西藏当雄错碳酸盐型盐湖卤水自然蒸发析盐规律研究

盐湖卤水中蕴藏有许多重要的无机盐资源,是多种无机化学品的重要来源。当雄错盐湖是我国藏北高原典型的碳酸盐型盐湖,卤水中蕴藏有丰富的锂、钾、硼等盐类,当地气候条件非常适宜采用盐田相分离技术进行盐湖卤水的综合开发和利用。本文以Na+,K+/CO32-,SO42-,Cl--H2O五元体系(25℃)介稳相图为指导,通过对当雄错盐湖卤水在湖区现场开展自然蒸发实验研究,考察了卤水中Li、K、B等元素的浓缩富集规律,获得了卤水夏季自然蒸发结晶路线及析盐次序为石盐、水碱、天然碱、钾石盐、钾芒硝、硼砂和碳酸锂,同时分析了夏、冬季卤水自然蒸发浓缩析盐规律的区别,为指导西藏当雄错碳酸盐型盐湖卤水的综合开发利用提供了盐田工艺设计基础和理论依据。     

盐卤硼酸盐化学(Ⅰ)——含硼盐卤天然蒸发过程中硼酸盐的行为

在进行青藏高原某硼酸盐盐湖卤水的天然蒸发实验中确定,该卤水的蒸发析盐顺序不是按平衡溶解度相图,而是按“太阳相图”预示的亚稳过程进行。从天然蒸发过程中盐卤的浓缩倍数与浓缩卤水中硼富集倍数的一致性认为,盐卤在天然蒸发浓缩析盐过程中硼酸盐并不以固体盐形式析出,而是被赋存于浓缩卤水中。     

合成盐湖卤水体系Li-Na-K-Mg-Cl-SO_4-H_2O25℃下的等压研究和离子相互作用模型的应用

根据我国青海一里坪和东台吉乃尔盐湖晶间卤水Li-Na-K-Mg-Cl-SO_4-H_2O体 系的组成制备了两种合成卤水储备溶液，采用等压法和改进的实验装置在25 ℃下 ，从稀释到溶液中溶质NaCl达到饱和的浓度范围，对合成卤水溶液进行了等压测定 ，确定了它们的水活度a_(H_2O)，和渗透系数ψ；比较了两种卤水的热力学性质及 其变化的规律，揭示了其天然卤水浓度差异的物理化学成因。用盐湖卤水体系离子 作用模型对水活度、渗透系数的计算值与本文的实验数据比较，对于一里坪和东台 合成卤水，渗透系数的标准偏差分别为0.0078和0.0145；用该模型计算了东台晶间 卤水，及其在25 ψ等温蒸发实验不同阶段的浓缩卤水中，离子强度从9.766到20. 52mol·kg~(-1)范围可能析出的盐类的饱和度，给出了其变化规律，并与文献的盐 类沉积和析盐顺序相比较，获得了合理一致的结果，从而证实了我们在Pitzer离子 相互作用模型基础上所发展的盐湖卤水体系模型对描述和预测复杂天然盐湖卤水体 系的热力学性质和蒸发析盐规律的适用性。     

盐卤硼酸盐化学——Ⅵ.扎仓茶卡盐湖卤水的蒸发和盐类的分离提取

扎仓茶卡盐湖是藏北地区具有经济开发远景的一个新类型硼酸盐盐湖。卤水在25℃蒸发浓缩过程中的析盐顺序符合"介稳相图"预示的结果。结合湖区地表卤水和晶间卤水化学组成,提出该盐湖卤水利用天然冷冻析出芒硝,利用夏季组成卤水日晒分离软钾镁矾,冬季析硝卤水日晒析出钾石盐的自然处理工艺,同时论述了加酸处理含硼浓缩卤水提取硼酸的原则流程。     

盐卤硼酸盐化学——Ⅺ.不同含硼浓缩盐卤的稀释实验

前文[1]报道高含硼浓缩盐卤加水稀释过程中硼酸盐的行为。考虑到青海省柴达木盆地大柴旦盐湖卤水日晒蒸发到钾盐析出阶段,浓缩卤水中含1.87％MgB_4O_7,蒸发到水氯镁石开始析出,浓缩卤水中含2.95％MgB_4O_7。本文报道,这两种不同含硼浓缩卤水按文献[1]中实验步骤进行加水稀释,室温放置过程中析出硼酸镁盐的某些不同结果。     

当雄错盐湖卤水提钾盐田日晒工艺扩大试验研究

西藏现代钾锂硼特种盐湖的钾盐开发将对我国钾盐需求形成有利补充。本文首次采用蒸发结晶、分步分离的方法,进行了当雄错盐湖碳酸盐型卤水提钾多级盐田日晒工艺扩大试验研究。通过对卤水蒸发析盐全过程做化学分析和物料衡算,确定了钾、硼等重要无机元素的成盐类型和析盐阶段,以及锂、铷等稀有元素的富集规律,最终获得了较高品位钾混盐和高浓母卤,并取得了大量第一手数据资料,为今后实现当雄错盐湖卤水钾盐资源的产业化开发提供了切实可靠的中试基础和设计参考。     

五元体系Li+/Cl-,CO2-3,SO2-4,B4O2-7-H2O 298 K相关系实验研究

青藏高原盐湖富含锂、钠、钾的氯化物、硫酸盐、碳酸盐和硼酸盐,尤以其高锂、硼而闻名于世….这些盐湖卤水大多属于Li+,Na+,K+,Mg2+/Cl-,SO2-4,CO32-,Borate-H2O体系.在卤水蒸发浓缩后期,由于绝大部分钠盐、钾盐均已结晶析出,所以卤水的化学组成实际变成Li+,Mg2++/Cl-,SO2-4,CO2-3,Borate-H2O体系.这种复杂水盐体系相关系的研究对于制定从天然卤水中提取稀有元素锂、硼的工艺过程,阐明含锂盐湖的形成和演化规律都有十分重要的意义,是乔必不可少的基础性研究工作.     

盐卤硼酸盐化学V:合硼浓缩盐卤稀释过程中硼酸盐的行为

经日晒蒸发制得的高含硼浓缩卤水加水稀释时, 溶液的pH随稀释度增大而明显上升. 不同稀释度卤水在室温放置过程中,有不同的硼酸镁水合盐结晶析出. 采用加水稀释法已经从含硼浓缩卤水中得到多水硼镁石(2MgO.3B2O3.15H2O), 章氏硼镁石(MgO.2B2O3.9H3O), 六硼酸镁(MgO.3B2O3.7H2O)和氯柱硼镁石(2MgO.2B2O3.MgCl2.14H2O).     

盐卤硼酸盐化学 Ⅴ.含硼浓缩盐卤稀释过程中硼酸盐的行为

经日晒蒸发制得的高含硼浓缩卤水加水稀释时,溶液的pH随稀释度增大而明显上升.不同稀释度卤水在室温放置过程中,有不同的硼酸镁水合盐结晶析出.采用加水稀释法已经从含硼浓缩卤水中得到多水硼镁石(2MgO·3B_2O_3·15H_2O),章氏硼镁石(MgO·2B_2O_3·9H_2O),六硼酸镁(MgO·3B_2O_3·7H_2O)和氯柱硼镁石(2MgO·2B_2O_3·MgCl_2·14H_2O).     

火焰原子发射光谱法测定卤水中锂

卤水是天然水中矿化度很高的水,也被称为液态矿。柴达木盆地具有非常丰富的盐湖资源,特别是锂资源,具有储量大、品位高、分布集中的特点,号称世界三大锂矿区之一。在利用盐湖锂资源开发制备锂盐的生产过程中,随着盐湖卤水的不断蒸发浓     

Salt crystallization during evaporation: impact of interfacial properties

Salt damage in stone results in part from crystallization of salts during drying. We study the evaporation of aqueous salt solutions and the crystallization growth for sodium sulfate and sodium chloride in model situations: evaporating droplets and evaporation from square capillaries. The results show that the interfacial properties are of key importance for where and how the crystals form. The consequences for the different forms of salt crystallization observed in practice are discussed.     

含氯化钠电解质水溶液体系热力学性质研究进展

总结了近几十年来含氯化钠电解质水溶液体系热力学性质的研究成果及其在盐湖、地下卤水、油田水和海盐制备等领域的应用,并对含钠水盐体系在不同温度下的热力学性质进行了总结,对于推动含钠水盐体系电解质溶液理论的发展和促进富盐湖卤水、地下卤水及海水的开发利用具有重要的意义。     

多格错仁盐湖卤水冷冻、日晒两步法浓缩制卤研究

藏北无人区的多格错仁盐湖水化学类型为氯化物型,该湖水钾、锂资源品位好;结合自然条件制定该低矿化度卤水在高寒区冬季制卤工艺路线。通过冷冻、日晒两步法成功制得了富含钾、锂的精制卤水;对硫酸钙在该卤水蒸发过程中的过饱和溶解度与石膏缓析现象进行了解析。     

The Significance of Interfacial Water Structure in Soluble Salt Flotation Systems

Flotation of soluble salts with dodecyl amine hydrochloride (DAH) and sodium dodecyl sulfate (SDS) collectors has demonstrated that the interfacial water structure and hydration states of soluble salt surfaces together with the precipitation tendency of the corresponding collector salts are of considerable importance in explaining their flotation behavior. In particular, the high concentration of ions in these soluble salt brines and their hydration appear to modify the bulk and interfacial structure of water as revealed by contact angle measurements and this effect is shown to be an important feature in the flotation chemistry of soluble salt minerals including alkali halide and alkali oxyanion salts. Depending on characteristic chemical features (salt type), the salt can serve either as a structure maker, in which intermolecular hydrogen bonding between water molecules is facilitated, or as a structure breaker, in which intermolecular hydrogen bonding between water molecules is disrupted. For structure making salts the brine completely wets the salt surface and no contact angle can be measured. For structure breaking salts the brine does not completely wet the salt surface and a finite contact angle is measured. In this regard it has been found that soluble salt flotation either with the cationic DAH or anionic SDS collector is possible only if the salt is a structure breaker. Copyright 2001 Academic Press.     

Solubility and binding properties of PEGylated lysozyme derivatives with increasing molecular weight on hydrophobic-interaction chromatographic resins

Dynamic binding capacities and resolution of PEGylated lysozyme derivatives with varying molecular weights of poly (ethylene) glycol (PEG) with 5 kDa, 10 kDa and 30 kDa for HIC resins and columns are presented. To find the optimal range for the operating conditions, solubility studies were performed by high-throughput analyses in a 96-well plate format, and optimal salt concentrations and pH values were determined. The solubility of PEG-proteins was strongly influenced by the length of the PEG moiety. Large differences in the solubilities of PEGylated lysozymes in two different salts, ammonium sulfate and sodium chloride were found. Solubility of PEGylated lysozyme derivatives in ammonium sulfate decreases with increased length of attached PEG chains. In sodium chloride all PEGylated lysozyme derivatives are fully soluble in a concentration range between 0.1 mg protein/ml and 10 mg protein/ml. The binding capacities for PEGylated lysozyme to HIC resins are dependent on the salt type and molecular weight of the PEG polymer. In both salt solutions, ammonium sulfate and sodium chloride, the highest binding capacity of the resin was found for 5 kDa PEGylated lysozyme. For both native lysozyme and 30 kDa mono-PEGylated lysozyme the binding capacities were lower. In separation experiments on a TSKgel Butyl-NPR hydrophobic-interaction column with ammonium sulfate as mobile phase, the elution order was: native lysozyme, 5 kDa mono-PEGylated lysozyme and oligo-PEGylated lysozyme. This elution order was found to be reversed when sodium chloride was used. Furthermore, the resolution of the three mono-PEGylated forms was not possible with this column and ammonium sulfate as mobile phase. In 4 M sodium chloride a resolution of all PEGylated lysozyme forms was achieved. A tentative explanation for these phenomena can be the increased solvation of the PEG polymers in sodium chloride which changes the usual attractive hydrophobic forces in ammonium sulfate to more repulsive hydration forces in this hydrotrophic salt.     

高镁含硼盐卤体系反常现象解析

高镁含硼盐卤体系中存在"过饱和溶解度"、"稀释成盐"和同名离子"增溶"等反常现象。研究发现:氯化镁溶液在中低浓度时显中性,在高浓度时显酸性,饱和时pH值小于4.5。而各种镁硼酸盐基本都是pH值大于8.0的碱性矿物。水溶液中酸碱难共存,但镁硼酸盐与氯化镁却因具有相同离子而能够在高镁含硼盐卤体系中共存。结合氯化镁溶液特殊酸度变化规律与相关相化学数据可较圆满的解释高镁含硼盐卤体系中的反常现象。     

Thermodynamic investigation of salting effect of ovalbumin in various salts solutions

Calorimetric and volumetric investigations of ovalbumin salting by sodium chloride, lithium chloride, potassium chloride, lithium sulfate and ammonium sulfate buffered solutions in the range of concentrations of about 0.2–1.2 M of salts are reported. The evolution of enthalpies and apparent molar volumes vs. salts concentration was investigated using ITC MicroCal titration microcalorimeter and Anton Paar DMA 60/602 digital densimeter. It was found that the changes in enthalpies of salting and apparent molar volumes follow a similar trend. Conclusions about the ability of salts: to precipitate ovalbumin solution are presented.     

Migration,Crystallization and Dissolution Changes of Salt Solution with Color Rendering Property in Porous Quartz Materials

In order to visually display the migration and crystallization process of salt solution in porous cultural relics, copper sulfate solution with color rendering property was selected to record the migration, crystallization and resolution of salt solution in simulated SiO₂ samples under different environmental conditions in real time through high-resolution recording system, scanning electron microscope system, salt phase X-ray diffraction system, and so on. The results showed the migration of salt solution in porous samples was related to the structural characteristics of the porous samples, the migration rate of salt solution, the evaporation rate and the change frequency of crystallization–resolution, etc., in which the large pore size of the sample, the higher the concentration and the faster migration and evaporation rate of salt solution, the greater the change rate of the brine accumulation zone or salt crystallization zone in the different porous samples. During the humidification–drying cycles of rainfall, the higher the cycle frequency of humidification–drying was, the higher the drying temperature was, the more frequent the crystallization-analysis change of salt in the salt-bearing sample was, and the more extensive the distribution of salt crystal zone was. This is the first time to visualize the salt belt by simulating the changing process of a salt solution with a color rendering property in porous samples. This has scientific theoretical guidance for the study of the migration–crystallization changes of soluble salts contained in porous silicate cultural relics. The visibility analysis results of multilayer salt crystal belts can also provide the preliminary basis for further effective desalination of salt bearing cultural relics.     

盐湖资源开发利用进展

本世纪头十年里,国际上再度掀起盐湖资源开发热潮。这很大程度上是由于锂的开发热带动的,同时也是和钾肥的广泛施用、价格一路走高有关。南美安第斯高原地区盐湖蕴藏世界70%以上的锂资源,且卤水锂、钾、硼浓度高。该地区极度干旱,少雨多风,非常适合采用卤水盐田蒸发的节能浓缩工艺技术。老的盐湖开发企业则在钾肥需求的带动下,稳步发展。在我国,新疆罗布泊和青海柴达木盆地盐湖则钾锂镁硼产品多元化,经营多元化取得长足进步。本文对近十年来,国内外盐湖开发的新动向做了概括介绍,特别着重于南美"锂三角"地区这一新的生长点。