大柴旦盐湖夏季组成卤水的天然蒸发

在进行大柴旦盐湖夏季组成卤水的天然蒸发实验中确定，该卤水的蒸发结晶路线不是按照Ｎａ＾＋、Ｋ＾＋、Ｍｇ＾２＋／Ｃｌ＾－、ＳＯ４＾２－－－Ｈ２Ｏ体系２５℃平衡溶解度相图，而是按照该体系的介稳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盐析过程中硼酸盐一般地并不以固体盐形式析出，而是赋存于浓缩卤水中。     

盐湖卤水的蒸发结晶过程

本文从实验和理论相结合的角度上，总结了三十多年我国数十个盐湖等温蒸发和天然蒸发研究结果和研究经验，概括了三种类型盐湖卤水蒸发结晶的规律性，推荐了卤水蒸发结晶的相化学基础数据．对氯化物型卤水，由于介稳程度小，可采用Ｚｄａｎｏｖｓｋｉｉ推荐的四元体系Ｎａ＋、Ｋ＋、Ｍｇ（２＋）∥Ｃｌ－—Ｈ２Ｏ平衡相图进行太阳池工艺计算；对于硫酸盐型卤水，宜用金作美五元体系Ｎａ＋、Ｋ＋、Ｍｇ（２＋）∥Ｃｌ－、ＳＯ，－Ｈ２Ｏ介稳相图，而不是Ｖａｎ’ｔＨｏｆｆ平衡相图；对于后期，锂盐高度浓缩，宜用我们的四元体系Ｌｉ＋、Ｍｇ（２＋）∥Ｃｌ－、ＳＯ－Ｈ２Ｏ介稳相因；对于碳酸盐型盐湖卤水，可用我们的五元体系Ｎａ＋、Ｋ＋∥Ｃｌ－、ＣＯ、ＳＯ－Ｈ２Ｏ介稳相图作为相化学基础，而不是Ｔｅｅｐｌｅ平衡相图．从相平衡热力学角度上，实现了对卤水蒸发结晶过程的理论描述、计算和预测．其中对一里坪、达布逊、东台吉乃尔、西台吉乃尔等盐湖卤水的研究结果尚属首次报道．     

东台吉乃尔盐湖卤水的相化学研究（Ⅰ）：25℃等温蒸发实验

为了研究东台吉乃尔盐湖卤水蒸发时的相化学，确定钾盐、镁盐和锂盐的结晶路线和结晶特性，在实验室内对卤水进行了２５℃等温蒸发结晶过程的研究．实验结果与Ｎａ＋、Ｋ＋、Ｍｇ（２＋）／／Ｃｌ－、ＳＯ—Ｈ２Ｏ五元水盐体系介稳相图进行了比较与讨论．     

东台吉乃尔盐湖卤水的相化学研究（Ⅱ）—冬夏季卤水蒸发实验

为了研究东台吉乃尔盐湖卤水蒸发时的相化学，确定钾、镁和锂盐的结晶特性，在实验室内２５℃等温蒸发实验基础上和自然条件下进行了冬夏季日晒蒸发试验．东台吉乃尔盐湖卤水是由氯化钠饱和的多组分复杂体系构成的．卤水中存在的离子是Ｎａ＋、Ｋ＋、Ｍｇ２＋、Ｌｉ＋、Ｃａ２＋、Ｂ３＋、ＳＯ４２－和Ｃｌ－．试验数据与Ｎａ＋、Ｋ＋、Ｍｇ２＋Ｃｌ－、ＳＯ４２－ＫＨ２Ｏ五元体系介稳平衡数据进行了讨论和比较．Ａｕｔｅｎｒｉｅｔｈ相图被用来表示各数据间的关系和证明冬夏季蒸发时结晶行为的差别．     

大柴旦盐湖冬季组成卤水的天然蒸发

进行天然蒸发实验用卤水是冬季气温最低的一月份取自大柴旦湖表卤水区，化学分析结果表明硫酸根含量明显地较夏季卤水低。在天然蒸发过程中顺次结晶析出ＮａＣｌ、ＫＣｌ，ＫＣｌ．ＭｇＣｌ２．６Ｈ２Ｏ，ＭｇＣｌ２．６Ｈ２Ｏ和ＭｇＳＯ４．６Ｈ２Ｏ。这显然与夏季组成卤水的蒸发结晶顺序存在明显不同。     

玻利维亚Uyuni盐湖卤水25 ℃等温蒸发实验

本文开展了玻利维亚Uyuni盐湖卤水25℃等温蒸发实验研究。参考Na~+、K~+、Mg~(2+)/Cl~-、SO~(2-)_4-H_2O五元体系298K(介稳)相图和Li~+、Mg~(2+)/Cl~-、SO~(2-)_4-H_2O四元交互体系298K(介稳)相图进行了理论分析,利用X射线衍射测试了析出矿物的物相,结合化学分析结果,研究了该卤水在等温蒸发过程盐类矿物的结晶路线和析出顺序,为Uyuni盐湖卤水的综合利用提供基础数据。     

盐卤硼酸盐化学ⅩⅩ.：天然含硼盐卤的蒸发相图

在进行青藏高原盐湖含硼盐卤天然蒸发和25℃等温蒸发实验的基础上,绘制成复杂盐卤的蒸发相图。该相图与Na~+、K~+、Mg~(2+)//Cl、SO_4~(2-)—H_2O体系25℃介稳相图基本上相符合。在将蒸发相图与该五元体系平衡溶解度相图进行比较后,从盐溶液化学的角度对蒸发相图的形成原因进行了解释。     

西藏扎北盐湖夏季卤水自然蒸发实验研究

西藏扎北盐湖位于藏北高原腹地,其卤水类型属硫酸钠亚型,富含Li、K、B等元素。为综合利用该湖的液态矿产资源,于西藏当地对该盐湖富锂卤水进行自然蒸发实验。实验以Na+,Mg2+//Cl-,SO42--H2O四元体系15℃等温相图及K+,Mg2+//SO42--H2O三元体系15℃介稳相图为参考,绘制了扎北盐湖夏季卤水在秋季自然蒸发结晶路线图,研究了卤水在蒸发过程中液相的化学组成变化以及其蒸发析盐规律。结果表明,在蒸发过程早期(成卤率23.9%),锂浓度达1.2 g/L时,锂开始以Na3LiSO4.3H2O等复盐形式大量分散析出;硼在整个蒸发过程中以硼砂(Na2B4O7.10H2O)等形式分散析出难于富集;钾以钾镁矾(K2SO4.MgSO4.6H2O)和钾石盐(KCl)形式蒸发浓缩的后期大量析出。实验为扎北盐湖的盐田工程设计及制卤工艺操作提供了必要的基础数据,也可为我国西藏硫酸钠亚型盐湖卤水的综合利用提供一定参考。     

西藏捌仟措盐湖卤水等温蒸发试验研究

以西藏捌仟措盐湖卤水为研究对象,依据Na+,K+,Mg2+//Cl-,SO24--H2O五元水盐体系相图,对该盐湖卤水进行了5℃等温蒸发试验,研究了卤水蒸发过程中盐类析出规律和钾、锂和硼在蒸发过程中的富集行为,为该盐湖卤水盐田规划设计、现场生产操作提供了依据。     

含锂盐湖卤水体系相关系的研究

用等温溶解平衡法研究了盐湖卤水体系Ｌｉ＋，Ｎａ＋，Ｋ＋，Ｍｇ２＋／ＳＯ＿４￣２－Ｈ２Ｏ２５℃溶解度，获得了该五元体系２５℃溶解度相图的十个无变量点和十个结晶区．十个结晶区分别对应于原始组份Ｋ２ＳＯ４、Ｌｉ２ＳＯ４·Ｈ２Ｏ、ＭｇＳＯ４·７Ｈ２Ｏ、Ｎａ２ＳＯ４·１０Ｈ２Ｏ、复盐３Ｋ２ＳＯ４·Ｎａ２ＳＯ４、Ｎａ２ＳＯ４·ＭｇＳＯ４·４Ｈ２Ｏ、Ｌｉ２ＳＯ４·３Ｎａ２ＳＯ４·１２Ｈ２Ｏ、２Ｌｉ２ＳＯ４·Ｎａ２ＳＯ４·Ｋ２ＳＯ４·Ｌｉ２ＳＯ４·Ｋ２ＳＯ４和Ｋ２ＳＯ４·ＭｇＳＯ４·６Ｈ２Ｏ，此外没有产生新的复盐或固溶体，用现代电解质溶液理论－Ｐｉｔｚｅｒ模型校验该体系的溶解度测定值，结果令人满意．     

大柴旦盐湖湖滨盐田日晒场施工建造

通过对盐湖湖区土壤调查，在对区域水文地质资料进行分析的基础上，认为在大柴旦地区建造日晒池，利用太阳能进行日晒卤水，分离一般盐类是经济可行的．制取高含硼和锂盐的氯化镁饱和卤水，供盐酸酸化分离硼酸，最后提取锂盐．     

A Raman Investigation on the Boron form Occurring in Salt Lake Brine during Evaporation

Boron resources are abundant in the Da Qaidam Salt Lake of the Qaidamu basin in China,which has generated significant attention due to the presence of polyborate species in brine from this lake. In this study,Raman spectroscopy was used to investigate the existing form of boron in brine during evaporation. MgO·2 B_2 O_3-H_2 O,MgO·2 B_2 O_3-MgCl_2-H_2 O,and MgO·2 B_2 O_3-MgSO_4~-H_2 O solutions were also studied to determine the influence of boron concentration,pH,and electrolytes on the borate speciation from brine. The mononborates B( OH)_3 and B( OH)_4~-were found to be the only forms present in natural salt lake brine. Brine evaporation promoted the formation of the polyborate anions B_3 O_3( OH)_4~-,B_5 O_6( OH)_4~-,and B_6 O_7( OH)_6~(2-)and also promoted the disappearance of the B( OH)_4~-ion from brine at boron concentrations of more than 11 g/L B_2 O_3. The pentaborate ion B_5 O_6( OH)_4~-was sensitive to the solution pH and appeared only at p H values less than 8. 0. Meanwhile,the hexaborate ion B_6 O_7( OH)_6~(2-)was observed to be more dependent on the electrolyte magnesium chloride due to its special properties,such as promoting boron accumulation,lowering solution pH,and also its strong affinity for water molecules,which were all beneficial for the polymerization of borate ions in brine. Interaction mechanisms between polyborate anions during evaporation are also proposed herein. ake; evaporation; polyborate species; interaction mechanism.     

A Raman investigation on the boron form occurring in salt lake brine during evaporation

Boron resources are abundant in Da Qaidam salt lake of Qaidamu Basin. It has been given great attention for the polyborate species present in brine. In this study, the Raman spectroscopy was applied to investigate the existing-form of boron in brine during evaporation. The prepared solutions of MgO·2B2O3-H2O, MgO·2B2O3-MgCl2 -H2O, and MgO·2B2O3-MgSO4-H2O was also evaporated and recorded to study the influence of boron concentration, pH, and electrolytes on the borate speciation in brine. The mononborates of B(OH)3 and B(OH)4- were found to be the only forms present in the original salt lake brine. Brine evaporation promotes the formation of polyborate anions B3O3(OH)4-, B5O6(OH)4-, and B6O7(OH)62- and also disappearance of the B(OH)4- ion in brine with boron concentration of more than 11 g/L in B2O3. The pentaborate ion of B5O6(OH)4- was sensitive to the solution pH and found to be appeared under the pH value of 8.0. While the hexaborate ion of B6O7(OH)62- was observed more dependent on the electrolyte of magnesium chloride due to its special properties, such as promoting boron accumulation, lowering solution pH, and also the strong af?nity for water molecules, which is beneficial to the polymerization of borate ions in brine. The interaction mechanisms among polyborate anions during evaporation had also been proposed.     

察尔汗盐湖卤水蒸发速度影响因素的量化研究

针对当前气象因素(辐照强度、风速、环境温度和相对湿度)与卤水因素(卤水温度和浓度)综合作用于卤水蒸发速度定量研究的数据缺乏等问题,采用室外蒸发装置及信号采集系统相结合的实验方法,开展了察尔汗盐湖卤水自然蒸发实验。借助多元线性回归分析方法对实验数据进行分析,建立了基于多因素共同作用下的卤水蒸发速度模型。实验结果表明,卤水蒸发速度随辐照强度、风速、环境温度和卤水温度的增加呈线性增加,而随相对湿度和浓度的增加呈线性减小。进一步得出各因素影响卤水蒸发速度的顺序为：辐照强度>风速>环境温度>卤水温度>相对湿度>浓度。     

察尔汗盐湖卤水蒸发速度影响因素的量化研究

针对当前气象因素(辐照强度、风速、环境温度和相对湿度)与卤水因素(卤水温度和浓度)综合作用于卤水蒸发速度定量研究的数据缺乏等问题,采用室外蒸发装置及信号采集系统相结合的实验方法,开展了察尔汗盐湖卤水自然蒸发实验.借助多元线性回归分析方法对实验数据进行分析,建立了基于多因素共同作用下的卤水蒸发速度模型.实验结果表明,卤水...     

Formation of Li Salts from Natural Brines during Isothermal Evaporation at 25℃

Li brines are the primary resources for Li salt industries. Evaporation is necessary to concentrate Li due to its low level of concentration in raw brines. The salt sequences during the evaporation of Li brines,especially the behavior of Li salts,represent key data for solar technologies. However,chemists cannot use any phase diagram to estimate Li salt sequences during evaporation at 25℃ . The thermodynamic model proposed by us in2003 represents the only tool for the prediction of equilibrium conditions during the evaporation of solutions containing Li~+,Na~+,K~+,Mg~(2+)/Cl~-,SO_4~(2-),and-H_2 O components at 25℃ . In this paper,the predicted salt sequences of 20 brines are reported. The results indicate that( 1) the first crystallized Li salt during evaporation of Li brine varies in brine composition;( 2) lithium sulfate is crystallized in many cases initially for brines of magnesium sulfate subtype,while Db4( Li_2 SO_4·K_2 SO_4) or Db3( 2 Li_2 SO_4·Na_2 SO_4·K_2 SO_4) appears first for sodium sulfate and magnesium sulfatesubtypes with lower Mg/Li composition,and the final eutectic point is H ~+ LiC ~+ Lc ~+ Ls ~+ Car;( 3) the final eutectic point is H ~+ LiC ~+ Lc ~+ Car for brines of chloride type; and( 4) Li content corresponding to the first crystallized Li salt is in the range of 0. 43%-1%. These findings enhance our knowledge of Li chemistry and provide insights into solar pond technology of the Li-brine process.     

盐田高浓度卤水蒸发的数学模型 及动力学研究

首次从化学工程的角度 ,将盐田系统作为一类特殊的化学反应器和无机盐分离设备进行了详细的论述。在大量试验基础上 ,系统地分析和研究了 Na+,K+,Mg2 +∥Cl-,- H2 O四元水盐体系卤水在天然蒸发状态下的宏观蒸发动力学参数。从理论上对与卤水蒸发相关的多种参数进行了分析和合理简化 ,概述了卤水蒸发过程中的质量传递规律。并在此基础上通过计算机模拟方法建立了四元水盐体系高浓度卤水在特定地域中进行天然蒸发的卤水宏观蒸发动力学模型 ,证明了多种简化和理论假设的合理性。对该数学模型在盐湖卤水开发中的盐田设计、盐田生产的现代化自动管理和控制等进行了探讨。在卤水蒸发动力学模型建立的过程中 ,针对实际生产过程的需要 ,通过多种参数的分析 ,建立了多种参数关系     

尕斯库勒盐湖卤水模拟自然蒸发试验研究

尕斯库勒湖是柴达木盆地众盐湖中较为典型的硫酸镁亚型盐湖。利用相图规律对该盐湖卤水自然蒸发的结晶路线进行了分析,并通过室内模拟自然蒸发试验进行了验证,最终获得了在自然条件下蒸发卤水分步结晶不同盐类的工艺路线,可为该盐湖资源综合利用提供依据。