膨润土作为药用赋形剂对Pb+2,Cd+2,Cr+6离子的吸附研究

本文选用吉林省九台、小梨河、净月产地的膨润土为原料,测试了不同粒级的膨润土对Pb 2、Cd 2、Cr 6离子的吸附时间、吸附温度、吸附量,同时,又在模拟人胃条件下进行了试验,结果证实膨润土可以作为药用赋形剂。     

改性膨润土在环保中的应用

综述了改性膨润土在环境保护中的应用:去除废水中的重金属(Pb、Cr、Hg、Ni)离子;催化水中苯胺的光化学降解;处理J酸废液;去除水中硝基苯和苯酚;对乳油废水破乳除油等。并探讨了形成的机理。     

改性膨润土去除水溶液中Cr^6＋的性能研究

文章研究了pH值、改性剂用量和改性时间对聚合氯化铝改性膨润土去除水溶液中Cr^6＋效率的影响。实验结果表明：（1）在不同pH值条件下改性得到的聚合氯化铝改性膨润土对水溶液中Cr^6＋的去除效果明显不同。在80℃反应5 h制得的聚合氯化铝改性膨润土,在pH值=7的中性条件下改性得到的改性膨润土对水溶液中Cr^6＋（取0.5g聚合氯化铝改性膨润土处理5mg/L重铬酸钾溶液100ml）的去除率达到最大值（98.35%）。（2）改性剂用量对聚合氯化铝改性膨润土去除水溶液中Cr^6＋影响很大。当pH值=7,在80℃反应5 h的条件下改性膨润土,改性剂聚合氯化铝选用13mmol/g膨润土为宜。（3）改性时间对聚合氯化铝改性信阳膨润土去除Cr^6＋有一定的影响。当改性剂的用量为15mmol/g,pH值=9,反应温度为80℃条件下,最佳改性反应时间是4 h。     

海泡石改性及吸附Zn2+研究

金属离子型无机抗菌剂具有安全性好、抗菌广谱、时效长和耐热等许多优良性能,在许多领域有广泛的应用价值。金属离子型无机抗菌剂由金属抗菌离子和无机载体材料组成,其抗菌性能与载体材料对抗菌金属离子的吸附量有关。本文初步研究了对海泡石进行酸改性及用海泡石载抗菌锌离子(Zn2+)的两种工艺方式对海泡石结构及载Zn2+量的影响。通过原子吸收发射光谱、X射线衍射、扫描能谱电子显微镜及傅立叶变换红外光谱等技术的分析表明,用体积浓度为5%的HCL,在70℃温度下对海泡石进行酸处理,在提高海泡石纯度,分散海泡石纤维束、使海泡石结构中孔隙扩大,进而达到更多载入Zn2+目的等方面都是十分必要和有效的方法;采用干湿循环方式将Zn2+载于海泡石能提高海泡石的载Zn2+量,但干湿循环方式操作更复杂,能耗更大,应视具体情况酌情选择使用。     

膨润土改性的研究

以吉林省净月潭膨润土、小梨河膨润土和刘房子膨润土为原料,对净月潭、小梨河钙基土进行提纯,用碱性钠盐为改性剂制成改性土,经X-射线衍射、差热、电镜、化学全分析等手段证实改性成功,并找出最佳活化条件。     

天然与改性膨润土组合处理难生物降解垃圾渗滤液的实验研究

以北京市阿苏卫垃圾填埋场中晚期渗滤液为研究对象,通过正交实验的方法分析了改性土、原土、明矾、改性土加明矾等的用量及搅拌速度、搅拌时间、静置时间等因素对垃圾渗滤液CODcr去除率的影响。通过对改性土、原土、明矾处理垃圾渗滤液的机理进行分析后,将改性土、原土分别用来处理垃圾渗滤液中可溶性物质中的疏水性物质和亲水性物质,并结合明矾的絮凝作用组合处理垃圾渗滤液。处理后垃圾渗滤液CODcr值从4700mg/L明显下降到839mg/L,CODcr去除率为82.15%,BOD5从700mg/L下降到263mg/L,BOD5去除率为62.43%。有机改性膨润土、明矾、原土组合处理是一种有效的处理垃圾渗滤液方法。     

Investigation of the hydro-mechanical behaviour of GMZ bentonite pellet mixtures

Bentonite pellet mixtures are considered as one of the candidate sealing materials for deep geological disposals of radioactive waste. One of the particularities of this material is the initial heterogeneous distribution of pellets and porosity within the mixture, leading to complex hydro-mechanical behaviour. In this paper, the hydro-mechanical properties of GMZ bentonite pellet mixtures were investigated in the laboratory by carrying out water retention tests on pellet mixtures under constant-volume condition and single pellets under free swelling condition, as well as a infiltration test on a column specimen of pellet mixture. In the infiltration test, the relative humidity and radial swelling pressure were monitored at five heights, the axial swelling pressure was also recorded. The instantaneous profile method was applied to determine the unsaturated hydraulic conductivities. Results show that, in high suction range (>?10 MPa) the water retention curve of pellet mixture under constant-volume condition was comparable to that of a single pellet under free swelling condition, while in low suction range (<?10 MPa) the latter exhibits a much higher water retention capacity. Due to clogging of large pores, the unsaturated hydraulic conductivity decreases as suction decreases to around 25 MPa. However, with further suction decrease, the hydraulic conductivity increases continuously until the value at saturated state, as in the case of most unsaturated soils. The radial swelling pressure at different heights develops with local sudden increase and decrease, which was attributed to local rearrangement of pellets upon wetting. By contrast, as the axial swelling pressure was measured on the global surface of the specimen, it develops in a more regular fashion.

     

用于除硅的铝盐改性膨润土的制备与表征

改变了传统制备铝盐改性膨润土工艺中原料的添加顺序,增强了膨润土的膨胀性能。对制备的铝盐改性膨润土进行SEM、XRD、粒径分布以及红外光谱表征,并与原料-钠基膨润土进行了对比,得到了改性的机理。最后,利用钠基膨润土和铝盐改性膨润土吸附硅酸盐的现象以及性能对铝盐改性膨润土进行了评估。结果表明：铝盐改性膨润土的制备方法较为简单,省去了传统工艺中加碱调节pH值,采用先将水浴钠基膨润土混合,再加改性剂的添加顺序,得到的铝盐改性的膨润土有很好的除硅效果,最高可达99%。     

Characterization and properties of boron-doped aluminum hydroxide for Mn2+ adsorption and soil acidification

Al hydroxide was prepared by hydrolysis of Al(NO₃)_3, and oc-B-Al hydroxide was prepared by hydrolysis of Al(NO₃)₃ in the presence of boric acid solution. Curve-fitted B_1s XPS spectrum of oc-B-Al hydroxide demonstrated that the boron atom was probably incorporated with Al hydroxide to some extent. The IR band of Al–OH at 1,074 cm^?1 of oc-B-Al hydroxide was weaker than that of Al hydroxide. This indicated some surface hydroxyl groups of Al–OH of oc-B-Al hydroxide had disappeared. These peaks at 1,320 and 1,458 cm^?1 bands found in the oc-B-Al hydroxide were closer together than the salts containing boron, which are attributed to an interaction of aluminum hydroxide with boron. Analysis of XRD patterns indicated that Al hydroxide was very poorly crystalline boehmite, and oc-B-Al hydroxide appeared to have crystallite dimensions slightly smaller than those present in Al hydroxide. TEM showed that the presence of boron significantly decreased the size of Al hydroxide particles. The specific surface area of oc-B-Al hydroxide (556.0 m² g^?1) using BET method was larger than that of Al hydroxide (421.6 m² g^?1). This indicated the likelihood of Mn²⁺ adsorption ability of oc-B-Al hydroxide than the Al hydroxide. Boron-doped Al hydroxide always adsorbed more Mn²⁺, stabilized the sample solution pH to a higher value and slowed soil acidification than the Al hydroxide. It is suggested that boron in soils not only serves as a plant nutrient, but can also decrease the Mn²⁺ toxicity and slows soil acidification by formation of oc-B-Al hydroxide.     

改性膨润土对水中氟离子吸附性能研究

含氟废水来源广,水中过量的氟对环境和人类危害大,研究开发除氟的方法具有十分重要的现实意义。本文选用吸附的方法对含氟废水进行处理,主要针对不同因素对膨润土吸附性能的影响进行研究。     

Characterization of geosynthetic clay liner bentonite using micro-analytical methods

In barrier design, familiarity of the structure and composition of the soil material at the micron scale is necessary for delineating the retention mechanisms of introduced metals, such as the formation of new mineral phases. In this study, the mineralogical and chemical makeup of the bentonite from a geosynthetic clay liner (GCL) was extensively characterized using a combination of conventional benchtop X-ray diffraction (XRD) and micro X-ray diffraction (μXRD) with synchrotron-generated micro X-ray fluorescence (μXRF) elemental mapping and μXRD (S-μXRD). These methods allow for the non-destructive, in situ investigation of a sample, with μm spatial resolution. Synchrotron-based hard X-ray microprobes are specifically advantageous to the study of trace metals due to higher spatial resolution (<10 μm) and higher analytical sensitivity (femtogram detection) than is possible using normal laboratory-based instruments. Minerals comprising less than 5% of the total bentonite sample such as gypsum, goethite and pyrite were identified that were not accessible by other conventional methods for the same GCL bentonite. Two dimensional General Area Diffraction Detector System (GADDS) images proved to be particularly advantageous in differentiating between the microcrystalline clay, which appeared as homogeneous Debye rings, and the ‘spotty’ or ‘grainy’ appearance of primary, more-coarsely-crystalline, accessory minerals. For S-μXRD, the tunability of the synchrotron X-rays allowed for efficient distinction of both clay minerals at low scattering angles and in identifying varying Fe oxide minerals at higher angles. GCL samples permeated with metal-bearing mining solutions were also examined in order to consider how mechanisms of metal attenuation may be identified using the same techniques. In addition to the cation exchange capacity from the montmorillonite clay, tests showed how minerals comprising only 1–2% of the bentonite such as goethite could potentially play a significant role in sequestering a range of metals, specifically Ni, Zn and Cu.     

Experimental study on the swelling behaviour of bentonite/claystone mixture

A mixture of the MX80 bentonite and the Callovo-Oxfordian (COx) claystone were investigated by carrying out a series of experiments including determination of the swelling pressure of compacted samples by constant-volume method, pre-swell method, zero-swell method and swell–consolidation method. Distilled water, synthetic water and humidity controlled vapour were employed for hydration. Results show that upon wetting the swelling pressure increases with decreasing suction; however, there are no obvious effects of synthetic water chemistry and hydration procedure on the swelling behaviour in both short and long terms. For the same initial dry density, the swelling pressure decreases with increasing pre-swell strain; whereas there is a well defined logarithmic relation between the swelling pressure and final dry density of the sample regardless of the initial dry densities and the experimental methods. It was also found that swelling pressure depends on the loading-wetting conditions as a consequence of the different microstructure changes occurred in different conditions. Furthermore, it was attempted to elaborate a general relationship between the swelling pressure and the final dry density for various reference bentonites.     

Insights into the water retention behaviour of GMZ bentonite pellet mixture

Bentonite pellets are recognized as good buffer/backfill materials for sealing technological voids in high-level radioactive waste (HLW) repository. Compared to that of a traditional compacted bentonite block, one of the most important particularities of this material is the initially discrete pellets and the inevitable heterogeneous porosity formed, leading to a distinctive water retention behaviour. In this paper, water retention and mercury intrusion porosimetry (MIP) tests were conducted on pellet mixture (constant volume), single pellet (free swelling) and compacted block (constant volume) of GMZ bentonite, water retention properties and pore structure evolutions of the specimens were comparatively investigated. Results show that the water retention properties of the three specimens are almost similar to each other in the high suction range (>?10 MPa), while the water retention capacity of pellet mixture is lower than those of the compacted block and single pellet in the low suction range (<?10 MPa). Based on the capillary water retention theory (the Young–Laplace equation), a new concept ‘saturated void ratio’ that was positively related to water content and dependent on pore size distribution of the specimen was defined. Then, according to the product of saturated void ratio and water density in saturated void, differences of water retention properties for the three specimens at low suctions were explained. Meanwhile, MIP tests indicate that as suction decreases, the micro- and macrovoid ratios of pellet mixture and compacted block decrease as the mesovoid ratio increases, while all the void ratios of single pellets increase. This could be explained that upon wetting, water is successively adsorbed into the inter-layer, inter-particle and inter-pellet voids, leading to the subdivision of particles and swelling of aggregates and pellets. Under constant volume condition, aggregates and pellets tend to swell and fill into the inter-aggregates or inter-pellets voids. While under free swelling condition, the particles and aggregates in a single pellet tend to swell outward rather than squeezing into the inter-aggregate voids, leading to the expansion of the pores and even formation of cracks. Results including the effects of initial conditions (initial dry density and fabric) and constraint conditions (constant volume or free swelling) on the water retention capacity and pore structure evolution reached in this work are of great importance in designing of engineering barrier systems for the HLW repository.

     

γ辐照对改性钠基膨润土影响的初步研究

为了确认γ辐照对改性钠基膨润土的影响,拓展高放地质处置缓冲材料性能评价范围,以内蒙古高庙子改性钠基膨润土为研究对象,利用红外光谱分析仪、同步热分析仪和X射线衍射仪分析了不同γ辐照剂量(1000、2000、3000、4000和5000 k Gy)对改性钠基膨润土性能和微观结构的影响。结果表明:在5000 k Gy大剂量γ辐照后,高庙子改性钠基膨润土中某些官能团发生了少量的化学转变,耐热性能有所提高,但对钠基膨润土中的层间水和吸附水影响不大;另外其微观结构变化不明显,只是晶胞尺寸有所减小;总体而言,高庙子钠基膨润土在大剂量γ辐照环境中稳定性是良好的。     

掺灰膨胀土表面吸附试验及吸水性验证

利用水蒸气吸附仪对石灰改性膨胀土进行水蒸气吸附试验,得出随着掺灰量的变化,膨胀土的吸水性先减小后增大,且在掺灰量为6%处取得最小值。为了研究引起膨胀土吸水性变化的主要原因,再对改性膨胀土进行氮气吸附试验,从而分析掺灰膨胀土孔隙结构的变化。研究发现,随着掺灰量的增加,BET微孔比表面积呈折线形变化,且在掺灰量为6%时取得最小值;中孔的累积容积随着掺灰量的增大而减小;随着掺灰量的增加,中孔孔径先增大后减小,且在掺灰量为6%处取得最大值。膨胀土的吸水性与中孔孔径的变化成负相关,且膨胀土的最佳掺灰量为6%。     

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。     

渗透条件对膨润土改性黄土渗透系数的影响

室内采用柔性壁渗透仪实测了膨润土改性黄土的渗透性能,分别在控制渗透时间、围压和渗透压等条件下探究了各自对改性黄土渗透系数的影响。研究表明,试验初期试样的渗透系数在同一数量级上有较大波动,随着持续时间增加渗透系数趋于稳定,稳定后几乎不随时间发生变化,增大围压和渗透压都可以引起改性黄土渗透系数在同一数量级上降低。因此,在填埋场设计时可以通过预测防渗衬里的围压和渗透压来预留渗透系数的安全储备。     

高压实膨润土的非饱和渗透膨胀模型

高放废弃物深地质处置库中,作为缓冲/回填材料的高压实膨润土的设计功能是,遇水吸湿导致土体膨胀变形,以密封高压实膨润土块体砌置时形成的块体与块体之间和块体与围岩之间的施工缝隙以及围岩中因处置库开挖卸载引起的裂缝,形成阻障围岩中地下水渗入内库引起核素迁移,与库内高放废物的辐射扩散的人工屏障。高压实膨润土在自由膨胀条件下的膨胀应变和非饱和渗透系数由渗透试验测得;孔隙比和吸力的关系由压汞试验测得。吸力和含水率的函数关系可由土-水特征曲线测试试验得到。因此,自由膨胀条件下膨润土的非饱和渗透膨胀模型由膨胀应变、非饱和渗透系数和孔隙比与吸力的函数关系建立。结果表明：渗透系数和体积应变都随吸力减小而增加,因为吸力减小会导致孔隙比增加。这一发现有助于设计高放废物的最终处置方案。     

Investigating the hydromechanical behaviour of bentonite pellets by swelling pressure tests and discrete element modelling

Acta Geotechnica - Bentonite pellet mixtures are candidate material for the sealing of galleries in radioactive waste disposals. The hydromechanical behaviour of assemblies of bentonite pellets is...     

Hydromechanical behaviour of an expansive bentonite/silt mixture in cyclic suction-controlled drying and wetting tests

To further our knowledge of coupling between the hydraulic cycles and mechanical behaviour of the swelling soils, this paper presents an experimental study on a bentonite/silt mixture using an odometer with suction controlled by the osmotic technique. A loading/unloading cycle was applied to each of the samples at different constant suctions (0, 2, 3 and 8 MPa). Moreover, successive wetting and drying cycles were applied under constant vertical stress at a suction range of 0 to 8 MPa, followed by a loading/unloading cycle at similar suctions (0, 2, 3 and 8 MPa). Finally, the compression curves of the aforementioned suctions with and without the application of suction cycles were compared, so as to analyse the influence of hydraulic cycles on the soil fabric and the mechanical parameters. It is observed that the wetting and drying cycles applied to both the micro- and macrostructure significantly influenced the virgin compression index λ(s), the apparent preconsolidation stress p₀(s) and the elastic compression index values κ. However, the hydraulic cycles imposed only on the micro- or macrostructure induce negligible changes in the mechanical parameters of the soil.