改性膨润土的制备及其吸附性能研究
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摘要
膨润土(Bentonite)是以蒙脱石(Montmorillonite)为主要成分的一类层状硅酸盐粘土矿物。利用膨润土的离子交换性,膨润土可以与简单金属离子、有机季胺盐阳离子进行层间离子交换,达到改性目的。改性后,其层间域、吸附性能等理化性能得到明显改善,并在环境治理领域得到广泛关注。论文针对鄂州膨润土开发应用研究比较薄弱的现状,详细研究了鄂州某地膨润土的基本理化性质和类型,并针对其性能指标重点研究了该膨润土的钠化改型和有机插层的最佳工艺及条件,并将所制备的改性膨润土应用于对含Cu~(2+)和餐饮含油废水中,详细研究了鄂州膨润土对水中重金属离子和有机物油份的吸附性能。
鄂州天然膨润土的纯度不高,蒙脱石含量为73.8%,而在膨润土的改性和深加工时,要求蒙脱石的含量达到90%以上,因此膨润土的提纯显得尤为重要。论文采用沉降提纯工艺提纯,通过对吸蓝量的测定,提纯后其蒙脱石含量提高到93.4%。
通过单因素实验,确定了膨润土钠化改型的较佳工艺条件:碳酸钠为改型剂,用量为5%,矿浆浓度15%,搅拌时间15min。钠化改型后膨润土的理化性能得到明显提高,胶质价和膨胀容分别由原矿的100mL/15g,11.0mL/g提高到500mL/15g,72.0mL/g,X射线衍射图谱分析表明d_(001)值由原来的1.53nm变为1.24nm,层间域的Ca~(2+)被Na~+交换,由钙基膨润土变为钠基膨润土。
膨润土的有机改性研究中,重点研究了十八烷基三甲基氯化铵(1831)改性膨润土的各项影响因素,并制备出了一系列有机膨润土。根据层间域的大小(即d_(001)值)作为有机膨润土制备效果评价指标,并结合衍射峰的数量、峰强、峰的尖锐性和峰的对称性来加以综合评价。确定了有机膨润土的较佳制备工艺:矿浆浓度5%,有机插层前洗涤3次,覆盖剂用量40%,反应温度65℃,反应时间7h。经有机改性后,其d_(001)值可达4.167nm。
论文利用提纯钙基膨润土、钠基膨润土和有机膨润土三种粉末作为吸附剂,分别对含Cu~(2+)废水和模拟餐饮含油废水进行系统吸附研究,通过吸附动力学曲线和等温吸附线来比较对重金属离子和含油废水的吸附性能。结果表明:钠基膨润土对Cu~(2+)的吸附效果最好,有机膨润土(1831-膨润土)对油份的吸附效果最好。论文通过建立膨润土改性模型,更加直观地说明了其改性机理,清晰地展示其内部变化过程。结合红外扫描技术,将有机膨润土对油份的吸附过程清晰地展现出来,并通过红外图谱来阐述其内部结构的变化,说明有机膨润土对油份的吸附包括物理吸附和化学吸附,主要为化学吸附。
Bentonite is a clay mineral with expandable layer structures that primary constituent of montmorillonite. Modification of bentonite can be prepared by exchanging the cation interbedded with simple metal cation, quaternary ammoniumcanons. The physical and chemical capability of the modified bentonite improved obviously, such as d_(001), adsorb hydrophobic contaminants after the modification. And the modified bentonites are used as sorbents to treat various wastewater and have a lot of applications in environmental protection.
There is little research on exploitation and application of Ezhou bentonite. In allusion to the actuality, this dissertation studies the basis physical and chemical characters and the types of Ezhou bentonite particularly. Special attention is paid to the best technical condition of Na-modification and organ-intercalation. And modified bentomtes are used as sorbents to treat Cu(II) wastewater and oily wastewater. The adsorption capability of Ezhou bentonite is discussed detailedly.
The montmorillonite content of nature bentonite in Ezhou is low, only 73.8%. It is obviously important to purify the bentonite as the require content is above 90% in the modification and farther process of bentonite. This article uses sedimentation technics to purify bentonite. The montmorillonite content increases to 93.4%.
The best technic conditions of Na-modification are ascertained via single factor experiment: selecting Na_2CO_3 as modifying addition, amount 5%, pulp density 15%, and stirring time 15min. The physical and chemical capability enhanced evidently, after the Na-modification. The colloid index and expansive capacity arrive to 500mL/15g, 72.0mL/g from the primary 100mL/15g, 11.0mL/g. It indicates that the Ca-bentonite changes into Na-bentonite as the d_(001) decreases to 1.24nm from 1.53nm and Ca~(2+) are changed by Na~+ in the X-ray diffraction patterns.
Diversified factors are studied the modification of octadecyl trimethyl ammonium chloride (1831) on Na-bentonite in the research of organ-modification. This dissertation prepares a series of organ-bentonite. It takes the size of interlayer field as estimate index to evaluate the preparation effect, combing with the intensity, the acuity and the symmetry of diffraction apices. The best technic conditions of organ-modification are: pulp density 5%, wash the sample for 3 times before organic intercalation, amount 30%, temperature 65℃, and stirring time 7h. The d_(001) increases to 4.167nm.
Systematic research of adsorption experiment is carried to study the each adsorption behavior of Cu(II) and oily wastewater on the three sorbents: purified Ca-bentonite, Na-bentonite and organobentonite. Comparer with the adsorption capacity of Cu(II) and oily wastewater through adsorption kinetic curve and isothermal absorption curve. Results show, the best adsorbent of Cu(II) is Na-bentonite while the best adsorbent of oily wastewater is organobentonite. Modification model is proposed to explain the modification mechanism and show the change process inside. Using FTIR, they show the adsorption process of oily wastewater on organobentonite, explain the inner structure change, and indicate that it includes physical adsorption and chemical adsorption for organobentonite to adsorb oily wastewater, and chemical adsorption takes advantage.
鄂州天然膨润土的纯度不高,蒙脱石含量为73.8%,而在膨润土的改性和深加工时,要求蒙脱石的含量达到90%以上,因此膨润土的提纯显得尤为重要。论文采用沉降提纯工艺提纯,通过对吸蓝量的测定,提纯后其蒙脱石含量提高到93.4%。
通过单因素实验,确定了膨润土钠化改型的较佳工艺条件:碳酸钠为改型剂,用量为5%,矿浆浓度15%,搅拌时间15min。钠化改型后膨润土的理化性能得到明显提高,胶质价和膨胀容分别由原矿的100mL/15g,11.0mL/g提高到500mL/15g,72.0mL/g,X射线衍射图谱分析表明d_(001)值由原来的1.53nm变为1.24nm,层间域的Ca~(2+)被Na~+交换,由钙基膨润土变为钠基膨润土。
膨润土的有机改性研究中,重点研究了十八烷基三甲基氯化铵(1831)改性膨润土的各项影响因素,并制备出了一系列有机膨润土。根据层间域的大小(即d_(001)值)作为有机膨润土制备效果评价指标,并结合衍射峰的数量、峰强、峰的尖锐性和峰的对称性来加以综合评价。确定了有机膨润土的较佳制备工艺:矿浆浓度5%,有机插层前洗涤3次,覆盖剂用量40%,反应温度65℃,反应时间7h。经有机改性后,其d_(001)值可达4.167nm。
论文利用提纯钙基膨润土、钠基膨润土和有机膨润土三种粉末作为吸附剂,分别对含Cu~(2+)废水和模拟餐饮含油废水进行系统吸附研究,通过吸附动力学曲线和等温吸附线来比较对重金属离子和含油废水的吸附性能。结果表明:钠基膨润土对Cu~(2+)的吸附效果最好,有机膨润土(1831-膨润土)对油份的吸附效果最好。论文通过建立膨润土改性模型,更加直观地说明了其改性机理,清晰地展示其内部变化过程。结合红外扫描技术,将有机膨润土对油份的吸附过程清晰地展现出来,并通过红外图谱来阐述其内部结构的变化,说明有机膨润土对油份的吸附包括物理吸附和化学吸附,主要为化学吸附。
Bentonite is a clay mineral with expandable layer structures that primary constituent of montmorillonite. Modification of bentonite can be prepared by exchanging the cation interbedded with simple metal cation, quaternary ammoniumcanons. The physical and chemical capability of the modified bentonite improved obviously, such as d_(001), adsorb hydrophobic contaminants after the modification. And the modified bentonites are used as sorbents to treat various wastewater and have a lot of applications in environmental protection.
There is little research on exploitation and application of Ezhou bentonite. In allusion to the actuality, this dissertation studies the basis physical and chemical characters and the types of Ezhou bentonite particularly. Special attention is paid to the best technical condition of Na-modification and organ-intercalation. And modified bentomtes are used as sorbents to treat Cu(II) wastewater and oily wastewater. The adsorption capability of Ezhou bentonite is discussed detailedly.
The montmorillonite content of nature bentonite in Ezhou is low, only 73.8%. It is obviously important to purify the bentonite as the require content is above 90% in the modification and farther process of bentonite. This article uses sedimentation technics to purify bentonite. The montmorillonite content increases to 93.4%.
The best technic conditions of Na-modification are ascertained via single factor experiment: selecting Na_2CO_3 as modifying addition, amount 5%, pulp density 15%, and stirring time 15min. The physical and chemical capability enhanced evidently, after the Na-modification. The colloid index and expansive capacity arrive to 500mL/15g, 72.0mL/g from the primary 100mL/15g, 11.0mL/g. It indicates that the Ca-bentonite changes into Na-bentonite as the d_(001) decreases to 1.24nm from 1.53nm and Ca~(2+) are changed by Na~+ in the X-ray diffraction patterns.
Diversified factors are studied the modification of octadecyl trimethyl ammonium chloride (1831) on Na-bentonite in the research of organ-modification. This dissertation prepares a series of organ-bentonite. It takes the size of interlayer field as estimate index to evaluate the preparation effect, combing with the intensity, the acuity and the symmetry of diffraction apices. The best technic conditions of organ-modification are: pulp density 5%, wash the sample for 3 times before organic intercalation, amount 30%, temperature 65℃, and stirring time 7h. The d_(001) increases to 4.167nm.
Systematic research of adsorption experiment is carried to study the each adsorption behavior of Cu(II) and oily wastewater on the three sorbents: purified Ca-bentonite, Na-bentonite and organobentonite. Comparer with the adsorption capacity of Cu(II) and oily wastewater through adsorption kinetic curve and isothermal absorption curve. Results show, the best adsorbent of Cu(II) is Na-bentonite while the best adsorbent of oily wastewater is organobentonite. Modification model is proposed to explain the modification mechanism and show the change process inside. Using FTIR, they show the adsorption process of oily wastewater on organobentonite, explain the inner structure change, and indicate that it includes physical adsorption and chemical adsorption for organobentonite to adsorb oily wastewater, and chemical adsorption takes advantage.
引文
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