有机膨润土吸附水中重金属和有机污染物的性能及机理研究

螯合剂柱撑有机膨润土IMB-TMA-Am能有效吸附水中有机物对硝基苯酚(PNP)和重金属离子Cu2 ,其中IMB为内蒙膨润土;CTMA为溴化十六烷基三甲基季铵盐阳离子;Am分别为有机螯合剂乙二胺(En)、三乙烯四胺(TETA)和四乙烯五胺(TEPA)。实验结果表明:螯合剂柱撑有机膨润土对有机污染物的吸附主要表现为有机物在长碳链疏水介质中的分配,其吸附能力和膨润土内有机碳、氮含量一致;对水中重金属离子的吸附机理是Cu2 和进入膨润土层间的有机螫合剂Am形成了配合物,其吸附能力和所形成配合物的稳定性一致。     

膨润土纳米复合材料的制备、表征及吸附性能研究

用有机螯合剂(CA)和十六烷基三甲基溴化铵(HDTMAB)共同改性膨润土(IMB)，制得一系列膨润土纳米复合材料IMB-HDTMA-CA。X射线衍射(XRD)、热分析(TG-DTA)、红外光谱(FTIR)以及N₂-吸附脱附技术等研究发现，HDTMA⁺和CA已稳定柱撑在膨润土的片层结构中，其层间距增大、比表面积减小而疏水性增强。吸附实验表明，IMB-HDTMA-CA能协同吸附水中有机物对硝基苯酚(PNP)和重金属镉(Cd²⁺)。对水中对硝基苯酚的吸附源于PNP在膨润土层间有机相中分配作用的增加，其吸附容量和膨润土内有机碳含量和层间距大小一致，而与比表面积无关，依次为IMB-HDTMA-TEPA>IMB-HDTMA-TETA>IMB-HDTMA-En>IMB-HDTMA 》IMB；FTIR图谱显示，IMB-HDTMA-CA吸附Cd²⁺后的N-H吸收峰向低频方向移动，其吸附能力和所形成配合物的稳定性一致。     

有机膨润土结构对吡虫啉吸附热力学和动力学的影响机理

为深入了解有机膨润土结构对农药吸附性能的影响机理,论文制备十六烷基三甲基氯化铵(HTMA)载量系列变化的有机膨润土,通过吸附热力学和动力学研究了新烟碱杀虫剂吡虫啉与改性有机膨润土的相互作用和影响农药分子在有机膨润土层间扩散的结构因素。结果显示,季铵盐改性削弱了膨润土片层与吡虫啉的静电结合,但是增强与吡虫啉的疏水相互作用。吡虫啉吸附动力学与有机膨润土层间结构密切相关,低载量(<0.8′CEC)的HTMA对膨润土层间距的影响很小,但是层间堆积密度的增加导致吡虫啉吸附速率常数急剧下降。HTMA载量的进一步增加导致其层间排列方式由单层平铺向双层平铺的转变,层间距急剧增加使得吡虫啉吸附速率常数略有增大。     

双阳离子复合改性膨润土的吸附性能与构效关系

膨润土是一种以蒙脱石为主要成分的天然吸附材料. 本文用2-巯基乙胺盐酸盐(MEA)与十六烷基三甲基溴化铵(HDTMA)复合改性内蒙钙基膨润土(IMB), 制得具有特殊结构与性能的吸附材料MEA-HDTMA-IMB. X射线衍射(XRD)、红外光谱(FT-IR)、热分析(TG-DTA)及比表面积(N2-BET)等结构表征表明: 复合改性膨润土的比表面积和层间距显著增大. 吸附研究发现: MEA-HDTMA-IMB能同时有效吸附混合水溶液中的有机物对硝基苯酚和重金属铜. 复合改性膨润土对水中有机物的吸附机理以分配作用为主, 其吸附能力强于用季铵盐阳离子单一改性的有机膨润土HDTMA-IMB; 对水中重金属的吸附主要为络合反应, 其吸附性能与用巯基铵阳离子单一改性的膨润土MEA-IMB相当.     

Fe-Al 柱撑膨润土的制备及其非均相Fenton降解橙黄II

通过离子交换方法制备不同Fe含量的Fe-Al柱撑膨润土,并且研究了其作为非均相Fenton催化剂降解橙黄II的性能.通过X射线粉末衍射(XRD),比表面积(SBET),傅里叶变换红外(FTIR)光谱,拉曼(Raman)光谱和扫描电子显微镜(SEM)研究其结构特征.结果显示,钠化膨润土的层间距为1.24 nm,经过柱撑之后,Al柱撑膨润土的层间距增大到1.77 nm,Fe-Al柱撑膨润土为1.72 nm左右,并且比表面积也有明显增大.XRD和Raman结果表明Fe/(Fe+Al)摩尔比达到20%时,样品中出现α-Fe2O3,膨润土未能形成柱撑.在橙黄II初始浓度为100 mg L-1,催化剂用量为1.0 g L-1,温度为40°C,pH为3.0,H2O2初始浓度为10 mmol L-1的条件下,考察了柱撑膨润土的Fenton催化活性.结果表明,Fe-Al柱撑膨润土的催化性能随着Fe含量的增多先增大后略有降低,当Fe/(Fe+Al)摩尔比为10%时达到最大,橙黄II溶液在4 h内色度去除率和化学需氧量(CODCr)去除率分别达到100%和87.73%,并且降解反应为非均相Fenton反应.研究了Fe-Al柱撑膨润土的重复使用性.催化剂循环使用4次,仍然具有良好的活性.     

铁柱撑膨润土的微波合成及对甲基橙的光催化氧化降解作用

在微波作用下,由钙基膨润土和铁溶胶快速制备铁柱撑膨润土,分别用XRD、BET、SEM-EDS和TC-DSC测试技术表征了催化剂的组成和结构,结果表明,羟基铁阳离子进入膨润土层间取代Ca2+形成柱撑,膨润土孔结构基本不变,比表面积增加.考察了铁柱撑膨润土对光催化降解甲基橙反应的催化活性,确定了最佳降解反应条件为:体系pH=3,微波500W、80℃辐射10min制备的铁柱撑膨润土为催化剂,用量1.5g/L,H2O2浓度为7.345×10-3mol/L,甲基橙浓度100mg/L,紫外光照射60min,甲基橙的降解率可达98.1％.     

铁钛双金属共柱撑膨润土光催化-Fenton降解苯酚

 通过简单的离子交换方法成功合成了铁钛双金属共柱撑膨润土催化剂, 并利用 N2 吸附、X 射线衍射和等离子体发射光谱对所合成的样品进行了表征. 以苯酚为目标污染物, 考察了 pH 值、催化剂的投加量以及双氧水的加入量等对苯酚降解性能的影响. 结果表明, 在中性条件和紫外光照射下, 铁钛双金属柱撑膨润土上苯酚降解率和矿化率都高达 95%, 且铁离子的溶出率始终低于 2 mg/L, 均优于单一铁柱撑膨润土催化剂. 经过五次循环测试, 催化剂均表现出较高的活性. 即使在碱性 (pH = 9.0) 条件下, 反应 180 min 苯酚降解率也高达 70.3%, 表现出较好的酸碱适应性. 并讨论了双金属柱撑土所具有较大的比表面积和较强的表面酸性与活性之间的关系.     

氟钒锰共掺对TiO2柱撑膨润土光催化脱硝性能的影响

采用溶胶-凝胶法制备氟钒锰共掺改性的TiO2柱撑膨润土,使用XRD、氮吸附、UV-vis光谱和SEM等手段对其进行了表征测试,并对其室温下的可见光催化脱硝性能进行了评价研究。结果表明,对于NO质量浓度为661μg/m3的气体,F-VM n共掺TiO2柱撑膨润土的光催化脱除效率近似达到100%,而NO质量浓度提升至1657μg/m3时,光催化效率为81.9%,与未柱撑的F-V-Mn共掺TiO2相比提高了33.8%。F-V-Mn共掺TiO2柱撑膨润土上光催化脱反应速率常数最大,是V-Mn共掺TiO2柱撑膨润土的2倍,且前者的抗水和抗SO2中毒能力也更强。TiO2柱撑不仅保留了膨润土的片状晶体结构,而且使膨润土层间距由0.667 nm增大至0.710 nm,吸附能力增强;同时,掺杂元素能抑制TiO2金红石相生长,降低TiO2禁带宽度,提高可见光响应,延长使用寿命,拓宽应用范围。     

有机膨润土改性高吸油树脂复合材料的合成及性质

以十六烷基三甲基溴化铵为表面改性剂制备了有机膨润土,并制备了以甲基丙烯酸十六酯为单体的吸油树脂/有机膨润土复合材料.采用X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)对样品进行分析.结果表明,经十六烷基三甲基溴化铵改性的膨润土层间距由原来的1.12 nm增大到1.87 nm;所得有机膨润土/吸油树脂复合材料对四氯化碳的饱和吸油率为16.3 g/g.     

氟钒锰共掺对TiO2柱撑膨润土光催化脱硝性能的影响

采用溶胶-凝胶法制备氟钒锰共掺改性的TiO₂柱撑膨润土，使用XRD、氮吸附、UV-vis光谱和SEM等手段对其进行了表征测试，并对其室温下的可见光催化脱硝性能进行了评价研究。结果表明，对于NO质量浓度为661 μg/m³的气体，F-V-Mn共掺TiO₂柱撑膨润土的光催化脱除效率近似达到100%，而NO质量浓度提升至1657 μg/m³时，光催化效率为81.9%，与未柱撑的F-V-Mn共掺TiO₂相比提高了33.8%。F-V-Mn共掺TiO₂柱撑膨润土上光催化脱反应速率常数最大，是V-Mn共掺TiO₂柱撑膨润土的2倍，且前者的抗水和抗SO₂中毒能力也更强。TiO₂柱撑不仅保留了膨润土的片状晶体结构，而且使膨润土层间距由0.667 nm增大至0.710 nm，吸附能力增强；同时，掺杂元素能抑制TiO₂金红石相生长，降低TiO₂禁带宽度，提高可见光响应，延长使用寿命，拓宽应用范围。     

Thermodynamics of Pb2+ and Ni2+ adsorption onto natural bentonite from aqueous solutions

Removal of Pb2+ and Ni2+ from aqueous solutions by sorption onto natural bentonite was investigated. Experiments were carried out as a function of particle size, the amount of bentonite, pH, concentration of metals, contact time, and temperature. The adsorption patterns of metal ions onto followed the Langmuir, Freundlich, and Dubinin-Radushkevich isotherms. This included adsorption isotherms of single-metal solutions at 303 K by batch experiments. The thermodynamic parameters (DeltaH,DeltaS,DeltaG) for Pb2+ and Ni2+ sorption onto bentonite were also determined from the temperature dependence. The adsorptions were endothermic reactions. The results suggested that natural bentonite is suitable as a sorbent material for recovery and adsorption of metal ions from aqueous solutions.     

有机改性膨润土对水中钙黄绿素的吸附性能

在微波作用下用十六烷基溴化吡啶(CPB)、十六烷基三甲基溴化铵(CTMAB)和盐酸萘乙二胺(NETH)对天然膨润土进行改性,制得了CPB-膨润土(CPB-Bt)、CTMAB-膨润土(CTMAB-Bt)和NETH-膨润土(NETH-Bt),并比较了它们对水中钙黄绿素的吸附性能.结果表明,在钙黄绿素浓度25 mg·L-1、...     

金属螯合亲和膜吸附分离与纯化溶菌酶的研究(Ⅱ)──不同金属螯合亲和膜对溶菌酶的吸附性能

采用低温氧或氨等离子体法改性聚丙烯微孔膜,基于等离子体改性膜的活化、偶联及螯合过程的机理,制备了Fe³⁺,Ni²⁺,Cu²⁺和Zn²⁺等金属离子螯合亲和膜,并用于溶菌酶的吸-脱附实验.实验结果表明,Ni²⁺和Cu²⁺离子螯合亲和膜对溶菌酶具有较高的吸附量,螯合过程中采用氯化物盐溶液制得的膜对溶菌酶吸附量比采用硫酸盐溶液制得的膜的吸附量高.两种膜的重复吸-脱附性能相近,而Fe³⁺螯合亲和膜基本上不能用于重复吸-脱附实验.采用补充金属螯合离子,能部分恢复亲和膜对溶菌酶的吸附量,是实现亲和膜重复使用的有效方法.     

Adsorption of benzoic acid from aqueous solution by three kinds of modified bentonites

Benzoic acid removal is important for the water treatment, and adsorption is an efficient treatment process. Three kinds of modified bentonites, hydroxy-aluminum pillared bentonite (Al(OH)-Bent), octadecyl trimethyl ammonium chloride modified bentonite (OTMAC-Bent), and both octadecyl trimethyl ammonium chloride and hydroxy-aluminum modified bentonite (Al(OH)-OTMAC-Bent) were prepared and characterized by XRD, FTIR, and BET analysis. Experiments were conducted on the adsorption of benzoic acid by the prepared modified bentonites at different temperatures in batch experiments. The results show benzoic acid adsorption capabilities of Na-Bent and Al(OH)-Bent are even low, but high for OTMAC-Bent and Al(OH)-OTMAC-Bent. Optimal conditions for the adsorption of benzoic acid on OTMAC-Bent and Al(OH)-OTMAC-Bent were as follows: pH of 3.5, 0.04 g/mL adsorbent, and contact time of 90 min. Increased adsorption with temperature indicates that the adsorptions of benzoic acid onto Al(OH)-OTMAC-Bent and OTMAC-Bent are spontaneous and endothermic. The adsorption data could be well interpreted by the Langmuir model and Temkin Equation. The adsorption efficiency was higher than 85%, suggesting that OTMAC-Bent and Al(OH)-OTMAC-Bent are excellent adsorbents for effective benzoic acid removal from water.     

New anion-exchange solid-phase extraction support used for preconcentration and determination of lead in water samples by flame atomic absorption spectrometry

A new chelating resin was prepared by coupling Amberlite XAD-2 with Brilliant Green through an azo spacer. The resulting resin has been characterized by FTIR spectrometry, elemental analysis, and thermogravimetric analysis and studied for the preconcentration and determination of trace Pb(II) ions from solution samples. The anionic complex of Pb(II) and iodide was retained on the resin by the formation of an ion associate with Brilliant Green on Amberlite XAD-2 in weak acidic medium. The optimum pH value for sorption of the metal ion was 5.5. The sorption capacity of the functionalized resin is 53.8 mg/g. The chelating resin can be reused for 20 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 103% was obtained for the metal ion with 0.1 M EDTA as the eluting agent. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The resin was subjected to evaluation through batch binding and column chromatography of Pb(II). The equilibrium adsorption data of Pb(II) on modified resin were analyzed by Langmuir, Freundlich, and Temkin models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined to be 0.192, 13.189, and 3.418 at pH 5.5 and 25 degrees C. The method was applied for lead ion determination in tap water samples.     

Modified bentonite by polyhedral oligomeric silsesquioxane and quaternary ammonium salt and adsorption characteristics for dye

To remove methylene blue dye from water by adsorption, bentonites were modified by polyhedral oligomeric silsesquioxane (POSS) and three kind of quaternary ammonium surfactants (dodecyl trimethyl ammonium bromide, tetrabutyl ammonium bromide, cetyl trimethylammonium bromide) in aqueous solution. Systematic adsorption experiments were carried out, the adsorption mechanism was studied, and the factors governing the adsorption of methylene blue on modified bentonite were discussed. The adsorption capacity of methylene blue on all three modified bentonites in 1000 mg·L⁻¹ solutions quickly reached equilibrium within 2000 s, and the removal rate was basically 100%; however, the removal rate in raw bentonite samples was only 60%. The pseudo second-order kinetic model can provide satisfactory kinetic data fitting. The obtained adsorption isotherms fit well with the Dubinin-Radushkevich isotherm model. The thermodynamic results showed that the adsorption process was a spontaneous endothermic physical adsorption process. With increasing pH and KCl concentration, the removal of methylene blue increased significantly. The results of this study confirmed that the modified bentonite is a candidate material as a cationic dye adsorbent.     

Preparation, Properties and Mechanism of Inhomogeneous Calcium Alginate Ion Cross-linking Gel Microspheres

Inhomogeneous calcium alginate ion cross-linking gel microspheres,a novel ion absorbent,were prepared by dropping a sodium alginate solution to a calcium chloride solutioin via an electronic droplet generator.Calcium alginate microspheres have uniform particle sizes.a smooth surface and a microporous structure.The electrode probe reveals the inhomogeneous distribution of calcium ions with the highest concentration on the surface,and the lowest concentration in the cores of the spheres.As a novel ion adsorbent,calcium alginate gel microspheres have a lower limiting adsorption mass concentration,a higher enrichment capacity and a higher adsorption capacity for Pb^2 than usual ion exchange resins.The highest percentage of the adsorption is 99.79%.The limiting adsorption mass concentration is 0.0426mg/L.The adsorption capacity for Pb^2 is 644mg/g,Calcium alginate gel microspheres have a much faster ion exchange velocity than D418 chelating resin and D113 polyacrylate resin.The moving boundary model was employed to interpret the ion exchange kinetics process,which indicates that the ion exchange process is controlled by intraparticle diffusion of adsorbable ions.So the formation of inhomogeneous gel microspheres reduces the diffusion distance of adsorbable ions within the spheres and enhances the ion exchange velocity.Alginate has a higher selectivity for pb^2 than for Ca^2 and the selectivity coefficient KCa^Pb is 316. As an ion cross-linking gel,calcium alginate inhomogeneous microspheres can effectively adsorb heavy metal Pb^2 at a higher selectivity and a higher adsorption velocity.It is a novel and good ion adsorbent.     

Grafting of poly[1-(N,N-bis-carboxymethyl)amino-3-allylglycerol-co-dimethylacrylamide] copolymer onto siliceous support for preconcentration and determination of lead (II) in human plasma and environmental samples

A method is reported for surface grafting of polymer containing a functional monomer for metal chelating, poly[1-(N,N-bis-carboxymethyl)amino-3-allylglycerol-co-dimethylacrylamide] (poly(AGE/IDA-co-DMAA) onto silica modified by silylation with 3-mercaptopropyltrimethoxysilane. Monomer 1-(N,N-bis-carboxymethyl)amino-3-allylglycerol (AGE/IDA) was synthesized by reaction of allyl glycidyl ether with iminodiacetic acid. The resulting sorbent has been characterized using FT-IR, elemental analysis, thermogravimetric analysis (TGA), FT-Raman and scanning electron microscopy (SEM) and evaluated for the preconcentration and determination of trace Pb(II) in human biological fluid and environmental water samples. The optimum pH value for sorption of the metal ion was 5.5. The sorption capacity of functionalized resin was 15.06 mg g⁻¹. The chelating sorbent can be reused for 15 cycles of sorption–desorption without any significant change in sorption capacity. A recovery of 96.2% was obtained for the metal ion with 0.5 M nitric acid as eluting agent. The profile of lead uptake by the sorbent reflects good accessibility of the chelating sites in the poly(AGE/IDA-co-DMAA)-grafted silica gel. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The equilibrium adsorption data of Pb(II) by modified resin were analyzed by Langmuir, Freundlich, Temkin and Redlich–Peterson models. On the basis of equilibrium adsorption data the Langmuir, Freundlich and Temkin constants were determined as 0.70, 1.35 and 2.7, respectively at pH 5.5 and 20 °C. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of adsorption.     

离子强度对膨润土/木质素磺酸钠接枝丙烯酰胺-马来酸酐复合吸附树脂吸附Pb2+/Cu2+的影响

为揭示外加电解质离子强度对重金属离子吸附的影响规律与内在机制, 制备了膨润土/木质素磺酸钠接枝丙烯酰胺-马来酸酐复合吸附树脂(BLPAMA), 研究了外加电解质离子强度对BLPAMA吸附单一和二元Pb²⁺/Cu²⁺的影响规律, 以及有、无外加0.2 mol/L NaNO₃时BLPAMA对二元Pb²⁺/Cu²⁺的吸附等温线、吸附热力学及吸附动力学。 结果表明, 在单一Pb²⁺或Cu²⁺溶液中, 随离子强度增加, Pb²⁺和Cu²⁺吸附量降低;在二元Pb²⁺/Cu²⁺溶液中, 随离子强度增加, Pb²⁺吸附量降低而Cu²⁺吸附量提高。