利用天然矿物承载TiO2制备光催化功能材料的研究

利用天然沸石、膨润土作载体制备的TiO2/矿物复合体光催化材料，在阳光照射下对有机染料罗丹明-B具分解脱色性能。实验证实未经高温处理的样品光催化性能优于经高温处理的，沸石的脱色率6小时达100%，膨润土的脱色率达94%。晶相分析和热分析证实锐钛矿在有沸石、膨润土存在的水相体系中可直接在矿物表面生成，结合牢固，同时引起矿物 结构的调整。     

河南信阳上天梯膨润土的矿物学特征与可控改造性技术研究

为实现河南信阳上天梯地区膨润土的高附加值开发利用,在矿物学属性研究基础上,采用自粉化提纯、常压低温焙烧活化及常压碱溶合成沸石技术对其进行了研究。结果表明,该区膨润土为钙基膨润土,主要矿物为钙蒙脱石,杂质矿物为斜发沸石和方石英;干燥膨润土经湿润后可实现膨胀自粉化,再经湿法筛分可获得吸蓝量高达38.55 g/100g提纯膨润土;常压低温焙烧活化技术获得脱色率达99.9%、活性度为308 mmol/kg的高质量活性白土;常压碱溶一步法合成的4?沸石为较理想的立方体与菱形十二面体的聚形,在合成过程中斜发沸石和方石英等杂质矿物均转变为沸石。     

膨润土的改性及在有机废水处理中的应用

膨润土是一种以蒙脱石为主要矿物的粘土岩，应用广泛，目前已越来越多的应用于废水处理中，但未经处理的膨润土吸附脱色的性能较差，故一般用于废水处理的膨润土往往要经过一次或两次改性处理，以增大其比表面积，改善其吸附能力，常用的改性方法有两种：活化法，添加改进剂法，改性膨润土具有吸附脱色性能优良，废水处理效果好等特点，从而扩大了其应用范围。     

掺铁-TiO2/膨润土复合光催化材料制备及性能

采用酸性溶胶法制备掺铁-TiO₂/膨润土复合光催化剂,利用XRD﹑IR等测试手段对其进行了表征。通过测试甲基橙溶液的脱色率和COD去除率对复合光催化剂的光催化活性进行了评价。结果表明,该催化剂有较高的催化氧化性能,在太阳光照射下,对pH=4﹑质量浓度为20 mg/L的甲基橙溶液进行降解时,其脱色率可达95%以上,COD去除率可达85%以上。该催化剂在经过200℃焙烧活化2.5 h后可多次重复利用。     

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。     

丝光沸石/TiO2复合体的特征及对甲苯光催化降解研究

在TiO2光催化剂的制备过程中加入一定比例的丝光沸石制备了丝光沸石／TiO2复合体光催化剂．对含甲苯废气进行光催化降解实验．同时运用X射线粉末衍射技术、红外光谱、激光拉曼光谱和紫外一可见漫反射光谱等技术对丝光沸石／TiO2复合体的结构特征和光催化性能进行研究结果表明：丝光沸石的加入能够显著地降低复合光催化剂中TiO2的纳米颗粒粒径、增强其对紫外光的吸收,同时复合光催化剂中TiO2与丝光沸石的结构羟基发生反应形成键合,从而增强了复合体的光催化活性。在丝光沸石和TiO2复合的质量配比为1：5时．复合光催化剂对甲苯的光催化降解率最高．达94．58％。     

可渗透反应墙对重金属离子Pb~(2+)、Cd~(2+)吸附效果的试验研究

以受尾矿库渗滤液重金属离子Pb2+、Cd2+污染的地下水为研究对象,用天然矿物材料红辉沸石与膨润土作为反应渗透墙(PRB)的活性介质填充材料,试验结果表明,膨润土∶红辉沸石=1∶7,PRB渗透系数处于10-4cm/s数量级且随时间下降最为缓慢;PRB对单一组分Pb2+和单一组分Cd2+去除率分别达99.95%和99.995%;但在双组分PRB体系中,重金属离子Pb2+的存在显著地抑制了PRB对Cd2+的吸附作用,优先选择性吸附顺序是Pb2+Cd2+。     

MX-80膨润土高温老化时间效应的细微观分析

在200℃高温条件下,对MX-80膨润土粉末进行了不同时长（0、15、30、60、90、120d）的热老化预处理;通过热重分析（thermogravimetric analysis,简称TGA）、X射线衍射（X-ray diffraction,简称XRD）和电镜扫描（electron microscope scanning,简称SEM）等试验探讨了MX-80膨润土中结合水、矿物成分、微观形貌等随热老化时间t的变化规律;基于蒙脱石矿物晶体结构学理论揭示了MX-80膨润土高温老化时间效应的细微观机制。试验结果表明：（1）膨润土中自由水、弱结合水和强结合水随热老化时间t的递增均发生不同程度的脱附现象,0～15 d变化显著,15 d后趋于稳定,120 d后三者降幅分别为82.6%、68.8%和96.5%;(2)随着热老化时间t的增加,膨润土主要矿物成分蒙脱石部分转化为稳定性较好的钠云母,0～15d变化显著,15d后趋向稳定,120d后二者的变化量分别为–12.57%和+12.47%;(3)高温热老化过程中,蒙脱石矿物的晶层间距减小,引起片层状矿物之间收缩变形,导致膨润土的微观形貌随着热老化时间...     

酸化条件对膨润土结构和脱色性能的影响

本项研究对不同酸度、不同时间条件下处理的膨润土进行了脱色力、比表面积、活性膨润土中硅铝比分析及扫描电镜测试，由此，总结出控制获得高效活性膨润土的最佳条件应是使比表面积尽可能大，硅铝比尽量高。在适当控制酸度情况下，可以通过调整活化处理时间来取得较理想的性能。     

酸化条件对膨润土结构和脱色性能的影响

本项研究对不同酸度、不同时间条件下处理的膨润土进行了脱色力、比表面积、活性膨润土中硅铝比分析及扫描电镜测试，由此总结出控制获得高效活性膨润土的最佳条件应是使比表面积尽可能大，硅铝比尽量高。在适当控制酸度情况睛，可以通过调整活化处理时间来取得较理想的性能。     

掺铜TiO2/膨润土光催化剂的制备及其光催化性能研究

以天然钠基膨润土为载体,利用四氯化钛水解法制备了掺铜TiO₂/膨润土复合光催化剂;比较了不同量Cu²⁺对TiO₂/钠基膨润土的修饰作用及不同光照条件对光催化性能的影响。采用分光光度计、XRD、IR及TG-DTA等测试手段对试验结果进行表征。结果表明,铜的掺入对TiO₂/膨润土光催化活性有显著提高:当掺铜量为原土阳离子交换量的10.9%时,紫外光下催化效果最好;16.4%时太阳光下催化效果最好。复合后样品热处理温度为500 ℃,获得较理想的光催化活性。     

Synthesis and Photocatalytic Activity of Ti-pillared Bentonite

Ti-pillared bentonite has been successfully prepared using a modified method that can induce the transformation of TiO2 pillar from amorphous to anatase phase at a low temperature （150℃）. The value of d0.01 =1.94 nm obtained by Ti-pillared bentonite is larger than that of corresponding raw clay （1.56 nm）. Due to large numbers of Ti-pillars formed, the Ti-pillared bentonite shows an excellent ability in adsorbing Rhodamine B （RB）. The photocatalytic activity and kinetic equation are investigated by decomposing RB solution under the UV irradiation. It is found that the Ti- pillared bentonite shows super photocatalytic activity for the degradation of RB solution compared with the untreated bentonite and pure TiO2, and the kinetic equation of the degradation of RB solution is a 1.5-oder equation.     

Modelling the interaction of bentonite with hyperalkaline fluids

Many designs for geological disposal facilities for radioactive and toxic wastes envisage the use of cement together with bentonite clay as engineered barriers. However, there are concerns that the mineralogical composition of the bentonite will not be stable under the hyperalkaline pore fluid conditions (pH > 12) typical of cement and its properties will degrade over long time periods. The possible extent of reaction between bentonite and cement pore fluids was simulated using the reaction-transport model, PRECIP. Key minerals in the bentonite (Na-montmorillonite, analcite, chalcedony, quartz, calcite) were allowed to dissolve and precipitate using kinetic (time-dependent) reaction mechanisms. Simulations were carried out with different model variants investigating the effects of: temperature (25 and 70 °C); cement pore fluid composition; dissolution mechanism of montmorillonite; rates of growth of product minerals; solubilities of product minerals; and aqueous speciation of Si at high pH. Simulations were run for a maximum of 3.2 ka. The results of all simulations showed complex fronts of mineral dissolution and growth, driven by the relative rates of these processes for different minerals. Calcium silicate hydrate (CSH) minerals formed closest to the cement-bentonite boundary, whereas zeolites and sheet silicates formed further away. Some growth of primary bentonite minerals (analcite, chalcedony, calcite and montmorillonite) was observed under certain conditions. Most alteration was associated with the fluid of highest pH, which showed total removal of primary bentonite minerals up to 60 cm from the contact with cement after ∼1 ka. The maximum porosity increase observed was up to 80–90% over a narrow zone 1–2 cm wide, close to the cement pore fluid- bentonite contact. All simulations (except that with alternative aqueous speciation data for Si) showed total filling of porosity a few cms beyond this interface with the cement, which occurred after a maximum of 3.2 ka. Porosity occlusion was principally a function of the growth of CSH minerals such as tobermorite. There was very little difference in the alteration attained using different model variants, suggesting that bentonite alteration was not sensitive to the changes in parameters under the conditions studied, so that transport of pore fluid through the bentonite governed the amount of alteration predicted. Principal remaining uncertainties associated with the modelling relate to assumptions concerning the evolution of surface areas of minerals with time, and the synergy between changing porosity and fluid flow/diffusion.     

Mineralogy and chemistry of bentonite (?) deposits at Minjingu, Lake Manyara, North Tanzania

Olive green clays likely to be bentonitic in composition have been mineralogically and chemically studied. They occur in association with other lacustrine sediments at Lake Manyara. Radiocarbon dates from four diatom horizons indicate ages ranging from 12 Ka to 135 Ka suggesting a Mid-Holocene age. Middle Pleistocene age have been assigned to the ridged oncolites of Lake Manyara. The olive green coloured clays in the Manyara basin are known to occur in association with other lake beds including phosphorite deposits, stromatolites, bioturbated silty clays, partly silicified marls, conglomerates and olive green coloured opal beds. The results presented herein are from the olive green coloured clays. The olive green clays (bentonite?) are a result of devitrification or alteration of volcanic ashes and/or pyroclasts. The green clays occur in different forms as they are separated from each other by other lacustrine sediments. The alteration might have taken place in slightly different environments in terms of salinity and alkalinity. One of the top layer is friable and shows conchoidal fractures when dry. The other beds below in the lacustrine sequence are cemented with calcite and some dolomite as well as zeolites. The lowermost layer in the sequence is friable and shows cracks filled with coarse crystalline calcite. Mineralogically the bentonite is composed of the clay minerals illite, illite-smectite mixed layer clays, and chlorite. Other authigenic minerals include various zeolites (analcime, clinoptilolite, erionite and some traces of mordenite), opal, and fluorapatite. The clays have magnesium contents varying from 3.01% to 7.43%. The calcium contents vary widely due to presence or absence of one of the two minerals calcite or apatite. Trace elements like Ba, Ce, Sr, Zr are equally attributed to the presence of calcite and apatite. The formation of the illite-smectite mixed layer clays in an alternating manner with other lake sediments depicts different episodes of volcanic eruptions in the area. The mineralogical composition of smectites, zeolites, and opal in the green clays suggests a deposition of pyroclasts and volcanic ashes in a closed lake system with fluctuating levels. Due to evaporation alkalinity and salinity levels were fluctuating. The clays might have been bentonite which have undergone illitisation, a phenomena noted in other neighbouring rift basins.     

A coupled non-isothermal reactive transport model for long-term geochemical evolution of a HLW repository in clay

A numerical model of coupled saturated/unsaturated water flow, heat transfer and multi-component reactive solute transport is presented to evaluate the long-term geochemical evolution in bentonite, concrete and clay formation for a potential geological radioactive waste repository. Changes in formation porosity caused by mineral dissolution/precipitation reactions are taken into account. Simulations were carried out with a general-purpose multicomponent reactive transport code, CORE^2D V4. Numerical results show that pH in the bentonite porewater can vary from neutral to up to 13 over a time scale of 1 Ma although dissolution of silica minerals and precipitation of secondary calcium silicate hydrate (CSH) minerals in bentonite buffer the effect of the hyperalkaline plume. Mineral precipitation reduces the volume of pore space in bentonite close to the bentonite–concrete interface due to the precipitation of CSH minerals. Model results indicate that bentonite porosity decreases less than 25%. The hyperalkaline plume from the concrete only extends to a distance of 0.7 m in the clay formation over the time range of 1 Ma.     

Geochemical constraints on the stability of zeolites and C-S-H in the high pH reaction of bentonite

Cement-bentonite interactions will occur in deep geological repositories for high level radioactive waste. We performed laboratory experiments in order to constrain some previous geochemical and mineralogical uncertainties in the formation of secondary minerals in the high pH reaction of FEBEX bentonite at moderate temperatures.The reactivity of a Mg-homoionic FEBEX bentonite was studied at 25, 60 and 90 °C in batch reactors using two solutions representative of short and long time evolution stages of cement degradation. These solutions were periodically renewed in order to maintain a constant pH regime for a period of almost 2 years.Chabazite and merlinoite were observed to be the main zeolites that formed at 60 °C, while merlinoite was the dominant zeolite formed at 90 °C with the hyperalkaline (K-Na-OH) solution. The alkaline experiments (Ca-OH solution) showed minor reactivity and negligible mineralogical alteration, but the overall results suggest that the reaction tends to equilibrium conditions between C-S-H and montmorillonite at high temperature and metastable conditions at low temperature. The montmorillonite dissolution rates were calculated for all experiments, showing good agreement with previous calculations.     

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。     

Zeolites in fissures of granites and gneisses of the Central Alps

Six different Ca‐zeolite minerals are widespread in various assemblages in late fissures and fractures in granites and gneisses of the Swiss Alps. The zeolites formed as a result of water–rock interaction at relatively low temperatures (<250 °C) in the continental upper crust. The zeolites typically overgrow earlier minerals of the fissure assemblages, but zeolites also occur as monomineralic fissure fillings. They represent the youngest fissure minerals formed during uplift and exhumation of the Alpine orogen. A systematic study of zeolite samples showed that the majority of finds originate from three regions particularity rich in zeolite‐bearing fissures: (i) in the central and eastern part of the Aar‐ and Gotthard Massifs; (2) Gibelsbach/Fiesch, in a fissure breccia located at the boundary of Aar Massif and Permian sedimentary rocks; and (3) in Penninic gneisses of the Simano nappe at Arvigo (Val Calanca). Rail and road tunnel construction across the Aar‐ and Gotthard Massif provided excellent data on zeolite frequency in Alpine fissures. It was found that 32% (Gotthard NEAT rail base tunnel, Amsteg section) and 18% (Gotthard road tunnel) of all studied fissures are filled with zeolites. The number of different zeolites is limited to six species: laumontite, stilbite and scolecite are abundant and common, whereas heulandite, chabazite and epistilbite occur occasionally. Calcium is the dominant extra‐framework cation, with minor K and Na. Heulandite and chabazite contain Sr up to 29 and 10 mol.% extra‐framework cations respectively. Na and K contents in zeolites tend to increase during growth as a result of changes in fluid composition and/or temperature. The K enrichment of stilbite found in surface outcrops compared to subsurface samples may indicate late stage cation exchange with surface water. Texture data, relative age sequences derived from fissure assemblages and equilibrium calculations show that the Ca‐dominated zeolites precipitated from fluid with decreasing temperature in the order (old to young = hot to cold): scolecite, laumontite, heulandite, chabazite and stilbite. The necessary components for zeolite formation are derived from dissolving primary granite and gneiss minerals. The nature of these minerals depends, among other factors, on the metamorphic history of the host rock. Zeolites in the Aar Massif derived from the dissolution of epidote, secondary calcite and albite that were originally formed during Alpine greenschist metamorphism from primary granite and gneiss assemblages. Zeolite fissures occur in areas of H₂O‐dominated fluids. This is consistent with equilibrium calculations that predict a low CO₂ tolerance of zeolite assemblages, particularly at low temperature.     

坡缕石/磁性铁氧化物/TiO2复合光催化剂性能实验研究

用醇盐水解法、硫酸亚铁-硝酸钾氧化法制备TiO2光催化剂、坡缕石/TiO2复合光催化剂和坡缕石/磁性铁氧化物/TiO2复合光催化剂.通过XRD、TEM、UV-Vis和MS分析光催化剂的物相组成、形貌特征、对紫外可见光的漫反射以及磁化率,并以甲基橙为处理对象,对比研究了TiO2光催化剂、坡缕石/TiO2复合光催化剂和坡缕石/磁性铁氧化物/TiO2复合光催化剂的光催化效果.结果表明:坡缕石/磁性铁氧化物的复合能降低复合光催化剂中锐钛矿的平均粒径,提高锐钛矿的分散性.铁的复合是否提高光催化剂的光催化效率与催化剂的煅烧温度有关.坡缕石的复合对光催化剂的最佳煅烧温度有影响.     

多钨酸钠超声高速离心法——分离提纯微细矿物的新方法

多乌酸钠是一种无毒、无气味、易溶解、易配制、稳定性好、回收率高、使用方便安全的新型无机重液，其密度变化范围为1．0g/cm^3-3.1g/cm^3，分离缙云沸石和粘土矿土矿物取得了良好的效果。详述了多钨酸钠溶液的配制和回收，分离缙云沸石和粘土的实验流程及其应用前景。