西藏当雄错盐湖卤水冬季日晒蒸发实验研究

西藏当雄错盐湖位于藏北高原腹地西南侧,其水化学类型属典型的中度碳酸盐型,具有很好的工业开发前景和价值.自然蒸发是盐田日晒工艺的应用基础工作,本文基于室内卤水等温蒸发实验的相关结果,在当雄错湖区现场开展了盐湖卤水冬季日晒蒸发实验,通过考察碳酸盐型盐湖卤水在现场低温条件下自然蒸发过程中液相各元素的富集规律以及矿物的结晶析盐规律,分析了锂、硼、钾等元素的集散行为,并根据卤水蒸发过程中的元素富集、蒸失水量、盐类析出顺序、矿物组合以及物化性质的变化探索了盐类分离的控制条件.以Na+,K+/CO2-3,SO2-4,Cl--H2O五元体系(25℃)介稳相图为参考依据,绘制了当雄错盐湖卤水冬季日晒蒸发的结晶析盐路线.实验结果表明,当雄错盐湖卤水在冬季日晒蒸发过程中依次析出石盐、泡碱、天然碱、硼砂、钾石盐和扎布耶石,另有少量芒硝和泡碱等低温产物会提前析出或被母液夹带析出,利用冬季低温蒸发可制取富锂卤水,蒸发后期的母卤还可用于提取硼砂和钾石盐等矿物资源.实验结果为下一步开展盐田工程设计及制卤工艺操作提供了必要的基础数据,同时也为碳酸盐型盐湖卤水的综合利用和开发提供了理论支持.     

西藏扎布耶盐湖卤水演化的Pitzer模型模拟

扎布耶盐湖是西藏高原代表性的富锂硼碳酸盐型盐湖。本文利用Pitzer模型模拟计算了西藏扎布耶盐湖冬季与夏季卤水、补给河流-泉水的低温(2℃)、常温(25℃)和高温(50℃)蒸发结晶过程,结果表明,扎布耶盐湖卤水可以由现代成分的河流-泉水蒸发浓缩形成,扎布耶盐湖的沉积组合与河泉水蒸发浓缩的矿物结晶规律吻合;而冬、夏卤水蒸发模拟结果与卤水蒸发实验结果基本吻合,但对矿物结晶顺序、矿物组合规律以及温度-季节性成分变化的影响等方面,提供了更多更详细的数据与认识。说明Pitzer模型对研究西藏富锂硼碳酸盐型盐湖的地球化学成因和盐田工艺都具有重要参考价值。     

硫酸钠亚型富锂卤水25℃等温蒸发过程的计算机模拟

我国青藏高原上分布有许多盐湖,其中扎布耶等碳酸盐型盐湖、东台吉乃尔等硫酸镁亚型盐湖是著名的富锂盐湖,已成功开发生产出碳酸锂产品。青藏高原上还有许多硫酸钠亚型盐湖,其卤水锂浓度高,钾、镁、硼等有用成分丰富。针对这些盐湖资源,目前尚未进行开发利用研究。这些卤水的等温蒸发实验研究,是必不可少的关键工作之一。本文使用我们由Pitzer电解质溶液理论建立的Li+,Na+,K+,Mg2+/Cl-,SO24--H2O体系的热力学模型,对25℃下几种硫酸钠亚型富锂卤水等温蒸发过程进行了计算机模拟,预测蒸发过程中盐类矿物的析出顺序、卤水组成变化规律、钠、钾、镁、锂盐的饱和点,并在此基础上进行卤水蒸发过程物料平衡关系的理论计算等。本文对西藏3种硫酸钠亚型卤水和国外2种硫酸钠亚型卤水25℃等温蒸发过程进行了模拟。其析盐顺序的特点是:在第一个矿物石盐饱和析出后,接着析出的含钾矿物是钾芒硝,而不是钾镁矾类矿物。其后钾盐则会以钾岩盐形式析出。锂盐饱和后则主要以复盐Li2SO4.K2SO4形式析出。美国银峰卤水的模拟结果与实验蒸发过程完全一致,并给出其继续蒸发时的析盐状况。另4种硫酸钠亚型卤水的模拟结果不仅可以作为未来实验研究的基本参考和注意点,同样也可作为其盐田设计和工艺安排的基本理论依据。本文研究为该类型卤水资源综合开发利用工艺路线的确立提供理论参考。     

西藏扎布耶盐湖夏季卤水盐田晒制研究

本文以西藏扎布耶盐湖卤水为研究对象，在夏季的大面积盐田中，记录了天然日晒蒸发过程中的卤水组分演化过程，分析了Li、B、K等组分的集散行为，为该湖卤水的综合利用提供了工业化参考数据。通过实验发现，扎布耶盐湖夏季卤水Li^ 富集较低，Li^ 浓度最高达到1.8g/L。Li^ 的析出较分散，在实验末期，固相Li2CO3析出达到高峰期，但Li2CO3的含量不超过4%。在实验后期，卤水中CO3^2-离子的浓度和卤水温度迅速升高，这是导致卤水中Li^ 快速析出的主要因素，蒸发后期，卤水中K^ 和B2O3迅速富集，母卤适于提取硼砂和钾石盐或硼钾盐。     

江陵凹陷沙钾3井古近系沙市组地球化学特征及成钾指示

在盐湖沉积演化过程中,钾镁盐在盐类矿物沉积的中晚期才开始结晶析出。因此,研究含盐系地层中盐类矿物的沉积地球化学特征,不仅可以从侧面获取岩盐的沉积物物质来源和成盐期古卤水蒸发浓缩程度等地球化学信息,而且可以直接揭示古盐湖期钾盐富集趋势及规律。目前,除在江陵凹陷的古近系沙市组等含盐系内发现了富钾卤水外,还在中-南部的钻孔盐矿盐岩中,发现了微量钾石盐和钾石膏,这些说明该凹陷古近纪具有成钾潜力。本文通过对SK3井蒸发岩特征研究及岩芯中K、Mg、Cl、Br离子含量与Br×103/Cl系数的垂向变化分析,揭示古盐湖浓缩演化与钾盐富集趋势,进一步揭示该层段沉积时期及所在凹陷古盐湖卤水钾的富集程度。     

罗布泊盐湖富钾卤水成因再探讨——碎屑层卤水蒸发实验分析

罗布泊盐湖钙芒硝岩孔隙中蕴藏有超大型规模的卤水钾矿,富钾卤水成因一直备受关注。罗北凹地从统一的罗布泊大湖区中分隔出来后,成盐过程中其湖水仍以南部大湖的补给为主,罗北凹地卤水化学演化与"大耳朵"湖水密切相关。"大耳朵"湖区含石膏碎屑层普遍储藏有卤水,应该是罗北凹地盐湖的"源卤水",钾离子(ρ(K~+)为3.12 g/L左右)已初步富集,平均矿化度为198.83 g/L。为了查明该卤水的化学演化趋势及析盐序列,笔者于2009年、2010年两次采集了大量卤水样品,分别进行室内等温蒸发和自然蒸发实验。蒸发实验结果表明:随着卤水浓缩首先析出(硬)石膏,随后析出大量石盐,最后出现少量钾石盐和光卤石,与EQL/EVP卤水蒸发模型模拟结果相似。将碎屑层卤水蒸发过程中化学组成变化与罗北凹地卤水进行对比,结果显示罗布泊古湖水蒸发至石膏沉积之后,在罗北凹地水化学组成明显发生变化,没有大量石盐沉积,而以钙芒硝沉积为主。推测应是受到深部"富钙水"的持续补给,而"大耳朵"湖起到"预备盆地"的作用,罗布泊古湖水经"大耳朵"湖蒸发浓缩后,钾离子得到初步富集,在流入罗北凹地后与深部"富钙"水混合,强烈蒸发浓缩,大量钙芒硝矿物析出,最后形成富钾卤水。     

罗布泊盐湖钙芒硝巨量堆积对富钾卤水形成的控制——来自流体包裹体组成的约束

<正>罗布泊盐湖位于新疆塔里木盆地东端,为我国最大的硫酸盐型卤水钾盐成矿区,富钾卤水主要赋存于巨量钙芒硝岩晶间孔隙中。一般海水和陆相盐湖需经历石盐沉积之后,才出现钾元素富集和钾盐矿物沉积,晶间卤水通常赋存于石盐晶间孔隙中。海水蒸发至石盐析出时卤水中KCl含量约0.52%(瓦里亚什科,1965)。然而,罗布泊盐湖在石膏沉积之后出现巨量钙芒硝沉积,石盐析出时间相对很晚,沉积量也相对很小。钙芒硝大量沉积后,晶间卤水钾元素出现超前富集,卤水KCl平均含量达1.40%,     

西藏扎布耶盐湖秋季卤水25℃等温蒸发研究

本文对西藏扎布耶盐湖秋季卤水进行了25℃等温蒸发试验,并参考Na 、K //CO32-、SO24-、Cl-—H2O五元水盐体系介稳相图和Li 、Na //Cl-、SO24-、CO32-、B4O27-—H2O六元(赝)体系(25℃,对NaCl及Li2CO3饱和)溶解度相图,研究了该季卤水25℃等温蒸发过程中盐类结晶路线和析出规律,为该盐湖卤水的综合开发利用提供重要的依据。     

碳酸盐型盐湖卤水的模拟太阳池结晶试验

在碳酸盐型盐湖提锂工艺中, 太阳池是一个重要组成部分, 目的是储存太阳能能量以结晶析出碳酸锂。文章利用加热方法首次在实验室条件下进行模拟太阳池结晶试验, 试验的蒸发量随着温度的升高而加大, 但蒸发量的不同对析盐结晶影响不大。在不同时间段模拟试验中, 24 h时间段的Mg2+析盐浓度较Li+大, 且随着时间的延长逐渐降低, 而Li+则相反;Mg2+析出速率随着时间的增加而逐渐降低, 而Li+析出速率基 本保持一致。在不同温度模拟试验中, 卤水主要组分总析出率与温度的升高呈正相关, 卤水中CO32?和Li+的浓度降低速度大于其他组分, CO32?和Li+的析出率远大于其他组分, 析出主要矿物鉴定结果均为扎布耶石     

中国西北地区典型盐湖铀富集特征初探

根据对中国西北地区典型盐湖水文地质、铀矿地质和卤水地球化学性质的调查,初步探讨了不同水化学类型盐湖铀的富集规律,以及铀在盐湖固液相中的选择性富集特征。结果表明,盐湖补给区的铀源条件,盐湖卤水（晶间卤水）的盐度（矿化度）是决定盐湖富铀的主要因素,大多数碳酸盐型盐湖中铀在固液相中的分配比远大于硫酸盐型。两类盐湖卤水和补给水中,铀主要以碳酸铀酰形式存在。浅层晶间卤水和盐湖盐类沉积物中的铀含量往往较高。     

中国盐湖锂资源的产业化现状-以西台吉乃尔盐湖和扎布耶盐湖为例

锂对国民经济和国家安全具有重要意义, 是21世纪的能源金属。近10年, 中国主要从国外进口碳酸锂产品。中国是一个多盐湖的国家, 盐湖锂占锂资源工业总储量的85%。现代第四纪盐湖主要分布在我国西北的青海、西藏、新疆和内蒙古四省区, 具有很好的开发前景。经过多年科研后, 目前国内已经在西台吉乃尔和扎布耶两个盐湖建立了卤水提锂产业。本文对比研究了这两个盐湖资源状况和地理气候条件, 以及由此而决定的盐湖资源开发工艺流程, 探讨了其工艺优化方向。并指出这两个盐湖具有锂资源储量大, 品位高的优势, 但是受盐湖类型或地理气候条件限制, 工艺上有待改善。建议继续加强对盐湖开发技术优化和对盐湖提锂产业的扶持。     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

西藏麻米错富硼锂盐湖成矿物质平衡计算与物质来源

麻米错盐湖是西藏境内发育的特大型锂矿床之一,目前对该盐湖的Li、B来源仍存在一定争议。文章系统采集麻米错盐湖水及周边补给水体样品,分析其主量元素特征,并使用多种水化学手段进行讨论,同时对盐湖水、河水及地热水进行蒸发模拟。结果表明,研究区河水及泉水中的主要离子受控于流域内岩石风化作用,其中碳酸盐岩矿物与蒸发岩矿物贡献最大,其次是硅酸盐矿物。文章对补给水体输入盐湖的Li、B资源进行定量计算,得出单纯通过河水和泉水的输入无法形成盐湖目前的探明储量。选择西藏地区最为富Li的地热水同补给水体按照一定比例混合后进行蒸发模拟,发现其析盐序列与盐湖水的析盐序列存在很大程度上的重叠,以上均证明麻米错盐湖中的Li、B资源除受到周边河水及泉水的补给外,还受到地热水的补给。     

Hydrochemical Dynamic Characteristics and Evolution of Underground Brine in the Mahai Salt Lake of the Qaidam Basin Qinghai-Tibet Plateau

The mineral rock salts present in the Mahai Salt Lake of the Qaidam basin exhibit high solubilities in water. In addition, the multicomponent underground brine exhibits a high salinity and is easily precipitated. In the natural state, brine transport in the brine layer is extremely slow, and the brine is in a relatively stable chemical equilibrium state with the rock salt media. However, during mining, both the seepage and the chemical fields fluctuate significantly, thereby disrupting the equilibrium and leading to variations in the chemical composition and dynamic characteristics of the brine. Therefore, we selected underground brine from the Mahai Salt Lake, collecting a total of 183 brine samples over three stages of mining (i.e., the early stage of underground brine extraction, the initial stage of mining, and the later stage of mining). Using a range of analytical techniques, the chemical dynamics of the underground brine water and its evolution were systematically studied. We found that evaporation and enrichment were the main mechanisms of underground brine evolution in the Mahai Salt Lake, with cation exchange and mineral dissolution/precipitation being key factors in determining the dynamic characteristics and evolution of the brine.     

Progress and Prospects of Salt Lake Research in China

China has unique salt lake resources, and they are distributed in the east of Eurasian salt lake subzone of the Northern Hemisphere Salt Lake Zone, mainly concentrated in the regions with modern mean annual precipitation lower than 500 mm. This paper preliminarily reviews the progress made in salt lake research in China for the past 60 years. In the research of Paleoclimate and paleoenvironment from salt lake sediments, a series of salts have been proposed to be indicators of paleoclimate, and have been well accepted by scholars. The chloride-sulfate depositional regions of the west Qaidam and the east Tarim have been revealed to be the drought center of China since the Quaternary, and more than 6 spreading stages of arid climate(salt forming) have been identified. Five pan-lake periods with highstands have been proved to exist during the late Quaternary on the Tibetan Plateau. In mineral resource prospecting and theories of the forming of salt deposits: the atlas(1:2500000) of hydrochemical zoning of salt lakes on the Tibetan Plateau has been compiled for the first time, revealing the zonal distribution and transition from carbonate type to chloride type from south to north and presenting corresponding mineral assemblages for different type of salt lakes; several large continental salt deposits have been discovered and the theory of continental potash deposition has been developed, including the salt deposition in deep basins surrounded by high mountains, the mineral deposition from multistage evolution through chains of moderate or shallow lakes with multilevels, the origin of potassium rich brines in gravel layers, and the forming of potassium deposits through the inheriting from ancient salt deposits, thus establishing the framework of "Continental Potash Deposition Theory"; several new types of Mg-borate deposits have been discovered, including the ulexite and pinnoite bed in Da Qaidam Lake, Qinghai, the pinnoite and kurnakovite bed in Chagcam Caka, Tibet, the kurnakovite bed in Lake Nyer, and the corresponding model of borate deposition from the cooling and dissolution of boron rich brines was proposed based on principles of geology, physics and chemistry. The anti-floatation-cold crystallization method developed independently has improved the capacity of KCl production to 3 million tons per year for the Qarham, serving the famous brand of potash fertilizer products. One 1.2 million ton K-sulfate production line, the biggest in the world, has been built in Lop Nor, and K-sulfate of about 1.6 million tons was produced in 2015. Supported by the new technology, i.e. brine preparation in winter-cooling-solarization-isolation-lithium deposition from salt gradient solar pond" the highest lithium production base at Zabuye Lake(4421 m), Tibet, has been established, which is the first lithium production base in China that reaches the year production of 5000 tons of lithium carbonate. The concept of Salt lake agriculture(Salt land agriculture) has been established based on the mass growth of Dunaliella and other bacillus-algae and the occurrence of various halophytes in saltmarsh and salt saline-alkali lands, finding a new way to increase arable lands and develop related green industry in salt rich environments. Finally this paper presents some new thoughts for the further research and development on salt science, and the further progress in salt science and technology will facilitate the maturing of the interdisciplinary science "Salinology".     

西藏扎北盐湖秋季卤水(硫酸钠亚型)5℃等温蒸发实验研究

西藏扎北盐湖硫酸钠亚型卤水中富含元素Li、B、K和微量元素Rb、Cs等.为了更好地了解卤水在自然条件下的蒸发结晶规律,需对相应卤水进行低温室内等温蒸发实验研究.本文对该盐湖卤水进行了5℃等温蒸发试验,并利用Na+、K+、Mg2+//Cl-、SO42--H2O五元水盐体系0℃相图,构筑了从干基立体图Na2SO4角顶的放射...     

西藏扎布耶盐湖超大型B、Li矿床成矿物质来源研究

扎布耶盐湖位于西藏高原腹地,是一个现代盐湖矿床。对扎布耶地区地球化学背景的研究表明:变质岩及蚀变岩石中硼锂含量很高以及电气石脉的出现,暗示着扎布耶地区深部曾产生含硼锂高的热流体;沉积岩中除晚石炭世砂岩含硼锂稍高外,其他岩石均低于同类岩石的平均含量;火山岩中除早白垩世基性岩的硼锂含量高于基性岩平均含量外,其他均很低;该区大量发育的第四纪钙华含硼锂非常高,表明早期的热水系统曾提供过大量的成矿物质;河流及泉水中的硼锂含量是世界河水平均含量的数倍至数百倍,表明地表和近地表条件下的水-岩相互作用的产物也是成矿物质来源之一。     

The Identification and Geological Significance of Fault Buried in the Gasikule Salt Lake in China based on the Multi-source Remote Sensing Data

The salinity of the salt lake is an important factor to evaluate whether it contains some mineral resources or not, the fault buried in the salt lake could control the abundance of the salinity. Therefore, it is of great geological importance to identify the fault buried in the salt lake. Taking the Gasikule Salt Lake in China for example, the paper established a new method to identify the fault buried in the salt lake based on the multi-source remote sensing data including Landsat TM, SPOT-5 and ASTER data. It includes the acquisition and selection of the multi-source remote sensing data, data preprocessing, lake waterfront extraction, spectrum extraction of brine with different salinity, salinity index construction, salinity separation, analysis of the abnormal salinity and identification of the fault buried in salt lake, temperature inversion of brine and the fault verification. As a result, the study identified an important fault buried in the east of the Gasikule Salt Lake that controls the highest salinity abnormal. Because the level of the salinity is positively correlated to the mineral abundance, the result provides the important reference to identify the water body rich in mineral resources in the salt lake.