有机改性凹凸棒土对阴离子的吸附研究
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摘要
凹凸棒土是我国储量丰富、来源广泛、成本低廉的一种无机纳米材料,具有化学稳定性强、吸附能力强的特点。本文对凹凸棒土进行酸活化后再经十八烷基三甲基氯化铵(OTMAC)改性制成有机改性凹凸棒土(SMP),以硫酸根离子为目标离子,考察其最佳改性条件。经实验得出SMP的最佳改性条件为:OTMAC的添加量为35 mmol/100 g,超声时间11 min,频极电流0.6 A,此时SMP对硫酸根离子的吸附量最大,用CHN元素分析可得到其含氮量达到3.01 At %,较未改性前提高1.8 At %。
采用红外光谱(FTIR)、热重分析(TG/TGA)、比表面积孔径分析、扫描电镜(SEM)、电子能谱(XPS)对改性前后的凹凸棒土进行结构变化分析,结果表明凹凸棒土有机改性后其表面积减少、孔道直径增加。根据扫描电镜图谱(SEM)可看出,凹凸棒土经过改性后细小的纤维状结构明显加粗;FTIR图谱可明显看到OTMAC的C-H伸缩振动,C-N的伸缩振动。综合考虑SMP的结构表征,以及OTMAC和凹凸棒土各自的结构特点,可推断出其作用机理为,凹凸棒土在溶液中表面呈现负电荷,吸引OTMAC的正电荷端,而其长碳链端在外部,同其他的OTMAC分子通过疏水键形成双分子层结构。
SMP吸附硫酸根离子的最佳工艺条件为:溶液初始pH为4,SMP添加量为0.4 g,时间为60 min,此条件下硫酸根吸附量为3.5 mg/g。通过对SMP吸附SO_4~(2-)的吸附等温线,吸附热力学,吸附动力学的研究,结果发现相较于Dubinin-Radushkevich方程和Langmuir方程,此吸附过程能够更好地符合Fredunlich方程。说明SO_4~(2-)在SMP表面上的吸附是不均匀的;热力学数据得出此吸附是吸热、熵增、自发性反应;此反应的动力学符合二级动力学方程,若将此过程分为三个阶段,每个阶段都符合粒间扩散模型。
通过对SO_4~(2-)、H_2PO_4~-、NO_3~-离子的吸附能力比较及混合体系竞争吸附试验,研究这三种离子之间的竞争关系。根据SO_4~(2-),H_2PO_4~-,NO_3~-的吸附等温线可知,最大吸附量H_2PO_4~->SO_4~(2-)>NO_3~-,由吸附量推断H_2PO_4~-的吸附较强,SO_4~(2-)和NO_3~-属于弱吸附,二者之间吸附量的差异主要由于含电量的差异。H_2PO_4~-和SO_4~(2-)两两竞争吸附中,H_2PO_4~-对SO_4~(2-)的影响远大于SO_4~(2-)对H_2PO_4~-的影响,说明H_2PO_4~-属于强竞争吸附质;而对于SO_4~(2-)和NO_3~-相比较,SO_4~(2-)属于强吸附竞争离子。
Palygorskite is a kind of low-cost and widely reserved inorganic nano-material which has the characteristics of chemical stability and strong adsorption. An extensive study on the preparation of surfactant (octodecyltrimethylammonium chloride, OTMAC) modified acid-activated palygorskite (SMP) by the method of ultrasound was performed in order to adsorb sulphate ions (SO_4~(2-)). The results showed that the optimum preparation conditions were: OTMAC addition/ acid-activated palygorskite 35 mmol/ 100 g; pH of OTMAC solution 8; reaction time 11 min; electric current 0.6 A. The adsorption amount per gram of SO_4~(2-) was the most under the condition, and its nitrogen content reached 3.01 At % according to CHN element analyzer.
In this paper, we adopted a series of characterization analysis methods, such as Fourier Transform Infrared Spectrophotometer (FTIR), Thermo gravimetric Analysis, N2-adsorption/desorption, Scanning Electron Microscope (SEM), X Ray Electron Spectrum (XPS), to analyze the structure of natural, acid-activated palygorskite and SMP. The specific surface area of SMP decreased while the average pore diameter increased, for the reason that OTMAC was too large to enter the hole of SMP, so OTMAC molecules covered on the surface and reduced its surface area. From SEM image we can see that the fibrous group got larger after modification; FTIR spectra showed that C-H stretches and C-N stretches which belong to OTMAC exist in SMP. All the analysis results showed that OTMAC had successfully grafted onto acid-activated palygorskite. Based on the molecular characteristic of OTMAC and palygorskite, the modification mechanism was that interaction between negatively charged palygorskite and positive charged end of OTMAC, and then, another OTMAC connected to it and formed bilayer structure through hydrophobic bond.
The optimum adsorption conditions were received by factorial test: pH of SO_4~(2-) solution 4; SMP addition 0.4 g; adsorption time 60 min. SO_4~(2-) adsorption amount could reach 3.5 mg/g.
The adsorption capacity of SO_4~(2-) onto SMP was investigated through adsorption isotherm equations. Compared to Dubinin-Radushkevich and Langmuir equation, the adsorption process was fit to Freundlich isotherm more, which indicated that adsorption took place at heterogeneous sites. The thermodynamics data showed that the process was an endothermic, entropy increase and spontaneous reaction. Results of kinetic experiments showed that this reaction was best described by second-order pseudo kinetics model. It was also fitted to inter-particle diffusion model when it divided to three parts.
The competition adsorption effect was investigated by contrast among SO_4~(2-), NO_3~- and H_2PO_4~- adsorption capacity and hybrid solution system of SO_4~(2-)/NO_3~- and H_2PO_4~-/SO_4~(2-). The single adsorption isotherms showed the orders of adsorption capacity were as follows: H_2PO_4~->SO_4~(2-)>NO_3~-. SO_4~(2-) and NO_3~- adsorption onto SMP was weak while H_2PO_4~- was strong from the magnitude of adsorption capacity. The difference between SO_4~(2-) and NO_3~- was due to their electric charge. The hybrid system adsorption also illustrated the competition of anions in the order of H_2PO_4~->SO_4~(2-)>NO_3~-.
采用红外光谱(FTIR)、热重分析(TG/TGA)、比表面积孔径分析、扫描电镜(SEM)、电子能谱(XPS)对改性前后的凹凸棒土进行结构变化分析,结果表明凹凸棒土有机改性后其表面积减少、孔道直径增加。根据扫描电镜图谱(SEM)可看出,凹凸棒土经过改性后细小的纤维状结构明显加粗;FTIR图谱可明显看到OTMAC的C-H伸缩振动,C-N的伸缩振动。综合考虑SMP的结构表征,以及OTMAC和凹凸棒土各自的结构特点,可推断出其作用机理为,凹凸棒土在溶液中表面呈现负电荷,吸引OTMAC的正电荷端,而其长碳链端在外部,同其他的OTMAC分子通过疏水键形成双分子层结构。
SMP吸附硫酸根离子的最佳工艺条件为:溶液初始pH为4,SMP添加量为0.4 g,时间为60 min,此条件下硫酸根吸附量为3.5 mg/g。通过对SMP吸附SO_4~(2-)的吸附等温线,吸附热力学,吸附动力学的研究,结果发现相较于Dubinin-Radushkevich方程和Langmuir方程,此吸附过程能够更好地符合Fredunlich方程。说明SO_4~(2-)在SMP表面上的吸附是不均匀的;热力学数据得出此吸附是吸热、熵增、自发性反应;此反应的动力学符合二级动力学方程,若将此过程分为三个阶段,每个阶段都符合粒间扩散模型。
通过对SO_4~(2-)、H_2PO_4~-、NO_3~-离子的吸附能力比较及混合体系竞争吸附试验,研究这三种离子之间的竞争关系。根据SO_4~(2-),H_2PO_4~-,NO_3~-的吸附等温线可知,最大吸附量H_2PO_4~->SO_4~(2-)>NO_3~-,由吸附量推断H_2PO_4~-的吸附较强,SO_4~(2-)和NO_3~-属于弱吸附,二者之间吸附量的差异主要由于含电量的差异。H_2PO_4~-和SO_4~(2-)两两竞争吸附中,H_2PO_4~-对SO_4~(2-)的影响远大于SO_4~(2-)对H_2PO_4~-的影响,说明H_2PO_4~-属于强竞争吸附质;而对于SO_4~(2-)和NO_3~-相比较,SO_4~(2-)属于强吸附竞争离子。
Palygorskite is a kind of low-cost and widely reserved inorganic nano-material which has the characteristics of chemical stability and strong adsorption. An extensive study on the preparation of surfactant (octodecyltrimethylammonium chloride, OTMAC) modified acid-activated palygorskite (SMP) by the method of ultrasound was performed in order to adsorb sulphate ions (SO_4~(2-)). The results showed that the optimum preparation conditions were: OTMAC addition/ acid-activated palygorskite 35 mmol/ 100 g; pH of OTMAC solution 8; reaction time 11 min; electric current 0.6 A. The adsorption amount per gram of SO_4~(2-) was the most under the condition, and its nitrogen content reached 3.01 At % according to CHN element analyzer.
In this paper, we adopted a series of characterization analysis methods, such as Fourier Transform Infrared Spectrophotometer (FTIR), Thermo gravimetric Analysis, N2-adsorption/desorption, Scanning Electron Microscope (SEM), X Ray Electron Spectrum (XPS), to analyze the structure of natural, acid-activated palygorskite and SMP. The specific surface area of SMP decreased while the average pore diameter increased, for the reason that OTMAC was too large to enter the hole of SMP, so OTMAC molecules covered on the surface and reduced its surface area. From SEM image we can see that the fibrous group got larger after modification; FTIR spectra showed that C-H stretches and C-N stretches which belong to OTMAC exist in SMP. All the analysis results showed that OTMAC had successfully grafted onto acid-activated palygorskite. Based on the molecular characteristic of OTMAC and palygorskite, the modification mechanism was that interaction between negatively charged palygorskite and positive charged end of OTMAC, and then, another OTMAC connected to it and formed bilayer structure through hydrophobic bond.
The optimum adsorption conditions were received by factorial test: pH of SO_4~(2-) solution 4; SMP addition 0.4 g; adsorption time 60 min. SO_4~(2-) adsorption amount could reach 3.5 mg/g.
The adsorption capacity of SO_4~(2-) onto SMP was investigated through adsorption isotherm equations. Compared to Dubinin-Radushkevich and Langmuir equation, the adsorption process was fit to Freundlich isotherm more, which indicated that adsorption took place at heterogeneous sites. The thermodynamics data showed that the process was an endothermic, entropy increase and spontaneous reaction. Results of kinetic experiments showed that this reaction was best described by second-order pseudo kinetics model. It was also fitted to inter-particle diffusion model when it divided to three parts.
The competition adsorption effect was investigated by contrast among SO_4~(2-), NO_3~- and H_2PO_4~- adsorption capacity and hybrid solution system of SO_4~(2-)/NO_3~- and H_2PO_4~-/SO_4~(2-). The single adsorption isotherms showed the orders of adsorption capacity were as follows: H_2PO_4~->SO_4~(2-)>NO_3~-. SO_4~(2-) and NO_3~- adsorption onto SMP was weak while H_2PO_4~- was strong from the magnitude of adsorption capacity. The difference between SO_4~(2-) and NO_3~- was due to their electric charge. The hybrid system adsorption also illustrated the competition of anions in the order of H_2PO_4~->SO_4~(2-)>NO_3~-.
引文
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