硅酸盐多元体系中硅酸中间体聚合理论研究
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摘要
本文研究了以水玻璃和氟硅酸为原料合成硅酸的聚合反应过程,并探讨氟硅酸-水玻璃体系的成胶规律,研究发现：体系pH、反应温度、外加电解质对硅酸聚合胶凝时间有不同程度的影响。胶凝时间与体系的pH值有较大的关系,在反应物浓度一定的条件下,胶凝时间lgt-pH曲线成“N”字形。结果表明：当pH<2时,随pH升高,硅酸聚合速度变慢；在pH≈7时,聚合速度达到极大值；pH>7时,聚合速度逐渐减小,这种趋势随pH进一步增大而逐步增强。
本课题还研究了在氟硅酸催化下分解含钾岩石工艺中硅酸聚合反应的过程,是对于低温湿法分解钾长石为代表的硅酸盐制取化工产品工艺后续产物分离利用的研究。此工艺是在一个含有硅酸及硅酸盐类物质和pH值非常低的体系中进行的,硅酸的凝聚不只是和它在溶液中的浓度有关,很重要的一个因素便是溶液的pH值、温度、离子强度等因素有关。通过对硅酸中间体进行转型的初步实验,探讨了铵法转型的分解状况。本文还在前人理论的基础上,分析实验现象和实验结果,对吸收法白炭黑聚合过程的机理作了总结和解释,对吸收法白炭黑生产和转型有一定的理论参考价值。
另外,通过实验研究发现,硅酸聚合反应产品的性能与沉淀pH值有直接的关系,在酸性条件下吸收法所得白炭黑具有低比表面积的缺点,是本课题解决的突出问题,为了拓展产品的使用范围,本文提出了对硅酸中间体的铵法改型工艺,采用了用氟化铵与吸收法白炭黑反应的方法；通过控制其反应过程中的pH值、反应时间、加氨浓度等条件,制取出较原料白炭黑具有更高利用价值的白炭黑,对白炭黑的生产以及新工艺的研究具有重要的指导意义。
The polymerization process of making silicic acid up of H2SiF6 and waterglass was investigated, the gelation process of H2SiF6-waterglass system was also studied. It was discovered that the pH value, the temperature and electrolytes had a different impact on the gelation time of H2SiF6-waterglass system. The pH value had a strong impact on the gelation time of H2SiF6-waterglass system. For the system with constant reactant concentrations, the relationship between gelation time and pH value showed an "N" shape curve. The results indicate that the polymerization speed of silicic acid decreased as pH was increased when pH<2; the polymerization speed of silicic acid was reached maximum when pH≈7; When pH>7, the polymerization speed of silicic acid decreased as pH was increased, and the reaction trend was strong as pH was increased.
The polymerization process of silicic acid which was made by decomposing potassium-bearing rocks under the condition of H2SiF6 was investigated, It was a study that was about the separation and utilization of the resultant of reaction with the process of decomposing potassium-bearing rocks. The process technology was reacting with existing silicic acid and silicate in a low pH value system. The polymerization of silicic acid was not only related the concentration, but to the pH value, the temperature, ionic strength and other factors, etc. The transition of white carbon black by ammonium method was discussed by some experiments. Based on previous theory, the polymerization process theory of white carbon black by ammonium method was summarized and explained through the phenomenons and results of experiments. It provided reference in order to produce and utilize the white carbon black which was made in absorption method.
Moreover, the results indicated that the function of product had direct relation with the pH value in the polymerization process of silicic acid. The main problem which was resolved in the paper was the weak point of white carbon black of low specific surface area by absorption method. The ammonium method put forward was applied in order to expand the serviceable range of product, by mixing NH4F with white carbon black of absorption method, by controlling the pH value, the reaction time, the concentration of the reactant and so on. The ammonium method made the higher value than it was. The results were of great significance in the new technology of white carbon black.
本课题还研究了在氟硅酸催化下分解含钾岩石工艺中硅酸聚合反应的过程,是对于低温湿法分解钾长石为代表的硅酸盐制取化工产品工艺后续产物分离利用的研究。此工艺是在一个含有硅酸及硅酸盐类物质和pH值非常低的体系中进行的,硅酸的凝聚不只是和它在溶液中的浓度有关,很重要的一个因素便是溶液的pH值、温度、离子强度等因素有关。通过对硅酸中间体进行转型的初步实验,探讨了铵法转型的分解状况。本文还在前人理论的基础上,分析实验现象和实验结果,对吸收法白炭黑聚合过程的机理作了总结和解释,对吸收法白炭黑生产和转型有一定的理论参考价值。
另外,通过实验研究发现,硅酸聚合反应产品的性能与沉淀pH值有直接的关系,在酸性条件下吸收法所得白炭黑具有低比表面积的缺点,是本课题解决的突出问题,为了拓展产品的使用范围,本文提出了对硅酸中间体的铵法改型工艺,采用了用氟化铵与吸收法白炭黑反应的方法；通过控制其反应过程中的pH值、反应时间、加氨浓度等条件,制取出较原料白炭黑具有更高利用价值的白炭黑,对白炭黑的生产以及新工艺的研究具有重要的指导意义。
The polymerization process of making silicic acid up of H2SiF6 and waterglass was investigated, the gelation process of H2SiF6-waterglass system was also studied. It was discovered that the pH value, the temperature and electrolytes had a different impact on the gelation time of H2SiF6-waterglass system. The pH value had a strong impact on the gelation time of H2SiF6-waterglass system. For the system with constant reactant concentrations, the relationship between gelation time and pH value showed an "N" shape curve. The results indicate that the polymerization speed of silicic acid decreased as pH was increased when pH<2; the polymerization speed of silicic acid was reached maximum when pH≈7; When pH>7, the polymerization speed of silicic acid decreased as pH was increased, and the reaction trend was strong as pH was increased.
The polymerization process of silicic acid which was made by decomposing potassium-bearing rocks under the condition of H2SiF6 was investigated, It was a study that was about the separation and utilization of the resultant of reaction with the process of decomposing potassium-bearing rocks. The process technology was reacting with existing silicic acid and silicate in a low pH value system. The polymerization of silicic acid was not only related the concentration, but to the pH value, the temperature, ionic strength and other factors, etc. The transition of white carbon black by ammonium method was discussed by some experiments. Based on previous theory, the polymerization process theory of white carbon black by ammonium method was summarized and explained through the phenomenons and results of experiments. It provided reference in order to produce and utilize the white carbon black which was made in absorption method.
Moreover, the results indicated that the function of product had direct relation with the pH value in the polymerization process of silicic acid. The main problem which was resolved in the paper was the weak point of white carbon black of low specific surface area by absorption method. The ammonium method put forward was applied in order to expand the serviceable range of product, by mixing NH4F with white carbon black of absorption method, by controlling the pH value, the reaction time, the concentration of the reactant and so on. The ammonium method made the higher value than it was. The results were of great significance in the new technology of white carbon black.
引文
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3.凌进中.硅酸盐岩石的分解方法[J].岩矿测试,1988,7(4)：317-319
4.孙德四,张强.硅酸盐细菌在资源工程中的应用研究现状[J].黄金,2006,27(1)：32
5. Zahra M K, Monib M, Abdel-AI S I, et al. Significance of soil inoculation with silicate bacteria[J]. Zentralbl Mikrobiol,1984,139(5):349-357
6. Groudeva Veneta I, Groudev Stoyan N(Bulg). Microorganisms improve kaolin properties [J]. Am eeram Soc Bull,1995,74(6):85-89
7. Stoyan Groudev, Fratio Genchev. Bioleaching of Bauxites By Wild and laboratory-bred microbial[M]. Department of mineral processing, Higher Institute of mining and Geology, Sofia 1156, Bulgaria
8. Andreev P, Polkin I, Shavlo R, et al. Microbiol dissoluton of silicono and aluminum from primary minerals[J]. Zvetnaja metallurgija(USSR),1975, (3):8-11
9.崔日成,杨洪英,王胜利.硅酸盐细菌在铝土矿脱硅中的应用现状[J].贵金属,2007,28(S1)：89-91
10.连宾.硅酸盐细菌的初步研究与应用[C].1995年全国微生物肥料专业会议论文集,1995
11.徐旺生,宣爱国.钾长石综合利用的新工艺[J].武汉化工学院学报,1998,20(3)：11
12.申军.钾长石综合利用综述[J].化工矿物与加工,2000,(10)：1
13.斐文洁.宝兴钾民石开发前景广阔[J].化工矿物与加工,2000,29(3)：30
14.闫福林.钾长石煅烧活化制备钾硅肥试验研究[J].非金属矿,1999,22(4)：21-22
15.邱龙会,王励生,金作美.用钾长石制备钾肥的方法[J].四川化工与腐蚀控制,1999,2(6)：17-21
16.吕一波.钾长石深加工及综合利用[J].中国非金属矿工业导刊,2001,22(4)：23-25
17.彭清静,邹晓勇,黄诚.氯化钠熔浸钾长石提钾过程[J].过程工程学报,2002,2(2)：146-151
18.于漧.不溶性钾资源制钾肥研究现状[J].化工矿物与加工,2002,(8)：1-3
19.姚卫堂,胡波,韩效钊.论钾长石的研究现状和开发前景[J].化工矿产地质,2002, 24(3)：151-156
20. Barthel H, Rosch L. Fumed Silica production, Properties and Applications[C]. Organosilicon Chemistry Ⅱ:From molecules to Materials, VCH, Weinheim,1996: 761-778
21.Kalkan E, Akbulut S. The positive effects of silica fume on the permeability, swellingpressure and compressive strength of natural clay liners[J]. Engineering Geology, 2004,(73):145-156
22.杨波,何慧,周扬波.气相法白炭黑的研究进展[J].化工进展,2005,24(3)：372-376
23.严大洲,汤传斌,谢正和.气相法白炭黑生产技术的研究[J].有色冶金节能,2010,(6)：33-34
24.张桂华,王玉瑛,赵金钊.国内外气相法白炭黑的生产及市场分析[J].无机盐工业,2004,36(5)：11-13
25.吴雪文,张海波,韩团辉.传统沉淀法制白炭黑的研究进展[J].无机盐工业,2006,38(4)：9-11
26.韩秀山.白炭黑生产工艺及应用综述[J].化工设计通讯,2004,30(3)：52-53
27.谭鑫,钟宏.白炭黑的制备研究进展[J].化工技术与开发,2010,39(7)：25-27
28.汪多仁.沉淀白炭黑的开发与应用进展[J].橡塑资源利用,2010,(6)：10-12
29.梅鑫东.白炭黑的生产工艺及其应用[J].江西化工,2006,(3)：39-40
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