KR20060033552A - Nanosized photocatalysts and process for preparing them - Google Patents
Nanosized photocatalysts and process for preparing them Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
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Abstract
본 발명은 나노 크기의 아나타제형 이산화티탄(TiO2) 분말 및 그의 제조방법에 관한 것으로서, 더욱 상세하게는 출발물질로 사염화티탄을 사용하여 이를 물과 알콜 혼합용매에 분산시키고 가수분해 및 겔화시킨 후 특히 켄칭 단계를 거쳐 소성시킴으로써, 기존의 이산화티탄 분말의 제조방법과는 달리 고가의 출발물질을 사용하지 않으면서도 복잡한 후처리 공정이 필요없는 간단한 방법으로 넓은 비표면적을 가지며 기존의 상용 광촉매보다 높은 광활성을 나타내는 나노 크기의 아나타제형 이산화티탄 분말을 고순도로 제조할 수 있는 효과가 있다.The present invention relates to nano-size anatase-type titanium dioxide (TiO 2 ) powder and a method for preparing the same, and more specifically, using titanium tetrachloride as a starting material, it is dispersed in a mixed solvent of water and alcohol, hydrolyzed and gelled, In particular, by quenching through a quenching step, unlike conventional methods for producing titanium dioxide powder, it does not require expensive starting materials and does not require complicated post-treatment processes. It has a large specific surface area and has a higher optical activity than conventional commercial photocatalysts. Nano size anatase titanium dioxide powder exhibiting an effect that can be produced with high purity.
이산화티탄, 광촉매, 사염화티탄, 아나타제Titanium dioxide, photocatalyst, titanium tetrachloride, anatase
Description
도 1은 본 발명의 이산화티탄 분말의 제조방법의 공정도이다.1 is a process chart of the method for producing a titanium dioxide powder of the present invention.
도 2는 실시예 1에서 얻어진 이산화티탄 분말에 대한 SEM 사진을 나타낸 것이다.Figure 2 shows a SEM photograph of the titanium dioxide powder obtained in Example 1.
도 3은 실시예 1에서 얻어진 이산화티탄 분말에 대하여 소성온도에 따라 측정한 XRD 패턴을 나타낸 그래프이다.3 is a graph showing an XRD pattern measured according to firing temperature for the titanium dioxide powder obtained in Example 1. FIG.
도 4는 실시예 1에서 얻어진 이산화티탄 분말의 MB 실험에서 자외선-가시광선 분광광도계를 통하여 시간에 따라 MB가 분해되는 정도를 나타낸 그래프이다. 4 is a graph showing the degree to which MB is decomposed with time through an ultraviolet-visible spectrophotometer in the MB experiment of the titanium dioxide powder obtained in Example 1. FIG.
도 5는 실시예 1에서 얻어진 이산화티탄 분말과 상용 광촉매로서 이산화티탄의 시간에 따른 MB의 상대적 농도변화를 나타내는 그래프이다.FIG. 5 is a graph showing a change in relative concentration of MB with time of titanium dioxide powder and a commercial photocatalyst obtained in Example 1;
도 6은 자외선없이 암실에서 이산화티탄만으로, 또한 이산화티탄 분말 없이 자외선만으로, 시간에 따른 MB의 상대적 농도변화를 나타내는 그래프이다.FIG. 6 is a graph showing the change in the relative concentration of MB over time with only titanium dioxide in the dark room without ultraviolet light and also with only ultraviolet light without titanium dioxide powder.
본 발명은 나노 크기의 아나타제형 이산화티탄(TiO2) 분말 및 그의 제조방법에 관한 것으로서, 더욱 상세하게는 출발물질로 사염화티탄을 사용하여 이를 물과 알콜 혼합용매에 분산시키고 가수분해 및 겔화시킨 후 특히 켄칭 단계를 거쳐 소성시킴으로써, 기존의 이산화티탄 분말의 제조방법과는 달리 고가의 출발물질을 사용하지 않으면서도 복잡한 후처리 공정이 필요없는 간단한 방법으로 넓은 비표면적을 가지며 기존의 상용 광촉매보다 높은 광활성을 나타내는 나노 크기의 아나타제형 이산화티탄 분말을 고순도로 제조할 수 있는 효과가 있다.The present invention relates to nano-size anatase-type titanium dioxide (TiO 2 ) powder and a method for preparing the same, and more specifically, using titanium tetrachloride as a starting material, it is dispersed in a mixed solvent of water and alcohol, hydrolyzed and gelled, In particular, by quenching through a quenching step, unlike conventional methods for producing titanium dioxide powder, it does not require expensive starting materials and does not require complicated post-treatment processes. It has a large specific surface area and has a higher optical activity than conventional commercial photocatalysts. Nano size anatase titanium dioxide powder exhibiting an effect that can be produced with high purity.
일반적으로 광촉매는 빛에너지를 받아 촉매작용이 일어나는 물질이다. 일정한 영역의 에너지가 광촉매에 가해지면 전자가 가전도대(Valence band)에서 전도대(Conduction band)로 여기되는데, 이때 전도대에는 전자들이 형성되고 가전도대에는 정공이 형성되게 된다. 이렇게 형성된 전자와 정공은 강한 산화·환원 능력에 의해 공기·대기 정화, 오·폐수 처리, 친수, 방오, 항균, 자외선 차단 등의 다양한 작용을 한다. In general, a photocatalyst is a substance that undergoes catalysis by receiving light energy. When a certain area of energy is applied to the photocatalyst, electrons are excited from the valence band to the conduction band. At this time, electrons are formed in the conduction band and holes are formed in the conduction band. The electrons and holes thus formed have various functions such as air and air purification, waste and wastewater treatment, hydrophilicity, antifouling, antibacterial and ultraviolet ray blocking by strong oxidation and reduction ability.
상기와 같은 광촉매 효과를 나타내는 물질에는 ZnO, WO3, SnO2, ZrO2, TiO 2, CdS 등이 있지만 물리·화학적으로 안정되고 광활성이 우수한 이산화티탄(TiO2)이 가장 일반적으로 사용되고 있다.Materials exhibiting such photocatalytic effects include ZnO, WO 3 , SnO 2 , ZrO 2 , TiO 2 , CdS and the like, but titanium dioxide (TiO 2 ), which is physically and chemically stable and has excellent photoactivity, is most commonly used.
이산화티탄은 미국에서는 1968년, 일본에서는 1983년에 식품첨가물로 인증 받았으며 화장품(기능성 화장품, 립스틱), 식품(초콜렛) 등에 많이 이용되고 있다. 특히, 일본의 경우 광촉매로 코팅한 타일로 일본 식품 분석센터 및 미쯔비시 화학안전과학연구소에서 피부 일시 자극시험 및 급성경구독성시험을 통해 그 안정성이 입증되었다. Titanium dioxide was certified as a food additive in 1968 in the United States and 1983 in Japan, and is widely used in cosmetics (functional cosmetics, lipsticks) and foods (chocolate). In particular, in Japan, photocatalyst-coated tiles have proven their stability through skin transient irritation tests and acute oral toxicity tests at Japan Food Analysis Center and Mitsubishi Chemical Safety Science Research Institute.
이러한 이산화티탄 분말을 제조하는 방법으로는 출발물질을 기준으로 분류하여 금속알콕사이드법과 염소법이 일반적으로 널리 알려져 있다.As a method for producing the titanium dioxide powder, the metal alkoxide method and the chlorine method are generally widely known based on the starting materials.
그러나 상기 금속알콕사이드법의 경우는 주원료인 알콕사이드가 매우 고가이기 때문에 제조 단가가 높다는 문제점을 가지고 있으며, 염소법의 경우는 금속알콕사이드법에 비해 제조된 이산화티탄 분말의 광활성이 낮다는 문제점을 가지고 있다.However, the metal alkoxide method has a problem in that the production cost is high because alkoxide, which is a main raw material, is very expensive, and in the case of the chlorine method, there is a problem in that the optical activity of the manufactured titanium dioxide powder is lower than that of the metal alkoxide method.
이에 본 발명자들은 상기 문제점을 해결하기 위해 노력한 결과, 금속알콕사이드가 아닌 사염화티탄(TiCl4)을 출발물질로 사용하여 졸을 거쳐 비정질 티탄 겔을 형성시키고, 이를 수열처리한 후 켄칭 및 소성하여 광활성 효과가 우수한 이산화티탄 분말을 제조하였다.Accordingly, the present inventors have tried to solve the above problems, using titanium tetrachloride (TiCl 4 ) rather than a metal alkoxide as a starting material to form an amorphous titanium gel through a sol, after hydrothermal treatment and quenched and calcined, the photoactive effect The excellent titanium dioxide powder was prepared.
본 발명에서는 특히 비정질 티탄 겔을 수열처리한 후 기존의 서서히 냉각시키던 방법과는 달리 켄칭시키므로써 수열처리시 생성된 입자가 커지는 것을 효과적으로 방지하여 이산화티탄 단위 입자의 크기를 5 ㎚ 이하로 조절할 수 있도록 하며, 이렇게 형성된 이산화티탄 단위 입자의 집합체로서 이산화티탄 분말은 상기 이 산화티탄 단위 입자 간에 존재하는 기공과 이산화티탄 단위 입자의 집합체 간에 존재하는 기공에 의하여 비표면적이 40 ~ 120 ㎡/g으로 증가되고, 평균 입경은 20 ~ 100 ㎚ 범위인 나노 크기의 아나타제형으로서 광활성능이 기존의 상용 광촉매보다 향상된다.In the present invention, unlike the conventional method of slowly cooling the amorphous titanium gel after the hydrothermal treatment, by quenching effectively prevents the particles produced during the hydrothermal treatment to increase effectively to control the size of the titanium dioxide unit particles to 5 nm or less The titanium dioxide powder as an aggregate of the titanium dioxide unit particles thus formed has a specific surface area of 40 to 120 m 2 / g due to pores existing between the titanium dioxide unit particles and pores existing between the aggregates of the titanium dioxide unit particles. The average particle size is in the range of 20 to 100 nm in the size of anatase, and the photoactivity is improved compared to the conventional commercial photocatalyst.
따라서, 본 발명은 사염화티탄을 출발물질로 사용하고, 기존의 졸겔법 및 수열처리법의 장점을 보다 효과적으로 개선하여 보다 간단하고 용이한 방법으로 저렴하면서도 상용 광촉매보다 광활성이 우수한 나노 크기의 아나타제형 이산화티탄 분말 및 그의 제조방법을 제공하는데 그 목적이 있다.
Therefore, the present invention uses titanium tetrachloride as a starting material, and improves the advantages of the conventional sol-gel method and hydrothermal treatment method more effectively, and in a simpler and easier way, nano-size anatase type titanium dioxide, which is inexpensive and superior in photoactivity than commercial photocatalysts It is an object to provide a powder and a method for producing the same.
본 발명은 입경 1 ~ 5 ㎚인 이산화티탄 단위입자의 집합체로서 근접한 상기 이산화티탄 단위입자 간에 기공이 형성되어 있고, 이산화티탄 단위입자 집합체의 평균입경이 20 ~ 100 ㎚이며, 비표면적이 40 ~ 120 ㎡/g인 광활성이 우수한 나노 크기의 아나타제형 이산화티탄 분말을 특징으로 한다.In the present invention, pores are formed between adjacent titanium dioxide unit particles as an aggregate of titanium dioxide unit particles having a particle diameter of 1 to 5 nm, the average particle diameter of the titanium dioxide unit particle aggregate is 20 to 100 nm, and the specific surface area is 40 to 120. It is characterized by a nano-size anatase-type titanium dioxide powder having excellent photoactivity of m 2 / g.
또한 본 발명은 물과 알콜 혼합용매에 사염화티탄(TiCl4)을 분산시킨 후 30 ~ 100 ℃에서 가수분해하여 졸을 형성시키는 단계; 상기 졸에 암모니아수를 가한 다음 세정 및 여과하여 비정질 티탄 겔을 형성시키는 단계; 및 상기 비정질 티탄 겔을 물에 분산시킨 후 10 ~ 100 atm, 100 ~ 300 ℃에서 수열처리하고, 켄칭 및 소성하여 이산화티탄 분말을 형성시키는 단계를 포함하여 이루어지는 광활성이 우수 한 나노 크기의 아나타제형 이산화티탄 분말의 제조방법을 포함한다.In another aspect, the present invention comprises the steps of dispersing titanium tetrachloride (TiCl 4 ) in a mixed solvent of water and alcohol to form a sol by hydrolysis at 30 ~ 100 ℃; Adding ammonia water to the sol, followed by washing and filtration to form an amorphous titanium gel; And dispersing the amorphous titanium gel in water, followed by hydrothermal treatment at 10 to 100 atm and 100 to 300 ° C. to form titanium dioxide powder by quenching and calcining to form titanium dioxide powder having excellent photoactivity. It includes a method for producing titanium powder.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 출발물질로 사염화티탄을 사용하여 이를 물과 알콜 혼합용매에 분산시키고 가수분해 및 겔화시킨 후 특히 켄칭 단계를 거쳐 소성시킴으로써, 기존의 이산화티탄 분말의 제조방법과는 달리 고가의 출발물질을 사용하지 않으면서도 복잡한 후처리 공정이 필요없는 간단한 방법으로 넓은 비표면적을 가지며 기존의 상용 광촉매보다 높은 광활성을 나타내는 나노 크기의 아나타제형 이산화티탄 분말을 고순도로 제조할 수 있는 효과가 있다.The present invention uses titanium tetrachloride as a starting material to disperse it in a mixed solvent of water and alcohol, hydrolyze and gelize it, and then calcinate it through a quenching step, unlike the conventional method for producing titanium dioxide powder, an expensive starting material is produced. It is possible to produce nano-size anatase-type titanium dioxide powder with a high specific surface area without using a complicated post-treatment process and to exhibit high photoactivity than conventional commercial photocatalysts.
이러한 본 발명을 제조방법을 위주로 보다 상세하게 설명한다.The present invention will be described in more detail based on the manufacturing method.
먼저, 물과 알콜 혼합용매에 사염화티탄(TiCl4)을 분산시킨 후 30 ~ 100 ℃에서 가수분해하여 졸을 형성시키는 단계이다. First, titanium tetrachloride (TiCl 4 ) is dispersed in a mixed solvent of water and alcohol and then hydrolyzed at 30 to 100 ° C. to form a sol.
본 발명은 이산화티탄 분말을 제조하기 위한 출발물질로서 사염화티탄을 사용함에 가장 큰 특징이 있는 것으로, 기존의 금속알콕사이드를 사용하던 방법을 개선하여 사염화티탄을 사용하면서도 제조방법을 다음에 제시하는 방법으로 개선하여 상용 광촉매보다 높은 광활성을 발현하도록 한 것이다.The present invention is characterized by the largest feature of using titanium tetrachloride as a starting material for producing titanium dioxide powder, by improving the existing method of using metal alkoxide, while using titanium tetrachloride as a method of presenting the following method It was improved to express higher photoactivity than commercial photocatalysts.
본 발명에서는 사염화티탄을 물과 알콜의 혼합용매에 분산시키는데, 상기 혼합용매는 물과 알콜이 1 ~ 5 : 5 ~ 1 부피비로 이루어진 것을 사용하며, 알콜의 사용량이 상기 범위 미만이면 입자가 잘 생성되지 않고, 상기 범위를 초과하면 입자크기가 마이크로 이상으로 커지게 된다. 상기 알콜로는 C1 ~ C8의 지방족알콜 을 사용할 수 있으며, 구체적으로 예를 들자면, 메탄올, 에탄올, 프로판올, 부탄올 및 옥탄올 등 중에서 선택하여 사용한다.In the present invention, the titanium tetrachloride is dispersed in a mixed solvent of water and alcohol, and the mixed solvent uses water and alcohol in a volume ratio of 1 to 5: 5 to 1, and particles are well formed when the amount of alcohol is less than the above range. If it exceeds the above range, the particle size becomes larger than micro. As the alcohol, C 1 to C 8 aliphatic alcohols may be used. Specifically, for example, methanol, ethanol, propanol, butanol and octanol may be used.
상기 혼합용매 내에 사염화티탄 분산은 0.1 ~ 3.0 M 농도가 되도록, 바람직하게는 0.5 ~ 1.5 M 범위가 되도록 수행하는 것이 좋으며, 사염화티탄 분산량이 과량일 경우 충분한 분산효과를 기대할 수 없게 된다. 혼합용매에 사염화티탄을 분산시킬 경우 비활성 가스 분위기 하에서 수행시키는 것이 바람직하며, 혼합용매의 온도가 4 ℃ 이하, 보다 바람직하게는 혼합용매의 온도를 1 ~ 4 ℃ 범위로 조절하여 수행하는 것이 나노입자를 형성시키는 측면에서 좋다. 이때, 분산제로서 하이드록시프로필셀룰로오스(Hydroxypropylcellulose, HPC)를 첨가하면 더욱 좋으며, 분산제의 첨가량은 0.010 ~ 0.064 g/L를 사용할 경우 바람직하다.Titanium tetrachloride dispersion in the mixed solvent is preferably performed so that the concentration is 0.1 ~ 3.0 M, preferably in the range of 0.5 ~ 1.5 M, if the amount of the titanium tetrachloride dispersion is excessive, sufficient dispersion effect can not be expected. In the case of dispersing titanium tetrachloride in the mixed solvent, it is preferable to carry out in an inert gas atmosphere. Good in terms of forming. At this time, it is more preferable to add hydroxypropyl cellulose (Hydroxypropylcellulose, HPC) as the dispersant, the amount of the dispersant is preferably in the case of using 0.010 ~ 0.064 g / L.
상기와 같은 조건의 혼합용매에 사염화티탄을 충분히 분산시킨 후 30 ~ 100 ℃에서 가수분해, 특히, 펩티제이션(Peptization)시켜 졸을 형성시킨다. 이때, 가수분해에 의하여 사염화티탄이 분산된 혼합용액이 투명한 상태에서 뿌옇게 흐려지는 것을 관찰할 수 있으며, 가수분해 시간은 10 ~ 60 분 정도 소요된다.Titanium tetrachloride is sufficiently dispersed in the mixed solvent under the above conditions, and then hydrolyzed at 30 to 100 ° C., in particular, peptization, to form a sol. At this time, it can be observed that the mixed solution in which the titanium tetrachloride is dispersed by the hydrolysis clouding in a transparent state, the hydrolysis time takes about 10 ~ 60 minutes.
다음으로, 상기 졸에 암모니아수를 가한 다음 세정 및 여과하여 비정질 티탄 겔을 형성시키는 단계이다. Next, ammonia water is added to the sol, followed by washing and filtration to form an amorphous titanium gel.
상기 가수분해 단계에서 얻어진 졸에 암모니아수를 pH 7 ~ 8이 되도록 첨가하며, 이때 생성된 침전물을 세정 및 여과하여 비정질 티탄 겔을 얻는다. 상기 세정 및 여과는 물, 아세톤 또는 이들의 혼합물로서 수행할 수 있다.Ammonia water is added to the sol obtained in the hydrolysis step so as to have a pH of 7 to 8, and the resulting precipitate is washed and filtered to obtain an amorphous titanium gel. The washing and filtration can be carried out as water, acetone or mixtures thereof.
마지막으로 상기 비정질 티탄 겔을 물에 분산시킨 후 10 ~ 100 atm, 100 ~ 300 ℃에서 수열처리하고, 켄칭 및 소성하여 이산화티탄 분말을 형성시키는 단계이다.Finally, the amorphous titanium gel is dispersed in water, followed by hydrothermal treatment at 10 to 100 atm and 100 to 300 ° C., quenching and calcining to form titanium dioxide powder.
상기 얻어진 비정질 티탄 겔은 물에 분산시킨 후 압력 용기에 담아 10 ~ 100 atm 범위로 조절하여 수열처리한다. 우수한 광활성을 지닌 이산화티탄 분말을 제조하기 위해 100 ~ 300 ℃에서 2 ~ 6 시간동안 수열처리를 수행하는 것이 바람직하다. The amorphous titanium gel thus obtained is dispersed in water and placed in a pressure vessel to be hydrothermally treated in a range of 10 to 100 atm. In order to produce titanium dioxide powder having excellent photoactivity, it is preferable to perform hydrothermal treatment at 100 to 300 ° C. for 2 to 6 hours.
일반적으로 수열처리 온도와 시간이 증가함에 따라 입자의 크기가 커진다고 한다. 그러나, 상기와 같이 입자가 커지는 것은 수열처리 조건에 의한 것이 아니라 수열처리 후 냉각이 서서히 이루어질 경우 생성된 입자(핵)끼리 응집되어 일어나는 현상이다. 즉, 수열처리후 온도가 높고, 냉각시 소요되는 시간이 증가함에 따라 입자의 크기가 커지는 상기한 문제점을 본 발명에서는 수열처리 후 켄칭(Quenching) 시킴으로서 해결하였다. 본 발명에서의 켄칭은 1 ~ 5 atm/min의 감압속도와 5 ~ 15 ℃/min의 감온속도로 수행되도록 하였으며, 감압속도와 감온속도가 상기 범위를 벗어나면 균일한 입자를 형성시킬 수 없다. 상기한 켄칭처리에 의하여 본 발명에서는 이산화티탄 단위 입자의 크기를 5 nm 이하로 제어할 수 있게 된다.In general, as the hydrothermal temperature and time increase, the particle size increases. However, the larger particles as described above are not caused by hydrothermal treatment conditions, but are caused by aggregation of particles (nuclei) generated when cooling is gradually performed after hydrothermal treatment. That is, in the present invention, the above-mentioned problem that the size of the particles increases as the temperature after the hydrothermal treatment is increased and the time required for cooling increases is solved by quenching after the hydrothermal treatment. In the present invention, the quenching was performed at a decompression rate of 1 to 5 atm / min and a deceleration rate of 5 to 15 ° C./min. By the above quenching treatment, in the present invention, the size of the titanium dioxide unit particles can be controlled to 5 nm or less.
상기 켄칭 후 분말을 소성하여 결정상이 아나타제형인 이산화티탄 분말을 제조하는데, 이때 소성온도는 400 ~ 800 ℃, 소성시간은 1 ~ 4 시간이 바람직하다. 만일, 소성온도가 400 ℃ 미만이면 아나타제형 결정도를 증가시키지 못하고, 800 ℃를 초과하면 이산화티탄 분말의 입자 크기가 커지고 비표면적이 급격히 작아지며, 광촉매로서 광활성 또한 현저히 낮아지는 문제가 발생된다.After quenching, the powder is calcined to produce titanium dioxide powder having anatase crystal phase, wherein the firing temperature is 400 to 800 ° C. and the firing time is 1 to 4 hours. If the firing temperature is less than 400 ° C., the anatase crystallinity cannot be increased. If the firing temperature is higher than 800 ° C., the particle size of the titanium dioxide powder is increased, the specific surface area is sharply decreased, and the photoactivity as the photocatalyst is also significantly lowered.
상기와 같은 본 발명의 이산화티탄 분말의 제조방법은 기존의 졸겔법과 같이 조성의 조절이 용이하고 고순도의 분말 제조가 가능하며, 기존의 수열합성법과 마찬가지로 분산성이 우수하며 후처리 공정이 필요하지 않기 때문에 다른 공정에 비하여 비교적 간단한 공정으로 고순도의 단일상의 분말을 제조할 수 있다.Titanium dioxide powder production method of the present invention as described above is easy to control the composition and the production of high-purity powder, like the conventional sol-gel method, like the conventional hydrothermal synthesis method, excellent dispersibility and does not require a post-treatment process As a result, a single phase powder of high purity can be produced in a relatively simple process compared to other processes.
더욱이 본 발명은 기존의 졸겔법의 문제점으로 지적되었던 분쇄공정이 필요하여 미세한 분말을 얻기가 곤란하거나, 원가가 높아 실제 적용시 고부가가치를 기대할 수 없었던 것을 해결한 것으로, 별도의 분쇄공정이 없이도 미세한 분말을 얻을 수 있다. 또한, 기존의 수열처리법이 출발원료에 따라 용해과정이 느려져 긴 반응시간을 필요로 하는 문제점을 졸겔법과 혼용함으로써 용해과정이 빠른 방법으로 해결하였다.Furthermore, the present invention solves the problem that it was difficult to obtain fine powder due to the pulverization process, which has been pointed out as a problem of the conventional sol-gel method, or the high cost value could not be expected in actual application. Powder can be obtained. In addition, the conventional hydrothermal treatment method solves the problem of requiring a long reaction time by mixing with the sol-gel method by slow dissolution process depending on the starting material, so that the dissolution process is solved in a fast manner.
즉, 본 발명에 의하면 이산화티탄 분말 조성의 조절이 용이하고, 고순도의 이산화티탄 분말을 비교적 간단한 공정으로 수득할 수 있다.That is, according to the present invention, the titanium dioxide powder composition can be easily controlled, and a high purity titanium dioxide powder can be obtained by a relatively simple process.
상술한 바와 같이 본 발명의 제조방법에 의하여 제조된 본 발명의 이산화티탄 분말은 입경 1 ~ 5 ㎚인 이산화티탄 단위입자의 집합체로서 근접한 상기 이산화티탄 단위입자 간에 기공이 형성되어 있고, 이산화티탄 단위입자 집합체의 평균입경이 20 ~ 100 ㎚이며, 비표면적이 40 ~ 120 ㎡/g로서 광활성이 기존의 상용 광촉 매보다 우수하며, 아나타제형의 결정상을 나타내어 광촉매로서의 효율성이 높다.As described above, the titanium dioxide powder of the present invention prepared by the production method of the present invention is a collection of titanium dioxide unit particles having a particle diameter of 1 to 5 nm, and pores are formed between adjacent titanium dioxide unit particles, and titanium dioxide unit particles. The average particle diameter of the aggregate is 20 to 100 nm, the specific surface area is 40 to 120 m 2 / g, the photoactivity is superior to the conventional commercial photocatalyst, exhibiting anatase type crystal phase and high efficiency as a photocatalyst.
이하 실시예에 의하여 본 발명을 더욱 구체적으로 설명하겠는바, 본 발명이 다음 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited by the following examples.
실시예 1Example 1
사염화티탄(Yakuri사 제조) 용액을 아르곤 존재하에 Ti 농도 1.0 M이 되도록 4 ℃ 탈이온수에 분산시킨 다음, 3-부탄올과 함께 HPC(Hydropropylcellulose)를 첨가하였다. 이때 물과 3-부탄올은 1 : 3 부피비가 되도록 혼합하며, 혼합 용액을 4 시간동안 빠르게 교반시킨 후 75 ℃에서, 30 분간 가수분해시켰다. 상기 가수분해에 의하여 생성된 졸에 암모니아수를 pH 7 ~ 8이 될 때 까지 적하하고, 생성된 침전물을 아세톤으로 세정하고 여과하여 비정질 티탄 겔을 제조하였다. The titanium tetrachloride (manufactured by Yakuri) solution was dispersed in deionized water at 4 ° C. to a Ti concentration of 1.0 M in the presence of argon, and HPC (Hydropropylcellulose) was added together with 3-butanol. At this time, water and 3-butanol were mixed in a volume ratio of 1: 3, and the mixed solution was rapidly stirred for 4 hours, and then hydrolyzed at 75 ° C. for 30 minutes. Ammonia water was added dropwise to the sol produced by the hydrolysis until the pH 7 ~ 8, and the resulting precipitate was washed with acetone and filtered to prepare an amorphous titanium gel.
상기의 비정질 겔을 증류수 속에 분산시킨 후 압력 용기에 담아 100 atm으로 300 ℃까지 가열한 후 4 시간 유지하는 방법으로 수열처리하고, 수열처리가 끝난 후 감압속도 3 atm/min, 감온속도10 ℃/min으로 급격히 켄칭(Quenching)하여 600 ℃로 소성하여 아나타제형 결정상의 이산화티탄 분말을 얻었으며, 첨부도면 도 2에 이산화티탄 분말의 SEM 사진을 나타내었다. 얻어진 이산화티탄 분말의 순도는 99.95 %이고, 비표면적은 116 ㎡/g 이다.After dispersing the above-mentioned amorphous gel in distilled water, it is placed in a pressure vessel and heated to 300 ° C. at 100 atm, followed by hydrothermal treatment for 4 hours, and after the hydrothermal treatment, the decompression rate is 3 atm / min and the deceleration rate is 10 ° C. / Quenched rapidly with min and fired at 600 ° C. to obtain anatase crystalline titanium dioxide powder. FIG. 2 shows an SEM image of the titanium dioxide powder. The purity of the obtained titanium dioxide powder is 99.95%, and the specific surface area is 116 m 2 / g.
실시예 2 ~ 8Examples 2-8
상기 실시예 1과 동일한 방법으로 이산화티탄 분말을 제조하되, 혼합용매에 사용된 알콜을 달리하였다. 즉, 알콜로서 1-프로판올(실시예 2), 2-프로판올(실시예 3), 1-부탄올(실시예 4), 2-부탄올(실시예 5), 에탄올(실시예 6), 메탄올(실시예 7) 및 옥탄올(실시예 8)을 사용하였다. 얻어진 이산화티탄 분말의 비표면적 및 입자 크기는 다음 표 1에 나타내었다.Titanium dioxide powder was prepared in the same manner as in Example 1, except that the alcohol used in the mixed solvent was changed. That is, 1-propanol (Example 2), 2-propanol (Example 3), 1-butanol (Example 4), 2-butanol (Example 5), ethanol (Example 6), methanol (Example) Example 7) and octanol (Example 8) were used. The specific surface area and particle size of the obtained titanium dioxide powder are shown in Table 1 below.
실험예 1 : 이산화티탄 분말의 형태 및 결정구조 분석Experimental Example 1 Analysis of Morphology and Crystal Structure of Titanium Dioxide Powder
상기 실시예 1 ~ 8에 의하여 제조된 이산화티탄 분말의 최종 형태를 보기 위해 SEM(Scanning Electron Microscopy)를 수행하였으며, 결정구조를 분석하기위해 XRD(X-ray Powder Diffraction)을 수행하였다. 또한 본 발명의 분말들에 대하여 BET로 비표면적을 측정하였으며, 그 결과 상기 표 1에 나타낸 바와 같이 본 발명의 실시예 1 ~ 8에 의해 제조된 이산화티탄 분말들의 비표면적은 약 40 ~ 120 ㎡/g임을 알 수 있었다. Scanning Electron Microscopy (SEM) was performed to see the final form of the titanium dioxide powder prepared in Examples 1-8, and XRD (X-ray Powder Diffraction) was performed to analyze the crystal structure. In addition, the specific surface area of the powders of the present invention was measured by BET. As a result, as shown in Table 1, the specific surface area of the titanium dioxide powders prepared by Examples 1 to 8 of the present invention was about 40 to 120 m 2 /. g was found.
도 2는 실시예 1에 의하여 제조된 이산화티탄 분말의 SEM 사진으로, 분산된 분말의 모습을 보여주고 있으며, 5 nm 이하의 이산화티탄 단위 입자들이 모여 20 ~ 100 nm 의 집합체를 형성하고 있는 모양을 이루고 있음을 알 수 있다. FIG. 2 is a SEM photograph of the titanium dioxide powder prepared according to Example 1, showing a state of a dispersed powder, wherein titanium dioxide unit particles of 5 nm or less are collected to form an aggregate of 20 to 100 nm. It can be seen that.
도 3은 실시예 1에 따른 분말의 XRD 패턴으로, 피크를 분석함으로서 분말의 결정상을 알 수 있다. 이산화티탄의 결정상은 아나타제, 루타일, 브로카이트의 결정상이 있는데 실시예 1에 따른 분말은 아나타제(Anatase)상의 이산화티탄이 생성되었고, 소성온도에 따라 600 ℃에서는 아나타제 결정도를 증가시키며 800 ℃를 초과할 경우에는 루타일 결정상이 나타나기 시작함을 확인할 수 있다.Figure 3 is an XRD pattern of the powder according to Example 1, by analyzing the peak can be seen the crystal phase of the powder. The crystal phases of titanium dioxide include anatase, rutile, and brothite. The powder according to Example 1 produced titanium dioxide in the anatase phase. In this case, it can be seen that the rutile crystal phase starts to appear.
실험예 2 : 이산화티탄 분말의 광촉매 활성Experimental Example 2 Photocatalytic Activity of Titanium Dioxide Powder
상기 실시예 1에서 얻어진 이산화티탄 분말을 사용하여 MB(Methylene Blue)의 분해실험을 통해 광촉매 활성을 측정하였다. The photocatalytic activity was measured through the decomposition experiment of MB (Methylene Blue) using the titanium dioxide powder obtained in Example 1.
1200 ml 증류수에 MB 20 ppm과 상기 실시예 1에서 제조한 이산화티탄 분말 1g을 첨가하고 용액이 잘 분산되도록 5 분 동안 초음파처리를 하여 제조한 시험용액에 9W의 광 강도를 지닌 자외선을 조사하여 MB를 광분해시켰다. 광분해 반응을 시킨 시험용액을 원심분리기를 사용하여 분리한 후 분해된 MB의 농도를 자외선-가시광선 분광광도계(UV/VIS Spectrophotometer)를 이용하여 측정하였으며, 그 결과로부터 얻어진 이산화티탄 분말에 의해 분해된 MB의 상대농도를 첨부도면 도 4에 나타내었다. 도 4에 따르면 시간에 따라 MB의 주피크가 사라지는 것, 즉 MB가 분해되는 것을 확인할 수 있다. 20 ml of MB and 1200 g of titanium dioxide powder prepared in Example 1 were added to 1200 ml of distilled water, and the test solution prepared by sonication for 5 minutes to disperse the solution was irradiated with ultraviolet light having a light intensity of 9 W. Photolysis. The test solution subjected to the photolysis reaction was separated using a centrifugal separator, and then the concentration of the decomposed MB was measured using a UV / VIS Spectrophotometer, which was decomposed by the titanium dioxide powder obtained from the result. The relative concentration of MB is shown in FIG. 4. According to FIG. 4, it can be seen that MB's main peak disappears over time, that is, MB is decomposed.
한편 상용 이산화티탄 분말인 P25(독일, Degussa), ST-01, ST-21, ST-31(일본, Ishihara)을 동량 첨가하여 동일한 실험을 수행하였으며, 첨부도면 도 5에 그 결과를 나타내었다 도 5에서 알 수 있듯, 본 발명의 실시예 1에 따라 제조된 이산화티탄 분말과 상용 이산화티탄 분말의 광활성을 비교해보면 본 발명의 실시예 1의 이산화티탄 분말이 P25보다 1.5 ~ 2 배, ST 시리즈 보다 2 ~ 10 배의 높은 광분해 효율을 보임을 확인할 수 있다. Meanwhile, the same experiment was performed by adding the same amount of commercial titanium dioxide powder P25 (Germany, Degussa), ST-01, ST-21, ST-31 (Japan, Ishihara), and the results are shown in the accompanying drawings. As can be seen from 5, when comparing the optical activity of the titanium dioxide powder prepared according to Example 1 of the present invention and commercial titanium dioxide powder, the titanium dioxide powder of Example 1 of the present invention is 1.5 to 2 times than P25, than the ST series It can be seen that it shows a high photolysis efficiency of 2 to 10 times.
실험예 3 : 자외선에 의한 MB의 분해실험Experimental Example 3 Disintegration Experiment of MB by Ultraviolet Rays
상기 실시예 1에서 얻어진 이산화티탄 분말의 MB 분해실험을 통한 정확한 광활성을 측정하기 위해 이산화티탄 분말 없이 9W의 광 강도를 지닌 자외선을 조사하여 MB을 분해하였다. MB was decomposed by irradiating with ultraviolet light having a light intensity of 9 W without titanium dioxide powder in order to measure accurate photoactivity through the MB decomposition experiment of the titanium dioxide powder obtained in Example 1.
그 결과로부터 자외선에 의해 분해된 MB의 상대농도를 도6에 나타내었으며, 도 6에 나타낸 바와 같이 이산화티탄 분말 없이 자외선만으로 MB는 거의 분해되지 않음을 알 수 있다.As a result, the relative concentration of MB decomposed by ultraviolet light is shown in FIG. 6, and as shown in FIG. 6, it can be seen that MB is hardly decomposed by ultraviolet light alone without titanium dioxide powder.
실험예 4 : 암실에서 이산화티탄에 의한 MB의 분해실험Experimental Example 4: Decomposition of MB by titanium dioxide in the dark room
상기 실시예에서 얻어진 이산화티탄 분말의 MB 분해실험을 통한 정확한 광활성을 측정하기 위해 암실에서 자외선 없이 이산화티탄 분말을 통하여 MB을 분해하였다. 그 결과로부터 암실에서 이산화티탄에 의해 분해된 MB의 상대농도를 도6에 나타낸 바와 같이, 자외선 없이 이산화티탄만으로 MB는 거의 분해되지 않음을 알 수 있다.MB was decomposed through the titanium dioxide powder without UV in the dark room in order to measure accurate photoactivity through the MB decomposition experiment of the titanium dioxide powder obtained in the above example. As a result, as shown in Fig. 6, the relative concentration of MB decomposed by titanium dioxide in the dark room, it can be seen that MB is hardly decomposed only by titanium dioxide without ultraviolet rays.
상술한 바와 같이, 사염화티탄을 출발물질로 사용하여 물과 알콜 혼합용매에 분산시키고 가수분해 및 겔화시킨 후 수열처리하고 특히 켄칭 단계를 거쳐 소성시킴으로써, 기존의 이산화티탄 분말의 제조방법인 금속알콕사이드법과는 달리 고가의 출발물질을 사용하지 않으면서도 복잡한 후처리 공정이 필요없는 간단한 방법으로 고순도의 이산화티탄 분말을 제조할 수 있다. As described above, by using titanium tetrachloride as a starting material, it is dispersed in a mixed solvent of water and alcohol, hydrolyzed and gelled, and then hydrothermally treated and calcined through a quenching step. Alternatively, high-purity titanium dioxide powder can be prepared by a simple method that does not require an expensive starting material and does not require a complicated post-treatment process.
본 발명은 특히 수열처리 후 켄칭(Quenching)을 함으로써 5 nm 이하의 직경을 가지는 이산화티탄 단위 입자가 집합체를 형성하여 20 ~ 100 nm 정도의 직경을 갖는 이산화티탄 분말 입자를 형성하고 입자 내부에 상기 이산화티탄 단위 입자간의 기공과 이산화티탄 단위 입자의 집합체 간의 기공이 형성된 구조를 갖으며 비표면적이 40 ~ 120 ㎡/g인 광촉매로서 우수한 광활성을 갖는 이산화티탄 분말 및 그 분말을 보다 경제적인 방법으로 제조하는 할 수 있는 효과를 나타낸다. In particular, the present invention is quenched after hydrothermal treatment to form an aggregate of titanium dioxide unit particles having a diameter of 5 nm or less to form titanium dioxide powder particles having a diameter of about 20 to 100 nm and the dioxide inside the particles Titanium dioxide powder having a structure in which pores between titanium unit particles and agglomerates of titanium dioxide unit particles are formed and having a specific surface area of 40 to 120 m 2 / g, which has excellent photoactivity, and a powder thereof are produced in a more economical manner. It shows the effect that can be done.
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