夏子街膨润土在碱性染料废水处理中的应用研究

以纳基和钙基夏子街膨润土为吸附剂,通过改变吸附时间、吸附剂用量、染料溶液浓度、初始pH值分析其对碱性红46和碱性兰41脱色率的影响,并对其吸附动力学、吸附热力学和吸附机理进行了研究.结果表明,2种膨润土对2种碱性染料废水的最佳脱色条件具有一定差异.准一级动力学模型对膨润土吸附碱性染料废水的过程描述更准确,膨润土对碱性红46的吸附是自发吸热反应,对碱性兰41的吸附是自发放热反应,膨润土对2种碱性染料废水的吸附既有物理吸附也存在离子交换吸附.     

Fe/Al交联改性膨润土(MB)对偶氮染料的脱色研究

以铁铝双金属离子低聚物为交联剂,制备了Fe/Al交联改性膨润土(MB),用于处理含偶氮染料的废水。通过改变吸附时间、pH和甲基橙废水浓度及掺加共存无机阴离子等因素,研究了MB对甲基橙的脱色效果。结果表明,改性后的膨润土吸附能力显著增强,对甲基橙有较好的吸附脱色性能。当材料用量0.0200 g,处理甲基橙废水20 mL,废水pH值小于4,处理时间2 h,甲基橙的脱色率可达95%。其吸附甲基橙的过程符合Fre-undlich等温吸附模式,对甲基橙的最大饱和吸附容量为384 mg/g。我国膨润土储量大、价格低,以Fe/Al交联剂为改性剂对天然膨润土进行了改性,得到的MB材料是一类很好的环境友好型吸附剂。     

粉煤灰/膨润土颗粒的制备与pb2+吸附实验

以天然钙基膨润土和燃料废弃物粉煤灰为原料,工业淀粉为致孔剂,采用挤出-滚圆技术,制备了粉煤灰/膨润土复合颗粒吸附剂,并用于含Pb~(2+)溶液的吸附。研究了吸附时间、pH、投样量和溶液初始浓度对吸附性能的影响。结果表明,采用挤出-滚圆法制得的复合颗粒吸附剂大小均匀,表面没有裂纹,具有良好的机械强度。吸附实验中,在投样量10.0 g/L,溶液pH为6,吸附时间120 min,溶液初始浓度100 mg/L时,复合颗粒吸附剂对Pb~(2+)的去除率达到97.40%,吸附量为9.74mg/g。热力学实验表明吸附剂对Pb~(2+)的吸附更符合Langmuir吸附等温模型。     

埃洛石对阳离子型和阴离子型染料的吸附研究

为研究不同产地埃洛石对阴、阳离子型染料的吸附性能差异,以产自山西临汾、四川广元、湖北丹江口的天然管状埃洛石作为阳离子型染料亚甲基蓝,以及有机硅烷接枝改性的湖北埃洛石作为阴离子型染料酸性橙Ⅱ的吸附剂进行实验研究。结果表明,天然埃洛石带有负电荷,适合作为阳离子型染料亚甲基蓝的吸附剂,其最大吸附量约为90 mg/g,吸附符合准二级动力学模型。埃洛石的微结构(零电荷点pH、表面位密度、孔结构等)对其吸附性能产生直接制约作用。有机硅烷接枝改性将埃洛石表面电荷调控为正电荷,将其开发为阴离子型染料酸性橙Ⅱ的吸附剂(需调节溶液pH=2),其最大吸附量为80 mg/g。     

即时合成层状双氢氧化物处理酸性大红GR染料实验研究

印染废水是重要的工业污染源之一,研究新的印染废水脱色技术是水污染控制技术领域重要课题之一。以酸性大红GR为典型代表,初步研究了镁-铝盐水解共沉淀法即时合成层状双氢氧化物(LDH)处理阴离子型染料溶液的效果、影响因素和染料去除机理。结果表明,镁-铝盐水解共沉淀法即时合成LDH对酸性大红GR染料溶液有非常好的脱色效果,影响处理效果的主要因素是Mg/Al比和pH值。在pH值8.5~10.0,Mg/Al比2∶1~4∶1,都可以获得较好的净化效果,酸性大红GR染料浓度0.65 mmol/L时,染料去除率达99%。其净化机理是,当在染料溶液中投加Mg2 、Al2 溶解盐和NaOH时,Mg2 、Al3 水解共沉淀形成LDH的同时,染料阴离子以平衡LDH结构电荷的形式进入LDH结构层间,含有染料的LDH通过沉淀分离从溶液中去除。     

海洋铁锰结核对次甲基蓝的氧化性脱色

利用锰氧化物具有高的吸附与氧化还原化学活性的特点,研究了采自东太平洋的铁锰结核对阳离子染料次甲基蓝氧化性脱色特征。结果表明,铁锰结核表面的非均相氧化是次甲基蓝脱色的主要机制。在通常的染料废水浓度范围内,铁锰结核可有效地对次甲基蓝染料废水氧化脱色。随染料浓度降低,铁锰结核投放量增加和粒度减小,次甲基蓝的脱色率明显提高。次甲基蓝的矿化程度(TOC去除率)较高,但仍低于脱色率。pH对次甲基蓝脱色的影响主要体现在对表面配位体形成和对体系还原电位的影响,当pH<4.0时,脱色率随酸度的增加明显提高;当pH在4.0~10.0时,溶液pH值对脱色率影响有限。在铁锰结核连续循环体系中,溶解Mn2 浓度和pH的增加是脱色率不断下降的主要原因。     

废弃染料基类水滑石原位制备磁性复合材料

<正>层状双金属氢氧化物(layered double hydroxide compounds,简称LDH)是一种阴离子型黏土矿物,具有层间阴离子可交换性、化学组成可调控性以及记忆效应等,在吸附催化等领域具有广泛的应用。近年来,LDH及其煅烧产物(calcined LDH,简称LDO)被证明是阴离子染料的高效吸附剂。然而,LDH/LDO处理阴离子染料废水后会产生大量废弃物,处置不当则会引发二次污染。因此,有必要研究废弃LDH/LDO     

累托石层孔材料处理含铬废水的研究

以累托石层孔材料为吸附剂、以FO2为添加剂对含铬电镀废水进行处理，并对其吸附性能做了初步的探讨，实验结果表明，在不改变原水pH值的条件下，吸附剂用量为2.5g/L，还原剂用量为0.5g/L，处理后水中残留铬浓度为0.2mg/L，远低于国标GB8978-1996一级排放标准，累托石吸附铬的反应符合Freundlich吸附经验式：lgQ=-1.9102 0.3545lgC。     

Fe2O3-TiO2复合光催化剂的制备及其对染料酸性大红降解的光催化活性研究

以氧化铁红粉末为载体,钛酸四丁酯为前驱体,无水乙醇为溶剂,制备了Fe2O3-TiO2光催化剂。用XRD、TEM等对催化剂的物相、形貌进行了表征,并通过对酸性大红GR染料废水进行光催化降解实验,研究了催化剂的投加量、光照时间以及起始浓度、pH值、回收方法及催化剂重复使用次数对酸性大红染料废水光降解作用的影响。实验结果表明,氧化铁红粉末负载TiO2催化剂有很好的吸附和光催化性能,并可以多次回收重复使用,在投加量为0.4g/L的条件下,光催化效果最好,1h后的脱色率可达95%以上。     

焙烧水滑石吸附脱除水中硫酸根离子的研究

利用焙烧水滑石对水中硫酸根离子进行吸附性能研究,考查了初始pH值、吸附时间、吸附剂用量等条件对吸附的影响。结果表明,焙烧水滑石对水中硫酸根离子具有良好的吸附能力。X射线衍射分析结果表明,水滑石及其焙烧产物对硫酸根的吸附机理不同。pH值对吸附的影响较大,pH值较低时吸附效果较好。吸附平衡符合Langmuir方程,室温下饱和吸附量为32.895 mg/g。     

Disposal of wastewater containing Congo Red by synthesizing layer double hydroxide in-situ

Based on the principle of synthesis, a new method was put forward to dispose Congo Red anion-containing dyestuff from wastewater and its feasibility was also examined. The principle of the method is described as follows： Mg^2＋ and Al^3＋ are hydrolyzed to form Mg/Al-LDH by adding Mg^2＋, Al^3＋ and NaOH in wastewater containing anion dyestuff, which is selectively intercalated with the interlayer of LDH in order to balance positive structural charge. While Mg^2＋ and Al^3＋ are co-precipitated to form LDH, the anion dyestuff in wastewater will be removed by LDH synthesized in-situ, as is confirmed by X-ray diffraction analysis of settlings and chemical analysis of aqueous samples. In this work, we studied the influence of Mg/Al mole ratio, pH value, time and temperature of reaction on the removal of anion dyestuff and the use of Mg and Al. The experimental results showed the maximum removal efficiency of anion dyestuff could be attained when pH value was 9.0, and Mg/Al mol ratio was 2 ： 1, reaction duration was 2 hours, and the effect of temperature was not remarkable, and the removal efficiency could reach 100%. Meanwhile, the Mg and Al added could be made good use of. This technology has the advantage of extraordinary efficiency of wastewater disposal.     

即时合成Zn-Mg-Al层状双氢氧化物处理含Zn2+废水实验研究

在模拟含Zn2 废水中加入Mg2 和Al3 ,以NaOH为沉淀剂,研究金属盐水解即时合成层状双氢氧化物(LDH)去除Zn2 的可行性。详细探讨了体系终点pH值、配料中Mg2 /Zn2 摩尔比值及反应温度和时间对Zn2 去除率的影响,结合X射线衍射分析(XRD)探讨了Zn2 去除机理,并与化学沉淀法进行了比较。结果表明,实验条件下只有pH值显著影响Zn2 去除率(p<0.05),在9.0~11.0范围内去除效果最佳,达99%以上。通过XRD分析结合即时合成法特点,废水中Zn2 主要是在晶体生成阶段以Zn-Mg-Al三元LDH化合物形式被去除的。与化学沉淀法相比,即时合成法效果更好,适用pH值范围更广,用来处理含Zn2 废水更具优势。     

贵州水银洞卡林型金矿床首次发现大量次显微-显微可见自然金颗粒

在贵州水银洞卡林型金矿床原生富矿石的一条含砷黄铁矿细脉中发现有100余粒次显微-显微自然金颗粒(0.1~6μm),并具有清晰的显微岩相学结构。提出了该类型金矿次显微-显微可见自然金颗粒的形成过程可能与含Au热液-岩石相互作用过程中含Fe碳酸盐矿物溶解释放Fe的大量硫化物化而导致热液中Au的过饱和有关,含Fe碳酸盐赋矿围岩是形成高品位大型卡林型金矿床最重要的控制因素之一。     

Disposal of wastewater containing Congo Red by synthesizing layer double hydroxide in-situ

Based on the principle of synthesis, a new method was put forward to dispose Congo Red anion-containing dyestuff from wastewater and its feasibility was also examined. The principle of the method is described as follows: Mg²⁺ and Al³⁺ are hydrolyzed to form Mg/Al-LDH by adding Mg²⁺, Al³⁺ and NaOH in wastewater containing anion dyestuff, which is selectively intercalated with the interlayer of LDH in order to balance positive structural charge. While Mg²⁺ and Al³⁺ are co-precipitated to form LDH, the anion dyestuff in wastewater will be removed by LDH synthesized in-situ, as is confirmed by X-ray diffraction analysis of settlings and chemical analysis of aqueous samples. In this work, we studied the influence of Mg/Al mole ratio, pH value, time and temperature of reaction on the removal of anion dyestuff and the use of Mg and Al. The experimental results showed the maximum removal efficiency of anion dyestuff could be attained when pH value was 9.0, and Mg/Al mol ratio was 2: 1, reaction duration was 2 hours, and the effect of temperature was not remarkable, and the removal efficiency could reach 100%. Meanwhile, the Mg and Al added could be made good use of. This technology has the advantage of extraordinary efficiency of wastewater disposal. Foundation item: Project supported by the National Natural Science Foundation of China (40472026).     

Structural Evolvement of Heating Treatment of Mg/AI-LDH and Preparation of Mineral Mesoporous Materials

Although hydrotalcite, or layered double hydroxides （LDHs）, is not a common mineral, it is an important material that can be easily synthesized in laboratory. In this study, structural evolvement and BET surface area changes of heat treated Mg/AI-LDH is evaluated by XRD, TEM and N2-BET analyses. The results indicate that the magnesium-aluminum LDH with carbonate as interlayer anion, periclase-like oxides was formed at temperatures of 400-800℃. Meanwhile, 2-3 nanometer mesoporous were formed during decomposition of LDH. However, the heat treated samples still preserve the morphology of the original LDH plates. Periclase-like formed from LDH heat treatment may re-hydrolyze and recover the structure of LDH. However, crystallinity of the recovered LDH is lower than that of the original LDH. This heat treatment will result in formation of （Mg, Al）-oxide nano-crystals and nanopores among the nano-crystals. When heating temperature exceeds 1000, the periclase-like （Mg, Al）-oxide is transformed into a composite with periclase （MgO） and spinel phases. The periclase can be re-hydrolyzed and dissolved in HCl solution. After acid treatment, the sample with a high surface area is composed of spinel nano-crystals and nanopores among them. Our results will provide a new and economic way to synthesize mesoporous materials through pathways of phase transformation of precursor materials with different composition.     

即时合成Cu/Mg/Al层状双氢氧化物处理含Cu2+废水实验研究

在模拟含Cu2+废水中加入Mg2+和Al3+,以NaOH为沉淀剂,研究金属盐水解即时合成层状双氢氧化物去除Cu2+的可行性,同时考察了体系终点pH值、配料中Mg/Cu摩尔比值及反应温度和时间对Cu2+去除率的影响,探讨了Cu2+去除机理及层状双氢氧化物形成过程。结果表明,实验条件下体系终点pH值显著影响Cu2+去除率,在pH值8.0~11.0范围内去除效果较好,达99%以上。通过X射线衍射分析结合即时合成法特点,废水中Cu2+主要是在晶核生成阶段以Cu/Mg/Al三元层状双氢氧化物形式被去除;三元层状双氢氧化物的形成由反应体系中Al3+、Cu2+、Mg2+分步水解导致,最适pH值约为9.0。     

Effectiveness of Mg–Al-layered double hydroxide for heavy metal removal from mine wastewater and sludge volume reduction

Health hazards from heavy metal pollution in water systems are a global environmental problem. Of similar concern is sludge that results from wastewater treatment due to unsatisfactory sludge management technology. Therefore, the effectiveness of using Mg–Al-layered double hydroxide in the removal of heavy metals from mine wastewater was tested and compared with that of calcium hydroxide [Ca(OH)₂], which is a common treatment method for heavy metal removal. Initially, the mine wastewater contained cations of the heavy metals iron (Fe), zinc (Zn), copper (Cu), and lead (Pb). The Mg–Al-layered double hydroxides were able to remove 371, 7.2, 121, and 0.4 mg/L of these pollutants, respectively, using the co-precipitation method. The removal of these metals is most effective using 0.5 g Mg–Al-layered double hydroxide (Mg/Al molar ratio 4) and 20 min of shaking. Zn was removed by the formation of Zn(NO₃)(OH)·H₂O and Zn₅(NO₃)₂(OH)₈ when LDH, Mg/Al molar ratios of 4 and 2, respectively, were used. Similarly, Fe, Cu, and Pb were removed by the formation of Fe–Al-layered double hydroxide, Cu₂(OH)₃·NO₃ and Pb₄(OH)₄(NO₃)₄, respectively. While Ca(OH)₂ is also capable of reducing the heavy metal concentrations below the Japanese recommended values, this analysis shows that using 0.5 g Mg–Al-layered double hydroxide is a better treatment condition for mine wastewater, because it generates lower sludge volumes than 0.1 g of Ca(OH)₂. The measured sludge volume was 1.5 mL for Mg–Al-layered double hydroxide and 2.5 mL for Ca(OH)₂, a nearly twofold further reduction.     

Influence of high-pressure processing on the structure and memory effect of synthetic layered double hydroxides

We investigate the structural evolution of synthetic layered double hydroxides (LDH) samples, processed at room temperature and high-pressure (up to 7.7 GPa) in a toroidal chamber with two pressure-transmitting media, lead and graphite, using X-ray diffraction, thermogravimetry and N₂-adsorption isotherms techniques. The X-ray patterns of compacted samples show a decrease in the peak intensities. For both pressure-transmitting media, our samples revealed a reduction of the basal d-spacing for the (003) plane when processed at 7.7 GPa. The expected high-pressure-induced amorphization was not observed. Surprisingly, we find high-pressure processing to have a strong influence on the memory effect of the LDH, due essentially to the reduction of the surface area and pore closing. Even when immersed in water, our samples did not recover the LDH structure, when either calcined at 450°C and compacted at 7.7 GPa, or calcined at 700°C and immediately compacted at 2.5 and 7.7 GPa.     

谷氨酸插层镁铝水滑石微观结构与性能:实验与理论研究

采用共沉淀法合成了谷氨酸插层镁铝水滑石(LDHs-Glu),并使用XRD表征技术以及分子动力学模拟方法对其微观结构与性能进行了研究。结果表明随着LDHs-Glu中水分子数量增加,层间距d003逐渐增大。XRD表征得到其层间距为1.328 nm,与理论模拟得到的当水分子数Nw=7时的水滑石层间距d003=1.323 nm相近。随着层间水分子数量增加,水合能逐渐增大,最终趋于流体水的特征值(-41.8 kJ/mol)。水合过程中,水滑石层板与阴离子间的氢键逐渐减少,而层板与水分子间的氢键逐渐增多,说明水分子与层板间的亲和力更强。实验表征与理论模拟相结合的研究方法,有望成为插层复合材料微观结构研究的重要手段。