斜发沸石对钾离子的吸附/解吸动力学研究

以KCl为钾源、新疆某地所产斜发沸石为吸附剂,研究斜发沸石对K+的动力吸附与解吸效果,并探讨吸附时间、K+初始浓度与吸附量的关系。用pH=5的HCl溶液和(Ca2++Mg2+)浓度/(mmol.L-1)为1.6,3.2,6.4,12.8,19.2,25.6的混合溶液对饱和吸附了K+的斜发沸石进行解吸,实验结果表明:沸石对K+的吸附在4min能达到最大吸附率的96%,30min内达到平衡。Langmuir吸附等温式能对吸附曲线进行很好的描述。单位质量沸石对K+的最大吸附量为44.53×10-3,以阳离子交换吸附为主。pH=5的HCl溶液对K+的解吸量最小,随解吸溶液中(Ca2++Mg2+)浓度增加,解吸滞后系数减小,解吸速率远小于吸附速率。解吸量的自然对数与解吸时间的自然对数呈现明显的线性关系,用指数方程对(Ca2++Mg2+)浓度为25.6mmol/L的解吸曲线进行拟合,R=0.998,拟合方程为qt=3.890t0.210。理论上将吸附的K+全部解吸出来需要74.4d。     

土壤有机碳含量及异质性对三氯乙烯的吸附影响实验

采取北京城区表土样品和土壤标准参考样共7件,对原土样以及经H2O2氧化处理去除低聚合有机碳后的土样分别采用静态批实验方法,研究其对三氯乙烯(TCE)的等温吸附方程。实验结果表明7种土样对TCE的吸附模式均符合线性等温吸附方程,采用H2O2氧化去除土壤样品中的低聚碳,并没改变等温吸附线型,只是方程的参数发生了变化。剩余有机碳的含量仍都大于0.1%,仍然以有机碳的吸附为主;原土样、高聚碳、低聚碳对TCE吸附均表明,有机碳的含量与样品吸附TCE的能力没有明显的关系,证实不管是总有机碳、低聚碳还是高聚碳都有明显的异质性,它们所表现出来的吸附能力并不相同,有机碳结构组成的差异往往是影响其吸附的关键因素。而土壤有机碳经历矿化和腐殖化程度的差异是造成土壤有机碳结构组成差异的主要原因。     

四氯乙烯的生物吸附和厌氧生物降解研究

四氯乙烯(PCE)的广泛使用和不合理的处置已经使其成为地下水中普遍存在的有毒有害的有机污染物。PCE在厌氧条件下通过还原脱氯发生生物降解,按照非水溶性生物降解模型,有机物先吸附到厌氧活性污泥中,解吸后再进行生物降解。利用间歇试验进行厌养污泥对PCE的吸附降解实验研究。试验结果表明：厌氧污泥对PCE的吸附在0.5 h达到吸附平衡,在1.0 h达到解吸平衡。对实验结果的回归分析表明：PCE的吸附和解吸均符合Freundlich等温吸附方程。厌氧污泥在微生物的作用下将PCE还原脱氯为TCE和DCEs。     

凹凸棒石缓释钾肥的制备及缓释效果研究

以凹凸棒石为缓释载体,研究凹凸棒石缓释钾肥的制备条件,并以其吸附时间、K+初始浓度与吸附量的关系,确定K+吸附量最大时的K+初始浓度缓释效果。用pH=5的HCl溶液和(Ca2++Mg2+)浓度为1.6mmol/L,3.2mmol/L,6.4mmol/L,12.8mmol/L,19.2mmol/L,25.6mmol/L的混合溶液对凹凸棒石缓释肥进行解吸。结果表明:凹凸棒石对K+的吸附量在30min内达到平衡,单位质量凹凸棒石对K+的最大吸附量为13.97×10-3;pH=5的HCl溶液对K+的解吸率最小,随解吸溶液中(Ca2++Mg2+)浓度增加,解吸率增大,凹凸棒石对K+的解吸过程符合Elovich方程,解吸速率远小于吸附速率;以pH=5的HCl溶液对凹凸棒石缓释钾肥进行动态解吸和静态解吸实验,动态解吸得出的解吸率较静态解吸的解吸率低,解吸液为450ml时,动态解吸和静态解吸的解吸率分别为35.5%和50.3%,前者能更真实地反应凹凸棒石缓释钾肥的缓释效果;该凹凸棒石是钾肥良好的缓释载体。     

蒙脱石与滑石矿物对菲吸附-解吸行为的对比研究

采用批量处理平衡实验,考察蒙脱石与滑石矿物对菲的吸附解吸行为。采用Henry和Freundlich方程对其吸附等温线进行分析比较,并着重考察软阳离子K+对上述两种矿物吸附菲的影响机制。研究结果表明:蒙脱石对菲的吸附等温线表现出明显的非线性,吸附/解吸有滞后现象,Freundlich方程最符合其吸附/解吸曲线;滑石吸附菲的能力较之蒙脱石的强,且吸附呈线性,其吸附曲线与Henry方程吻合程度最好。此外,随着溶液中K+离子浓度增加,蒙脱石吸附菲的能力增强,而滑石吸附菲的能力减弱,说明软阳离子K+对蒙脱石吸附菲有明显的强化作用,而对滑石吸附菲却有抑制作用。说明黏土矿物内部结构与表面理化性质控制着污染物的吸附-解吸环境行为,从而影响着PAHs等污染物的迁移转化。     

污灌土壤对铅的吸附和解吸特性

为了解污灌土壤对铅的吸附-解吸机制,进行不同条件下的吸附-解吸试验。结果表明：污灌土壤对铅的吸附量随铅初始浓度的增大,呈现先强烈吸附再缓和的过程。Langmuir模式对污灌土壤等温吸附铅的拟合效果最好,其饱和吸附量为7.84 mg/g。亚砷酸盐的存在会阻碍污灌土壤对Pb²⁺的吸附,亚砷酸盐加入前后污灌土壤对铅的吸附率从99.9％～100％下降到97.8％～99.0％。加亚砷酸盐条件下污灌土壤对铅的等温吸附模式以Freundlich模式的拟合效果最好。污灌土壤对吸附态铅的解吸量随解吸振荡时间的延长而不断增加,且解吸率随时间增加总体趋于降低。Elovich方程和幂函数方程均能很好地拟合污灌土壤对铅的解吸动力学过程,尤其是Elovich方程的拟合效果最为显著。     

天然锰钾矿吸附水溶液中Hg^2＋的实验研究

利用粉碎分级的天然锰钾矿去除水溶液中Hg^2 的实验研究表明：反应平衡时间约为20小时；pH值对其吸附率影响很大，在中性（氯化物在偏碱性）条件下吸附率较高；溶液中阳离子的存在会产生竞争吸附而降低对Hg^2 的吸附量，2价金属离子较1价金属离子对Hg^2 竞争干扰明显；溶液中Cl^-的存在能明显降低对Hg^2 的吸附量。对等温吸附曲线的回归分析得出在浓度为5～350mg/L段能很好地符合Langmuir单吸附位吸附曲线，并计算出在该实验条件下其最大理论吸附量为27.6mg/g。解吸实验结果表明，在无其他电解质参与的条件下解吸量较少，受多种电解质干扰时其解吸率不超过20%。     

模拟土样有机碳和矿物质对TCE吸附贡献的实验研究

为研究均一介质条件下有机碳含量及矿物质对TCE吸附行为的影响,简化了土壤环境的复杂性和异质性,以固定矿物质(高岭土∶石英砂=3∶7)作为土壤基体,添加不同质量分数的腐殖质(foc=0.16%~2.29%)配制成模拟土样,进行矿物质和模拟土样对TCE的吸附批实验。实验结果显示,TCE的吸附等温线呈非线性。随有机碳含量增加,表现为线性吸附增强,矿物质对TCE的吸附贡献随有机碳含量增加而减小。foc>0.82%时,矿物质对吸附作用的贡献率<5%;foc>1%时,可以基本忽略矿物质对吸附的影响。此外,TCE初始浓度也会影响有机碳和矿物质的吸附能力。用Freundlich模型分别拟合TCE吸附等温线的低浓度段和高浓度段(以Ce=500μg/L为浓度高低的分界),Freundlich指数n值呈现由大到小的趋势;TCE初始浓度越高,有机碳的吸附贡献率相对上升,而矿物质的贡献率则下降。TCE初始浓度在50~500μg/L之间、foc由0.16%增大到1%时,矿物质的吸附贡献率范围由28%~16%缩小到3%~1%之间,此时TCE初始浓度对有机碳和矿物质的吸附贡献率基本没有影响。     

斜发沸石对模拟核素Sr2+的吸附/解吸动力学研究

以Sr（NO3）2为核素源、新疆富蕴县所产斜发沸石为吸附剂,研究斜发沸石对Sr2＋的动力吸附/解吸效果。探讨吸附时间、Sr2＋初始浓度与吸附量的关系以及吸附机理。用pH=6的水溶液对饱和吸附了Sr2＋的斜发沸石进行解吸。结果表明：斜发沸石对Sr2＋的吸附在4 h能达到最大吸附率的99%,Freundlich吸附等温式能对吸附曲线进行很好的描述,单位质量沸石对Sr2＋的最大吸附量为38.34 mg/g,以阳离子交换吸附为主。4.5 h后解吸率为1.78%,解吸速率远小于吸附速率,解吸量与解吸时间的自然对数呈现明显的线性关系,用Elovich方程对解吸曲线进行拟合,R=0.9994,拟合方程为：qt=0.03375＋0.11916lnt。理论上将5%的Sr2＋解吸出来约需5044 d。该斜发沸石固Sr2＋能力很强,对于处理含Sr2＋放射性废液具有重要的意义。     

1,2-二氯乙烷和1,2-二氯丙烷在某污染场地包气带的吸附-解吸特性

1,2-二氯乙烷(1,2-DCA)和1,2-二氯丙烷(1,2-DCP)是某污染场地地下水中检出最高的挥发性有机污染物。文中采用批试验方法,研究污染场地包气带中三种不同深度土壤样品对1,2-DCA和1,2-DCP的吸附-解吸特性。结果表明:土壤中有机质决定其吸附行为,三种土壤对1,2-DCA和1,2-DCP的吸附符合Henry线性等温方程,分配系数在20.49～22.43L.kg-1,1,2-DCA和1,2-DCP在三种土壤中分别具有相似的吸附能力;同一土壤中两种目标污染物的吸附能力为Kd(1,2-DCA)>Kd(1,2-DCP),但差别不大。1,2-DCA和1,2-DCP在三种土壤中的解吸可用Freundlich等温方程拟合,解吸的难易程度与土壤中黏粒含量相关,黏粒含量越高,目标污染物的解吸越困难,第三层(地下4.9～5.1m)土壤的防污能力较强;两种污染物在三种土壤中的解吸都存在明显的滞后效应,1,2-DCP的滞后指数比1,2-DCA的大。     

苏州城市河道底泥对磷酸盐的吸附与释放特征

为了探讨苏州古城区河道底泥对磷酸盐的吸附-释放特征,文中分别从改变上覆水的pH值、底泥吸附-释放动力学和等温吸附实验三个方面进行了研究。结果表明:(1)随着上覆水pH值的增大,苏州河道底泥对磷的吸附量逐渐减小;(2)底泥对磷的吸附过程是一个复合动力学过程,通常包括快吸附和慢吸附两个过程。底泥对磷的快速吸附在2h内快速进行,之后为慢吸附过程,到6h左右,基本达到一种动态吸附平衡;底泥对磷释放的动力学过程也包括快释放和慢释放过程。底泥释放磷在1·5h内快速进行,之后进入慢释放过程,磷酸盐含量基本稳定,达到释放平衡;(3)底泥具有较大的吸附磷的能力。随着上覆水的磷酸盐浓度增高,底泥吸附磷酸盐的量也增加。上覆水与底泥的比值越大,底泥对磷的吸附率越小。     

Understanding pH effects on trichloroethylene and perchloroethylene adsorption to iron in permeable reactive barriers for groundwater remediation

Metallic iron filings have been increasingly used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for trichloroethylene and perchloroethylene were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated trichloroethylene and perchloroethylene complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of trichloroethylene complexes more than those for perchloroethylene. Attractions between atomic hydrogen and iron atoms were more favorable when trichloroethylene versus perchloroethylene was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect trichloroethylene reaction rates more than those for perchloroethylene.     

An Experimental Study on the Conductivity Changes in Coal during Methane Adsorption-Desorption and their Influencing Factors

During the processes of methane adsorption and desorption, the internal structure of coal changes, accordingly leading to changes in electrical conductivity. In this paper, using low rank coal seams of the Yan’an Formation in the Dafosi field as the research subject, the relationship between coal resistivity, methane adsorption quantity, and equilibrium pressure is analyzed through proximate analysis, mercury injection tests, low temperature liquid nitrogen adsorption tests, and coal resistivity measurements during methane adsorption and desorption. The results show that during the process of pressure rise and methane adsorption, the conductivity of coal increases, resulting from heat release from methane adsorption, coal matrix swelling and adsorbed water molecules replaced by methane, but the resistivity reduction gradually decreases. The relationship between coal resistivity and methane adsorption quantity and equilibrium pressure can be described by a quadratic function. During the processes of depressurization and desorption, the resistivity of coal rebounds slightly, due to decalescence of methane desorption, coal matrix shrinkage and water-gas displacement, and the relationship coincides with a linear function. Methane adsorption leads to irreversible changes in coal internal structure and enhances the coal conductivity, and resistivity cannot be restored to the initial level even after methane desorption. The resistivity and reduction rate of durain are higher than those of vitrain, with relatively greater homogeneous pore throat structure and fewer charged particles in the double electric layer. In addition, moisture can enhance the conductivity of coal and makes it change more complexly during methane adsorption and desorption.     

无机盐与表面活性剂对菲在黄土上吸附/解吸行为的联合影响

以NaCl和MgCl₂、十二烷基苯磺酸钠(SDBS)分别作为无机盐、表面活性剂的代表, 研究两者共存对菲在黄土中吸附/解吸行为联合影响的特点及其形成机制.结果表明, NaCl(≥0.1 mol/L)、MgCl₂或SDBS的单独介入, 可缩短吸附平衡时间、增加吸附容量等, 即对吸附具促进作用, 随着介入浓度的升高, 促进作用越明显, 促进能力为MgCl₂＞SDBS＞NaCl; 不改变吸附模式, 仍较好地符合F型与H型.NaCl与MgCl₂同时介入, 对菲吸附的影响仍表现为促进作用, 呈现相加作用的特点, 且随着MgCl₂浓度的升高, 促进作用更明显.NaCl(或及MgCl₂)与SDBS的同时介入对吸附的联合影响, 总体上表现为相加作用, 但还呈拮抗作用的特点, 尤其MgCl₂浓度较高时.NaCl或(及)MgCl₂的存在, 或与SDBS共存时, 与纯水相比, 菲的解吸速度较快、解吸率较高、平衡时间较短, 且无滞后效应.可见, 无机盐与表面活性剂同时适量介入, 以强化菲等污染地下水系统的修复功效具一定的可行性.      

铁氧化物对土壤解吸阿特拉津的影响

阿特拉津是一种典型的环境激素, 铁氧化物是土壤矿物质的主要成分之一, 研究铁氧化物对阿特拉津的吸附行为有助于深入了解环境激素在环境中的行为.在研究阿特拉津的污染土壤与铁氧化物的混合物对阿特拉津吸附与解吸作用机理的基础上, 通过采用不同配比的土壤与铁氧化物的混合物对农药阿特拉津进行解吸行为过程的模拟, 并改变解吸时间、温度、pH值等因素, 研究影响解吸行为的主要因素.结果表明: 温度、pH值、铁氧化物与土壤的不同配比等因素均会对阿特拉津的解吸作用产生不同程度的影响.混合物对阿特拉津的解吸一般在4h左右便可达到动态平衡, 酸性或碱性环境以及适当的温度条件均会在一定程度上增强解吸作用, 且发现混合物比原土壤的解吸效果更明显.      

远红外作用下不同含水率煤体吸附/解吸能量变化规律

煤体对气体进行吸附/解吸过程的本质是气体分子和煤基质表面分子或原子相互作用的过程，而发生相互作用的本质是能量变化，为了深入研究远红外作用下煤层气吸附/解吸过程及能量变化规律，利用自主研制装置进行远红外作用下不同含水率煤样对CO₂的吸附/解吸实验，然后利用远红外热辐射原理所得的吸附/解吸能量公式对实验结果进行计算，得到不同含水率煤体吸附/解吸过程能量变化规律。结果表明:在远红外作用下，解吸率虽然随含水率增大呈下降趋势，但是下降幅度明显减小，远红外作用可以降低水分对煤层气吸附/解吸能力的影响；远红外作用下不同含水率煤体对气体吸附/解吸过程是一个物理变化，从能量角度可以解释该过程，其变化规律与等温吸附/解吸过程相吻合。研究结果丰富了煤层气增产技术理论。      

Kinetics of neptunium(V) sorption and desorption on goethite: An experimental and modeling study

Various sorption phenomena, such as aging, hysteresis and irreversible sorption, can cause differences between contaminant (ad)sorption and desorption behavior and lead to apparent sorption ‘asymmetry’. We evaluate the relevance of these characteristics for neptunium(V) (Np(V)) sorption/desorption on goethite using a 34-day flow-cell experiment and kinetic modeling. Based on experimental results, the Np(V) desorption rate is much slower than the (ad)sorption rate, and appears to decrease over the course of the experiment. The best model fit with a minimum number of fitting parameters was achieved with a multi-reaction model including (1) an equilibrium Freundlich site (site 1), (2) a kinetically-controlled, consecutive, first-order site (site 2), and (3) a parameter ψ_2,de, which characterizes the desorption rate on site 2 based on a concept related to transition state theory (TST). This approach allows us to link differences in adsorption and desorption kinetics to changes in overall reaction pathways, without assuming different adsorption and desorption affinities (hysteresis) or irreversible sorption behavior a priori. Using modeling as a heuristic tool, we determined that aging processes are relevant. However, hysteresis and irreversible sorption behavior can be neglected within the time-frame (desorption over 32 days) and chemical solution conditions evaluated in the flow-cell experiment. In this system, desorption reactions are very slow, but they are not irreversible. Hence, our data do not justify an assumption of irreversible Np(V) sorption to goethite in transport models, which effectively limits the relevance of colloid-facilitated Np(V) transport to near-field environments. However, slow Np(V) desorption behavior may also lead to a continuous contaminant source term when metals are sorbed to bulk mineral phases. Additional long-term experiments are recommended to definitely rule out irreversible Np(V) sorption behavior at very low surface loadings and environmentally-relevant time-scales.     

Adsorption of oxyanions by spent western oil shale: II. selenite

The adsorption and desorption behavior of selenite by processed Green River Formation oil shales were examined. The selenite adsorption data could be quantitatively described by both the Freundlich and Langmuir isotherms. However, greaterR ² values were obtained for the Freundlich isotherms. Furthermore, selenite adsorption was not a function of the extraction process. The adsorption of selenite by the processed oil shales was irreversible. Upon dilution of the equilibrium systems, additional selenite removal from solution occurred. A thermochemical analysis of the adsorption and desorption equilibrium solutions indicated that the solutions were undersaturated with respect to a number of metal selenite solids. This indicates that precipitation processes are not influencing selenite behavior. However, not all selenite minerals were examined in the evaluation because of the lack of thermochemical data. An insufficient equilibration period for the adsorption study or the alteration of processed oil shale solids as a result of hydration reactions may also have hastened the additional removal of selenite during the desorption studies.