硫酸法钛白短流程工艺水热合成高纯二氧化钛

田从学

doi:10.7513/j.issn.1004-7638.2021.03.004

硫酸法钛白短流程工艺水热合成高纯二氧化钛

doi: 10.7513/j.issn.1004-7638.2021.03.004

田从学

攀枝花学院，四川攀枝花 617000

基金项目: 国家自然科学基金（50804025）；四川省科技计划项目（2014JY0197，2019GFW001-04）；攀枝花市科技计划项目（2018CY-G-16，20180816，201810），四川省高校重点实验室项目（LYJ1907），省、市级人才培养项目

详细信息

作者简介:
田从学（1973—），男，四川广汉人，博士（后），教授，长期从事二氧化钛的制备与应用研究工作，E-mail：tcx7311@163.com

中图分类号: TF823
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- 被引次数: 0
出版历程
- 收稿日期: 2020-04-04
- 刊出日期: 2021-06-10

Hydrothermal synthesis of high purity TiO₂ from metatitanic acid via short sulfate process

Tian Congxue

Panzhihua University, Panzhihua 617000, Sichuan, China

摘要

摘要: 以低浓度工业钛液经钛白短流程工艺水解所制的偏钛酸为原料，经水热工艺制备出高纯二氧化钛，考察了浆料浓度、水热温度、水热时间等对产物结构与纯度的影响，采用XRD、粒度分析、BET、SEM和TiO₂含量测定等对样品进行了表征。认为：水热条件影响水热偏钛酸的溶解、成核、晶体生长、聚合与团聚等，并影响偏钛酸的结构、粒径分布和比表面积，改变其杂质吸附量，并最终影响高纯TiO₂的结构与纯度。最佳水热条件为：料浆浓度160 g/L，水热温度140 ℃，水热时间36 h，所得高纯二氧化钛含量为99.99%。
- 高纯二氧化钛 /
- 偏钛酸 /
- 低浓度工业钛液 /
- 水热合成 /
- 短流程工艺
Abstract: High purity titanium dioxide was prepared through the hydrothermal synthesis route, using metatitanic acid as precursor which was hydrolyzed from low concentration industrial titanyl sulfate solution via short sulfate process. The effects of slurry mass concentration, hydrothermal temperature and hydrothermal time on the structure and purity of the products were investigated. The samples were characterized by XRD, particle size distribution, BET analysis, SEM and TiO₂ content determination. The hydrothermal conditions, e.g. slurry mass concentration, hydrothermal temperature and hydrothermal time influence the dissolution, nucleation, crystal growth, polymerization and agglomeration of the precipitates, and the structure, particle size distribution and specific surface area of the hydrothermal metatitanic acid are also affected, which leads to the content variation of the adsorbed impurities and ultimately influences the structure and purity of TiO₂. The optimized hydrothermal conditions are the slurry concentration of 160 g/L, hydrothermal temperature of 140 ℃ for 36 h, with the high purity TiO₂ (99.99%) obtained.
- high purity titanium dioxide /
- metatitanic acid /
- industrial low concentration titanyl sulfate solution /
- hydrothermal synthesis /
- short sulfate process

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图 1 不同浆料浓度所得水热偏钛酸的XRD谱图

Figure 1. XRD patterns of metatitanic acid from slurries with different concentrations

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图 2 不同浆料浓度所得高纯TiO₂的XRD谱图

Figure 2. XRD patterns of high purity TiO₂ from slurries with different concentrations

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图 3 不同浆料浓度所得偏钛酸的N₂吸附-脱附等温线

Figure 3. Nitrogen adsorption-desorption isotherms of hydrothermal metatitanic acid samples

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图 4 高纯TiO₂的SEM照片

Figure 4. SEM of high purity TiO₂

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表 1 浆料浓度对偏钛酸结构和高纯二氧化钛的结构与含量影响

Table 1. Effect of slurry concentration on structure and TiO₂ content of metatitanic acid and high purity TiO₂

MA	浆料浓度/(g·L⁻¹)	L_{（101），MA}/nm	D_AV，MA /µm	S_BET/(m²·g⁻¹)	TiO₂	D_AV，TiO2 /µm	L_（110）/nm	w(TiO₂)/%
	80	8.8	0.84	116.1	A1	0.25	112	99.87
B	120	8.4	0.78	102.8	B1	0.23	101	99.95
C	160	8.2	0.71	96.93	C1	0.21	98.2	99.97
D	200	8.3	0.80	100.2	D1	0.24	101	99.93
E	240	8.6	0.85	108.4	E1	0.26	109	99.85

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表 2 水热温度对偏钛酸和二氧化钛的影响

Table 2. Effect of hydrothermal temperature on the structures and composition of metatitanic acid and TiO₂

MA	水热温度/℃	S_BET/(m²·g⁻¹)	D_AV，PTS /µm	TiO₂	D_AV，TiO2 /µm	w(TiO₂)/%
F	105	125.1	0.84	F1	0.37	99.25
G	120	107.2	0.79	G1	0.30	99.76
H	140	96.93	0.71	H1	0.21	99.97
I	160	100.7	0.78	I1	0.26	99.81
J	180	113.9	0.83	J1	0.33	99.28

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表 3 水热时间对偏钛酸和高纯二氧化的影响

Table 3. Effect of hydrothermal time on the structure and composition for metatitanic acid and TiO₂

MA	水热时间/h	S_BET /(m²·g⁻¹)	D_AV，PTS /µm	TiO₂	D_AV，TiO2 /µm	w（TiO₂）/%
K	12	107.4	0.79	K1	0.28	99.83
L	24	96.93	0.71	L1	0.21	99.97
M	36	91.58	0.69	M1	0.20	99.99
N	48	104.5	0.76	N1	0.24	99.95
Q	60	111.8	0.81	Q1	0.30	99.85

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