WO2014123284A1 - Method for producing iron oxide pigment using electroplating - Google Patents

Method for producing iron oxide pigment using electroplating Download PDF

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WO2014123284A1
WO2014123284A1 PCT/KR2013/006866 KR2013006866W WO2014123284A1 WO 2014123284 A1 WO2014123284 A1 WO 2014123284A1 KR 2013006866 W KR2013006866 W KR 2013006866W WO 2014123284 A1 WO2014123284 A1 WO 2014123284A1
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iron oxide
iron
oxide pigment
electroplating
oxide powder
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PCT/KR2013/006866
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French (fr)
Korean (ko)
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원종일
박성범
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동국대학교 경주캠퍼스 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals

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  • the present invention relates to a method for producing environmentally friendly iron oxide pigments using the electroplating method.
  • One common method of utilizing FeCl 2 waste is a spray roasting process that oxidatively hydrolyzes ferric chloride (II) and ferric chloride (III) at high temperatures (typically above 1000 ° C.).
  • Hydrochloric acid which may be recycled as a useful material, such as iron oxide, typically hematite, and to the pickling process, is the final product in this process.
  • iron oxide suitable for the production of light ferrite is obtained from this process without any specific purification step. If a soft ferrite is to be prepared from iron oxide obtained in this way, the iron chloride solution used is quite expensive because it requires further purification in advance. In addition, more iron, mainly of lower quality, is produced, and the capacity of the ferrite market is limited, and alternatives are being made to produce useful materials from these iron chlorides.
  • Iron oxide metal particle production method is carried out in various ways, a few of the representative will be described as follows.
  • mechanical grinding is a method of grinding a large volume of metal by physical mechanical force to make it smaller.
  • an evaporative condensation method is rapidly heated by liquid nitrogen after evaporating by heating the bulk phase of a metal to a high temperature. It is a method of cooling to obtain nanometer-sized particles.
  • the colloid method is a method of obtaining nano-sized particles by dissolving metal salts in molecular units in an aqueous solution or an anhydrous solution and then reducing them using various reducing agents.
  • the conventional nanometer-sized metal particle manufacturing method as described above has been pointed out as a problem such as a complicated process and a difficulty in controlling the size to obtain a small particle size.
  • the inventors of the present invention have been studying an efficient process for controlling the size of iron metal particles from pickling liquor or iron chloride starting materials. It was confirmed that the control of, and completed the present invention.
  • the present invention is to provide a method for producing an iron oxide pigment using the electroplating method.
  • the present invention is an iron oxide using an electroplating method that can easily adjust the size of the iron metal particles at low cost by using the electroplating method when the iron metal particles are formed from pickling waste liquid or iron chloride starting material by using the applied voltage and the concentration of the electrolyte as a variable It provides a method for producing a pigment.
  • iron oxide pigments can be prepared.
  • FIG. 1 is a view showing a schematic diagram of an electrolytic cell for producing iron oxide powder using the electroplating method of the present invention.
  • FIG. 2 is a diagram showing an electrode of an electrolytic cell (left: positive electrode, right: negative electrode).
  • FIG. 3 is a diagram showing an iron oxide powder prepared by applying a current density of 0.1 A / cm 2 to an electrolytic cell.
  • Figure 4 is a diagram showing the iron oxide powder prepared by applying a current density of 0.2A / cm 2 to the electrolytic cell.
  • the present invention is a.
  • step (b) applying an electric current to an electrolytic cell composed of the electrolyte solution and the electrode prepared in step (a) to produce iron oxide powder;
  • step (c) performing a water washing process using the iron oxide powder prepared in step (b), followed by heat treatment; It provides a method of producing an iron oxide pigment.
  • step (a) is a step of removing impurities from the pickling waste solution and preparing an electrolyte solution to be used in the electrolytic cell.
  • the pickling waste solution is repeatedly filtered using a filter paper to remove impurities, and
  • the pH is adjusted using hydrochloric acid (HCl) and sodium hydroxide (NaOH) to prepare an electrolyte solution.
  • the said electrolyte solution is 0.1-1 M in metal salt ion concentration.
  • concentration of the electrolyte increases, the size of the iron oxide powder increases, because the smaller the iron salt concentration in the aqueous solution, the stronger the nucleation and the smaller the grain size.
  • Step (b) is a step of applying a current to the electrolytic cell using the electrolyte prepared in step (a) to produce iron oxide powder, the electrolytic cell is composed of an electrolyte, a positive electrode and a negative electrode.
  • the positive electrode and the negative electrode are preferably at least two kinds selected from the group consisting of iron, stainless steel, zinc, copper, and platinum, and more preferably, high purity iron and high purity stainless steel are used as the positive electrode.
  • the current is preferably added to the current density of 0.1A to 0.5A / cm 2 of the current to be applied according to the area of the cathode. This is because an overcurrent must be applied to the electrode of the electrolytic cell rather than a general thin film plating condition in order to grow into a powder form rather than a thin film.
  • the size of the powder increases, because the higher the current density, the better the grain growth and the larger the grain size.
  • Step (c) is a step of performing a water washing process using the iron oxide powder prepared in step (b), followed by heat treatment to produce an iron oxide pigment, the water washing process using a hydrochloric acid and sodium hydroxide pH 6 After adjusting to ⁇ 11 and reacting, the reaction is performed several times using a centrifuge. The washing process produces nanometer-sized iron oxide powder near pH 7.
  • the heat treatment is preferably performed while changing from 120 °C to 400 °C.
  • heat treatment is performed at 120 ° C. or higher, red to yellow iron oxide may be formed depending on the heat treatment temperature.
  • color reproducibility problems may occur due to carbon dioxide and water vapor during drying, which can be solved by a change in heat treatment conditions.
  • the iron oxide pigment is manufactured by the method for producing the iron oxide pigment according to the present invention, it is possible to easily prepare a high quality nanometer-sized iron oxide powder in a pickling waste solution at low cost, and the iron oxide pigment does not contain heavy metals. Can be prepared.
  • FIG. 1 shows a cell for producing iron oxide particles by the electroplating method.
  • a cell is constructed, and general rail gold conditions include iron salt dissolved in distilled water as an electrolyte, and a working electrode and a counter electrode are iron, stainless steel, zinc, copper, and platinum.
  • Plating was performed using two selected from the group consisting of. Iron oxide powder was prepared by applying an overcurrent for growing into a powder rather than a thin film. In order to prepare the iron oxide powder, the electrolyte was used as a pickling solution from which impurities were removed, and the pH of the electrolyte was adjusted by using HCl and NaOH. In order to use the electroplating method, the anode was made of high purity iron, and the plated anode was substantially experimented by using a high purity stainless steel plate. One of the experimental conditions, the current density was applied by calculating the area of the cathode and the experiment was performed.
  • the concentration of the electrolyte was 1M, 0.5M, and 0.1M using the pickling waste liquid from which impurities were removed, and the current density was measured by changing the current density to 200mA / cm 2 starting with 100mA / cm 2 .
  • Photographs of the iron oxide powder prepared by applying a current are shown in FIGS. 3 (100 mA / cm 2 ) to 4 (200 mA / cm 2 ).
  • the size of the powder changes depending on the concentration and current density of the electrolyte, which is an important variable in the production of iron oxide powder, the size of the powder increases as the concentration or current density of the electrolyte Confirmed. It is thought that the smaller the concentration of the metal salt in the aqueous solution in relation to the concentration of the metal salt ions, the stronger the nucleation and the smaller the crystal grains to obtain the small particles. In addition, it is thought that the thickening of the plating thickness is excellent in the growth of the particles themselves, and the grains become large and the particles become large.
  • the pH of iron oxide powders of various sizes (several ⁇ m to several nm) prepared in Example 1 was adjusted to 6-11 using HCl and NaOH, and the precipitate was washed several times using a centrifuge.
  • a nanometer-sized iron oxide powder having a pH of 7, and heat treatment while changing the heat treatment conditions from 120 °C to 400 °C conditions to oxidize the iron oxide powder to implement the color was prepared.
  • the heat treatment condition is less than 120 °C akaganeite (Akaganeite) structure is formed, at a temperature above 120 °C Hematite (Fe 2 O 3 ) Is produced, it can be seen that the iron oxide of the yellow-based series is formed by controlling the heat treatment temperature of 130 °C or more.
  • Color reproducibility problems may occur under the influence of iron carbonate (Iron Cabonate) or agaganate (Akaganeite), which can solve the problem caused by impurities by raising the heat treatment temperature to 120 °C or more.

Abstract

The present invention relates to a method for producing an iron oxide pigment using electroplating. The method for producing an iron oxide pigment according to the present invention is configured such that by using electroplating and with current density and concentration as variables, a high-quality, nanometer-sized iron oxide powder can be produced from waste pickle liquor in an easy and inexpensive manner, and an iron oxide pigment containing no heavy metal can be produced.

Description

전기도금법을 이용한 산화철 안료의 제조방법Manufacturing Method of Iron Oxide Pigment Using Electroplating Method
본 발명은 전기도금법을 이용한 환경친화적인 산화철 안료의 제조방법에 관한 것이다.The present invention relates to a method for producing environmentally friendly iron oxide pigments using the electroplating method.
산화철 제조를 위한 침전법은 오래 전부터 알려져 왔다. 이런 방법의 통상적인 과정이 예를 들어, 문헌 [Ullmanns Enzyklopaedie der technischen Chemie, 5판, volume A 20, p. 297 이하]에 기재되어 있다. 강판의 산세척 중에 형성된 황산 제1철(II), 또는 황산법 (sulfate process)에 의한 이산화 티타늄의 제조 중에 형성된 황산 제1철(II)이 원료로 보통 사용된다.Precipitation methods for iron oxide production have long been known. Conventional procedures of this method are described, for example, in Ullmanns Enzyklopaedie der technischen Chemie, 5th edition, volume A 20, p. 297 and below. Ferrous sulfate (II) sulfate formed during pickling of the steel sheet or ferrous sulfate (II) sulfate formed during the production of titanium dioxide by the sulfate process is usually used as a raw material.
산세척 산업에서는 산세액으로 염산을 사용하려는 추세가 수 년간 증가되어 왔고, 그로 인해 다량의 FeCl2가 형성된다. 또한, 이산화 티타늄을 제조하기 위해 소위 염화법 (chloride process)을 체계적으로 점점 더 사용하고 있다. TiO2 제조용 합성 루틸 (rutile) 제조 중에 다량의 FeCl2가 형성된다. 따라서, 유용한 물질로 가능한 한 많이 전환시켜야 하는 염화 제1철(II) 함유 용액이 이런 방법들로부터 점점 더 많이 형성되고 있다.In the pickling industry, the tendency to use hydrochloric acid as a pickling liquid has increased over the years, resulting in the formation of large amounts of FeCl 2 . In addition, the so-called chloride process is increasingly used systematically to produce titanium dioxide. A large amount of FeCl 2 is formed during the production of synthetic rutile for the production of TiO 2 . Therefore, more and more ferrous chloride (II) -containing solutions that must be converted as much as possible into useful materials are being formed from these methods.
FeCl2 폐액을 활용하는 한가지 통상적인 방법은 (통상 1000 ℃가 넘는) 고온에서 염화 제1철(II) 및 염화 제2철(III)을 산화적 가수분해시키는 분무 배소법 (spray roasting process)이다. 산화철, 통상적으로 적철광, 및 산세척 공정으로의 재순환과 같이 유용한 물질로서 재순환될 수도 있는 염산이 이 방법에서는 최종 생성물이다. 일반적으로, 경질 아철산염 제조에 적당한 산화철이 어떠한 특정 정제 단계 없이 이 방법으로부터 얻어진다. 이런 방법으로 얻어진 산화철로부터 연질 아철산염을 제조하고자 할 경우, 사용된 염화철 용액은 미리 추가의 정제 작업을 거쳐야 하기 때문에 상당히 고비용이 든다. 또한, 주로 하등 품질의 염화철이 더욱 많이 제조되고, 아철산염 시장의 수용량이 제한되어 있으므로, 이런 염화철로부터 유용한 물질을 제조하는 대안을 모색하고 있다. One common method of utilizing FeCl 2 waste is a spray roasting process that oxidatively hydrolyzes ferric chloride (II) and ferric chloride (III) at high temperatures (typically above 1000 ° C.). . Hydrochloric acid, which may be recycled as a useful material, such as iron oxide, typically hematite, and to the pickling process, is the final product in this process. In general, iron oxide suitable for the production of light ferrite is obtained from this process without any specific purification step. If a soft ferrite is to be prepared from iron oxide obtained in this way, the iron chloride solution used is quite expensive because it requires further purification in advance. In addition, more iron, mainly of lower quality, is produced, and the capacity of the ferrite market is limited, and alternatives are being made to produce useful materials from these iron chlorides.
종래의 기술에 따른 산화철 금속 입자 제조방법은 다양하게 실시되고 있으며, 대표적인 몇 가지를 설명하면 다음과 같다. 첫째로, 기계적 분쇄법은 큰 부피(bulk) 상의 금속을 물리적 기계적 힘으로 분쇄하여 작게 만드는 방법이며, 둘째로, 증발 응축법은 금속의 부피 상을 고온으로 가열하여 증발시킨 후 액체 질소에 의해 급속히 냉각시켜서 나노미터 크기의 입자를 얻는 방법이다. 마지막으로, 콜로이드(Colloid)법은 금속 염을 수용액 혹은 무수용액 중에 분자 단위로 녹인 후 다양한 환원제를 이용하여 환원시켜서 나노 크기 입자를 얻는 방법이다. 그러나, 상기와 같은 종래의 나노미터 크기 금속 입자 제조방법들은 입자 크기를 작게 얻기 위한 복잡한 공정 및 크기조절의 어려움 등이 문제점으로 지적되었다. Iron oxide metal particle production method according to the prior art is carried out in various ways, a few of the representative will be described as follows. First, mechanical grinding is a method of grinding a large volume of metal by physical mechanical force to make it smaller. Second, an evaporative condensation method is rapidly heated by liquid nitrogen after evaporating by heating the bulk phase of a metal to a high temperature. It is a method of cooling to obtain nanometer-sized particles. Finally, the colloid method is a method of obtaining nano-sized particles by dissolving metal salts in molecular units in an aqueous solution or an anhydrous solution and then reducing them using various reducing agents. However, the conventional nanometer-sized metal particle manufacturing method as described above has been pointed out as a problem such as a complicated process and a difficulty in controlling the size to obtain a small particle size.
따라서, 산세폐액 또는 염화철 출발 물질로부터 철 금속입자를 형성시킬 때에 있어서, 그 크기를 조절할 수 있는 효율적인 공정에 대한 개발의 필요성이 절실히 요구되고 있다.Therefore, when forming ferrous metal particles from pickling liquor or iron chloride starting materials, there is an urgent need for the development of an efficient process capable of controlling the size thereof.
본 발명자들은 산세폐액 또는 염화철 출발물질로부터 철 금속입자를 형성시킬 때, 그 크기를 조절할 수 있는 효율적인 공정에 대해 연구하던 중, 전기도금법을 이용하여 인가 전압 및 전해액의 농도를 변수로 둘 경우 그 크기의 조절이 가능함을 확인하고, 본 발명을 완성하였다.The inventors of the present invention have been studying an efficient process for controlling the size of iron metal particles from pickling liquor or iron chloride starting materials. It was confirmed that the control of, and completed the present invention.
따라서, 본 발명은 전기도금법을 이용한 산화철 안료의 제조방법을 제공하고자 한다.Accordingly, the present invention is to provide a method for producing an iron oxide pigment using the electroplating method.
본 발명은 산세폐액 또는 염화철 출발물질로부터 철 금속입자를 형성시킬 때 전기도금법을 이용하여 인가전압 및 전해액의 농도를 변수로 함으로써 저비용으로 철 금속입자의 크기를 용이하게 조절할 수 있는 전기도금법을 이용한 산화철 안료의 제조방법을 제공한다.The present invention is an iron oxide using an electroplating method that can easily adjust the size of the iron metal particles at low cost by using the electroplating method when the iron metal particles are formed from pickling waste liquid or iron chloride starting material by using the applied voltage and the concentration of the electrolyte as a variable It provides a method for producing a pigment.
본 발명에 따른 산화철 안료의 제조방법은, 전기도금법을 이용하여 전류밀도와 농도를 변수로 하여, 산세폐액에서 고품질의 나노미터 크기의 산화철 분말을 저비용으로 간단하게 제조할 수 있으며, 중금속이 포함되지 않은 산화철 안료를 제조할 수 있다.In the method for preparing the iron oxide pigment according to the present invention, by using the electroplating method as a variable current density and concentration, high-quality nanometer-sized iron oxide powder can be easily produced at low cost in pickling liquor, and heavy metals are not included. Iron oxide pigments can be prepared.
도 1은 본 발명의 전기도금법을 이용한 산화철 분말을 제조하기 위한 전해 셀의 모식도를 나타낸 도이다.1 is a view showing a schematic diagram of an electrolytic cell for producing iron oxide powder using the electroplating method of the present invention.
도 2는 전해 셀의 전극을 나타낸 도이다[왼쪽: 양극, 오른쪽: 음극].2 is a diagram showing an electrode of an electrolytic cell (left: positive electrode, right: negative electrode).
도 3은 전해 셀에 전류밀도를 0.1A/cm2로 가하여 제조된 산화철 분말을 나타낸 도이다.3 is a diagram showing an iron oxide powder prepared by applying a current density of 0.1 A / cm 2 to an electrolytic cell.
도 4는 전해 셀에 전류밀도를 0.2A/cm2로 가하여 제조된 산화철 분말을 나타낸 도이다.Figure 4 is a diagram showing the iron oxide powder prepared by applying a current density of 0.2A / cm 2 to the electrolytic cell.
본 발명은The present invention
(a) 산세폐액의 불순물을 제거하고 전해액을 제조하는 단계;(a) removing impurities from the pickling waste solution and preparing an electrolyte solution;
(b) 상기 (a)단계에서 제조된 전해액 및 전극으로 구성된 전해 셀에 전류를 가하여 산화철 분말을 제조하는 단계; 및(b) applying an electric current to an electrolytic cell composed of the electrolyte solution and the electrode prepared in step (a) to produce iron oxide powder; And
(c) 상기 (b)단계에서 제조된 산화철 분말을 이용해 수세 공정을 수행 후, 열처리하는 단계; 를 포함하는, 산화철 안료의 제조방법을 제공한다.(c) performing a water washing process using the iron oxide powder prepared in step (b), followed by heat treatment; It provides a method of producing an iron oxide pigment.
이하, 본 발명에 대해서 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명의 산화철 안료의 제조방법에서 (a)단계는 산세폐액의 불순물을 제거하고 전해 셀에 사용될 전해액을 제조하는 단계로서, 산세폐액을 여과지를 이용하여 반복적으로 여과하여 불순물을 제거하고, 전해액의 pH는 염산(HCl)과 수산화나트륨(NaOH)을 이용하여 조절하여 전해액을 제조한다. In the method for preparing the iron oxide pigment of the present invention, step (a) is a step of removing impurities from the pickling waste solution and preparing an electrolyte solution to be used in the electrolytic cell. The pickling waste solution is repeatedly filtered using a filter paper to remove impurities, and The pH is adjusted using hydrochloric acid (HCl) and sodium hydroxide (NaOH) to prepare an electrolyte solution.
상기 전해액은 금속염 이온의 농도가 0.1~1M인 것이 바람직하다. 전해액의 농도가 증가할수록 산화철 분말의 크기는 커지는데, 이는 수용액 중의 철염(iron salt)의 농도가 작을수록 핵 생성이 강하게 되어 결정립이 작게 되기 때문이다.It is preferable that the said electrolyte solution is 0.1-1 M in metal salt ion concentration. As the concentration of the electrolyte increases, the size of the iron oxide powder increases, because the smaller the iron salt concentration in the aqueous solution, the stronger the nucleation and the smaller the grain size.
상기 (b)단계는 상기 (a)단계에서 제조된 전해액을 이용한 전해 셀에 전류를 가해 산화철 분말을 제조하는 단계로서, 전해 셀은 전해액, 양극 및 음극으로 구성된다. Step (b) is a step of applying a current to the electrolytic cell using the electrolyte prepared in step (a) to produce iron oxide powder, the electrolytic cell is composed of an electrolyte, a positive electrode and a negative electrode.
상기 양극 및 음극은 철, 스테인리스 스틸, 아연, 구리, 백금으로 이루어진 군으로부터 선택된 2종 이상인 것이 바람직하며, 양극으로 순도가 높은 철, 음극으로 순도가 높은 스테인리스 스틸을 사용하는 것이 더욱 바람직하다.The positive electrode and the negative electrode are preferably at least two kinds selected from the group consisting of iron, stainless steel, zinc, copper, and platinum, and more preferably, high purity iron and high purity stainless steel are used as the positive electrode.
상기 전류는 음극의 면적에 따라 가하는 전류의 전류밀도를 0.1A~0.5A/cm2 로 가하는 것이 바람직하다. 이는 전해 셀의 전극에서 박막이 아닌 분말 형태로 성장시키기 위해 일반적인 박막 도금 조건보다 과전류를 인가하여야 하기 때문이다.The current is preferably added to the current density of 0.1A to 0.5A / cm 2 of the current to be applied according to the area of the cathode. This is because an overcurrent must be applied to the electrode of the electrolytic cell rather than a general thin film plating condition in order to grow into a powder form rather than a thin film.
상기 전류밀도가 증가할수록 분말의 크기가 증가하는데, 이는 전류밀도가 높을수록 입자의 성장이 뛰어나 결정립이 커지게 되기 때문이다.As the current density increases, the size of the powder increases, because the higher the current density, the better the grain growth and the larger the grain size.
상기 (c)단계는 상기 (b)단계에서 제조된 산화철 분말을 이용해 수세 공정을 수행 후, 열처리하여 산화철 안료를 제조하는 단계로서, 상기 수세 공정은 산화철 분말을 염산과 수산화나트륨을 이용하여 pH 6~11로 조절하고 반응시킨 후, 원심분리기를 이용하여 수차례 수행한다. 수세 공정을 통해 pH 7 부근의 나노미터 크기의 산화철 분말이 제조된다.Step (c) is a step of performing a water washing process using the iron oxide powder prepared in step (b), followed by heat treatment to produce an iron oxide pigment, the water washing process using a hydrochloric acid and sodium hydroxide pH 6 After adjusting to ˜11 and reacting, the reaction is performed several times using a centrifuge. The washing process produces nanometer-sized iron oxide powder near pH 7.
상기 열처리는 120℃에서 400℃로 변화시키면서 수행하는 것이 바람직하다. 열처리 조건이 120℃ 이상에서 열처리를 하게 될 경우 열처리 온도에 따라 적색에서 황색 계열의 산화철이 형성될 수 있다. 또한, 건조 중에 이산화탄소와 수증기에 의해 색상의 재현성 문제가 발생할 수 있는데, 이는 열처리 조건의 변화로 해결 가능하다.The heat treatment is preferably performed while changing from 120 ℃ to 400 ℃. When heat treatment is performed at 120 ° C. or higher, red to yellow iron oxide may be formed depending on the heat treatment temperature. In addition, color reproducibility problems may occur due to carbon dioxide and water vapor during drying, which can be solved by a change in heat treatment conditions.
상기한 바와 같이, 본 발명에 따른 산화철 안료의 제조 방법으로 산화철 안료를 제조할 경우, 산세폐액에서 고품질의 나노미터 크기의 산화철 분말을 저비용으로 간단하게 제조할 수 있으며, 중금속이 포함되지 않은 산화철 안료를 제조할 수 있다.As described above, when the iron oxide pigment is manufactured by the method for producing the iron oxide pigment according to the present invention, it is possible to easily prepare a high quality nanometer-sized iron oxide powder in a pickling waste solution at low cost, and the iron oxide pigment does not contain heavy metals. Can be prepared.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 실시예에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited by the examples.
<실시예 1> 전기도금법에 의한 산화철 금속 입자의 제조 Example 1 Preparation of Iron Oxide Metal Particles by Electroplating Method
도 1에 전기도금법에 의한 산화철 입자를 제조하기 위한 셀을 나타내었다.1 shows a cell for producing iron oxide particles by the electroplating method.
도 1에 나타난 바와 같이 셀을 구성하고, 일반적인 철도금 조건은 증류수에 용해시킨 철염을 전해액으로 사용하고 작동전극(working electrode)과 상대전극(counter electrode)이 철, 스테인리스 스틸, 아연, 구리, 백금으로 이루어진 군으로부터 선택된 2종으로 사용하여 도금을 진행하였다. 박막이 아닌 분말 형태로 성장시키기 위한 과전류를 인가하여 산화철분말을 제조하였다. 산화철 분말을 제조하기 위해 전해액은 불순물을 제거한 산세폐액을 사용하고 전해액의 pH는 HCl과 NaOH를 이용하여 조절하여 실험을 진행하였다. 전기도금법을 이용하기 위하여 양극은 순도가 높은 철을 사용하고 실질적으로 도금이 이루어지는 음극은 순도가 높은 스테인리스스틸 판을 사용하여 실험을 실시하였다. 실험 조건 중 하나인 전류밀도를 음극의 면적을 계산하여 인가하고 실험을 실시하였다. As shown in FIG. 1, a cell is constructed, and general rail gold conditions include iron salt dissolved in distilled water as an electrolyte, and a working electrode and a counter electrode are iron, stainless steel, zinc, copper, and platinum. Plating was performed using two selected from the group consisting of. Iron oxide powder was prepared by applying an overcurrent for growing into a powder rather than a thin film. In order to prepare the iron oxide powder, the electrolyte was used as a pickling solution from which impurities were removed, and the pH of the electrolyte was adjusted by using HCl and NaOH. In order to use the electroplating method, the anode was made of high purity iron, and the plated anode was substantially experimented by using a high purity stainless steel plate. One of the experimental conditions, the current density was applied by calculating the area of the cathode and the experiment was performed.
구체적으로, 불순물을 제거한 산세폐액을 이용하여 전해액의 농도는 1M과 0.5M, 및 0.1M의 농도로, 전류밀도는 100mA/cm2으로 시작하여 200mA/cm2로 변화시켜 측정하였다. 전류를 가하여 제조된 산화철 분말의 사진을 도 3(100mA/cm2) 내지 도 4(200mA/cm2)에 나타내었다. Specifically, the concentration of the electrolyte was 1M, 0.5M, and 0.1M using the pickling waste liquid from which impurities were removed, and the current density was measured by changing the current density to 200mA / cm 2 starting with 100mA / cm 2 . Photographs of the iron oxide powder prepared by applying a current are shown in FIGS. 3 (100 mA / cm 2 ) to 4 (200 mA / cm 2 ).
도 3 및 도 4에 나타난 바와 같이, 산화철 분말 제조 시 중요한 변수인 전해액의 농도와 전류밀도에 따라 분말의 크기가 달라지는 것을 확인할 수 있었는데, 전해액의 농도 또는 전류밀도가 증가할수록 분말의 크기가 커지는 것을 확인하였다. 이는 금속염 이온의 농도와 관련하여 수용액 중의 금속염의 농도가 작을수록 핵 생성이 강하여 결정립이 작게 되어 작은 입자를 얻을 수 있는 것으로 생각된다. 또한, 도금 두께가 두꺼워지는 것은 입자의 성장 자체가 뛰어나 결정립이 커지게 되어 입자가 커지게 되는 것으로 생각된다.As shown in Figure 3 and 4, it can be seen that the size of the powder changes depending on the concentration and current density of the electrolyte, which is an important variable in the production of iron oxide powder, the size of the powder increases as the concentration or current density of the electrolyte Confirmed. It is thought that the smaller the concentration of the metal salt in the aqueous solution in relation to the concentration of the metal salt ions, the stronger the nucleation and the smaller the crystal grains to obtain the small particles. In addition, it is thought that the thickening of the plating thickness is excellent in the growth of the particles themselves, and the grains become large and the particles become large.
<실시예 2> 산화철 분말을 이용한 산화철 안료의 제조Example 2 Preparation of Iron Oxide Pigment Using Iron Oxide Powder
상기 실시예 1에서 제조된 다양한 크기(수 ㎛ ~ 수 ㎚)의 산화철 분말의 pH를 6~11로 HCl과 NaOH를 이용하여 조절하여 반응시키고, 침전물을 원심분리기를 이용하여 수차례 수세공정을 수행하여, pH가 7인 나노미터 크기의 산화철 분말을 제조하고, 열처리 조건을 120℃에서 400℃ 조건으로 변화하면서 열처리를 실시하여 산화철분말을 산화시켜 색상을 구현하였다.The pH of iron oxide powders of various sizes (several μm to several nm) prepared in Example 1 was adjusted to 6-11 using HCl and NaOH, and the precipitate was washed several times using a centrifuge. To prepare a nanometer-sized iron oxide powder having a pH of 7, and heat treatment while changing the heat treatment conditions from 120 ℃ to 400 ℃ conditions to oxidize the iron oxide powder to implement the color.
일반적으로 열처리 조건이 120℃ 미만에서는 아카가네이트(Akaganeite) 구조가 형성되고, 120℃ 이상의 온도에서는 적철석(Hematite)(Fe2O3)이 생성되는데, 130℃ 이상의 열처리 온도 조절에 따라 적색에서 황색 계열의 산화철이 형성됨을 알 수 있었다. 또한, 건조 중에 일부 결정 수의 존재와 공기 중 불순물의 이산화탄소(CO2)나 수증기(H2O)에 의해 건조 중 능철석(Iron Cabonate)이나 아카가네이트(Akaganeite)의 불순물의 영향으로 색상의 재현성 문제가 발생할 수 있는데, 이는 열처리 온도를 120℃ 이상으로 상승시켜 불순물에 의한 문제를 해결할 수 있다.In general, when the heat treatment condition is less than 120 ℃ akaganeite (Akaganeite) structure is formed, at a temperature above 120 ℃ Hematite (Fe2O3) Is produced, it can be seen that the iron oxide of the yellow-based series is formed by controlling the heat treatment temperature of 130 ℃ or more. In addition, the presence of some crystalline water during drying and carbon dioxide (CO)2) And water vapor (H2During drying by o) Color reproducibility problems may occur under the influence of iron carbonate (Iron Cabonate) or agaganate (Akaganeite), which can solve the problem caused by impurities by raising the heat treatment temperature to 120 ℃ or more.

Claims (4)

  1. (a) 산세폐액의 불순물을 제거하고 전해액을 제조하는 단계;(a) removing impurities from the pickling waste solution and preparing an electrolyte solution;
    (b) 상기 (a)단계에서 제조된 전해액 및 전극으로 구성된 전해 셀에 전류를 가하여 산화철 분말을 제조하는 단계; 및(b) applying an electric current to an electrolytic cell composed of the electrolyte solution and the electrode prepared in step (a) to produce iron oxide powder; And
    (c) 상기 (b)단계에서 제조된 산화철 분말을 이용해 수세 공정을 수행 후, 열처리하는 단계; 를 포함하는, 산화철 안료의 제조방법.(c) performing a water washing process using the iron oxide powder prepared in step (b), followed by heat treatment; A method for producing an iron oxide pigment, comprising.
  2. 제1항에 있어서, 상기 (b)단계의 전극은 철, 스테인리스 스틸, 아연, 구리, 백금으로 이루어진 군으로부터 선택된 2종 이상인 것을 특징으로 하는, 산화철 안료의 제조방법.The method of claim 1, wherein the electrode of step (b) is at least two selected from the group consisting of iron, stainless steel, zinc, copper, and platinum.
  3. 제1항에 있어서, 상기 (c)단계의 수세 공정은 pH 6~11에서 원심분리기를 이용하여 수행하는 것을 특징으로 하는, 산화철 안료의 제조방법.The method of claim 1, wherein the washing process of step (c) is carried out using a centrifuge at pH 6 ~ 11, the iron oxide pigment production method.
  4. 제1항에 있어서, 상기 (c)단계의 열처리는 120℃에서 400℃로 변화시키면서 수행하는 것을 특징으로 하는, 산화철 안료의 제조방법.The method of claim 1, wherein the heat treatment of step (c) is performed while changing from 120 ° C to 400 ° C.
PCT/KR2013/006866 2013-02-06 2013-07-31 Method for producing iron oxide pigment using electroplating WO2014123284A1 (en)

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KR19990085118A (en) * 1998-05-14 1999-12-06 조헌영 Process for producing hydrogen and iron nitrate (3) from pickling liquor of iron by electrolysis
KR100262493B1 (en) * 1996-12-19 2000-08-01 이구택 Method for remove chlorine ion
US6179987B1 (en) * 1999-08-11 2001-01-30 Ut Battelle, Llc Method and apparatus to electrolytically produce high-purity magnetite particles

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KR100262493B1 (en) * 1996-12-19 2000-08-01 이구택 Method for remove chlorine ion
KR19990085118A (en) * 1998-05-14 1999-12-06 조헌영 Process for producing hydrogen and iron nitrate (3) from pickling liquor of iron by electrolysis
US6179987B1 (en) * 1999-08-11 2001-01-30 Ut Battelle, Llc Method and apparatus to electrolytically produce high-purity magnetite particles

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