贵州织金寒武纪磷块岩中磷灰石和白云石稀土元素的LA-ICP-MS分析:对沉积环境和成岩过程的指示意义

贵州织金富稀土磷矿是典型的早寒武世肖滩阶海相沉积磷块岩矿床,主要由碳氟磷灰石和白云石组成,其中丰富的小壳动物化石、普遍发育的生物碎屑结构和潮汐层理等特征综合反映了充氧、动荡的潮汐环境,为探讨成磷环境下磷灰石和白云石在沉积成岩过程中稀土元素的地球化学行为提供了理想的制约。通过激光剥蚀-电感耦合等离子体-质谱(LA-ICP-MS)对织金磷块岩钻孔样品中胶状磷灰石、磷酸盐化小壳动物化石和成岩期白云石的稀土及相关主微量元素进行原位分析,根据主微量元素特征分析研究对象中的污染来源,进而提出在成磷环境下使用白云石和磷酸盐矿物稀土元素反映同期海水化学特征的数据筛选指标,最后通过筛选样品的稀土元素特征值讨论当时海水化学特征。结果表明:三种研究对象均具有显著的Ce的负异常(δCe为0.29～0.40)和La正异常(δLa为1.85～2.00)及较高的Y/Ho比值(47.25～56.91),表现出与现代海洋环境相似的氧化特征。磷酸盐矿物表现为一定程度的MREE富集和HREE"右倾"模式,可能与当时浮游生物繁盛并在深部水体中的降解有关,代表了深部富磷洋流的特征;成岩期白云石稀土模式与现代浅海海水相似但HREE为"左倾"模式,代表了同期浅海海水的特征,但白云石与磷酸盐矿物的HREE耦合特征反映了胶磷矿沉积成矿过程中对浅海海水HREE的选择性富集;肖滩阶的浅海海水与深部洋流都具有现代海洋的氧化特征,可能是促使当时小壳动物繁盛的重要因素。     

苯甲羟肟酸和水杨醛肟在白云石表面的吸附特性研究

以苯甲羟肟酸和水杨醛肟在白云石表面的吸附动力学、扩散模型和药剂的量化特性研究为切入点,系统探讨了药剂的同分异构效应对其吸附特性及吸附机理的影响。吸附特性研究结果表明,苯甲羟肟酸和水杨醛肟在白云石表面的吸附量均随p H值的变化表现出先上升后下降的趋势,苯甲羟肟酸的饱和吸附量远远大于水杨醛肟。动力学模型研究显示,二者在白云石表面的吸附均符合准二级动力学模型且水杨醛肟的吸附动力学参数大于苯甲羟肟酸。药剂的量化特性研究表明,苯甲羟肟酸在白云石表面以五元螯合环的形式吸附,而水杨醛肟则以离子键的形式与矿物表面发生作用。研究结果为白云石矿物的高效浮选分离提供了一定的理论基础。     

双子型阴离子表面活性剂的合成及浮选性能

分别以辛酰氯、癸酰氯、十二酰氯为原料,经加成、酰化及皂化等反应合成了3种双子型阴离子表面活性剂。产物结构经IR、1HNMR和13CNMR等波谱测试技术确定。25℃时测定了表面活性参数,结果表明随分子中疏水链增长,临界胶束浓度及表面张力均降低。目标化合物能一定程度增强油酸对胶磷矿中白云石的浮选能力。     

织金新华含稀土磷矿浮选动力学及三维图形表征

对织金新华含稀土磷矿浮选动力学进行了研究,在典型的一级浮选动力学理论模型ε=ε∞(1-e-kl)的基础上,推出磷矿反浮选速率模型ε=ε∞+(100-ε∞)e-k(t+θ),并根据动力学正交实验,采用三维表面图和等高线图对织金新华磷矿浮选动力学参数进行了表征.结果表明,反浮选速率模型能很好地描述含稀土磷矿物(以∑REO表...     

X射线荧光光谱法测定沙特碳酸盐型磷块岩的主次组分

<正>沙特爱加拉米德磷矿属典型的碳酸盐型磷块岩,主要有用矿物是碳氟磷灰石,其次为方解石,其他矿物有石英、白云石等~([1])。沙特爱加拉米德磷矿石含40%~50%碳酸盐、8%~10%有机物和16%~25%P_2O_5,因此,必须采用磷矿浮选工艺生产高品质磷肥~([2])。由于该磷矿原矿灼烧减量大于15%、浮选精矿小于5%、浮选尾矿灼烧减量大于30%,若在建立校准曲线时不考虑灼烧减量的影响,则磷矿中CaO和P_2O_5的测定结果误差较大。仅有     

碳酸盐岩油藏提高采收率研究的新认识:固液界面影响

碳酸盐岩油藏开发是目前增加我国原油产量的主攻方向之一.本文针对碳酸盐岩油藏岩石及模拟岩石样品开展固液界面作用的研究工作,从岩石的化学组成、比表面积、表面荷电情况、接触角及表面活性剂吸附量等方面,系统考察了方解石、白云石以及中东油藏碳酸盐岩样品在洗油过程中的固液界面相互作用结果,并分析了相关体系的洗油效率.结果证实了方解石、白云石样品与中东油藏碳酸盐岩样品在组成、结构及表面性质等方面高度一致,可用于碳酸盐岩油藏固液相互作用研究的模拟样品.进而揭示了表面活性剂在碳酸盐岩表面吸附量低、对其表面润湿性改变小且洗油效率相关性差的特点,表明固液界面相互作用不是影响碳酸盐岩油藏提高采收率效果的关键因素.     

白云石添加剂对稻秆灰熔融特性及固钾能力的影响

在管式炉中研究了稻草秸秆的结渣特性与白云石作为添加剂对稻秆燃烧结渣的影响及其机理。采用电感耦合等离子体发射光谱(ICP-OES)和X射线衍射(XRD)表征了稻秆灰分与白云石之间的相互作用。结果表明,当白云石添加质量分数为5%时,对稻秆的结渣特性具有明显的改善。白云石具有较好的固钾能力,在900和1000℃下尤为明显。白云石中富含的Mg和Ca元素能够与稻秆灰分中的SiO₂反应形成高熔点的硅酸盐矿物,包括透辉石、钙镁橄榄石和镁硅钙石。     

高镁磷尾矿中钙、镁、磷赋存状态研究

选择了贵州省重要磷矿生产基地—瓮福磷矿浮选尾矿为代表,对其中钙、镁、磷的矿物学重要特征进行了比较系统的研究,获得了一些重要结论,从而为高镁磷尾矿的综合利用、白云石与胶磷矿的分离等提供理论依据,对实现磷尾矿资源的二次利用、指导开发者设计科学合理的矿石选冶工艺流程都有十分重要的意义。按照元素赋存形态分析的方法,选用了化学成分、化学物相、电子能谱、扫描电子显微镜、X射线粉晶衍射分析方法等多种手段系统、全面地测定了磷尾矿结构、形貌的重要特征,获得了钙、镁、磷赋存状态的重要结论,发现了尾矿及其原矿的异同性:磷尾矿中含量最高的组分及其含量分别是:氧化钙34.11%,氧化镁17.65%,五氧化二磷5.30%;镁主要以白云石的形式赋存,并有少量以磷酸盐、硅酸盐形式存在,其在各相占的比例分别为99.80%、0.10%、0.10%;磷主要以磷灰石的形式赋存(占97.08%),并有少量以铁氧化物(1.04%)、独居石(0.19%)、磷钇矿(1.83%)形式存在;钙主要以白云石的形式赋存(占96.95%),并有少量以方解石(1.11%)、磷酸盐(1.94%)形式存在。贵州瓮福地区高镁磷尾矿中的镁、磷、钙主要赋存形式分别为白云石、磷灰石、白云石。     

表面活性剂对3-甲基吡啶电氧化制取烟酸的影响

研究了在阳极液中加入不同类型和不同浓度表面活性剂对3-甲基吡啶电氧化的影响. 结果表明, 十六烷基三甲基溴化铵、脂肪醇聚氧乙烯醚硫酸钠、十二烷基苯磺酸钠、十二烷基二甲基甜菜碱和山梨醇酐单硬脂酸酯的胶团对3-甲基吡啶电氧化有明显的促进作用. 实验结果还表明, 在低浓度的硫酸为支持电解质阳极液中加入表面活性剂与不加表面活性剂相比, 3-甲基吡啶电氧化制取烟酸的选择性和电流效率明显提高.     

新型阴离子Gemini表面活性剂与非离子表面活性剂C10E6混合溶液的胶团化的研究

研究了烷基苯磺酸盐Gemini表面活性剂Ia与非离子表面活性剂C10E6溶液混合胶团中分子间的相互作用. 通过表面张力法测定了Ia 和C10E6不同比例不同温度下的临界胶束浓度(cmc). 结果表明, 两种表面活性剂以任何比例复配的cmc比单一表面活性剂的cmc都低, 表现出良好的协同效应. 传统型非离子表面活性剂C10E6、Gemini表面活性剂Ia及混合物的cmc都随着温度升高而降低. 而且, 任何配比的混合胶团中两种表面活性剂分子间的相互作用参数β都是负值, 这说明两种表面活性剂在混合胶团中产生了相互吸引的作用. 混合表面活性剂体系的胶团聚集数比单一Ia的大, 但比单一C10E6的小. 向Gemini表面活性剂Ia胶束中加入非离子表面活性剂C10E6会使胶束的微观极性变小.     

Study on the effect of collector and inhibitor acid on the floatability of collophane and dolomite in acidic media by TOF-SIMS and XPS

Most of the phosphate ore in southern China is contained within siliceous dolomite phosphate rock, and more than 90% of it is medium and low-grade collophane. Reverse flotation of carbonate gangue minerals (dolomite) from phosphate in acidic media is still the most economical method for the reduction of carbonate in collophane concentrates. It has been recognized that the collophane and dolomite in acidic media affect the surface properties of minerals, thereby affecting their flotation properties. In this paper, HCl and H₃PO₄ were used as regulators or inhibitors to study the flotation behaviour of collophane and dolomite. The inhibition mechanism of collophane and dolomite in two acid media was studied by time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) analyses. It was found that the addition of an inhibiting acid can partially depress the collophane and improve the flotation of dolomite, thus achieving their flotation separation, and the inhibition effect of H₃PO₄ on collophane is better than that of HCl. And it was found by TOF-SIMS analysis that the increase in acid concentration did not reduce the adsorption concentration of the collector, and the main reason for the inhibition was not the decrease in the adsorption concentration of the collector. The adsorption capacity of collector on dolomite surface with H₃PO₄ is greater than that with HCl. The XPS test indicated that metaphosphate (PO₃⁻¹) is the pivotal ion for depressing collophane under acid conditions.     

Effect of dispersants on dispersion stability of collophane and quartz fines in aqueous suspensions

A stable dispersion of fine mineral particles in an aqueous system facilitated by dispersants is an essential prerequisite for their successful separation. We investigated the dispersion stability and mechanism of suspensions of aqueous collophane and quartz fines (10?µm) in the presence of sodium hexametaphosphate (SHMP), sodium silicate or sodium carbonate using the sedimentation balance method, zeta potential measurements, contact angle measurements, micro-flotation tests and theoretical calculation of Extended-DLVO (Derjaguin-Landau-Verwey-Overbeek). The results showed that three dispersants significantly enhanced the dispersion stability of collophane in the following descending order SHMP?>?sodium silicate?>?sodium carbonate. This is because they increased the zeta potential of collophane in the same order; meanwhile, the SHMP made the collophane more hydrophilic compared to two other dispersants. These results illustrated that the dispersion stability was attributed to electrostatic repulsion and hydration repulsion and that the hydration repulsion had a greater influence on the stability than electrostatic repulsion based on the calculation of Extended-DLVO. However, the quartz suspension always maintained a stable dispersion in the absence or presence of dispersants, since there was a higher zeta potential and stronger hydrophilicity for natural quartz. These provide a theoretical direction for the dispersion of fine-disseminated siliceous phosphorites and phosphate slimes in separations.     

Room temperature conductance switching in a molecular iron(iii) spin crossover junction

Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction. The junction is constructed from [Fe^III(qsal-I)₂]NTf₂ (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate) molecules self-assembled on graphene surfaces with conductance switching of one order of magnitude associated with the high and low spin states of the SCO complex. Normalized conductance analysis of the current–voltage characteristics as a function of temperature reveals that charge transport across the SCO molecule is dominated by coherent tunnelling. Temperature-dependent X-ray absorption spectroscopy and density functional theory confirm the SCO complex retains its SCO functionality on the surface implying that van der Waals molecule—electrode interfaces provide a good trade-off between junction stability while retaining SCO switching capability. These results provide new insights and may aid in the design of other types of molecular devices based on SCO compounds.

Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction.     

Theoretical investigation of the reactions of La atom and La<Superscript>+</Superscript> cation with carbonyl sulfide

The potential energy surfaces for the La+SCO and La⁺+ SCO reactions have been theoretically investigated by using the DFT (B3LYP/ECP/6-311+G(2d)) level of theory. Both ground and excited state potential energy surfaces (PES) are discussed. The present results show that the reaction mechanism is insertion mechanism both along the C-S and C-O bond activation branches, but the C-S bond activation is much more favorable in energy than the C-O bond activation. The reaction of La atom with SCO was shown to occur preferentially on the ground state (doublet) PES throughout the reaction process, and the experimentally observed species, have been explained according to the mechanisms revealed in this work. While for the reaction between La⁺ cation with SCO, it involves potential energy curve-crossing which dramatically affects reaction mechanism, and the crossing points (CPs) have been localized by the approach suggested by Yoshizawa et al. Due to the intersystem crossing existing in the reaction process of La⁺ with SCO, the products SLa⁺(η²CO) and OLa⁺(η²CS) may not form. This mechanism is different from that of La + SCO system. All our theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.     

A density functional theory study on the reactions of Y atom and Y+ cation with carbonyl sulfide

The mechanism of the title reactions have been studied by using the DFT (B3LYP/ECP/6‐311+G*) level of theory. Both ground and excited state potential energy surfaces are discussed. It is found the reaction mechanism is insertion mechanism both along the C? S and C? O bond activation branches, but the C? S bond activation is much more favorable in energy than the C? O bond activation. The reaction of Y atom with SCO was shown to occur preferentially on the ground state (doublet) PES throughout the reaction process, and the experimentally observed species, have been explained according to the mechanism revealed in this work. Different from that of Y + SCO system, the reaction between Y⁺ cation and SCO involves potential energy curve‐crossing which dramatically affects reaction mechanism. Due to the intersystem crossing existing in the reaction process of Y⁺ with SCO, the intermediates SY⁺(η²CO) and OY⁺(η²CS) may not form. All our theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Laser-induced breakdown spectroscopy analysis of minerals: Carbonates and silicates

Laser-induced breakdown spectroscopy (LIBS) provides an alternative chemical analytical technique that obviates the issues of sample preparation and sample destruction common to most laboratory-based analytical methods. This contribution explores the capability of LIBS analysis to identify carbonate and silicate minerals rapidly and accurately. Fifty-two mineral samples (18 carbonates, 9 pyroxenes and pyroxenoids, 6 amphiboles, 8 phyllosilicates, and 11 feldspars) were analyzed by LIBS. Two composite broadband spectra (averages of 10 shots each) were calculated for each sample to produce two databases each containing the composite LIBS spectra for the same 52 mineral samples. By using correlation coefficients resulting from the regression of the intensities of pairs of LIBS spectra, all 52 minerals were correctly identified in the database. If the LIBS spectra of each sample were compared to a database containing the other 51 minerals, 65% were identified as a mineral of similar composition from the same mineral family. The remaining minerals were misidentified for two reasons: 1) the mineral had high concentrations of an element not present in the database; and 2) the mineral was identified as a mineral with similar elemental composition from a different family. For instance, the Ca–Mg carbonate dolomite was misidentified as the Ca–Mg silicate diopside. This pilot study suggests that LIBS has promise in mineral identification and in situ analysis of minerals that record geological processes.     

白云石和灰石灰对废轮胎热解产物的影响

据估计 ,美国每年有大约 2亿 5千万条废轮胎[1] ,中国约有 1亿条 ,香港约有 10 0万条。如何处理这样大量的废轮胎引起了一系列的环境与经济问题。目前 ,世界各国较常用的废轮胎处理方式可分为堆置和填埋、资源回收后的原型利用及粉碎再利用、作为能源利用的燃烧、热解及气化等。国内外虽然对废轮胎热解技术进行了一些研究[2～ 5] ,但以产气为目的的研究尚未被成功应用。废轮胎具有高挥发组份与低灰份等优点 ,产生的气体燃料可以贮存、运输又可方便地应用于锅炉或其它各种形式的燃烧器 ,而无需对现有设备进行改装。所以废轮胎气化技术是有效…     

Thermal Decomposition of Dolomite in an Atmosphere of Carbon Dioxide: The effect of procedural variables in thermal analysis

The effects of procedural variables on dolomite decomposition in carbon dioxide were investigated. The partial pressure of carbon dioxide causes dolomite decomposition to split into a two-stage process. It was observed that the first stage of dolomite decomposition is progressively displaced to higher temperatures with an increase in heating rate. However, the second stage is not affected significantly by changes in the heating rate. These studies also indicate that decrepitation analysis on dolomite in CO₂ provides better information as compared to experiments in other atmospheres. The flow rate of the purge gas does not influence the thermal behavior of dolomite.This revised version was published online in November 2005 with corrections to the Cover Date.     

Quantitative lateral force microscopy study of the dolomite (104)-water interface

The friction and lateral stiffness of the contact between an atomic force microscopy (AFM) probe tip and an atomically flat dolomite (104) surface were investigated in contact with two aqueous solutions that were in equilibrium and supersaturated with respect to dolomite, respectively. The two aqueous solutions yielded negligible differences in friction at the native dolomite-water interface. However, the growth of a Ca-rich film from the supersaturated solution, revealed by X-ray reflectivity measurements, altered the probe-dolomite contact region sufficiently to observe distinct friction forces on the native dolomite and the film-covered surface regions. Quantitative friction-load relationships demonstrated three physically distinct load regimes for applied loads up to 200 nN. Similar friction forces were observed on both surfaces below 50 nN load and above 100 nN load. The friction forces on the two surfaces diverged at intermediate loads. Quantitative measurements of dynamic friction forces at low load were consistent with the estimated energy necessary to dehydrate the surface ions, whereas differences in mechanical properties of the Ca-rich film and dolomite surfaces were evidently important above 50 nN load. Attempts to fit the quantitative stiffness-load data using a Hertzian contact mechanical model based on bulk material properties yielded physically unrealistic fitting coefficients, suggesting that the interfacial contact region must be explicitly considered in describing the static and dynamic contact mechanics of this and similar systems.     

Selective adsorption of Mycobacterium Phlei on pyrite and sphalerite

The adsorption of Mycobacterium Phlei cells on the surfaces of pyrite and sphalerite was studied as functions of time and pH. The results indicated that a higher amount of cells adsorbing onto pyrite compared with that onto sphalerite under neutral and alkaline conditions, and it was also observed from photographs of scanning electron micrograph. To gain a better insight into the mechanisms of differential adsorption, the functional groups on cell surfaces and the chemical states of each element on mineral surfaces before and after interaction with bacterial cells were investigated. The results showed that many groups presented on cells surface, such as C-O-H, C-O-C, C=O, C-N, N-H and P=O. The change in state of each element on pyrite and sphalerite surfaces after interaction with bacterial cells revealed that there were chemical reactions between metal ions and S on mineral surface and atoms like N, O, P, etc. on cell surface, and the shifts in binding energy of each element on pyrite surface is larger than that of sphalerite. Possible mechanisms for selective adsorption of bacterial cells onto pyrite and sphalerite were discussed in the latter part of this paper.