流化床气相水解制备高纯二氧化钛

doi:10.11949/j.issn.0438-1157.20170515

化工学报 ›› 2017, Vol. 68 ›› Issue (10): 3978-3984.DOI: 10.11949/j.issn.0438-1157.20170515

• 材料化学工程与纳米技术 • 上一篇下一篇

流化床气相水解制备高纯二氧化钛

赵玉仲^1,2, 孙建军², 李军¹, 朱庆山¹

1 中国科学院过程工程研究所, 多相复杂系统国家重点实验室, 北京 100190;
2 北京化工大学化学工程学院, 北京 100029

收稿日期:2017-05-02 修回日期:2017-07-06 出版日期:2017-10-05 发布日期:2017-10-05
通讯作者: 李军,junli@ipe.ac.cn
基金资助:
国家自然科学基金项目（21325628，U1462128）；国家重点基础研究发展计划项目（2015CB251402）；国家重大科学仪器设备开发专项项目（2011YQ12003908）。

Synthesis of high purity TiO₂ powders by fluidized gas hydrolysis

ZHAO Yuzhong^1,2, SUN Jianjun², LI Jun¹, ZHU Qingshan¹

1 State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academic Sciences, Beijing 100190, China;
2 College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2017-05-02 Revised:2017-07-06 Online:2017-10-05 Published:2017-10-05
Supported by:
supported by the National Natural Science Foundation of China (21325628, U1462128), the National Basic Research Program of China (2015CB251402) and the National Special Project for Development of Major Scientific Equipment (2011YQ12003908).

摘要/Abstract

摘要：

针对TiCl₄气相水解制备TiO₂粉体存在Cl含量高的问题，开展了流化床TiCl₄气相水解制备高纯TiO₂。系统地研究了反应条件、煅烧后处理对TiO₂粉体的纯度、形貌、晶型、比表面积的影响。结果表明，TiO₂内部结构和晶型的转变有利于Cl的脱除；提高煅烧温度使TiO₂的内部结构由多孔疏松向致密结构转变，晶型结构由锐钛矿相向金红石相转变，从而有利于提高Cl的脱除率；与空气煅烧比较，水蒸气气氛下的脱氯效率明显提高，归因于水蒸气与TiO₂颗粒内残余的多羟基氯化物进一步反应；氢气气氛下可进一步提高Cl的脱除率，800℃煅烧2 h后Cl的脱除率达到95%，主要归因于氢气还原TiO₂使其晶型结构发生转变。

关键词: 流化床, 水解, 二氧化钛, 超细粉体, 团聚

Abstract:

Synthesis of high purity TiO₂ powder by fluidized gas hydrolysis method is investigated.To tackle the problem of high Cl content remained in the TiO₂ powder,the hydrolysis reaction conditions and subsequently calcination at air,steam and H₂ are mainly investigated for dechlorination.The results show that the structure and phase transition of TiO₂ are two key factors that affect the efficiency of dechlorination.With the increase of the calcination temperature,the internal structure of TiO₂ is changed from porous to dense structure,and the crystalline structure is transformed from anatase to rutile.The structure and phase transition of TiO₂ are beneficial to increasing the removal rate of Cl.Compared with the air calcination,the dechlorination efficiency in water vapor atmosphere is obviously improved,which is attributed to the further reaction of water vapor and the multi hydroxyl chloride in the TiO₂ particles.Compared with air and steam calcination,the removal rate of Cl can be further improved up to 95% under the atmosphere of hydrogen at 800℃ for 2h,which is mainly attributed to the reduction of TiO₂ structure by hydrogen reduction.

Key words: fluidized-bed, hydrolysis, TiO₂, ultrafine powders, agglomeration

中图分类号:

TQ031.5

赵玉仲, 孙建军, 李军, 朱庆山. 流化床气相水解制备高纯二氧化钛[J]. 化工学报, 2017, 68(10): 3978-3984.

ZHAO Yuzhong, SUN Jianjun, LI Jun, ZHU Qingshan. Synthesis of high purity TiO₂ powders by fluidized gas hydrolysis[J]. CIESC Journal, 2017, 68(10): 3978-3984.

参考文献 30

[1]	MA T, AKUYAMA M, ABE E, et al. High-efficiency dye-sensitized solar cell based on a nitrogen-doped nanostructured titania electrode[J]. Nano. lett., 2005, 12(5):2543-2547.
[2]	廖永进, 张亚平, 余岳溪, 等. MnOx/WO3/TiO2低温选择性催化还原NOx机理的原位红外研究[J]. 化工学报, 2016, 67(12):5031-5039. LIAO Y J, ZHANG Y P, YU Y X, et al. In situ FT-IR studies on low temperature NH3-SCR mechanism of NOx over MnOx/WO3/TiO2 catalyst[J]. CIESC Journal, 2016, 67(12):5031-5039.
[3]	刘芳, 樊丰涛, 吕玉翠, 等. 石墨烯/TiO2复合材料光催化降解有机污染物的研究进展[J]. 化工学报, 2016, 67(5):1635-1643. LIU F, FAN F T, LÜ Y C, et al. Research progress on photocatalytic degradation of organic pollutants by graphene/TiO2 composite materials[J]. CIESC Journal, 2016, 67(5):1635-1643.
[4]	LIANG B, LI C, ZHANG C G, et al. Leaching kinetics of panzhihua ilmenite in sulfuric acid[J]. Hydrometallurgy, 2005, 76(3/4):173-179.
[5]	罗志强, 杜剑桥. 电子用高纯二氧化钛制备方法研究[J]. 涂料工业, 2011, 41(8):31-38. LUO Z Q, DU J Q. Research on preparation of high-purity TiO2 for electronic industry[J]. Paint and Coatings Industry, 2011, 41(8):31-38.
[6]	方世杰, 徐明霞, 纳米TiO2光催化剂的制备方法[J]. 硅酸盐通报, 2002, 21(2):38-42. FANG S J, XU M X. Preparation of nanocrystalline TiO2 photocatalyst[J]. Bulletin of the Chinese Ceramic Society, 2002, 21(2):38-42.
[7]	HANAOR D A H, CHIRONI I, KARATCHEVTSEVA I, et al. Single and mixed phase TiO2 powders prepared by excess hydrolysis of titanium alkoxide[J]. Advances in Applied Ceramics, 2012, 111(3):149-158.
[8]	AKHTAR M K, XIONG Y, PRATSINIS S E. Vapor synthesis of titania powder by titanium tetrachloride oxidation[J]. American Institute of Chemical Engineers, 1991, 37(10):1561-1570.
[9]	XIA B, LI W B, ZHANG B, et al. Low temperature vapor phase preparation of TiO2 nanopowders[J]. J. Mat. Sci., 1999, 34(14):3505-3511.
[10]	YEOM S M, KIM K H, SHIN D W, et al. Preparation and characterization of fine TiO2 powders by vapor-phase hydrolysis of TiCl4[J]. Journal of the Korean Ceramic Society, 1992, 29(7):525-532.
[11]	JOHN A K, SAVITHRI S, SURENDER G D. Characterization of titania nanoparticles synthesized through low temperature aerosol process[J]. Aerosol and Air Quality Research, 2005, 5(1):1-13.
[12]	ZHU X L, ZHANG Q, WANG Y, et al. Review on the nanoparticle fluidization science and technology[J]. Chinese J. Chem. Eng., 2016, 24(1):9-22.
[13]	陆金东, 陈爱平, 马磊, 等. 流化床CVD法原位合成CNTs-Ni-TiO2及其光催化性能[J]. 化工学报, 2012, 63(4):1070-1075. LU J D, CHEN A P, MA L, et al. Synthesis of CNTs-Ni-TiO2 nanocomposites by in-situ fluidized bed CVD and its photocatalytic activity[J]. CIESC Journal, 2012, 63(4):1070-1075.
[14]	LI J, KONG J, ZHU Q S, et al. Efficient synthesis of iron nanoparticles by self-agglomeration in a fluidized bed[J]. AIChE Journal[J]. 2017, 63(2):459-468.
[15]	LI J, LIU X W, ZHOU L, et al. A two-stage reduction process for production of high purity ultrafine Ni particle in a micro-fluidized bed reactor[J]. Particuology, 2015, 19(2):27-34.
[16]	LI J, ZHOU L, ZHU Q S, et al. Decoupling reduction-sulfurization synthesis of inorganic fullerene-like WS2 nanoparticles in a particulately fluidized bed[J]. Chem. Eng. J., 2014, 249(1):54-62.
[17]	ZHANG Q, ZHAO M Q, HUANG J Q, et al. Mass production of aligned carbon nanotube arrays by fluidized bed catalytic chemical vapor deposition[J]. Carbon, 2010, 48(4):1196-1209.
[18]	WANG C J, WANG T F, LI P L, et al. Recycling of SiCl4 in the manufacture of granular polysilicon in a fluidized bed reactor[J]. Chem. Eng. J., 2013, 220(6):81-88.
[19]	PEAN D A, UPHADE B S, SMIMIOTIS P G. TiO2-supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH3:evaluation and characterization of first row transition metals[J]. J. Catal., 2004, 221(2):421-431.
[20]	姜贵民, 严继康, 杨钢, 等. TiO2晶型转变(A R)的影响因素[J]. 材料导报A, 2016, 30(10):95-100. JIANG G M, YAN J K, YANG G, et al. Influencing factors of crystal phase transformation (A R) of TiO2[J]. Materials Review A, 2016, 30(10):95-100.
[21]	唐爱东, 任艳萍. 二氧化钛催化剂晶型调控技术的研究进展[J]. 中国粉体技术, 2010, 16(3):69-73. TANG A D, REN Y P. Recent advances in phase transition of titania cayalyst[J]. China Powder Science and Technology, 2010, 16(3):69-73.
[22]	MACKENZIE K J D, MELLING P J. The calcination of titania. Ⅱ. Influence of atmosphere on crystal growth in anatase powders[J]. Trans. J. Br. Ceram. Soc., 1974, 73(6):179-183.
[23]	刘秀红, 赵尹, 姜海波, 等. 扩散火焰法制备TiO2纳米晶及其光催化活性[J]. 华东理工大学学报(自然科学版), 2007, 33(2):200-204. LIU X H, ZHAO Y, JIANG H B, et al. Preparation of TiO2 nanocrystallite by co-flow diffusion flames and their photocatalytic activity[J]. Journal of East China University of Science and Technology (Natural Science Edition), 2007, 33(2):200-204.
[24]	吕林英, 蓝兴英, 吴迎亚, 等. FCC提升管反应器中颗粒聚团对裂化反应的影响[J]. 化工学报, 2015, 66(8):2920-2928. LÜ L Y, LAN X Y, WU Y Y, et al. Effect of particles cluster on behavior of catalytic cracking reaction in FCC riser[J]. CIESC Journal, 2015, 66(8):2920-2928.
[25]	JOHN A K, SAVITHRI S, KUNDUCHI P, et al. Density functional theory study of gas phase hydrolysis of titanium tetrachloride[J]. Bull. Chem. Soc. Jpn., 2010, 83(9):1030-1036.
[26]	LEE K R, KIM S J, SONG J S, et al. Effect of vapor pressure of H2O on the formation of nano-crystalline TiO2 ultrafine powders[J]. MRS Online Proceedings Library, 1999, 58(1):33-39.
[27]	陈瑞澄. 四氯化钛水解过程的研究[J]. 湿法冶金, 1999, 71(3):1-7. CHEN R C. Study on the hydrolysis of four titanium chloride[J]. Hydrometallurgy of China, 1999, 71(3):1-7.
[28]	张煜昌. 3D-TiO2-Ag复合材料对水体中碘离子的吸附性能研究[D]. 天津:天津大学, 2013. ZHANG Y C. A study on the adsorption properties of iodine ion on 3D-TiO2-Ag composites in water solution[D]. Tianjin:Tianjin University, 2013.
[29]	ZHANG X Y, LIU Y, YE J W. Fabrication and characterisation of magneli phase Ti4O7 nanoparticles[J]. Micro & Nano Letters, 2013, 8(5):251-253.
[30]	操小鑫, 陈亦琳, 林碧洲, 等. 氧缺陷型TiO2-x可见光催化性能的研究[J]. 无机材料学报, 2012, 27(12):1301-1305. CAO X X, CHEN Y L, LIN B Z, et al. Study of the photocatalytic performance of oxygen-deficient TiO2 active in visible light[J]. Journal of Inorganic Materials, 2012, 27(12):1301-1305.

流化床气相水解制备高纯二氧化钛

Synthesis of high purity TiO₂ powders by fluidized gas hydrolysis

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	董茂林, 陈李栋, 黄六莲, 吴伟兵, 戴红旗, 卞辉洋. 酸性助水溶剂制备木质纳米纤维素及功能应用研究进展[J]. 化工学报, 2023, 74(6): 2281-2295.
[2]	张媛媛, 曲江源, 苏欣欣, 杨静, 张锴. 循环流化床燃煤机组SNCR脱硝过程气液传质和反应特性[J]. 化工学报, 2023, 74(6): 2404-2415.
[3]	杨峥豪, 何臻, 常玉龙, 靳紫恒, 江霞. 生物质快速热解下行式流化床反应器研究进展[J]. 化工学报, 2023, 74(6): 2249-2263.
[4]	陈巨辉, 张谦, 舒崚峰, 李丹, 徐鑫, 刘晓刚, 赵晨希, 曹希峰. 基于DEM方法的旋转流化床纳米颗粒流动特性研究[J]. 化工学报, 2023, 74(6): 2374-2381.
[5]	袁子涵, 王淑彦, 邵宝力, 谢磊, 陈曦, 马一玫. 基于幂律液固曳力模型流化床内湿颗粒流动特性的研究[J]. 化工学报, 2023, 74(5): 2000-2012.
[6]	张浩, 徐惠斌, 高健, 刘帝宏, 周泽华. Geldart-D类湿颗粒倾斜落料行为及其强化[J]. 化工学报, 2023, 74(4): 1519-1527.
[7]	任金胜, 刘克润, 焦志伟, 刘家祥, 于源. 涡流空气分级机近导叶处团聚体解团机理研究[J]. 化工学报, 2023, 74(4): 1528-1538.
[8]	刘定平, 陈爱桦, 张向阳, 何文浩, 王海. 铝灰半干法水解脱氮研究[J]. 化工学报, 2023, 74(3): 1294-1302.
[9]	张梦波, 楼琳瑾, 冯艺荣, 郑雨婷, 张浩淼, 王靖岱, 阳永荣. 烷基铝氧烷合成技术研究进展[J]. 化工学报, 2023, 74(2): 525-534.
[10]	朱莲峰, 王超, 张梦娟, 刘方正, 贾鑫, 安萍, 许光文, 韩振南. 水蒸气/氧流化床两段煤气化制备低焦油合成气工艺实验[J]. 化工学报, 2022, 73(8): 3720-3730.
[11]	姚翰林, 辛忠. 液相沉淀反应在管式微通道反应器中的流动行为研究[J]. 化工学报, 2022, 73(8): 3518-3528.
[12]	王凯玥, 马永丽, 李琛, 刘明言. 气液固微型流化床的气液传质系数[J]. 化工学报, 2022, 73(8): 3529-3540.
[13]	张东旺, 杨海瑞, 周托, 黄中, 李诗媛, 张缦. 生物质锅炉对流受热面积灰冷态模拟实验研究[J]. 化工学报, 2022, 73(8): 3731-3738.
[14]	刘新华, 韩振南, 韩健, 梁斌, 张楠, 胡善伟, 白丁荣, 许光文. 基于热解与燃烧反应重构的低NO _x 解耦燃烧原理与技术[J]. 化工学报, 2022, 73(8): 3355-3368.
[15]	王刚, 夏志豪, 李希艳, 张虹, 韩振南, 宋兴飞, 许光文. 不同气氛下流化床菱镁矿轻烧产物特性研究[J]. 化工学报, 2022, 73(8): 3699-3707.

流化床气相水解制备高纯二氧化钛

Synthesis of high purity TiO2 powders by fluidized gas hydrolysis

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

Synthesis of high purity TiO₂ powders by fluidized gas hydrolysis