预还原对含杂硫酸氧钛溶液水热水解除铁影响

doi:10.19964/j.issn.1006-4990.2023-0123

Abstract

Abstract:

The effect of pre-reduction treatment by adding aluminum powder to titanium oxysulfate solution containing magnesium，aluminum，and iron impurities and changing the valence of some elements on the process of iron removal from titanium liquid by hydrothermal hydrolysis was investigated.Under the guidance of electrode potential theory，all Fe（Ⅲ） in titanium liquid was reduced to Fe（Ⅱ），and a small amount of Ti（Ⅳ） was reduced to Ti（Ⅲ）.Subsequently，hydrothermal reaction was conducted at 120 ℃ for 4 h.Titanium hydrolysis efficiency of samples with and without pre-reduction were 98.59% and 97.47%，and iron content in the hydrolysate was 115 mg/kg and 11 710 mg/kg（based on TiO₂），respectively.Combining the thermodynamic equilibrium constant of each reaction at 110~150 ℃ with the relevant equilibrium equation，the concentration of each component in the equilibrium system at different temperatures was obtained by Newton-Raphson iterative method，and the change law of Mg，Al and Fe impurities in the solution with and without pre-reduction during the hydrothermal hydrolysis process was illustrated.The strengthening mechanism of pre-reduction on the deferrization in the hydrothermal hydrolysis process of titanium sulfate solution containing impurities was revealed through mutual verification of experiments and thermodynamics.

Key words: pre-reduction, titanyl sulfate, hydrothermal hydrolysis, deferrization, hydrolysis efficiency

CLC Number:

TQ134.11

PENG Qiugui, YANG Fan, LÜ Renliang, XIANG Lan. Effect of pre-reduction on deferrization in hydrothermal hydrolysis process of Mg/Al/Fe-bearing TiOSO₄ solution[J]. Inorganic Chemicals Industry, 2023, 55(12): 95-101.

Figures/Tables 7

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References 28

1	郝百川，李子越，贾东方，等. 含钛高炉渣的综合利用［J］. 矿产综合利用， 2020（6）：1-6.
	HAO Baichuan， LI Ziyue， JIA Dongfang， et al. Comprehensive utilization of blast furnace slag containing titanium［J］. Multipurpose Utilization of Mineral Resources， 2020（6）：1-6.
2	向兰，王明亮，杨卓颖，等. 一种由含钛的高炉渣制备高纯二氧化钛的方法：中国， 112047377A［P］. 2021-11-23.
3	J.A. 迪安. 兰氏化学手册［M］.魏俊发，译. 2版. 北京：科学出版社， 2003.
4	张益都. 硫酸法钛白粉生产技术创新［M］. 北京：化学工业出版社， 2010.
5	ZHANG Wu， Changrui OU， YUAN Zhigang. Precipitation and growth behaviour of metatitanic acid particles from titanium sulfate solution［J］. Powder Technology， 2017， 315：31-36. doi: 10.1016/j.powtec.2017.03.047
6	ZENG Fanbo， LUO Dongmei， ZHANG Zhao， et al. Study on the behavior of sulfur in hydrolysis process of titanyl sulfate solution［J］. Journal of Alloys and Compounds， 2016， 670：249-257. doi: 10.1016/j.jallcom.2016.02.031
7	TIAN Congxue. A novel preparation of high purity TiO₂ from industrial low concentration TiOSO₄ solution via short sulfate process［J］. Materials Science in Semiconductor Processing， 2022， 137：106166. doi: 10.1016/j.mssp.2021.106166
8	邹建新，王荣凯. 钛渣替代钛矿制备钛白酸解试验研究［J］. 现代化工， 2006， 26（S1）：273-276.
	ZOU Jianxin， WANG Rongkai. Study on acid digesting titania slag during titanium dioxide production［J］. Modern Chemical Industry， 2006， 26（S1）：273-276.
9	廖鑫，杨绍利，马兰，等. 以钛精矿和钛渣为原料制备硫酸法钛白粉的对比分析［J］. 无机盐工业， 2019， 51（10）：7-11.
	LIAO Xin， YANG Shaoli， MA Lan， et al. Comparison and analysis of sulfuric acid process titanium dioxide prepared with titanium concentrate and titanium slag as raw materials respectively［J］. Inorganic Chemicals Industry， 2019， 51（10）：7-11.
10	陈朝华，刘长河. 钛白粉生产及应用技术［M］. 北京：化学工业出版社， 2006.
11	LOAN T T， HUONG V H， HUYEN N T， et al. Anatase to rutile phase transformation of iron-doped titanium dioxide nanoparticles：The role of iron content［J］. Optical Materials， 2021， 111：110651. doi: 10.1016/j.optmat.2020.110651
12	WERMINK W N， VERSTEEG G F. The oxidation of Fe（Ⅱ） in acidic sulfate solutions with air at elevated pressures.part 2.influence of H₂SO₄ and Fe（Ⅲ）［J］. Industrial & Engineering Chemistry Research， 2017， 56（14）：3789-3796. doi: 10.1021/acs.iecr.6b04641
13	DONG Chunying， PANG Yuang， CHEN Yan， et al. Fe-Ti bimetals catalyst derived from biowaste for highly efficient persulfate activation：Performance and mechanisms［J］. Process Safety and Environmental Protection， 2022， 168：654-667. doi: 10.1016/j.psep.2022.10.038
14	左定财，钟永科，范会，等. 铁掺杂介孔水合TiO₂光催化剂性能研究［J］. 化工新型材料， 2020， 48（9）：207-211.
	ZUO Dingcai， ZHONG Yongke， FAN Hui， et al. Influence of mesoporous hydrogen TiO₂ doped with Fe³⁺ on its photocatalytic activity［J］. New Chemical Materials， 2020， 48（9）：207-211.
15	杨颖. 工业钛液制备铁掺杂硫酸化多孔二氧化钛及其机理研究［D］. 成都：成都理工大学， 2012.
	YANG Ying. Study on preparation and mechanism of Fe-doped sulfated mesoporous titania from industrial titanyl sulfate soluti-on［D］. Chengdu： Chengdu University of Technology， 2012.
16	苏淑芬，杨发福. 手持技术探究离子浓度对沉淀溶解平衡的影响：同离子效应和盐效应［J］. 化学教育（中英文）， 2023， 44（1）：107-112.
	SU Shufen， YANG Fafu. Exploring influence of ion concentration on precipitation-dissolution equilibrium based on handheld technology：Co-ionic effect and salt effect［J］. Chinese Journal of Che-Education mical ， 2023， 44（1）：107-112.
17	GRZMIL B， GRELA D， KIC B， et al. The influence of admixtures on the course of hydrolysis of titanyl sulfate［J］. PJCT， 2008， 10（3）：4-12.
18	KARTHIK P， VINESH V， MAHAMMED SHAHEER A R， et al. Self-doping of Ti³⁺ in TiO₂ through incomplete hydrolysis of titanium（Ⅳ） isopropoxide：An efficient visible light sonophotocatalyst for organic pollutants degradation［J］. Applied Catalysis A：General， 2019， 585：117208.
19	KOMARAIAH D， RADHA E， KALARIKKAL N， et al. Structural，optical and photoluminescence studies of sol-gel synthesized pure and iron doped TiO₂ photocatalysts［J］. Ceramics International， 2019， 45（18）：25060-25068. doi: 10.1016/j.ceramint.2019.03.170
20	SCHERRER P. Bestimmung der gross under linneren strukur von kolloidteilchen mittels rontgenstrahlen［J］. Gottinger Nachr Math Phys， 1918， 2：98-100.
21	LI Hexing， LI Guisheng， ZHU Jian， et al. Preparation of an active SO₄ ^2-/TiO₂ photocatalyst for phenol degradation under supercritical conditions［J］. Journal of Molecular Catalysis A：Chemical， 2005， 226（1）：93-100.
22	PRADUBKORN P， MAENSIRI S， SWATSITANG E， et al. Preparation and characterization of hollow TiO₂ nanospheres：The effect of Fe³⁺ doping on their microstructure and electronic structure［J］. Current Applied Physics， 2020， 20（1）：178-185. doi: 10.1016/j.cap.2019.11.002
23	RATHORE N， KULSHRESHTHA A， SHUKLA R K， et al. Defect-mediated optical properties of Fe-substituted TiO₂ nanoparticl-es［J］. International Journal of Applied Ceramic Technology， 2022， 19（3）：1766-1778. doi: 10.1111/ijac.v19.3
24	JAFARI A J， MOSLEMZADEH M. Synthesis of Fe-doped TiO₂ for photocatalytic processes under UV-visible light：Effect of preparation methods on crystal size a systematic review study［J］. Comments on Inorganic Chemistry， 2020， 40：327-346. doi: 10.1080/02603594.2020.1821674
25	SANTOS R DA S， FARIA G A， GILES C， et al. Iron insertion and hematite segregation on Fe-doped TiO₂ nanoparticles obtained from sol-gel and hydrothermal methods［J］. ACS Applied Materials & Interfaces， 2012， 4（10）：5555-5561.
26	梁英教车荫昌. 无机物热力学数据手册［M］. 沈阳：东北大学出版社， 1993.
27	杨显万. 高温水溶液热力学数据计算手册［M］. 北京：冶金工业出版社， 1983.
28	杨卓颖，杨帆，易美桂，等. 含镁铝杂质硫酸氧钛溶液水热水解规律［J］. 无机盐工业， 2021， 53（12）：113-116.
	YANG Zhuoying， YANG Fan， YI Meigui， et al. Rule of hydrothermal hydrolysis of Mg/Al-bearing TiOSO₄ solution［J］. Inorganic Chemicals Industry， 2021， 53（12）：113-116.

样品	2θ/（°）	β_1/2	D/nm	晶型
含铁量11 710 mg/kg	25.19	1.407	5.75	100%A
含铁量115 mg/kg	25.25	1.229	6.58	100%A
含铁量0	25.28	1.158	6.99	100%A

[1]	YANG Zhuoying,YANG Fan,YI Meigui,XIANG Lan. Rule of hydrothermal hydrolysis of Mg/Al-bearing TiOSO₄ solution [J]. Inorganic Chemicals Industry, 2021, 53(12): 113-116.
[2]	Lu Ruifang，Wu Jianchun，Liu Chan. Influence of titanyl sulfate solution hydrolysis process on tintreducing power of rutile titanium dioxide [J]. Inorganic Chemicals Industry, 2019, 51(12): 44-48.
[3]	WANG Bin, LAN Guang-Ming, DU Jian-Qiao, CHENG Xiao-Zhe, WU Jian-Chun. Research on impurity components and filtration performance of titanyl sulfate solution [J]. INORGANICCHEMICALSINDUSTRY, 2014, 46(2): 54-.
[4]	Zhao Yanyu;Li Yong;Shang Liandi;Wang Huihui;Yuan Yingxian. Preparation and characterization of nano-sized TiO2 by atmospheric hydrolysis method [J]. INORGANICCHEMICALSINDUSTRY, 2010, 0(6): 0-0.

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Effect of pre-reduction on deferrization in hydrothermal hydrolysis process of Mg/Al/Fe-bearing TiOSO₄ solution

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Effect of pre-reduction on deferrization in hydrothermal hydrolysis process of Mg/Al/Fe-bearing TiOSO4 solution