热水太阳池在西藏当雄错盐湖卤水提锂中的应用研究
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摘要
西藏当雄错盐湖位于藏北高原腹地西南处，该湖湖水类型属于中度碳酸盐型，湖水Mg/Li<0.1。原始湖水中富含Na、K、Br、B、Li、Rb等具有经济价值的元素，卤水经过日晒蒸发浓缩以后K、B、Li、Rb浓度显著增高，并达到工业开发品位。本文以西藏当雄错碳酸盐型低镁锂比盐湖卤水为对象，采用自主设计研发的热水太阳池提锂工艺，在继钾提取基础上针对富锂卤水中的锂进行提取研究。
热水太阳池技术首次将地热资源和盐梯度太阳池结合，通过在盐梯度太阳池底部加设热交换器，利用地热水循环来对池内卤水进行加热，加速卤水升温，并最终获得高品位的碳酸锂。热水太阳池技术可以解决目前针对高原盐湖提锂过程中遇到的问题，如生产周期长、卤水温度低以及盐藻问题等，在不加入任何化学试剂的前提下，从卤水中提取碳酸锂。
热水太阳池池壁由钢筋、混凝土和砖块垒砌而成，池壁与地平夹角为当雄错地区冬至日的太阳高度角，这样有利于加热池中的卤水在一天之内接受更多的太阳辐射；池底为长方形结构，长2m、宽1m；加热池内壁铺有10cm厚的保温材料。热水太阳池中的卤水分为下对流层（浓缩卤水层）、非对流层（盐梯度层）和上对流层（淡水层）三个部分。下对流层由富锂卤水组成，高矿化度的卤水可以吸收和储存来自热交换器和太阳辐射的热量；非对流层中卤水盐度从上至下呈指数递增，热量不易在这一层中穿透因而具有保温作用；上对流层由淡水组成，用来保护盐梯度层不被破坏。
论文研究内容围绕热水太阳池展开，通过热、盐扩散研究、模拟提锂对比研究和热交换器研究对热水太阳池性能进行表征，并利用热水太阳池技术在当雄错盐湖现场进行提锂实验。
首先通过对富锂卤水进行提锂实验，考察了热交换器在下对流层中的不同位置对温度分布的影响。当热交换器位于下对流层、距离底部5cm时，下对流层中的最大温差只有10℃，平均温度最高能达到55℃。此外，下对流层的温度分布还影响碳酸锂的结晶析出，通过实验发现碳酸锂在温度大于45℃的卤水中结晶较为理想。随着加热的进行，热水太阳池中的卤水温度分布会出现分异现象，并形成高温带和低温带。
盐梯度层在热水太阳池中起着关键作用，实验对加设热交换器以后的卤水动态变化进行了考察和分析。实验结果显示在没有盐梯度层存在时，搅拌作用能够加速卤水升温，但同时由于水分蒸发导致NaCl、硫酸盐、碱类矿物因为过饱和而提前大量析出，最终使得析出的盐类矿物中碳酸锂含量下降；稳定的盐梯度层可以提高下对流层的平均温度，并改变碳酸锂的析出品位；实验中还发现盐梯度层的厚度对其保温作用有很大影响，厚度越厚保温效果越明显，下对流层中卤水的平均温度越高。
通过对比50℃模拟太阳池提锂实验，探讨和分析了现场提锂实验中的共性和差异。实验对提锂完成后的卤水离子含量进行了对比研究，发现除Na~+以外，其他离子含量均有降低，尤其是Li~+和CO_3~(2-)。同时对Na~+含量的不规律变化进行了讨论；通过对两次实验的矿物鉴定发现，现场实验析出的盐类矿物中碳酸锂含量要高于50℃模拟实验。
热交换器是热水太阳池的核心部件，选择间壁式热交换器有利于我们针对热水太阳池结构进一步开展实验。针对间壁式热交换器的结构特点设计了L4(32)类型的正交实验，分别对影响热交换效率的三个因素热交换器材料、热交换管形状以及管道内部热水流速进行考察和分析。实验结果显示不锈钢材料的性能要高于PERT材料；使用“回”形加热器要比使用“U”形加热器效率高一点，但是程度不明显；热水在加热管内的流速同样会影响热交换器的效率，流速越大，加热效率越高。同时通过正交实验中的R极值进行分析后认为：在影响热交换器热交换效率高低的这三个因素中，材料因素>流体流速>加热管形状。
The Damxung Co salt lake is located on the southwest of the northern Tibetplateau hinterland, the water of which is a moderate carbonate type and its Mg/Li<0.1.The water is rich in elements with great economic value, like Na、K、Br、B、Li、Rb. After insolating and evaporating brine, the concentration of K、B、Li、Rb increasessignificantly and meets the criteria of industrial development. This paper takes theDamxung Co salt lake of a low ratio of Mg/Li carbonate type as research object. Theexperiments of Li extraction from lithium-rich brine are taken based on K extractionby using hot water solar pond (HWSP) technology for the first time.
The HWSP technology combines the geothermal energy and the salt gradientsolar pond (SGSP) for the first time. The heat exchanger is installed at the bottom onthe basis of SGSP and the energy is transferred from the heat exchanger to the brineby using hot water circulation so that the temperature of the brine is raised rapidly andeventually obtained the high grade lithium carbonate. The HWSP technology cansolve the problems we have encountered in the process of lithium extraction fromplateau salt lakes, for instance the long production cycle, the lower brine temperatureand the dunaliella salina problems. Most of all, lithium carbonate can be extractedfrom brine without adding any chemical reagent.
The walls of hot water solar pond (HWSP) are made of reinforced concrete andbricks. The angle between sidewall and horizontal plane is exactly the same as thesolar altitude of Damxung Co area at winter solstice, thus the brine in HWSP canreceive more solar radiation within a day. The bottom of HWSP has a shape ofrectangular, which is2meters long and1meter wide. The internal walls of HWSP arecovered with10centimeters thick insulation material to keep brine warm in the following experiments. The brine in the hot water solar pond can be divided into threeparts of Lower Convective Zone (LCZ, concentrated brine layer), NonconvectiveZone (NCZ, salt gradient layer) and Upper Convective Zone (UCZ, fresh water layer).The LCZ is composed of lithium-rich brine and the high salinity brine can absorb andstore the heat from the heat exchanger and solar radiation; the salinity of LCZincreases exponentially from top to bottom, which contributes to prevent the heatfrom penetrating, thus it has the insulation effect; the UCZ is composed of freshwaterand is used to protect the underlying brine from destroyed.
This research is mainly revolve round the HWSP, of which the performance ischaracterized through the study of heat and salinity diffusion, lithium extractingsimulation and the heat exchanger. The HWSP technology is used in lithiumextracting experiments on Damxung Co salt lake.
The experiment of lithium extraction from the rich lithium brine inspected theinfluence of the heat exchanger in the different LCZ position on the distribution oftemperature. When the heat exchanger is on LCZ and5cm distant from the bottom ofthe pool, the maximum temperature difference is only10℃and the highest averagetemperature could reach55℃. On the other hand, the experiment shows that theLCZ temperature distribution also affects the crystallization of lithium carbonate. Thebest crystallization temperature of lithium carbonate is above45℃in the brine.With continuously heating, the temperature distribution of the brine will change andform high temperature zone and low temperature zone.
The salt gradient layer makes an important role on HWSP. The experimentsinspected and analyzed the brine dynamical change after the heat exchanger isinstalled on the brine pool. The experiment shows that without the salt gradient layer,blending can speed up the brine warming, but at the same time due to the waterevaporation, sodium chloride, sulfate and alkali mineral in great quantities areseparated in advance for supersaturate precipitation, eventually the content of lithiumcarbonate mineral drops. The stability of salt gradient layer would raise the averagetemperature of the LCZ and change the grade of lithium carbonate mineral. Theexperiment also found that the thickness of the salt gradient layer takes great effect onheat preservation. The thicker the salt gradient layer is, the better effect of heatpreservation and higher the average temperature of brine on LCZ will be.
The general similarity and difference of lithium extraction on the fieldexperiment is researched and analyzed by comparing with50℃simulated the solarpond experiment. The experiments analyzed the amount of ion of brine in which lithium is extracted and found except Na~+, the amount of all ions drop, especially Li~+and CO_3~(2-)and discussed the irregular change of the amount of Na~+. Throughcomparing mineral identification of two experiments, the amount of carbonate oncrystal mineral precipitation by the field experiment is higher than that in simulatedexperiment.
The heat exchanger is the core component of HWSP. The surface type of heatexchanger is conducive to carry out the further experiments for HWSP. Therefore,according to the structural characteristics of the surface type heat exchanger,orthogonal experiment of L4(32) was used to examine and analyze the three factors ofimpacting the heat exchange efficiency. The three factors are the materials of heatexchangers, the shape of the heat exchange tube and the hot water flow rate in thepipeline. The experimental results show that the properties of thermal conductivity ofstainless steel are better than PERT material. The heating efficiency of spiral-typeheater exchanger is better than that of the U-type, but the difference is not significant.The flow rate of hot water on the heating tube also affects the efficiency of the heatexchanger. The quicker the flow rate is, the higher the heating efficiency will be. Atthe same time by the comparison and analysis of extreme value R in the orthogonalexperiment, the sequence of three factors impacting the heat exchanging efficiency is:the material factors> flow rate> the tube shape.
热水太阳池技术首次将地热资源和盐梯度太阳池结合，通过在盐梯度太阳池底部加设热交换器，利用地热水循环来对池内卤水进行加热，加速卤水升温，并最终获得高品位的碳酸锂。热水太阳池技术可以解决目前针对高原盐湖提锂过程中遇到的问题，如生产周期长、卤水温度低以及盐藻问题等，在不加入任何化学试剂的前提下，从卤水中提取碳酸锂。
热水太阳池池壁由钢筋、混凝土和砖块垒砌而成，池壁与地平夹角为当雄错地区冬至日的太阳高度角，这样有利于加热池中的卤水在一天之内接受更多的太阳辐射；池底为长方形结构，长2m、宽1m；加热池内壁铺有10cm厚的保温材料。热水太阳池中的卤水分为下对流层（浓缩卤水层）、非对流层（盐梯度层）和上对流层（淡水层）三个部分。下对流层由富锂卤水组成，高矿化度的卤水可以吸收和储存来自热交换器和太阳辐射的热量；非对流层中卤水盐度从上至下呈指数递增，热量不易在这一层中穿透因而具有保温作用；上对流层由淡水组成，用来保护盐梯度层不被破坏。
论文研究内容围绕热水太阳池展开，通过热、盐扩散研究、模拟提锂对比研究和热交换器研究对热水太阳池性能进行表征，并利用热水太阳池技术在当雄错盐湖现场进行提锂实验。
首先通过对富锂卤水进行提锂实验，考察了热交换器在下对流层中的不同位置对温度分布的影响。当热交换器位于下对流层、距离底部5cm时，下对流层中的最大温差只有10℃，平均温度最高能达到55℃。此外，下对流层的温度分布还影响碳酸锂的结晶析出，通过实验发现碳酸锂在温度大于45℃的卤水中结晶较为理想。随着加热的进行，热水太阳池中的卤水温度分布会出现分异现象，并形成高温带和低温带。
盐梯度层在热水太阳池中起着关键作用，实验对加设热交换器以后的卤水动态变化进行了考察和分析。实验结果显示在没有盐梯度层存在时，搅拌作用能够加速卤水升温，但同时由于水分蒸发导致NaCl、硫酸盐、碱类矿物因为过饱和而提前大量析出，最终使得析出的盐类矿物中碳酸锂含量下降；稳定的盐梯度层可以提高下对流层的平均温度，并改变碳酸锂的析出品位；实验中还发现盐梯度层的厚度对其保温作用有很大影响，厚度越厚保温效果越明显，下对流层中卤水的平均温度越高。
通过对比50℃模拟太阳池提锂实验，探讨和分析了现场提锂实验中的共性和差异。实验对提锂完成后的卤水离子含量进行了对比研究，发现除Na~+以外，其他离子含量均有降低，尤其是Li~+和CO_3~(2-)。同时对Na~+含量的不规律变化进行了讨论；通过对两次实验的矿物鉴定发现，现场实验析出的盐类矿物中碳酸锂含量要高于50℃模拟实验。
热交换器是热水太阳池的核心部件，选择间壁式热交换器有利于我们针对热水太阳池结构进一步开展实验。针对间壁式热交换器的结构特点设计了L4(32)类型的正交实验，分别对影响热交换效率的三个因素热交换器材料、热交换管形状以及管道内部热水流速进行考察和分析。实验结果显示不锈钢材料的性能要高于PERT材料；使用“回”形加热器要比使用“U”形加热器效率高一点，但是程度不明显；热水在加热管内的流速同样会影响热交换器的效率，流速越大，加热效率越高。同时通过正交实验中的R极值进行分析后认为：在影响热交换器热交换效率高低的这三个因素中，材料因素>流体流速>加热管形状。
The Damxung Co salt lake is located on the southwest of the northern Tibetplateau hinterland, the water of which is a moderate carbonate type and its Mg/Li<0.1.The water is rich in elements with great economic value, like Na、K、Br、B、Li、Rb. After insolating and evaporating brine, the concentration of K、B、Li、Rb increasessignificantly and meets the criteria of industrial development. This paper takes theDamxung Co salt lake of a low ratio of Mg/Li carbonate type as research object. Theexperiments of Li extraction from lithium-rich brine are taken based on K extractionby using hot water solar pond (HWSP) technology for the first time.
The HWSP technology combines the geothermal energy and the salt gradientsolar pond (SGSP) for the first time. The heat exchanger is installed at the bottom onthe basis of SGSP and the energy is transferred from the heat exchanger to the brineby using hot water circulation so that the temperature of the brine is raised rapidly andeventually obtained the high grade lithium carbonate. The HWSP technology cansolve the problems we have encountered in the process of lithium extraction fromplateau salt lakes, for instance the long production cycle, the lower brine temperatureand the dunaliella salina problems. Most of all, lithium carbonate can be extractedfrom brine without adding any chemical reagent.
The walls of hot water solar pond (HWSP) are made of reinforced concrete andbricks. The angle between sidewall and horizontal plane is exactly the same as thesolar altitude of Damxung Co area at winter solstice, thus the brine in HWSP canreceive more solar radiation within a day. The bottom of HWSP has a shape ofrectangular, which is2meters long and1meter wide. The internal walls of HWSP arecovered with10centimeters thick insulation material to keep brine warm in the following experiments. The brine in the hot water solar pond can be divided into threeparts of Lower Convective Zone (LCZ, concentrated brine layer), NonconvectiveZone (NCZ, salt gradient layer) and Upper Convective Zone (UCZ, fresh water layer).The LCZ is composed of lithium-rich brine and the high salinity brine can absorb andstore the heat from the heat exchanger and solar radiation; the salinity of LCZincreases exponentially from top to bottom, which contributes to prevent the heatfrom penetrating, thus it has the insulation effect; the UCZ is composed of freshwaterand is used to protect the underlying brine from destroyed.
This research is mainly revolve round the HWSP, of which the performance ischaracterized through the study of heat and salinity diffusion, lithium extractingsimulation and the heat exchanger. The HWSP technology is used in lithiumextracting experiments on Damxung Co salt lake.
The experiment of lithium extraction from the rich lithium brine inspected theinfluence of the heat exchanger in the different LCZ position on the distribution oftemperature. When the heat exchanger is on LCZ and5cm distant from the bottom ofthe pool, the maximum temperature difference is only10℃and the highest averagetemperature could reach55℃. On the other hand, the experiment shows that theLCZ temperature distribution also affects the crystallization of lithium carbonate. Thebest crystallization temperature of lithium carbonate is above45℃in the brine.With continuously heating, the temperature distribution of the brine will change andform high temperature zone and low temperature zone.
The salt gradient layer makes an important role on HWSP. The experimentsinspected and analyzed the brine dynamical change after the heat exchanger isinstalled on the brine pool. The experiment shows that without the salt gradient layer,blending can speed up the brine warming, but at the same time due to the waterevaporation, sodium chloride, sulfate and alkali mineral in great quantities areseparated in advance for supersaturate precipitation, eventually the content of lithiumcarbonate mineral drops. The stability of salt gradient layer would raise the averagetemperature of the LCZ and change the grade of lithium carbonate mineral. Theexperiment also found that the thickness of the salt gradient layer takes great effect onheat preservation. The thicker the salt gradient layer is, the better effect of heatpreservation and higher the average temperature of brine on LCZ will be.
The general similarity and difference of lithium extraction on the fieldexperiment is researched and analyzed by comparing with50℃simulated the solarpond experiment. The experiments analyzed the amount of ion of brine in which lithium is extracted and found except Na~+, the amount of all ions drop, especially Li~+and CO_3~(2-)and discussed the irregular change of the amount of Na~+. Throughcomparing mineral identification of two experiments, the amount of carbonate oncrystal mineral precipitation by the field experiment is higher than that in simulatedexperiment.
The heat exchanger is the core component of HWSP. The surface type of heatexchanger is conducive to carry out the further experiments for HWSP. Therefore,according to the structural characteristics of the surface type heat exchanger,orthogonal experiment of L4(32) was used to examine and analyze the three factors ofimpacting the heat exchange efficiency. The three factors are the materials of heatexchangers, the shape of the heat exchange tube and the hot water flow rate in thepipeline. The experimental results show that the properties of thermal conductivity ofstainless steel are better than PERT material. The heating efficiency of spiral-typeheater exchanger is better than that of the U-type, but the difference is not significant.The flow rate of hot water on the heating tube also affects the efficiency of the heatexchanger. The quicker the flow rate is, the higher the heating efficiency will be. Atthe same time by the comparison and analysis of extreme value R in the orthogonalexperiment, the sequence of three factors impacting the heat exchanging efficiency is:the material factors> flow rate> the tube shape.
引文
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