利用非金属矿制备白炭黑现状及发展前景

简术了白炭黑的用途和制备方法，综述了利用非金属矿制备白炭黑的方法和技术现状，对充分利用非金属矿制备白炭黑提供思路并展望其发展前景。     

油页岩灰渣提取白炭黑的方法

以油页岩灰渣制备的水玻璃为原料,结合传统沉淀法和热风干燥工艺成功地制备了白炭黑。实验过程中研究了各种因素对白炭黑性质的影响,并确定了白炭黑的最佳制备工艺：水玻璃中w（SiO₂）为8.1%、c（H₂SO₄）为1.5 mol/L,陈化时间为8 h,反应温度为70～80 ℃,pH值为8.0。透射电镜分析结果表明：采用热风干燥技术制备的白炭黑平均粒径约为50 nm,而且团聚体较少,性能优于烘箱干燥制备的白炭黑。     

大洋粘土制备白炭黑后的铝回收实验研究

为了回收大洋粘土制备白炭黑后残液中的Al3 ,并获得氧化铝超细粉体,实验选用NH3.H2O为沉淀剂,在常温下采用沉淀法使残液中Al3 以氢氧化铝形式沉淀并去除其它杂质离子,然后将得到的沉淀在1200℃灼烧,保温1h。利用IR和XRD测试了产物的物相组成和结构,证实实验可以获得纯度较高的α-Al2O3;而SEM和粒度分析结果显示产物粒度细小,部分颗粒可以达到纳米级;BET结果显示Al2O3的比表面积可达32m2/g。根据氧化铝结构和性能等优选的实验条件为大洋粘土的进一步开发利用提供了参考依据。     

由高岭土转化来的片状白炭黑的特征

文章报道了由高岭土转化成的片状白炭黑的特征。这种高白度、高纯度、高表面积的白炭黑的Ｘ射线谱线具无定形二氧化硅的宽峰，其构成颗粒在透射电镜下呈六方片状，继承了原高岭石的颗粒形态及大小。在转化及干燥过程中未发生原高岭石片的坍塌，是颇为特殊的。     

纳米纤维状白炭黑的孔隙特征

在与传统白炭黑对比研究基础上,利用TEM、XRD、FT_IR和氮吸附法对纳米纤维状白炭黑(MLD为92.73%)进行研究,主要讨论了纳米纤维状白炭黑多孔结构的成因、孔径大小、孔分布及孔类型等特征。分析表明纤蛇纹石中氢氧镁石八面体层被酸溶蚀和硅氧四面体层的塌陷是导致这种白炭黑具有多孔纳米纤维结构的直接原因;有两种孔隙类型,即纤维上的孔隙和纤维的堆积孔隙;纤维上的孔隙包括SiO_2微粒间的孔隙、其聚结体间的孔隙、残余纳米管的管道和毛细管道;孔径2.1和3.8nm处的孔隙数量多,并且在纳米纤维(或管)上存在大量小于5nm左右的微孔。研究证明了在用于橡胶、塑料填充补强剂和催化剂载体等方面,纳米纤维状白炭黑更优于传统白炭黑。     

蛋白土和硅藻土制取水玻璃和白炭黑的工艺研究

介绍了利用蛋白土和硅藻土制取水玻璃和白炭黑的工艺。该工艺不但可以生产优质白炭黑，还可以生产不同模数的水玻璃，是开发利用蛋白土和硅藻土类非晶质ＳｉＯ２的有效途径。     

纳米纤维状白炭黑的孔隙特征

在与传统白炭黑对比研究的基础上,利用TEM和氮吸附法对纳米纤维状白炭黑(MLD为92.73%)进行研究,主要讨论了纳米纤维状白炭黑多孔结构的成因、孔径大小、孔分布及孔类型等特征分析表明:纤蛇纹石中氢氧镁石八面体层被酸溶蚀和硅氧四面体层的塌陷是导致这种白炭黑具有多孔纳米纤维结构的直接原因。这种白碳黑的长度为微米级或纳米级,其孔隙以小于6.5nm的中孔为主,其中又以孔径2.1nm和3.8nm处的孔隙数量最多。它有两种孔隙类型:纤维上的孔隙和纤维的堆积孔隙。纤维上的孔隙包括SiO2微粒间的孔隙、其聚结体间的孔隙、残余纳米管的管道和毛细…     

应用新的地球化学方法寻找铀矿床

本文介绍了3种新的寻找铀矿床的地球化学方法，即元素扩散提取法及其变种和气相离子方法，同时阐述了新方法的理论基础、使用条件及实际试验取得的效果。文章最后对新方法作出了肯定的结论。     

Methodologies for amorphous silica analysis

Different methodologies have been investigated for their ability to extract amorphous silica (ASi) from soils and plant phytoliths. Methodologies typically used in soil science, including oxalate, acetate and citric extractions, were used in addition to an alkaline digestion technique commonly used in the aquatic sciences. Initial results show that the alkaline technique extracts nearly an order of magnitude greater amount of ASi. The alkaline extraction technique was tested on soil samples with and without acid and peroxide pre-cleaning. Samples, which were not pre-cleaned, showed a poor extraction efficiency of amorphous silica and poor reproducibility, while cleaned soil samples gave better reproducibility and an increase in the amount of Si extracted.     

The preparation of silica from the olivine process and its possible use as a catalyst support

The production of silica from the dissolution of olivine in sulphuric acid has been studied. Variations in grainsize of the olivine result in different specific surface areas of the silica. The microporosity of the silica supports an aggregative growth model responsible for the increasing particle size. The silica is used in the preparation of a nickel catalyst. The performance of the produced catalyst is equal to a nickel catalyst based on commercially available silica     

Excess silica in omphacite and the formation of free silica in eclogite

Silica lamellae in eclogitic clinopyroxene are widely interpreted as evidence of exsolution during decompression of eclogite. However, mechanisms other than exsolution might produce free silica, and the possible mechanisms depend in part on the nature and definition of excess silica. 'Excess' silica may occur in both stoichiometric and non-stoichiometric pyroxene. Although the issue has been debated, we show that all common definitions of excess silica in non-stoichiometric clinopyroxene are internally consistent, interchangeable, and therefore equivalent. The excess silica content of pyroxene is easily illustrated in a three-component, condensed composition space and may be plotted directly from a structural formula unit or recalculated end-members. In order to evaluate possible mechanisms for the formation of free silica in eclogite, we examined the net-transfer reactions in model eclogites using a Thompson reaction space. We show that there are at least three broad classes of reactions that release free silica in eclogite: (i) vacancy consumption in non-stoichiometric pyroxene; (ii) dissolution of Ti-phases in pyroxene or garnet; (iii) reactions between accessory phases and either pyroxene or garnet. We suggest that reliable interpretation of the significance of silica lamellae in natural clinopyroxene will require the evaluation not only of silica solubility, but also of titanium solubility, and the possible roles of accessory phases and inclusions on the balance of free silica.     

The transformation of amorphous silica to crystalline silica under hydrothermal conditions

Hydrothermal syntheses were made mainly in the binary system SiO₂-H₂O in a temperature range between 300 ° C and 500 ° C and pressures from 0.2 kbar up to 4.0 kbar with various starting materials. In this way the transformation behavior of different amorphous silicas via cristobalite and keatite to quartz were observed. This behavior depends mainly on the parameters: pressure, temperature, run duration and state of the starting material. Four reaction paths have been observed: in most experiments the complete reaction sequence “amorphous silica→cristobalite→keatite→quartz” took place. Less often the reactions: “amorphous silica→cristobalite→quartz” and: “amorphous silica→keatite→quarts” were observed. Very few samples were found with a direct transition of amorphous silica into quartz at high pressures. A kinetic model is given in form of a pressure-temperature-time diagram of the system SiO₂-H₂O under hydrothermal conditions.     

生物膜脂参与的非晶碳酸钙形成和稳定

非晶碳酸钙(amorphous calcium carbonate,ACC)是碳酸钙矿物体系中极不稳定的矿物相。但由海鞘类动物的研究表明,ACC可作为碳酸钙晶体矿物的前驱体在生物体内稳定存在,并且这些生物成因的ACC常常是由膜包裹着的。文中选用生物膜的主要成分卵磷脂(PC)为主要矿化调节剂,通过调控与碳酸钙矿化过程密切相关的无机离子Mg2+的浓度,模拟生物膜表面碳酸钙矿化作用过程。在空气/水界面处的膜脂调控下合成出可在溶液中稳定存在数天的非晶碳酸钙。该结果有力地证明了在生物矿化过程中,除了受生物体中可溶性有机大分子调控外,生物膜可能对ACC的形成和稳定也有显著的调控作用。     

Solubility of silica polymorphs in electrolyte solutions, II. Activity of aqueous silica and solid silica polymorphs in deep solutions from the sedimentary Paris Basin

Activity coefficient for aqueous silica in saline waters and brines from the Paris Basin was calculated using Pitzer's specific interaction model. Quartz and chalcedony are the only reported authigenic silica minerals in the Dogger aquifer of the Paris Basin (France). However, the measured silica concentrations fall between those of these two phases. The silica concentrations measured in Dogger fluids seem to be controlled by a microcrystalline quartz phase with a grain size computed to be about 20 nm. Studies have shown that pressure can preserve small grain size for a long time at the geological scale. The effective mechanism of pressure action is probably linked to the fact that pressure simultaneously favours dissolution at the grain-contact inducing a quartz supersaturation and prohibits the increase in size of reprecipitated microcrystalline quartz grains. This hypothesis is supported by other studies reported in the literature. The proposed model, which incorporates silica mineralogy and a precise calculation of aqueous silica activity, allows us to explain measured silica concentrations in the deep sedimentary solutions of the Dogger aquifers. In the Keuper brines, silica solubility can in most cases be explained by an equilibrium with either chalcedony or quartz. Another application of the present work is shown by an example, where we examined the importance of precisely evaluating the activity coefficient in basin characterisation, as the goal of reservoir characterisation is to describe the spatial distribution of petrophysical parameters such as porosity, permeability, and saturations.     

Solubility of silica polymorphs in electrolyte solutions, I. Activity coefficient of aqueous silica from 25° to 250°C, Pitzer''s parameterisation

Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ_SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na⁺), 0.032 (K⁺), 0.165 (Li⁺), 0.292 (Ca²⁺, Mg²⁺), −0.139 (SO₄²⁻), and −0.009 (NO₃⁻). A set of polynomial equations has been derived which can be used to calculate λ_SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ_SiO2(aq)−i) and the surface electrostatic field (Z_i/r_e,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ_SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ_SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ_SiO2(aq) in the Na---K---Ca---Mg---Cl---SO₄---HCO₃---SiO₂---H₂O system, over a large range of salt concentrations and up to temperatures of 250°C.     

菊花石中纳米矿物的微观组织研究

采用扫描电镜、透射电镜和能谱分析研究了浏阳产菊花石的微观组织,发现浏阳菊花石的花瓣保留了原生矿物——天青石SrSO₄及其单晶体的外形,但是花瓣内部出现了硅化现象;菊花石中存在多种纳米矿物材料,例如非晶纳米硅氧线、颗粒状纳米CaCO₃和SrSO₄、CaCO₃的二维纳米片和纳米带等。某些非晶纳米硅氧线外包覆了纳米晶化层,镁含量越高,非晶纳米线越容易晶化。     

Surface complexation model for strontium sorption to amorphous silica and goethite

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr²⁺ and SrOH⁺ complexes on the β-plane and a monodentate Sr²⁺complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH⁺ complexes and a tetradentate binuclear Sr²⁺ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr²⁺ and SrOH⁺ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces.