되도록 알칼리를 첨가함으로써 하기식 7과 같이 수산화니켈 침전물을 형성하게 된다.In step (e), the alkali hydroxide is added to the filtrate containing the nickel chloride separated during the filtration to have a pH of 10 or more to form a nickel hydroxide precipitate as shown in Equation 7 below.
상기식에 의해 생성된 수산화니켈 침전물을 여과 및 수세하여 용액에서 분리하게 되며 이때 부산물인 KCl이나 NaCl이 함께 제거되므로 고순도 수산화니켈을 얻는다.The nickel hydroxide precipitate produced by the above formula is filtered and washed to separate it from the solution. At this time, by-product KCl or NaCl are removed together to obtain high purity nickel hydroxide.
나아가 이와 같이 제조된 고순도 수산화니켈을 800∼1200℃의 온도에서 열처리함으로써 고순도의 NiO이 형성되며, 이는 녹색 안료 및 전자재료 원료로 사용된다. 800℃이하의 온도에서 열처리하게 되면 비정질(amorphous)의 상태로 흑색이 되며, 1200℃이상의 온도에서 열처리하면 입자가 소결 반응에 의해 입자 크기가 증가되게 되어 안료로 사용하기에 적절하지 않다.Furthermore, NiO of high purity is formed by heat-treating the high purity nickel hydroxide manufactured in this way at the temperature of 800-1200 degreeC, and it is used as a green pigment and an electronic material raw material. If the heat treatment at a temperature of 800 ℃ or less becomes black in an amorphous (amorphous) state, when the heat treatment at a temperature of 1200 ℃ or more increases the particle size by the sintering reaction is not suitable for use as a pigment.
본 발명의 방법에 따르면, Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 황색 슬러지를 재활용함으로써 수산화철(FeOOH)과 고순도의 수산화니켈을 제조할 수 있으며, 이들을 각각 600∼1000℃ 및 800∼1200℃의 온도 범위에서 열처리함으로써 산화철(Fe2O3) 안료 및 고순도의 산화니켈이 수득된다. 이와 같이 형성된 수산화철은 황색 안료로, 산화철은 적색 안료로 그리고 산화니켈은 녹색 안료로 각각 사용되며, 특히 산화니켈은 순도가 높은 것으로 페라이트용 전자재료 원료로서 이용가능한 것이다.According to the method of the present invention, iron hydroxide (FeOOH) and high-purity nickel hydroxide can be produced by recycling FeNi yellow sludge generated in the Ni-containing etching waste recycling process, and the temperature is 600-1000 ° C and 800-1200 ° C, respectively. By heat-treating in the range, an iron oxide (Fe 2 O 3 ) pigment and high purity nickel oxide are obtained. The iron hydroxide thus formed is used as a yellow pigment, iron oxide as a red pigment, and nickel oxide as a green pigment, and nickel oxide is particularly high in purity and can be used as a raw material for ferrite electronic materials.
이하, 실시예를 통하여 본 발명에 대하여 설명한다.Hereinafter, the present invention will be described through examples.
<실시예 1><Example 1>
pH 및 알칼리 첨가량에 따른 생성 산물 비교 Comparison of products produced by pH and alkali addition
염산 6몰 수용액 1ℓ에 샤도우마스크 재활용 공정에서 발생하는 FeNi 합금 슬러지 400g을 투여하여 반응시킨 결과, 3시간후 pH가 3.5에 도달하였으며, 잔류 염산을 제거하여 반응을 종료시켰다.When 1 g of 6 mol aqueous solution of hydrochloric acid was reacted with 400 g of FeNi alloy sludge generated in the shadow mask recycling process, the pH reached 3.5 after 3 hours, and the reaction was terminated by removing residual hydrochloric acid.
그후 미반응 슬러지를 여과하여 Fe, Ni이 혼합된 수용액을 제조하였다. 이 용액을 분석한 결과, Fe가 1.6몰/ℓ 및 Ni이 1.4몰/ℓ였다. 이 용액에 공기를 불어넣은 결과 3가 철을 얻었으며, 계속 공기를 불어넣고 하기표 1에 기재한 바와 같이 pH를 2.5∼5.5로 유지하면서 NaOH를 Fe몰수의 1∼4배가 되도록 첨가하였다. 그후 황색 슬러지가 생성되면 이를 여과 및 수세하였다.Thereafter, unreacted sludge was filtered to prepare an aqueous solution in which Fe and Ni were mixed. As a result of analyzing this solution, Fe was 1.6 mol / l and Ni was 1.4 mol / l. Air was blown into the solution to obtain trivalent iron, and air was continuously blown and NaOH was added to 1 to 4 times the number of moles of Fe while maintaining the pH at 2.5 to 5.5 as shown in Table 1 below. Yellow sludge then formed and was filtered and washed with water.
pH 및 알칼리 첨가량에 따른 생성산물을 X선회절분석기(XRD)로 분석하여 조사 비교한 결과를 하기표 1에 나타내었다. 또한 잔류 용액중에 Fe가 존재하는지 여부를 산화제를 첨가하여 육안으로 확인하였으며, 그 결과를 하기표 1에 나타내었다.Table 1 shows the results of the investigation by analyzing the product according to the pH and alkali addition amount by X-ray diffractometer (XRD). In addition, whether Fe is present in the residual solution was visually confirmed by adding an oxidizing agent, and the results are shown in Table 1 below.
*발명예 3은 발명예 1에서 얻어진 황색의 FeOOH를 600℃의 온도에서 열처리한 경우 얻어지는 산물을 기재한 것이다.Inventive Example 3 describes a product obtained when the yellow FeOOH obtained in Inventive Example 1 is heat-treated at a temperature of 600 ° C.
상기표에서 보듯이, 알칼리 첨가량이 용액내 존재하는 Fe몰수의 2배보다 작은 경우(비교예 1∼4)에는 수산화철 여과후 여액에 미반응 Fe가 존재하였으며, 2배보다 큰 경우에는(비교예 6∼14) 생성산물에 Ni(OH)2가 혼입되었다.As shown in the table above, when the amount of alkali added was less than twice the number of moles of Fe present in the solution (Comparative Examples 1 to 4), unreacted Fe was present in the filtrate after iron hydroxide filtration, and when it was larger than 2 times (Comparative Example). 6-14) Ni (OH) 2 was incorporated into the product.
또한 알칼리 첨가량이 용액내 존재하는 Fe몰수의 2배이더라도 pH가 2.5로 낮은 비교예 7의 경우에는 알칼리 첨가량의 2배를 첨가하는데 12시간이상이 소요되어 반응이 극도로 느리다는 단점이 있다. 반면 pH가 높으면 반응 종료 시간은 1시간 정도까지 단축되나 Ni(OH)2혼입이 일어나는 단점이 있다.In addition, even if the alkali addition amount is twice the number of Fe moles present in the solution, Comparative Example 7 having a low pH of 2.5 has a disadvantage in that the reaction is extremely slow because it takes 12 hours or more to add twice the alkali addition amount. On the other hand, if the pH is high, the reaction termination time is shortened to about 1 hour, but there is a disadvantage in that Ni (OH) 2 is mixed.
따라서 pH를 3∼5로 하고 알칼리 첨가량을 용액내 존재하는 Fe 몰수의 2배로 할 경우, Ni(OH)2의 혼입도 없으면서 반응도 2∼5시간내에 종료되게 되어 여액내 Fe이 존재하는 등의 문제가 발생하지 않았다.Therefore, when the pH is set to 3 to 5 and the alkali addition amount is twice the number of moles of Fe present in the solution, the reaction is terminated within 2 to 5 hours without the incorporation of Ni (OH) 2 , such as the presence of Fe in the filtrate. Did not occur.
또한 본 발명의 발명예 1에 속하는 조건으로 제조된 황색의 FeOOH를 여과 및 수세한 다음 600℃의 온도로 열처리한 경우(발명예 3)에는 적색 안료로서 사용가능한 Fe2O3를 얻을 수 있었다.In addition, Fe 2 O 3 usable as a red pigment was obtained when yellow FeOOH prepared under the conditions belonging to Inventive Example 1 of the present invention was filtered and washed, and then heat-treated at a temperature of 600 ° C. (Invention Example 3).
<실시예 2><Example 2>
제조된 NiO와 출발 원료 불순물 비교Comparison of NiO Prepared and Starting Material Impurities
실시예 1에서 pH를 3.5로 하고 알칼리 첨가량을 용액내 존재하는 Fe몰수의 2배로한 발명예 1의 용액을 여과한 여액에 NaOH를 pH10.5가 될 때까지 첨가하여 Ni(OH)2를 합성한 후 여과 및 수세 공정을 3회 반복하여 NaCl을 제거하였다.Ni (OH) 2 was synthesized by adding NaOH to the filtrate of the filtrate obtained by filtering the solution of Inventive Example 1 in which the pH was set to 3.5 and the alkali addition amount was twice the number of Fe moles present in the solution until the pH was 10.5. After repeated filtration and washing three times to remove NaCl.
그후 제조된 Ni(OH)2를 850℃의 온도에서 열처리하여 녹색의 NiO를 제조하고 제조된 NiO내 불순물의 농도를 유도결합플라즈마(Inductively Coupled Plasma, ICP)를 사용하여 분석하고, 출발 원료로 사용한 FeNi 폐기물과 대비하여 하기표 2에 나타내었다.Thereafter, the prepared Ni (OH) 2 was heat-treated at a temperature of 850 ° C. to produce green NiO, and the concentration of impurities in the prepared NiO was analyzed using an inductively coupled plasma (ICP) and used as a starting material. It is shown in Table 2 below in comparison with the FeNi waste.
상기표 2에서 보듯이, 제조된 NiO는 초기 출발 원료에 비하여 Al, Fe, Cu,Pb등이 대부분 제거되었으며, 얻어진 Ni함량은 78.55중량%로서 NiO의 이론값 78.58중량%와 거의 일치하는 고순도 분말이었다. 따라서 제조된 NiO는 녹색 안료뿐만 아니라 전자재료 원료로도 이용가능한 고순도임을 확인할 수 있었다.As shown in Table 2, the prepared NiO was mostly removed Al, Fe, Cu, Pb, etc. compared to the initial starting material, the obtained Ni content is 78.55% by weight, high purity powder almost in agreement with the theoretical value of 78.58% by weight of NiO It was. Therefore, the prepared NiO was confirmed to be a high purity that can be used as a raw material for electronic materials as well as green pigment.
상기한 바에 따르면, Ni 함유 에칭폐액 재활용 공정에서 발생하는 FeNi 슬러지에서 별도의 폐기물을 생성하지 않으면서 수산화철, 산화철 및 산화니켈을 수득할 수 있다.According to the above, it is possible to obtain iron hydroxide, iron oxide and nickel oxide in FeNi sludge generated in the Ni-containing etching waste recycling process without generating a separate waste.
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| KR100811872B1 (en) | 2006-12-20 | 2008-03-10 | 재단법인 포항산업과학연구원 | Method of manufacturing raw material for stainless melting using feni containing sludge |
| KR100874740B1 (en) | 2007-05-15 | 2008-12-19 | 재단법인 포항산업과학연구원 | Method for producing iron nickel-containing raw material from iron nickel-containing waste liquid and method for producing stainless melt-dissolved raw material using iron nickel-containing raw material |
| KR100988462B1 (en) | 2007-09-21 | 2010-10-20 | 재단법인 포항산업과학연구원 | Method of Manufacturing Fe and Ni Containing Material and Co Containing Material Using Recycling Residue of Spent Catalyst and Method of Manufacturing Raw Material for Stainless Using the Fe and Ni Containing Material and Method of Manufacturing Fe-Ni Alloy |
| WO2012081897A2 (en) * | 2010-12-15 | 2012-06-21 | 재단법인 포항산업과학연구원 | Method for enrichment-recovering ferronickel from raw material containing nickel, method for recovering nickel from enriched ferronickel, and method for recycling solution containing iron produced from same |
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| KR100912522B1 (en) * | 2007-11-08 | 2009-08-18 | 재단법인 포항산업과학연구원 | Ferronickel Mass and Method for Manufacturing the Ferronickel Mass |
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| KR100874740B1 (en) | 2007-05-15 | 2008-12-19 | 재단법인 포항산업과학연구원 | Method for producing iron nickel-containing raw material from iron nickel-containing waste liquid and method for producing stainless melt-dissolved raw material using iron nickel-containing raw material |
| KR100988462B1 (en) | 2007-09-21 | 2010-10-20 | 재단법인 포항산업과학연구원 | Method of Manufacturing Fe and Ni Containing Material and Co Containing Material Using Recycling Residue of Spent Catalyst and Method of Manufacturing Raw Material for Stainless Using the Fe and Ni Containing Material and Method of Manufacturing Fe-Ni Alloy |
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| WO2012081897A3 (en) * | 2010-12-15 | 2012-10-04 | 재단법인 포항산업과학연구원 | Method for enrichment-recovering ferronickel from raw material containing nickel, method for recovering nickel from enriched ferronickel, and method for recycling solution containing iron produced from same |
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| CN103370428B (en) * | 2010-12-15 | 2015-06-17 | 浦项产业科学研究院 | Method for enrichment-recovering ferronickel from raw material containing nickel, method for recovering nickel from enriched ferronickel, and method for recycling solution containing iron produced from same |
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