硫酸钙处理含磷废水特性研究及机理探讨
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摘要
目前,应用工业副产物吸附处理含磷废水的水处理技术是研究热点。本文以硫酸钙为研究对象,首先制备了微米硫酸钙晶须及纳米硫酸钙粉体二种具有特殊结构的硫酸钙产品。微米硫酸钙晶须采用水热法制备,探讨了成核剂ZWP-A、表面活性剂CTAB及温度的影响。纳米硫酸钙采用乳液法,探讨了原料浓度、偶联剂KH550、CTAB、温度、超声辅助、搅拌强度的影响。试验表明:在适量的ZWP-A溶液中,加入少量的CTAB即可在常温下制备得到微米硫酸钙晶须;控制原料浓度(Na_2SO_4和CaCl_2)均为0.10mol/L,CTAB浓度为1.8mmol/L,偶联剂KH550为0.027mol/L,搅拌转速为700r/min,超声时间1h,可制备出直径为50~100nm硫酸钙纳米棒。对常用工业级硫酸钙、微米硫酸钙晶须、纳米硫酸钙粉体进行除磷试验,考查不同参数对除磷效果的影响。研究结果表明:工业级硫酸钙1h对磷去除率稳定在80%,而微米硫酸钙晶须及纳米硫酸钙则在相同条件下15min内去除率即达到95%,处理完废水磷含量达到国家废水一级排放标准;硫酸钙粒径、废水酸碱度、含磷初始浓度、投加量对除磷影响较大,硫酸钙处理含磷废水较佳的工艺参数为:偏碱性的废水(pH>10)、较小的含磷浓度(<20mg/L)、投加量0.5~0.8g/L。
本文通过热力学和动力学方程线性拟合,研究了硫酸钙在处理含磷废水时的相关特性,探讨了硫酸钙除磷机理。结果表明,工业级硫酸钙等温除磷过程符合D-R方程模型,粒径尺寸对其动力学过程影响较大;微米硫酸钙晶须除磷过程类似理想化学吸附特性,符合Langmuir方程、Temkin方程,线性相关度都达到了0.99,动力学拟合结果符合准二级反应动力学模型方程;纳米硫酸钙除磷等温过程最适模型为Temkin方程,其最适合动力学方程为准二级反应动力学模型方程。
In recent years, industrial by-products have been used as adsorbents for the removal of phosphate from wastewater.In the study,calcium sulfate was taken for trial. Micron-Calcium Sulfate whisker and nano-Calcium Sulfate were synthesized firstly. The ZWP-A,CTAB,temperature were investigated in the hydrothermal method. Nano-calcium sulfate was Synthesized by emulsion menthod. Raw material concentration, silane coupling agent KH550, temperature, ultrasonic, mixing intensity which were accounted as the mainly factors in the Synthesis were discussed in the exeperiment. It is showed that diameter 50 ~ 100nm calcium sulfate nano-tube could be synthesized when Na_2SO_4 and CaCl_2 concentration was 0.10mol/L, the concentration of CTAB was 1.8mmol/L, the concentration of KH550 was 0.027mol/L under 700r/min stirring speed and 1h ultrasonic .
Industrial grade calcium sulfate, micron -calcium sulfate whisker, nano- Calcium sulfate were applied for Phosphorus Removal trial. The different effects were investigated.The results showed that removal rate of Industrial grade calcium sulfate stabilize at 80% in 1h ,and the micron -calcium sulfate whisker, nano-Calcium sulfate apparently had a higher Efficiency.The removal rate was more than 90% in 15min Operating time , and drainage comply with the national standard. Generally ,advantageous process parameters for phosphorus removal was below:alkaline waste water (pH> 10), the lower phosphorus concentration (<20mg/L), dosage of 0.5~0.8g/L.
Linear fit of thermodynamics and kinetics equation was applied for the phosphorus removal mechanism discuss on the base of experiment.The results showed that D-R isothermal equation suited to describe three kinds of different size range of industrial-grade calcium sulfate with higher Linear correlation.Factually,the dynamic process was so complex, the results showed the particle size has a greater impact through the proess. Removal process of Micron-calcium sulfate whisker is in line with the characteristics of ideal chemical adsorption. Langmuir equation, Temkin equation has a high degree of linear correlation above 0.99, Kinetic fitting results showed that quasi-second kinetic equation fit to the proess. Removal process of Nano-calcium sulfate is in line with Temkin isothermal equation, and the most appropriate kinetic equation subject to second-order reaction kinetic equation.
本文通过热力学和动力学方程线性拟合,研究了硫酸钙在处理含磷废水时的相关特性,探讨了硫酸钙除磷机理。结果表明,工业级硫酸钙等温除磷过程符合D-R方程模型,粒径尺寸对其动力学过程影响较大;微米硫酸钙晶须除磷过程类似理想化学吸附特性,符合Langmuir方程、Temkin方程,线性相关度都达到了0.99,动力学拟合结果符合准二级反应动力学模型方程;纳米硫酸钙除磷等温过程最适模型为Temkin方程,其最适合动力学方程为准二级反应动力学模型方程。
In recent years, industrial by-products have been used as adsorbents for the removal of phosphate from wastewater.In the study,calcium sulfate was taken for trial. Micron-Calcium Sulfate whisker and nano-Calcium Sulfate were synthesized firstly. The ZWP-A,CTAB,temperature were investigated in the hydrothermal method. Nano-calcium sulfate was Synthesized by emulsion menthod. Raw material concentration, silane coupling agent KH550, temperature, ultrasonic, mixing intensity which were accounted as the mainly factors in the Synthesis were discussed in the exeperiment. It is showed that diameter 50 ~ 100nm calcium sulfate nano-tube could be synthesized when Na_2SO_4 and CaCl_2 concentration was 0.10mol/L, the concentration of CTAB was 1.8mmol/L, the concentration of KH550 was 0.027mol/L under 700r/min stirring speed and 1h ultrasonic .
Industrial grade calcium sulfate, micron -calcium sulfate whisker, nano- Calcium sulfate were applied for Phosphorus Removal trial. The different effects were investigated.The results showed that removal rate of Industrial grade calcium sulfate stabilize at 80% in 1h ,and the micron -calcium sulfate whisker, nano-Calcium sulfate apparently had a higher Efficiency.The removal rate was more than 90% in 15min Operating time , and drainage comply with the national standard. Generally ,advantageous process parameters for phosphorus removal was below:alkaline waste water (pH> 10), the lower phosphorus concentration (<20mg/L), dosage of 0.5~0.8g/L.
Linear fit of thermodynamics and kinetics equation was applied for the phosphorus removal mechanism discuss on the base of experiment.The results showed that D-R isothermal equation suited to describe three kinds of different size range of industrial-grade calcium sulfate with higher Linear correlation.Factually,the dynamic process was so complex, the results showed the particle size has a greater impact through the proess. Removal process of Micron-calcium sulfate whisker is in line with the characteristics of ideal chemical adsorption. Langmuir equation, Temkin equation has a high degree of linear correlation above 0.99, Kinetic fitting results showed that quasi-second kinetic equation fit to the proess. Removal process of Nano-calcium sulfate is in line with Temkin isothermal equation, and the most appropriate kinetic equation subject to second-order reaction kinetic equation.
引文
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