【作者】 刘梅；

【导师】 巢艳红；

【作者基本信息】 江苏大学 ， 制药工程（专业学位）， 2021， 硕士

【摘要】 随着制药化工行业的发展,制药废水的排放和治理问题逐渐成为社会关注的重点。传统废水处理工艺难以高效去除制药废水中的抗生素,导致全球的湖泊河流等各类水体,甚至日常饮用水中检测出大量抗生素残留。残留的抗生素在大自然生态系统中不断蓄积,微生物耐药现象日趋严重,严重威胁生态系统平衡和人类健康。针对制药废水中抗生素的高效治理,吸附法由于绿色环保、价格低廉、无二次污染和操作简单等优点,被认为是最具有应用前景的技术之一。近几年来,高效吸附剂的研发已成为一项研究热点。本文通过引入不同碱（土）金属,采用热解法高效合成了一系列金属掺杂氮化硼（BN）基纳米吸附剂,并将其用于制药废水中抗生素的吸附分离研究。采用SEM、FT-IR、XPS、TEM、N₂吸附-脱附曲线等表征对材料的结构和理化性质进行分析,通过吸附条件优化、吸附动力学、吸附热力学和等温线性质研究等探究吸附过程及机理,最后,通过循环稳定性实验考察氮化硼基纳米吸附剂的稳定性。1.原位引入不同摩尔比的碱金属钠源,建立一步热解合成碱金属钠掺杂氮化硼纳米片（Na-BN）新方法。在高温热解过程中同步实现薄层BN纳米片合成和Na金属活性中心的掺杂。通过钠源和掺量筛选,引入0.075 mol Na₂CO₃原位合成的Na-BN对水中四环素（TC）的脱除率相较于BN提升了29.78%。Na-BN可有效吸附分离水中多种抗生素,对环丙沙星（CIP）的平衡吸附容量高达211mg/g,吸附过程遵守准二级动力学模型和Freundlich等温线模型,其中π-π相互作用、疏水作用和静电相互作用为主要吸附作用力。6次吸附-脱附-吸附循环实验结果显示,Na-BN具有良好循环稳定性。2.原位引入不同摩尔比的碱土金属钙源,建立一步热解合成碱土金属钙掺杂氮化硼纳米片（Ca-BN）新方法。在高温热解过程中同步实现薄层BN纳米片合成和Ca金属活性中心掺杂。通过Ca掺量筛选,引入0.07 mol Ca CO₃原位合成的Ca-BN对水中TC的脱除率相较于BN提升了34.47%。Ca-BN对TC的平衡吸附容量高达346 mg/g,吸附动力学遵循准二级模型,吸附等温线模型拟合度依次为:Freundlich>Tempkin>Langmuir>D-R,吸附主要为非均质固体表面的多分子层吸附,吸附过程自发吸热,除π-π作用、疏水和静电相互作用外,碱土金属钙与TC间的阳离子桥作用为吸附性能的显著提升发挥了关键作用。6次循环实验结果表明,Ca-BN循环稳定性良好。3.以羧甲基纤维素钠作为碳源和碱金属钠源,原位引入不同摩尔比的碱土金属镁源,建立一步热解合成碱（土）双金属钠/镁掺杂薄层硼碳氮纳米吸附材料（Na/Mg-BCN）新方法。通过碳、钠、镁掺量的筛选,引入0.5 g CMC-Na和0.15mol Mg CO₃原位合成的Na/Mg-BCN对水中TC的脱除率相当于相较于BN提升了41.13%。Na/Mg-BCN对CIP的平衡吸附容量高达964.38 mg/g,吸附动力学遵循准二级模型,吸附等温线模型拟合度依次为:Freundlich>Tempkin≈Langmuir>D-R,吸附主要为非均质固体表面的多分子层吸附,吸附过程自发放热,吸附主要作用力推测为π-π作用、金属-π络合作用、疏水作用和静电相互作用。Na/Mg-BCN稳定性好,6次循再生后对CIP的脱除率仍保持在97.4%。更多还原

【Abstract】 With the development of pharmaceutical and chemical industry,the discharge and treatment of pharmaceutical wastewater has gradually become the focus of social attention.Traditional wastewater treatment technology is difficult to effectively removal antibiotics from pharmaceutical wastewater,which leads to a large number of antibiotic residues detected in lakes,rivers and other water bodies around the world,even in daily drinking water.Residual antibiotics continue to accumulate in the natural ecosystem,and the phenomenon of microbial drug resistance is becoming more and more serious,which seriously threatens the balance of ecosystem and human health.For the effective treatment of antibiotics in pharmaceutical wastewater,adsorption is considered as one of the most promising technologies due to its advantages of environmental protection,low price,no secondary pollution and simple operation.In recent years,the research and development of high-efficiency adsorbents has become a research hot-spot.In this paper,a series of metal-doped boron nitride（BN）-based nano-adsorbents were synthesized by pyrolytic method by introducing different alkali（earth）metals,and they were used to study the adsorption and separation of antibiotics in pharmaceutical wastewater.SEM,FT-IR,XPS,TEM,N₂ adsorption-desorption curves were used to analyze the material structure and the physical and chemical properties.The mechanism of adsorption process was discussed through optimizing conditions of adsorption,kinetics,thermodynamics and isotherm properties.Finally,through the recycling experiment to investigate the stability of the boron nitride nanotubes adsorbent.1.A new method for the synthesis of alkali sodium doped boron nitride（Na-BN）nanosheets by one-step pyrolysis was established by introducing alkali metal sodium sources with different molar ratios in situ.The synthesis of thin layer BN nanosheets and doping of Na metal active sites were realized simultaneously by high temperature pyrolysis.Through the screening of sodium source and dosage,the removal rate of tetracycline TC in water by in-situ synthesis of Na-BN with the introduction of 0.075mol Na₂CO₃ was increased by 29.78%compared with that by BN.The equilibrium adsorption capacity of ciprofloxacin CIP was as high as 211 mg/g.The adsorption process follows the pseudo-second-order kinetic model and Freundlich isotherm model.The main adsorption forces areπ-πhydrophobic interaction and electrostatic interaction.The experimental results of 6 adsorption-desorption-adsorption cycles show that Na-BN has good cyclic stability.2.A new method for the synthesis of alkaline earth metal calcium doped boron nitride nanosheets（Ca-BN）by one-step pyrolysis was established by introducing alkaline earth metal calcium sources with different molar ratios in situ.The preparation of thin BN nanosheets and the doping of Ca active sites were completed simultaneously during the pyrolysis process.The removal rate of TC in water by Ca-BN was 34.47%higher than that by BN.The equilibrium adsorption capacity of Ca-BN for TC was 346mg/g,and the adsorption kinetics followed the pseudo-second-order model.The fitting degree of adsorption isotherm model was Freundlich>Tempkin>Langmuir>D-R.The adsorption process is spontaneous heat absorption.In addition toπ-πhydrophobic interaction and electrostatic interaction,the cationic bridge between alkaline earth metal calcium and TC plays a key role in the significant improvement of adsorption performance.The experimental results of 6 cycles show that the Ca-BN cycle has good stability.3.Using sodium methylcellulose as carbon source,a new method of one-step pyrolysis synthesis of alkali（earth）bimetallic sodium/magnesium doped thin layer boron carbon nitrogen nano-adsorbent（Na/Mg-BCN）was established by introducing alkaline earth metal magnesium source with different molar ratio in situ.Through the selection of carbon and magnesium content,the removal rate of TC in water by Na/Mg-BCN synthesized by 0.5 g CMC-Na and 0.15 mol Mg CO₃ in situ is 41.13%higher than that by BN.The equilibrium adsorption capacity of CIP was 964.38 mg/g,and the adsorption kinetics followed the quasi second order model.The order of fitting degree of adsorption isotherm model was Freundlich>Tempkin≈Langmuir>D-R.The adsorption was mainly multi-layer adsorption on heterogeneous solid surface,and the adsorption process was self exothermic.The main adsorption forces areπ-πinteraction,metal-πcomplexation,hydrophobic interaction and electrostatic interaction.The stability of Na/Mg-BCN is good,and the removal rate of CIP remains at 97.4%after six cycles of regeneration.更多还原