WO2013032253A2 - 이산화티타늄 제조방법 - Google Patents
이산화티타늄 제조방법 Download PDFInfo
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- WO2013032253A2 WO2013032253A2 PCT/KR2012/006956 KR2012006956W WO2013032253A2 WO 2013032253 A2 WO2013032253 A2 WO 2013032253A2 KR 2012006956 W KR2012006956 W KR 2012006956W WO 2013032253 A2 WO2013032253 A2 WO 2013032253A2
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- titanium dioxide
- transition metal
- tio
- dioxide powder
- titanium
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 28
- 150000003624 transition metals Chemical class 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- -1 titanium alkoxide Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
Definitions
- the present invention relates to a method for producing titanium dioxide, and more particularly, to a method for producing titanium dioxide by applying heat and pressure to titanium metal to make titanium dioxide.
- the titanium dioxide (TiO 2 ) powder which is an overcatalyst, functions to quickly and effectively remove substances which have a harmful effect on the human body or the environment, such as organic halogen compounds, odor gases, oils, bacteria, fungi and algae.
- photocatalysts are used in the Advanced Oxidation Process (AOP), where photocatalysts act as an aid to decompose environmental pollutants by absorbing sunlight in a specific wavelength band to completely decompose environmental pollutants at room temperature. do.
- AOP Advanced Oxidation Process
- the treatment efficiency is high, and the reaction product does not cause incidental environmental pollution, and there is an advantage that the reaction process is simple and can quickly decompose the environmental pollutants.
- Titanium dioxide powder can be classified into rutile structure and anatase structure according to its crystal structure.
- anatase-type titanium dioxide has a relatively high photoactivity and is known as a photocatalyst in a system for photodegrading trichloroethene and a solar energy change system.
- the sulfuric acid method is a method of producing a liquid TiO 2 from a solid state that is dissolved completely in sulfuric acid after pulverizing ilmenite, which is a titanium gemstone, and hydrolyzing it.
- hydrolysis of the titanium dioxide powder requires a calcination / crushing process of the hydrate, there is a problem in that the quality of the final product is greatly reduced due to the incorporation of many impurities in the process.
- the chlorine method is a method of producing anatase titanium dioxide (TiO 2 ) by reacting chlorine gas with ilmenite to produce titanium tetrachloride (TiCl 4 ), and then reacting it with oxygen gas.
- this method generates high-risk corrosive gases (HCl, Cl 2 ) during the reaction, requires a protective device for this, there is a problem that the production cost is high because the raw material is not abundant.
- P-25 of Degussa, Germany known as an excellent photocatalyst, is produced by such a chlorine method, but is known to have a problem of low photoactivation.
- the sol-gel method has the advantage of being able to manufacture titanium dioxide for high-purity photocatalyst, its quality is fine and its properties can be easily controlled in the process, but it is a starting material of titanium alkoxide (Ti (OC 3 H 7 )). 4 ), Ti (OC 2 H 5 ) 4 ) is expensive, its toxicity and stability is a problem.
- the conventional titanium dioxide (TiO 2 ) manufacturing process for photocatalysts has a problem of being complicated and costly, or handling materials and processes. Therefore, there is a need in the art for a method for producing titanium dioxide powder having excellent photoactivity and light efficiency through a simpler process.
- the present invention has been made to solve the above problems, and its object is to provide a method for producing titanium dioxide by a forging process safely and simply.
- the present invention for achieving the above object, relates to a method for producing titanium dioxide powder, the first step of forming a rutile titanium dioxide (TiO 2 ) by heat-treating and pressurizing Ti, and grinding the titanium dioxide powder A second step, a third step of mixing and doping the titanium dioxide (TiO 2 ) and the transition metal (M) so that the transition metal (M) is contained in 0.01 ⁇ 0.1mol%, and the transition metal (M) is And a fourth step of forming doped titanium dioxide (Ti 1- xM x O 2 ), wherein x is 0.01 ⁇ x ⁇ 0.1.
- the transition metal (M) is characterized in that it is composed of any one of Pt, Pd, Ru, Cr, Ni, Mo, V, Nb, Mn, Si and Al.
- the heating is characterized in that it is maintained at 500 to 1300 at 0.1 to 100 / min in an atmospheric pressure furnace.
- the pressurization is characterized in that for 100 to 1000 seconds maintained at a pressure of 10 to 500.
- the TiO 2 powder doped with the desired metal may be manufactured by using a direct oxidation method in the process of applying heat to titanium, the stability and practicality of the process is superior to other conventional manufacturing methods.
- the titanium dioxide powder obtained in the present invention is capable of acting in visible light through the doping effect of the transition metal, there is an effect that can be utilized as a photocatalyst having excellent light activation and light efficiency.
- FIG. 1 is a flow chart showing a process for producing titanium dioxide powder according to the present invention.
- Figure 2 is a graph showing the results of X-ray diffraction analysis of the titanium dioxide powder prepared according to the present invention titanium dioxide powder manufacturing process.
- Figure 3 is a photograph taken with a scanning electron microscope (SEM) of titanium dioxide powder prepared according to the inventors titanium dioxide powder manufacturing process.
- Figure 4 is a graph showing the results of the thermal analysis (TG / DSC) of titanium dioxide powder prepared according to the present invention titanium dioxide powder manufacturing process.
- the manufacturing process of the titanium dioxide powder of the present invention as shown in FIG. 1, the first step of forming a rutile titanium dioxide (TiO 2 ) by heat-treating and pressurizing Ti, and the first step of grinding the titanium dioxide Step 2 , a third step of mixing and doping the titanium dioxide (TiO 2 ) and the transition metal (M) so that the transition metal (M) is contained in 0.01 ⁇ 0.1mol%, and the transition metal (M) is doped And a fourth step of forming the prepared titanium dioxide (Ti 1 -xM x O 2 ).
- the range of x is preferably 0.01 ⁇ x ⁇ 0.1.
- titanium for preparing the titanium dioxide powder of the present invention is provided.
- the pressurization is performed by maintaining the preheated titanium at a pressure of 10 to 500 MPa for 100 to 1000 seconds.
- titanium dioxide is spontaneously generated on the surface of titanium under each condition (S2).
- air may be added to blow air.
- the titanium dioxide powder produced here varies in crystalline phase, size, distribution, and shape of the powder depending on the conditions.
- the titanium dioxide is ground (S3).
- the produced titanium dioxide powder is collected and ground by a ball mill and classified for each size.
- the ground titanium dioxide is mixed with a transition metal (S4).
- a mechanical alloying method may be applied to the mixture of titanium dioxide (TiO 2 ) and the transition metal (M) to form titanium dioxide (Ti 1 -xM x O 2 ) doped with the transition metal (M).
- the mechanical alloying method it is preferable to perform a ball milling process.
- the ball milling process is preferably carried out under the condition that the weight ratio of the mixture and the ball is 13: 1 to 25: 1, the ball milling process employed in the present invention is carried out for at least 8 hours at a rotational speed of 100 ⁇ 300rpm It is desirable to. Furthermore, it is preferable to use a grinding ball made of STS 313 material and a ball having a diameter of 2 to 16 inches (JIS standard).
- the transition metal (M) may be at least one selected from the group consisting of Fe, Cr, V, Nb, Sb, Sn, Si, and Al.
- the mixing ratio of the TiO 2 powder and the transition metal (M) is preferably such that the transition metal is 0.01 to 1 mol% in the whole mixture.
- the transition metal when the transition metal is less than 0.01 mol%, there is almost no doping effect, and when it exceeds 1 mol%, the crystal structure of the final titanium dioxide oxide itself is damaged.
- titanium dioxide doped with transition metal (M) (Ti 1 -xM x O 2 ) can be obtained.
- the energy bandgap of the conventional titanium dioxide that is not doped with a transition metal is limited to only the ultraviolet band ( ⁇ 380) to react to sunlight.
- the energy bandgap of TiO 2 is formed by doping the transition metal.
- Titanium dioxide powder (Ti 1- xMxO 2 ) doped with the completed transition metal was collected and subjected to phase analysis through XRD, as shown in FIG. 2.
- Compositional analysis was performed by inductively coupled plasma-atomic emission spectrometry (ICP), and the specific surface area was measured by a Brunauer-Emmett-Teller surface area analyzer.
- ICP inductively coupled plasma-atomic emission spectrometry
- the doped transition metal content was 6.445wt%
- the BET result showed that the specific surface area was about 160m 2 / g.
- FIG 3 is a SEM photograph of a titanium dioxide powder doped with a metal prepared according to the present embodiment.
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Abstract
본 발명은 이산화티타늄분말 제조방법에 관한 것으로, 그 구성은 Ti을 열처리하고 가압하여 루타일상의 이산화티타늄(TiO2)을 형성하는 제 1단계와, 상기 이산화티타늄분말을 분쇄하는 제 2단계와, 상기 전이금속(M)이 0.01~0.1mol%로 포함되도록 상기 이산화티타늄(TiO2)과 전이금속(M)을 혼합하여 도핑하는 제 3단계와, 상기 전이금속(M)이 도핑된 이산화티타늄(Ti1-xMxO2)을 형성하는 제 4단계를 포함하고, 상기 x는 0.01≤x≤0.1인 것을 특징으로 한다.
Description
본 발명은 이산화티타늄 제조방법에 관한 것으로, 더욱 상세하게는 티타늄 금속에 열과 압력을 가하여 이산화티탄을 만드는 이산화티타늄 제조방법에 관한 것이다.
일반적으로, 과촉매제인 이산화티타늄(TiO2)분말은 인체 또는 환경에 유해한 영향을 주는 물질, 예컨대 유기 할로겐 화합물, 악취 가스, 오일류, 세균류, 균류 및 조류 등을 신속하게 효과적으로 제거하는 작용을 한다.
따라서, 오폐수, 매립지 침수 등 난분해서 유기물을 포함한 폐수의 수질정화, 배기가스 및 실내 공기정화, 조명기구, 위생도기 등의 항균, 방취 등의 환경제품으로서 각광을 받고 있다.
특히, 광촉매제는 고도산화처리방식(AOP: Advanced Oxidation Process)에 사용되는데, 이 때에 광촉매제는 환경오염물을 상온에서 완전히 분해하기 위해 특정 파장대의 태양광을 흡수하여 환경오염물을 분해시키는 보조물로서 작용한다. 또한, 그 처리효율이 높고 반응생성물이 부수적인 환경오염을 유발시키지 않을 뿐만 아니라, 반응공정이 간소하여 환경오염물을 신속하게 분해시킬 수 있다는 장점이 있다.
이산화티타늄 분말은 그 결정구조에 따라 크게 루타일(rutile)구조와 아나타제(anatase)구조로 구분할 수 있다. 특히, 아나타제상 이산화티타늄은 비교적 광활성도가 높아 트리클로로에텐을 광분해시키는 시스템과 태양에너지 변화시스템 등에서 광촉매제로 알려져 있다.
종래의 광촉매용 이산화티타늄 분말 제조방법으로는, 염소법(chloride process), 황산법(sulfate process) 및 졸-겔법(sol-gel process)이 있다. 우선, 황산법은, 티타늄원석인 일메나이트(ilmenite)를 분쇄한 후에 황산에 용해시켜 완전히 녹지 않은 고체상태로부터 액상의 TiO2를 얻고 이를 가수분해하여 제조하는 방법이다. 하지만, 이산화티타늄 분말을 가수분해 후에 수한화물을 하소/분쇄과정을 많은 공정을 거쳐야 하므로, 그 과정에서 많은 불순물들의 혼입으로 인해 최종 제품의 품질이 크게 저하되는 문제점이 있다.
이와 달리, 염소법은, 일메나이트에 염소가스를 반응시켜 사염화티타늄(TiCl4)를 생성하고, 이를 다시 산소가스와 반응시킴으로써 아나타제상의 이산화티타늄(TiO2)을 제조하는 방법이다. 하지만, 이 방법은 반응 중에 위험성이 높은 부식성가스(HCl, Cl2)가 발생되어, 이에 대한 보호설비가 요구되며, 원료가 풍부하지 못해, 생산단가가 높다는 문제점이 있다.
우수한 광촉매제로 알려진 독일 데구사(Degussa)의 P-25는 이러한 염소법으로 제조된 것이나, 광활성화도가 낮다는 문제가 있는 것으로 알려져 있다.
또한, 졸-젤법은 고순도 광촉매용 이산화티타늄을 제조할 수 있는 이점에도 불구하고, 그 품질이 정교하고 공정상 물성제어가 용이하다는 장점이 있으나, 출발물질인 티타늄알콕사이드(Ti(OC3H7)4), Ti(OC2H5)4)가 고가이며, 그 독성과 안정성이 문제된다.
이와 같이, 종래의 광촉매용 이산화티타늄(TiO2)제조공정은 복잡하면서 큰 비용이 소모되거나, 취급물질과 공정이 위험하다는 문제가 있다. 따라서, 당 기술분야에서는 우수한 광활성도와 광효율을 갖는 이산화티타늄 분말을 보다 간소한 공정을 통해 제조할 수 있는 방법이 요구되어 왔다.
본 발명은 상술한 문제점을 해결하기 위한 것으로, 그 목적은 안전하고 간단하게 티타늄 단조공정에 의한 이산화티타늄 제조방법을 제공하는 것이다.
상술한 목적을 달성하기 위한 본 발명은, 이산화티타늄분말 제조방법에 관한 것으로서, Ti을 열처리하고 가압하여 루타일상의 이산화티타늄(TiO2)을 형성하는 제 1단계와, 상기 이산화티타늄분말을 분쇄하는 제 2단계와, 상기 전이금속(M)이 0.01~0.1mol%로 포함되도록 상기 이산화티타늄(TiO2)과 전이금속(M)을 혼합하여 도핑하는 제 3단계와, 상기 전이금속(M)이 도핑된 이산화티타늄(Ti1-xMxO2)을 형성하는 제 4단계를 포함하고, 상기 x는 0.01≤x≤0.1인 것을 특징으로 한다.
상기 전이금속(M)은 Pt, Pd, Ru, Cr, Ni, Mo, V, Nb, Mn, Si 및 Al 중 어느 하나로 구성되는 것을 특징으로 한다.
상기 제 1단계에서, 가열은 상압로에서 0.1 내지 100/min으로 500 내지 1300에서 유지하는 것을 특징으로 한다.
상기 제 1단계에서, 가압은 10 내지 500의 압력으로 100 내지 1000초 동안 유지하는 것을 특징으로 한다.
본 발명에 의한 티타늄 단조공정에 의한 이산화티타늄 제조방법에서는 다음과 같은 효과가 있다.
티타늄에 열을 가하는 공정 상에서 직접산화법을 이용하여 원하는 금속이 도핑된 TiO2분말을 제조할 수 있으므로, 다른 종래의 제조방법에 비해 공정의 안정성과 실용성이 우수한 효과가 있다.
또한, 본 발명에서 얻어진 이산화티탄늄 분말은 전이금속의 도핑효과를 통해 가시광선에서도 작용이 가능하므로, 우수한 광활성화도와 광효율을 갖는 광촉매제로서도 활용될 수 있는 효과가 있다.
도 1은 본 발명에 따른 이산화티타늄분말 제조과정을 보인 순서도.
도 2는 본 발명인 이산화티타늄분말 제조과정에 따라 제조된 이산화티타늄분말을 X-ray 회절분석한 결과를 보인 그래프.
도 3은 본 발명인 이산화티타늄분말 제조과정에 따라 제조된 이산화티타늄분말을 주사전자현미경(SEM)으로 촬영한 도면.
도 4는 본 발명인 이산화티타늄분말 제조과정에 따라 제조된 이산화티타늄분말을 열분석(TG/DSC)한 결과를 보인 그래프.
이하, 본 발명에 의한 이산화티타늄분말 제조과정의 바람직한 실시예가 첨부된 도면을 참고하여 상세하게 설명한다.
먼저, 본 발명인 이산화티타늄분말의 제조과정은, 도 1에 도시된 바와 같이, Ti을 열처리하고 가압하여 루타일상의 이산화티타늄(TiO2)을 형성하는 제 1단계와, 상기 이산화티타늄을 분쇄하는 제 2단계와, 상기 전이금속(M)이 0.01~0.1mol%로 포함되도록 상기 이산화티타늄(TiO2)과 전이금속(M)을 혼합하여 도핑하는 제 3단계와, 상기 전이금속(M)이 도핑된 이산화티타늄(Ti1-xMxO2)을 형성하는 제 4단계를 포함하여 구성될 수 있다.
여기서, 상기 x의 범위는 0.01≤x≤0.1인 것이 바람직하다.
먼저, 본 발명인 이산화티타늄분말을 제조하기 위한 티타늄이 마련된다. 상기 티타늄을 열처리하고 가압한다(S1). 보다 구체적으로, 상기 열처리는 상기 티타늄을 상압로에서 승온온도 0.1 내지 100℃/min으로 500 내지 1300℃에서 유지하여 처리한다.
그리고, 상기 가압은 상기 예열된 티타늄을 10 내지 500MPa의 압력으로 100 내지 1000초 동안 유지하여 처리한다.
이렇게 하면, 각 조건에서 티타늄이 표면에서 산화반응이 자발적으로 발생하게 되어 이산화티타늄이 만들어진다(S2). 또한, 상기 산화반응을 촉진하기 위해, 공기압을 가하여 공기를 불어줄 수 있다. 여기서 제조되는 이산화티타늄분말은 각 조건에 따라서 분말의 결정상, 크기 및 분포, 모양이 달라진다.
그리고, 상기 이산화티타늄을 분쇄한다(S3). 이때, 제조된 이산화티탄분말을 회수하여 볼밀로 분쇄하여 각 크기별로 분급한다.
그리고, 상기 분쇄된 이산화티타늄을 전이금속과 혼합한다(S4). 이때, 상기 이산화티타늄(TiO2)과 전이금속(M)의 혼합물에 기계적 합금법을 적용하여, 전이금속(M)이 도핑된 이산화티타늄(Ti1-xMxO2)을 형성할 수 있다.
상기 기계적 합금법을 구현하기 위해, 볼밀링공정을 실시하는 것이 바람직하다. 상기 볼밀링공정은 바람직하게는 상기 혼합물과 볼의 중량비를 13:1~25:1로 하는 조건에서 실시하며, 본 발명에 채용되는 볼밀링 공정은 100~300rpm의 회전속도로 적어도 8시간이상 실시하는 것이 바람직하다. 나아가, 볼밀링에 사용되는 볼로는 STS 313 물질로 이루어지고 2~16인치(JIS규격)인 연마볼을 사용하는 것이 바람직하다.
상기 전이금속(M)은 Fe, Cr, V, Nb, Sb, Sn, Si 및 Al로 이루어진 그룹에서 선택된 적어도 하나일 수 있다. 그리고, 본 발명에서, TiO2분말과 전이금속(M)의 혼합비율은 전체 혼합물에서 전이금속이 0.01 ~ 1mol%가 되도록 하는 것이 바람직하다.
여기서, 전이금속이 0.01mol% 미만일 경우에는 도핑효과가 거의 없으며, 1mol%를 초과하는 경우에는 최종 이산화티탄늄 산화물의 결정구조 자체가 손상되는 문제가 있다.
이와 같은 전이금속 도핑공정을 통해, 전이금속(M)이 도핑된 이산화티타늄(Ti1-xMxO2)을 얻을 수 있다. 전이금속이 도핑되지 않은 통상의 이산화티타늄의 에너지밴드갭은 자외선대역(~380)에만 한정되어 태양광에 대한 반응하는 문제가 있었으나, 본 발명과 같이 전이금속을 도핑하여 TiO2의 에너지밴드갭을 낮춤으로써 가시광선대역의 파장도 흡수할 수 있는 광효율성이 대폭 개선된 새로운 형태의 이산화티타늄(Ti1-xMxO2)을 제공할 수 있다.
완료된 전이금속이 도핑된 이산화티타늄 분말(Ti1-xMxO2)을 수거하여, 도 2에 도시된 바와 같이, XRD를 통하여 상분석을 실시하였다. ICP(Inductively Coupled Plasma-Atomic Emission Spectrometry)를 통해 조성분석을 실시하였으며, BET(Brunauer-Emmett-Teller) 표면적 분석기를 통하여 비표면적을 측정하였다. ICP 조성분석결과, 도핑된 전이금속함량은 6.445wt%로 나타났으며, BET측정결과가 비표면적이 약 160m2/g으로 높게 나타났다.
그리고, 도 3은 본 실시예를 통해 제조된 금속이 도핑된 이산화티타늄분말을 촬영한 SEM 사진이다.
본 발명의 권리는 위에서 설명된 실시예에 한정되지 않고 청구범위에 기재된 바에 의해 정의되며, 본 발명의 분야에서 통상의 지식을 가진 자가 청구범위에 기재된 권리범위 내에서 다양한 변형과 개작을 할 수 있다는 것은 자명하다.
Claims (4)
- Ti을 열처리하고 가압하여 루타일상의 이산화티타늄(TiO2)을 형성하는 제 1단계;상기 이산화티타늄분말을 분쇄하는 제 2단계;상기 전이금속(M)이 0.01~0.1mol%로 포함되도록 상기 이산화티타늄(TiO2)과 전이금속(M)을 혼합하여 도핑하는 제 3단계; 그리고,상기 전이금속(M)이 도핑된 이산화티타늄(Ti1-xMxO2)을 형성하는 제 4단계를 포함하고, 상기 x는 0.01=x=0.1인 것을 특징으로 하는 이산화티타늄분말 제조방법.
- 제 1항에 있어서,상기 전이금속(M)은 Pt, Pd, Ru, Cr, Ni, Mo, V, Nb, Mn, Si 및 Al 중 어느 하나로 구성되는 것을 특징으로 하는 이산화티타늄분말 제조방법.
- 제 1항에 있어서,상기 제 1단계에서, 가열은 상압로에서 0.1 내지 100/min으로 500 내지 1300에서 유지하는 것을 특징으로 하는 이산화티타늄분말 제조방법.
- 제 1항에 있어서,상기 제 1단계에서, 가압은 10 내지 500의 압력으로 100 내지 1000초 동안 유지하는 것을 특징으로 하는 이산화티타늄분말 제조방법.
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| KR100539613B1 (ko) * | 2003-08-28 | 2005-12-29 | 학교법인 한양학원 | 광촉매제용 이산화티타늄 분말 제조방법 및 그로부터 제조된 이산화티타늄 분말 |
| WO2006044495A1 (en) * | 2004-10-14 | 2006-04-27 | Tokusen U.S.A., Inc. | Method for synthesizing nano-sized titanium dioxide particles |
| KR100803738B1 (ko) * | 2006-08-31 | 2008-02-15 | 오한준 | 티타늄-페르옥시겔을 이용한 산화티타늄 광촉매 제조방법 |
| KR101015911B1 (ko) * | 2003-05-20 | 2011-02-23 | 하진욱 | 티타늄 금속판을 산화처리한 이산화티타늄판 |
-
2011
- 2011-09-02 KR KR1020110088902A patent/KR20130025536A/ko not_active Application Discontinuation
-
2012
- 2012-08-30 WO PCT/KR2012/006956 patent/WO2013032253A2/ko active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101015911B1 (ko) * | 2003-05-20 | 2011-02-23 | 하진욱 | 티타늄 금속판을 산화처리한 이산화티타늄판 |
| KR100539613B1 (ko) * | 2003-08-28 | 2005-12-29 | 학교법인 한양학원 | 광촉매제용 이산화티타늄 분말 제조방법 및 그로부터 제조된 이산화티타늄 분말 |
| WO2006044495A1 (en) * | 2004-10-14 | 2006-04-27 | Tokusen U.S.A., Inc. | Method for synthesizing nano-sized titanium dioxide particles |
| KR100803738B1 (ko) * | 2006-08-31 | 2008-02-15 | 오한준 | 티타늄-페르옥시겔을 이용한 산화티타늄 광촉매 제조방법 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013032253A9 (ko) | 2013-04-25 |
| KR20130025536A (ko) | 2013-03-12 |
| WO2013032253A3 (ko) | 2013-06-06 |
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