KR100343395B1 - Method for production of titanium dioxide ultrafine powders with rutile phase from titanium sulfate - Google Patents
Method for production of titanium dioxide ultrafine powders with rutile phase from titanium sulfate Download PDFInfo
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- KR100343395B1 KR100343395B1 KR1019990019400A KR19990019400A KR100343395B1 KR 100343395 B1 KR100343395 B1 KR 100343395B1 KR 1019990019400 A KR1019990019400 A KR 1019990019400A KR 19990019400 A KR19990019400 A KR 19990019400A KR 100343395 B1 KR100343395 B1 KR 100343395B1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000000843 powder Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 title claims abstract description 16
- 229910000348 titanium sulfate Inorganic materials 0.000 title claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 title description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011550 stock solution Substances 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 230000008676 import Effects 0.000 abstract description 4
- 238000007865 diluting Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- -1 alkali metal titanate Chemical class 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- WRWQVSOJXAVREP-UHFFFAOYSA-J tetrachlorotitanium hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Cl-].[Cl-].[Ti+4] WRWQVSOJXAVREP-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-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
- C01G23/053—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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
본 발명은 황산티타늄을 이용하여 미세하고 균일한 크기의 루틸상 이산화티탄 분말을 제조하는 방법에 관한 것으로서, 구체적으로는 농축 황산티타늄 원액에 강알칼리를 첨가하여 수산화티탄 (TiO(OH)2) 침전물을 형성시키는 단계; 상기 침전물을 증류수로 여과 및 세척하는 단계; 상기 세척한 침전물을 염산 수용액에 녹여 티타닐클로라이드 (TiOCl2) 수용액을 제조하는 단계; 상기 티타닐클로라이드 수용액에 물을 더 첨가해 티타닐클로라이드 수용액을 희석하는 단계; 상기 희석된 티타닐클로라이드 수용액을 저온 균일 침전법에 의해 침전물을 제조하는 단계; 및 상기 침전물을 여과, 세척 및 건조하는 단계로 이루어지는 초미립 루틸상 이산화티탄 분말의 제조방법에 관한 것이며, 본 발명의 제조방법은 고온 및 저온 장치 등의 특별한 추가장치 없이도 침전 반응 속도가 빠르고 수율이 향상되며 또한 공정이 간단하고 연속작업이 가능하다. 더욱이 사염화티탄 (TiCl4)보다 가격이 저렴한 황산티타늄을 초기물질로서 사용하므로 루틸상 이산화티탄 분말의 생산성, 경제성 및 실용성을 향상시킬 수 있고, 나아가 루틸상 이산화티탄의 막대한 수입량을 대체할 수 있는 효과가 있다.The present invention relates to a method for producing rutile titanium dioxide powder having a fine and uniform size using titanium sulfate, and specifically, a strong alkali is added to a concentrated titanium sulfate stock solution to prepare a titanium hydroxide (TiO (OH) 2 ) precipitate. Forming; Filtering and washing the precipitate with distilled water; Dissolving the washed precipitate in an aqueous hydrochloric acid solution to prepare a titanyl chloride (TiOCl 2 ) aqueous solution; Adding water to the titanyl chloride aqueous solution to dilute the titanyl chloride aqueous solution; Preparing a precipitate by diluting the diluted titanyl chloride aqueous solution by low temperature homogeneous precipitation; And relates to a method for producing ultra-fine rutile titanium dioxide powder consisting of the step of filtering, washing and drying the precipitate, the production method of the present invention is fast and the yield reaction rate without special additional equipment such as high temperature and low temperature equipment It is improved and the process is simple and continuous work is possible. Furthermore, the use of titanium sulfate, which is cheaper than titanium tetrachloride (TiCl 4 ), as an initial material can improve the productivity, economics and practicality of the rutile titanium dioxide powder, and can replace the enormous import amount of rutile titanium dioxide. There is.
Description
본 발명은 황산티타늄을 이용하여 미세하고 균일한 크기의 루틸상 이산화티탄 분말을 제조하는 방법에 관한 것으로서, 구체적으로는 농축 황산티타늄 원액에 강알칼리를 첨가하여 수산화티탄 (TiO(OH)2) 침전물을 형성시키는 단계; 상기 침전물을 증류수로 여과 및 세척하는 단계; 상기 세척한 침전물을 염산 수용액에 녹여 티타닐클로라이드 (TiOCl2) 수용액을 제조하는 단계; 상기 티타닐클로라이드 수용액에 물을 더 첨가해 티타닐클로라이드 수용액을 희석하는 단계; 상기 희석된 티타닐클로라이드 수용액을 저온 균일 침전법에 의해 침전물을 제조하는 단계; 및 상기 침전물을 여과, 세척 및 건조하는 단계로 이루어지는 초미립 루틸상 이산화티탄 분말의 제조방법에 관한 것이다.The present invention relates to a method for producing rutile titanium dioxide powder having a fine and uniform size using titanium sulfate, and specifically, a strong alkali is added to a concentrated titanium sulfate stock solution to prepare a titanium hydroxide (TiO (OH) 2 ) precipitate. Forming; Filtering and washing the precipitate with distilled water; Dissolving the washed precipitate in an aqueous hydrochloric acid solution to prepare a titanyl chloride (TiOCl 2 ) aqueous solution; Adding water to the titanyl chloride aqueous solution to dilute the titanyl chloride aqueous solution; Preparing a precipitate by diluting the diluted titanyl chloride aqueous solution by low temperature homogeneous precipitation; And it relates to a method for producing ultrafine rutile titanium dioxide powder consisting of the step of filtering, washing and drying the precipitate.
이산화티탄 분말은 열역학적으로 안정하고 무독성이며 백색도 및 은폐력이 좋으므로 페인트, 플라스틱, 종이 등의 백색 도료의 원료로 대량 이용되고 있다. 특히 루틸상 이산화티탄은 자외선 차단 능력이 뛰어나 화장품의 UV 차단제, 여름철 빌딩 및 자동차의 냉방을 위한 자외선 차단용 페인트로 사용되고 있고, 플라스틱과 섬유 등의 안료, 타이어의 충진제로 사용되고 있으며 다른 재료에 비해 유전상수와 굴절률이 높고 기름의 흡착 및 착색력이 우수할 뿐만 아니라 강산성이나 강염기성에서도 화학적으로 안정하므로 광학기기의 비반사 코팅막, 빔 스플리터, 렌즈 첨가제 등에 사용되고 있다. 또한 최근에는 이산화티탄의 강유전성 특성 때문에 전자세라믹 소자의 근간재료, 산화물 반도체, 산소 센서 및 필터 재료로 사용되어 그 용도가 우리 일상 생활과 밀접하게 관련되어 크게 확대되고 있는 실정이다.Titanium dioxide powder is thermodynamically stable, non-toxic, and has good whiteness and hiding power, so it is used in large quantities as a raw material for white paints such as paint, plastic, and paper. In particular, rutile titanium dioxide has excellent UV protection ability, so it is used as a UV blocker for cosmetics, UV protection paint for cooling buildings and automobiles in summer, pigments such as plastics and textiles, and fillers for tires. It has high constant and refractive index, excellent oil adsorption and coloring power, and is chemically stable in strong acidity and strong basicity, so it is used for non-reflective coating film, beam splitter, lens additive of optical equipment. In addition, recently, due to the ferroelectric properties of titanium dioxide, it is used as a base material of an electronic ceramic device, an oxide semiconductor, an oxygen sensor, and a filter material, and its use is being closely related to our daily lives.
이산화티탄은 상압 하에서 루틸상 (rutile), 아나타제상 (anatase), 부루카이트상 (brookite) 등 3종류의 결정 형태를 가지고 있으며 루틸상 (d:4.25 g/cm3)과 아나타제상 (d:3.89 g/m3)은 정방정계 (tetragonal, a=b≠c, α=β=γ=90°)에 속하며 모두 티타늄 (Ti)을 중심으로 하는 TiO6팔면체를 기본구조로 갖고 있다. 루틸상은 2개의 모서리, 2개의 꼭지점을 공유하고 아나타제상은 4개의 모서리를 공유한다. 이때 기본구조를 이루고 있는 TiO6팔면체는 정팔면체에서 비틀어진 구조이며, 루틸상보다 아나타제상이 더 많이 비틀려져 있다. 이러한 여러 종류의 이산화티탄중에서도 루틸상이 에너지적으로 가장 안정하고, 아나타제상은 루틸상에 비해 준안정한 상태이기 때문에 고온에서 열처리하면 루틸상으로의 상전이가 일어난다. 특히 루틸상 이산화티탄은 아나타제상에 비하여 그 물리화학적인 성질이 전술한 바와 같이 안정하기 때문에 응용 분야가 매우 넓다.Titanium dioxide has three types of crystal forms under normal pressure: rutile, anatase, and brookite. Rutile (d: 4.25 g / cm 3 ) and anatase (d: 3.89) g / m 3 ) belongs to tetragonal system (tetragonal, a = b ≠ c, α = β = γ = 90 °) and all have TiO 6 octahedron centered on titanium (Ti) as basic structure. The rutile phase shares two corners, two vertices, and the anatase phase shares four corners. At this time, the TiO 6 octahedron constituting the basic structure is a twisted structure in the octahedron, and the anatase phase is twisted more than the rutile phase. Among these various types of titanium dioxide, the rutile phase is the most stable energy, and the anatase phase is metastable in comparison with the rutile phase, so phase transition to the rutile phase occurs at high temperature. In particular, since the physicochemical properties of rutile titanium dioxide are stable as described above, compared to the anatase phase, the field of application is very wide.
루틸상 이산화티탄을 제조하는 방법의 가장 대표적인 예로는 염소법 (chloride process)과 황산법 (sulfate process)이 있다. 염소법은 1956년 미국의 듀퐁 (Du Pont)사가 공업화한 방법으로서 공기 중의 수분과 반응하여 심한 가수분해를 일으키는 사염화티탄 (TiCl4)을 출발 원료로 하여 1000 ℃ 이상의 온도에서 얻어지는데, 여기에서 얻어진 이산화티탄 분말은 미세하지만 거칠고, 반응 중에 생기는 부식성 가스 (Cl2, HCl)로 인해 추가적인 부대 보호장치 설비가 필요하므로 제품의 생산 단가가 높다. 또한, 입자의 형상과 크기가 조절된 이산화티탄 분말을 제조하기 위해서는 반응 중에 전기장을 가하거나 반응 물질의 혼합비를 정확히 조절해야 하므로 특수한 장치들을 추가로 더 부착해야 한다.The most representative examples of the method for producing rutile titanium dioxide are the chloride process and the sulfate process. The chlorine method was industrialized by Du Pont in 1956 and is obtained from titanium tetrachloride (TiCl 4 ), which reacts with moisture in the air and causes severe hydrolysis, as a starting material. Titanium dioxide powder is fine but coarse, and the production cost of the product is high because additional corrosive protection equipment is required due to the corrosive gases (Cl 2 , HCl) generated during the reaction. In addition, in order to prepare titanium dioxide powder in which the particle shape and size are controlled, special devices must be further attached because an electric field is applied during the reaction or the mixing ratio of the reactants is precisely controlled.
한편, 1916년 노르웨이의 티탄 회사 (Titan Co.)가 공업화한 TiOSO4를 출발원료로 하는 황산법 공정에서는, 이산화티탄 분말을 가수 분해하여 얻어진 비정질 수산화물을 다시 하소한 후 분쇄 공정을 거쳐야 얻어지기 때문에 이 과정에서 많은 불순물들이 유입되어 최종 제품의 품질이 크게 떨어지는 단점이 있다. 게다가 800∼1100 ℃에서 12시간 이상의 하소 공정을 통해 아나타제상 이산화티탄 분말이 제조되고 그 이상의 온도에서 하소 공정을 거쳐야만 루틸상 이산화티탄 분말이 제조되므로, 고온 열처리와 분쇄 공정으로 인해 최종 분말의 특성이 크게 저하되는 단점이 있다. 이와 같이 이산화티탄 분말 제조를 위한 원료로 사용되는 황산티타늄 (TiOSO4)은 현재의 기술로는 1000 ℃ 이상의 고온 열처리 공정을 거치지 않고는 루틸상 이산화티탄 분말을 생산하지 못하고 있다.On the other hand, in the sulfuric acid process using TiOSO 4, which was commercialized by the Titan Co. of Norway in 1916, as a starting material, the amorphous hydroxide obtained by hydrolyzing titanium dioxide powder was calcined again before being obtained through a grinding process. Many impurities are introduced in the process, and the quality of the final product is greatly reduced. In addition, the anatase titanium dioxide powder is produced through a calcination process at 800 to 1100 ° C. for more than 12 hours, and the rutile titanium dioxide powder is produced only after the calcination process at a higher temperature. There is a disadvantage that is greatly reduced. As such, titanium sulfate (TiOSO 4 ), which is used as a raw material for the production of titanium dioxide powder, does not produce rutile titanium dioxide powder without a high temperature heat treatment process of 1000 ° C. or higher.
그러나, 이러한 황산법으로 대표되는 액상법은 기상법에 비해 그 반응온도가 낮고 대량생산이 쉽다는 장점이 있으므로, 공정이 개선된 제조방법이나 기상법의 원료였던 사염화티타늄을 이용한 새로운 액상법이 보고되어 왔다. 최근 액상법의 예로 러시아 특허 SU-1398321 호에 기재된 바에 의하면, 적당량의 아나타제상 침전 시드 (titaniferous seed)를 사염화티타늄 용액에 첨가한 상태에서 가열방법으로 가수분해시켜 수화된 이산화티탄을 침전시키고, 다시 고온 열처리의 후처리 공정을 거쳐 이산화티탄을 제조한다. 그러나 이 방법은 제조 공정이 비교적 단순한 반면, 아나타제상 이산화티탄을 얻기 위해서는 600∼650 ℃에서의 추가적인 고온 열처리가 필요하며, 루틸상 이산화티탄을 얻기 위해서는 더 높은 온도의 열처리가 필요하다는 단점이 있다.However, the liquid phase method represented by the sulfuric acid method has the advantage that the reaction temperature is lower than that of the gas phase method and easy to mass production, and thus a new liquid phase method using titanium tetrachloride, which is a raw material of the improved production method or the gas phase method, has been reported. As an example of a liquid phase method, as described in Russian Patent SU-1398321, a suitable amount of anatase phase precipitation seed is added to a titanium tetrachloride solution by hydrolysis by heating to precipitate hydrated titanium dioxide, followed by high temperature. Titanium dioxide is produced through a post-treatment process of heat treatment. However, this method has a disadvantage in that, while the manufacturing process is relatively simple, an additional high temperature heat treatment is required at 600 to 650 ° C. to obtain anatase titanium dioxide, and a higher temperature heat treatment is required to obtain rutile titanium dioxide.
일본 특개평 제1-301518호에서는 사염화티타늄 수용액에 소량의 황산을 가한 후 여기에 알칼리 수용액을 가해 중화반응을 거쳐 수산화티탄 침전물을 생성시키기고 고온 열처리 공정을 거쳐 이산화티탄을 제조하는 방법을 제시하였는데, 이 방법도 추가의 열처리가 필요하고 이산화티탄의 물성이 크게 떨어지는 단점이 있다.In Japanese Patent Laid-Open No. 1-301518, a small amount of sulfuric acid was added to an aqueous solution of titanium tetrachloride, and then an aqueous alkali solution was added thereto to produce a titanium hydroxide precipitate through a neutralization reaction, and a method of producing titanium dioxide through a high temperature heat treatment process was presented. However, this method also requires additional heat treatment and has a disadvantage in that the physical properties of titanium dioxide are greatly reduced.
일본 특개평 제4-280816호에서는 2 또는 3 염기성 유기카르본산 등을 첨가해 제조한 알칼리 수용액에 사염화티타늄 수용액을 가하여 축합반응을 시키고, 생성된 반응 축합물을 여과, 수세한 후 이것의 수현탁 침전물액에 다시 수산화 알칼리 금속을 첨가해 pH 8 이상, 50 ℃ 온도에서 티탄산알칼리 용액으로 만든 다음, 이를 다시 여과, 수세한 후 이것의 수현탁액에 산을 첨가해 pH 3 이하, 50 ℃ 이상의 온도에서 처리하여 티탄산알칼리 금속으로 중화시킨 후 여과, 수세, 건조 등의 후처리 공정을 거쳐 이산화티탄을 제조하는 방법을 제시하였다. 이 방법에 의하면 물성이 양호한 초미립상의 이산화티탄이 생성되지만 값이 비싼 유기 카르본산과 같은 제 3의 첨가제들을 사용하고 여러 번의 제조 공정을 거치기 때문에 공정관리가 까다롭고 여러 공정 과정 중 생성된 다량의 폐수를 각각 처리해야 하는 문제점이 있다.In Japanese Patent Laid-Open No. 4-280816, an aqueous solution of titanium tetrachloride is added to an aqueous alkali solution prepared by adding 2 or tribasic organic carboxylic acid or the like to carry out condensation reaction, and the resulting reaction condensate is filtered and washed with water. The alkali metal hydroxide was added to the precipitate, and the alkali titanate solution was formed at a pH of 8 or more and a temperature of 50 DEG C, and then filtered and washed again. After treating and neutralizing with alkali metal titanate, a method of preparing titanium dioxide through a post-treatment process such as filtration, washing with water and drying was proposed. This method produces ultra fine titanium dioxide with good physical properties, but it is difficult to control because it uses third-party additives such as expensive organic carboxylic acid and goes through several manufacturing processes. There is a problem that each of the waste water must be treated.
한편, 대한민국 특허 출원 제98-28928호에서는 사염화티타늄으로부터 상온 합성 방법으로 결정성 이산화티탄 단분산구를 제조하는 경제적인 방법이 제시되었다. 그러나 이 방법에서는 초기 원료로 사용되는 사염화티탄이 공기 중에서 심한 가수분해를 일으키기 때문에 초기에 티타릴클로라이드로 희석할 때 반응속도를 제어하기 위해 온도를 낮추어 0 ℃ 이하로 유지하는 특별한 용기를 필요로 하고 전적으로 수입에 의존하고 있는 원료인 사염화티탄은 특수한 수송 용기가 필요하기 때문에 제조단가가 비싸다는 단점이 있다.Meanwhile, Korean Patent Application No. 98-28928 discloses an economical method for producing crystalline titanium dioxide monodispersed sphere from room temperature synthesis method using titanium tetrachloride. However, this method requires a special vessel to keep the temperature lower than 0 ℃ to control the reaction rate when the initial dilution of the titanium tetrachloride used in the raw material causes severe hydrolysis in the air, when dilution with titaniumyl chloride Titanium tetrachloride, a raw material that depends entirely on imports, has a disadvantage in that the manufacturing cost is expensive because a special transport container is required.
이에 본 발명자들은 전술한 초미립 루틸상 이산화티탄 분말 제조방법의 문제점을 해결하고자 연구한 결과, 농축 황산티타늄 원액에 pH 12 이상이 되도록 강알칼리를 첨가하여 수산화티탄 침전물을 형성시켜 증류수로 여과 및 세척하고 5 M 이상의 염산 수용액에 녹여 티타닐클로라이드 수용액을 제조한 후, 물을 더 첨가해 Ti4+농도를 0.03∼1.6 M로 희석시키고 100 ℃ 이하의 온도로 2∼5 시간 가열하여 침전물을 얻고 여과, 세척 및 건조하는 과정을 거침으로써 초미립 루틸상 이산화티탄 분말을 제조할 수 있고, 상기 방법은 고온 및 저온 장치 등의 특별한 추가장치 없이도 침전 반응 속도가 빠르고 수율이 향상되며 또한 공정이 간단하고 연속작업이 가능할 뿐만 아니라, 사염화티탄보다 가격이 저렴한 황산티타늄을 초기물질로서 사용하므로 루틸상 이산화티탄 분말의 생산성, 경제성 및 실용성을 향상시킬 수 있고, 나아가 루틸상 이산화티탄의 막대한 수입량을 대체할 수 있는 효과가 있다는 것을 알아내어 본 발명을 완성하였다.Therefore, the present inventors have studied to solve the problems of the above-described method for preparing ultra-fine rutile titanium dioxide powder, and added a strong alkali to the concentrated titanium sulfate stock solution to pH 12 or more to form a titanium hydroxide precipitate, filtered and washed with distilled water. After dissolving in 5 M hydrochloric acid solution to prepare a titanyl chloride aqueous solution, water was further added to dilute the concentration of Ti 4+ to 0.03 to 1.6 M, and heated to a temperature of 100 ° C. or lower for 2 to 5 hours to obtain a precipitate to obtain a precipitate, By washing and drying, ultrafine rutile titanium dioxide powder can be produced, and the method can quickly settle the reaction rate and improve the yield without any additional equipment such as high temperature and low temperature equipment, and also the process is simple and continuous operation. Not only is this possible, but since it uses titanium sulfate, which is cheaper than titanium tetrachloride, as an initial material, It is possible to improve the productivity of the titanium powder, the economics and practicability, taking out that there is an effect that it is possible to replace the vast import of the addition of rutile titanium oxide and completed the present invention.
본 발명의 목적은 황산티타늄을 이용하여 특별한 추가장치 없이도 간단하고 빠른 공정으로 초미립 루틸상 이산화티탄 분말을 제조하는 방법을 제공하는 것이다.It is an object of the present invention to provide a method for producing ultrafine rutile titanium dioxide powder in a simple and fast process using titanium sulfate without a special additional device.
상기 목적을 달성하기 위하여 본 발명에서는,In the present invention to achieve the above object,
(1) 농축 황산티타늄 (TiOSO4또는 Ti(SO4)2) 원액에 강알칼리를 첨가하여 수산화티탄 (TiO(OH)2) 침전물을 형성시키는 단계 (제 1 단계);(1) adding strong alkali to a concentrated titanium sulfate (TiOSO 4 or Ti (SO 4 ) 2 ) stock solution to form a titanium hydroxide (TiO (OH) 2 ) precipitate (first step);
(2) 상기 침전물을 증류수로 여과 및 세척하는 단계 (제 2 단계);(2) filtering and washing the precipitate with distilled water (second step);
(3) 상기 세척한 침전물을 염산 (HCl) 수용액에 녹여 티타닐클로라이드 (TiOCl2) 수용액을 제조하는 단계 (제 3 단계);(3) dissolving the washed precipitate in an aqueous hydrochloric acid (HCl) solution to prepare an aqueous solution of titanyl chloride (TiOCl 2 ) (third step);
(4) 상기 티타닐클로라이드 수용액에 물을 더 첨가해 티타닐클로라이드 수용액을 희석하는 단계 (제 4 단계);(4) further adding water to the aqueous titanyl chloride solution to dilute the titanyl chloride solution (fourth step);
(5) 상기 희석된 티타닐클로라이드 수용액을 저온 균일 침전법에 의해 침전물을 제조하는 단계 (제 5 단계); 및(5) preparing a precipitate by the low temperature homogeneous precipitation method of the diluted titanyl chloride aqueous solution (step 5); And
(6) 상기 침전물을 여과, 세척 및 건조하는 단계 (제 6 단계)로 이루어지는 초미립 루틸상 이산화티탄 분말의 제조방법을 제공한다.(6) It provides a method for producing ultrafine rutile titanium dioxide powder consisting of the step of filtering, washing and drying the precipitate (sixth step).
이 때, 제 1 단계의 강알칼리는 NH4OH, KOH, NaOH 또는 LiOH인 것이 바람직하고, 강알칼리는 용액의 pH가 12 이상이 되도록 첨가하는 것이 바람직하다.At this time, the strong alkali of the first step is preferably NH 4 OH, KOH, NaOH or LiOH, and the strong alkali is preferably added so that the pH of the solution is 12 or more.
또한 제 3 단계의 염산 수용액은 5 M 이상인 것을 사용하는 것이 바람직하다.In addition, it is preferable to use the hydrochloric acid aqueous solution of a 3rd step 5 M or more.
제 4 단계에서는 Ti4+농도가 0.03∼1.6 M이 되도록 티타닐클로라이드 용액을 희석시키는 것이 바람직하다.In the fourth step, it is preferable to dilute the titanyl chloride solution such that the concentration of Ti 4+ is 0.03 to 1.6 M.
또한 제 5 단계의 저온 균일 침전법은 100 ℃ 이하의 온도에서 2∼5시간 동안 실시하는 것이 바람직하다.In addition, the low temperature homogeneous precipitation method of the fifth step is preferably carried out for 2 to 5 hours at a temperature of 100 ℃ or less.
제 6 단계의 여과 및 세척 단계는 0.1 M 이상의 알칼리 할라이드 수용액으로 실시하는 것이 바람직하다.The filtration and washing step of the sixth step is preferably performed with an aqueous solution of alkali halide of 0.1 M or more.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
티타늄 원광을 황산에 녹여 추출한 농축 황산티타늄 수용액에, 전체 용액의 pH가 12 이상이 되도록 NH4OH, KOH, NaOH, LiOH와 같은 강알칼리 수용액을 다량 첨가시킨다. 다량의 강알칼리 수용액을 첨가하면 급격한 중화반응이 일어나 안정한수산화티탄 (Ti(OH)4) 화합물보다 불안정한 수산화티탄 (TiO(OH)2) 침전물들이 형성된다. 이러한 불안정한 수산화티탄 (TiO(OH)2) 침전물들이 안정한 수산화티탄 (Ti(OH)4) 화합물로 변하기 전에 신속히 증류수로 침전물을 여과 및 세척한다.To the concentrated titanium sulfate aqueous solution obtained by dissolving titanium ore in sulfuric acid, a large amount of strong alkali aqueous solution such as NH 4 OH, KOH, NaOH, LiOH is added so that the pH of the entire solution is 12 or more. When a large amount of strong alkaline aqueous solution is added, a rapid neutralization reaction results in the formation of unstable titanium hydroxide (TiO (OH) 2 ) precipitates than the stable titanium hydroxide (Ti (OH) 4 ) compound. The precipitate is quickly filtered and washed with distilled water before these labile titanium hydroxide (TiO (OH) 2 ) precipitates are converted to stable titanium hydroxide (Ti (OH) 4 ) compounds.
강알칼리로 NH4OH을 사용한 경우, 중화반응으로 얻어진 수산화티탄 침전물에는 황산 이온 (SO4 2+)과 암모늄 이온 (NH4 +)이 존재하는데, 침전물의 크기를 조절하여 침전반응 시 여과 공정의 효율성과 침전물의 수율을 증가시키기 위해 상기 이온을 일부 남겨둘 수도 있으며, 그 양은 전체 침전물의 약 2.5% 이하가 적당하다. 그러나 철은 불순물로 작용하여 분말의 질을 크게 떨어뜨리고 흰색 분말을 누렇게 변하게 하므로 완전히 제거되어야 한다. 따라서 상기 강알칼리와 황산티타늄 용액의 가수 분해 침전 반응으로 얻어진 수산화티탄 (TiO(OH)2) 침전물은 황산과 철 성분이 제거되도록 2 시간 이내에 빠르게 깨끗한 증류수로 세척하여야 한다.When NH 4 OH is used as a strong alkali, the titanium hydroxide precipitate obtained by the neutralization reaction contains sulfate ions (SO 4 2+ ) and ammonium ions (NH 4 + ), and the efficiency of the filtration process during the precipitation reaction by controlling the size of the precipitate Some of the ions may be left to increase the yield of the precipitate and the amount is suitably about 2.5% or less of the total precipitate. However, iron acts as an impurity, greatly reducing the quality of the powder and causing the white powder to turn yellow, which must be completely removed. Therefore, the titanium hydroxide (TiO (OH) 2 ) precipitate obtained by the hydrolytic precipitation reaction of the strong alkali and titanium sulfate solution should be washed quickly with clean distilled water within 2 hours to remove sulfuric acid and iron components.
다음으로 상기 세척한 수산화티탄 침전물은 염산 (HCl)에 녹여 안정한 티타닐클로라이드 (TiOCl2) 용액이 형성되도록 한다. 한편 수산화티탄 침전물을 세척할 때 공기 중에 노출된 시간이 너무 길었을 경우, 염산의 농도가 5 M 이하인 경우, 및 질산 등의 다른 강산을 사용한 경우에는, 상기 수산화티탄 침전물이 녹지 않으므로 침전물을 신속하게 세척한 후 5 M 이상인 강산성의 염산을 사용해서 녹여야 한다.Next, the washed titanium hydroxide precipitate is dissolved in hydrochloric acid (HCl) to form a stable solution of titanyl chloride (TiOCl 2 ). On the other hand, if the time of exposure to air is too long when washing the titanium hydroxide precipitate, when the concentration of hydrochloric acid is 5 M or less, and when other strong acids such as nitric acid are used, the titanium hydroxide precipitate does not dissolve, so that the precipitate can be quickly removed. After washing, dissolve with strong acid hydrochloric acid at least 5 M.
이렇게 제조된 티타닐클로라이드 용액에 물을 가하여 Ti4+이온의 농도가 0.03∼1.6 M이 되도록 하고 100 ℃ 이하의 온도로 2∼5시간 가열하면 자발적인 침전 반응이 일어난다. 생성된 침전물은 0.1M 이상의 NaCl, KCl 등의 알칼리 할라이드 수용액으로 세척하여 남아있는 염소 이온 (Cl-)을 제거하고, 다시 증류수로 세척하여 남아 있는 알칼리 할라이드를 제거하고, 마지막으로 분말의 응집 현상을 억제하기 위하여 알콜로 세척한 후 건조 공정을 거쳐 초미립 루틸상 이산화티탄 분말을 얻는다.Water was added to the prepared titanyl chloride solution so that the concentration of Ti 4+ ions was 0.03 to 1.6 M, and heating at a temperature of 100 ° C. or lower for 2 to 5 hours resulted in spontaneous precipitation. The resulting precipitate is washed with an aqueous alkali halide solution such as NaCl or KCl of 0.1 M or more to remove the remaining chlorine ions (Cl − ), and then washed with distilled water to remove the remaining alkali halide, and finally to agglomerate the powder. In order to suppress, it is washed with alcohol and then subjected to a drying process to obtain ultrafine rutile titanium dioxide powder.
이하 본 발명을 실시예에 의하여 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
단, 하기 실시예들은 본 발명을 예시하는 것으로 본 발명의 내용이 실시예에의해 한정되는 것은 아니다.However, the following examples are illustrative of the present invention, and the content of the present invention is not limited by the examples.
<실시예 1> 초미립 루틸상 이산화티탄 분말의 제조 (1)Example 1 Preparation of Ultrafine Rutile Titanium Dioxide Powder (1)
먼저, 다음과 같은 방법에 의해 티타닐클로라이드 (TiOCl2) 수용액을 제조하였다.First, titanyl chloride (TiOCl 2 ) aqueous solution was prepared by the following method.
티타늄 원광을 황산에 녹여 추출한 농축 황산티타늄 수용액에 pH가 12 이상이 되도록 NH4OH를 첨가하여 수산화티탄 (TiO(OH)2) 침전물을 형성시켰다. 이 수산화티탄 침전물은 즉시 증류수로 여과 및 세척하여 남아있는 황산 이온을 제거한 후, 신속하게 10 M 염산 (HCl) 수용액에 녹여 안정한 티타닐클로라이드 (TiOCl2) 수용액을 제조하였다.Titanium hydroxide (TiO (OH) 2 ) precipitate was formed by adding NH 4 OH to a concentrated titanium sulfate solution extracted by dissolving titanium ore in sulfuric acid to have a pH of 12 or more. The titanium hydroxide precipitate was immediately filtered and washed with distilled water to remove residual sulfate ions, and then quickly dissolved in 10 M hydrochloric acid (HCl) aqueous solution to prepare a stable aqueous solution of titanyl chloride (TiOCl 2 ).
상기와 같이 제조된 티타닐클로라이드 수용액에 물을 첨가하여 Ti4+의 농도가 0.86 M이 되도록 한 후, 55℃의 침전반응 온도에서 3시간 동안 그대로 유지하여 초미립 루틸상 이산화티탄 (TiO2) 분말의 침전물을 제조하였다.Water was added to the aqueous titanyl chloride solution prepared as described above to make the concentration of Ti 4+ 0.86 M, and then maintained at 55 ° C. for 3 hours at a precipitation temperature of ultrafine rutile titanium dioxide (TiO 2 ). A precipitate of powder was prepared.
상기 반응이 끝난 후, 침전물 내의 염소 이온 (Cl-)을 제거하기 위하여 막 (Membrane) 여과지를 이용하여 0.1M KCl 수용액으로 침전물을 여러 번 세척하였다. 그리고 다시 KCl을 제거하기 위하여 침전물을 증류수로 세척하고 분말이 응집되는 것을 억제하기 위하여 알콜로 세척한 후, 150 ℃에서 10시간 동안 건조하여 최종적으로 하얀 초미립 루틸상 이산화티탄 분말을 얻었다. 이 때 제조된 초미립 루틸상이산화티탄 분말의 일차입자의 크기는 약 20 nm 이내이고 이차입자의 크기는 0.5∼1.0 ㎛였으며 비표면적은 약 115 ㎡/g 이었다.After the reaction was completed, the precipitate was washed several times with an aqueous 0.1 M KCl solution using membrane filter paper to remove chlorine ions (Cl − ) in the precipitate. Then, the precipitate was washed with distilled water to remove KCl again, and washed with alcohol to prevent agglomeration of the powder, followed by drying at 150 ° C. for 10 hours to obtain a white ultrafine rutile titanium dioxide powder. At this time, the size of the primary particles of the ultrafine rutile titanium dioxide powder prepared was within about 20 nm, the size of the secondary particles was 0.5 ~ 1.0 ㎛ and the specific surface area was about 115 m 2 / g.
<실시예 2> 초미립 루틸상 이산화티탄 분말의 제조 (2)Example 2 Preparation of Ultrafine Rutile Titanium Dioxide Powder (2)
실시예 1에서와 똑같은 방법으로 제조된 티타닐클로라이드 수용액에 물을 첨가하여 Ti4+의 농도가 0.43 M가 되도록 한 후, 90 ℃의 침전반응 온도에서 2시간 동안 그대로 유지하여 초미립 루틸상 이산화티탄 분말의 침전물을 제조하였다.Water was added to the aqueous solution of titanyl chloride prepared in the same manner as in Example 1 to make the concentration of Ti 4+ 0.43 M, and then maintained at 90 ° C. for 2 hours to maintain ultrafine rutile phase dioxide. A precipitate of titanium powder was prepared.
상기 반응이 끝난 후, 침전물 내의 염소 이온을 제거하기 위하여 막 여과지를 이용하여 0.1M KCl 수용액으로 침전물을 여러 번 세척하였다. 그리고 다시 KCl을 제거하기 위하여 침전물을 증류수로 세척하고 분말이 응집되는 것을 억제하기 위하여 알콜로 세척한 후, 150 ℃에서 10시간 동안 건조하여 최종적으로 하얀 초미립 루틸상 이산화티탄 분말을 얻었다. 이 때 제조된 초미립 루틸상 이산화티탄 분말의 일차입자의 크기는 약 16 nm 이내이고 이차입자의 크기는 0.5∼1.0 ㎛였으며 비표면적은 약 123 ㎡/g 이었다.After the reaction was completed, the precipitate was washed several times with an aqueous 0.1 M KCl solution using membrane filter paper to remove chlorine ions in the precipitate. Then, the precipitate was washed with distilled water to remove KCl again, and washed with alcohol to prevent agglomeration of the powder, followed by drying at 150 ° C. for 10 hours to obtain a white ultrafine rutile titanium dioxide powder. At this time, the size of the primary particles of the ultrafine rutile titanium dioxide powder prepared was within about 16 nm, the size of the secondary particles was 0.5 ~ 1.0 ㎛ and the specific surface area was about 123 m 2 / g.
<실시예 3> 초미립 루틸상 이산화티탄 분말의 제조 (3)Example 3 Preparation of Ultrafine Rutile Titanium Dioxide Powder (3)
실시예 1에서와 똑같은 방법으로 제조된 티타닐클로라이드 수용액에 물을 첨가하여 Ti4+의 농도가 0.50 M가 되도록 한 후, 50 ℃의 침전반응 온도에서 3시간 동안 그대로 유지하여 초미립 루틸상 이산화티탄 분말의 침전물을 제조하였다.Water was added to the aqueous solution of titanyl chloride prepared in the same manner as in Example 1 to make the concentration of Ti 4+ 0.50 M, and then maintained at 50 ° C. for 3 hours to maintain ultrafine rutile phase dioxide. A precipitate of titanium powder was prepared.
상기 반응이 끝난 후, 침전물 내의 염소 이온을 제거하기 위하여 막 여과지를 이용하여 0.1 M KCl 수용액으로 침전물을 여러 번 세척하였다. 그리고 다시 KCl을 제거하기 위하여 침전물을 증류수로 세척하고 분말이 응집되는 것을 억제하기 위하여 알콜로 세척한 후, 150℃에서 10시간 동안 건조하여 최종적으로 하얀 초미립 루틸상 이산화티탄 분말을 얻었다. 이 때 제조된 초미립 루틸상 이산화티탄 분말의 일차입자의 크기는 약 20 nm 이내이고 이차입자의 크기는 0.5∼1.0 ㎛였으며 비표면적은 약 118 ㎡/g 이었다.After the reaction was completed, the precipitate was washed several times with 0.1 M aqueous KCl solution using membrane filter paper to remove chlorine ions in the precipitate. Then, the precipitate was washed with distilled water to remove KCl again, and washed with alcohol to prevent agglomeration of the powder, followed by drying at 150 ° C. for 10 hours to finally obtain white ultrafine rutile titanium dioxide powder. At this time, the size of the primary particles of the ultrafine rutile titanium dioxide powder prepared was less than about 20 nm, the size of the secondary particles was 0.5 ~ 1.0 ㎛ and the specific surface area was about 118 m 2 / g.
이상 살펴본 바와 같이, 본 발명의 제조방법에 의하여 초미립 루틸상 이산화티탄 분말을 제조할 수 있고, 특히 본 발명은 고온 및 저온 장치 등의 특별한 추가장치 없이도 침전 반응 속도가 빠르고 수율이 향상되었으며 또한 공정이 간단하고 연속작업이 가능한 초미립 루틸상 이산화티탄 분말의 제조방법을 제공하며, 더욱이 사염화티탄보다 가격이 저렴한 황산티타늄을 초기물질로서 사용하므로 루틸상 이산화티탄 분말의 생산성, 경제성 및 실용성을 향상시킬 수 있고, 나아가 루틸상 이산화티탄의 막대한 수입량을 대체할 수 있다.As described above, the ultrafine rutile titanium dioxide powder can be produced by the production method of the present invention, and in particular, the present invention has a fast precipitation reaction speed and improved yield even without special additional devices such as high temperature and low temperature equipment. It provides a simple and continuous process for producing ultra fine rutile titanium dioxide powder, and further improves the productivity, economy and practicality of rutile titanium dioxide powder by using titanium sulfate which is cheaper than titanium tetrachloride as an initial material. It can also replace the enormous import of rutile titanium dioxide.
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| US4073877A (en) * | 1974-07-26 | 1978-02-14 | Kronos Titan G.M.B.H. | Manufacture of titanium dioxide pigment seed from a titanium sulfate solution |
| JPS59223231A (en) * | 1983-05-31 | 1984-12-15 | Teikoku Kako Kk | Manufacture of fine-grained rutile type titanium oxide |
| JPH02196028A (en) * | 1989-01-21 | 1990-08-02 | Agency Of Ind Science & Technol | Production of titanium oxide fine powder |
| US5527469A (en) * | 1995-06-12 | 1996-06-18 | Lawhorne; Earl R. | Method for the preparation of desulfurized titanium oxide hydrolysate of high purity |
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