不同改性黏土矿物吸附净化磷污染水体的性能比较

比较了酸、热及其复合改性对凹凸棒石黏土、膨润土和高岭土等3种黏土矿物吸附净化不同程度磷污染水体能力的影响。结果发现,2%浓度酸处理、300℃热活化及酸热复合改性均可以显著提高凹凸棒石黏土的磷吸附净化能力,且以复合改性效果最好,Ⅴ类和劣Ⅴ类水的磷去除率均比原土提高30%以上;酸、热改性均能显著提高膨润土的磷吸附净化能力,但综合不同程度磷污染水体来看,热活化略优于酸改性,但酸热复合改性没有呈现更佳的效果;热改性显著提高高岭土的磷吸附净化能力,而酸改性却不同程度地降低了高岭土的磷吸附净化能力,酸热复合改性的效果亦不如热单独改性。结果表明,在针对不同程度磷污染水体时需根据黏土矿物特性选用酸处理、热活化或酸热复合改性方法来提高污水的吸附净化效率。     

Removal of Fluoride from Water by Adsorption onto Lanthanum Oxide

Rare earth mineral based adsorbent viz. lanthanum oxide was investigated for potential application in defluoridation of drinking water for isolated and rural communities. Results of batch experiments indicated about 90% removal in 30 min from a 4 mg L⁻¹ synthetic fluoride solution. The effects of various parameters like contact time, pH, initial concentration, and sorbent dose on sorption efficiency were investigated. Adsorption efficiency was dependent on initial fluoride concentration and the sorption process followed BET model. Variation of pH up to 9.5 has insignificant effect on sorption and beyond a pH of 9.5, the effect was drastic. Among anions investigated, carbonates exhibited high detrimental effect on fluoride adsorption while anions like bicarbonates, chlorides, and sulfates did not seriously affect the process. Adsorbent showed negligible desorption of fluoride in distilled water. Alum was more effective regenerant than HCl and NaOH. Results of cyclic regeneration with alum indicated that the sorbent could be regenerated for ten cycles without significant loss of sorption capacity. Studies with upflow fixed-bed continuous flow columns indicated the usefulness of sorbent for fluoride removal in continuous flow process.     

BS-12改性不同磁性黏土矿物对苯酚吸附及机制的比较

采用共沉淀法制备磁性海泡石（MST）、磁性沸石（MZT）和磁性凹凸棒石（MAT）,并以两性表面活性剂十二烷基二甲基甜菜碱（BS-12）对其进行改性,以X射线衍射（XRD）对不同吸附剂材料进行表征分析,通过批处理法比较了BS-12改性不同磁性黏土矿物对苯酚的吸附特征,同时考察了温度、pH和离子强度对不同磁性黏土矿物间及不同改性比例下吸附苯酚的影响。结果表明,三种黏土矿物原样和磁化样对苯酚的吸附能力分别呈NAT＞NST＞NZT、MAT＞MST＞MZT的大小顺序,磁化对凹凸棒石的苯酚吸附能力影响最大,这与Fe3O4在凹凸棒石上的覆盖度较高有关。经BS-12改性后,三种改性磁性黏土矿物对苯酚的吸附量均随改性比例的增大而增加,具有一致性;三种磁性黏土矿物中,BS-12改性对磁性海泡石的苯酚吸附能力提升最多,这与BS-12在磁性海泡石的改性率较高有关。温度和溶液初始pH值的升高不利于BS-12改性磁化样对苯酚的吸附,但离子强度的增加对BS-12改性磁化样吸附苯酚具有促进作用。BS-12改性磁性黏土矿物对苯酚的吸附以疏水分配作用为主,吸附能力取决于有机碳含量。三种改性磁性黏土矿物中,BS-12改性磁性凹凸棒石上的有机碳含量最高,对苯酚的吸附能力最强,且吸附受温度、pH和离子强度的影响最小。     

Two-stage Batch Adsorber Design: A Time-Dependent Langmuir Model for Adsorption of Pb2+ and Cd2+ onto Modified Kaolinite Clay

The kinetics of the adsorption of Pb²⁺ and Cd²⁺ by sodium tetraborate (NTB)-modified kaolinite clay adsorbent was studied. A one-stage and two-stage optimization of equilibrium data were carried out using the Langmuir and time-dependent Langmuir models, respectively. Increasing temperature was found to increase the pseudo-second order kinetic rate constant and kinetic data for Pb²⁺ adsorption were found to fit well with the pseudo-second order kinetic model (PSOM) while that for Cd²⁺ were found to show very good fit to the modified pseudo-first order kinetic model (MPFOM). Binary solutions of Pb²⁺ and Cd²⁺ reduced the adsorption capacity of the modified adsorbent for either metal ion with increased initial sorption rate due to competition of metal ions for available adsorption sites. The use of NTB-modified kaolinite clay adsorbent reduces by approximately 72.2% and 96.3% the amount of kaolinite clay needed to adsorb Pb²⁺ and Cd²⁺ from wastewater solutions. From the two-stage batch adsorber design study, the minimum operating time to determine a specified amount of Pb²⁺ and Cd²⁺ removal was developed. The two-stage batch adsorption process predicted less than half the minimum contact time to reach equilibrium in the one-stage process for the adsorption of Pb²⁺ and Cd²⁺ by NTB-modified kaolinite clay adsorbent and requires 0.05 times the mass of the adsorbent for the single-stage batch adsorption at the same operating conditions.     

Electrokinetic Remediation of Pentachlorophenol Contaminated Clay Soil

This paper presents a bench-scale experimental study performed to investigate the remediation of low permeable soil contaminated with pentachlorophenol (PCP) using the electrokinetic technique. A total of six electrokinetic tests were performed using kaolin soil spiked with 100 mg/kg of PCP. The first three tests were performed with an applied voltage gradient of 1 VDC/cm, where each test employed one of the three different flushing solutions: deionized water, electrolyte, or buffered electrolyte. The other three tests were performed using the same electrolyte solution, but each employed voltage gradient of 2 VDC/cm under constant and periodic application modes and constant voltage gradient with electrode liquid recirculation. The results of this study showed that PCP can be degraded in an electrokinetic system due to the direct electrochemical reduction process at the electrodes. The degradation of PCP ranged from 52% to about 78% depending on the conditions present. As the applied voltage gradient across the PCP-contaminated soil increased, the electroosmotic flow and PCP migration toward the cathode increased, resulting in higher PCP degradation by the direct reduction process. In the tests with electrolyte flushing solution, PCP degradation was about 58% and 65% under the applied voltage gradients of 1 and 2 VDC/cm, respectively. The mode of application of voltage potential across the PCP-contaminated soil showed noticeable effect on the system pH and electroosmotic flow and hence the PCP degradation. The highest PCP degradation (i.e., 78%) was in the test with constant 2 VDC/cm voltage gradient and recirculation application. Overall, this study demonstrated that electrokinetic technology has the potential to remediate PCP-contaminated clay soils by the direct reductive process. The electroosmatic flow as well as degree of PCP degradation during electrokinetics depend on the applied potential gradient and properties of the aqueous phase such as pH, ionic strength, and presence of carbonates.     

Methylene Blue Adsorption onto Water Hyacinth: Batch and Column Study

The adsorption of methylene blue cationic dye by water hyacinth root was studied in a batch system. The experimental data isotherms were analyzed using the Langmuir and Freundlich equations. The monolayer adsorption capacity for methylene blue dye was found as 0.187?kg?kg^?1. Three kinetic models (the pseudo-first order, the pseudo-second order, and the unified approach) were used to calculate the adsorption rate constants. The kinetic data along with equilibrium constants (maximum monolayer capacity and Langmuir constant) fitted well with unified approach model for different initial concentrations, and the rate constants were determined. Laboratory column experiments were conducted to evaluate the performance of water hyacinth root for methylene blue sorption under dynamic flow conditions. Breakthrough curves were plotted for the methylene blue adsorption on the adsorbent using continuous flow column operation by varying the bed height (0.06?C0.12?m) and the feed concentrations (0.1?C0.2?kg?m^?3). Different column design parameters, such as depth of exchange zone, adsorption rate, and adsorption capacity, were calculated. At the end, an attempt has also been made to model the data generated from column studies using the empirical relationship based on Bohart?CAdams model.     

Adsorption of Nonylphenol onto Granular Activated Carbon

The applicability of granular activated carbon (GAC)filtration for the removal of the xeno-estrogenicmicropollutant nonylphenol (NP) is evaluated using batchadsorption data. From the obtained adsorption data, it wasapparent that with contact times of 4 d and 24 hr and GACdosages of 1 and 0.1 g L^-1 no saturationof the GAC could be obtained with NP total contaminantloadings up to 10 000 μg L^-1.Higher NP concentrations could not be applied due to its lowwater solubility (～5 mg L^-1). The influence of temperature(4 or 28 °C) on NP sorption onto GAC was negligible.The results showed that the sorption capacity of GAC for NPwas at least 100 mg g^-1 GAC. According to thesedata it can be concluded that a full-scale GACfilter unit will be sufficient to remove environmentallyrelevant NP concentrations of 10 μg L^-1.Consequently, the existing GAC treatment technology indrinking water treatment should protect the consumer from theintake of the xeno-estrogenic micropollutant NP via drinkingwater. The sorption capacity of dissolved humic acids (DHA)for NP is considerable at liquid NP concentrations of 10 μgL^-1 and the affinity of DHA for GAC is not significant.These observations suggest that interference on removal of NP onGAC, due to the presence of DHA, can be expected at microgramper liter concentrations of NP. They may warrant the removalof humic substances in treatment steps preceding GAC-filtration.     

Remediation of Atrazine-contaminated Soil and Water by Nano Zerovalent Iron

Atrazine-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of nano zerovalent iron (nano ZVI) to dechlorinate atrazine (2-chloro-4ethylamino-6-iso-propylamino-1,3,5-triazine) in contaminated water and soil. This study determined the effects of iron sources, solution pH, Pd catalyst and presence of Fe or Al sulfate salts on the destruction of atrazine in water and soil. Our results indicate nano ZVI can be successfully used to remediate atrazine in water and soil. Aqueous solution of atrazine (30 mg l^?1) was treated with 2% (w/v) of nano ZVI and 5% (w/v) of commercial ZVI. Although, iron dose in nano ZVI treatment was less than that in commercial ZVI treatment, atrazine destruction kinetic rate (k _obs) of nano ZVI treatment (1.39 days^?1) was around seven times higher than that of commercial ZVI treatment (0.18 days^?1). Reductive dechlorination was the major process in destruction of atrazine by nano ZVI. The dechlorination product was 2-ethyl-amino-4-isopropylamino-1,3,5-triazine. Lowering the pH from 9 to 4 increased the destruction kinetic rates of atrazine by nano ZVI. Moreover, nano ZVI/Pd enhanced destruction kinetic rates of atrazine (3.36 day^?1). Pd played the important role as a catalyst during treatment of atrazine by nano ZVI. Atrazine destruction kinetic rates were greatly enhanced in both contaminated water and soil treatments by nano ZVI when sulfate salts of Fe(II), Fe(III) or Al(III) was add with the following order of removal rates: Al (III) (2.23 day^?1) > Fe (III) (2.04 day^?1) > Fe(II) (1.79 day^?1). The same results were found in atrazine-nano ZVI-soil incubation experiments.     

Remediation of Organochlorine Pesticide-Contaminated Soils by Surfactant-Enhanced Washing Combined with Activated Carbon Selective Adsorption

Remediation of organochlorine pesticide (OCP)-contaminated soils is urgently required especially in China. The present study investigated the removal of OCPs from two soils by triton X-100 (TX-100)-enhanced washing coupled with powdered activated carbon (PAC) adsorption treatment of the solution. Two contaminated soils, including a silt clay contaminated with chlordene, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethanes (DDDs), and dichlorodiphenyltrichloroethane (DDT) and a sandy loam containing chlordanes and mirex, were selected. Effects of varied operating parameters, including TX-100 dosage, liquid/soil (L/S) ratio, and extraction time, on the contaminant removal were examined. For both soils, OCP removal was clearly enhanced with increasing TX-100 in extraction solution and L/S ratio. Meanwhile, the removal efficacy was also impacted by soil texture and characteristics and contents of the contaminants. Moreover, by using PAC as an absorbent, a significant decrease in the contaminants in the extraction solutions was detected, and TX-100 could be further reused. Our investigation suggests that surfactant-enhanced washing combined with activated carbon selective adsorption would be an alternative to remediate OCP-contaminated soils.     

纳米粘土矿物对阿特拉津的吸附-解吸特性研究

采用批量平衡实验,研究了纳米粘土矿物与原粘土矿物对除草剂阿特拉津的吸附解吸特陛。结果表明,粘土矿物对阿特拉津的吸附-解吸均能用Freundlich方程很好地拟合。随着溶液中阿特拉津浓度的增加,粘土矿物对阿特拉津的吸附量增加;粘土矿物粒径越小,吸附量越大,纳米粘土矿物的吸附量显著大于原粘土矿物。粘土矿物对阿特拉津吸附量大小顺序为：纳米SiO2）纳米蒙脱石〉凹凸棒石〉蒙脱石〉SiO2。粘土矿物对阿特拉津的解吸表现出一定的滞后效应,即粘土矿物吸附的阿特拉津越多,解吸的越少。粘土矿物对阿特拉津的解吸率大小顺序为：SiO2〉凹凸棒石〉纳米蒙脱石〉纳米SiO2〉蒙脱石。     

几种土壤及黏土矿物对多氯联苯吸附特性的研究

采用批量平衡试验,研究了不同土壤及长黏土矿物对多氯联苯吸附特性。结果表明:多氯联苯浓度范围为0.25~5.0mg L-1时,不同土壤及黏土矿物对多氯联苯的吸附均能用Freundlich方程很好地拟合,随着溶液中多氯联苯浓度的增加,土壤及黏土矿物对多氯联苯的吸附量增加;几种土壤对多氯联苯吸附量大小顺序为:红壤>黄褐土>砂姜黑土,土壤有机质、粘粒等对多氯联苯吸附起主要作用,土壤更易吸附高氯代PCB77;黏土矿物对多氯联苯吸附量大小顺序为:纳米蒙脱石>纳米SiO2>凹凸棒石,黏土矿物吸附多氯联苯能力的大小与黏土矿物的比表面积、粒径、层状结构等有关;多氯联苯本身分子的大小影响其在黏土矿物上的吸附;土壤中添加黏土矿物可以提高对多氯联苯的吸附。     

超声波十六烷基三甲基溴化铵改性斜发沸石的制备及其对水体中六六六的吸附

利用超声波对天然斜发沸石进行进行有机改性,提高了天然沸石对有机污染物六六六的吸附能力,在单因素实验的基础上对改性条件进行了优化,得出超声波十六烷基三甲基溴化铵有机改性天然斜发沸石的最优实验条件为:十六烷基三甲基溴化铵的浓度为55.1 mmol/L,沸石400℃培烧2 h,50℃超声波处理时间10 min.在此条件下改性的天然斜发沸石在水中加入2 g/L,对水中六六六的去除率达74.1%.     

Adsorption behavior of the catechins and caffeine onto polyvinylpolypyrrolidone

Adsorbent is one of the most important factors for separation efficiency in fixed-bed purification techniques. The adsorption behavior of catechins and caffeine onto polyvinylpolypyrrolidone (PVPP) was investigated by static adsorption tests. The results showed that catechins rather than caffeine were preferred to adsorb onto PVPP since the adsorption selectivity coefficient of total catechins vs caffeine was around 22.5, and that adsorption of catechins could be described by the pseudo-second-order model. Adsorption amount of caffeine onto PVPP in green tea extracts solution was much higher than that in purified caffeine solution although the initial concentration of caffeine was similar in the two solutions, indicating the caffeine might be attached with catechins which were adsorbed by PVPP instead of being adsorbed by PVPP directly. The results also showed that the adsorption capacity of catechins and caffeine decreased with an increase in temperature, and that Freundlich and Langmuir models were both suitable for describing the isothermal adsorption of catechins, but not suitable for caffeine. The predicted maximum monolayer adsorption capacity of total catechins by PVPP was 671.77 mg g(-1) at 20 °C, which was significantly higher than that by other reported adsorbents. The thermodynamics analyses indicated that the adsorption of catechins onto PVPP was a spontaneous and exothermic physisorption process, revealing lower temperature was favorable for the adsorption of catechins. Elution tests showed that the desorption rates of catechins and caffeine were higher than 91% and 99% after two elution stages; in detail, almost all of the caffeine could be washed down at the water eluting stage, while catechins could be recovered at the dimethyl sulfoxide/ethanol solution eluting stage. Thus, the PVPP could be used as an excellent alternative adsorbent candidate for separating catechins from crude tea extracts, although some investigations, such as exploring the new eluants with low boiling point and high desorption efficiency, should be conducted furthermore.     

磷酸盐在水铁矿及水铁矿-胡敏酸复合体表面的吸附

The adsorption of phosphate onto ferrihydrite (FH) and two FH-humic acid (HA) complexes, obtained by co-precipitating FH with low (FH-HA1) and relatively high amounts of humic acid (FH-HA2), was studied through kinetics and isotherm experiments to determine the differences in phosphate adsorption between FH-HA complexes and FH and to reveal the mechanism of phosphate adsorption onto two soil compositions. The isoelectric point (IEP) and the specific surface area (SSA) of the mineral decreased as the particle porosity of the mineral increased, which corresponded to an increase in the amount of organic carbon. The adsorption capacity of phosphate was higher on FH than on FH-HA1 and FH-HA2 at the scale of micromoles per kilogram. The initial adsorption rate and adsorption affinity of phosphate decreased with an increase in the amount of HA in the mineral. The sensitivity of phosphate adsorption to the change in the pH was greater for FH than for FH-HA complexes. Ionic strength did not affect the adsorption of phosphate onto FH and FH-HA1 at a lower pH, and the increase in the ionic strength promoted phosphate adsorption at a higher pH. However, for the FH-HA2 complex, the increase in the ionic strength inhibited the adsorption of phosphate onto FH-HA2 at a lower pH and increased the adsorption at a higher pH.     

Adsorption of Methylene Blue from Aqueous Solution onto Perlite

Adsorption of methylene blue from aqueous solutionsonto unexpanded and expanded perlite samples activatedby H₂SO₄ and NaCl solutions has beeninvestigated, to assess the possibility of usingperlite for removing cationic dyes from aqueoussolutions. The effects of pH and temperature of dyesolution on the adsorption capacities have beenevaluated. The experimental data were correlatedreasonably well by the Langmuir adsorption isothermand the isotherm parameters (Q _m and K) have beencalculated. The removal efficiency (P) anddimensionless separation factor (R) have shown thatperlite can be used for removal of methylene blue fromaqueous solutions, but unexpanded perlite is more effective.     

几种吸附剂对阿特拉津的吸附及其 Zeta 电位特性研究

通过振荡吸附平衡试验,研究了蒙脱石、凹凸棒石、竹炭、木炭对阿特拉津的吸附行为,讨论了pH值、离子强度对吸附的影响,并考察了吸附剂表面的Zeta电位变化。结果表明,几种吸附剂对阿特拉津的吸附均符合Freundlich方程;竹炭、木炭的吸附能力明显高于蒙脱石和凹凸棒石。吸附剂对阿特拉津的吸附量随着悬液离子强度的增加而增加,在悬液pH一定(pH=6),离子强度为10-3mol/L NaNO3时,蒙脱石、凹凸棒石对阿特拉津的吸附量分别为538.30、609.68 mg/kg,当离子强度增加为10-2mol/L时,吸附量分别增至611.26、731.63 mg/kg;当离子强度由10-3增至10-1mol/L NaNO3时,竹炭、木炭对阿特拉津的吸附量有较多增加。当悬液pH在3~8范围时,几种吸附剂表面均带负电荷,其Zeta电位值随着pH的增加而增加,随离子强度的增加而减小。悬液离子强度一定时,随着pH的增加,吸附阿特拉津后吸附剂表面Zeta电位变化不显著。研究结果有助于从机理上解析吸附剂对有机污染物的吸附行为。     

铁锰镁离子改性生物炭对溶液硝态氮的吸附性能研究

为突破生物炭对硝态氮吸附的局限性,以花生壳为原料,在600℃条件下热解制备生物炭(BC),分别用FeCl₃、MnCl₂、MgCl₂对其进行金属负载改性(BC-Fe、BC-Mn和BC-Mg),设计批量吸附试验,结合扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)和X射线衍射(XRD)等进行表征分析。结果表明,铁、锰、镁离子改性使生物炭的比表面积增大6.67～12.16倍,孔容增加3.30～6.00倍,并显著增强了对硝态氮(NO^-₃-N)的吸附性能(P<0.05),吸附量较BC增加11.5%～17.1%,BC-Fe、BC-Mn和BC-Mg对NO^-₃-N的最大吸附量分别为41.58、39.04、39.58 mg·g^-1,铁、锰、镁离子与炭的最佳质量比分别为0.80、0.20、0.20,铁离子改性效果最好;酸性条件有利于改性生物炭对NO^-₃-N的吸附,吸附动态符合Lan...     

砂土和黏土的颗粒差异对土壤斥水性的影响

斥水性土壤广泛存在于自然界中,并且对土壤环境和作物生长等有重要影响。建立理想化的土壤颗粒模型对砂土和黏土的斥水特性进行计算分析。结果表明:当接触角很小时,砂土中不存在斥水现象。随着接触角的增大,砂土斥水性与含水率密切相关,砂土的密实度对其斥水性也有重要影响,当砂土比较密实时,土壤的"亲水"与"斥水"特性对含水率特别敏感,随着含水率的变化,砂土可能由亲水性较好的土壤转变为斥水性土壤;当砂土比较松散时,土壤颗粒的斥水性对含水率并不敏感。当黏土接触角略小于90°且湿润半径b也较小时,黏土也存在斥水现象。如果黏土颗粒的接触角较小或接触角小于90°且湿润半径b较大,黏土总是亲水的。黏土含水率较大时,斥水特性由土壤颗粒的接触角决定。     

褐煤基材料对Cd~(2+)的吸附机制

为筛选稳定、高效、环境友好的重金属污染修复材料,利用批吸附试验研究了不同温度下褐煤、腐植酸、活性炭对镉(Cd~(2+))的吸附特征,采用非线性χ~2检验辅助决定系数判断等温线模型拟合度,用红外光谱对材料功能团进行了识别。结果表明,Temkin模型能最好拟合3种材料对Cd~(2+)的等温吸附过程,Langmuir和Freundlich模型也能较好拟合但与温度有关。吸附热力学参数表明,3种材料对Cd~(2+)的吸附为优惠发生的物理吸附,并且是自发的吸热过程,3种材料与Cd~(2+)之间均有较强的作用力。在温度294.55~313.15 K时腐植酸、褐煤和活性炭对Cd~(2+)的最大吸附量分别为36.14~44.09、29.63~38.20 mg·g~(-1)和21.04~30.34 mg·g~(-1),吸附量随温度升高而升高,吸附自由能随着温度升高而降低,说明升温吸附更容易发生。准二级动力学拟合数据最好,表明3种材料对Cd~(2+)的吸附存在着化学过程。褐煤基活性炭和褐煤基腐植酸具有丰富的孔隙结构。红外光谱图表明腐植酸和褐煤较大的吸附量与其含氧功能团种类较多以及在波数2 360 cm~(-1)和2 342 cm~(-1)附近吸收峰有关。因此,褐煤基3种材料对Cd~(2+)的吸附是自发的吸热过程,腐植酸对Cd~(2+)的最大吸附量和吸附能力最大,用Temkin等温方程和准二级动力学曲线能最适宜描述褐煤基材料对Cd~(2+)的吸附特征。