河北围场天然沸石的矿物学特征及吸附性研究

河北承德围场地区含有储量丰富的天然沸石资源,然而目前关于该地区天然沸石的研究较少。本文利用X射线衍射仪、X射线荧光光谱仪、红外光谱仪、比表面积及孔隙度分析仪和扫描电镜及能谱分析仪等对围场天然沸石的矿物学特征进行了研究,并分析了围场天然沸石对苯、甲苯和水蒸气等的吸附性。结果发现,该地区天然沸石主要含斜发沸石和石英,硅铝比为5. 3,样品中含有少量微孔和大量介孔,具有相对较高的比表面积;样品对苯、甲苯和水蒸气均具有良好的吸附效果。     

沸石改性处理高氟地下水的适宜工艺试验研究

通过3种改性方法的对比试验,确定天然斜发沸石的适宜改性工艺,即将沸石分别经马弗炉700℃焙烧5h,然后用10%盐酸溶液浸泡12h,清水冲洗至中性后用2%的氢氧化钠溶液煮6h,最后用pH=3的水冲至中性后,用10%的70℃明矾溶液浸泡24h,清水简单冲洗后80℃烘干。通过改性增大了沸石的内部孔隙通透性和比表面积,有利于增强沸石的吸附性,同时降低了沸石的硅铝比,有利于增强改性沸石的离子交换能力,提高除氟能量。     

我国斜发沸石、丝光沸石的阳离子类型和硅铝比

 本文根据大量样品数据,提出划分沸石离子类型的主、次阳离子原则和单离子类型原则。进而对我国几十个矿点的大量随机样品进行分类,结果形成Ca、K、Na三个系列,K-Ca.Ca-K等12种离子类型。同时弄清了我国沸石的特点是以各种Ca型为主,以各种K型居其次。     

天然沸石吸附性能与阳离子组分之间的关系

吸附性能是沸石矿物的重要特性之一，也是相关领域应用的重要依据。以嫩江、海林和穆棱三大沸石矿床为例，通过对天然沸石矿的化学成分、沸石类型、矿石品位（CEC值）、比表面积及吸附性能的系统研究与对比分析，总结天然沸石矿附吸性能差异变化规律与原因。研究表明，天然沸石对气体CO2、H2S、SO2、NO2和气态H2O的吸附容量均与其（CaO MgO)/(Na2O K2O)比值之间呈正相关性关系，富二价阳离子组分者吸附容量大，富一价阳离子组分者吸附容量较小。据此，可作为天然沸石矿吸附性能预测评价的重要依据。     

牡丹江东部高品级天然沸石矿的研究

牡丹江东部天然沸石矿床敦化－密山深大断裂带中段，含矿层位为下白垩统东大岭组（K1d)，矿化原岩为流纹质火山熔岩，沸石类型为丝光石和斜发沸石，已查证有7个主要矿体均由高品级石矿组成，矿体平均品位为75．26％－84．02％，NH^ 4交换容量为1640.6-1831.7mmol/kgK^ 交换容量为8．03－16.28mg/g，热失重值为12．4％－15．35％，热稳定性＞900℃，耐盐酸性＞12mol/L，比辐射率为0.82-0.91等，矿石品位达尖端技术级，且综合物理化学性能优异，应用潜力巨大。     

非对称天然沸石陶瓷膜的制备及其性能表征

利用天然沸石为主要原料,制备出具有过滤功能和重金属离子吸附功能的天然沸石非对称陶瓷膜。非对称膜中支撑体、中间层膜和顶层膜的平均孔径分别为6.6μm、0.6μm和0.1μm。非对称膜单位压力降(1 MPa)下的氮气通量和水通量分别为:24.69×103m3/(m2h)和1.87×103m3/(m2h);对重金属离子(铅离子)吸附交换能力为7.13 mg/g。     

天然沸石负载二氧化钛光催化剂的制备与性能研究

以钛酸丁酯为钛源，天然沸石为载体，用溶胶．凝胶法制备了天然沸石负载TiO2光催化剂，用紫外可见吸收光谱、比表面积、红外光谱和X射线衍射等分析技术对沸石负载TiO2光催化剂进行了表征，以甲基橙为目标降解染料，考察了TiO2负载量、催化剂用量、热处理温度等不同条件下催化剂的光催化活性，结果表明，用天然沸石为载体所制得的TiO2光催化剂对于甲基橙具有较好的光催化降解效果。     

改性天然沸石去除水中砷的研究

众所周知,砷的化合物具有相当的毒性.在自然界中砷主要以硫化物存在[1],且三价砷化物的毒性比五价砷化物要高得多[2].据不完全统计,通过各种途径进入水圈的砷,全世界每年约11万吨[2].     

天然沸石的铵吸附容量研究

为了探讨天然沸石对NH4^＋的吸附规律,以江苏镇江的天然沸石为实验对象,测试其矿物组成与化学成分,通过静态摇床法实验研究其对铵离子的吸附特性及阳离子的交换特性,进行吸附等温线实验。结果表明,实验沸石对NH4^＋吸附等温线符合Langmuir公式。根据数学分析,确定沸石的铵吸附容量。     

碱活化条件对粉煤灰合成不同类型沸石的影响

用高硅铝比粉煤灰水热合成Y型、P型和HS型沸石。讨论了碱活化粉煤灰的条件,包括焙烧方法、碱灰比和碱度对合成产物的影响。XRD分析表明:碱活化条件将直接影响沸石的晶型、晶粒尺寸和相对含量。采用620℃低温、两次短时间焙烧工艺明显地改善了活化效果。研究同时发现,低碱灰比和碱度条件下生成P型沸石;高碱灰比和碱度条件下生成HS沸石;Y型沸石的生成条件介于二者之间。合成产物纯度高,结晶好,具有高的阳离子交换容量。     

四川昭觉地区优质偏硅酸地下水的特征、成因及其开发利用建议

【研究目的】近年来,随着生活水平的不断提高,人们对健康饮水的要求也在不断提高,寻找与开发富含H₂SiO₃等矿物质优质地下水已成为关键。【研究方法】本文以昭觉地区水文地质调查工程、地下水污染调查工程所获取的地下水化学数据为基础,探讨了昭觉地区富H₂SiO₃地下水的分布特点、元素水文地球化学特征、形成条件及成因。【研究结果】结果显示：（1）全县富H₂SiO₃（≥25 mg/L）地下水均属于低矿化度偏碱性水,分布在基底岩石为玄武岩的6个片区,H₂SiO₃含量一般介于25.74~46.04 mg/L,pH含量一般介于7.4~8.58,TDS含量一般介于49.4~333 mg/L;（2）玄武岩地下水存在HCO₃－Ca、HCO₃－Ca·Mg、HCO₃－Ca·Na、HCO₃－Ca·Mg·Na、HCO₃－Na等5种水化学类型,总体以HCO₃－Ca · Mg为主,其次为HCO₃－Ca,再次为HCO₃－Ca · Na,三者分别占总采样点数的50.00%、25.76%、12.12%;（3）全县富H₂SiO₃地下水的形成受水岩相互作用、硅酸盐矿物的分布范围及其可溶性、围岩裂隙发育程度、水源涵养及补给条件等四方面因素影响,其中水岩相互作用占据主导作用;（4）在后续开发利用过程中,需进一步揭示影响地下水中H₂SiO₃分布与迁移的因素。【结论】研究结果可以为昭觉地区矿泉水产业的发展及城乡优质水源地的建设提供依据。创新点：系统总结了昭觉县优质偏硅酸地下水空间分布特征和水化学特征;从形成条件与水岩作用的角度探讨了优质偏硅酸地下水的形成机制。     

Deformation-induced polymorphic transformation: experimental deformation of kyanite, andalusite, and sillimanite

Torsion experiments were performed on the Al₂SiO₅ polymorphs in the sillimanite stability field to determine basic rheological characteristics and the effect of deformation on polymorphic transformation. The experiments resulted in extensive transformation of andalusite and kyanite to sillimanite. No transformation occurred during the hot-press (no deformation) stage of sample preparation, which was carried out at similar P–T conditions and duration as the torsion experiments. Experiments were conducted on fine-grained (< 15 µm) aggregates of natural andalusite, kyanite and sillimanite at 1250 °C, 300 MPa, and a constant shear strain rate of 2 × 10^− 4/s to a maximum shear strain of 400%. Electron back-scattered diffraction (EBSD) analysis of the experiments revealed development of lattice-preferred orientations, with alignment of sillimanite and andalusite [001] slightly oblique to the shear plane. The kyanite experiment could not be analyzed using EBSD because of near complete transformation to sillimanite. Very little strain ( 30%) is required to produce widespread transformation in kyanite and andalusite. Polymorphic transformation in andalusite and kyanite experiments occurred primarily along 500 µm wide shear bands oriented slightly oblique and antithetic to the shear plane and dominated by sub-µm (100–150 nm) fibrolitic sillimanite. Shear bands are observed across the entire strain field preserved in the torsion samples. Scanning transmission electron microscope imaging shows evidence for transformation away from shear bands; e.g. fibrolitic rims on relict andalusite or kyanite. Relict grains typically have an asymmetry that is consistent with shear direction. These experimental results show that sillimanite is by far the weakest of the polymorphs, but no distinction can yet be made on the relative strengths of kyanite and andalusite. These observations also suggest that attaining high bulk strain energy in strong materials such as the Al₂SiO₅ polymorphs is not necessary for triggering transformation. Strain energy is concentrated along grain boundaries, and transformation occurs by a dynamic recrystallization type process. These experiments also illustrate the importance of grain-size sensitive creep at high strains in a system with simultaneous reaction and deformation.     

吉林南部辉南-靖宇地区岩石圈地幔氧化-还原状态及研究意义

吉林省南部辉南-靖宇地区第四纪碱性玄武岩中的地幔包体主要为尖晶石相二辉橄榄岩和方辉橄榄岩。二辉橄榄岩和方辉橄榄岩的平衡温度分别为770~1000℃和850~1025℃,对应的氧逸度 (f_O2)值分别为FMQ -0.70至+0.34 (均值为FMQ -0.06) 和FMQ -0.46至+0.05 (均值为FMQ -0.15),它们与深海橄榄岩(abyssal peridotites)以及软流圈地幔的f_O2相似。橄榄岩的f_O2值,连同其全岩化学成分(如Mg^#、Al₂O₃、CaO、Ni、Co和Cr)和矿物化学成分(如橄榄石的Fo、尖晶石的Cr^#和Mg^#,以及辉石的Mg^#)特征,表明辉南-靖宇地区龙岗火山群下面的岩石圈地幔很可能是在晚中生代以来,伴随着华北克拉通和扬子板块的碰撞以及来自东侧太平洋板块和北侧蒙古-额霍次克(Mongolo-Okhotsk)板块分别向西和向南的俯冲叠加,原来的古老岩石圈失衡、塌陷(拆沉？),取而代之的深部软流圈底辟、上涌,又经历了低度部分熔融的产物。     

Decomposition of kyanite and solubility of Al2O3 in stishovite at high pressure and high temperature conditions

In order to constrain the high-pressure behavior of kyanite, multi-anvil experiments have been carried out from 15 to 25 GPa, and 1,350 to 2,500°C. Both forward and reversal approaches to phase equilibria were adopted in these experiments. We find that kyanite breaks down to stishovite + corundum at pressures above ∼15 GPa, and stishovite + corundum should be the stable phase assemblage at the pressure–temperature conditions of the transition zone and the uppermost part of the lower mantle of the Earth, in agreement with previous multi-anvil experimental studies and ab initio calculation results, but in disagreement with some of the diamond-anvil cell experimental studies in the literature. The Al₂O₃ solubility in nominally dry stishovite has been tightly bracketed by forward and reversal experiments; it is slightly but consistently reduced by pressure increase. Its response to temperature increase, however, is more complicated: increases at low temperatures, maximizes at around 2,000°C, and perhaps decreases at higher temperatures. Consequently, the Al₂O₃ solubility in dry stishovite at conditions of high temperature–high pressure is very limited.     

Hydrometallurgical processing and recovery of molybdenum trioxide from spent catalyst

Hydrometallurgical processing of spent hydrodesulphurisation (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixtures was investigated. The results indicated that the recovery of molybdenum was largely dependent on the concentrations of Na₂CO₃ and H₂O₂ in the reaction medium, which controls the acidity of the leach liquor and carry over of impurities such as Al, Ni, P, Si and V. Leaching process was exothermic and leaching efficiency of molybdenum decreased with increasing solid to liquid ratio. Large scale leaching of spent catalyst, under optimum conditions: 20% pulp density, 85 g/L Na₂CO₃, 10 vol.% H₂O₂ and 1 h reaction, resulted a leaching efficiency of 84% Mo. The obtained leach liquor contained (g/L): Mo — 22.0, Ni — 0.015 and Al — 0.82, P — 1.1, Si — 0.094 and minor quantities of V — 8 mg/L, As and Co — < 1 mg/L. Recovery of Mo from leach solution as MoO₃ of 97.30% purity was achieved by ammonium molybdate precipitation method.     

Yellow fluorescence from baghdadite and synthetic Ca3(Zr,Ti)Si2O9

Baghdadite from Fuka, Okayama Prefecture, Japan shows a bright yellow fluorescence under UV (Hg 253.7 nm) excitation. The photoluminescence (PL) spectrum at 300 K consists of one large band near 580 nm and two small UV bands at 318 and 397 nm. The optical excitation spectrum of the bright yellow fluorescence consists of two bands near 220 and 250 nm. The temperature dependence of the PL intensity exhibits linear thermal quenching. To reveal the origin of the bright yellow fluorescence from baghdadite, powder Ca₃(Zr,Ti)Si₂O₉ crystals are synthesized. Synthetic Ca₃(Zr,Ti)Si₂O₉ shows luminescence spectra similar to those of baghdadite, and the intensity of the yellow fluorescence is markedly increased by titanium addition. The origin of the bright yellow fluorescence from baghdadite is ascribed to the existence of titanium.     

Inhibiting effects of lanthanum ion on calcite formation from CaCL2-NaHCO3 solutions at 25°C

The influence of La³⁺ on calcite formation was studied using CaCl₂-NaHCO₃ solutions. We adopted a closed system, where the pH change of the solutions was monitored in a closed vessel. The closed system reduces a number of thermodynamic variables of the solution, thus enabling us to calculate the amount of CaCO₃ precipitate only from pH with the assumption of equilibria among dissolved components in solution. After the analytical inspection of the calculation and assumption on which the calculation is based on, it was applied to experiments of the calcite formation in a Teflon vessel. The mole concentration of lanthanum added in the experiments was smaller than 1/3000 of that of calcium ion in the solutions. The addition of lanthanum oxide, chloride, and nitrate caused the difference in the pH change of the solution. The decrease of pH was smaller when lanthanum reagents were added, indicating that the amount of CaCO₃ precipitate decreased. The smallest decrease was observed when lanthanum chloride or nitrate salt was added. The X-ray diffraction study showed that the CaCO₃ precipitated in any solutions were calcite. If an equilibrium is assumed, which is considered to be likely from the pH change, the ion activity product (IAP) calculated in this study increased about 6 times when lanthanum ion, whose concentration is only 1/14 000 mole of calcium ion, was present.     

江西九瑞矿集区成矿与未成矿中酸性侵入岩年代学、岩石化学、矿物化学特征的异同及地质意义

江西九瑞矿集区主要发育有斑岩型、矽卡岩型及块状硫化物型三种类型的铜多金属矿床,其中斑岩型与矽卡岩型为典型的岩浆热液矿床,块状硫化物型矿床产在五通组砂岩与黄龙组白云岩界面之中,但多数也均位于侵入体附近,通常认为岩浆热液对层状黄铁矿体的叠加作用对其成矿起了重要作用。区内同时发育有大量与成矿岩体岩性相似的未成矿侵入岩,长期以来,一直未能找出成矿侵入岩的判别标志和侵入岩成矿与否的原因。本文对区内岩性为花岗闪长斑岩、石英闪长玢岩的成矿与未成矿侵入岩进行了锆石U-Pb定年、岩石主量元素分析以及造岩矿物电子探针测试工作,结果显示,九瑞地区岩浆活动的时代相对集中,成矿侵入岩的年龄分布于138.2±1.8Ma至148.0±1.0Ma之间,未成矿侵入岩的年龄分布于139.0±1.3Ma至149.6±3.0Ma之间,成矿与未成矿侵入岩的侵位时代基本相同,年龄在误差范围内一致。二者的SiO₂以及其它9种主量元素含量的变化范围都非常接近,或有很大重叠,表明成矿与未成矿侵入岩的主要岩石化学成分基本相同。通过造岩矿物成份计算了岩浆开始固结的温度和侵位压力,成矿侵入岩的平均温度769℃与未成矿侵入岩的平均温度723℃在误差范围内大体一致,但成矿侵入岩的温度变化范围（580~915℃）明显大于未成矿侵入岩（656~796℃）。侵位压力方面,未成矿侵入岩的压力值（平均5.7kbar）显著大于成矿侵入岩（平均1.4kbar）。因此我们认为,成矿与未成矿侵入岩相比,前者经历了更为显著的减压过程,该过程也许对形成岩浆热液矿床非常重要,可能是产生独立热液相的一个主要途径,并且能够在岩体内及围岩中造成大量裂隙,为热液循环提供通道。但是,数据同时显示,并非经历了显著减压过程的侵入岩都能够成矿,最终成矿与否是受到不同阶段多种因素联合控制的,因此显著减压并不是成矿的充要条件,而更可能是前提条件。由已获得的未成矿侵入岩数据来推测,在九瑞地区,侵位压力大于4kbar的中酸性侵入岩,成矿潜力可能较小。由黑云母成份估算的氧逸度显示,成矿侵入岩的氧逸度变化较大并且覆盖了未成矿侵入岩的氧逸度范围,但是未成矿侵入岩的氧逸度均没有超过HM（Fe₃O₄-Fe₂O₃）缓冲线,而成矿侵入岩中有一半左右的数据点高于该缓冲线,表明较高的氧逸度对成矿更为有利,在九瑞地区,氧逸度高于HM（Fe₃O₄-Fe₂O₃）缓冲线的侵入岩,其成矿潜力可能更大。     

Al_2O_3/Ti:风化与蚀变过程中的原岩示踪

Al_2O_3和Ti在风化和热液蚀变等地球化学过程中通常被认为是不活动元素,两者的比值Al_2O_3/Ti常被用来指示地球化学作用过程。通过对中国157件火成岩样品元素含量平均值的统计发现,火成岩样品中Al_2O_3/Ti与SiO_2含量值之间存在着较好的幂函数关系:ln(Al_2O_3/Ti)=0.073×SiO_2-0.89,式中Al_2O_3和SiO_2和Ti含量单位均为%。本文基于得到的经验方程和TAS图解构建了一个新的判别岩石类型的图解——Al_2O_3-Ti图解。该图解可以区分酸性岩、中酸性岩、中性岩、中基性岩-基性岩四类岩性。通过对三个火成岩风化剖面的研究发现,花岗岩风化剖面从新鲜基岩到风化形成的土壤在Al_2O_3-Ti图解中均落在酸性岩区,花岗闪长岩风化剖面从新鲜基岩到风化形成的土壤样品均落在中酸性岩区,玄武质安山岩风化剖面从新鲜基岩到风化形成的土壤样品均落在中基性岩-基性岩区。不同风化程度的风化产物与其母岩在Al_2O_3-Ti图解中所在的区域一致,即Al_2O_3-Ti图解可以用来追溯火成岩风化产物的母岩岩性。通过对胶东焦家金矿和豫西牛头沟金矿两个矿区岩石的研究发现,黑云母花岗岩从新鲜岩石到其蚀变岩及其形成矿石的样品在Al_2O_3-Ti图解中均落在酸性岩区。玄武质安山岩从新鲜岩石到其蚀变岩及其形成矿石的样品在Al_2O_3-Ti图解中均落在中基性岩-基性岩区。即不同蚀变程度的蚀变产物与其原岩在Al_2O_3-Ti图解中所在的区域一致,这表明新构建的Al_2O_3-Ti图解可以用来示踪蚀变岩的原岩性质。