Zr~(4+)掺杂对Mg/Al水滑石磷酸根吸附行为的影响

采用共沉淀法制备了系列不同Zr~(4+)含量的Mg/Al/Zr三元类水滑石材料,研究了其对废水中磷酸根离子的吸附性能。采用XRD、DRIFTS、氮气吸脱附等对材料的结构及织构性质进行了表征,并研究了溶液初始pH以及竞争阴离子对磷吸附量的影响。结果表明:掺杂Zr~(4+)能提高类水滑石层板正电荷密度以及增大层间距,有利于磷酸根阴离子的吸附;Mg/Al/Zr类水滑石对磷的吸附过程符合准二级动力学模型,吸附等温线符合Langmuir模型,当n(Zr~(4+))/(Al~(3+)+Zr~(4+))=0.3时,理论饱和吸附量最大,达到76.6 mg/g,比Mg/Al水滑石高出28.7%;酸性环境有利于磷酸根的吸附,而二价阴离子的竞争吸附作用会显著降低磷吸附效果。Mg/Al/Zr类水滑石对磷的吸附机理为静电吸引和阴离子交换协同作用。     

Mn2+掺杂Mg/Al水滑石强化水中磷酸盐吸附性能

由于磷酸盐过量引起的富营养化对生态系统和人类健康产生的不利影响，已成为迫切需要解决的全球性环境问题。采用共沉淀法制备了Mn²⁺掺杂的Mg/Al/Mn三元类水滑石材料，实现了废水中磷酸盐的有效去除。采用X射线衍射(XRD)技术对Mg/Al/Mn类水滑石的结构进行了表征，并考察了吸附时间、初始磷浓度以及溶液pH值对磷酸盐吸附效果的影响。结果表明：适量掺杂Mn²⁺能增大类水滑石的层间距，有利于磷酸盐的吸附。Mg/Al/Mn类水滑石对磷酸盐的吸附动力学过程符合准二级动力学模型，而吸附等温线适合用Langmuir模型描述。当Mn²⁺占所有金属离子百分比为2.5%时，理论饱和吸附量最大，达到119.7 mg/g,约为Mg/Al水滑石的2倍。此外，Mg/Al/Mn类水滑石还具有宽的pH值适应范围(3～11)。以上结果表明Mg/Al/Mn三元类水滑石是一种有前途的吸附剂，可用于废水中磷酸盐的高效处理。     

磁性类水滑石的制备和吸附水中磷的研究

采用共沉淀制备一系列磁性Mg-Al、Zn-Al、Mg-Fe和Zn-Fe类水滑石磷吸附剂,并研究了磁性类水滑石的组成、摩尔比、pH值、吸附剂用量等对含磷酸盐废水的吸附性能影响。结果表明,磁性类水滑石对磷酸根有良好的吸附效果,磁性类水滑石的金属组成对磷酸根吸附有显著影响,其中Mg/Al摩尔比为2∶1的磁性类水滑石在pH=5～7范围内吸附效果最好,吸附剂最佳投加量0.5 g,最高吸附量达47.1 mg/g。     

ZnAlLa类水滑石对污泥脱水液中磷酸根的吸附

通过共沉淀法合成了ZnAlLa三元类水滑石,并考察了其结构特征和对磷酸根的吸附性能。结果表明,在保持类水滑石层状结构的条件下,La的适量掺杂可增强吸附剂对磷酸根的吸附。当Zn∶Al∶La摩尔比为2.00∶0.90∶0.10时,ZnAlLa类水滑石在24h内对污泥脱水液中磷酸根的吸附量为35.15mgP.g-1,比无La时的吸附量提高了41.9%。300℃焙烧处理后,ZnAlLa样品转化为亚稳态的复合金属氧化物,同时比表面积明显增加,其磷酸根吸附量约为焙烧前的1.48倍。ZnAlLa对磷酸根的吸附在pH变化及竞争离子存在时表现出较强的稳定性。该吸附剂对污泥脱水液中磷酸根的吸附符合假二级吸附动力学;吸附等温线表现为Langmuir型。     

铁镁铝三元类水滑石对磷的吸附特性研究

采用低饱和共沉淀的方法合成了n(Fe)∶n(Mg)∶n(Al)=1∶1∶1的铁镁铝三元类水滑石。研究其对磷的吸附特性,考察了吸附时间、投加量、温度、p H等因素对吸附效果的影响。结果表明:此类水滑石对磷的吸附在前20 min吸附量急剧增加,40 min之后趋于稳定;当投加量为1.0 g/L时,吸附率和吸附容量都相对较高;初始p H为3~10时,对吸附效果无明显影响;温度对吸附效果影响较大,温度升高吸附量增加,表明此吸附过程是吸热过程。此类水滑石对磷的等温吸附数据与Langmuir方程的相关系数很高,45℃时饱和吸附量高达13.15 mg/g,同时吸附过程符合二级动力学模型。     

Mg(Zn)-Al(Fe)层状双氢氧化物磷酸根吸附性能研究

采用共沉淀法合成Mg-Al-LDH、Mg-Fe-LDH和Zn-Al-LDH三类不同的层状双金属氢氧化物,系统研究其磷酸根吸附行为和影响因素。结果表明,Mg-Al-LDH对于磷酸根的饱和吸附量可达99.17 mg/g,吸附过程符合Langmuir模型和准二级动力学模型,弱酸性环境和金属阳离子的存在有利于磷酸根的吸附,而阴离子的加入则会抑制磷酸根的吸附。磷酸根在Mg-Al-LDH表面的吸附是静电吸引、化学吸附和阴离子插层共同作用的结果。     

水热法制备Mg-Fe类水滑石及对水中硫酸根离子吸附的研究

采用尿素分解水热合成法制备Mg-Fe类水滑石,并通过XRD,FF-IR表征.利用Mg-Fe类水滑石焙烧产物对水中硫酸根离子进行一定条件的吸附去除.结果表明,Mg-Fe类水滑石层间阴离子为碳酸根,结晶效果较好.焙烧后Mg-Fe类水滑石在pH =4～8,温度为35℃,对初始浓度500 mg/L硫酸根离子具有较好的吸附能力,90 min可快速达到吸附平衡,吸附数据表明该吸附符合准二级动力学方程,吸附等温线符合Langmuir吸附模型,最大吸附量为151.51 mg/g.     

Mg(Zn)-Al(Fe)层状双氢氧化物磷酸根吸附性能研究

采用共沉淀法合成Mg-Al-LDH、Mg-Fe-LDH和Zn-Al-LDH三类不同的层状双金属氢氧化物,系统研究其磷酸根吸附行为和影响因素。结果表明,Mg-Al-LDH对于磷酸根的饱和吸附量可达99.17 mg/g,吸附过程符合Langmuir模型和准二级动力学模型,弱酸性环境和金属阳离子的存在有利于磷酸根的吸附,而阴离子的加入则会抑制磷酸根的吸附。磷酸根在Mg-Al-LDH表面的吸附是静电吸引、化学吸附和阴离子插层共同作用的结果。     

响应面法优化焙烧Mg/Al水滑石同时吸附水中F~-和硬度

采用焙烧Mg/Al水滑石同时去除微污染水体中的F~-和硬度。通过Plackett-Burman实验设计选出影响F~-和硬度去除率的主要因素,利用响应面法中Box-Behnken实验设计进行优化设计并得到回归模型。结果表明,pH、反应时间、焙烧Mg/Al水滑石投加量对F~-和硬度的去除率均有显著影响,最佳吸附条件:pH为9.40,反应时间为239.33 min,焙烧Mg/Al水滑石投加量为5.61 g/L。在此最优条件下,F~-和硬度的去除率分别为97.55%、58.09%。     

磷钨杂多阴离子P2W18O626-插层水滑石的制备

采用离子交换法,以镁铝硝酸根型水滑石(MgAl-NO3-LDHs)为前体,利用其独特的层状结构,进行了磷钨杂多酸阴离子P2W18O626-插层水滑石的制备研究,通过X射线衍射(XRD)、红外光谱(FT-IR)、热重-差热(TG-DTA)和紫外-可见光谱(UV-vis)等手段对样品结构进行了分析.结果表明,离子交换法制备得到了磷钨杂多酸阴离子P2W18O626-插层水滑石产物(MgAl-P2W18O626-LDHs),插层产物保持了原有的层状结构,且合适层板Mg2+/Al3+有利于形成晶体结构规整的插层产物.     

Synthesis of p-sulfonated calix[4]arene-intercalated layered double hydroxides and their adsorption properties for organic molecules

Calixarenes are macrocyclic organo anions, which cavity is capable of molecular recognition, while layered double hydroxides (LDHs) are widely known as hydrotalcite-like compounds, anion exchangers and host–guest materials. In this study, the intercalation of water-soluble p-sulfonated calix[4]arene (CS4) in the interlayer of the Mg–Al and Zn–Al LDHs (M²⁺/Al ratio = 3) by the coprecipitation method has been investigated as well as the adsorption property of the resulting CS4/LDHs for benzyl alcohol (BA) and p-nitrophenol (NP). It was found that the CS4/LDHs with the molar ratio of CS4/Al = 0.25 (Mg–Al LDH) and 0.12 (Zn–Al LDH) were obtained as a single phase. The arrangement of CS4 in the LDH interlayer was different by the kind of the host metal ions as CS4 cavity axis perpendicular (Mg–Al LDH) and parallel (Zn–Al LDH) to the basal layer, influencing strongly on the BET surface area, N₂ adsorbed volume and adsorption property for BA and NP.     

The adsorption behavior of C.I. Acid Blue 9 onto calcined Mg–Al layered double hydroxides

Mesoporous calcined Mg–Al layered double hydroxides with different Mg/Al molar ratios were investigated for their ability to adsorb the commercial dye, C.I. Acid Blue 9, with a view to exploring their suitability as inorganic pigments in Ink Receptive Layer formulation. Uptake capacity was characterized using the Langmuir model and the resulting L-2/H-2 type plots indicated that the acid dye anions were adsorbed onto the surface by strong interactions. Optimum dye adsorption was achieved for a Mg/Al molar ratio ≈5.6. A surface adsorption mechanism is proposed to account for the adsorption of the dye onto the calcined Mg–Al layered double hydroxides. X-ray powder diffraction analysis indicated that given sufficient time it is possible to intercalate the dye within the layered double hydroxides' interlayer via a reconstruction mechanism. Scanning electron microscopy, N₂ adsorption–desorption analysis and helium pycnometry were employed to examine the textural properties of the materials, which were correlated with their adsorption properties.     

Memory effect-enhanced catalytic ozonation of aqueous phenol and oxalic acid over supported Cu catalysts derived from hydrotalcite

Mg/Al supported metal (Fe, Co, Ni and Cu) oxide catalysts were prepared by co-precipitation of hydrotalcite-like clay materials as precursors, calcined, and used for the ozonation reaction of phenol and oxalic acid. The reaction was carried out using the catalyst and aqueous solution of phenol or oxalic acid in an O₃/O₂ mixed gas-flow at 20 °C. In the ozonation of phenol, the combination of ozone and supported metal oxide catalysts was effective for the removal of total organic carbon (TOC). Also in the ozonation of oxalic acid as the main TOC component, Cu/Mg/Al catalysts showed the highest activity, followed by Ni/Mg/Al catalyst, while both Fe/Mg/Al and Co/Mg/Al catalysts were not active. Leaching of Cu and Ni, probably due to the chelation of metals by oxalic acid, was significantly observed at the beginning of the reaction. However the metal leaching disappeared at the end of the reaction possibly due to the entire consumption of oxalic acid during the reaction. The best result of oxalic acid mineralization was observed over Cu/Mg/Al catalyst calcined at 600 °C, on which least leaching of the metal was detected. Moreover, a “memory effect” of hydrotalcite accelerated the mineralization of oxalic acid over the Cu/Mg/Al catalyst; oxalate anions were captured and decomposed in the reconstituted hydrotalcite interlayer space on the surface of the Cu/Mg/Al catalyst, resulting in a remarkable enhancement in the catalytic activity of the ozonation.     

Heterogeneous basic catalysts as alternatives to homogeneous catalysts: reactivity of Mg/Al mixed oxides in the alkylation of m-cresol with methanol

Mg/Al mixed oxides, obtained by decomposition of hydrotalcite-like precursors, represent interesting heterogeneous catalytic systems for basic-catalyzed reactions, as an alternative to environmentally unfriendly homogeneous catalysts. The reactivity of these oxides was evaluated using the methylation of m-cresol as a test reaction and relationships between catalytic performance and chemical–physical features were established. The basicity of the samples was evaluated by CO₂ adsorption and thermal-programmed-desorption. The presence of Al in the mixed oxides considerably affected the density and the strength of the basic sites with respect to MgO. These basic properties in turn influenced the catalytic performance of the materials. Under the reaction conditions used in the present work, medium strength basic sites played the major role in the reaction.     

湿法磷酸制取磷酸脲工艺优化及杂质行为研究

二水法生产的湿法磷酸中存在大量的阴离子和阳离子,这些离子很难在磷酸净化过程中除去。用湿法磷酸直接制取磷酸脲时,杂质离子会影响介稳区宽度,进而影响产品的产率和质量。通过改变原料配比、反应时间、反应温度、降温速度、结晶温度和搅拌速度等因素探索了湿法磷酸直接生产磷酸脲的最佳工艺条件,并分析湿法磷酸中存在 的SO42-、SiF62-、Fe3+、Al3+和Mg2+几种主要杂质离子对磷酸脲的产率和产品质量的影响。实验发现,保持一定量的SiF62-浓度有利于提高产品产率,但是其浓度不宜太高。SO42-、Fe3+、Al3+和Mg2+等会降低磷酸脲的产率,并且 Fe3+和Al3+对产率影响较大。     

镧-钙双金属凝胶微球对水中低磷含量的去除性能

以粉煤灰为基本骨架,将镧、钙双金属作为交联剂对海藻酸钠进行交联制备得到镧-钙双金属凝胶微球,并通过批量吸附实验和表征分析研究了镧-钙双金属凝胶微球对水中低含量磷的去除性能和去除机理.结果表明,镧-钙双金属凝胶微球具有不规则多孔结构,镧和钙2种金属被交联在了微球上,磷主要通过与微球上的La3+和Ca2+发生化学沉淀而被去...     

生物除磷颗粒污泥去除Pb2+的效能机制

以好氧颗粒污泥的吸附作用和磷酸盐对重金属的螯合作用为基础,采用富含磷酸盐的生物除磷颗粒污泥作为吸附剂来处理含铅废水,考察了不同吸附条件（pH、Pb²⁺的初始浓度、吸附反应时间）下,颗粒污泥对Pb²⁺的去除效果。结果表明,除磷颗粒污泥在pH为4,初始Pb²⁺浓度为150 mg·L^-1时,对铅的去除率最高（为99.9%）;在吸附反应20 min时即可达到吸附平衡。生物除磷颗粒污泥对Pb²⁺的吸附可以用Langmuir模型拟合（R²=0.993）,最大吸附量为49.5 mg·g^-1。其中离子交换和磷酸盐与Pb²⁺的螯合作用对除磷颗粒污泥去除Pb²⁺起到重要作用;傅里叶变换红外光谱（FTIR）测定表明-COOH、-OH、磷酰基等多种官能团也参与了除磷颗粒污泥除Pb²⁺过程。     

胶原纤维负载锆对氟离子和磷酸根的吸附去除

将Zr(Ⅳ)负载在胶原纤维基质上制备吸附材料,研究了该吸附材料对水溶液中氟离子和磷酸根离子的吸附特性。结果表明,胶原纤维负载Zr(Ⅳ)(ZrCF)对氟离子和磷酸根离子均有较强的吸附能力,在pH=4～9,胶原纤维负载Zr(Ⅳ)对氟离子保持较高的吸附容量;ZrCF吸附磷酸根的适宜pH=3.0～6.0。胶原纤维负载Zr(Ⅳ)对氟离子和磷酸根离子的吸附等温线均符合Langmuir方程;吸附动力学研究表明,胶原纤维负载Zr(Ⅳ)对氟离子和磷酸根离子的吸附动力学可以用准二级速率方程来描述。水中常见的Cl-、NO3-、CO23-和SO24-对ZrCF吸附氟离子和磷酸根离子的影响不大,模拟地下水体系的动态实验结果表明,ZrCF对磷酸根的亲和力更强。     

Zn/Al类水滑石及其插层材料的光催化性能

以氨水为共沉淀剂,采用低温共沉淀法合成了不同摩尔比的Zn/Al类水滑石,并通过离子交换法在层板间引入磷钨酸根离子,经焙烧后得到具有光催化性能的催化材料,研究插层前后类水滑石焙烧产物对甲基橙等染料的光催化降解性能。结果表明,CZn-Al-r催化剂具有优良的光催化降解有机染料的性能,通过调整催化剂前驱体中金属元素的比例,甲基橙和亚甲基蓝的降解率可在2 h内接近100%。而经磷钨酸插层后,IZnAl-2的光催化降解速率较CZnAl-2有所下降。     

镁铝阴离子粘土对砷酸根离子的吸附作用

利用共沉淀水热法制备了镁铝阴离子粘土材料，研究了其水溶液对砷酸根离子的去除能力。结果表明：镁铝阴离子粘土对砷酸根离子具有较高的去除率和吸附容量、较快的吸附速度。砷酸根离子的吸附平衡数据很好的符合Freundlich型吸附等温方程。同时，吸附动力学数据完全符合Lagergren二级速度方程。吸附砷酸根离子后的阴离子粘土材料，用稀NazCO3溶液可以很好的洗脱再生。阴离子粘土对砷酸根离子的吸附属于层间离子交换作用。