微波强化水合碱式碳酸镁反应结晶过程研究
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摘要
水合碱式碳酸镁是一种应用广泛的重要镁质无机化工产品。以氯化镁为原料,制备高性能、高附加值的功能碳酸镁材料,将碳酸镁产品系列化、功能化、微细化、专用化是镁资源开发利用的一个重要发展方向。
本文在微波外场下,以MgCl2溶液为镁源,Na2CO3或NaHCO3溶液为沉淀剂,选择合适条件与MgCl2溶液进行均相结晶反应,直接合成水合碱式碳酸镁。通过对反应液中Mg2+含量追踪及产物XRD、FT-IR、EM表征研究该反应结晶历经过程,考察了反应温度、物料浓度、NaCl底料添加、pH值及溶液搅拌等主要工艺参数对反应过程和水合碱式碳酸镁最终形貌的影响。
水合碱式碳酸镁晶体的合成是通过形成絮状无定形物或是介稳溶液,逐步相转移的反应结晶过程。实验表明：温度、反应物浓度、体系pH值、搅拌等反应条件都对反应结晶过程有较大影响；温度升高、反应物浓度增大、pH值升高、搅拌转速增大均能加快反应速度；而各工艺参数对于产物形貌影响较为复杂,温度升高,物料浓度较低,粒径越大；pH值较高,则片层变薄易结块团聚；搅拌转速降低,粒径越大。通过条件优化,获得了制备的比表面积较大的球状颗粒的方法。
通过考察微波和水浴加热方式对水合碱式碳酸镁反应结晶过程影响,发现：微波能强化该反应结晶体系,促进反应结晶的成核、相转移、生长各个阶段,反应速率更快,产物颗粒粒径较大。
以粒数衡算方程为理论基础,对微波场下的碱式碳酸镁结晶生长动力学进行研究。通过对经典的反应结晶生长速率模型进行筛选对比,发现Bransom模型能较好的描述水合碱式碳酸镁结晶生长过程。在微波条件下,晶体生长速率方程为Gt=0.25×L-0.2；在水浴下,晶体生长速率与粒度L的指数关系为L-1.24。实验数据表明,加热方式对晶体生长速率方程与粒度关系有影响,在微波条件下晶体生长速率的受粒度影响小。
Hydromagnesite (hydrated magnesium carbonate hydroxide) is a kind of important and widely used magnesium inorganic materials. The new development direction for magnesium resources utilization is that the inexpressive and abundant magnesium chloride in salt lake is used as raw material to prepare the functional magnesium carbonate with excellent performance and high additional value, making the product serialization, functionalization and specialization.
In this article, MgCl2 solution was used as magnesium source and Na2CO3 or NaHCO3 solution was used as precipitant, and hydromagnesite was directly synthesis by the reaction crystallization process when the two solutions were mixed under the microwave field. The prepared hydromagnesite was characterized by XRD, FT-IR, and SEM. The effects of the reaction conditions on the crystal product and the reaction course were investigated, where the reaction conditions included reaction temperature, reactant concentrations, NaCl concentration, pH value, stirring speed and so on.
The results showed that the reaction crystallization process in this system involved the phase transition. That is, the amorphous material or metastable solution was formed firstly, and then it gradually transited to hydromagnesite crystal. Reaction temperature, reactant concentrations, pH value and stirring speed had great influences on the reaction crystallization process. Increase of reaction temperature, reactant concentrations, pH value and stirring speed could accelerate the reaction rate, while the effect of these reaction conditions on the morphology of hydromagnesite crystal became more complex. The higher the reaction temperature was, the larger the particle size of the prepared hydromagnesite crystal was. The higher the reactant concentration was, the smaller the crystal size of hydromagnesite was. With the increase of pH value in the solution, the layers of the crystal became thinner and the crystal particle became easy to agglomerate. With the decrease of stirring speed, the particle size of crystal increased. Based on the experimental optimization, a new method to prepare the spherical crystal of hydromagnesite with a large specific surface area was developed.
Comparing the reaction crystallization processes carried out under microwave field and under water-bath, it was found that microwave could enhance the reaction crystallization process, especially for the nucleation, phase transfer, growth of hydromagnesite crystal. And it also could increase the reaction rate and make the particle size of crystal bigger under microwave field.
Furthermore, the crystallization kinetics of hydromagnesite under microwave field was studied. Based on the PBE (population balance equation) and the population density data of hydromagnesite crystal, the growth rate model of crystal was determined by comparing the classical size-dependent growth rate models. It was found that the Bransom model could easily and accurately describe the crystal growth for this reaction system. Under the microwave field, the growth rate equation of hydromagnesite crystal was obtained as Gt=0.25 x L-0.2. In the water-bath, the relationship between the crystal growth rate and the particle size L of crystal was L-1.24. This result proved that the heating method affected the relationship between the crystal growth rate and the crystal particle size, and the crystal size had less effect on the crystal growth rate under the microwave field.
本文在微波外场下,以MgCl2溶液为镁源,Na2CO3或NaHCO3溶液为沉淀剂,选择合适条件与MgCl2溶液进行均相结晶反应,直接合成水合碱式碳酸镁。通过对反应液中Mg2+含量追踪及产物XRD、FT-IR、EM表征研究该反应结晶历经过程,考察了反应温度、物料浓度、NaCl底料添加、pH值及溶液搅拌等主要工艺参数对反应过程和水合碱式碳酸镁最终形貌的影响。
水合碱式碳酸镁晶体的合成是通过形成絮状无定形物或是介稳溶液,逐步相转移的反应结晶过程。实验表明：温度、反应物浓度、体系pH值、搅拌等反应条件都对反应结晶过程有较大影响；温度升高、反应物浓度增大、pH值升高、搅拌转速增大均能加快反应速度；而各工艺参数对于产物形貌影响较为复杂,温度升高,物料浓度较低,粒径越大；pH值较高,则片层变薄易结块团聚；搅拌转速降低,粒径越大。通过条件优化,获得了制备的比表面积较大的球状颗粒的方法。
通过考察微波和水浴加热方式对水合碱式碳酸镁反应结晶过程影响,发现：微波能强化该反应结晶体系,促进反应结晶的成核、相转移、生长各个阶段,反应速率更快,产物颗粒粒径较大。
以粒数衡算方程为理论基础,对微波场下的碱式碳酸镁结晶生长动力学进行研究。通过对经典的反应结晶生长速率模型进行筛选对比,发现Bransom模型能较好的描述水合碱式碳酸镁结晶生长过程。在微波条件下,晶体生长速率方程为Gt=0.25×L-0.2；在水浴下,晶体生长速率与粒度L的指数关系为L-1.24。实验数据表明,加热方式对晶体生长速率方程与粒度关系有影响,在微波条件下晶体生长速率的受粒度影响小。
Hydromagnesite (hydrated magnesium carbonate hydroxide) is a kind of important and widely used magnesium inorganic materials. The new development direction for magnesium resources utilization is that the inexpressive and abundant magnesium chloride in salt lake is used as raw material to prepare the functional magnesium carbonate with excellent performance and high additional value, making the product serialization, functionalization and specialization.
In this article, MgCl2 solution was used as magnesium source and Na2CO3 or NaHCO3 solution was used as precipitant, and hydromagnesite was directly synthesis by the reaction crystallization process when the two solutions were mixed under the microwave field. The prepared hydromagnesite was characterized by XRD, FT-IR, and SEM. The effects of the reaction conditions on the crystal product and the reaction course were investigated, where the reaction conditions included reaction temperature, reactant concentrations, NaCl concentration, pH value, stirring speed and so on.
The results showed that the reaction crystallization process in this system involved the phase transition. That is, the amorphous material or metastable solution was formed firstly, and then it gradually transited to hydromagnesite crystal. Reaction temperature, reactant concentrations, pH value and stirring speed had great influences on the reaction crystallization process. Increase of reaction temperature, reactant concentrations, pH value and stirring speed could accelerate the reaction rate, while the effect of these reaction conditions on the morphology of hydromagnesite crystal became more complex. The higher the reaction temperature was, the larger the particle size of the prepared hydromagnesite crystal was. The higher the reactant concentration was, the smaller the crystal size of hydromagnesite was. With the increase of pH value in the solution, the layers of the crystal became thinner and the crystal particle became easy to agglomerate. With the decrease of stirring speed, the particle size of crystal increased. Based on the experimental optimization, a new method to prepare the spherical crystal of hydromagnesite with a large specific surface area was developed.
Comparing the reaction crystallization processes carried out under microwave field and under water-bath, it was found that microwave could enhance the reaction crystallization process, especially for the nucleation, phase transfer, growth of hydromagnesite crystal. And it also could increase the reaction rate and make the particle size of crystal bigger under microwave field.
Furthermore, the crystallization kinetics of hydromagnesite under microwave field was studied. Based on the PBE (population balance equation) and the population density data of hydromagnesite crystal, the growth rate model of crystal was determined by comparing the classical size-dependent growth rate models. It was found that the Bransom model could easily and accurately describe the crystal growth for this reaction system. Under the microwave field, the growth rate equation of hydromagnesite crystal was obtained as Gt=0.25 x L-0.2. In the water-bath, the relationship between the crystal growth rate and the particle size L of crystal was L-1.24. This result proved that the heating method affected the relationship between the crystal growth rate and the crystal particle size, and the crystal size had less effect on the crystal growth rate under the microwave field.
引文
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[2]青海省科学技术厅高新技术及产业化处.盐湖资源综合利用金属镁一体化项目及其发展前景展望[J].青海科技,2010,17(1)：9-12.
[3]王渠东,丁文江.镁合金研究开发现状与展望[J].世界有色金属,2004,(7)：8-11.
[4]胡庆福.镁化合物生产与应用[M].北京：化学工业出版社,2004.
[5]天津化工研究院.无机盐工业手册(下册)[M].第二版.北京：化学工业出版社,1996.
[6]吴健失,方建华.碱式碳酸镁对高冲聚苯乙烯的阻燃作用[J].兰化科技,1989,7(3)：175-179.
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