两种碳酸系Fe-LDHs负载改性沸石对Cd(Ⅱ)吸附特性对比研究

为提升以沸石为代表的天然吸附材料对重金属污染物吸附效果,并将新型功能材料层状双金属氢氧化物（layered double hydroxides,LDHs）有效应用于实际工程,采用水浴-共沉淀法制备两种Fe系碳酸型LDHs即时负载于沸石填料表面,利用场发射扫描电子显微镜（SEM）、能谱分析仪（EDS）和X射线衍射仪（XRD）对改性前后的沸石表面形态、化学成分和晶体结构进行表征;通过等温吸附及解吸附、吸附动力学、吸附热力学、竞争离子吸附和不同pH吸附试验,对比原始及改性沸石对Cd（Ⅱ）的吸附效果及其作用机理.结果表明:①改性沸石对Cd（Ⅱ）的吸附过程更符合Langmuir等温吸附模型和准二级动力学模型.②相较于原始沸石,两种改性沸石对Cd（Ⅱ）的吸附性能明显提升,且MgFe-LDHs负载改性沸石理论最大饱和吸附容量更高.③沸石改性后对Cd（Ⅱ）的吸附由放热过程变为吸热过程.④吸附时间、竞争离子及pH对沸石吸附Cd（Ⅱ）的效果产生不同程度的影响.研究显示,MgFe-LDHs负载改性沸石最大饱和吸附容量显著提升,吸附能力更强,且在不同条件下均表现出优良的吸附特性,具有作为高效除镉填料的潜力.      

新型复合材料处理氮磷废水的性能研究

采用阳离子表面活性剂十六烷基三甲基溴化铵（Hexadecyl Trimethyl Ammonium Bromide，HDTMA）和稀土溶液氯化镧（LaCl₃）对人造沸石进行改性，以增强其对水中氨氮和总磷的同步去除效果.结果表明，HDTMA和LaCl₃可有效负载于人造沸石表面，且在pH为7的条件下，改性沸石对氨氮和总磷的去除率分别由改性前的75%和1%提高到95.67%和91.96%.影响因素的实验表明，改性沸石对不同浓度废水的氨氮和总磷去除率均达到90%以上；氮、磷的去除率随改性沸石投加量的增加而上升；准二级动力学模型适合描述改性沸石对氨氮吸附的动力学过程，准一级动力学模型适合描述改性沸石对总磷吸附的动力学过程；吸附等温线说明改性沸石对水中氨氮的吸附属于离子交换，对水中磷酸盐的吸附包含离子交换和化学吸附两种过程.此外，通过再生性能、负载强度和离子竞争的试验证明改性沸石能应用于实际生化尾水的氮、磷去除.     

天然沸石吸附低浓度氨氮废水的研究

采用浙江某地天然沸石吸附废水中低浓度氨氮,研究了pH、天然沸石投加量对吸附的影响,分析了吸附等温线和吸附动力学,并进行了动态吸附和脱附研究。结果表明,pH对天然沸石吸附有较大影响,吸附的最佳pH为8.0;随着天然沸石投加量的增加,氨氮的去除率逐渐增大,但吸附量随之减小。Freundlich方程比Langmuir方程更好地描述氨氮在天然沸石上的吸附行为,且此吸附是优惠吸附。假二级方程很好地拟合吸附动力学实验数据,吸附速率常数k2随着天然沸石投加量的增大而增大。装填105g天然沸石吸附柱处理含氨氮20mg/L废水的水量为15L,出水氨氮浓度小于5mg/L。用含氯化钠和氢氧化钠的溶液作为脱附剂,脱附率为95.5%。     

HDTMA改性沸石的制备及吸附废水中对硝基苯酚的性能和动力学

采用十六烷基三甲基溴化铵(HDTMA)对天然沸石进行改性,研究了沸石的改性条件、改性沸石投加量、废水p H值、反应时间等对HDTMA改性沸石去除废水中对硝基苯酚性能的影响,并分析了吸附动力学和吸附等温线.结果表明,改性沸石对废水中对硝基苯酚的吸附效果明显高于天然沸石,当制备改性沸石的HDTMA溶液的质量分数为1.2%,且其p H值为10时,改性沸石对废水中对硝基苯酚的吸附量达到2.53 mg·g~(-1),远高于天然沸石的0.54 mg·g~(-1).吸附实验中,改性沸石投加量8 g·L~(-1),反应时间90 min,p H=6的条件下,HDTMA改性沸石对废水中对硝基苯酚的去除率高达93.9%.吸附动力学和等温线研究表明,一级动力学方程能够更好地拟合沸石吸附对硝基苯酚的过程(R20.90),不同温度条件下Langmuir等温线拟合方程的相关系数均在0.90以上,数据和方程拟合性较好.     

Fe3O4/GO对水溶液中Cd(II)去除的影响因素

为探索高效且快速去除水溶液中Cd （Ⅱ）污染方法,采用自制磁性四氧化三铁负载氧化石墨烯（Fe₃O₄/GO）纳米复合材料对水溶液中Cd （Ⅱ）进行去除,利用单因素实验确定影响因素水平范围（初始Cd （Ⅱ）浓度、温度、反应时间、初始pH值）,并采用响应面法（RSM）及人工神经网络-遗传算法（ANN-GA）对去除水溶液中Cd （Ⅱ）的影响因素（4因素3水平）进行优化,利用等温吸附、动力学及热力学参数研究吸附剂性能.通过扫描电子显微镜（SEM）、X射线衍射仪及超导量子干涉器件（SQUID）对复合材料表征.结果表明,平均粒径为30.9nm的磁性Fe₃O₄/GO纳米复合材料被成功制备.RSM用于磁性Fe₃O₄/GO纳米复合材料对水溶液中Cd （Ⅱ）去除条件优化,预测去除率达到86.451%,验证试验为82.220%,对应条件：温度为20.14℃,反应时间为57.78min,初始pH值为6.41和初始Cd （Ⅱ）浓度为11.18mg/L; ANN-GA优化条件后的预测去除率为89.722%,验证试验为87.723%,相应条件：温度为29.96℃,pH值为5.49,初始Cd （Ⅱ）浓度为28.36mg/L,反应时间为65.78min.根据模型R²值,预测的最大去除率及验证试验,ANN-GA模型性能及预测能力均高于RSM.RSM方差分析表明4个因素对磁性Fe₃O₄/GO纳米复合材料去除水溶液中Cd （Ⅱ）的影响大小为：初始Cd （Ⅱ）浓度>温度>反应时间>pH值.吸附机理分析结果显示,Fe₃O₄/GO纳米复合材料对Cd （Ⅱ）吸附过程同时存在着物理吸附和化学吸附.结合ANN-GA优化,利用磁铁实现且快速分离,磁性Fe₃O₄/GO纳米复合材料用于去除Cd （Ⅱ）是可行的.关键字：Cd （Ⅱ）;四氧化三铁负载氧化石墨烯;单因素实验;响应面法;人工神经网络-遗传算法中图分类号：X53     

氧化铁改性沸石对Se(Ⅳ)的吸附性能及试验废物再利用研究

为解决天然沸石去除废水中Se（Ⅳ）能力低的问题,采用氯化铁对天然沸石进行改性,制备表面负载氧化铁的改性沸石,即氧化铁改性沸石,并将其应用于去除水体中Se（Ⅳ）.首先对比天然沸石和氧化铁改性沸石的结构特征,研究二者对Se（Ⅳ）溶液的吸附特性,并通过X射线荧光光谱（XRF）、X射线衍射图谱（XRD）、扫描电镜（SEM）和氮气吸附孔径分布测试（BET）对二者进行表征;其次进行吸附试验,考虑接触时间、pH、吸附剂投加量、初始溶液反应浓度的影响,并通过天然沸石和氧化铁改性沸石的吸附动力学及吸附等温线对吸附的机理进行阐述.结果表明:①氧化铁改性沸石表面形成细碎的球状颗粒,分布在沸石的表面.②氧化铁改性沸石能够高效地吸附水体中的Se（Ⅳ）,且在pH为3时吸附效率最高,其对Se（Ⅳ）溶液的去除率最高达97.7%,其理论最大吸附量为46.901 mg/g.③氧化铁改性沸石对Se（Ⅳ）的吸附过程符合准二级动力学模型和Langmuir等温吸附模型.④添加负载Se（Ⅳ）后的氧化铁改性沸石土壤均达到富硒土壤标准（>0.4 mg/kg）.研究显示,氧化铁改性沸石吸附Se（Ⅳ）的效果较好,显著优于天然沸石的吸附效果,且吸附Se（Ⅳ）废水后的废弃氧化铁改性沸石还可应用于土壤改良方向.      

Removal of humic acid from aqueous solution by cetylpyridinium bromide modified zeolite

Natural zeolite was modified by loading cetylpyridinium bromide (CPB) to create more e cient sites for humic acid (HA) adsorption. The natural and CPB modified zeolites were characterized with X-ray di raction, field emission scanning electron microscopy, Fourier transform infrared spectroscopy and elemental analysis. The e ects of various experimental parameters such as contact time, initial HA concentration, solution pH and coexistent Ca2+, upon HA adsorption onto CPB modified zeolites were evaluated. The results showed that natural zeolite had negligible a nity for HA in aqueous solutions, but CPB modified zeolites exhibited high adsorption e ciency for HA. A higher CPB loading on natural zeolites exhibited a larger HA adsorption capacity. Acidic pH and coexistent Ca2+ were proved to be favorable for HA adsorption onto CPB modified zeolite. The kinetic process was well described by pseudo second-order model. The experimental isotherm data fitted well to Langmuir and Sips models. The maximum monolayer adsorption capacity of CPB modified zeolite with surfactant bilayer coverage was found to be 92.0 mg/g.     

NaCl改性沸石对水中氨氮的吸附机制

通过颗粒强度测定、扫描电镜分析（SEM）、X射线能谱分析（EDS）和零电点测定（pHPZC）考察改性前后沸石表面特性的变化,考察pH值、沸石投加量、初始氨氮浓度以及温度对吸附过程的影响,并通过吸附等温式和吸附动力学对吸附机制进行描述.经过NaCl改性后的沸石的颗粒强度明显增大,表面更加粗糙,孔径增大,钠离子通过交换作用进入到沸石内部.pH值为7,沸石投加量为8g/L,温度为35℃时吸附效果最好,平衡吸附量（qe）与氨氮初始浓度呈正相关性.Langmuir等温线比Freundlich等温线更适合描述实验数据,最大饱和吸附量为13.210mg/g.吸附动力学符合准二级动力学模型.实验表明NaCl改性沸石能够有效去除水中的氨氮.     

铬、砷离子吸附剂的制备及其吸附性能的研究

通过对沸石的改性,在沸石表面形成了一层纳米态的二氧化锰,而纳米态的二氧化锰及沸石都对水中重金属有强烈的吸附性能,从而达到对铬、砷离子的吸附作用。通过沸石与二氧化锰的配比、吸附溶液的pH值、吸附时间、改性沸石的用量对其去除效果的影响,探讨了吸附作用机理。通过吸附测定,改性沸石的最佳配比沸石：MnO2为2：1;改性沸石对As（III）的最佳吸附pH和时间为5.0和30 min;对Cr（VI）的最佳吸附pH和时间为7.0和30 min的条件下吸附效果最佳。     

锆改性沸石对水中磷酸盐和铵的吸附特性

采用锆对天然沸石进行改性,并研究了锆改性沸石对水中磷酸盐和铵的吸附特性.结果表明,锆改性沸石对水中磷酸盐和铵均具有很好的吸附能力.锆改性沸石对水中磷酸盐和铵的吸附动力学过程满足准二级动力学模型.Langmuir、Freundlich和Dubinin–Radushkevich(D–R)等温吸附模型可以很好地描述锆改性沸石对水中磷酸盐的等温吸附行为.Langmuir等温吸附模型可以很好地描述锆改性沸石对水中铵的等温吸附行为.由Langmuir等温吸附模型计算得到锆改性沸石对磷酸盐和铵的最大吸附容量分别达到26.2,7.82 mg/g.热力学参数表明锆改性沸石对水中磷酸盐的吸附是自发的吸热反应过程.锆改性沸石对水中磷酸盐的吸附能力随着pH值的增加而降低.当pH4~8时,锆改性沸石对水中铵的吸附能力较高;当pH低于4或高于8时,对铵的吸附能力下降.水中共存的Cl-、SO42-、HCO3-和NO3-等阴离子对锆改性沸石吸附磷酸盐的影响很小,而共存的SiO32-对磷酸盐的吸附则具有较强的负面影响.水中共存的Ca2+和Mg2+对锆改性沸石吸附铵的影响较小,而共存的K+和Na+对铵的吸附则具有较强的负面影响.锆改性沸石吸附水中磷酸盐的主要机制是阴离子配位体的交换,吸附水中铵的主要机制是与沸石中可交换阳离子的离子交换.     

Evaluation of zeolites synthesized from fly ash as potential adsorbents for wastewater containing heavy metals

Both pure-form zeolites (zeolites A and X) were synthesized by applying a two-stage method during hydrothermal treatment of fly ash prepared initial gel. The difference of adsorption capacity of both fly ash-synthesized zeolits was assessed under the same adsorption conditions. Copper and zinc were chosen as target heavy metal ions. It was found that adsorption capacity of zeolite A showed much higher value than that of zeolite X. Thus, attention was focused on investigating the removal performance of heavy metal ions in aqueous solution on the synthetic pure-form zeolite A from fly ash, zeolite HS (hydroxyl-solidate) prepared from the residual fly ash (after synthesis of pure-form zeolite A from fly ash) and a commercial grade zeolite A. Batch method was employed to study the influential parameters such as initial pH value, adsorbents dosage and adsorption temperature on the adsorption process. The equilibrium data were well fitted by the Langmuir model and showed the affinity: Cu2+ > Zn2+ (adsorbent FA-ZA). The removal mechanism of metal ions followed adsorption and ion exchange processes. Attempts were also made to recover heavy metal ions and regenerate adsorbents (adsorbent FA-ZA).     

Adsorption of humic acid from aqueous solution on bilayer hexadecyltrimethyl ammonium bromide-modified zeolite

Surfactant-modified natural zeolites (SMNZ) with different coverage types were prepared by loading hexadecyltrimethyl ammonium bromide (HTAB) onto the surface of a natural zeolite. The adsorption behavior of humic acid (HA) on SMNZ was investigated. Results indicate that the adsorbent SMNZ exhibited a higher affinity toward HA than the natural zeolite. HA removal efficiency by SMNZ increased with HTAB loading. Coexisting Ca²⁺ in solution favored HA adsorption onto SMNZ. Adsorption capacity decreased with an increasing solution pH. For typical SMNZ with bilayer HTAB coverage, HA adsorption process is well described by a pseudo-second-order kinetic model. The experimental isotherm data fitted well with the Langmuir model. Calculated maximum HA adsorption capacities for SMNZ with bilayer HTAB coverage at pH 5.5 and 7.5 were 63 and 41 mg·g⁻¹, respectively. E2/E3 (absorbance at 250 nm to that at 365 nm) and E4/E6 (absorbance at 465 nm to that at 665 nm) ratios of the residual HA in solution were lower than that of the original HA solution. This indicates that the HA fractions with high polar functional groups, low molecular weight (MW), and aromaticity had a stronger tendency for adsorption onto SMNZ with bilayer HTAB coverage. Results show that HTAB-modified natural zeolite is a promising adsorbent for removal of HA from aqueous solution.     

Biosorption of cadmium(Ⅱ) and lead(Ⅱ) ions from aqueous solutions onto dried activated sludge

The removal of heavy-metal ions from aqueous solutions by using dried activated sludge has been investigated in batch systems. Effect of solution pH, initial metal ion concentration, and temperature were determined. The results of the kinetic studies showed that the uptake processes of the two metal ions（Cd（Ⅱ） and Pb（Ⅱ）） followed the pseudo-second-order rate expression. The equilibrium data fitted very well to both the Langmuir and Freundlich adsorption models. The FT-IR analysis showed that the main mechanism of Cd（Ⅱ） and Pb（Ⅱ） biosorption onto dried activated sludge was their binding with amide I group.     

Biosorption of cadmium(Ⅱ) and lead(Ⅱ) ions from aqueous solutions onto dried activated sludge

The removal of heavy-metal ions from aqueous solutions by using dried activated sludge has been investigated in batch systems. Effect of solution pH, initial metal ion concentration, and temperature were determined. The results of the kinetic studies showed that the uptake processes of the two metal ions(Cd(Ⅱ) and Pb(Ⅱ)) followed the pseudo-second-order rate expression. The equilibrium data fitted very well to both the Langmuir and Freundlich adsorption models. The FT-IR analysis showed that the main mechanism of Cd(Ⅱ) and Pb(Ⅱ) biosorption onto dried activated sludge was their binding with amide I group.     

Biosorption of cadmium(II) and lead(II) ions from aqueous solutions onto dried activated sludge

Introduction Toxic metal compounds are frequently used in industrial processes and are widely distributed in the environment. Due to their extended persistence in biological systems and tendency to bioaccumulate as they move up the food chain, they repres…     

磷酸改性生物炭负载硫化锰去除废水中重金属镉

采用磷酸作为活化剂对黍糠生物炭进行改性,得到富含活性官能团的功能性生物炭（fCBC）,并将其作为硫化锰（MnS）的载体,最终成功制备出硫化锰负载的磷酸改性生物炭（MnS-fCBC）,可用于水体中镉（Cd）的高效去除.系统评价了初始浓度、初始pH值以及MnS-fCBC投加量对于吸附反应的影响. MnS-fCBC表现出优越的吸附Cd的能力,在初始Cd浓度为200mg/L、pH=6和投加量1g/L的条件下,MnS-fCBC对于Cd的吸附容量最大,达145.15mg/g.吸附反应受pH值影响显著,在偏酸性条件下能取得较好的去除效果.通过X射线衍射仪（XRD）和拉曼光谱仪（Raman）对MnS-fCBC进行结构表征分析,结合批次试验探讨了Cd的去除机理.结果表明,表面络合和化学沉淀是Cd去除的主要机理.材料的回用性能试验显示,在5次循环使用后,材料依然有较高的Cd去除能力,表明其具有较高的可重用性.因此,MnS-fCBC可作为一种高效的Cd吸附剂,应用于含Cd废水处理.     

白银天然沸石对磷的吸附机理及性能研究

为探明天然沸石对磷的吸附机理,首先利用扫描电镜、X射线衍射、X荧光分析等对甘肃白银产天然沸石进行了表征,然后通过静态实验探讨了吸附时间、磷初始浓度、pH值等因素对沸石除磷性能的影响.研究结果表明：沸石对水溶液中磷的吸附动力学过程符合Pseudo second-order模型;Freudlich和Langmuir模型均可较好地描述沸石对磷的吸附特征;沸石对磷的吸附量随pH值增大而明显减小.     

利用粉煤灰合成沸石处理重金属污水研究

本研究中利用粉煤灰合成沸石对含有Cu^2 、Pb^2 、Cd^2 的制备水样进行批处理振荡实验，其吸附容量分别为9．56、0．89和0．25mg／l。实验证明，用合成沸石处理含重金属离子污水达到平衡所需的时间约为3h。对污水中重金属离子的去除率随pH值降低而降低，随沸石用量增加而增加。同等条件下，利用粉煤灰处理含Cu^2 的污水，其吸附容量仅为6．49mg／l，低于合成沸石。     

臭氧/沸石工艺处理水中硝基苯的机理探讨

考察了臭氧在H型沸石上吸附与分解情况,发现臭氧在H型沸石上发生了吸附与分解,并且吸附过程与脱附过程是不可逆的,其脱附速率很快.在吸附分解平衡后,臭氧在H型沸石上的吸附分解量与进水臭氧浓度成正比.而在1×10^-3 mol/L Na⁺存在条件下,被Na⁺交换的H型沸石基本不吸附分解臭氧.考察不同阳离子和不同型号沸石对臭氧/沸石工艺去除硝基苯的影响,发现Ca²⁺的影响最大,另外Na型沸石和NH₄型沸石在降解硝基苯的过程中,硝基苯的去除效率逐渐提高,并且Na型沸石中的Na⁺发生溶出,表明盐析效应影响臭氧扩散进入沸石孔道进行自分解和催化分解的能力.脱铝后的H型沸石没有体现降解硝基苯的效果.最后在pH 3.0时,H型沸石也能吸附分解一部分臭氧,说明H⁺的影响不如其它阳离子.     

羧基甲壳素对Pb(Ⅱ)的吸附性能及机理研究

为了提高甲壳素对Pb²⁺吸附性能,采用2,2,6,6-四甲基哌啶-1-氧基（TEMPO）/次氯酸钠（NaClO）/溴化钠（NaBr）氧化体系对甲壳素羧基化改性.采用FTIR、Solid ¹³C-NMR、XRD和SEM-EDX等对羧基甲壳素结构和形貌进行表征,考察了不同NaClO用量制备的羧基甲壳素、溶液pH值、Pb（Ⅱ）初始浓度、吸附时间和离子强度对吸附量的影响,利用XPS探究其吸附机理.结果表明,氧化改性不改变甲壳素的晶型,羧基出现在甲壳素晶体表面;NaClO用量和溶液pH值对吸附量影响显著,pH值为4.0~6.0,NaClO用量为30mL制备的羧基甲壳素吸附效果好,60min达到平衡,室温下饱和吸附量达233.64mg/g;吸附动力学符合准二阶动力学方程,吸附等温线符合Freundlich等温吸附模型,吸附机理包括静电作用、络合配位和离子交换.