十八烷基三甲基铵用量与蒙脱石/烷基铵复合物结构关系研究

利用小角X射线衍射技术对在不同的十八烷基三甲基氯化铵用量下制备的蒙脱石/烷基铵复合物的结构特征进行研究,结果发现:十八烷基三甲基氯化铵的用量和制备的蒙脱石/烷基铵复合物的结构有明显的相关性,当十八烷基三甲基氯化铵的用量小于0.7 CEC时,十八烷基三甲基铵阳离子在蒙脱石层间呈单层平卧排布;当十八烷基三甲基铵用量在0.9 CEC～1.8 CEC时,十八烷基三甲基铵阳离子在蒙脱石层间呈现单层倾斜排列;当十八烷基三甲基铵用量大于2.3 CEC时,十八烷基三甲基铵阳离子在蒙脱石层间呈现一种大尺寸胶束结构和小角倾斜结构的混层结构模型排布.     

蒙脱石层电荷与有机改性蒙脱石凝胶性能关系研究

利用自然沉降法提取了山东两不同产地膨润土中的钙基蒙脱石矿物M1和M2,利用结构式推算法计算了两提纯蒙脱石的层电荷:M1单位半晶胞的层电荷为0.38,M2单位半晶胞的层电荷为0.59;利用十八烷基三甲基氯化铵对蒙脱石进行有机改性,并对有机蒙脱石凝胶性能和层电荷的相关关系进行研究。研究发现:蒙脱石单位半晶胞的层电荷越低,在水中的分散性越好,越有利于十八烷基三甲基铵阳离子的插层,相应有机改性蒙脱石在二甲苯和乙醇体系中的凝胶性能越好(如M1);蒙脱石单位半晶胞的层电荷越高,在水中的分散性越差,越不利于十八烷基三甲基铵阳离子的插层,相应有机改性蒙脱石产品的凝胶性能较差(如M2)。     

十八烷基三甲基铵改性蒙脱石的结构和凝胶性能关系研究

利用小角X射线衍射技术研究在不同的十八烷基三甲基铵盐用量下制备的有机蒙脱石的结构特征,将具有不同晶体结构特征的有机蒙脱石分别分散在二甲苯、乙醇混合相和0#柴油中,测定在相应溶剂体系中的凝胶性能,研究发现当十八烷基三甲基铵盐的用量小于0.9 CEC时,十八烷基三甲基铵盐阳离子在蒙脱石层间呈单层平卧排列,由于在有机溶剂中蒙脱石得不到充分的剥离而导致有机蒙脱石的凝胶性能较差,表现为有机凝胶的粘度和胶体率都较低;当十八烷基三甲基铵盐的用量在0.9 CEC~1.8 CEC时,十八烷基铵阳离子在蒙脱石层间呈单层倾斜排列,在有机相中蒙脱石不仅能得到充分的剥离,而且能形成稳定的"卡房式结构",使有机凝胶的黏度和胶体率分别最高达到23 000mPa.s和100%;而当十八烷基铵盐的用量大于1.8 CEC时,十八烷基铵有机物在蒙脱石层间呈胶束排列,尽管在有机相中能得到充分的剥离,但由于过量的有机阳离子中和了蒙脱石层面的负电荷,在体系中不能形成稳定的"卡房式结构",使有机蒙脱石的凝胶粘度较低,而胶体率较高。     

不同类型烷基铵在蒙脱石中的吸附动力学特性北大核心CSCD

蒙脱石/烷基铵改性产物是一种重要的高附加值矿物材料,蒙脱石对烷基铵的吸附特性决定所制备的改性产物在各类溶剂体系中的凝胶性能和应用特性。本文以两种层电荷不同的膨润土为原料,在提纯、钠化的基础上,系统研究了80℃恒温条件下十八烷基三甲基铵(OTAC)、十六烷基三甲基铵(CTAC)及十四烷基三甲基铵(TTAC)在两种蒙脱石上的吸附动力学特性。研究结果表明:80℃的恒温条件下,烷基铵插层剂的浓度对等温吸附进程影响显著。当三种烷基铵用量较低(1.0CEC)时,在5min左右就可以达到饱和吸附;当烷基铵用量较高(2.0CEC)时,在30min^60min可以达到饱和吸附;两种蒙脱石对三种烷基铵吸附动力学数据均符合准二级反应动力学方程,相应三种烷基铵在两种蒙脱石中平衡吸附量的实验值和计算值qe基本相等;交换液中烷基铵浓度高低对吸附反应的速率常数影响显著,烷基铵在低用量(1.0CEC)下在蒙脱石中的吸附反应速率常数明显高于其在较高用量(2.0CEC)下的吸附反应常数;烷基铵在高层电荷Na-HLCM中的吸附反应速率常数总体上较低层电荷Na-HLCM的略高。     

不同类型烷基铵在蒙脱石中的吸附动力学特性

蒙脱石/烷基铵改性产物是一种重要的高附加值矿物材料,蒙脱石对烷基铵的吸附特性决定所制备的改性产物在各类溶剂体系中的凝胶性能和应用特性。本文以两种层电荷不同的膨润土为原料,在提纯、钠化的基础上,系统研究了80℃恒温条件下十八烷基三甲基铵(OTAC)、十六烷基三甲基铵(CTAC)及十四烷基三甲基铵(TTAC)在两种蒙脱石上的吸附动力学特性。研究结果表明:80℃的恒温条件下,烷基铵插层剂的浓度对等温吸附进程影响显著。当三种烷基铵用量较低(1.0CEC)时,在5min左右就可以达到饱和吸附;当烷基铵用量较高(2.0CEC)时,在30min~60min可以达到饱和吸附;两种蒙脱石对三种烷基铵吸附动力学数据均符合准二级反应动力学方程,相应三种烷基铵在两种蒙脱石中平衡吸附量的实验值和计算值qe基本相等;交换液中烷基铵浓度高低对吸附反应的速率常数影响显著,烷基铵在低用量(1.0CEC)下在蒙脱石中的吸附反应速率常数明显高于其在较高用量(2.0CEC)下的吸附反应常数;烷基铵在高层电荷Na-HLCM中的吸附反应速率常数总体上较低层电荷Na-HLCM的略高。     

C10TAB,C14TAB,C18TAB柱撑蒙脱石层间域有机柱排布研究

用十烷基三甲基溴化铵（C10TAB）、十四烷基三甲基溴化铵（C14TAB）和十八烷基三甲基溴化铵（C18TAB）制备有机柱撑蒙脱石,并对产物进行X射线衍射表征。研究结果表明：柱化剂的浓度和烷基季铵离子的性质能影响烷基季铵离子在蒙脱石层间的排布模式。在柱化剂浓度较低时易形成平卧排列,柱化剂达到一定浓度时石蜡型结构方能形成,且直链烷基越长,烷基季铵离子在蒙脱石层问越易形成石蜡型倾斜排列。在平卧结构向石蜡型结构转化过程中可出现多种排列共存。     

不同链长烷基季铵离子在蒙脱石层间域内排列方式的对比

选用含不同烷基长链的三种季铵盐——十二烷基三甲基溴化铵(DDTMAB)、十四烷基三甲基溴化铵(TDTMAB)、十六烷基三甲基溴化铵(HDTMAB)，对河北钠交换蒙脱石进行了有机柱撑实验，以X射线衍射分析方法对实验产物进行了对比研究。结果表明，由于烷基链中所含的碳原子数目不同，三种长链季铵离子对蒙脱石的柱撑效果不同，DDTMA^ 在蒙脱石层间域内可形成平卧单层、平卧双层和假三层三种不同排列方式；TDTMA^ 与DDTMA^ 在低浓度条件下形成的前两种排列方式相同，而第三种则不同，为倾斜单层排列；HDTMA^ 有机柱撑产物中除了具有前两者的排列方式外，还具有倾斜双层排列方式。不同排列方式的复合产物可以多相共存。此外，随着柱撑剂浓度的增加，三种长链烷基季铵离子在蒙脱石层间域内的排列方式及其演化是不同的。     

四川三台钙蒙脱石的矿物学与有机化处理研究

对四川三台钙蒙脱石进行了矿物学和有机化处理研究。化学成分分析、晶体化学式与层间可交换阳离子数计算、X射线衍射分析和热分析都表明三台膨润土属钙基膨润土，属型为切托-Otay型。用十八烷基三甲基氯化铵、十八烷基二甲基苄基氯化铵、十二烷基二甲基苄基氯化铵三种季铵盐阳离子表面活性剂对四川三台钙蒙脱石进行了有机化处理。结果表明，用十八烷基三甲基氯化铵处理的效果最好。     

不同分子质量聚乙二醇在蒙脱石层间的吸附作用

用蒙脱石(Mont)吸附水溶液中不同分子质量的聚乙二醇(PEG)，制备PEG／Mont复合物，采用XRD、FTIR和DTA／TG表征PEG／Mont复合物的结构。结果表明：PEG通过置换部分层间水合离子进入蒙脱石层间通道内；PEG以单层或双层平卧于蒙脱石层间；大分子质量的PEG容易形成双层复合物，但双层复合物的热稳定性较差。     

交换液酸碱度对OTAC在蒙脱石中吸附及复合物凝胶粘度影响

在蒙脱石有机改性体系中,交换液酸碱度对蒙脱石荷电性以及十八烷基三甲基氯化铵(OTAC)的电离度影响很大,进而影响OTAC在蒙脱石中的吸附以及制备复合物的凝胶粘度。研究发现,在pH=3的强酸性交换体系中,蒙脱石端面可变电荷为正电荷,OTAC阳离子和蒙脱石之间静电斥力的存在不利于OTAC在蒙脱石上的吸附,吸附量和吸附率分别是0.943CEC和85.7%,制备复合物的凝胶粘度最低,分别是μ0min为45.67Pa·s,μ30min为16.52Pa·s;在pH=10的弱碱性交换体系中,由于蒙脱石层面和端面均带有负电荷,静电引力更有利于OTAC阳离子在蒙脱石层间交换及表面吸附,其吸附量和吸附率最高,分别为1.097CEC和99.71%,制备复合物的凝胶粘度也较高,分别是μ0min为95.93Pa·s,μ30min为37.67Pa·s;在强碱性交换体系中,当pH=11和13时,蒙脱石对OTAC的吸附量和吸附率降低明显,吸附量分别为1.08CEC和1.058CEC,吸附率分别降到98.20%和96.18%,对应复合物的μ0min分别为96.52Pa·s和93.52Pa·s,μ30min分别为36.57Pa·s和36.53Pa·s,究其原因由于交换液中OTAC阳离子和高浓度的钠离子在蒙脱石层间和表面存在竞争吸附导致蒙脱石层间钠离子的交换难度加大。     

天然膨润土中蒙脱石丰度的定量方法研究

基于膨润土中蒙脱石的基本结构单元在X射线衍射空间的相干散射的分布和总量是一不变量,同一膨润土矿中单位质量蒙脱石的阳离子交换容量和层电荷密度专一性的特点,本研究提出了阳离子交换容量／层电荷密度、阳离子交换容量和X射线衍射多相Rietveld分析三种蒙脱石丰度的定量方法,并测定了我国不同产地、矿物组成和物化性质各异的10种天然膨润土中蒙脱石丰度,分析了可能的干扰因素。结果表明,三种方法测得的蒙脱石丰度值在3％范围内吻合良好,且具有一致的自相关性。     

含膨胀性晶层层状硅酸盐矿物的层电荷表征方法及其原理

依据含膨胀性晶层层状硅酸盐矿物(PSEL)层电荷的大小把膨胀性晶层分为蒙皂石晶层和蛭石晶层两类。讨论了PSEL层电荷的产生与类型,综述了国内外关于PSEL层电荷的测试和表征方法的研究现状;分析了晶体化学式计算法、烷基季铵盐法和阳离子交换容量法的测定原理和计算方法。以四川三台蒙脱石样品为例分别用晶体化学式计算法及烷基季铵盐法计算了蒙脱石的层电荷,认为含膨胀性晶层层状硅酸盐矿物的层电荷研究对于层状硅酸盐矿物晶体化学具有重要的理论意义。     

Assessing Cd,Co, Cu,Ni, and Pb Sorption on montmorillonite using surface complexation models

Cadmium, Co, Cu, Ni and Pb adsorption is measured on montmorillonite as a function of pH (3–11), ionic strength (0.001–0.1 M NaNO₃), and sorbate concentration (0.1–10 μM metal on 0.5 g/L solid). Sorption of all metals shows strong dependence on ionic strength and sorbate concentration, as well as a break in the slope of the edge, indicative of a 2-site interaction with montmorillonite. The resulting adsorption edges are used to parameterize diffuse layer surface complexation models (DLMs) for each metal. A 2-site DLM with a bidentate variable charge surface hydroxyl site and a bidentate permanent charge exchange site produced good fits for the individual experiments, but lacked the robustness to accurately predict adsorption across the entire experimental range. Other models, such as CCM, TLM, or CD-MUSIC may be required for more accurate predictions across broad ranges of solution conditions.     

蒙脱石热处理产物的微结构变化研究

本文对广东和平蒙脱石及其热处理产物进行了化学分析、差热和热重分析、X射线粉末衍射分析、红外吸收光谱分析、扫描电镜、原子力显微镜及魔角旋转核磁共振等研究。结果表明,蒙脱石在热处理温度为126℃-148℃时,主要脱出吸附水和层间水,这一脱水过程是可逆的。当热处理温度达到659℃时,蒙脱石八面体片中的羟基开始脱失,但层状结构仍然保持,这种羟基的脱失过程对应着八面体片中AlⅥ向AlⅣ的转变。当温度达到900℃时,蒙脱石的层状结构完全被破坏,并有新的矿物相μ-堇青石产生。当温度为1200℃时,则出现方英石及莫来石相。当热处理温度达到1350℃时,方英石及莫来石的含量略有减少,并出现较多的含铁堇青石相。     

Enhancing the Adsorption Capacity of TMA-montmorillonite Toward HOCs

Organoclays synthesized with small organic cations can effectively adsorb hydrophobic organic compounds (HOCs), and the hydrophobic siloxane surfaces of clay minerals have been considered as the main adsorption sites for HOCs. Therefore, reducing charge density of clay minerals which can effectively increase the exposed siloxane surface areas has been generally used to enhance the adsorption capacity of organoclays towards HOCs. In this work, we will present a new method to increase the exposed siloxane surface areas of the synthesized organoclays and enhance their adsorption capacity. Firstly, the original inorganic cations on montmorillonite were exchanged with Li+, and then part of the Li+ (i.e., 20% to 60% of the montmorillonite’s CEC) were further exchanged with tetramethylammonium cation (TMA). After that ,the samples were heated at 200 ℃ for 12 h to make sure most of the Li+ were transferred to montmorillonite layers. With this method the layer charge of montmorillonite can be effectively reduced while the layered structure of montmorillonite will be preserved by pre-exchanged TMA. Finally, the remaining Li+ cations were further exchanged with TMA. The structural and adsorptive characteristics of the resulting organoclays were compared with those synthesized using traditional method (i.e., first reducing the charge density and then exchanging TMA).     

Mineral chemistry of clays associated with the Jhilmili intertrappean bed in the eastern Deccan volcanic province: Palaeoenvironmental inferences and KTB transition

Jhilmili intertrappean bed (～13 m thick) attains its significance with the recent discovery of brackish water ostrocod and planktonic foraminifera fossils (Keller et al. 2009; Khosala et al. 2009). Present XRD data revealed abundance of montmorillonite > montmorillonite/chlorite mixed layer > palygorskite in five physically distinct lithounits namely: (a) lower chocolate brown siltstone with green patches, followed by (b) brick red clayey siltstone, (c) greenish grey clay, (d) yellowish brown clay and (e) uppermost olive grey to dark brown silt layers in the successionrepresent higher weathering indices and annual precipitation, reflecting cyclic, but longer spells of weathering. Occurrence of M/C mixed layer with the smectite in Jhilmili area is suggestive of their derivation from the later, whilst montmorillonite to palygorskite transformation is ascribed to the drastic changes in the humid to arid climate, where former served as a source of Al and some of the Si and Mg ions for the later. Jhilmili and Anjar clays represent similar charge occupancies at different sites, but later contains relatively higher amount of palygorskite, formed in the arid environment. Majority of the trace elemental data plots for Jhilmili clays lie within the upper and lower limits of infra (Lametas)-/inter-trappeans clays. The continuous release of Cu throughout the succession (mainly in the palygorskite dominated clays) indicates oxidizing conditions. PAAS normalized REE data plots for these clays show progressive enrichment in the HREE contents in the lower part, but, upper part of the succession is marked by positive cerium anomaly, reflecting oxidizing conditions prevailed at the later stage of the succession. These conditions continued, but, were not conducive to HREE enrichment as evidenced by their depletion in the upper part of the succession. The Ce anomaly observed in the middle part of the succession is similar to that form by continental weathering of the basalt, ascribed to Ce precipitation in the oxic environment, thus suggestive of drastic changes in the oxidizing conditions. Thermodynamic data-sets for Jhilmili clays show I/S mixed layer and celadonite compositions, whereas, Jabalpur infra-/inter-trappean clays correspond to Mg smectites and celadonite end members, thus, representing compositional commonality with those of the other clays derived from the continental weathering of basalt protolith. Jhilmili smectites and smectite-chlorite mixtures show compositional similarity with the dioctahedral and trioctahedral smectites and the smectites formed at 250°C, having compositions between trioctahedral smectite and chlorite, thus, assigning high temperatures for their formation, where the heat required for the formation of these clays was possibly derived from the hydrothermal fluids, associated with the Deccan volcanism.     

Sorptive removal of ibuprofen from water using selected soil minerals and activated carbon

Pharmaceuticals have gained significant attention in recent years due to the environmental risks posed by their versatile application and occurrence in the natural aquatic environment. The transportation and distribution of pharmaceuticals in the environmental media mainly depends on their sorption behavior in soils, sediment?Cwater systems and waste water treatment plants, which varies widely across pharmaceuticals. Sorption of ibuprofen, a non-steroidal anti-inflammatory drug, onto various soil minerals, viz., kaolinite, montmorillonite, goethite, and activated carbon, as a function of pH (3?C11), ionic strength (NaCl concentration: 0.001?C0.5?M), and the humic acid concentration (0?C1,000?mg/L) was investigated through batch experiments. Experimental results showed that the sorption of ibuprofen onto all sorbents was highest at pH 3, with highest sorption capacity for activated carbon (28.5?mg/g). Among the minerals, montmorillonite sorbed more ibuprofen than kaolinite and goethite, with sorption capacity increasing in the order goethite (2.2?mg/g)?<?kaolinite (3.1?mg/g)?<?montmorillonite (6.1?mg/g). The sorption capacity of the selected minerals increased with increase in ionic strength of the solution in acidic pH condition indicating that the effect of pH was predominant compared to that of ionic strength. An increase in humic acid concentration from low to high values made the sorption phenomena very complex in the soil minerals. Based on the experimental observations, montmorillonite, among the selected soil minerals, could serve as a good candidate to remove high concentrations of ibuprofen from aqueous solution.