钛白粉制备技术的研究及发展?
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摘要
综述了钛白粉制备的不同工艺,总结了硫酸法和氯化法在钛白粉制备中的优缺点,分析了传统硫酸法的水解过程以及氯化法中的气相氧化、内表面结疤等问题,展望了钛工业的发展趋势。结果表明,硫酸法制备钛白粉的技术日趋成熟,在实验室条件下,硫酸法中水解过程遇到的问题得以解决,但是在工业化生产时,无法做到兼顾优化水解和提高TiO2颜料的性能,难以满足工业生产需要。氯化法被认为是当今钛白粉制取技术的发展趋势,与硫酸法相比,氯化法有巨大的环保优势,而且易于实现连续化和自动化,经济效益较好。但是氯化法对生产技术和装备材料的要求高,关键设备结构复杂,在国内的推广受到限制。国内钛白粉产业应提升现有的硫酸法工艺水平,同时对硫酸法工艺向氯化法工艺转变做出调整,还需研发新的污染物处置技术和治理方法,实现钛白粉产业的可持续发展。
The preparation technology of titanium dioxide was summarized in this paper. The advantages and disadvantages of sulfuric acid method and chlorination process in titanium dioxide preparation were studied. The hydrolysis process in traditional sulfuric acid method and the gas phase oxidation and internal surface crustification in chlorination method were analyzed. The future development of the titanium industry was expected. In the results, the sulfuric acid method for titanium dioxide preparation is increasingly improved. In the laboratory conditions, the problem of hydrolysis process in sulfate acid method can be solved, but the combination between hydrolysis optimization and the improvement of TiO_2 pigment performance can't be achieved in industrial production, which is difficult to meet the needs of industrial production. Compared with the sulfuric acid method, the chlorination process is considered as the development trend of titanium dioxide preparation, which shows the greater environmental advantages and better economic efficiency, and is easy to realize the continuous and automation production. The chlorination process has the high requirements for preparation technology and equipment materials, and the key equipment structure is complex, limiting the domestic promotion. Domestic titanium dioxide industry should improve the technological level of sulfuric acid process, make adjustments from sulfuric acid method to chlorination process, and develop new pollutant disposal technology and treatment methods to achieve the ustainable development of titanium dioxide industry.
The preparation technology of titanium dioxide was summarized in this paper. The advantages and disadvantages of sulfuric acid method and chlorination process in titanium dioxide preparation were studied. The hydrolysis process in traditional sulfuric acid method and the gas phase oxidation and internal surface crustification in chlorination method were analyzed. The future development of the titanium industry was expected. In the results, the sulfuric acid method for titanium dioxide preparation is increasingly improved. In the laboratory conditions, the problem of hydrolysis process in sulfate acid method can be solved, but the combination between hydrolysis optimization and the improvement of TiO_2 pigment performance can't be achieved in industrial production, which is difficult to meet the needs of industrial production. Compared with the sulfuric acid method, the chlorination process is considered as the development trend of titanium dioxide preparation, which shows the greater environmental advantages and better economic efficiency, and is easy to realize the continuous and automation production. The chlorination process has the high requirements for preparation technology and equipment materials, and the key equipment structure is complex, limiting the domestic promotion. Domestic titanium dioxide industry should improve the technological level of sulfuric acid process, make adjustments from sulfuric acid method to chlorination process, and develop new pollutant disposal technology and treatment methods to achieve the ustainable development of titanium dioxide industry.
引文
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[4]Mo W,Deng G Z,Luo F C.Titanium Metallurgy.2nd Ed.Beijing:Metallurgical Industry Press,2007(莫畏,邓国珠,罗方承.钛冶金.2版.北京:冶金工业出版社,2007)
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[10]Feng Y,Gu L T.Shallow talk of chlorination titanium dioxide and post treatment.Anhui Chem Ind,2011,37(1):31(封燕,谷林涛.浅谈氯化法钛白及其后处理工艺.安徽化工,2011,37(1):31)
[11]Liu Z Z.Present status of supply and demand of domestic titanium pigment and development prospect.China Chlor-Alkali,2007(3):1(刘自诊.我国钛白粉产需现状与发展前景.中国氯碱,2007(3):1)
[12]Zhang F P.Study on Preparation of Titanium Dioxide by Leaching Acid-Soluble Titanium Residue with Waste Hydrochloric Acid[Dissertation].Guiyang:Guizhou University,2015(张风平.废盐酸浸出酸溶性钛渣制备钛白粉工艺研究[学位论文].贵阳:贵州大学,2015)
[13]Grzmil B U,Grela D,Kic B.Hydrolysis of titanium sulphate compounds.Chem Pap,2008,62(1):18
[14]Tian C X.Effects of hydrolysis parameters on TiO2 white pigment from low concentration industrial TiOSO4solution via sulfate process.Adv Mater Res,2013,602-604:1243
[15]Grzmi B,Grela D,Kic B,et al.The influence of admixtures on the course of hydrolysis of titanyl sulfate.Pol J Chem Technol,2008,10(3):4
[16]Denisova T A,Maksimova L G,Polyakov E V,et al.Metatitanic acid synthesis and properties.Russ J Inorg Chem,2006,51(5):691
[17]Zhang T H,Piao L Y,Zhao S L,et al.Application of TiO2with different structures in solara cells.Chin Phys B,2012,21(11):518
[18]Li D C,Zhou D L,Liu H,et al.Technical advances of titanium white production in China.Sichuan Nonferrous Met,2005(2):4(李大成,周大利,刘恒,等.我国钛白生产的技术进步.四川有色金属,2005(2):4)
[19]Przepiera A,Jabloński M.Thermal transformations of titanium slag of high titania content.J Therm Anal Calorim,2003,74(2):631
[20]Taylor M L,Morris G E,Smart R S.Influence of aluminum doping on titania pigment structural and dispersion properties.J Colloid Interface Sci,2003,262(1):81
[21]Gesenhues U.Calcination of metatitanic acid to titanium dioxide white pigments.Chem Eng Technol,2001,24(7):685
[22]Zhang Z T.Research on Surface Modification of Titanium Dioxide Coating[Dissertation].Kunming:Yunnan University,2013(张智涛.钛白粉表面包膜改性技术研究[学位论文].昆明:云南大学,2013)
[23]Zhou E,Chen S H,Yuan Z F,et al.Structure analysis and modeling on the oxidation reactor in the titanium white synthesis with chloride process.Titanium Ind Prog,2004,21(6):35(周峨,郑少华,袁章福,等.氯化法钛白氧化反应器结构分析与模拟.钛工业进展,2004,21(6):35)
[24]Zhao W A,Liu Z L,Bai C P,et al.Simulation experiment on gas current mixing in a titanium white reactor.Chem Metall,1987,8(1):66(赵维安,刘洲林,白春沛,等.钛白反应器气流混合模化实验.化工冶金,1987,8(1):66)
[25]Zhang S M.Cold analog experiment for chloride process TiO2 production.Paint Coat Ind,2000,30(5):20(张曙明.氯化法钛白冷模实验研究.涂料工业,2000,30(5):20)
[26]LüZ Z,Li C Z,Cong D Z,et al.Study on jet mixing characters in the oxidation reactor for titanium dioxide powder production by chloride process.Chem Eng,2001,29(3):25(吕志敏,李春忠,丛德滋,等.氯化法制备钛白氧化反应器内射流混合特性研究.化学工程,2001,29(3):25)
[27]Cheng Y,Liu Z,Luo P C,et al.Gas cross-flow mixing in TiO2 oxidation reactor of chloride process.CIESC J,2006,57(12):2840(程易,刘喆,骆培成,等.氯化法钛白氧化反应器气体错流混合.化工学报,2006,57(12):2840)
[28]Liang X B,Wu P,LüL,et al.Effect of preoxidation on hydrochloric acid leaching of Panzhihua ilmenite.Chin JProcess Eng,2010,10(5):939(梁相博,吴潘,吕莉,等.氧化方式对盐酸浸出攀枝花钛铁矿的影响.过程工程学报,2010,10(5):939)
[29]Zhao W A.Experimental study on optimum condition of initial gases mixing in a tubular reactor.Chem Eng(China),1991,19(4):31(赵维安.管式反应器气相初始混合最佳条件的实验研究.化学工程,1991,19(4):31)
[30]Xu H W,Zhang S.Numerical simulation of flow field in a non-deposite Ti Cl4-oxidizing reactor with gas film.Eng Chem Metall,1988,9(3):1(许厚文,张森.气膜除疤氧化炉内流场的数值模拟.化工冶金,1988,9(3):1)
[31]Jiang H B.Engineering Research on Preparation of Rutile Titanium Dioxide by Gas Phase Oxidation of Titanium Tetrachloride[Dissertation].Shanghai:East China University of Science and Technology,2000(姜海波.四氯化钛气相氧化制备金红石型钛白粉工程研究[学位论文].上海:华东理工大学,2000)
[32]Zhu Y H,Chen A P,Li C Z,et al.Mechanism of powder deposition on cool wall during the process of chemical synthesis of Ti O2 in vapor phase.J East China Univ Sci Technol,1999,25(4):382(朱以华,陈爱平,李春忠,等.化学气相合成TiO2过程中的冷壁凝结机理.华东理工大学学报,1999,25(4):382)
[33]Verhulst D,Sabacky B,Spitler T,et al.The Altair TiO2pigment process and its extension into the field of nanomaterials.CIM Bull,2002,1065(95):89
[34]Zhang X H,Xiao P A,Liu S H,et al.Study of sintering processes for powder injection molding of TiH2.Powder Metall Technol,2012,30(4):293(张小虎,肖平安,刘素红,等.TiH2粉末注射成形坯烧结工艺研究.粉末冶金技术,2012,30(4):293)
[35]Zou J X,Yang C,Peng F C.Technical status of composite titanium dioxide and its trend.Light Met,2008(8):47(邹建新,杨成,彭富昌.复合钛白的制备技术现状与趋势.轻金属,2008(8):47)
[2]Li D C,Liu H,Zhou D L.Titanium Smelting Process.Beijing:Chemical Industry Press,2009(李大成,刘恒,周大利.钛冶炼工艺.北京:化学工业出版社,2009)
[3]Yang S L,Sheng J F.Titanium Slag Melting and Pig Iron Technology in Ilmenite.Beijing:Metallurgical Industry Press,2006(杨绍利,盛继孚.钛铁矿熔炼钛渣与生铁技术.北京:冶金工业出版社,2006)
[4]Mo W,Deng G Z,Luo F C.Titanium Metallurgy.2nd Ed.Beijing:Metallurgical Industry Press,2007(莫畏,邓国珠,罗方承.钛冶金.2版.北京:冶金工业出版社,2007)
[5]Hu K J,Xi G,Yao J,et al.Status quo of domestic titanium slag production technology.World Nonferrous Met,2007(5):29(胡克俊,锡淦,姚娟,等.我国钛渣生产技术研究现状.世界有色金属,2007(5):29)
[6]Chen G,Chen J,Srinivasakannan C,et al.Application of response surface methodology for optimization of the synthesis of synthetic rutile from titania slag.Appl Surf Sci,2012,258(7):3068
[7]Zou J X,Yang C,Peng F C.Domestic state and trend of production for titania powder.Rare Met Lett,2007,26(4):7(邹建新,杨成,彭富昌.我国钛白生产技术现状与发展趋势.稀有金属快报,2007,26(4):7)
[8]Deng K,Tang Y,Sun Y G,et al.The production processes of titaniumdioxide produced by chlorination process and its technical and economic analysis.China Chlor-Alkali,2012(1):23(邓科,唐勇,孙永贵,等.氯化法钛白粉的生产工艺与技术经济分析.中国氯碱,2012(1):23)
[9]Tian F Z.A new process for the preparation of nanometer titanium dioxide by hydrochloric acid method using high titanium slag as raw material.Adv Mater Ind,2007(2):63(田福祯.以高钛渣为原料的盐酸法-纳米二氧化钛制备新工艺.新材料产业,2007(2):63)
[10]Feng Y,Gu L T.Shallow talk of chlorination titanium dioxide and post treatment.Anhui Chem Ind,2011,37(1):31(封燕,谷林涛.浅谈氯化法钛白及其后处理工艺.安徽化工,2011,37(1):31)
[11]Liu Z Z.Present status of supply and demand of domestic titanium pigment and development prospect.China Chlor-Alkali,2007(3):1(刘自诊.我国钛白粉产需现状与发展前景.中国氯碱,2007(3):1)
[12]Zhang F P.Study on Preparation of Titanium Dioxide by Leaching Acid-Soluble Titanium Residue with Waste Hydrochloric Acid[Dissertation].Guiyang:Guizhou University,2015(张风平.废盐酸浸出酸溶性钛渣制备钛白粉工艺研究[学位论文].贵阳:贵州大学,2015)
[13]Grzmil B U,Grela D,Kic B.Hydrolysis of titanium sulphate compounds.Chem Pap,2008,62(1):18
[14]Tian C X.Effects of hydrolysis parameters on TiO2 white pigment from low concentration industrial TiOSO4solution via sulfate process.Adv Mater Res,2013,602-604:1243
[15]Grzmi B,Grela D,Kic B,et al.The influence of admixtures on the course of hydrolysis of titanyl sulfate.Pol J Chem Technol,2008,10(3):4
[16]Denisova T A,Maksimova L G,Polyakov E V,et al.Metatitanic acid synthesis and properties.Russ J Inorg Chem,2006,51(5):691
[17]Zhang T H,Piao L Y,Zhao S L,et al.Application of TiO2with different structures in solara cells.Chin Phys B,2012,21(11):518
[18]Li D C,Zhou D L,Liu H,et al.Technical advances of titanium white production in China.Sichuan Nonferrous Met,2005(2):4(李大成,周大利,刘恒,等.我国钛白生产的技术进步.四川有色金属,2005(2):4)
[19]Przepiera A,Jabloński M.Thermal transformations of titanium slag of high titania content.J Therm Anal Calorim,2003,74(2):631
[20]Taylor M L,Morris G E,Smart R S.Influence of aluminum doping on titania pigment structural and dispersion properties.J Colloid Interface Sci,2003,262(1):81
[21]Gesenhues U.Calcination of metatitanic acid to titanium dioxide white pigments.Chem Eng Technol,2001,24(7):685
[22]Zhang Z T.Research on Surface Modification of Titanium Dioxide Coating[Dissertation].Kunming:Yunnan University,2013(张智涛.钛白粉表面包膜改性技术研究[学位论文].昆明:云南大学,2013)
[23]Zhou E,Chen S H,Yuan Z F,et al.Structure analysis and modeling on the oxidation reactor in the titanium white synthesis with chloride process.Titanium Ind Prog,2004,21(6):35(周峨,郑少华,袁章福,等.氯化法钛白氧化反应器结构分析与模拟.钛工业进展,2004,21(6):35)
[24]Zhao W A,Liu Z L,Bai C P,et al.Simulation experiment on gas current mixing in a titanium white reactor.Chem Metall,1987,8(1):66(赵维安,刘洲林,白春沛,等.钛白反应器气流混合模化实验.化工冶金,1987,8(1):66)
[25]Zhang S M.Cold analog experiment for chloride process TiO2 production.Paint Coat Ind,2000,30(5):20(张曙明.氯化法钛白冷模实验研究.涂料工业,2000,30(5):20)
[26]LüZ Z,Li C Z,Cong D Z,et al.Study on jet mixing characters in the oxidation reactor for titanium dioxide powder production by chloride process.Chem Eng,2001,29(3):25(吕志敏,李春忠,丛德滋,等.氯化法制备钛白氧化反应器内射流混合特性研究.化学工程,2001,29(3):25)
[27]Cheng Y,Liu Z,Luo P C,et al.Gas cross-flow mixing in TiO2 oxidation reactor of chloride process.CIESC J,2006,57(12):2840(程易,刘喆,骆培成,等.氯化法钛白氧化反应器气体错流混合.化工学报,2006,57(12):2840)
[28]Liang X B,Wu P,LüL,et al.Effect of preoxidation on hydrochloric acid leaching of Panzhihua ilmenite.Chin JProcess Eng,2010,10(5):939(梁相博,吴潘,吕莉,等.氧化方式对盐酸浸出攀枝花钛铁矿的影响.过程工程学报,2010,10(5):939)
[29]Zhao W A.Experimental study on optimum condition of initial gases mixing in a tubular reactor.Chem Eng(China),1991,19(4):31(赵维安.管式反应器气相初始混合最佳条件的实验研究.化学工程,1991,19(4):31)
[30]Xu H W,Zhang S.Numerical simulation of flow field in a non-deposite Ti Cl4-oxidizing reactor with gas film.Eng Chem Metall,1988,9(3):1(许厚文,张森.气膜除疤氧化炉内流场的数值模拟.化工冶金,1988,9(3):1)
[31]Jiang H B.Engineering Research on Preparation of Rutile Titanium Dioxide by Gas Phase Oxidation of Titanium Tetrachloride[Dissertation].Shanghai:East China University of Science and Technology,2000(姜海波.四氯化钛气相氧化制备金红石型钛白粉工程研究[学位论文].上海:华东理工大学,2000)
[32]Zhu Y H,Chen A P,Li C Z,et al.Mechanism of powder deposition on cool wall during the process of chemical synthesis of Ti O2 in vapor phase.J East China Univ Sci Technol,1999,25(4):382(朱以华,陈爱平,李春忠,等.化学气相合成TiO2过程中的冷壁凝结机理.华东理工大学学报,1999,25(4):382)
[33]Verhulst D,Sabacky B,Spitler T,et al.The Altair TiO2pigment process and its extension into the field of nanomaterials.CIM Bull,2002,1065(95):89
[34]Zhang X H,Xiao P A,Liu S H,et al.Study of sintering processes for powder injection molding of TiH2.Powder Metall Technol,2012,30(4):293(张小虎,肖平安,刘素红,等.TiH2粉末注射成形坯烧结工艺研究.粉末冶金技术,2012,30(4):293)
[35]Zou J X,Yang C,Peng F C.Technical status of composite titanium dioxide and its trend.Light Met,2008(8):47(邹建新,杨成,彭富昌.复合钛白的制备技术现状与趋势.轻金属,2008(8):47)