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).     

铝污泥酸化提取液改性沸石的除磷特性及机制

为了提高沸石的除磷能力并降低改性成本,以给水厂铝污泥为铝源,采用酸化提取液合成层状双氢氧化物(LDHs)覆膜于沸石表面制备改性沸石,分别测定原沸石、Al-Zn改性沸石及铝污泥改性沸石的表面特性和化学组分,分析等温吸附及吸附动力学特性,探讨铝污泥改性沸石的除磷性能及除磷机制.结果表明,最佳酸化提取条件为60 min、150 r·min~(-1)和p H1. 0,该条件下1 g铝污泥(干重)可提取77 mg的铝;改性沸石的饱和吸附容量和解吸性能较原沸石显著提高,尤其是铝污泥改性沸石,其理论最大吸附量从30. 24 mg·kg~(-1)提升至170. 40 mg·kg~(-1);改性使得沸石对磷酸盐的主要吸附类型由物理吸附向化学吸附转变.以铝污泥为铝源改性沸石能有效地提高其对磷酸盐的吸附能力及再生能力,在降低磷浓度过高引发的水体富营养化风险的同时,实现以废治废的目的.     

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.      

Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution

A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH₂-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu^2 + adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N₂ adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH₂-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu^2 + on NH₂-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH₂-Mn-SBA-15 for Cu^2 + was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu^2 + by NH₂-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu^2 +. The NH₂-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption–desorption experiments showed that the NH₂-Mn-SBA-15 could be regenerated by acid treatment without altering its properties.     

Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution

A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH₂-Mn-SBA- 15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganeseloaded SBA-15 (Mn-SBA-15) and used as a Cu²⁺ adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N₂ adsorption/ desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH₂-Mn-SBA-15. The orderedmesoporous structure of SBA-15 was remained aftermodification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu²⁺ on NH₂-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH₂-Mn-SBA-15 for Cu²⁺ was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu²⁺ by NH₂-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu²⁺. The NH₂-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption-desorption experiments showed that the NH₂-Mn-SBA-15 could be regenerated by acid treatment without altering its properties.     

活性炭/高分子复合水凝胶对水中亚甲基蓝和Cu(Ⅱ)的去除性能

采用活性炭/海藻酸钠-聚乙烯醇复合水凝胶(CAP)为吸附剂,以水溶液中的亚甲基蓝(MB)和Cu~(2+)为目标污染物,考察了固液比、p H、温度、反应时间、MB和Cu~(2+)的初始浓度等因素对吸附过程的影响.通过SEM、FTIR、BET等手段对CAP物化性质进行了表征.结果表明,CAP内部呈现互穿的三维网络多孔结构,成功复合了活性炭,具有丰富的—COOH和—OH官能团,比表面积可达112.7 m~2·g~(-1).CAP对MB和Cu~(2+)的吸附量随着固液比、温度的增大而降低,随着溶液初始p H的升高而增大;吸附属于Langmuir单层吸附,对MB和Cu~(2+)的最大吸附量分别为1 940.75 mg·g~(-1)和190.48 mg·g~(-1);反应时间在5 h内吸附量可达最大吸附量的90%,吸附动力学过程符合准二级动力学方程;活性炭/高分子复合水凝胶经过5次吸附-脱附循环再生后,仍能保持优异的吸附性能.     

选择性吸附法处理含表面活性剂和多环芳烃的土壤淋洗液研究

比较研究了H103树脂、活性炭、沸石、硅藻土和膨润土等5种吸附剂对土壤淋洗液中TX-100与PAHs的吸附性能.批实验结果表明,H103树脂、活性炭、沸石、硅藻土和膨润土吸附后,淋洗液中T-PAHs及TX-100浓度分别为0.03和0 mg·L~(-1)、0.16和3623 mg·L~(-1)、15.21和6175 mg·L~(-1)、15.98和6555 mg·L~(-1)、9.49和4332 mg·L~(-1),选择性吸附系数排序依次为活性炭膨润土沸石硅藻土H103树脂.其中,活性炭能够去除淋洗液中99%的PAHs,同时保留51.33%的TX-100回收再利用,选择吸附系数达到109.5.活性炭固定床实验中,由淋洗液溶质的穿透曲线计算出物质的吸附容量.当空隙体积为2.5-7PV时,活性炭能够去除淋洗液中72%的PAHs,同时保留81%的TX-100,平均选择吸附系数为10.08.由此可见,活性炭固定床可有效处理含表面活性剂土壤淋洗液中的多环芳烃,同时实现表面活性剂的回收再利用.     

不同类型酸修饰-磁化海泡石对水体Cd(II)的吸附研究

采用无机或有机酸修饰-磁化的方法研制海泡石吸附材料H-Sep(盐酸修饰)、N-Sep(硝酸修饰)、P-Sep(磷酸修饰)和A-Sep(醋酸修饰),并借助SEM、TEM、EDS、BET、FT-IR、VSM及XPS等手段表征分析改性前后海泡石的结构特征.同时,在不同投加量、pH、温度和溶液浓度等因素条件下,考察了酸修饰-磁化海泡石对水体Cd(II)吸附效果的影响.结果表明,改性材料取得最佳吸附效果时的投加量为5g·L^-1,pH为6.5,拟合结果更符合准二级动力学方程和Langmuir等温方程.其中,P-Sep的吸附效果最好,其最大理论吸附量为52.6 mg·g^-1.VSM结果表明,H-Sep、N-Sep和A-Sep是磁化分离效果较好的材料,而P-Sep的磁化分离效果不佳.此外,Na⁺、Cl^-等阴阳离子对酸修饰-磁改性海泡石吸附性能没有太大影响,而重金属离子如Pb(II)、Zn(II)会对其吸附过程产生抑制作用.XPS吸附机理分析表明,酸修饰-磁化改性将新的功能基团引入海泡石结构,极大地提升了吸附性能.     

Pb（II） biosorption using chitosan and chitosan derivatives beads： Equilibrium, ion exchange and mechanism studies

The study examined the adsorption of Pb(II) ions from aqueous solution onto chitosan, chitosan-GLA and chitosan-alginate beads. Several important parameters influencing the adsorption of Pb(II) ions such as initial pH, adsorbent dosage and di erent initial concentration of Pb(II) ions were evaluated. The mechanism involved during the adsorption process was explored based on ion exchange study and using spectroscopic techniques. The adsorption capacities obtained based on non–linear Langmuir isotherm for chitosan, chitosan-GLA and chitosan-alginate beads in single metal system were 34.98, 14.24 and 60.27 mg/g, respectively. However, the adsorption capacity of Pb(II) ions were reduced in the binary metal system due to the competitive adsorption between Pb(II) and Cu(II) ions. Based on the ion exchange study, the release of Ca2+, Mg2+, K+ and Na+ ions played an important role in the adsorption of Pb(II) ions by all three adsorbents but only at lower concentrations of Pb(II) ions. Infrared spectra showed that the binding between Pb(II) ions and the adsorbents involved mostly the nitrogen and oxygen atoms. All three adsorbents showed satisfactory adsorption capacities and can be considered as an e cient adsorbent for the removal of Pb(II) ions from aqueous solutions.     

磁性高分子复合水凝胶的制备及其对水中铜离子的吸附性能

以海藻酸钠和聚乙烯醇为骨架负载磁性纳米Fe_3O_4颗粒合成了两种磁性高分子复合水凝胶材料:一种是以Ca~(2+)交联制备的磁性海藻酸钙单网络水凝胶(SAPFe),另一种是以海藻酸钙和聚乙烯醇经循环冷冻解冻制成的磁性双网络水凝胶(DAPFe).利用SEM、FTIR、BET对合成的材料进行表征,并研究了SAPFe和DAPFe对Cu~(2+)的吸附性能.结果表明,DAPFe比表面积达89.01 m~2·g~(-1),平均孔径为2.2 nm,DAPFe比SAPFe具有更低的含水率、更高的交联程度、更发达的孔隙结构和更高的比表面积.DAPFe对Cu~(2+)的最大吸附量可达207.01 mg·g~(-1),远大于SAPFe(173.01 mg·g~(-1)).SAPFe和DAPFe对Cu~(2+)的吸附等温线均符合Langmuir模型,吸附动力学符合准二级吸附动力学模型.通过分析SAPFe和DAPFe吸附Cu~(2+)前后官能团的变化,发现磁性高分子复合水凝胶具有丰富的羧基和羟基功能性官能团,并通过与Cu~(2+)产生螯合作用实现去除.     

生物沸石对吡啶、喹啉的降解与吸附作用

探讨了通过生物沸石的降解及吸附作用,解决吡啶、喹啉及转化产物NH 4+-N的污染问题.结果表明,生物沸石中的吡啶降解菌Shinella zoogloeoides BC026及喹啉降解菌Pseudomonas sp.BW003能有效去除吡啶、喹啉,同时转化后的NH 4+-N也能被天然沸石或改性沸石所吸附.尽管改性沸石吸附能力不如天然沸石,但其表面能更有效附着微生物,在实际工程应用上更具前景.     

两性膨润土增强不同层次紫色土吸附Cu2+的研究

为了证实两性粘土对不同层次紫色土吸附Cu~(2+)的促进作用,以不同比例(25%、50%和100%)十四烷基二甲基甜菜碱(BS-14)修饰膨润土作为两性基质,将其分别以5%的比例(质量比)添加至表层和粘化层紫色土中,采用批处理法研究不同两性基质添加比例对表层紫色土(ZS)和粘化层紫色土(ZA)吸附Cu~(2+)的等温吸附特征,并对比温度、p H值和离子强度对Cu~(2+)吸附效果的影响。结果表明:(1)表层紫色土添加BS膨润土(ZS-BS)和粘化层紫色土添加BS膨润土(ZA-BS)对Cu~(2+)的吸附量均随着BS膨润土中BS-14修饰比例的增大而增加,且相同BS-14修饰比例下ZA-BS对Cu~(2+)的吸附量高于ZS-BS。(2)p H值在3~5范围内,表层和粘化层紫色土对Cu~(2+)的吸附量均随p H值的升高而增大。温度从20℃增加到40℃时,两层次土样对Cu~(2+)的吸附量均随温度的升高而增加。土样对Cu~(2+)的吸附量在离子强度I=0.1 mol/L时最大,在I=0.01 mol/L时最小。(3)热力学参数结果表明添加BS膨润土后,不同层次紫色土吸附Cu~(2+)是一个自发、吸热和熵增的过程。     

硅铝比和NiO对ZSM-5协同低温等离子体降解甲苯的影响

研究了不同硅铝比的ZSM-5与Ni/ZSM-5分子筛协同低温等离子体技术对甲苯降解性能的影响.以Ni O(Nickel Oxide)为活性组分,采用浸渍法对ZSM-5分子筛进行改性,利用氮气吸附脱附(BET)、X射线衍射仪(XRD)、X射线光电子能谱分析(XPS)、H_2程序升温还原(H_2-TPR)、NH_3程序升温脱附(NH_3-TPD)、Toluene程序升温脱附(Toluene-TPD)等技术表征样品的物理化学性质.考察了硅铝比对ZSM-5与Ni/ZSM-5分子筛体系中甲苯的吸附性能,研究了不同放电电压下硅铝比对甲苯降解率、碳平衡及二氧化碳选择性的影响,并采用气相色谱-质谱联用仪(GC-MS)分析了催化剂表面的有机产物.结果表明:硅铝比不但影响分子筛本身的物理化学特性(比表面积、氧化还原性能、表面酸性、疏水性等),还会影响Ni的负载形态和方式,更高的硅铝比与Ni O的负载能促进甲苯深度氧化,减少副产物,提高碳平衡和二氧化碳选择性.     

MFI型沸石吸附分离水体中混合硝基氯苯的研究

采用MFI型沸石(HZSM-5与Silicalite-1沸石)为吸附剂分别吸附水体中的对硝基氯苯和邻硝基氯苯,研究了温度与沸石的结构特性对硝基氯苯吸附的影响,以及2种硝基氯苯分子在MFI型沸石中的扩散行为．结果表明,在不同温度下,对硝基氯苯与邻硝基氯苯在HZSM-5与Silicalite-1沸石中的吸附行为明显不同;对硝基氯苯在2种MFI型沸石中的扩散系数都显高于邻硝基氯苯．对硝基氯苯与邻硝基氯苯在吸附量与扩散性上的差异导致HZSM-5与Silicalite-1沸石对对硝基氯苯的吸附具有良好的选择性．尤其HZSM-5沸石在低温下更有利于从水体中选择性吸附分离混合硝基氯苯。     

海州香薷根细胞壁对铜的吸附固定机制研究

海州香薷是铜耐性植物,细胞壁是其吸收积累铜的重要场所.本文利用细胞壁化学改性结合吸附动力学试验和红外光谱学研究了海州香薷根细胞壁及其组分对Cu2+的吸附动力学特征,以及它们吸附固定Cu2+的功能基团.吸附动力学试验表明,海州香薷根细胞壁对Cu2+吸附300 min后,吸附量已接近饱和水平,达到最大吸附量的90%左右;500 min时达到吸附饱和,饱和吸附量为5.85 mg·g-1.当细胞壁进行化学改性后,如氨水处理细胞壁使果胶变成低酯化的酰胺类果胶或者去除细胞壁中的纤维素,根细胞壁对铜的吸附量会显著降低.果胶和纤维素分别吸附了19.85%和25.48%的Cu2+,是细胞壁吸附固定Cu2+的两大主要组分.红外光谱研究也表明,在海州香薷根细胞壁吸附Cu2+的过程中,羟基、羧基和氨基是Cu2+的主要结合位点.其中,果胶为Cu2+的结合提供了羟基官能团,纤维素和半纤维素为Cu2+的结合提供了羧基官能团,而细胞壁蛋白提供了氨基官能团等结合位点.由此可见,根细胞壁及其各个组分对Cu2+具有较高的吸附固定能力,是海州香薷根系Cu耐性的重要机制.     

几种吸附材料对磷吸附性能的对比研究

针对白洋淀府河水体磷污染问题,研究了天然沸石、硅藻土、粉煤灰、赤泥、铁铝泥五种材料对磷的吸附性能,并利用盐酸改性铁铝泥、铁盐改性粉煤灰和赤泥,对比研究了改性后材料对磷的吸附能力,探讨了水体pH值和其他离子对其吸附性能的影响。结果表明:沸石、硅藻土、粉煤灰、赤泥对磷的吸附符合一级动力学模型,而铁铝泥和改性后材料吸附磷符合准二级动力学模型;改性前后各材料吸附磷等温线均符合Langmuir方程。各材料吸附磷能力为:改性赤泥>改性粉煤灰>改性铁铝泥>铁铝泥>赤泥和粉煤灰>沸石>硅藻土,改性材料吸附磷能力明显提高。溶液pH值显著影响改性材料吸附磷效果,pH为7时吸附量最大;硫酸根和碳酸氢根离子抑制磷的吸附,氯离子和硝酸根离子没有明显影响。     

Effect of biomass addition on the surface and adsorption characterization of carbon-based adsorbents from sewage sludge

Sewage sludge with the additive corn cob was used as prescusor to prepare sludge-based carbon adsorbents by pyrolysis method. And then, the carbonizated products were activated with potassium hydroxide. The mixing ratio of the corn cob to sewage sludge was investigated. The surface area and pore size distribution, elemental composition, surface chemistry structure and the surface physical morphology were determined and compared. The results demonstrated that the addition of corn cob into the sewage sludge sample could effectively improve the surface area (from 287 to 591 m 2 /g) and the microporosity (from 5% to 48%) of the carbon based adsorbent, thus enhancing the adsorption behavior. The sulfur dioxide adsorption capacity was measured according to breakthrough test. It was found that the sulfur dioxide adsorption capacity of the adsorbents was obviously enhanced after the addition of the corn cob. It is presumed that not only highly porous adsorbents, but also a high metallic content of these materials are required to achieve good performances.     

Application of high silica zeolite ZSM-5 in a hybrid treatment process based on sequential adsorption and ozonation for VOCs elimination

In this study, a hydrophobic synthetic zeolite, namely ZSM-5 is chosen as an adsorbent/catalyst for toluene removal. Experimental results showed that toluene adsorption onto ZSM-5 was favourable, following a Langmuir adsorption isotherm model. ZSM-5 zeolite was regenerated using gaseous ozone at low temperature. Adsorbed toluene was oxidised, releasing mainly CO₂ and H₂O. Traces of oxidation by-products such as acetic acid and acetaldehyde were formed and remained adsorbed after the oxidativate regeneration with ozone. After four successive cycles of adsorption/ozonation, the adsorption efficiency was not affected (92%–99%). These results showed that volatile organic compound (VOC) removal by adsorption onto ZSM-5 zeolite followed by ozone regeneration could be used as a promising hybrid process for the control of VOC emissions in terms of efficiency.     

施加生物炭对河流沿岸土吸附铜的影响机制

为探究生物炭施加对河流沿岸土吸附铜的影响机制,采集嘉陵江流域(川渝段)内苍溪(CX)、南部(NB)、嘉陵(JL)和合川(HC)沿岸土表层(S,0～20 cm)、亚表层(D,20～40 cm)共8种土样,分别将1%(质量比)生物炭(B)加入到8种土样中形成混合土样(CX_(SB)、NB_(SB)、JL_(SB)和HC_(SB); CX_(DB)、NB_(DB)、JL_(DB)和HC_(DB))。以原始土样作为对照,批处理法研究各供试土样在不同温度、pH和离子强度下的Cu~(2+)吸附和热力学特征,并分析Cu的吸附形态。结果显示:(1)各供试土样对Cu~(2+)的等温吸附都适用Langmuir模型描述,Cu~(2+)的最大吸附量q_m在62. 20～363. 64 mmol/kg之间,S层土样对Cu~(2+)的吸附量均呈现JL NB CXHC的趋势,而D层土样呈现JL CX NB HC的趋势。施加生物炭有助于增强D层土壤对Cu~(2+)的吸附。(2) 20～40℃范围内,各供试土样对Cu~(2+)的吸附量均随温度的升高而升高,表现为增温正效应。热力学参数结果表明各混合土样对Cu~(2+)的吸附是一个自发、吸热和熵增的过程。(3) pH的升高有利于各供试土样对Cu~(2+)的吸附。随着离子强度的增加,各混合土样(HC_S和HC_D除外)对Cu~(2+)的吸附量均呈现先增后降的趋势,0. 1 mol/L时最大。(4)土样中吸附的铜主要以碳酸盐结合态和铁锰氧化物结合态铜存在,生物炭的施加增加了土样中可交换态(HC除外)和有机结合态铜含量,而对碳酸盐结合态和铁锰氧化物结合态铜影响较小。供试土样对Cu~(2+)的q_m主要是由CEC和比表面积决定的。     

N-TiO2/PSF中空纤维复合膜光催化烟气脱硝研究

采用溶胶-凝胶法以聚砜(PSF)中空纤维膜为载体制备了N-Ti O2/PSF中空纤维复合膜催化剂,考察其光催化烟气脱硝性能.紫外光催化的NO去除效率可达63%,去除负荷可达213.6 g·m-3·h-1.采用紫外-可见光谱(UV-Vis)、X-射线光电子能谱(XPS)和傅里叶变换红外光谱(FTIR)表征了N-Ti O2/PSF中空纤维复合膜催化剂.UV-Vis光谱分析表明,掺杂N改性的Ti O2复合膜光催化层在紫外和可见光波段的吸收性能都有极大的改善.XPS证明了O—Ti—N键能的存在.N-Ti O2/PSF中空纤维膜光催化处理NO的作用机制为NO气体通过中空纤维膜传质到NTi O2催化膜,光催化产生羟基自由基和超氧负离子,NO气体被羟基自由基和超氧负离子氧化成易处理的NO2和HNO3.