溴化十六烷基吡啶改性沸石对水中甲基橙的吸附

采用溴化十六烷基吡啶(CPB)对天然沸石进行改性制备得到了CPB改性沸石,通过批量吸附实验考察了CPB改性沸石对水中阴离子染料甲基橙的去除作用。结果表明,天然沸石对水中甲基橙的吸附能力很差,而CPB改性沸石则可以有效吸附去除水中的甲基橙。CPB改性沸石对水中甲基橙的吸附能力随CPB负载量的增加而增加,CPB负载量最大的改性沸石对水中甲基橙的吸附能力最强。双分子层CPB改性沸石对水中甲基橙的去除率随吸附剂投加量的增加而增加,而CPB改性沸石对水中甲基橙的单位吸附量则随吸附剂投加量的增加而降低。双分子层CPB改性沸石对水中甲基橙的吸附平衡数据可以采用Langmuir等温吸附模型加以描述。根据Langmuir模型计算得到的CPB负载量为341 mmol/(kg沸石)的双分子层CPB改性沸石对水中甲基橙的最大吸附容量为63.7 mg/g(303 K和pH 7)。准二级动力学模型适合用于描述双分子层CPB改性沸石对水中甲基橙的吸附动力学过程。pH和反应温度对双分子层CPB改性沸石吸附水中甲基橙的影响较小。以上结果说明,双分子层CPB改性沸石适合作为一种吸附剂用于去除废水中的甲基橙。     

Preparation and characterization of surfactant-modified hydroxyapatite/zeolite composite and its adsorption behavior toward humic acid and copper(II)

A novel composite material, i.e., surfactant-modified hydroxyapatite/zeolite composite, was used as an adsorbent to remove humic acid (HA) and copper(II) from aqueous solution. Hydroxyapatite/zeolite composite (HZC) and surfactant-modified HZC (SMHZC) were prepared and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and field emission scanning electron microscope. The adsorption of HA and copper(II) on SMHZC was investigated. For comparison purposes, HA adsorption onto HZC was also investigated. SMHZC exhibited much higher HA adsorption capacity than HZC. The HA adsorption capacity for SMHZC decreased slightly with increasing pH from 3 to 8 but decreased significantly with increasing pH from 8 to 12. The copper(II) adsorption capacity for SMHZC increased with increasing pH from 3 to 6.5. The adsorption kinetic data of HA and copper(II) on SMHZC obeyed a pseudo-second-order kinetic model. The adsorption of HA and copper(II) on SMHZC took place in three different stages: fast external surface adsorption, gradual adsorption controlled by both film and intra-particle diffusions, and final equilibrium stage. The equilibrium adsorption data of HA on SMHZC better fitted to the Langmuir isotherm model than the Freundlich isotherm model. The equilibrium adsorption data of copper(II) on SMHZC could be described by the Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. The presence of copper(II) in solution enhanced HA adsorption onto SMHZC. The presence of HA in solution enhanced copper(II) adsorption onto SMHZC. The mechanisms for the adsorption of HA on SMHZC at pH 7 may include electrostatic attraction, organic partitioning, hydrogen bonding, and Lewis acid–base interaction. The mechanisms for the adsorption of copper(II) on SMHZC at pH 6 may include surface complexation, ion exchange, and dissolution–precipitation. The obtained results indicate that SMHZC can be used as an effective adsorbent to simultaneously remove HA and copper(II) from water.     

天然沸石同步去除水中氨氮和磷酸盐

通过静态吸附实验考察了浙江缙云产天然沸石对溶液中氨氮和磷酸盐的同步去除能力及机制,结果表明,天然沸石对溶液中氨氮的吸附过程较好地满足拟二级动力学模型、Langmuir和Dubinin-Radushkevich等温吸附模型。天然沸石对磷酸盐的去除能力随溶液中初始氨氮浓度的增加而增加。当溶液pH由7.0增加到9.0时,天然沸石对氨氮的吸附能力随之增加,而当pH由9.0增加到10时,天然沸石对氨氮的吸附能力则下降。当溶液pH低于7.5时,天然沸石对溶液中的磷酸盐无去除能力,当溶液pH位于7.5～9.0时,天然沸石对磷酸盐的去除能力随pH的增加急剧增加,当溶液pH大于9.0时,天然沸石对磷酸盐的去除能力随pH的增加则呈下降趋势。天然沸石对溶液中氨氮和磷酸盐的同步去除过程是自发进行、吸热及熵增加的过程。天然沸石对溶液中氨氮的吸附机制为离子交换,对磷酸盐的去除机制则为化学沉淀作用。     

CPB改性沸石对磷酸盐的吸附-解吸性能研究

采用溴化十六烷基吡啶(CPB)对天然沸石进行改性,并考察了CPB改性沸石对磷酸盐的吸附-解吸性能。结果表明,CPB改性沸石对磷酸盐具备一定的吸附能力,且吸附行为满足Langmuir等温吸附模型;粒径、改性剂投加量、反应温度、pH值及共存阴离子等因素均会影响CPB改性沸石对磷酸盐的吸附能力;减小粒径和降低反应温度均有利于CPB改性沸石对磷酸盐的吸附去除;粒径≤0.18 mm CPB改性沸石吸附磷酸盐较优的改性剂投加量为250 mmol/kg;当溶液的初始pH值位于4~10之间时CPB改性沸石对磷酸盐的吸附能力随pH值的增加而增强;SO42-的存在会明显降低CPB改性沸石对磷酸盐的吸附效率,而提高溶液的pH值有助于消除SO42-存在对CPB改性沸石吸附磷酸盐的负面影响;HCO3-的存在会一定程度上抑制CPB改性沸石对磷酸盐的吸附去除,而提高溶液的pH值无法消除HCO3-存在对CPB改性沸石吸附磷酸盐的负面影响;CPB改性沸石吸附磷酸盐后一定条件下可以重新解吸出来,且随着解吸液SO42-浓度的增加解吸率明显增大。     

改性沸石吸附低浓度氨氮废水及其脱附的研究

采用氯化钠溶液对浙江某地天然沸石改性,以低浓度氨氮废水为处理对象,比较了天然沸石和改性沸石的吸附等温线、吸附动力学和动态吸附,并进行了改性沸石的动态脱附研究.结果表明,沸石的平衡吸附量随着平衡浓度的增大而增大;Freundlich方程比Langmuir方程更好地描述沸石吸附低浓度氨氮废水的行为,改性沸石比天然沸石具有更...     

改性沸石对低浓度氨氮废水的动态吸附

采用氯化钠溶液对甘肃白银天然沸石改性,以低浓度氨氮(NH4+-N)废水为处理对象,对比了天然沸石和改性沸石的动态吸附特性并绘制穿透曲线,利用Origin软件对实验数据分析处理,得出穿透曲线的通式。结果表明:在相同条件下,改性沸石的穿透时间和吸附饱和时间都比天然沸石的长约1.5倍;沸石经氯化钠改性后,对NH4+-N的吸附速率和饱和吸附量都明显提高,吸附性能显著改善。Origin软件对水溶液中NH4+-N的吸附穿透曲线的Logistic模型回归式具有较高的精度,该模型可以很好地反映沸石吸附剂的动态吸附过程。     

Fine route for an efficient removal of 2,4-dichlorophenoxyacetic acid (2,4-D) by zeolite-supported TiO2

Zeolites HY, Hbeta and HZSM-5 with different physico-chemical properties were chosen as support for TiO2 to illustrate their adsorption, dispersion and electronic structure in photocatalysis. The extent of TiO2 loading was monitored by XRD and BET surface area measurements. The adsorption capacity of HY zeolite was found to be high and hence chosen for further modification to continue the investigation. Photodegradation kinetics were carried out with 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. The extent of 2,4-D degradation on TiO2/HY loading revealed the importance of adsorption in photocatalysis. Mineralisation studies on all three zeolites with 1 wt.% TiO2 loading demonstrated the good dispersion properties of TiO2/HY. Its photocatalytic activity was found to be excellent with formulated 2,4-D. Comparison of relative photonic efficiencies demonstrated that supported photocatalysts exhibited higher activity than some of the commercial photocatalysts. The high activity of supported TiO2 is due to synergistic effects of improved adsorption of 2,4-D and efficient delocalisation of photogenerated electrons by zeolite support.     

粘土矿物材料吸附去除水中痕量邻苯二甲酸酯

研究了天然沸石、2种有机改性沸石及Mg/Al水滑石对水中痕量邻苯二甲酸二甲酯、邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯的等温吸附情况和吸附机理,并与活性炭的吸附性能进行了比较。结果表明,Freundlich和Langmuir吸附等温方程均可以很好地描述天然沸石和Mg/Al水滑石对邻苯二甲酸酯的吸附,2种有机改性沸石对邻苯二甲酸酯的吸附更符合Linear吸附等温方程。与活性炭相比,天然沸石对邻苯二甲酸酯的吸附效果较差;2种有机改性沸石和Mg/Al水滑石对分子尺寸较小的邻苯二甲酸酯物质邻苯二甲酸二甲酯的去除率较低,分别低31.8%、31.4%和19.8%,但对分子较大的邻苯二甲酸酯物质邻苯二甲酸二(2-乙基己基)酯和邻苯二甲酸二辛酯的去除效果相差不大。     

4A沸石对复合污染水体中Pb2+、Cu2+和Cd2+的去除

采用静态吸附法以4A沸石为吸附剂研究其对复合污染水体中Pb2+、Cu2+和Cd2+的竞争吸附特性,并探讨了影响吸附的环境因素。实验表明,在室温条件下,溶液pH5～6,4A沸石15 mg对10 mL复合污染溶液(Pb2+、Cu2+和Cd2+浓度分别为100 mg/L)吸附20 min时,对溶液中3种重金属的吸附去除率均可达99.8%以上。反应过程中4A沸石对3种重金属的吸附速率大小为Pb2+>Cu2+>Cd2+。复合污染水体中4A沸石对Pb2+、Cu2+和Cd2+的吸附符合Langmuir和Fre-undlich等温吸附方程,相关系数分别为0.9981、0.9901、0.9916和0.9638、0.9194、0.9689。经计算,4A沸石对Pb2+、Cu2+和Cd2+的饱和吸附量分别为129.9 mg/g、107.5 mg/g和99.0 mg/g。4A沸石吸附重金属离子达到吸附平衡的时间较短,对溶液pH值的适应性较好。吸附后的4A沸石可以再生利用,对铅离子洗脱重复利用性较铜离子和镉离子强。     

Applying Hexagonal Nanostructured Zeolite Particles for Acetone Removal

Abstract

This study examines the performance of a new adsorbent, hexagonal nanostructured zeolite particles (HNZP) for acetone adsorption and compares the results with that of commercial mobil synthetic zeolite-5 (ZSM-5) type zeolite. The HNZP is a pure siliceous adsorbent with different values of pore diameter and surface area being adjustable by the manufacturing condition. The results indicate that a slight increase in the average pore diameter (d) of HNZP from 2 to 2.5 nm leads to an increase in the acetone adsorption capacity, although its surface area is decreased, in which case (d = 2.5 nm) the adsorption capacity of fresh HNZP is better than that of ZSM-5 zeolite. Even for the fresh HNZP (d = 2 nm) of which the adsorption capacity is less than that of the ZSM-5 zeolite at relative humidity (RH) of 0%, its adsorption capacity is not deteriorated after repeated regeneration, but the adsorption capacity of regenerated ZSM-5 zeolite decays markedly. Thus, after only one regeneration, the adsorption capacity of HNZP (d = 2 nm) becomes better than that of the ZSM-5 zeolite. The decrease in the adsorption capacity of regenerated ZSM-5 zeolite might be because of its aluminum content that catalyzes the acetone into coke and, thus, blocks the adsorption sites. Furthermore, result on the moisture effect shows that because the pure siliceous HNZP was more hydrophobic than the ZSM-5 zeolite, the acetone adsorption efficiency of fresh HNZP (d = 2 nm) is better than that of ZSM-5 zeolite at RH = 50%.     

Applying hexagonal nanostructured zeolite particles for acetone removal

This study examines the performance of a new adsorbent, hexagonal nanostructured zeolite particles (HNZP) for acetone adsorption and compares the results with that of commercial mobil synthetic zeolite-5 (ZSM-5) type zeolite. The HNZP is a pure siliceous adsorbent with different values of pore diameter and surface area being adjustable by the manufacturing condition. The results indicate that a slight increase in the average pore diameter (d) of HNZP from 2 to 2.5 nm leads to an increase in the acetone adsorption capacity, although its surface area is decreased, in which case (d = 2.5 nm) the adsorption capacity of fresh HNZP is better than that of ZSM-5 zeolite. Even for the fresh HNZP (d = 2 nm) of which the adsorption capacity is less than that of the ZSM-5 zeolite at relative humidity (RH) of 0%, its adsorption capacity is not deteriorated after repeated regeneration, but the adsorption capacity of regenerated ZSM-5 zeolite decays markedly. Thus, after only one regeneration, the adsorption capacity of HNZP (d = 2 nm) becomes better than that of the ZSM-5 zeolite. The decrease in the adsorption capacity of regenerated ZSM-5 zeolite might be because of its aluminum content that catalyzes the acetone into coke and, thus, blocks the adsorption sites. Furthermore, result on the moisture effect shows that because the pure siliceous HNZP was more hydrophobic than the ZSM-5 zeolite, the acetone adsorption efficiency of fresh HNZP (d = 2 nm) is better than that of ZSM-5 zeolite at RH = 50%.     

Experimental study and modelling of zinc adsorption by granular activated carbon and natural zeolite

The metal removal capability of Granular Activated Carbon (GAC) and natural zeolite is evaluated in this study using zinc as a model adsorbate. The equilibrium and kinetic characteristics of zinc adsorption on GAC and natural zeolite were studied in batch stirred tank experiments. The adsorption data for both systems were fitted by Langmuir, Freundlich, Langmuir-Freundlich, and Redlich-Peterson models. The parameters in the adsorption isotherms were estimated from the experimental equilibrium data using MATLAB. Using these data the best isotherm can be selected. The effect of initial concentration on the transient behaviour of zinc removal by GAC and natural zeolite was investigated. In this work two surface reaction models, namely a second order reversible reaction model and a second order irreversible reaction model for describing Zn(II) removal by GAC and natural zeolite, were employed. Modelling studies using two different second order surface reaction models demonstrated that it is very difficult to come to a general conclusion about which model has better ability.     

Multiple copper adsorption and regeneration by zeolite 4A synthesized from bauxite tailings

Copper ions were first adsorbed by zeolite 4A synthesized from bauxite tailings, the desorption of Cu(II) using Na₂EDTA solutions was performed, and the recycling of zeolite 4A in adsorption and desorption was systematically investigated. It was observed that the Cu(II) removal efficiency was directly dependent on the initial pH value. The maximum removal efficiency of Cu(II) was 96.2% with zeolite 4A when the initial pH value was 5.0. Cu(II) was completely absorbed in the first 30 min. It was also observed that the desorption efficiency and zeolite recovery were highly dependent on the initial pH and concentration of Na₂EDTA in the solution. The desorption efficiency and percent of zeolite recovered were 73.6 and 85.9%, respectively, when the Na₂EDTA solution concentration was 0.05 mol L^?1 and the pH value was 8. The recovered zeolites were pure single phase and highly crystalline. After 3 cycles, the removal efficiency of Cu(II) was as high as 78.9%, and the zeolite recovery was 46.9%, indicating that the recovered zeolites have good adsorption capacity and can repeatedly absorb Cu(II).

     

4A沸石去除水中Pb~(2+)的研究

在静态条件下,研究了4A沸石对废水中Pb2+的吸附性能,并探讨了影响吸附的因素。实验表明:当温度为30℃,废水pH为5~6,0.01 g4A沸石对100 mg/LPb2+溶液10 mL吸附20 min,Pb2+的去除率可达到99%以上。在实验研究条件下,4A沸石对Pb2+的吸附符合Langmuir和Freundlich等温吸附方程,相关系数为0.9819和0.9998。经计算,4A沸石对Pb2+的饱和吸附量为125 mg/g。4A沸石吸附水中Pb2+,达到吸附平衡的时间较短;溶液pH值的变化对吸附效果影响不显著;温度从室温略微升高,Pb2+的去除率略有增大。吸附在4 A沸石上的Pb2+可回收利用,处理后的4A沸石可以再生,且重复使用性能较好。     

活性炭和沸石对氨氮的吸附特性及生物再生

采用活性炭和沸石作为吸附材料,分别考察了这两种吸附材料对水体中氨氮的吸附特性及其生物再生性能。实验结果表明,活性炭和沸石对水体中氨氮的等温吸附符合Freundlich等温式,其拟合度分别为0.9783和0.9303;静态吸附结果表明活性炭和沸石均具有较好的氨氮吸附性能,24 h内沸石对氨氮的吸附能力为1.27 mg/g,高于活性炭的0.53 mg/g;动态吸附中沸石达到吸附饱和的时间为96 h,较活性炭达到吸附饱和的时间长,沸石显示出作为氨氮吸附剂的优越性;活性炭和沸石经过96 h的生物再生后吸附性能获得一定程度的再生,出水中氨氮浓度比未进行生物再生前分别降低17.31 mg/L和8.32 mg/L,且都在表面形成了稳定的生物膜。     

Physical and chemical regeneration of zeolitic adsorbents for dye removal in wastewater treatment

Natural zeolite and synthetic zeolite, MCM-22, were employed as effective adsorbents for a basic dye, methylene blue, removal from wastewater. Two methods, Fenton oxidation and high temperature combustion, have been used for regeneration of used materials. It is found that MCM-22 exhibits equilibrium adsorption at 1.7 x 10(-4) mol g(-1), much higher than the adsorption of natural zeolite (5 x 10(-5) mol g(-1)) at initial dye concentration of 2.7 x 10(-5)M and 30 degrees C. Solution pH will affect the adsorption behaviour of MCM-22. Higher solution pH results in higher adsorption capacity. The regenerated adsorbents show different capacity depending on regeneration technique. Physical regeneration by high temperature combustion will be better than chemical regeneration using Fenton oxidation in producing effective adsorbents. Regeneration of MCM-22 by high temperature treatment can make the adsorbent exhibit comparable or superior adsorption capacity as compared to the fresh sample depending on the temperature and time. The optimal temperature and time will be 540 degrees C and 1h. The Fenton oxidation will recover 60% adsorption capacity. For natural zeolite, regeneration can not fully recover the adsorption capacity with the two techniques and the regenerated natural zeolites by the two techniques are similar, showing 60% adsorption capacity of fresh sample. Kinetic studies indicate that the adsorption follows pseudo-second-order kinetics.     

天然沸石吸附氨氮的影响因素

对比研究了沸石对生活污水和人工配制氯化铵溶液中氨氮的吸附特性,考察了沸石投加量、反应时间、悬浮物、阳离子和阴离子对沸石吸附氨氮的影响。结果表明,沸石对生活污水中氨氮的吸附能力明显低于人工配制氯化铵溶液,氨氮去除率随着沸石投加量的增加而增加,但单位质量沸石的氨氮吸附量却随之减小,吸附过程呈现快速吸附,缓慢平衡的特点。生活污水中悬浮物的存在,会削减沸石对氨氮的吸附能力。不同类型的阳离子和阴离子的加入都能导致人工配制氯化铵溶液中氨氮在沸石上的吸附量存在差异。阳离子的影响趋势主要为价态的影响,即价态越高,对氨氮吸附阻碍作用越显著,当阳离子当量浓度〉2meq／L时,影响吸附强弱的顺序为Ca2＋〉Mg2＋ 〉Na＋;阴离子影响沸石吸附强弱的顺序受初始氨氮的浓度影响较大。Langmuir等温方程式较Freundich、DubininRadushkevich、KobleCorrigan和Temkin等温方程式更好地描述沸石吸附氨氮的行为。     

4A沸石去除水中Pb2＋的研究

在静态条件下,研究了4A沸石对废水中Pb2＋的吸附性能,并探讨了影响吸附的因素。实验表明：当温度为30℃,废水pH为5～6,0．01g4A沸石对100mg／LPb2＋溶液10mL吸附20min,Pb2＋的去除率可达到99％以上。在实验研究条件下,4A沸石对Pb2＋的吸附符合Langmuir和Freundlich等温吸附方程,相关系数为0．9819和0．9998。经计算,4A沸石对Pb2＋的饱和吸附量为125mg／g。4A沸石吸附水中Pb2＋达到吸附平衡的时间较短;溶液pH值的变化对吸附效果影响不显著;温度从室温略微升高,Pb2＋的去除率略有增大。吸附在4A沸石上的Pb“可回收利用,处理后的4A沸石可以再生,且重复使用性能较好。     

VOCs和水在Y型分子筛表面的竞争吸附

采用水热处理方法合成了具有不同硅铝比的超稳Y型分子筛,考察了苯、甲苯、二甲苯、苯乙烯和乙酸乙酯与水在Y分子筛表面的竞争吸附。结果表明,随着Si/Al比的增加,Y分子筛表面的有机分子选择性吸附位数量增加,有机分子竞争吸附能力增加。低硅Y型分子筛只有在吸附偶极距>1.0的高极性有机分子时才能与水分子产生有力的竞争吸附,而高硅超稳Y分子筛则对偶极距在0～0.5范围的有机分子就表现出很强的竞争吸附能力。     

天然及CaCl2改性沸石对四环素的吸附

通过静态吸附实验研究了水中四环素在天然和CaCl2改性沸石上的吸附行为及机制。实验表明,天然沸石对四环素具有吸附能力,CaCl2改性可以提高沸石对四环素的吸附能力。天然和改性沸石对四环素的吸附符合拟二级动力学模型,颗粒内扩散不是吸附过程的主要控制步骤。Freundlich和Dubinin-Radushkevich(D-R)等温吸附模型可以较好地描述实验所用2种沸石对四环素的吸附行为,D-R等温方程拟合结果显示吸附过程包含离子交换作用。通过对天然和改性沸石吸附四环素前后溶液中主要阳离子浓度变化分析证实了该吸附过程包含离子交换作用。实验研究了pH值变化对沸石吸附四环素的影响,当pH=3～5时,天然和改性沸石对四环素的吸附量均随pH值的增加而急剧下降,而pH=5～10时,天然和改性沸石对四环素的吸附量变化均不明显,推测可能是离子交换作用和化学沉淀吸附作用所致。另外,实验还初步探索了溶液离子强度对沸石吸附四环素的影响情况,随着溶液中Na+和Ca2+离子强度的增加,吸附量先急剧降低随后趋向平稳,进一步说明了沸石对四环素的吸附过程不是由单一机制控制的。