KR20020083652A - Preparation of TiO2 fine powder from titanium tetrachloride with Alcohol or Acetone - Google Patents

Preparation of TiO2 fine powder from titanium tetrachloride with Alcohol or Acetone Download PDF

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KR20020083652A
KR20020083652A KR1020010023137A KR20010023137A KR20020083652A KR 20020083652 A KR20020083652 A KR 20020083652A KR 1020010023137 A KR1020010023137 A KR 1020010023137A KR 20010023137 A KR20010023137 A KR 20010023137A KR 20020083652 A KR20020083652 A KR 20020083652A
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KR100420277B1 (en
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양영석
박정식
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(주)아해
양영석
박정식
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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Abstract

PURPOSE: Provided is a method for preparing TiO2 ultrafine particle, which comprises the steps of forming a solution of titanium tetrachloride(TiCl4) by using aqueous acetone or alcohol, and producing TiO2 ultrafine particle by improved precipitation and washing. CONSTITUTION: The method comprises the steps of (i) introducing titanium tetrachloride(TiCl4) into reactor at -10deg.C to 10 deg.C, (ii) adding an aqueous solution of 0.95 wt% acetone or alcohols(CH3OH, C2H5OH, C3H7OH, C4H9OH) into the reactor to form aqueous Ti4+ solution of 1.4 M or less, which consists of TiOCl2 and HCl, (iii) adding distilled water to the solution of the step(ii) at ambient temperature to dilute the concentration of the Ti4+ to 0.01-1.4M, (iv) placing the diluted solution of the step(iii) at 15-200 deg.C to form the precipitate(TiO2) in the solution, (v) filtrating the precipitate and diluting slurry with distilled water, and adding an aqueous solution of strong alkali into the diluted solution to adjust a pH of the solution to 6-8, so as to form a colloid solution, and (vi) precipitating and filtrating the solution of the step(v), and washing the filtrate in 1-3 times, removing a remaining base from the solution and drying the solution.

Description

알콜 또는 아세톤을 이용한 사염화티타늄으로부터 TiO₂ 초미립 분말의 제조 방법{Preparation of TiO2 fine powder from titanium tetrachloride with Alcohol or Acetone}Preparation method of TiO₂ ultrafine powder from titanium tetrachloride using alcohol or acetone {Preparation of TiO2 fine powder from titanium tetrachloride with Alcohol or Acetone}

본 발명은 용액상태에서 결정성 이산화티타늄을 제조하는 것이며, 출발물질로서 사염화티타늄(TiCl4)을 이용하여 나노크기를 갖고 입도 분포가 균일한 TiO2분말 제조방법에 관한 것이다. 본 발명에 따른 결정성 이산화 티타늄(TiO2)의 제조방법은 교반이 가능한 반응기에 사염화티타늄(TiCl4)을 주입하여 0∼95wt% 아세톤 또는 알콜류(CH3OH, C2H5OH, C3H7OH, C4H9OH등)의 수용액을 첨가하여 TiOCl2및 HCl이혼합된 1.4M 이상의 Ti4+수용액을 제조한다. 제조된 용액에 증류수를 첨가하여 Ti4+농도가 0.01∼1.4M이 되게 희석하고 15℃∼200℃ 온도 범위에서 방치하면 용액내에서 TiO2입자가 생성된다. 생성된 침전물의 세정을 위해 먼저 침전물을 여과하여 슬러리를 증류수로 희석하고, 희석용액에 강알카리 수용액을 첨가하여 pH 6∼8 범위로 조절하면 콜로이드 용액이 생성된다. 이 용액을 침전한 후 여과하여 증류수로 1∼3차 세정하여 용액속에 남아있는 염기를 제거한 다음 건조시켜 결정성 TiO2나노(nano) 분말을 제조하는 것이다.The present invention relates to the preparation of crystalline titanium dioxide in solution, and to a method for producing TiO 2 powder having a nano size and uniform particle size distribution using titanium tetrachloride (TiCl 4 ) as a starting material. In the method for preparing crystalline titanium dioxide (TiO 2 ) according to the present invention, 0 to 95 wt% acetone or alcohols (CH 3 OH, C 2 H 5 OH, C 3 ) are injected by adding titanium tetrachloride (TiCl 4 ) to a stirred reactor. An aqueous solution of H 7 OH, C 4 H 9 OH, etc.) is added to prepare a 1.4 M or more Ti 4+ aqueous solution in which TiOCl 2 and HCl are mixed. Distilled water was added to the prepared solution to dilute the Ti 4+ concentration to 0.01-1.4M, and left at 15 ° C. to 200 ° C. to produce TiO 2 particles in the solution. To wash the resulting precipitate, the precipitate is first filtered, the slurry is diluted with distilled water, and a strong alkaline aqueous solution is added to the dilute solution to adjust the pH to a range of 6 to 8 to produce a colloidal solution. The solution is precipitated and filtered, and then washed first to third with distilled water to remove the base remaining in the solution, followed by drying to prepare crystalline TiO 2 nano (nano) powder.

일반적으로 이산화티타늄(TiO2)은 도료, 잉크, 제지, 법랑 및 도자기 안료, 산화티탄자기, glass, 시멘트, 용접봉, 티탄연와 등 98%이하 순도와 3 ㎛이상의 입도를 갖는 것이 널리 사용되어 왔으나, 최근 고기능 전자세라믹스의 MLCC, 콘덴서, 압전체, 써미스터, 센서, 광촉매 등에 쓰이기 위해서는 99%이상의 순도와 0.1∼1.0 ㎛의 입도분포를 갖는 초립자가 널리 이용되고 있다. 특히 photo catalyst, photo-electrode, semiconductor에 사용되는 것은 0.01∼0.2 ㎛일 때 nano composite를 설계할 수 있는 최적 입도크기이며 입도분포 범위가 좁아야 반도체 성질과 산란 및 굴절 특성이 우수해진다.Generally, titanium dioxide (TiO 2 ) has a purity of 98% or less and a particle size of 3 μm or more, such as paint, ink, paper, enamel and porcelain pigment, titanium oxide, glass, cement, welding rod, titanium lead, etc. Recently, microparticles having a purity of 99% or more and a particle size distribution of 0.1 to 1.0 µm are widely used for MLCCs, capacitors, piezoelectrics, thermistors, sensors, and photocatalysts of high-performance electronic ceramics. Particularly used for photo catalysts, photo-electrodes, and semiconductors is the optimum particle size for designing nano composites at 0.01 to 0.2 μm, and the semiconductor distribution, scattering, and refraction characteristics are excellent when the particle size distribution range is narrow.

이산화티탄늄의 제조방법은 크게 황산법과 염소법 두 가지로 나눈다. 황산법은 건조, 분쇄된 ilmenite에 황산을 작용시켜서 용해하고, 불용해 된 찌꺼기를 분리해서 황산티타닐 용액을 얻고, 다음에 가수 분해 공정에 들어간다. 가수 분해 공정은 황산법중에서 가장 중요한 공정으로, 이 공정에서 TiO2입자의 기본 물성이 대체적으로 결정되며, 소성 공정을 거친 후 TiO2분말이 얻어진다. 이 공정은 현재 TiO2소요량의 약 70%가 이 방법으로 제조되고 있다.The production method of titanium dioxide is largely divided into sulfuric acid method and chlorine method. In the sulfuric acid method, sulfuric acid is applied to the dried and pulverized ilmenite to dissolve it, and the insoluble residue is separated to obtain a titanyl sulfate solution, which is then subjected to a hydrolysis process. The hydrolysis process is the most important of the sulfuric acid methods, in which the basic physical properties of the TiO 2 particles are generally determined, and the TiO 2 powder is obtained after the calcination process. This process currently produces about 70% of the TiO 2 requirement in this way.

① 용해 공정 : FeO ·TiO2+ 2H2SO4= TiOSO4+ FeSO4+ 2H2O (1)① Dissolution process: FeOTiO 2 + 2H 2 SO 4 = TiOSO 4 + FeSO 4 + 2H 2 O (1)

② 가수분해 공정 : TiOSO4+ mH2O = TiO2·nH2O + H2SO4(2)② hydrolysis process: TiOSO 4 + mH 2 O = TiO 2 · nH 2 O + H 2 SO 4 (2)

③ 소성 공정 : TiO2·nH2O = TiO2+ nH2O (3)③ calcination process: TiO 2 · nH 2 O = TiO 2 + nH 2 O (3)

그리고 염소법은 출발물질로서 사염화티타늄(TiCl4)을 사용하는데, TiCl4는 비점(沸点, boiling point)이 낮은 136℃인 액체이므로 증류 등에 의하여 정제하기가 매우 용이하다. 그리고 균일 조건하에서의 결정생성(結晶生成)이기 때문에 생성 입자가 균일하다. 그리고 공정 중의 취급 물체가 가스, 액체가 대부분이므로 공정의 연속화, 자동화가 쉽고, 폐기물(棄物)등에 의한 환경규제에도 대체하기 쉽다는 장점이 있지만 반면에 취급물질이 위험성이 있고, 고온에서 폐쇄하여야 하는 등의 장치 공학적으로 고도의 기술이 필요하고, 또 원료로 rutile type의 TiO2를 사용하는데 이것이 세계적으로 풍부하지 못하는 등 황산법에 비하여 어려운 점도 있지만 정제가 비교적 용이하고, 입자가 비교적 균일하다는 장점이 있다.In addition, the chlorine method uses titanium tetrachloride (TiCl 4 ) as a starting material. TiCl 4 is a liquid having a boiling point of 136 ° C. having a low boiling point, and thus is easily purified by distillation. In addition, the particles produced are uniform because of crystal formation under uniform conditions. And because most of the handling objects in the process are gas and liquid, it is easy to continually process and automate the process. It is easy to replace the environmental regulations due to chemicals, etc. On the other hand, there is a risk of handling materials, and it requires high technology in device engineering such as closing at high temperature, and rutile type TiO 2 is used as raw material. Although it is difficult to use compared to the sulfuric acid method, such as it is not rich in the world, it is advantageous in that the purification is relatively easy and the particles are relatively uniform.

선진국에서는 TiO2초미립자를 제조하기 위하여 sol-gel법, 기상법, 습식법, 열가수분해법을 사용하여 다량으로 고기능 전자세라믹스 소재를 생산공급하고 있으며, 국내에서도 많은 연구가 진행되고 있다. 기존에 알려진 액상법에 의한 TiO2제조는 일본 특개평 4-280816호에서는 염기성 유기카르본산 등을 첨가해 제조한 알칼리 수용액에 사염화티타늄 용액을 가하여 생성된 반응 축합물을 여과, 수세하고 수세한 현탁수용액에 수산화 알칼리 금속을 첨가해 pH 8 이상, 50℃의 온도에서 처리하여 티탄산 알칼리 용액으로 만든다. 이용액을 다시 여과, 수세한 후 이것의 현탁수용액에 산을 첨가해 pH 3 이하, 50℃ 이상의 온도에서 티탄산 알칼리 금속으로 중화 후 이를 여과, 수세, 건조 등의 후처리 공정을 거쳐 이산화티타늄을 제조하는 방법을 제시하였다. 또한 대한민국 특허공고 제91-9589호에서는 TiOCl2를 함유하는 용액을 불소이온과 핵 존재하에서 가압가열시킴으로써, TiOCl2를 가수분해시켜 아나타제형 및 거의 입방체형의 이산화티탄을 침전시켜 이산화티탄을 제조하는 방법을 제시하였으나, 이 방법은 고온, 고압에서 반응을 행하기 때문에 제조상 공정관리가 까다롭고 설비비와 운전비용이 많이드는 문제가 있다.In developed countries, sol-gel method, gas phase method, wet method, and thermal hydrolysis method are used to produce TiO 2 ultrafine particles in large quantities, and many researches are being conducted in Korea. In Japanese Patent Laid-Open Publication No. 4-280816, TiO 2 is prepared by a known liquid phase method. A suspension solution obtained by adding a titanium tetrachloride solution to an aqueous alkali solution prepared by adding basic organic carboxylic acid or the like is filtered, washed, and washed with water. An alkali metal hydroxide was added to the mixture and the mixture was treated at a temperature of pH 8 or higher and 50 ° C. to obtain an alkali titanate solution. After filtering and washing the solution again, acid is added to the suspended aqueous solution and neutralized with alkali metal titanate at a pH of 3 or less and a temperature of 50 ° C or higher, followed by post-treatment processes such as filtration, washing and drying to produce titanium dioxide. The method is presented. In addition, Korean Patent Publication No. 91-9589 discloses a method in which titanium dioxide is prepared by hydrolyzing TiOCl 2 by precipitating a solution containing TiOCl 2 in the presence of fluorine ions and a nucleus to precipitate titanium in anatase and almost cubic forms. Although the method has been proposed, this method has a problem in that the manufacturing process is difficult because of the reaction at high temperature and high pressure, and the equipment cost and operation cost are high.

그리고, 대한민국 특허출원 제2000-13284호에서는 사염화티타늄에 얼음 또는 얼음물을 첨가하여 불안정한 수산화물을 먼저 형성시킨 후 물을 더 첨가해 수산화물을 용해시켜 Ti4+농도가 0.15∼1.2M인 티타닐클로라이드(TiOCl2) 수용액을 만들어 초음파 교반 또는 암모니아수를 첨가하고 65 ℃이하의 온도에서 가열하여 침전물을 생성시키며, 0.1 M 이상의 알칼리 할라이드 수용액으로 여과 및 세척하여 루틸상 TiO2초미분체를 제조하는 방법이 제시되었다. 그러나 이 방법에서는 초기에 사염화티타늄을 얼음 또는 얼음물을 첨가하여 티타닐클로라이드(TiOCl2)로 희석할 때 증류수를 미량씩 첨가하여 반응시키기 때문에 반응속도가 느린 단점을 가지고 있다. 또한, 여과 및 세척시 침전체의 해교 현상이 쉽게 발생하는 것을 해결하기 위해 염화나트륨(NaCl), 염화칼륨(KCl)과 같은 0.1 M 이상의 알칼리 할라이드 수용액을 사용하여 침전체를 여과하는 방법을 사용하였는데, 이 방법은 침전체의 해교현상이 전혀 일어나지 않으면서도 중성 상태까지 가기 위해서는 많은 알칼리 할라이드 수용액이 필요하게 된다.In addition, in Korean Patent Application No. 2000-13284, ice or ice water is added to titanium tetrachloride to form an unstable hydroxide first, and then water is further added to dissolve the hydroxide to titanyl chloride having a Ti 4+ concentration of 0.15 to 1.2M. TiOCl 2 ) was prepared to form an aqueous solution by adding ultrasonic stirring or ammonia water and heating at a temperature below 65 ° C. to produce a precipitate, and filtering and washing with an aqueous alkali halide solution of 0.1 M or more to provide a rutile phase TiO 2 ultrafine powder. . However, this method has a disadvantage in that the reaction rate is slow because titanium tetrachloride is initially added with ice or ice water and reacted with a small amount of distilled water when dilution with titanyl chloride (TiOCl 2 ). In addition, in order to solve the easy occurrence of peptization of the precipitate during filtration and washing, a precipitate was filtered using an aqueous alkali halide solution of 0.1 M or more such as sodium chloride (NaCl) and potassium chloride (KCl). The process requires a lot of aqueous alkali halide solution to reach neutral state without any peptizing of the precipitate.

따라서, 발명자들은 대한민국 특허출원 제2000-13284호에서 전술한 초미립 루틸상 이산화티타늄 분말 제조 방법의 문제점을 해결하고자 연구한 결과, 사용 원료인 사염화티타늄 원액에 0∼95wt% 아세톤 또는 알콜류(CH3OH, C2H5OH, C3H7OH, C4H9OH 등)의 수용액을 첨가하여 티타닐클로라이드(TiOCl2)의 생성속도를 증가시켜 보다 효율적인 방법으로 결정성 TiO2분말을 제조할 수 있는 방법을 완성하였다.Therefore, the inventors have studied in order to solve the problems of the method for producing ultrafine rutile titanium dioxide powder described above in Korean Patent Application No. 2000-13284, 0 to 95wt% acetone or alcohols (CH 3 Aqueous solution of OH, C 2 H 5 OH, C 3 H 7 OH, C 4 H 9 OH, etc. was added to increase the production rate of titanyl chloride (TiOCl 2 ) to produce crystalline TiO 2 powder in a more efficient manner. Completed the way to do it.

본 발명이 이루고자하는 기술적 과제는 나노 크기의 결정성 이산화티타늄(TiO2)을 제조하는데 있어서, 출발물질로서 사염화티타늄(TiCl4)을 이용하여 아세톤 수용액 또는 알콜 수용액으로 용액을 제조하고, 개선된 침전반응과 세정 공정을 통하여 TiO2초미분체를 제조방법을 제공하고자 한다.The technical problem to be achieved in the present invention is to prepare a nano-sized crystalline titanium dioxide (TiO 2 ), to prepare a solution in an aqueous solution of acetone or an alcohol solution using titanium tetrachloride (TiCl 4 ) as a starting material, improved precipitation It is to provide a method for producing a TiO 2 ultra fine powder through a reaction and washing process.

도 1은 아세톤 수용액을 이용하여 제조된 TiO2분말의 X-선 회절곡선을 나타낸 것이다.Figure 1 shows the X-ray diffraction curve of TiO 2 powder prepared using acetone aqueous solution.

도 2는 에탄올 수용액을 이용하여 제조된 TiO2분말의 X-선 회절곡선을 나타낸 것이다.Figure 2 shows the X-ray diffraction curve of TiO 2 powder prepared using an ethanol aqueous solution.

상기의 목적을 달성하기 위하여 본 발명은 용액 상태에서 결정성 이산화티타늄을 제조하기 위해 출발물질로서 사염화티타늄(TiCl4)과 알콜 수용액 또는 아세톤 수용액을 이용하여 나노 크기의 TiO2분말 제조방법에 관한 것이다.In order to achieve the above object, the present invention relates to a method for preparing nano-sized TiO 2 powder using titanium tetrachloride (TiCl 4 ) and an aqueous alcohol solution or an acetone aqueous solution as a starting material to produce crystalline titanium dioxide in a solution state. .

본 발명에 따른 결정성 이산화티타늄(TiO2)의 구체적인 제조방법은Specific method for producing crystalline titanium dioxide (TiO 2 ) according to the present invention

(1) -10℃∼10℃의 온도로 조절된 반응기에 사염화티타늄(TiCl4)을 주입하는 단계(제 1단계);(1) injecting titanium tetrachloride (TiCl 4 ) into a reactor adjusted to a temperature of −10 ° C. to 10 ° C. (first step);

(2) 반응기 속에 0∼95wt% 아세톤 또는 알콜류(CH3OH, C2H5OH, C3H7OH, C4H9OH 등)의 수용액을 첨가하여 TiOCl2및 HCl이 혼합된 1.4M 이상의 Ti4+수용액을 제조하는 단계(제 2단계);(2) 1.4 M of TiOCl 2 and HCl mixed with an aqueous solution of 0-95 wt% acetone or alcohols (CH 3 OH, C 2 H 5 OH, C 3 H 7 OH, C 4 H 9 OH, etc.) in the reactor Preparing a Ti 4+ aqueous solution (second step);

(3) 상온에서 제 2단계 용액에 증류수를 첨가하여 Ti4+농도가 0.01∼1.4M의 농도로 희석시키는 단계(제 3단계);(3) distilling water to a solution of the second step at room temperature to dilute the Ti 4+ concentration to a concentration of 0.01 to 1.4 M (third step);

(4) 제 3단계의 희석용액을 15℃∼200℃ 온도 범위에서 방치하여 용액내에서 침전물(TiO2)을 제조하는 단계(제 4단계);(4) preparing a precipitate (TiO 2 ) in the solution by leaving the dilution solution of the third step in a temperature range of 15 ° C. to 200 ° C. (fourth step);

(5) 제 4단계에서 생성된 침전물의 세정을 위해 먼저 침전물을 여과하여 슬러리를 증류수로 희석하고, 희석용액에 강알카리 수용액을 첨가하여 pH6∼8 범위로 조절하면 콜로이드 용액이 생성되는 단계(제 5단계);(5) To wash the precipitate produced in the fourth step, the precipitate is first filtered and the slurry is diluted with distilled water, and a strong alkaline aqueous solution is added to the dilute solution to adjust the pH to a range of 6 to 8 to produce a colloidal solution. Step 5);

(6) 제 5단계의 용액을 침전시킨 후 여과하여 증류수로 1∼3차 세정하고 용액속에 남아있는 염기를 제거한 다음 건조시키는 단계(제 6단계)로 구성된다.(6) Precipitating the solution of the fifth step, followed by filtration to wash the first to third with distilled water, and to remove the base remaining in the solution, followed by drying (sixth step).

여기에서, 제 1단계의 알콜 수용액은 CH3OH, C2H5OH, C3H7OH, C4H9OH 등으로 구성되며, 그 이외의 R-OH로 이루어진 모든 수용성 알콜류 등을 포함하는 것이 바람직하고, 아세톤 또는 알콜 수용액의 농도는 0∼95 wt%의 범위에서 첨가하는 것이 바람직하다.Here, the first aqueous solution of alcohol is composed of CH 3 OH, C 2 H 5 OH, C 3 H 7 OH, C 4 H 9 OH, and the like, and all other water-soluble alcohols including R-OH and the like. It is preferable to add, and it is preferable to add the density | concentration of an acetone or aqueous alcohol solution in the range of 0-95 wt%.

또한, 제 4단계의 알칼리 수용액은 NaOH, KOH, NH4OH 등의 비금속수산화물을 첨가하는 것이 바람직하고, 이때 산 농도를 pH 6∼8 범위로 조절하는 것이 바람직하다.In addition, it is preferable to add a nonmetallic hydroxide such as NaOH, KOH, NH 4 OH, etc. in the fourth aqueous alkali solution, and at this time, it is preferable to adjust the acid concentration to a pH range of 6-8.

이하의 실시예들은 본 발명을 예증하기 위한 것으로서 본 발명의 범위를 국한시키는 것으로 이해되어져서는 안 된다.The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

〈실시예 1〉아세톤 수용액을 이용한 초미립 이산화티타늄 분말의 제조<Example 1> Preparation of ultrafine titanium dioxide powder using acetone aqueous solution

먼저, 사용 원료인 사염화티타늄(TiCl4)을 반응기에 주입하여 0℃로 유지시킨 후, 75 wt%의 아세톤 수용액을 첨가하여 TiOCl2, HCl 및 아세톤 화합물이 혼합된 1.4M 이상의 TiOCl2수용액을 제조하였으며, 이 용액은 상온에서도 매우 안정한 화합물로 존재한다. 제조된 용액을 상온에서 증류수를 첨가하여 Ti4+농도가 0.7M의 농도가 되게 희석 및 30분 동안 교반하였다.First, titanium tetrachloride (TiCl 4 ), which is a raw material to be used, is injected into a reactor and maintained at 0 ° C., followed by addition of 75 wt% acetone aqueous solution to prepare an aqueous solution of 1.4 M or more TiOCl 2 mixed with TiOCl 2 , HCl, and acetone compounds. This solution is present as a very stable compound even at room temperature. The prepared solution was diluted with distilled water at room temperature so that the Ti 4+ concentration was 0.7M and stirred for 30 minutes.

그리고 침전반응은 희석용액을 60℃ 온도에서 12 시간의 반응시간이 경과한후, 용액내에서 침전물(TiO2)을 제조하였다. 침전물의 세정을 위해 먼저 침전물을여과하여 슬러리를 증류수로 희석하고, 희석용액을 1 M의 NaOH 수용액을 pH 7이 되게 첨가·교반하여 여과 특성을 개선하였다. 위의 용액을 침전시킨 후 여과하여 증류수로 1∼3차 세정하고 용액속에 남아있는 NaCl을 제거한 다음 건조시켜 결정성 TiO2나노(nano) 분말을 얻었다. 이 때 제조된 초미립 이산화티타늄의 X-선 회절선을 도 1에 나타내었는데, 제조된 분말은 루틸상(rutile phase)의 초미세 분말이었다.In the precipitation reaction, after the reaction time of 12 hours at 60 ° C., the precipitate (TiO 2 ) was prepared in the solution. In order to clean the precipitate, the precipitate was first filtered to dilute the slurry with distilled water, and a dilute solution was added and stirred at a pH of 1 M NaOH to improve the filtration characteristics. The precipitated solution was precipitated, filtered and washed 1 to 3 times with distilled water, followed by removal of NaCl remaining in the solution, followed by drying to obtain crystalline TiO 2 nano (nano) powder. An X-ray diffraction line of the ultrafine titanium dioxide prepared at this time is shown in FIG. 1, wherein the prepared powder was a rutile phase ultrafine powder.

〈실시예 2〉에탄올 수용액을 이용한 초미립 이산화티타늄 분말의 제조Example 2 Preparation of Ultrafine Titanium Dioxide Powder Using Ethanol Aqueous Solution

먼저, 사용 원료인 사염화티타늄(TiCl4)을 반응기에 주입하여 0℃로 유지시킨 후, 75 wt%의 에탄올(C2H5OH) 수용액을 첨가하여 TiOCl2, HCl 및 에탄올 화합물이 혼합된 1.4M 이상의 TiOCl2수용액을 제조하였으며, 이 용액은 상온에서도 매우 안정한 화합물로 존재한다. 제조된 용액을 상온에서 증류수를 첨가하여 Ti4+농도가 0.7M의 농도가 되게 희석 및 30분 동안 교반하였다. 그리고 침전반응은 희석용액을 60℃ 온도에서 12 시간의 반응시간이 경과한 후, 용액내에서 침전물(TiO2)을 제조하였다. 침전물의 세정을 위해 먼저 침전물을 여과하여 슬러리를 증류수로 희석하고, 희석용액을 1 M의 KOH 수용액을 pH 7이 되게 첨가·교반하여 여과 특성을 개선하였다. 위의 용액을 침전시킨 후 여과하여 증류수로 1∼3차 세정하고 용액속에 남아있는 KCl을 제거한 다음 건조시켜 결정성 TiO2나노(nano) 분말을 얻었다. 이 때 제조된 초미립 이산화티타늄의 X-선 회절선을 도 2에 나타내었는데, 제조된 분말은 루틸상(rutile phase)의 초미세 분말이었다.First, titanium tetrachloride (TiCl 4 ), which is a raw material used, is injected into a reactor and maintained at 0 ° C., followed by addition of 75 wt% ethanol (C 2 H 5 OH) aqueous solution to mix TiOCl 2 , HCl, and ethanol compound 1.4. A TiOCl 2 aqueous solution of M or more was prepared, and the solution was present as a very stable compound even at room temperature. The prepared solution was diluted with distilled water at room temperature so that the Ti 4+ concentration was 0.7M and stirred for 30 minutes. In the precipitation reaction, after the reaction time of 12 hours was elapsed at 60 ° C., a precipitate (TiO 2 ) was prepared in the solution. In order to wash the precipitate, the precipitate was first filtered to dilute the slurry with distilled water, and the dilution solution was added and stirred at a pH of 1 M KOH aqueous solution to improve the filtration characteristics. The precipitated solution was precipitated, filtered, washed 1 to 3 times with distilled water, KCl remaining in the solution was removed, and dried to obtain crystalline TiO 2 nano (nano) powder. An X-ray diffraction line of the ultrafine titanium dioxide prepared at this time is shown in FIG. 2, wherein the prepared powder was a rutile phase ultrafine powder.

이상에서 살펴본 바와 같이, 본 발명에서 아세톤 수용액 또는 알콜 수용액을 이용하여 결정성 TiO2초미분체 분말을 제조할 수 있으며, 고온 분위기로 소성하는 장치가 필요하지 않으며, 대량생산 뿐만아니라 경제적인 면에서 생산비용을 낮출 수 있는 매우 실용적인 제조방법으로서 TiO2나노(nano) 분말의 시장성을 확대시킬 것이다.As described above, in the present invention, crystalline TiO 2 ultrafine powder may be prepared using an acetone aqueous solution or an aqueous alcohol solution, and does not require an apparatus for firing in a high temperature atmosphere, and is economical in mass production. As a very practical manufacturing method that can lower the cost, it will expand the marketability of TiO 2 nano powder.

Claims (4)

본 발명은 용액 상태에서 결정성 이산화티타늄을 제조하는 것으로 초기 출발물질로서 사염화티타늄(TiCl4)을 이용하여 나노 크기를 갖고 입도 분포가 균일한 TiO2분말을 제조하는데 있어서The present invention is to prepare crystalline titanium dioxide in the solution state using titanium tetrachloride (TiCl 4 ) as an initial starting material in the production of TiO 2 powder having a nano size and uniform particle size distribution (1) -10℃∼10℃의 온도로 조절된 반응기에 사염화티타늄(TiCl4)을 주입하는 단계(제 1단계);(1) injecting titanium tetrachloride (TiCl 4 ) into a reactor adjusted to a temperature of −10 ° C. to 10 ° C. (first step); (2) 반응기 속에 0∼95wt% 아세톤 또는 알콜류(CH3OH, C2H5OH, C3H7OH, C4H9OH 등)의 수용액을 첨가하여 TiOCl2및 HCl이 혼합된 1.4M 이상의 Ti4+수용액을 제조하는 단계(제 2단계);(2) 1.4 M of TiOCl 2 and HCl mixed with an aqueous solution of 0-95 wt% acetone or alcohols (CH 3 OH, C 2 H 5 OH, C 3 H 7 OH, C 4 H 9 OH, etc.) in the reactor Preparing a Ti 4+ aqueous solution (second step); (3) 상온에서 제 2단계 용액에 증류수를 첨가하여 Ti4+농도가 0.01∼1.4M의 농도로 희석시키는 단계(제 3단계);(3) distilling water to a solution of the second step at room temperature to dilute the Ti 4+ concentration to a concentration of 0.01 to 1.4 M (third step); (4) 제 3단계의 희석용액을 15℃∼200℃ 온도 범위에서 방치하여 용액내에서 침전물(TiO2)을 제조하는 단계(제 4단계);(4) preparing a precipitate (TiO 2 ) in the solution by leaving the dilution solution of the third step in a temperature range of 15 ° C. to 200 ° C. (fourth step); (5) 제 4단계에서 생성된 침전물의 세정을 위해 먼저 침전물을 여과하여 슬러리를 증류수로 희석하고, 희석용액에 강알카리 수용액을 첨가하여 pH 6∼8 범위로 조절하면 콜로이드 용액이 생성되는 단계(제 5단계);(5) To wash the precipitate produced in the fourth step, the precipitate is first filtered, the slurry is diluted with distilled water, and a strong alkaline aqueous solution is added to the dilute solution to adjust the pH to a range of 6 to 8 to produce a colloidal solution ( The fifth step); (6) 제 5단계의 용액을 침전시킨 후 여과하여 증류수로 1∼3차 세정하고 용액속에 남아있는 염기를 제거한 다음 건조시키는 단계(제 6단계)로 구성된 결정성 TiO2나노(nano) 분말의 제조방법(6) Precipitating the solution of the fifth step, filtered and washed first to third with distilled water to remove the base remaining in the solution and dried (step 6) of the crystalline TiO 2 nano (nano) powder Manufacturing method 제 1항의 (2)에 있어서, 아세톤 수용액 또는 알콜 수용액을 사용하여 제조하는 것과 알콜 수용액은 CH3OH, C2H5OH, C3H7OH, C4H9OH 등으로 구성된 수용액이며, 그 이외의 R-OH로 이루어진 모든 수용성 알콜류 등을 포함하는 것을 특징으로 하는 초미립 이산화티타늄 분말의 제조방법The method according to claim 1 (2), wherein the aqueous solution prepared by using an acetone aqueous solution or an aqueous alcohol solution is an aqueous solution composed of CH 3 OH, C 2 H 5 OH, C 3 H 7 OH, C 4 H 9 OH, and the like. Method for producing ultrafine titanium dioxide powder, characterized in that it comprises all other water-soluble alcohols made of other R-OH, etc. 제 1항의 (2)에 있어서, 첨가하는 아세톤 수용액 및 알콜 수용액의 농도를 0∼95 wt% 범위에서 제조하는 것과 아세톤 수용액 또는 알콜 수용액을 첨가할 때 Ti4+의 농도가 1.4M 이상의 수용액을 특징으로 하는 초미립 이산화티타늄 분말의 제조방법The method of claim 1, wherein the concentration of the acetone aqueous solution and the alcohol aqueous solution to be added is prepared in the range of 0 to 95 wt%, and the concentration of Ti 4+ is 1.4 M or more when the acetone or alcohol aqueous solution is added. Method for producing ultrafine titanium dioxide powder 제 1항의 (3)에 있어서, 상온에서 제 2단계 용액에 증류수를 첨가하여 Ti4+농도를 0.01∼1.4M로 희석 및 교반하여 침전반응이 이루어지는 것을 특징으로 하는 초미립 이산화티타늄 분말의 제조방법The method for producing ultrafine titanium dioxide powder according to claim 1, wherein the precipitation is performed by adding distilled water to the second stage solution at room temperature, diluting and stirring the Ti 4+ concentration to 0.01 to 1.4 M.
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Cited By (4)

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KR100413720B1 (en) * 2001-06-04 2003-12-31 (주)아해 Preparation of anatase type TiO2 ultrafine powders from TiCl4 with acetone by the advanced washing method
US7662359B2 (en) 2004-02-06 2010-02-16 Sachtleben Pigments Oy Titanium oxide product method for making the same and its use as a photocatalyst
CN104459019A (en) * 2014-12-12 2015-03-25 国家纳米科学中心 Method for detecting content of free hydrochloric acid content in titanium tetrachloride water solution
CN117410365A (en) * 2023-12-15 2024-01-16 宁波长阳科技股份有限公司 Solar cell module reflective film and preparation method and application thereof

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JPH01301518A (en) * 1988-05-28 1989-12-05 Sakai Chem Ind Co Ltd Production of titanium dioxide
US4923682A (en) * 1989-03-30 1990-05-08 Kemira, Inc. Preparation of pure titanium dioxide with anatase crystal structure from titanium oxychloride solution
DE4216122A1 (en) * 1992-05-15 1993-11-18 Bayer Ag Highly pure titanium di:oxide prodn. from titanium tetra:halide - by reacting with aq. sulphuric acid without crystallisation of titanyl sulphate, removing hydrogen halide, hydrolysis and calcination
KR100224732B1 (en) * 1996-08-07 1999-10-15 김성년 Process for producing a micropowder type crystalline titanium oxide
KR100350226B1 (en) * 2000-02-29 2002-08-27 나노케미칼 주식회사 Photocatalytic TiO2 powder with large specific surface area by homogeneous precipitation process at low temperature and method for manufacturing

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100413720B1 (en) * 2001-06-04 2003-12-31 (주)아해 Preparation of anatase type TiO2 ultrafine powders from TiCl4 with acetone by the advanced washing method
US7662359B2 (en) 2004-02-06 2010-02-16 Sachtleben Pigments Oy Titanium oxide product method for making the same and its use as a photocatalyst
CN104459019A (en) * 2014-12-12 2015-03-25 国家纳米科学中心 Method for detecting content of free hydrochloric acid content in titanium tetrachloride water solution
CN104459019B (en) * 2014-12-12 2016-05-11 国家纳米科学中心 A kind of method that detects free content of hydrochloric acid in titanium tetrachloride aqueous solution
CN117410365A (en) * 2023-12-15 2024-01-16 宁波长阳科技股份有限公司 Solar cell module reflective film and preparation method and application thereof

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