Polymerization behavior of silicic acid with coexisting magnesium and aluminum ions

doi:10.3969/j.issn.0438-1157.2014.03.047

Abstract

Abstract: Gel time, polymerization rate of monosilicic acid, and thermal performance of gel of silicic acid system with coexisting Mg²⁺ and Al³⁺ ions were investigated. At pH<4, gel time of silicic acid system decreased with the increase of coexisting concentration of Mg²⁺ and Al³⁺ ions, and Al³⁺ ions played an important role in the coagulation process. Polymerization reaction rate constant of monosilicic acid, for silicic acid system with coexisting Mg²⁺ and Al³⁺ ions, was higher than that for silicic acid without metallic ions, and average rate constant for MA_0.1+0.1system was k₀=7.28×10^-4, k₁=5.62×10^-4. Crystallization temperature and crystal transformation temperature of silicic acid system with coexisting Mg²⁺ and Al³⁺ ions were lower than those of silicic acid without metallic ions, and chemical formula of hydrated silicon dioxide for MA_0.1+0.1system calculated by TG curve was SiO₂·0.556 H₂O.

Key words: silicic acid system, magnesium and aluminum ions, gel time, polymerization, gels, silica

摘要： 通过对镁铝离子共存硅酸体系中硅酸胶凝时间、单硅酸聚合反应速率以及凝胶热性能的研究，得出：在pH<；4的微酸性条件下，硅酸体系的胶凝时间随镁铝离子共存浓度的增大而减小，且铝离子在对硅酸体系的促凝过程中起主要作用。镁铝离子共存硅酸体系的单硅酸反应速率常数比不含金属离子硅酸体系的有所增大，计算得出MA_0.1+0.1硅酸体系的单硅酸平均速率常数为：k₀=7.28×10^-4，k₁=5.62×10^-4。镁铝离子共存硅酸体系凝胶的晶化转变温度与晶型转变温度，相较于不含金属离子硅酸体系的均有所降低，根据热重曲线计算出MA_0.1+0.1硅酸体系水合二氧化硅的化学式为：SiO₂·0.556 H₂O。

关键词: 硅酸体系, 镁铝离子, 胶凝时间, 聚合, 凝胶, 二氧化硅

CLC Number:

TQ170.9

SHEN Xingmei, LI Liaosha, WU Xingrong, WANG Ping, LUO Tao. Polymerization behavior of silicic acid with coexisting magnesium and aluminum ions[J]. CIESC Journal, 2014, 65(3): 1104-1110.

申星梅, 李辽沙, 武杏荣, 王平, 罗涛. 镁铝离子共存硅酸体系的聚合行为[J]. 化工学报, 2014, 65(3): 1104-1110.

References 28

[1]	Maurizia S, Sandra V. Recovery of silica gel from blast furnace slag[J]. Resour. Conserv. Recy., 2003, 40: 71-80
[2]	Lieftink D J, Geus J W. The preparation of silica from the olivine process and its possible use as a catalyst support[J]. J. Geochem. Explor., 1998, 62: 347-350
[3]	Wang Ping(王平), Li Liaosha(李辽沙). Research on preparation of silica white from fly ash[J]. China Resource Comprehensive Utilization (中国资源综合利用), 2004, 23: 25-27
[4]	Yu Honghao(于洪浩), Xue Xiangxin(薛向欣), He Yan(贺燕), Huang Dawei(黄大威). Preparation of high purity precipitated silica from iron ore tailings by molten salt method[J]. CIESC Journal (化工学报), 2009, 60: 2124-2129
[5]	Jing Hongxia(景红霞), Li Qiaoling(李巧玲), Wang Yakun(王亚昆), Zhao Jin'an(赵金安), Pei Wangjun(裴王军). Study on the preparation of polyaluminum ferric silicate from coal ash[J]. Chem. Eng. (China) (化学工程), 2006, 19: 9-11
[6]	Li Canhua(李灿华). Study on the preparation of polymeric ferric silicate sulfate using the metallurgical slags[J]. J. Colloid & Polym. (胶体与聚合物), 2006, 24: 29-30
[7]	Wang Lei(王蕾), Ma Hongwen(马鸿文), Nie Yimiao(聂轶苗), Li Hexiang(李贺香). Experimental research on preparation of high specific surface area SiO2 from fly ash[J]. Bull. Ceram. Soc. (硅酸盐通报), 2006, 27: 3-7
[8]	Li Ge(李歌), Ma Hongwen(马鸿文), Liu Hao(刘浩), Zou Dan(邹丹). Preparation of precipitated silica from desilicated solution of high-alumina fly ash by dissolution with alkali: experiment and principle of polymerization of silicic acid[J]. CIESC Journal (化工学报), 2011, 62: 3580-3587
[9]	Lin Qinü(林七女), Li Zhifeng(李志峰), Guan Shanji(管山吉), Yang Guangyi(杨光义). Study on hydrated silicon dioxide produced by blast furnace slag[J]. China Resource Comprehensive Utilization (中国资源综合利用), 2010, 28: 33-34
[10]	Yu Shangqing(俞尚清), Fu Tianhang(傅天杭), Pan Zhiyan(潘志彦). Studies on the preparation of polysilicate aluminum ferric chloride (PSAFC) coagutants with fly ash[J]. Fly Ash Comprehensive Utilization (粉煤灰综合利用), 2003, 17: 9-11
[11]	Du Zichuan(杜淄川), Li Huiquan(李会泉), Bao Weijun(包炜军), Li Shaopeng(李少鹏), Cai Weiquan(蔡卫权). Reaction mechanism of desilification process of high aluminum fly ash by alkali solution[J]. Journal of Process Engineering (过程工程学报), 2011, 11: 442-447
[12]	Iler R K. The Chemistry of Silica[M]. New York: John Wiley & Sons, 1979: 97
[13]	Moulik S P, Mullick D K. Catalysis in the polymerization of silicic acid[J]. Polymer Sci. (Part A-1), 1966, 4: 811-820
[14]	Dai Anbang(戴安邦), Jiang Long(江龙). Studies on silicic acid and its salts(Ⅰ): Rate of gelation and mechanism of polymerization of silicic acid[J]. Aata Chimica Sinica (化学学报), 1957, 23: 90-98
[15]	Zhu Tun(朱屯), Qian Baohua(钱保华), Chen Rongsan(陈荣三), Dai Anbang(戴安邦). Studies on silicic acid and its salts(Ⅹ): Kinetics of polymerization of monosilicic acid[J]. Aata Chimica Sinica (化学学报), 1981, 39: 1-11
[16]	Dai Anbang(戴安邦), Chen Rongsan(陈荣三), Zhu Tun(朱屯). Studies on silicic acid and its salts (Ⅶ): A more complete N-curve[J]. Journal of Nanjing University (南京大学学报), 1963, 7: 20-29
[17]	Dai Anbang(戴安邦), Chen Rongsan(陈荣三), Liu Haicheng(柳海澄), Chen Yuehua(陈月华). Studies on silicic acid and its salts (ⅩⅢ): Dissociation constants of monosilicic acid in the gelation process[J]. Aata Chimica Sinica(化学学报), 1982, 40: 767-769
[18]	Dai Anbang(戴安邦), Chen Rongsan(陈荣三). Studies on silicic acid and its salts(Ⅴ): Effect of fluoride ions on polymerization of silicic acid[J]. Aata Chimica Sinica (化学学报), 1963, 29: 384-389
[19]	Dai Anbang(戴安邦), Chen Rongsan(陈荣三), Ji Mingde(季明德), Dai Qingping(戴庆平), Zhang Xueqin(张雪琴), Wang Bokang(王伯康). Studies on silicic acid and its salts(Ⅸ): Effect of added salt and concentration on rate of polymerization of monosilicic acid[J]. Journal of Nanjing University (南京大学学报), 1964, 8: 80-95
[20]	Lee H J, Moon S H. Influences of colloidal stability and electrokinetic property on electrodialysis performance in the presence of silica sol[J]. J. Colloid Interface Sci., 2004, 270: 406-412
[21]	Spadini L, Schindler P W, Sjoberg S. On the stability of the AlOSi(OH)32+ complex in aqueous solution[J]. Aquat. Geochem., 2005, 11: 21-31
[22]	Xu Yunhua(许韵华), Yin Chenglong(尹承龙), Zhu Hong(朱红), Wang Yongsheng(王永生). Study on effect of metal ions on polymerization and gel reaction of silicic acid[J]. Journal of Northern Jiaotong University (北方交通大学学报), 2003, 27: 97-100
[23]	Yin Chenglong(尹承龙), Xu Yunhua(许韵华), Zhao Haiying(赵海英). Study on acidify effect to silicic acid polymerization and gel reaction[J]. Journal of Northern Jiaotong University (北方交通大学学报), 2004, 28: 65-68
[24]	Jia Guangyao(贾光耀), Deng Yuxin(邓育新). Investigation on the gelation process of silica sol[J]. Bull. Ceram. Soc. (硅酸盐通报), 2004, 25: 91-93
[25]	Shen Xingmei(申星梅), Li Liaosha(李辽沙), Luo Tao(罗涛), Wu Xingrong(武杏荣), Gao Zhifang(高志芳), Lü Huihong(吕辉鸿). Preparation method of high purity silica sol without metallic ions[P]: CN, 201210354108. 2012-12-26
[26]	Thilo E, Miedreich W. Die konstitution der wasser-haltigen natriumsilicate[J]. Z. Anorg. Allg. Chem., 1951, 267: 76-79
[27]	Li Shougui(李守贵), Mao Yachun(毛亚春), Xu Ruren(徐如人), Tang Aoqing(唐敖庆). Studies on the polymerization between high polymeric silicate anions and mono-aluminate anions and the hydrothermal crystallization behaviour[J]. Chemical Journal of Chinese Universities (高等学校化学学报), 1995, 16: 1491-1494
[28]	Shen Xingmei(申星梅), Luo Tao(罗涛), Ai Jin(艾进), Wu Xingrong(武杏荣), Lü Huihong(吕辉鸿), Li Liaosha(李辽沙). Polymerization behavior of intermediate in the process of fine chemicals preparation by metallurgical solid waste[J]. Journal of Process Engineering (过程工程学报), 2013, 13: 86-90