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。     

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。     

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...     

Attempt to adsorb N-nitrosamines in solution by use of zeolites

The strong adsorption of zeolite for N-nitrosamines in solution was first revealed by use of adsorption, and temperature programmed surface reaction (TPSR) techniques. N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) as well as N-nitrosohexamethyleneimine (NHMI) can be adsorbed on zeolite Y, ZSM-5 and A in the solution of methylene chloride or water, which will be helpful for removal of the N-nitrosamines pollution in environmental protection. The equilibrium data were fitted to Freundlich-type isotherms, but the adsorption capacity of zeolites mainly depended on their pore size, surface area and acid-basic properties. Molecular size of adsorbate and solute-solvent interaction also strongly affected the adsorption of N-nitrosamines on zeolite in solution. The extraordinary adsorption properties of NaA zeolite for N-nitrosamines in aqueous solution is first reported and discussed.     

The removal of reactive black 5 from aqueous solutions by cotton seed shell

This study investigated the removal of Reactive Black 5 (RB5) textile dye from aqueous solutions using cotton (Gossypium hirsutum) seed shell (CSS) as low cost adsorbents. The data were described according to the Freundlich and Langmuir isotherm models. Of these, the Langmuir model provided the best fit for the experimental data. The highest measured adsorption density was 12.19 mg/g at pH 2. An equilibrium adsorption rate of RB5 by CSS (q(e) = 11.879 mg/g) was observed at 30 minutes. In order to evaluate the adsorption kinetic mechanisms, pseudo first and second order rate kinetic models and an intraparticle diffusion model were applied, with the pseudo second order model providing an excellent fit for the data.     

天然和CPB改性沸石对Hg^2＋的吸附特征

通过静态实验研究溴代十六烷基吡啶（CPB）改性沸石和天然沸石对废水中Hg^2＋的吸附特性，探讨了吸附动力学、吸附平衡和吸附热力学机制。研究表明：Langmuir方程能较好地描述2种沸石对Hg^2＋的吸附，CPB改性沸石对Hg^2＋的吸附率得到显著提高。实验条件下，改性沸石对Hg^2＋的吸附率从67．5％提高到98．9％，吸附容量从0．521mg／g提高到3．07mg／g。利用准一级动力学方程、假二级动力学方程、颗粒内扩散模型和Elovich方程分别对动力学过程进行拟合，发现2种沸石对Hg^2＋的吸附均满足假二级动力学方程，且离子的颗粒内扩散对整个吸附过程有影响。动力学拟合、D-R方程拟合和热力学研究综合表明：2种沸石对Hg^2＋的吸附既存在化学吸附又存在物理吸附，吸附吉布斯自由能变（△G^0）、焓变（△H^0）、熵变（△S^0）均小于0，反应为自发的放热反应，低温有利于吸附的进行。     

Adsorption behavior of alpha -cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of alpha -cypermethrin [R)-alpha -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze alpha -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time - 24 hours for both cork (1-2 mm and 3-4 mm) and GAC. For the studied alpha -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1-2 mm have the maximum amount of adsorbed alpha-cypermethrin (q(m)) (303 microg/g); followed by GAC (186 microg/g) and cork 3-4 mm (136 microg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the alpha -cypermethrin adsorption phenomena on GAC, while alpha -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing alpha -cypermethrin from water.     

天然及CaCl_2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。     

Adsorption behavior of α -cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of α -cypermethrin [R)-α -cyano-3-phenoxybenzyl(1S)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze α -cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time—24 hours for both cork (1–2 mm and 3–4 mm) and GAC. For the studied α -cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1–2 mm have the maximum amount of adsorbed α-cypermethrin (q_m) (303 μg/g); followed by GAC (186 μ g/g) and cork 3-4 mm (136 μg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the α -cypermethrin adsorption phenomena on GAC, while α -cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing α -cypermethrin from water.     

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。     

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.     

Adsorption of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-metylphenoxyacetic acid onto activated carbons derived from various lignocellulosic materials

Adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-metylphenoxyacetic acid (MCPA) from aqueous solution onto activated carbons derived from various lignocellulosic materials including willow, miscanthus, flax, and hemp shives was investigated. The adsorption kinetic data were analyzed using two kinetic models: the pseudo-first order and pseudo-second order equations. The adsorption kinetics of both herbicides was better represented by the pseudo-second order model. The adsorption isotherms of 2,4-D and MCPA on the activated carbons were analyzed using the Freundlich and Langmuir isotherm models. The equilibrium data followed the Langmuir isotherm. The effect of pH on the adsorption was also studied. The results showed that the activated carbons prepared from the lignocellulosic materials are efficient adsorbents for the removal of 2,4-D and MCPA from aqueous solutions.     

Removal of nickel (II) from aqueous solutions using marine macroalgae as the sorbing biomass

In the present study biosorption technique, the passive accumulation of metals by biomass, is used for the removal of nickel from aqueous medium. The brown algae, Sargassum sp., in its natural and acid treated forms are used as a low cost sorbent. The adsorption characteristics of nickel on Sargassum sp. are evaluated as a function of time, pH, adsorbent dosage and initial concentration of nickel. The equilibrium adsorption data are fitted to Freundlich and Langmuir adsorption isotherm models and the model parameters are evaluated. Both the models represent the experimental data satisfactorily. The adsorption follows Lagergren first order kinetic model. The monolayer adsorption capacities of natural and acid treated forms of algae as obtained from Langmuir adsorption model are found to be 181 and 250mg g(-1) respectively.     

Application of zeolite-activated carbon macrocomposite for the adsorption of Acid Orange 7: isotherm, kinetic and thermodynamic studies

In this study, the adsorption behavior of azo dye Acid Orange 7 (AO7) from aqueous solution onto macrocomposite (MC) was investigated under various experimental conditions. The adsorbent, MC, which consists of a mixture of zeolite and activated carbon, was found to be effective in removing AO7. The MC were characterized by scanning electron microscopy (SEM), energy dispersive X-ray, point of zero charge, and Brunauer–Emmett–Teller surface area analysis. A series of experiments were performed via batch adsorption technique to examine the effect of the process variables, namely, contact time, initial dye concentration, and solution pH. The dye equilibrium adsorption was investigated, and the equilibrium data were fitted to Langmuir, Freundlich, and Tempkin isotherm models. The Langmuir isotherm model fits the equilibrium data better than the Freundlich isotherm model. For the kinetic study, pseudo-first-order, pseudo-second-order, and intraparticle diffusion model were used to fit the experimental data. The adsorption kinetic was found to be well described by the pseudo-second-order model. Thermodynamic analysis indicated that the adsorption process is a spontaneous and endothermic process. The SEM, Fourier transform infrared spectroscopy, ultraviolet–visible spectral and high performance liquid chromatography analysis were carried out before and after the adsorption process. For the phytotoxicity test, treated AO7 was found to be less toxic. Thus, the study indicated that MC has good potential use as an adsorbent for the removal of azo dye from aqueous solution.     

矸石基X型分子筛对水中Co2+、Cu2+、Cd2+和Cr3+的去除

以煤矸石为原料,采用碱熔后水热合成法制备X型分子筛并进行XRD、SEM、BET和Zeta电位分析。研究其对水中Co2+、Cu2+、Cd2+和Cr3+4种离子的吸附性能,包括吸附等温线、吸附动力学以及初始金属离子浓度、pH值对吸附性能的影响。所合成的矸石基X型分子筛的BET比表面积为676.02 m2/g,微孔孔容为0.263 cm3/g。吸附实验表明,矸石基X型分子筛能有效去除上述4种离子,同时实现煤矸石的资源化和金属离子的去除。4种离子的平衡吸附量均随初始浓度的增大而增大,相同条件下平衡吸附量的大小顺序为Cd2+>Cr3+>Cu2+>Co2+。准二级动力学模型能很好地描述4种离子的吸附动力行为。Langmuir模型对Co2+、Cu2+和Cd2+吸附的拟合较Freundlich模型高,说明其主要表现为物理吸附过程。4种离子的吸附速率均由液膜扩散和颗粒内扩散共同控制。     

天然和巯基改性沸石吸附水溶液中重金属Hg^2＋的特征研究

为了提高沸石对汞的吸附性，利用半胱胺盐酸盐对天然斜发沸石进行改性，制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg^2＋浓度和吸附时间对沸石和巯基改性沸石吸附Hg^2＋的影响，并进一步研究了吸附机理。结果表明，巯基改性沸石吸附Hg^2＋受pH值、温度的影响较小，吸附机制主要是沸石表面的硫与Hg^2＋的化学反应。而天然沸石对Hg^2＋的吸附主要是离子交换作用，受温度、pH值等的影响较大，随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1h、巯基改性沸石在0．5h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明，巯基改性沸石对Hg^2＋的吸附能力得到了很大的提高，吸附容量由8．06mg／g提高到19．88mg／g，提高了146．65％。     

天然和巯基改性沸石吸附水溶液中重金属Hg2+的特征研究

为了提高沸石对汞的吸附性，利用半胱胺盐酸盐对天然斜发沸石进行改性，制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg²⁺浓度和吸附时间对沸石和巯基改性沸石吸附Hg²⁺的影响，并进一步研究了吸附机理。结果表明，巯基改性沸石吸附Hg²⁺受pH值、温度的影响较小，吸附机制主要是沸石表面的硫与Hg²⁺的化学反应。而天然沸石对Hg²⁺的吸附主要是离子交换作用，受温度、pH值等的影响较大，随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1 h、巯基改性沸石在0.5 h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明，巯基改性沸石对Hg²⁺的吸附能力得到了很大的提高，吸附容量由8.06 mg/g 提高到19.88 mg/g，提高了146.65%。     

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。     

粉煤灰砖块对磷酸盐的吸附特性

以建筑废料粉煤灰砖块为吸附剂材料,通过静态吸附实验研究其对磷酸盐的吸附特征,以及磷酸盐初始浓度、吸附剂投加量、pH等因素对吸附反应的影响。Langmuir、Freundlich和Temkin等温模型的分析发现,Langmuir等温式方程最适合描述吸附过程,对磷酸盐的理论饱和吸附容量为44.62 mg/g。利用伪一级动力学模型、伪二级动力学模型和颗粒内扩散模型考察了吸附过程特征,其中伪二级动力学模型为最适于描述粉煤灰砖块对磷酸盐的吸附过程的动力学模型。通过颗粒内扩散模型、Bangham方程及Boyd模型对吸附动力学机理进行的探讨表明,颗粒内扩散速率不是粉煤灰砖块吸附磷酸盐反应的惟一速率控制步,膜扩散速率和颗粒内扩散速率共同影响着吸附反应速率。磷酸盐浓度较低时主要是膜扩散限制吸附反应速率,而磷酸盐浓度较高时则颗粒内扩散成为速率控制步。研究证明,粉煤灰砖块粉末作为湿地基质具有对磷酸盐很强的吸附能力,在减少了固体废弃物的数量的同时又可以实现水污染控制的目的。