From illite/smectite clay to mesoporous silicate adsorbent for efficient removal of chlortetracycline from water

A series of mesoporous silicate adsorbents with superior adsorption performance for hazardous chlortetracycline(CTC) were sucessfully prepared via a facile one-pot hydrothermal reaction using low-cost illite/smectite(IS) clay,sodium silicate and magnesium sulfate as the starting materials.In this process,IS clay was "teared up" and then "rebuilt" as new porous silicate adsorbent with high specific surface area of 363.52 m~2/g(about 8.7 folds higher than that of IS clay) and very negative Zeta potential(- 34.5 mV).The inert Si- O- Si(Mg,Al) bonds in crystal framework of IS were broken to form Si(Al)- O~- groups with good adsorption activity,which greatly increased the adsorption sites served for holding much CTC molecules.Systematic evaluation on adsorption properties reveals the optimal silicate adsorbent can adsorb 408.81 mg/g of CTC(only 159.7 mg/g for raw IS clay) and remove 99.3%(only 46.5%for raw IS clay) of CTC from 100 mg/L initial solution(pH 3.51;adsorption temperature 30℃;adsorbent dosage,3 g/L).The adsorption behaviors of CTC onto the adsorbent follows the Langmuir isotherm model,Temkin equation and pseudo second-order kinetic model.The mesopore adsorption,electrostatic attraction and chemical association mainly contribute to the enhanced adsorption properties.As a whole,the high-efficient silicate adsorbent could be candidates to remove CTC from the wastewater with high amounts of CTC.     

不同极性有机污染物在腐殖质-蒙脱石复合物上的吸附特性

研究了3种具有不同结构和极性的芳香类疏水有机污染物(非极性的菲和1,2,4,5-四氯苯、极性的1,2-二氯苯)在蒙脱石及富里酸/胡敏酸-蒙脱石复合物上的界面行为.由于疏水性分配作用,与富里酸和胡敏酸复合后的蒙脱石对非极性的菲和1,2,4,5-四氯苯的吸附量增加.元素分析结果表明,胡敏酸的(N+ O)/C值低于富里酸,因此其疏水性强于富里酸,这使得菲和1,2,4,5-四氯苯在胡敏酸-蒙脱石复合物上的吸附量均高于富里酸-蒙脱石复合物.极性的1,2-二氯苯在水中的溶解度最高(131 mg/L),其在蒙脱石上的吸附量远高于非极性的菲和1,2,4,5-四氯苯.1,2-二氯苯主要通过与蒙脱石表面形成偶极作用吸附在蒙脱石上,且富里酸和胡敏酸对蒙脱石吸附1,2-二氯苯的影响较小.1,2-二氯苯的Freundlich吸附曲线的n大于1,表明1,2-二氯苯之间能形成偶极-偶极作用,进一步加大其在蒙脱石上的吸附量.富里酸和胡敏酸降低了菲在蒙脱石上的解吸率,且菲在疏水性最强的胡敏酸-蒙脱石复合物上的解吸率最低,表明菲与胡敏酸-蒙脱石复合物的作用力最强.     

Effects of clay minerals on Cr(VI) reduction by organic compounds

The objective of this study is to examine the effect of clayminerals (illite, montmorillonite, and kaolinite) on chromate (Cr(VI)) reduction by several low molecular weightorganic compounds. Batch experiments at pH ranging from 3.0 to6.0 and 25 °C showed that 2:1 layered clays illite andsmectite catalyzed Cr(VI) reduction by oxalate. The catalyticeffect increased as pH was decreased. The 1:1 clay kaolinite hadno catalytic effect under comparable conditions. Direct Cr(VI)reduction by reactive moieties associated with illite andmontmorillonite was observed, but at a much slower rate than thecatalytic pathway. Cr(VI) reduction by glyoxylic acid, glycolicacid, lactic acid, and mandelic acid was accelerated by illite,although aqueous phase reduction might occur in parallel. Theseresults suggest that Cr(VI) reduction rates in subsurfaceenvironments rich in organic compounds may be elevated throughcatalysis of surface-bound metals and/or soluble species from theclay minerals, and as a result, higher than those expected fromaqueous phase reaction alone. Such rate enhancement for Cr(VI)reduction needs to be accounted for when developing new remedialtechniques for chromium site remediation or assessing its naturalattenuation.     

纳米伊/蒙黏土对水体中重金属的吸附去除效果

为明确纳米伊/蒙黏土(下称伊/蒙黏土)作为修复材料在去除水体重金属方面的应用潜力,研究了伊/蒙黏土对水体中Ni2+、Cu2+和Cd2+的去除效果与吸附规律,并通过小麦水培试验分析伊/蒙黏土降低水体重金属在小麦地上部分的累积和缓解重金属对小麦的毒害效应等效果. 结果表明:伊/蒙黏土可以吸附去除水体中的Ni2+、Cu2+和Cd2+,当水体中ρ(Ni2+)、ρ(Cu2+)和ρ(Cd2+)分别为5、10、2 mg/L时,添加2%(以w计)的伊/蒙黏土对3种重金属的去除率均达到95%以上. 伊/蒙黏土对重金属的吸附等温线符合Langmuir方程,对Ni2+、Cu2+和Cd2+的理论最大吸附量分别为2.13、8.52和1.56 mg/g. 在培养液中添加2%伊/蒙黏土可降低小麦对Ni2+、Cu2+和Cd2+的累积富集,缓解重金属对小麦生长的毒害效应. 研究显示,纳米伊/蒙黏土可有效去除水体中的Ni2+、Cu2+和Cd2+,并缓解其对小麦的毒性,因此其在修复水体重金属污染、恢复水环境生态功能方面具有潜在的应用前景.      

Mechanochemical removal of organo-chlorinated compounds by inorganic components of soil

The purpose of this work is to evaluate the catalytic efficiency of two metal oxides, ferrihydrite and birnessite and of a ferruginous smectite, towards organic molecules such as 4-chloroaniline (4-CA), pentachlorophenol (PCP), and five polychlorinated biphenyls (PCBs) characterised by different number and position of chlorine atoms. Mechanochemical dry contacts with light grinding between catalytic surfaces and pollutants have been carried out.

The efficiency of the mechanochemical removal was compared with batch experiments for the soluble compounds (PCP and 4-CA). The removal of 4-CA and PCP by the mechanochemical procedure resulted more effective than by batch contact in the presence of birnessite and ferrihydrite, particularly at higher pH (100% removal of 4-CA by birnessite in 30 min at pH 8.6 after the mechanochemical contact compared to 20% removal using the batch interaction at the same pH).

The mechanochemical contact of PCBs and birnessite produced a removal of pollutant that was a function of the number of chlorine atoms (complete removal of 2,2^′-dichlorobiphenyl in 10 days and a removal of 30% and 20% of 2^′,3,4-trichlorobiphenyl and 3,3^′,4,4^′-tetrachlorobiphenyl, respectively in 90 days) and of the position of chlorine atoms about the biphenyl rings (100% of 2,2^′-dichlorobiphenyl in 10 days, 84% of 3,3^′-dichlorobiphenyl in 15 days and 40% of 4,4^′-dichlorobiphenyl in 27 days).     

天然消化道粘膜保护剂思密达的成分及物相分析

分析研究了天然消化道粘膜保护剂思密达的化学成分、物相组成和矿物形态,查明其基本矿物成分为钙钠质蒙脱石,系由天然膨润土经过精细加工而成。本实验结果有助于合理开发利用我国丰富的膨润土及其它药用矿石     

负载型混晶相TiO2光催化剂的低温制备及其光催化活性

以蒙皂石为载体，钛酸四丁酯为前驱物，在较低温度下由溶胶凝胶法制备得到负载型TiO₂光催化剂。研究了理论负载量、固定化温度、干燥、焙烧温度对TiO₂/蒙皂石复合光催化剂光催化性能的影响。采用XRD分析技术对复合材料进行了表征。结果表明，负载的TiO₂以锐钛矿-金红石的混晶相存在。当TiO₂理论负载量为15 mmol/g、溶胶反应温度为25℃、干燥温度为70℃时，TiO₂/蒙皂石复合光催化剂对偶氮染料光催化反应1 h降解率达93.40%。该制备技术的特点是在省去高温焙烧的条件下，制备出光催化活性高的负载型光催化剂。     

牛骨炭与伊/蒙黏土组配改良剂对土壤中Cd的钝化效果

农田土壤Cd污染是我国最为突出的环境问题之一,开展新型钝化修复Cd污染土壤材料的研究和技术开发对保障农产品安全及保护人体健康具有重要意义.以北京某蔬菜生产基地设施大棚Cd污染土壤为试验对象,温室条件下采用盆栽试验,研究牛骨炭与伊/蒙黏土复合组配的改良剂对Cd污染土壤的钝化效果,探讨不同配比的组配改良剂对土壤Cd有效态含量以及小白菜Cd吸收量的影响.结果表明:在污染土壤中添加1%、2%和5%的组配改良剂,可明显降低土壤有效态Cd含量及小白菜对Cd的吸收,土壤有效态Cd含量降幅最大值达42.3%,小白菜地上部分Cd含量降幅最大值达22.7%,组配改良剂中骨炭成分比例越高,钝化效果越好,尤其以添加5%组配改良剂（添加组配改良剂中牛骨炭含量为50%）对Cd的稳定化效果最佳,且不同组配改良剂处理均不会对小白菜生长产生不良影响,表明牛骨炭与伊/蒙黏土组配的改良剂在修复Cd污染土壤上具有较好的应用潜力.研究显示,牛骨炭与伊/蒙黏土组配的改良剂符合绿色修复技术的发展要求,可作为钝化修复农田重金属污染土壤的环保新材料.      

富里酸和胡敏酸在蒙脱石上的吸附特性

为进一步揭示有机污染物在黏土矿物上的迁移转化规律,运用1H核磁共振光谱、高效体积排阻色谱、扫描电镜、比表面分析以及傅里叶变换红外光谱等多种分析技术综合分析了富里酸和胡敏酸在蒙脱石上的吸附行为. 结果表明,由于不同官能团与蒙脱石的亲和性不同,富里酸和胡敏酸在吸附过程中均产生组分分级,大分子被优先吸附在蒙脱石表面. 由于疏水性作用,蒙脱石对疏水性更强的胡敏酸的吸附量更大. 蒙脱石吸附富里酸后比表面积和孔容分别下降3.67m2/g和0.005cm3/g,而吸附胡敏酸后则均略微增大,说明具有较大颗粒尺寸的胡敏酸更多地堆积在蒙脱石外表面,而富里酸则更易进入蒙脱石孔隙. 蒙脱石吸附富里酸和胡敏酸后溶液pH分别升高了0.44和0.41,说明发生了配体交换反应. 蒙脱石对富里酸和胡敏酸的吸附量随pH增大和离子强度的降低而减少,表明羟基能够抑制富里酸/胡敏酸负电基团与蒙脱石表面羟基的配体交换反应,而盐离子则能降低蒙脱石和腐殖质间的静电斥力.