KR20040008969A - MANUFACTURING METHOD OF Fe INORGANIC PIGMENT USING FERROUS SULFATE - Google Patents

MANUFACTURING METHOD OF Fe INORGANIC PIGMENT USING FERROUS SULFATE Download PDF

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KR20040008969A
KR20040008969A KR1020020042732A KR20020042732A KR20040008969A KR 20040008969 A KR20040008969 A KR 20040008969A KR 1020020042732 A KR1020020042732 A KR 1020020042732A KR 20020042732 A KR20020042732 A KR 20020042732A KR 20040008969 A KR20040008969 A KR 20040008969A
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ferrous sulfate
hydroxy
solution
iron
iii
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KR1020020042732A
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Korean (ko)
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김창욱
김규환
김정권
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김창욱
김규환
김정권
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Priority to KR1020020042732A priority Critical patent/KR20040008969A/en
Publication of KR20040008969A publication Critical patent/KR20040008969A/en

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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
    • 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
    • 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
    • C09C3/043—Drying, calcination
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Abstract

PURPOSE: A method for preparing an iron-based inorganic pigment by using ferrous sulfate is provided, to reduce remarkably the reaction time by employing air oxidation and to obtain an orange-yellow pigment having a fine and uniform particle size of 1.2-1.5 micrometers, a large specific surface area and an excellent concealing power. CONSTITUTION: The method comprises the steps of adding a small quantity of an ammonium chloride solution to a ferrous sulfate solution, maintaining the temperature to be 50-70 deg.C and adding a sodium hydroxide solution to control the pH to be 6.8; stirring the mixture solution to form uniform and fine ferrous hydroxysulfate nuclei by suspension; controlling the size of the nuclei with adding an ammonium chloride solution to prevent the flocculation of nuclei; adding zeolite-XA to disperse air in the solution to activate oxygen on the surface of the zeolite-XA for growing the nuclei into the uniform ferric hydroxy oxide particles by air oxidation and for synthesizing the pure α-ferric hydroxy oxide; and separating the α-ferric hydroxy oxide by centrifugation and heating and drying it at 120 deg.C for 1 hour.

Description

황산 제1철을 이용한 철계 무기안료의 제조방법{MANUFACTURING METHOD OF Fe INORGANIC PIGMENT USING FERROUS SULFATE}Manufacturing method of iron-based inorganic pigments using ferrous sulfate {MANUFACTURING METHOD OF Fe INORGANIC PIGMENT USING FERROUS SULFATE}

본 발명은 황산 제1철을 이용한 철계 무기안료의 제조방법에 관한 것으로서, 특히 황산 제1철 수용액에 수산화나트륨과 염화암모늄 용액을 첨가하여 하이드록시 황산 제1철로 서스펜션화하여 미세한 입자의 핵을 형성시키고, 공기산화에 의하여 미세한 입자의 핵을 성장시키면서 α형 하이드록시 산화철(III)로 산화시켜 은폐력이 좋고 색상이 밝은 오렌지 색상의 철계안료를 값싸게 제조할 수 있는 황산 제1철을 이용한 철계 무기안료의 제조방법에 관한 것이다.The present invention relates to a method for producing an iron-based inorganic pigment using ferrous sulfate, and in particular, by adding sodium hydroxide and ammonium chloride solution to the ferrous sulfate aqueous solution is suspended in hydroxy ferrous sulfate to form a nucleus of fine particles Ferrous sulfate using ferrous sulfate, which can produce iron-based pigments with good hiding power and bright orange color by oxidizing with α-hydroxy iron (III) while growing nuclei of fine particles by air oxidation. It relates to a method for producing a pigment.

종래로 부터 황산 제1철을 이용하여 황색의 철계 무기안료인 하이드록시 산화철(III)의 제조방법은 황산 제1철에 수산화나트륨 용액을 첨가하여 서스펜션화된 하이드록시 황산 제1철의 작은 입자를 핵으로 형성시켰으나, 핵 입자의 크기가 크고 응집현상이 일어나 입도분포가 균일하지 못하여, 공기산화에 의하여 하이드록시 황산 제1철 입자의 핵이 성장되면서 철계 황색안료인 하이드록시 산화철(III)로 산화될 때에도 영향을 주어 입도가 크고 입도분포가 균일하지 못하여 안료의 은폐력이 저하되고 비표면적이 적어 미세한 두께로 도포할 때 코팅상태가 나쁘다는 문제점이 있었다.Conventionally, a method for preparing hydroxy iron (III), a yellow iron-based inorganic pigment, using ferrous sulfate is obtained by adding sodium hydroxide solution to ferrous sulfate to remove small particles of hydroxy ferrous sulfate. Although formed as a nucleus, the nuclei of hydroxy ferrous sulfate particles are grown by air oxidation and oxidized to hydroxy iron oxide (III), which is an iron-based yellow pigment, due to the large size of the nucleus particles and coagulation. When the coating is affected, the particle size is large and the particle size distribution is not uniform, so the hiding power of the pigment is lowered and the specific surface area is small.

다시 말하면, 황산 제1철 용액에 수산화나트륨 용액을 첨가하여 서스펜션화된 하이드록시 황산 제1철의 미세입자를 형성시킬 때 황산 제1철 용액에 수산화나트퓸 용액을 첨가하는 순간에 부분적으로 빠른 시간에 서스펜션화가 일어나서 하이드록시 황산 제1철의 입도가 2∼2.3㎛ 정도로 클 뿐만 아니라, 응집현상이 일어난다는 문제점이 있었다..In other words, when the sodium hydroxide solution is added to the ferrous sulfate solution to form microparticles of the suspended hydroxy ferrous sulfate, a partially fast time at the moment of adding the sodium hydroxide solution to the ferrous sulfate solution There was a problem in that the suspension was formed to cause the ferrous hydroxy sulfate to have a particle size of about 2 to 2.3 µm, as well as agglomeration.

또한, 서스펜션된 하이드록시 황산 제1철을 공기산화시킬 때 공기중의 산소를 폭기에 의하여 반응시킴으로 반응속도가 24∼48시간 소요되었으며, 생성되는 하이드록시 산화철은 초록색과 노랑색을 띄는 β형과 노랑색과 적색을 띄는 α형의 혼합물로 생성되므로, 안료의 색상이 약간 초록색을 띄는 어두운 오렌지 색상의 안료로 제조되어 색상품위가 저하될 뿐 아니라, 제조할 때마다 균일성이 결여되어 균일한 색상의 제품을 제조할 수 없다는 등의 여러 가지 문제점이 있었다.In addition, when air oxidizing the suspended hydroxy ferrous sulfate, the reaction rate was 24 to 48 hours by reacting oxygen in the air by aeration, and the hydroxy iron oxide produced was β- and yellow in green and yellow color. Since it is made of a mixture of type α and red, the color of the pigment is made of a dark orange pigment with a slightly green color, so that the color quality is not deteriorated. There were various problems such as the inability to manufacture.

따라서, 본 발명은 상기 여러 가지 문제점을 감안하여 이루어진 것으로써, 본 발명의 목적은 비표면적이 크고 은폐력이 우수한 황산 제1철을 이용한 철계 무기안료의 제조방법을 제공하는데 있다.Accordingly, the present invention has been made in view of the above various problems, and an object of the present invention is to provide a method for producing an iron-based inorganic pigment using ferrous sulfate having a large specific surface area and excellent hiding power.

본 발명의 다른 목적은 밝은 오렌지 색상의 황색 무기안료를 제조할 수 있는 황산 제1철을 이용한 철계 무기안료의 제조방법을 제공하는데 있다It is another object of the present invention to provide a method for preparing an iron-based inorganic pigment using ferrous sulfate, which can produce a bright orange yellow inorganic pigment.

본 발명의 또 다른 목적은 제조코스트를 절감할 수 있는 황산 제1철을 이용한 철계 무기안료의 제조방법을 제공하는데 있다.Still another object of the present invention is to provide a method for preparing an iron-based inorganic pigment using ferrous sulfate, which can reduce manufacturing cost.

상기 목표를 달성하기 위하여 본 발명은 황산 제1철 용액에 미량의 염화암모늄 용액을 첨가하고 50∼70℃로 유지함과 동시에, 수산화나트륨 용액을 넣으면서 pH를 6.8로 조절하는 산도조절스텝과, 상기 산도조절스텝에서 산도가 조절된 상기 혼합용액을 계속 교반시키면서 서스펜션화시켜서 하이드록시 황산 제1철의 미세하고 균일한 입자핵을 형성시키는 입자핵 형성스탭과, 상기 입자핵 형성스탭에서 입자핵이 형성된 황산 제1철의 엉김을 방지하도록 염화암모늄 용액의 첨가하면서 하이드록시 황산 제1철의 미세한 입자 핵의 크기를 조절하는 입자핵 크기조절스텝과, 상기 입자핵 크기조절스텝에서 조절된 하이드록시 황산 제1철의 미세한 입자핵을 형성한 용액에 제올라이트-XA를 첨가하여 공기를 분산시켜서 제올라이트-XA 표면에서 산소를 활성화해서 공기산화에 의하여 하이드록시 산화철(III)의 미세하고 균일한 입자로 성장시킴과 동시에, 순수한 α형 하이드록시 산화철(III)을 합성하는 α형 하이드록시 산화철(III) 합성스텝과, 상기 α형 하이드록시 산화철(III) 합성스텝에서 합성된 α형 하이드록시 산화철(III)을 원심분리기를 이용하여 분리하고 120℃의 온도에서, 1시간 동안 가열 건조하는 건조스텝으로 이루어진 것을 특징으로 한다.In order to achieve the above object, the present invention adds a small amount of ammonium chloride solution to the ferrous sulfate solution and maintains it at 50-70 ° C, and simultaneously adjusts the pH to 6.8 while adding sodium hydroxide solution and the acidity. A particle nucleation step for forming fine and uniform particle nuclei of hydroxy ferrous sulfate by continuing to stir the mixed solution of which acidity is adjusted in the adjusting step, and sulfuric acid having particle nuclei formed in the particle nucleation step; A particle nucleus sizing step of adjusting the size of the fine particle nucleus of ferrous hydroxy sulfate while adding ammonium chloride solution to prevent agglomeration of ferrous iron, and the first hydroxy sulfate controlled in the particle nucleus sizing step Zeolite-XA is added to the solution that forms the fine particle nucleus of iron to disperse air to activate oxygen on the zeolite-XA surface. An α-hydroxy iron oxide (III) synthesis step of growing into fine and uniform particles of hydroxy iron (III) oxide by air oxidation and synthesizing pure α-hydroxy iron oxide (III), and the α-hydroxy The hydroxy iron (III) hydroxy iron oxide (III) synthesized in the synthesis step is characterized by consisting of a drying step of separating by using a centrifugal separator and heat drying at a temperature of 120 ℃ for 1 hour.

본 발명자는 염화 제1철 용액에 수산화나트륨 용액을 첨가하면, 하이드록시 염화철로 서스펜션이 일어나지 않고 용액의 혼합상태로 존재한다는 점을 발견하였다. 즉, 철의 염에서 황산이온은 하이드록시화된 입자가 빨리 형성되나, 염화이온은 하이드록시화된 입자가 형성되지 않고 입자형성을 억제시키는 역할을 하는 현상을 발견하고 본 발명을 완성하게 되었다.The inventors found that when sodium hydroxide solution is added to the ferrous chloride solution, no suspension occurs with hydroxy iron chloride and the solution is present in the mixed state. That is, in the salt of iron, sulfate ions quickly form hydroxylated particles, but chloride ions do not form hydroxylated particles and find a phenomenon that serves to suppress particle formation, thereby completing the present invention.

따라서, 1.0몰 황산 제1철 용액 1.0ℓ에 0.1몰 수산화나트륨 용액을 첨가하여 하이드록시 황산 제1철의 입자를 형성시키면 서스펜션이 빨리 일어나고 입자의 크기가 매우 크며 입자의 엉김현상이 일어나지만, 침전화를 억제하는 염소이온을 갖는 0.02몰 염화암모늄 용액 20㎖을 첨가하면, 서스펜션화하는 시간은 1시간 정도로 지연되지만, 서스펜션화된 하이드록시 황산 제1철 입자는 0.3∼0.5㎛의 매우 미세하게 형성되며 입자간의 엉김이 나타나지 않아 입도, 입도분포가 균일한 입자의 종자결정 핵을 형성시킬 수 있었다.Therefore, when 1.0 mole of ferrous sulfate solution is added with 0.1 mole of sodium hydroxide solution to form particles of hydroxy ferrous sulfate, the suspension takes place quickly, the particle size is very large and particle entanglement occurs. When 20 ml of 0.02 mol ammonium chloride solution having chlorine ions which inhibit the conversion is added, the suspension time is delayed by about 1 hour, but the suspension of hydroxy ferrous sulfate particles is formed very finely at 0.3 to 0.5 µm. As the particles did not exhibit entanglement, seed crystal nuclei of particles with uniform particle size and particle size distribution could be formed.

또한, 서스펜션화된 하이드록시 황산 제1철의 종자결정핵을 하이드록시 산화철(III)로 결정성장시키는 공기산화 반응에서 반응액에 다공성 제올라이트-XA를 첨가하고 공기를 공급하면 공기의 기포를 미세하게 분산시켜 접촉면적을 크게 하고, 제올라이트-XA에 내포된 많은 기공과 표면에서 공기중의 산소를 활성화시켜 공기산화를 촉진시키므로, 반응시간을 5시간 이내로 단축시킬 수 있을 뿐 아니라 제올라이트-XA의 표면활성화에 의하여 α형 하이드록시 산화철(III)만 선택적으로 합성되므로, 색상이 밝은 오렌지색인 황색안료를 제조할 수 있다.In addition, in the air oxidation reaction in which the seed crystal nucleus of the suspended hydroxy ferrous sulfate is crystallized with hydroxy iron (III) oxide, porous zeolite-XA is added to the reaction solution, and air is supplied finely. By dispersing, the contact area is increased, and oxygen in the air is activated in many pores and surfaces contained in zeolite-XA to promote air oxidation, so that the reaction time can be shortened to within 5 hours as well as surface activation of zeolite-XA. Since only α-hydroxy iron (III) oxide is selectively synthesized, a yellow pigment having a bright orange color can be produced.

이하, 본 발명의 바람직한 실시예에 의하여 상세히 설명한다.Hereinafter, a preferred embodiment of the present invention will be described in detail.

[실시예]EXAMPLE

1.0몰 황산 제1철 용액 1.0ℓ에 0.02몰 염화암모늄 용액 20㎖를 넣고 잘 혼합시킨 후 50∼70℃의 온도를 유지하면서 교반기를 이용하여 120rpm의 속도로 교반하면서 0.1몰 수산화나트륨 용액 135㎖를 2시간 동안 적하교반하면서 pH가 6.8로 유지유지하여 서스펜션화된 하이드록시 황산 제1철의 미세한 종자결정핵을 형성하였다.20 ml of 0.02 mol ammonium chloride solution was added to 1.0 liter of 1.0 mol ferrous sulfate solution, and the mixture was mixed well. Then, 135 ml of 0.1 mol sodium hydroxide solution was stirred at a speed of 120 rpm using a stirrer while maintaining a temperature of 50 to 70 ° C. While stirring dropwise for 2 hours, the pH was maintained at 6.8 to form fine seed crystal nuclei of suspended hydroxy ferrous sulfate.

이와 같이 형성된 황산 제1철의 미세한 종자결정핵은 입자의 엉김이 전혀 일어나지 않았으며, 이 때 미세한 종자결정핵의 입자의 크기를 한솔과학(주)제 SEM(모델명 ; ERA-8800)을 사용하여 입자크기를 측정하여 본 결과, 입자의 크기가 0.3∼0.5㎛로 매우 미세하였고 균일하였다.The fine seed crystal nuclei of ferrous sulfate formed as described above did not cause particle entanglement at all, and at this time, the size of the fine seed crystal nuclei was measured using a SEM (model name: ERA-8800) manufactured by Hansol Science, Inc. As a result of measuring the particle size, the particle size was very fine and uniform with 0.3 to 0.5㎛.

또한 상기 반응액인 서스펜션화된 하이드록시 황산 제1철 용액 1.0ℓ에 제올라이트-XA 25g을 첨가하고 70∼75℃의 온도를 유지시키면서 5시간 동안 300㎖/sec의 속도로 공기를 통과시키면 종자결정핵을 성장시켜 하이드록시 산화철(III)을 합성하였다.In addition, 25 g of zeolite-XA was added to 1.0 L of the fermented hydroxy ferrous sulfate solution, which was the reaction solution, and passed through the air at a rate of 300 ml / sec for 5 hours while maintaining a temperature of 70 to 75 ° C. to determine seed crystals. Nuclei were grown to synthesize hydroxy iron (III) oxide.

이와 같이 합성한 하이드록시 산화철(III)을 원심분리기를 이용하여 분리시키고 120℃의 온도에서, 1시간 가열 건조하여 무게를 측정한 결과 105g이었다.The hydroxy iron (III) thus synthesized was separated using a centrifugal separator, heated at 120 ° C. for 1 hour, and weighed to obtain 105 g.

이 때 합성된 하이드록시 산화철(III)의 입도는 1.2∼1.5㎛로써 입자의 크기가 균일하였으며 서울옵티콤(주)제 분광 반사측정기(모델명 ; CM-512m1)를 이용하여 최대반사율의 파장을 측정하였더니, 합성된 하이드록시 산화철(III)의 반사파장은 578∼610㎚로써 색상이 매우 밝은 오렌지색이었다.At this time, the particle size of the synthesized hydroxy iron (III) was 1.2-1.5 μm, and the particle size was uniform. The wavelength of the maximum reflectance was measured using a spectroscopic reflectometer (model name: CM-512m1) manufactured by Seoul Opticom Co., Ltd. As a result, the reflected wavelength of the synthesized hydroxy iron (III) oxide was 578-610 nm, which was very bright orange.

또한 합성된 하이드록시 산화철(III) 분말의 비표면적을 비표면적 측정기(모델명 ; NOVA 4000, Quantachrome. Co., USA)를 사용하여 측정하여 본 결과 115m/g로써 은폐력이 매우 우수함을 확인할 수 있었다.In addition, the specific surface area of the synthesized hydroxy iron oxide (III) powder was measured using a specific surface area measuring instrument (model name: NOVA 4000, Quantachrome. Co., USA), and as a result, it was confirmed that the hiding power was very excellent at 115 m / g.

[비교예][Comparative Example]

1.0몰 황산 제1철 용액 1.0㎖을 50∼70℃로 유지하면서 교반기를 이용하여 120rpm의 속도로 교반하면서 염화암모늄 용액을 첨가하지 않고, 0.1몰 수산화나트륨 용액 135㎖를 적하하여 pH가 6.8로 유지하였다.While maintaining 1.0 ml of 1.0 mol ferrous sulfate solution at 50-70 ° C., stirring at a speed of 120 rpm using a stirrer, without adding ammonium chloride solution, 135 ml of 0.1 mol sodium hydroxide solution was added dropwise to maintain pH at 6.8. It was.

이 때, 수산화나트륨 용액을 넣는 순간 서스펜션화된 하이드록시 황산 제1철의 입자가 형성되었으며, 입자의 엉김현상이 많이 일어났고, 형성된 하이드록시 황산 제1철의 입자의 크기는 0.5∼17.2㎛로 입자가 매우 컸으며 입도가 균일하지 못하였다.At this time, when the sodium hydroxide solution was added, suspended hydroxy ferrous sulfate particles were formed, and agglomeration of particles occurred a lot, and the size of the hydroxy ferrous sulfate particles was 0.5 to 17.2 μm. The particles were very large and the particle size was not uniform.

이와 같이 서스펜션화된 하이드록시 황산 제1철 용액 1.0ℓ를 70∼75℃의 온도로 유지시키면서 300㎖/sec의 속도로 공기를 통과시키면서 결정성장시켜 하이드록시 산화철(III)을 합성시키는데 24∼32시간이 소요되었다.Thus, 1.0 L of the suspended hydroxy ferrous sulfate solution was crystallized while passing air at a rate of 300 mL / sec while maintaining the temperature of 70-75 ° C. to synthesize hydroxy iron (III) 24-32. It took time.

이와 같이 합성한 하이드록시 산화철(III)을 원심분리기를 이용하여 분리시키고 120℃의 온도에서 1시간 동안 가열 건조한 후, 무게를 측정한 결과 103g이었다.The hydroxy iron oxide (III) thus synthesized was separated using a centrifugal separator, heated and dried at a temperature of 120 ° C. for 1 hour, and weighed as a result of 103 g.

이 때 합성된 하이드록시 산화철(III)의 입도는 0.7∼21.7㎛로 입도가 매우 컸고, 입도분포 역시 균일하지 못하였으며, 분광 반사 측정기를 이용하여 최대반사율의 파장을 측정하여 본 결과 반사파장이 553∼630로써 약간 녹색을 띈 적황색으로서, 색상이 밝지 못한 오렌지색이었다.At this time, the particle size of the synthesized hydroxy iron (III) oxide was 0.7-21.7 μm, the particle size was very large, and the particle size distribution was not uniform. The wavelength of the maximum reflectance was measured using a spectroscopic reflectometer. It was slightly reddish-yellow to -630, and it was orange with a light color.

또한, 비표면적 측정기(모델명 ; NOVA 4000, Quantachrome. Co., USA)를 사용하여 비표면적을 측정하여 본 결과 80∼92㎡/g으로 은폐력이 불량하였다.In addition, the specific surface area was measured using a specific surface area measuring instrument (model name: NOVA 4000, Quantachrome. Co., USA). As a result, the hiding power was poor at 80 to 92 m 2 / g.

상기 설명에 있어서, 특정 실시예를 들어서 도시하고 설명하였으나, 본 발명은 이에 한정되는 것은 아니며, 예를 들면 본 발명의 개념을 이탈하지 않는 범위내에서 이 기술 분야의 통상의 지식을 가진 자에 의해 여러가지로 설계변경할 수 있음은 물론이다.In the above description, the specific embodiments have been shown and described, but the present invention is not limited thereto, for example, by those skilled in the art without departing from the concept of the present invention. Of course, the design can be changed in various ways.

앞에서 설명한 바와 같이 본 발명의 황산 제1철 용액을 이용한 철계 무기안료의 제조방법에 의하면, 공기산화에 의한 반응시간을 크게 단축시킬 뿐 아니라 합성된 하이드록시 산화철(III) 입자의 크기가 1.2∼1.5㎛로써 매우 작고 균일하여 안료로써의 특성이 우수한 제품을 제조할 수 있으며, 특히 분광 최대 반사파장이 587∼610㎚로써 밝은 오렌지 색상의 α형 하이드록시 산화철(III)을 합성할 수 있으며, 비표면적이 크고 은폐력이 우수하고, 밝은 오렌지 색상의 황색 무기안료를 제조할 수 있을 뿐만 아니라, 제조코스트를 절감할 수 있다는 매우 뛰어난 효과가 있다.As described above, according to the method for preparing an iron-based inorganic pigment using the ferrous sulfate solution of the present invention, the reaction time by air oxidation is greatly shortened and the size of the synthesized hydroxy iron (III) oxide particles is 1.2 to 1.5. It is very small and uniform in size, making it possible to produce products with excellent pigment properties. Particularly, the spectral peak reflection wavelength is 587 to 610 nm, and it is possible to synthesize α-hydroxy iron oxide (III) of bright orange color. Not only can this large, concealable, bright orange yellow inorganic pigment be manufactured, but the manufacturing cost can be reduced.

Claims (4)

황산 제1철 용액에 미량의 염화암모늄 용액을 첨가하고 50∼70℃로 유지함과 동시에, 수산화나트륨 용액을 넣으면서 pH를 6.8로 조절하는 산도조절스텝과,Adding a small amount of ammonium chloride solution to the ferrous sulfate solution and maintaining it at 50-70 ° C., and adding a sodium hydroxide solution to adjust the pH to 6.8, 상기 산도조절스텝에서 산도가 조절된 상기 혼합용액을 계속 교반하여 서스펜션화시켜서 하이드록시 황산 제1철의 미세하고 균일한 입자핵을 형성시키는 입자핵 형성스탭과,A particle nucleation formation step of forming a fine and uniform particle nucleus of ferrous hydroxy sulfate by continuously stirring and suspension of the mixed solution in which the acidity is adjusted in the acidity adjusting step; 상기 입자핵 형성스탭에서 입자핵이 형성된 황산 제1철의 엉김을 방지하도록 염화암모늄 용액의 첨가하면서 하이드록시 황산 제1철의 미세한 입자 핵의 크기를 조절하는 입자핵 크기조절스텝과,A particle nucleus size adjusting step of adjusting the size of the fine particle nucleus of ferrous hydroxy sulfate while adding ammonium chloride solution to prevent agglomeration of ferrous sulfate in which particle nuclei are formed in the particle nucleation forming step; 상기 입자핵 크기조절스텝에서 조절된 하이드록시 황산 제1철의 미세한 입자핵을 형성한 용액에 제올라이트-XA를 첨가하여 공기를 분산시켜서 제올라이트-XA 표면에서 산소를 활성화해서 공기산화에 의하여 하이드록시 산화철(III)의 미세하고 균일한 입자로 성장시킴과 동시에, 순수한 α형 하이드록시 산화철(III)을 합성하는 α형 하이드록시 산화철(III) 합성스텝과,Zeolite-XA is added to a solution in which fine particle nuclei of hydroxy ferrous sulfate controlled in the particle nucleus size adjusting step are added to disperse air, thereby activating oxygen on the surface of zeolite-XA and hydroxy iron oxide by air oxidation. An α-hydroxy iron (III) synthesis step of growing into fine and uniform particles of (III) and synthesizing pure α-hydroxy iron oxide (III), 상기 α형 하이드록시 산화철(III) 합성스텝에서 합성된 α형 하이드록시 산화철(III)을 원심분리기를 이용하여 분리하고 120℃의 온도에서, 1시간 동안 가열 건조하는 건조스텝으로 이루어진 것을 특징으로 하는 황산 제1철을 이용한 철계 무기안료의 제조방법.The α-hydroxy iron oxide (III) synthesized in the α-hydroxy iron oxide (III) synthesis step is separated by a centrifugal separator, characterized in that the drying step of heat drying for 1 hour at a temperature of 120 ℃ Method for producing iron-based inorganic pigments using ferrous sulfate. 제1항에 있어서, 상기 산도조절스텝은 1.0몰 황산 제1철 수용액 1.0ℓ에 서스펜션 억제 및 엉김방지를 위하여 0.02몰 염화암모늄 용액 20㎖를 첨가하는 것을 특징으로 하는 황산 제1철을 이용한 철계 무기안료의 제조방법.According to claim 1, wherein the acidity adjusting step is iron-based inorganic ferrous sulfate using ferrous sulfate, characterized in that 20 ml of 0.02 molar ammonium chloride solution is added to 1.0 L of 1.0 mol ferrous sulfate aqueous solution to suppress suspension and prevent entanglement Method for producing a pigment. 제1항에 있어서, 상기 입자핵 크기조절스텝은 입자간의 엉김이 방지되도록 서스펜션화된 하이드록시 횡산 제1철의 입자크기가 0.3∼0.5㎛로 조절하는 것을 특징으로 하는 황산 제1철을 이용한 철계 무기안료의 제조방법.According to claim 1, wherein the particle size adjustment step is iron-based using ferrous sulfate, characterized in that the particle size of the hydroxy ferric acid ferric suspension is adjusted to 0.3 ~ 0.5㎛ to prevent entanglement between particles Method of preparing inorganic pigments. 제1항에 있어서, 상기 α형 하이드록시 산화철(III) 합성스텝은 서스펜션화된 하이드록시 황산 제1철 용액 1.0ℓ에 제올라이트-XA 25g을 첨가하고 70∼75℃의 온도를 유지시키면서 5시간 동안 300㎖/sec의 속도로 공기를 통과시키면 종자결정핵을 성장시켜 하이드록시 산화철(III)을 합성하는 것을 특징으로 하는 황산 제1철을 이용한 철계 무기안료의 제조방법.The method of claim 1, wherein the α-hydroxy iron (III) synthesis step is performed by adding 25 g of zeolite-XA to 1.0 L of suspended hydroxy ferrous sulfate solution and maintaining a temperature of 70 to 75 ° C. for 5 hours. A method for producing an iron-based inorganic pigment using ferrous sulfate, characterized in that when seeded through the air at a rate of 300ml / sec to grow seed crystal nuclei to synthesize hydroxy iron (III).
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US4129454A (en) * 1975-01-03 1978-12-12 Societe De Prayon Iron oxide based pigment and process for preparing such a pigment
WO1999048815A1 (en) * 1998-03-20 1999-09-30 Bayer Aktiengesellschaft METHOD FOR PRODUCING IRON OXIDE PIGMENTS FROM WASTE ACID RESULTING FROM TiO2 PRODUCTION
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