硅镁吸附材料的制备与性能研究
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摘要
本文在实验室前期工作基础上，以硅酸钠和氯化镁为原料，经过溶胶-凝胶法和水热法，控制合成条件，制备出11种新型的硅镁胶。采用差热分析(DTG-DTA)、红外光谱(FT-IR)、X射线衍射光谱(XRD)、比表面及孔结构分析等现代仪器分析手段对硅镁胶材料进行了结构表征和性质测定。探讨硅镁胶对水溶液中的亚甲基蓝和弱酸性红的吸附性能。考察吸附时间、吸附剂投加量、溶液的初始pH值、温度、初始浓度等因素对吸附性能的影响，计算该新型吸附剂的吸附等温线和动力学方程。
溶胶-凝胶法和水热法制备的硅镁胶都是白色的无定形态颗粒，分散性和化学稳定性较好，表面含有丰富的硅羟基活性基团，氮气吸附脱附曲线都有明显的滞后环，易发生毛细凝结现象；溶胶-凝胶法制备的硅镁胶的比表面积介于120.22~330.39m2·g-1之间，水热法制备的硅镁胶的比表面积可达560.40m2·g-1，在温度为110℃和水热12h的条件下制备出的硅镁胶具有最大的比表面积，焙烧温度对样品的比表面积和孔结构的影响很大。
利用溶胶-凝胶法制备的8种硅镁胶对亚甲基蓝和弱酸性红的吸附实验，结果发现镁硅比为1:5的硅镁胶对亚甲基蓝吸附效果最好，吸附量为80mg·g-1；镁硅比为3:1的硅镁胶对弱酸性红的吸附效果最好，吸附量为200mg·g-1。Langmuir吸附模型能够很好描述硅镁胶对两种染料的吸附，伪二级动力学方程能够很好地描述两种染料的吸附行为，吸附平衡在很短的时间内完成。
经高温焙烧，将海泡石、凹凸棒石和商品硅酸镁进行了改性处理。通过研究海泡石、凹凸棒石和商品硅酸镁对系列有机酸的吸附过程，确定硅酸镁材料对有机酸的吸附脱除效果。通过测定海泡石、凹凸棒石和商品硅酸镁对系列有机酸的吸附性能发现，等温线为S型、C型、H型和L型。经过计算，Freundlich吸附等温模型能够较好的描述系列有机酸在凹凸棒石、海泡石和硅酸镁上的的吸附过程，硅酸镁系列材料对有机酸有较好的吸附处理效果。
在此基础上，研究了11种新型硅镁胶和3种商品硅酸镁等全部硅镁吸附材料对生物柴油中有机酸的吸附性能，考察了吸附时间、吸附剂投加量等条件对吸附性能的影响。发现水热法制备的9:1的硅镁胶有最好的吸附效果，最佳吸附条件是：焙烧温度为450℃，焙烧时间为4h，吸附时间为6h，吸附剂投加质量为0.50g·L-1，吸附温度为25℃，硅镁胶的最大吸附量可达980mg·g-1，等温吸附过程更符合Freundlich吸附等温式。
通过上述实验发现，硅镁胶作为一种新型的硅镁吸附材料，对于染料废水有较好的处理效果，对于有机酸的吸附处理，生物柴油的精制过程同样具有较为理想的处理结果，是一种可以广泛应用的优良、高效、经济的新产品。
In this paper, on the basis of previous work in the laboratory,11new typemagnesium silica gels were synthetized by using sodium silicate and magnesiumchloride through Sol-gel method and hydrothermal method. Magnesium silica gelswere characterized by analytical methods of scanning electron microscopy analysis,fourier transform infrared spectroscopy analysis, hermogravimetry and differentialscanning calorimetry analysis and X-ray powder diffraction analysis. The adsorptionperformance of Magnesium silica gel adsorbed methylene blue and weak acid red wasstuyed. The adsorption time, adsorbent additive amount, initial solution pH value,temperature, the effect of initial concentration, the adsorption isotherm and kineticsequation were stuyed on adsorption performance.
Magnesium silica gel that synthetized through Sol-gel and hydrothermal arewhite functional particles, dispersion and chemical stability is good, active group isalso rich in surface, nitrogen adsorption stripping curve has obvious hysteresis loop,prone to capillary condensation phenomenon. The specific surface of magnesiumsilica gel by Sol-gel method is between120.22~330.39m2·g-1, the hydrothermalpreparation specific surface is560.40m2·g-1, with the temperature110℃andhydrothermal12h the magnesium silica gel has the largest specific surface.Roasting temperature has an important influence of specific surface and porestructure.
Through the experiment of eight kinds of sol-gel method sythtized magnesiumsilica gel adsorbed methylene blue and weak acid red, the results showed that1:5magnesium silica gel had the best adsorption effect of methylene blue, the adsorptionquantity is80mg·g-1.3:1magnesium silica gel had the best adsorption effect of weakacid red best, the adsorption quantity is200mg·g-1. Langmuir adsorption model candescribe the adsorption well, the adsorption is monolayer adsorption; Pseudo secondary dynamics equation can effectively describe the adsorption behavior, theadsorption equilibrium in was arrived in a very short period of time.
Through high temperature roasting, sepiolite, attapulgite, and commoditymagnesium silica gel were modified. By measuring the organic acid adsorption ofsepiolite, attapulgite and commodity, found that isotherm included S, C, H and L type,the Freundlich adsorption isothermal model can better describe the adsorption processof series of organic acid of attapulgite, sepiolite and magnesium silica gel, magnesiumsilica gel series materials have good adsorption treatment effect on organic acid.
On this basis, study the adsorption with11new type magnesium silica gel and3goods silicon magnesium adsorption materials of organic acids in biological diesel oil,research adsorption time, adsorbent dosing quantity and other conditions on theinfluence of adsorption performance, found that the9:1hydrothermal preparation ofmagnesium silica gel has the best adsorption, the optimum adsorption conditions is:the calcination temperature is450℃, roasting time is4h, adsorption time is6h,adsorbent additive quality is0.50g·L-1, adsorption temperature is25℃, themaximum adsorption quantity of magnesium silica gel can be up to980mg·g-1, theisothermal adsorption process accords with the Freundlich adsorption isotherm well.
Through the above experiment process, as a new adsorbent, magnesium silica gelhas good treatment effect on the adsorption of printing and dyeing wastewater,organic acids and refining process of biodiesel, is a widely used, high efficiency andlow cost product.
溶胶-凝胶法和水热法制备的硅镁胶都是白色的无定形态颗粒，分散性和化学稳定性较好，表面含有丰富的硅羟基活性基团，氮气吸附脱附曲线都有明显的滞后环，易发生毛细凝结现象；溶胶-凝胶法制备的硅镁胶的比表面积介于120.22~330.39m2·g-1之间，水热法制备的硅镁胶的比表面积可达560.40m2·g-1，在温度为110℃和水热12h的条件下制备出的硅镁胶具有最大的比表面积，焙烧温度对样品的比表面积和孔结构的影响很大。
利用溶胶-凝胶法制备的8种硅镁胶对亚甲基蓝和弱酸性红的吸附实验，结果发现镁硅比为1:5的硅镁胶对亚甲基蓝吸附效果最好，吸附量为80mg·g-1；镁硅比为3:1的硅镁胶对弱酸性红的吸附效果最好，吸附量为200mg·g-1。Langmuir吸附模型能够很好描述硅镁胶对两种染料的吸附，伪二级动力学方程能够很好地描述两种染料的吸附行为，吸附平衡在很短的时间内完成。
经高温焙烧，将海泡石、凹凸棒石和商品硅酸镁进行了改性处理。通过研究海泡石、凹凸棒石和商品硅酸镁对系列有机酸的吸附过程，确定硅酸镁材料对有机酸的吸附脱除效果。通过测定海泡石、凹凸棒石和商品硅酸镁对系列有机酸的吸附性能发现，等温线为S型、C型、H型和L型。经过计算，Freundlich吸附等温模型能够较好的描述系列有机酸在凹凸棒石、海泡石和硅酸镁上的的吸附过程，硅酸镁系列材料对有机酸有较好的吸附处理效果。
在此基础上，研究了11种新型硅镁胶和3种商品硅酸镁等全部硅镁吸附材料对生物柴油中有机酸的吸附性能，考察了吸附时间、吸附剂投加量等条件对吸附性能的影响。发现水热法制备的9:1的硅镁胶有最好的吸附效果，最佳吸附条件是：焙烧温度为450℃，焙烧时间为4h，吸附时间为6h，吸附剂投加质量为0.50g·L-1，吸附温度为25℃，硅镁胶的最大吸附量可达980mg·g-1，等温吸附过程更符合Freundlich吸附等温式。
通过上述实验发现，硅镁胶作为一种新型的硅镁吸附材料，对于染料废水有较好的处理效果，对于有机酸的吸附处理，生物柴油的精制过程同样具有较为理想的处理结果，是一种可以广泛应用的优良、高效、经济的新产品。
In this paper, on the basis of previous work in the laboratory,11new typemagnesium silica gels were synthetized by using sodium silicate and magnesiumchloride through Sol-gel method and hydrothermal method. Magnesium silica gelswere characterized by analytical methods of scanning electron microscopy analysis,fourier transform infrared spectroscopy analysis, hermogravimetry and differentialscanning calorimetry analysis and X-ray powder diffraction analysis. The adsorptionperformance of Magnesium silica gel adsorbed methylene blue and weak acid red wasstuyed. The adsorption time, adsorbent additive amount, initial solution pH value,temperature, the effect of initial concentration, the adsorption isotherm and kineticsequation were stuyed on adsorption performance.
Magnesium silica gel that synthetized through Sol-gel and hydrothermal arewhite functional particles, dispersion and chemical stability is good, active group isalso rich in surface, nitrogen adsorption stripping curve has obvious hysteresis loop,prone to capillary condensation phenomenon. The specific surface of magnesiumsilica gel by Sol-gel method is between120.22~330.39m2·g-1, the hydrothermalpreparation specific surface is560.40m2·g-1, with the temperature110℃andhydrothermal12h the magnesium silica gel has the largest specific surface.Roasting temperature has an important influence of specific surface and porestructure.
Through the experiment of eight kinds of sol-gel method sythtized magnesiumsilica gel adsorbed methylene blue and weak acid red, the results showed that1:5magnesium silica gel had the best adsorption effect of methylene blue, the adsorptionquantity is80mg·g-1.3:1magnesium silica gel had the best adsorption effect of weakacid red best, the adsorption quantity is200mg·g-1. Langmuir adsorption model candescribe the adsorption well, the adsorption is monolayer adsorption; Pseudo secondary dynamics equation can effectively describe the adsorption behavior, theadsorption equilibrium in was arrived in a very short period of time.
Through high temperature roasting, sepiolite, attapulgite, and commoditymagnesium silica gel were modified. By measuring the organic acid adsorption ofsepiolite, attapulgite and commodity, found that isotherm included S, C, H and L type,the Freundlich adsorption isothermal model can better describe the adsorption processof series of organic acid of attapulgite, sepiolite and magnesium silica gel, magnesiumsilica gel series materials have good adsorption treatment effect on organic acid.
On this basis, study the adsorption with11new type magnesium silica gel and3goods silicon magnesium adsorption materials of organic acids in biological diesel oil,research adsorption time, adsorbent dosing quantity and other conditions on theinfluence of adsorption performance, found that the9:1hydrothermal preparation ofmagnesium silica gel has the best adsorption, the optimum adsorption conditions is:the calcination temperature is450℃, roasting time is4h, adsorption time is6h,adsorbent additive quality is0.50g·L-1, adsorption temperature is25℃, themaximum adsorption quantity of magnesium silica gel can be up to980mg·g-1, theisothermal adsorption process accords with the Freundlich adsorption isotherm well.
Through the above experiment process, as a new adsorbent, magnesium silica gelhas good treatment effect on the adsorption of printing and dyeing wastewater,organic acids and refining process of biodiesel, is a widely used, high efficiency andlow cost product.
引文
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