CN110603339A - 使用纳滤软化锂盐水的方法 - Google Patents
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- 238000001728 nano-filtration Methods 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 20
- 239000012466 permeate Substances 0.000 claims abstract description 42
- 239000012267 brine Substances 0.000 claims abstract description 34
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 33
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 16
- 238000000638 solvent extraction Methods 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 32
- 229910052744 lithium Inorganic materials 0.000 claims description 32
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 8
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 abstract description 9
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 6
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 239000012465 retentate Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 101000720704 Homo sapiens Neuronal migration protein doublecortin Proteins 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 102100025929 Neuronal migration protein doublecortin Human genes 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- -1 underground brine Chemical compound 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
- B01D61/0271—Nanofiltration comprising multiple nanofiltration steps
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
锂盐水用多道次纳滤(NF)膜系统处理。将硫酸根加入到来自上游道次的渗透物，之后将来自上游道次的渗透物流过下游道次。任选，通过渗透物与硫酸或盐(例如硫酸钠)一起投配，可将硫酸根加入到渗透物中。随后可将经软化的盐水进一步加工，例如通过溶剂提取、电解、结晶和干燥的组合，以产生可用于制造电池的氢氧化锂产品。
Description
领域
本说明书涉及膜分离方法和软化盐水，特别是锂盐水。
背景
锂例如用于制造锂离子电池。全球约一半的锂从地下盐水提取。盐水的锂浓度可为约100-1,400 mg/L或更高。当前的商业盐水提取方法通常采用在大的池中蒸发，接着浸出或吸收，以从盐水提取锂。整个过程需要超过一年，并且只能回收盐水中约60%的锂。
提取锂的其他方法包括例如溶剂提取。溶剂提取方法描述于国际公开号WO 2013/065050，Process for Metal Ions Removal From Aqueous Solutions (用于从水溶液去除金属离子的方法)。用于锂盐水的溶剂提取系统由Tenova Bateman Technologies以LISX商标出售。在溶剂提取之前，将盐水软化以除去钙和镁离子。随后溶剂提取过程产生氯化锂溶液。后来通过电解将氯化锂溶液转化为氢氧化锂或溶液。随后使用结晶器浓缩氢氧化锂，以产生可用于制造电池的氢氧化锂水合物。
锂盐水可通过离子交换来软化。替代地，国际公开号WO 2015/177705，SelectiveSeparation Process (选择性分离方法)，描述了在亚渗透压下使用反渗透膜，以保留一部分钙和镁离子在盐水中，同时允许大多数锂离子通过，到达渗透物。
国际公开号WO 2014/089796，Method for Treating High Strength WastewaterSuch as RO Brine (用于处理高强度废水如RO盐水的方法)，描述了用纳滤膜单元处理高强度工业废水如反渗透盐水的系统和方法。
介绍
本说明书描述用于软化锂盐水的系统和方法。可开采锂盐水，即，地下的盐水。盐水可具有超过100 mg/L的锂浓度，和在15-35%范围内的总溶解固体(TDS)浓度。软化后，盐水可进一步处理以提取锂。例如，可用溶剂提取、电解、结晶和干燥的组合来处理盐水。
在本文所述的方法中，使锂盐水流过上游纳滤(NF)膜单元，以产生上游渗透物。将硫酸根加入到上游渗透物中。任选，通过将上游渗透物与硫酸或盐(例如硫酸钠)一起投配(dosing)，可将硫酸根加入到上游渗透物中。随后上游渗透物流过下游纳滤膜单元，以产生经软化的渗透物。在至少一些情况下，经软化的渗透物的钙浓度可为20 ppm或更小。在至少一些情况下，经软化的渗透物的镁浓度可为20 ppm或更小。在至少一些情况下，经软化的渗透物的钙和镁的合并组合或硬度浓度可为20 ppm或更小。
本文所述的系统具有带硫酸根投配系统的多道次纳滤(NF)膜系统。
附图简述
图1显示锂盐水处理系统的示意性工艺流程图。
详述
图1显示用于处理锂盐水12的锂盐水处理系统10。锂盐水12可具有下述的一个或多个：锂浓度超过100 mg/L；钠浓度超过20,000 mg/L；硫酸根浓度为5,000 mg/L或更高；且钙和镁的组合浓度为1000 mg/L或更高。处理系统10具有软化部分14、溶剂提取部分16、电解部分18以及结晶和干燥部分20。
软化部分14具有上游纳滤膜单元(NF单元) 22和下游NF单元24。任选，可存在与上游NF单元22或下游NF单元24中的一个或二者串联或并联的附加NF单元。每个NF单元22、24可具有多个NF膜模块。合适的NF模块的实例包括来自Osmonics的DK和DL模块或类似物。模块可具有例如平板或螺旋缠绕的膜。在到达软化部分之前，锂盐水12任选被预处理，例如通过过滤以除去悬浮的固体。
在多道次或串联构造中，使锂盐水12通过NF单元22、24，其中锂盐水12渗透至少两次，以产生经软化的盐水26。第一渗透物28离开上游NF单元22的渗透物侧，并进料到下游NF单元24。上游NF单元22产生上游保留物30，下游NF单元24产生下游保留物32。保留物30、32含有在锂盐水12中存在的大多数钙和镁离子以及其他被排斥的离子。可将保留物30、32进一步加工以回收另外的组分，或者可将其排出。例如，可将保留物30、32泵送回锂盐水从中抽出或结晶的盐湖。
NF膜主要排斥多价离子。因此，经软化的盐水26仍具有存在于锂盐水12中的锂的大多数。在每个道次(pass)中，相对于给水的渗透物回收率可为80-95%。
尽管NF膜排斥二价离子，但NF膜对阴离子比对阳离子可更具选择性。特别是，比起Ca2+和Mg2+离子，按比例更多的硫酸根离子(SO4 2-)被排斥。当给水的二价阴离子低时，二价阳离子的排斥进一步降低。不旨在受理论的限制，当给水中存在足够浓度的二价阴离子时，二价阴离子的优先排斥可通过静电吸引而促进二价阳离子的排斥。通常，NF膜的硬度去除可随给水的组成而变化。
比起镁和钙的组合浓度，锂盐水12倾向于具有更高浓度的硫酸根。因此，相对于锂盐水12，第一渗透物28具有显著降低的硬度。然而，第一渗透物28的硫酸根降低至甚至更大的程度。如果将第一渗透物28不改变地进料到第二NF单元24，则不太可能产生软化至期望水平的第二渗透物。
为了提高在第二NF单元24中的硬度排斥，将硫酸根34加入到第一渗透物28中。可例如在硫酸钠或硫酸的水溶液中提供硫酸根。第二NF单元24的硬度去除效率可提高至98%或更高。以一定量将硫酸根加入到第一渗透物28中，该量足以使硫酸根离子的摩尔浓度近似等于例如Ca2+和Mg2+离子的摩尔浓度之和的至少70%或更多。提供较高的硫酸根浓度，例如，硫酸根与硬度离子的接近1:1摩尔比，对于高TDS水(如锂盐水)提供有限的改进。当通过投配硫酸根使得硫酸根离子的摩尔浓度为Ca2+和Mg2+离子的摩尔浓度之和的至少70%但小于80%来加工锂盐水时，可以较少的硫酸根消耗实现良好的硬度排斥。所得到的经软化的盐水26的钙或镁或二者的浓度可为20 ppm或更低。经软化的盐水26的钙和镁的合并组合或硬度浓度也可为20 ppm或更低。
任选，经软化的盐水26可在精制单元36中进一步处理。精制单元36可为石灰或苏打软化剂。在这种情况下，精制单元36包括用于接收经软化的盐水26的混合罐。将沉淀剂38，例如苏打(碳酸钠，Na2CO3)、石灰(氢氧化钙Ca(OH)2)、或者石灰或苏打与NaOH的组合投配至罐中，并与经软化的盐水26混合。如果需要，在精制单元36中使用NaOH以产生约10-11的pH。比起石灰，优选苏打。在精制单元36中，沉淀剂38与经软化的盐水26中的硬度反应，以产生包含碳酸钙的沉淀物。分离出沉淀物，以产生精制的盐水40。例如，可用孔径为约10微米或更小，优选2微米或更小的微滤器过滤出沉淀物。
将精制的盐水40送至溶剂提取部分16。溶剂提取部分16具有锂提取单元42、洗涤单元44和汽提单元46。溶剂通过这三个单元再循环。经汽提的溶剂48从汽提单元46再循环到锂提取单元42。负荷溶剂50在锂提取单元42中产生并流向洗涤单元44。经纯化的溶剂52从洗涤单元44流向汽提单元46。将洗涤溶液58加入到洗涤单元44。在所示的实例中，将精制的盐水40与从洗涤单元44流向锂提取单元42的废洗涤液56混合。从锂提取单元42抽出提余液60。汽提单元46排出氯化锂溶液54。任选，溶剂提取部分16可为由Tenova BatemanTechnologies以LISX商标出售的商业系统。
使氯化锂溶液54流向电解部分18。硫酸氢盐溶液62从电解部分18流回到溶剂提取部分16的汽提单元46。氢氧化锂64通过电解产生，并流向结晶和干燥部分20。结晶和干燥部分产生氢氧化锂水合物66和水68。将水68返回到电解部分18。氢氧化锂水合物66为可用于制造锂离子电池的产品。任选，电解部分18以及结晶和干燥部分20可为由Tenova BatemanTechnologies以LIEL商标出售的商业系统。
实施例
对示例性多道次纳滤系统建立模型。假定给水具有钙、镁、硫酸根和锂的下示浓度，分别如下：121、3907、6051和354 mg/L。进水还具有其他组分，例如89026 mg/L的钠，以代表在智利开采的锂盐水。第一道次渗透物的钙、镁、硫酸根和锂的浓度如下：31、467、91和354 mg/l。在有和没有硫酸根加入到第一道次渗透物的情况下，对第二道次建立模型。在没有硫酸根加入的情况下，第二道次渗透物的钙、镁、硫酸根和锂的浓度如下：7.71、80.42、1.14、354 mg/l。在有1550 mg/L硫酸根加入到第一道次渗透物的情况下，第二道次渗透物的钙、镁、硫酸根和锂的浓度如下：7.96、18.83、22.89和354 mg/l。
本书面描述使用实例来公开本发明，包括最佳模式，并且还使任何本领域技术人员能够实践本发明，包括制造和使用任何装置或系统以及执行任何结合的方法。本发明的可取得专利的范围由权利要求书限定，并且可包括本领域技术人员想到的其他实例。如果这样的其他实例具有与权利要求书的字面语言没有不同的结构要素，或者如果它们包括与权利要求书的字面语言无实质差异的等同结构要素，则它们旨在处于权利要求书的范围内。
Claims (7)
1.一种锂盐水处理系统，包含：
a) 上游纳滤膜单元；
b) 下游纳滤膜单元；和，
c) 硫酸根投配系统，
其中所述上游纳滤系统的渗透物出口与所述下游纳滤单元的进料入口连接，并且所述硫酸根投配系统在所述上游纳滤单元和所述下游纳滤单元之间连接。
2.一种软化锂盐水的方法，包括以下步骤：
a) 使锂盐水流向纳滤膜单元中，以产生第一渗透物；
b) 将硫酸根加入到所述第一渗透物中；和，
c) 使所述第一渗透物流向另一个纳滤膜单元，以产生经软化的渗透物。
3.权利要求2的方法，其中在步骤b)中，将一定量的硫酸根加入到第一渗透物中，使得在第一渗透物中硫酸根离子的摩尔浓度为在第一渗透物中Ca2+和Mg2+的摩尔浓度之和的70%或更高。
4.权利要求2的方法，其中通过将硫酸钠或硫酸的水溶液加入到第一渗透物中，来将硫酸根加入到第一渗透物中。
5.权利要求2的方法，其中通过溶剂提取来处理所述第一渗透物，以产生硫酸锂。
6.权利要求3的方法，其中将所述量的硫酸根加入到第一渗透物中，使得在第一渗透物中硫酸根离子的摩尔浓度小于在第一渗透物中Ca2+和Mg2+的摩尔浓度之和的80%。
7.权利要求2的方法，其中所述锂盐水的总溶解固体浓度为15-35%。
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