ZnAl类水滑石吸附水中磷的特征和机制研究
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摘要
本文以处理废水中的磷为目的,研制出不同沉淀反应时间的ZnAl类水滑石吸附剂,分析了该吸附剂对水中磷(磷酸根)的吸附特征和作用机制。
本文采用尿素分解共沉淀法制备了一系列ZnAl类水滑石,考察了制备ZnAl类水滑石的沉淀反应时间对其结构和吸附磷性能的影响。研究结果表明,随着沉淀反应时间由12h增加至96h,制得的ZnAl化合物均具有典型的类水滑石层状晶体结构,但其中的Zn/Al摩尔比由2.06降至0.70,比表面积由14.12升至112.68m2.g-1,平均孔径由104.023nm降至59.552nm。样品中A13+比例升高引起的层板正电性增强以及样品比表面积的升高引起了ZnAl类水滑石对水中磷酸根的吸附性能总体上呈现随着其沉淀反应时间增加而逐渐增强的趋势。但是,当沉淀反应时间为24h时,得到的ZnAl类水滑石(ZnAl-24)由于其很高的可交换阴离子含量而具有较高的磷酸根吸附性能,其在25℃的饱和吸附量(以P计)约为34.5mg P·g-1,吸附过程主要以层间阴离子交换作用为主。沉淀反应时间为96h时,制得的ZnAl类水滑石(ZnAl-96)也具有很高的磷吸附性能,25℃的饱和吸附量约为25mgP·g-1。此外,不同沉淀反应时间制得的ZnAl类水滑石在不同温度(25℃、30℃、40℃、50℃、60℃)下测定的磷吸附等温线结果显示ZnAl-24表现为Langmuir型,ZnAl-96则表现为Freundlich型；两者吸附磷动力学方程均符合准二级。ZnAl-24吸附磷酸根的过程中△H0<0,属于放热反应；而ZnAl-96吸附磷酸根的过程中△H0>0,为吸热反应。pH值对ZnAl类水滑石中Zn2+和A13+的溶出变化影响不大,但对其吸附磷的性能影响较大。在酸性和中性条件下磷的吸附量较大,碱性条件下磷吸附量急剧减少。共存离子对ZnAl类水滑石吸附磷的性能均有不同程度抑制作用,并且随共存离子浓度的增加抑制作用增强,原因被认为是共存离子与磷酸根形成了竞争吸附。
类水滑石吸附磷酸根后固液相的变化结果分析发现,载磷ZnAl类水滑石的XRD图谱并无明显变化,说明磷酸盐沉淀很少,表面沉淀在ZnAl类水滑石吸附磷酸根的过程中作用不大, FT-IR图谱分析说明吸附在类水滑石上的磷是以磷酸根的形态存在的。对比分析ZnAl类水滑石吸附磷酸根前后的固液组成,溶液pH值的变化和解吸实验结果,得出ZnAl-24对水中磷的吸附是以层间阴离子交换作用为主；而ZnAl-96是以表面物理化学吸附为主。
On the purpose of removing phosphorus from wastewater, ZnAl layered double hydroxides (LDH) with different precipitation time were developed and their phosphate adsorption characteristics and mechanisms were analyzed.
A series of ZnAl LDH were prepared and the effect of reaction time of precipitation on the structure and phosphate adsorption capacity was studied. The results show that all the samples had a typical structure of LDH. With the reaction time extending from12h to96h, the Zn/Al molar ratio decreased from2.06to0.70, average pore size reduced from104.02to59.55nm and specific surface area increased from14.12to112.68m2·g-1.Phosphate adsorption capacity of the ZnAl was in general increased gradually with the reaction time extending, which can be attributed to the surface area rising as well as the increased positive charge of the LDHs layer caused by a higher proportion of Al. With a preparation time of24h, however, a high amount of exchangeable interlayer anions was seen, giving rise to a highest phosphate uptake of34.5mg P·g-1by the ZnAI-24. This reveals that ion exchange would have played an important role during the phosphate adsorption. When the preparation time was96h, the obtained LDH also had a high capacity of phosphate of25mg P·g-1at25℃. Isotherms of phosphate adsorption by ZnAI-24(LDH with a preparation time of24h) fit well with a Langmuir equation; whereas the isotherms with ZnAl-96(LDH with a preparation time of96h) had a good agreement with a Freundlich equation. The adsorption kinetics of both ZnAl fit well with pseudo-second-order models. For the phosphate adsorption on ZnAl-24, ΔH0is less than0suggesting an exodothemic process; as for ZnAl-96the adsorption is endothermic sinceΔH0is positive. pH level of the solution did not impose an markedly influence on the dissolution of ZnAl, but obviously affected the phosphate adsorption capacity. In alkaline environment, phosphate adsorption capacity of ZnAl decreased dramatically. All the coexisting ions investigated had noticeable inhibition on the phosphate adsorption on ZnAl, which was more obvious with the concentration of ions rose. The reason could be the competition of adsorption sites for phosphate and coexisting ions.
Analyses of solid and liquid phases during phosphate adsorption show that the variation of XRD patterns of LDH was negligible, which indicates that surface precipitation of phosphate did not contribute much to the total phosphate removal. FT-IR spectra confirm phosphate ions on the phosphated LDH. By comparing the composition of solid and liquid phases and pH during the phosphate adsorption, and the results from desorption assays, it is suggested that phosphate uptake on ZnAl-24is mainly due to ion exchange between the interlayer anions and phosphate ions while the phosphate uptake on ZnAI-96is largely attributed to physico-chemical adsorption.
本文采用尿素分解共沉淀法制备了一系列ZnAl类水滑石,考察了制备ZnAl类水滑石的沉淀反应时间对其结构和吸附磷性能的影响。研究结果表明,随着沉淀反应时间由12h增加至96h,制得的ZnAl化合物均具有典型的类水滑石层状晶体结构,但其中的Zn/Al摩尔比由2.06降至0.70,比表面积由14.12升至112.68m2.g-1,平均孔径由104.023nm降至59.552nm。样品中A13+比例升高引起的层板正电性增强以及样品比表面积的升高引起了ZnAl类水滑石对水中磷酸根的吸附性能总体上呈现随着其沉淀反应时间增加而逐渐增强的趋势。但是,当沉淀反应时间为24h时,得到的ZnAl类水滑石(ZnAl-24)由于其很高的可交换阴离子含量而具有较高的磷酸根吸附性能,其在25℃的饱和吸附量(以P计)约为34.5mg P·g-1,吸附过程主要以层间阴离子交换作用为主。沉淀反应时间为96h时,制得的ZnAl类水滑石(ZnAl-96)也具有很高的磷吸附性能,25℃的饱和吸附量约为25mgP·g-1。此外,不同沉淀反应时间制得的ZnAl类水滑石在不同温度(25℃、30℃、40℃、50℃、60℃)下测定的磷吸附等温线结果显示ZnAl-24表现为Langmuir型,ZnAl-96则表现为Freundlich型；两者吸附磷动力学方程均符合准二级。ZnAl-24吸附磷酸根的过程中△H0<0,属于放热反应；而ZnAl-96吸附磷酸根的过程中△H0>0,为吸热反应。pH值对ZnAl类水滑石中Zn2+和A13+的溶出变化影响不大,但对其吸附磷的性能影响较大。在酸性和中性条件下磷的吸附量较大,碱性条件下磷吸附量急剧减少。共存离子对ZnAl类水滑石吸附磷的性能均有不同程度抑制作用,并且随共存离子浓度的增加抑制作用增强,原因被认为是共存离子与磷酸根形成了竞争吸附。
类水滑石吸附磷酸根后固液相的变化结果分析发现,载磷ZnAl类水滑石的XRD图谱并无明显变化,说明磷酸盐沉淀很少,表面沉淀在ZnAl类水滑石吸附磷酸根的过程中作用不大, FT-IR图谱分析说明吸附在类水滑石上的磷是以磷酸根的形态存在的。对比分析ZnAl类水滑石吸附磷酸根前后的固液组成,溶液pH值的变化和解吸实验结果,得出ZnAl-24对水中磷的吸附是以层间阴离子交换作用为主；而ZnAl-96是以表面物理化学吸附为主。
On the purpose of removing phosphorus from wastewater, ZnAl layered double hydroxides (LDH) with different precipitation time were developed and their phosphate adsorption characteristics and mechanisms were analyzed.
A series of ZnAl LDH were prepared and the effect of reaction time of precipitation on the structure and phosphate adsorption capacity was studied. The results show that all the samples had a typical structure of LDH. With the reaction time extending from12h to96h, the Zn/Al molar ratio decreased from2.06to0.70, average pore size reduced from104.02to59.55nm and specific surface area increased from14.12to112.68m2·g-1.Phosphate adsorption capacity of the ZnAl was in general increased gradually with the reaction time extending, which can be attributed to the surface area rising as well as the increased positive charge of the LDHs layer caused by a higher proportion of Al. With a preparation time of24h, however, a high amount of exchangeable interlayer anions was seen, giving rise to a highest phosphate uptake of34.5mg P·g-1by the ZnAI-24. This reveals that ion exchange would have played an important role during the phosphate adsorption. When the preparation time was96h, the obtained LDH also had a high capacity of phosphate of25mg P·g-1at25℃. Isotherms of phosphate adsorption by ZnAI-24(LDH with a preparation time of24h) fit well with a Langmuir equation; whereas the isotherms with ZnAl-96(LDH with a preparation time of96h) had a good agreement with a Freundlich equation. The adsorption kinetics of both ZnAl fit well with pseudo-second-order models. For the phosphate adsorption on ZnAl-24, ΔH0is less than0suggesting an exodothemic process; as for ZnAl-96the adsorption is endothermic sinceΔH0is positive. pH level of the solution did not impose an markedly influence on the dissolution of ZnAl, but obviously affected the phosphate adsorption capacity. In alkaline environment, phosphate adsorption capacity of ZnAl decreased dramatically. All the coexisting ions investigated had noticeable inhibition on the phosphate adsorption on ZnAl, which was more obvious with the concentration of ions rose. The reason could be the competition of adsorption sites for phosphate and coexisting ions.
Analyses of solid and liquid phases during phosphate adsorption show that the variation of XRD patterns of LDH was negligible, which indicates that surface precipitation of phosphate did not contribute much to the total phosphate removal. FT-IR spectra confirm phosphate ions on the phosphated LDH. By comparing the composition of solid and liquid phases and pH during the phosphate adsorption, and the results from desorption assays, it is suggested that phosphate uptake on ZnAl-24is mainly due to ion exchange between the interlayer anions and phosphate ions while the phosphate uptake on ZnAI-96is largely attributed to physico-chemical adsorption.
引文
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