CN102348817B - 提纯碳酸氢锂的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 41
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 title claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000005342 ion exchange Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 230000008929 regeneration Effects 0.000 claims abstract description 9
- 238000011069 regeneration method Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 24
- 229910052744 lithium Inorganic materials 0.000 claims description 24
- 239000011734 sodium Substances 0.000 claims description 16
- 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 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
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- 238000000746 purification Methods 0.000 abstract description 5
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 2
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- 239000011575 calcium Substances 0.000 description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
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- 229910001947 lithium oxide Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
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- 229910052742 iron Inorganic materials 0.000 description 3
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- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
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- 229920001429 chelating resin Polymers 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
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- 230000001172 regenerating effect Effects 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001466077 Salina Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- -1 aluminum ion Chemical class 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical compound OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
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- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
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- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
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- B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
- B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
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Abstract
本发明涉及一种利用阳离子交换树脂对不纯的碳酸氢锂进行提纯的方法。除了利用离子交换对溶液进行提纯之外，所述处理阶段还包括对与所述树脂结合的杂质金属进行再生。所述再生由以下过程组成：利用水对所述树脂进行洗涤、利用酸溶液进行洗脱、利用水进行洗涤、利用碱溶液进行中和以及利用水进行洗涤。所述方法的特征在于，利用氢氧化钠溶液进行中和。
Description
技术领域
本发明涉及使用离子交换对碳酸氢锂溶液进行提纯的方法。碳酸氢锂溶液的提纯形成了制造纯锂化学品中的子方法。
发明背景
含锂的矿物主要为锂辉石、透锂长石和锂云母。另外，在盐水湖的下层滞水带中也存在锂，但是在所述下层滞水带中锂与镁的比例对于工业应用是决定性的。同样地，在海水中也存在锂。目前，锂的最大用户是玻璃和陶瓷工业、以及蓄电池和电池工业。后者的份额一直在增大，因为锂蓄电池例如在开发电动汽车中发挥着重要的作用。将某些锂用作碳酸锂或者某些锂至少是工业中间产物。
在锂的回收中，对锂矿物进行浓缩，其后，浓缩物的加工通常包括在高温下晶体结构发生改变、加压浸出、二氧化碳处理、以及对所产生的碳酸氢锂LiHCO3进行过滤和提纯。能够根据液-液萃取原理或通过离子交换进行提纯。美国专利公布6048507描述了一种方法，其中通过二氧化碳处理和离子交换对碳酸氢锂进行提纯。离子交换的目的是从含锂溶液中除去二价金属离子例如钙、镁、铁和铝离子。其后，对纯碳酸氢锂进行结晶，从而产生纯的碳酸锂Li2CO3。
典型地，利用选择性阳离子交换树脂实施离子交换，其中所述离子交换基团为例如亚氨二乙酸(IDA)或氨基膦酸(APA)。例如，利用Rohm & Haas下的商品名称Amberlite IRC 748(IDA)和Amberlite IRC 747(APA)的产品来制造所涉及的树脂。所述树脂对多价金属离子具有选择性并可用于在氯碱工业中从浓缩的NaCl盐溶液中除去钙和镁等。所述树脂的离子交换基团是弱有机酸。所述树脂对重金属离子(Cu2+、Pb2+、Ni2+)具有特殊的选择性。在柱法中，需要提纯的溶液通过柱并从离开所述柱的溶液中收集提纯的溶液。当树脂不能再制造纯溶液时，利用酸溶液对与树脂结合的金属进行洗脱，并将所述树脂转换成酸型。必须使用相对于离子交换基团来说过量的酸。在酸型中，离子交换基团在水溶液中未离解且不能与金属离子结合；相反，其在进入下列提纯循环之前必须被中和。
通常将选择性阳离子交换树脂用于从例如废水和酸洗溶液中回收金属且所回收的金属通常为上面提到的重金属例如铜、镍和铅。在此情况中，通常根据下列顺序对树脂进行再生；
利用水进行洗涤，以在酸阶段与碱阶段之间从树脂柱中置换在先溶液。
美国专利公布6048507描述了通过离子交换对碳酸氢锂溶液进行提纯，其中将金属杂质、特别是二价金属杂质与所使用的树脂结合。当树脂例如相对于钙饱和时，对其进行再生。再生由以下过程组成：首先用水进行洗涤并随后利用盐酸进行处理以从树脂中将钙离子除去。当已经从树脂中将钙离子或其他金属离子除去时，再次用水对其进行洗涤。在下列提纯循环之前，将氢氧化锂溶液用于用碱再生。根据专利的上下文，在必须进行更换之前，所使用的氢氧化锂溶液和盐酸溶液两者都可以多次使用。
发明目的
在根据现有技术的方法中，相当量的锂损失到再生化学品中。另外，氢氧化锂和盐酸是昂贵的试剂。特别地，用于离子交换树脂的再生的大部分(估计超过95％)氢氧化锂转移到不纯的盐酸溶液中。如上所述，能够将盐酸溶液在洗脱中循环且利用电渗析也能够将所述酸再生。然而，在盐酸应用中再生方法和设备材料通常价格昂贵。现在开发本发明的目的是获得比先前提纯碳酸氢锂更成本有效的方法。
发明概述
在附属的权利要求书中，使得本发明的基本特征变得清楚。
本发明涉及在柱中利用阳离子交换树脂对不纯的碳酸氢锂进行提纯的方法。除了利用离子交换对溶液进行提纯之外，所述处理阶段还包括对与树脂结合的杂质金属进行再生。再生由以下过程组成：利用水对树脂进行洗涤、利用酸溶液进行洗脱、利用水进行洗涤、利用碱溶液进行中和以及利用水进行洗涤。所述方法的特征在于，利用氢氧化钠溶液进行中和。
根据所述方法的一个实施方案，利用硫酸溶液进行洗脱。
根据所述方法的另一个实施方案，利用盐酸溶液进行洗脱。
在所述方法的实施方案中，用于中和的所述氢氧化钠溶液的浓度为0.5～2mol/l。
在所述方法的实施方案中，用于洗脱的所述酸溶液的浓度为0.5～2mol/l。
根据所述方法的一个典型实施方案，首先单独提取在利用氢氧化钠进行中和之后所实施的溶液提纯阶段中的第一溶液部分，并在所述阶段末尾在再生之前将其返回所述柱中，其中所供应的溶液的钠至少部分地取代与树脂结合的锂。所述第一部分的体积优选为树脂床大小的约两倍。
附图详述
通过作为柱法的离子交换，对碳酸氢锂溶液进行提纯。所述方法特别开发了树脂的选择性顺序：Li+＜Na+＜＜多价金属离子＜H+。在根据本发明的方法中，将氢氧化钠用作树脂中和中的碱，而不是氢氧化锂溶液，即，所述树脂最初处于钠型。源自LiHCO3溶液的金属杂质(例如Fe、Ca、Mg、Al)自身与树脂结合。在离子交换循环一开始时，钠型树脂与浓锂溶液寻求平衡，由此在产物溶液中Li的含量下降而Na的含量升高。
从离开所述柱的溶液中单独提取含NaHCO3的第一部分。该第一部分的体积为树脂床大小的约两倍。其后，从所述柱中得到产物溶液，其中在离子交换期间锂和钠的含量几乎保持在进料水平上。在处理溶液的进料之后，在实际再生之前，将开始时收集的富集NaHCO3的部分循环回所述柱中。以此方式，钠置换与树脂结合的锂的大部分，且在离开所述柱的溶液中锂的含量高。能够将这种溶液与最易于进行离子交换进料的方法相结合。在根据本发明的方法中，与现有技术所述的方法相比，离子交换的锂损失大大下降，在现有技术中将树脂中和为锂的形式。在实际的离子交换阶段之后，对树脂进行再生，其中第一步骤是利用酸溶液对金属进行洗脱。
现在开发的方法的优势在于，当树脂用尽或被杂质金属填充时，其大部分仍处于最初的中和形式，即处于根据本发明的钠型。所述树脂绝不会充满杂质。当树脂进入洗脱阶段时，所有与其结合的金属，包括Li/Na，在酸中释放出去并结束，其与酸的分离要求相对昂贵的分离方法。因此，在酸中的该部分是废物或难以利用，即为了回收钠或锂，例如，需要电渗析。因此，根据现在开发的方法，除了要除去的杂质之外，进入洗脱的树脂仅含有钠，不含锂。当酸必须作为废物排出时，将其仅与相对廉价的钠一起从所述工艺中除去，而不是有价值的锂。
利用酸溶液完成从树脂洗脱金属，由此根据所述方法，有利地是使用具有约0.5～2mol/l、优选1mol/l的硫酸溶液，而不是盐酸。在根据现有技术的方法中，就我们所知，利用盐酸进行洗脱，因为其可阻止钙作为石膏而沉淀。然而，在所实施的试验中，已经发现，杂质金属均匀分布在树脂块中，因此未观察到钙作为石膏在树脂中发生沉淀，至少钙的量小于10mg/L时未观察到。已经发现，在洗脱中已经将所有的钙从树脂中除去。有可能利用石灰石对有利地使用的硫酸进行中和，由此也将其他杂质金属沉淀入石膏沉淀物中。使用硫酸作为所述酸比使用盐酸更简单，因为所使用的设备不必为如同使用盐酸中所需要的特殊材料。在洗脱之后，利用水对树脂进行洗涤并在下列提纯循环之前利用0.5～2mol/l、优选1mol/l的氢氧化钠溶液将其中和为钠型。
如果待提纯的溶液含有大量的钙，则还可能使用盐酸溶液进行洗脱。
通过结晶，换言之，通过将溶液加热至70～90℃，从提纯的溶液中产生碳酸锂，由此放出二氧化碳且碳酸锂产物发生结晶。对沉淀物进行过滤并干燥。为了降低产物的钠含量并除去其他水溶性杂质，利用热水对所述沉淀物进行洗涤并再次过滤。
能够将用于提纯上述碳酸锂溶液的方法用作从矿物源的原料如锂辉石中生产碳酸锂的工艺的一部分。还可将其用于不纯碳酸锂的提纯工艺。利用所述方法能够制造＞99.9％的纯碳酸锂，且能够对其进一步提纯并转化成其它纯的锂化学品(如LiCl、LiF)。
在所进行的试验中，已经发现，当根据本发明的方式从锂辉石浓缩物中生产碳酸锂时，产物的杂质为例如下列水平：Pb＜1ppm、Mg和Fe＜5ppm、S＜10ppm、Ca＜20ppm、以及Al为12ppm且Na为57ppm。具有＞99.9％的含量的碳酸锂是工业级产品或电池级产品。
Claims (6)
1.一种在柱中利用阳离子交换树脂对不纯的碳酸氢锂进行提纯的方法，由此，除了通过离子交换对溶液进行提纯之外，所述方法还包括除去与树脂结合的杂质金属，所述除去包括利用水对所述树脂进行洗涤、利用酸溶液进行洗脱、利用水进行洗涤、利用碱溶液进行中和以及利用水进行洗涤，其特征在于，利用氢氧化钠溶液进行中和，且首先单独提取在利用氢氧化钠溶液进行中和之后所实施的溶液提纯阶段中的第一溶液部分，并在所述阶段末尾在再生之前将其返回所述柱中，其中所供应的溶液的钠至少部分地取代与所述树脂结合的锂。
2.权利要求1所述的方法，其特征在于利用硫酸溶液进行洗脱。
3.权利要求1所述的方法，其特征在于利用盐酸溶液进行洗脱。
4.权利要求1所述的方法，其特征在于用于中和的所述氢氧化钠溶液的浓度为0.5～2mol/l。
5.权利要求1所述的方法，其特征在于用于洗脱的所述酸溶液的浓度为0.5～2mol/l。
6.权利要求1所述的方法，其特征在于所述第一溶液部分的体积为树脂床大小的约两倍。
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Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8936770B2 (en) | 2010-01-22 | 2015-01-20 | Molycorp Minerals, Llc | Hydrometallurgical process and method for recovering metals |
| AU2011376865A1 (en) | 2011-09-15 | 2013-05-02 | Orocobre Limited | Process for producing lithium carbonate from concentrated lithium brine |
| AU2013237292B2 (en) * | 2012-03-19 | 2015-09-10 | Outotec (Finland) Oy | Method for recovering lithium carbonate |
| DK3824991T3 (da) | 2012-04-23 | 2022-10-31 | Nemaska Lithium Inc | Fremgangsmåde til forberedelse af lithiumsulfat |
| AU2013270412C1 (en) | 2012-05-30 | 2017-04-06 | Nemaska Lithium Inc. | Processes for preparing lithium carbonate |
| PL2971252T3 (pl) | 2013-03-15 | 2021-07-12 | Nemaska Lithium Inc. | Procesy dla sporządzania wodorotlenku litu |
| RU2564806C2 (ru) * | 2013-08-28 | 2015-10-10 | Общество с ограниченной ответственностью "Экостар-Наутех" (ООО"Экостар-Наутех") | Способ получения ультрачистого карбоната лития из технического карбоната лития и установка для его осуществления |
| KR102445712B1 (ko) | 2013-10-23 | 2022-09-20 | 네마스카 리튬 인코포레이션 | 리튬 카보네이트의 제조방법 |
| CN106103806B (zh) | 2014-02-24 | 2019-07-12 | 内玛斯卡锂业有限公司 | 处理含锂材料的方法 |
| FI127782B (en) | 2014-12-02 | 2019-02-15 | Keliber Oy | A process for the production of lithium metal phosphates |
| CA2996651C (en) | 2015-08-27 | 2021-06-01 | Nemaska Lithium Inc. | Method for preparing lithium hydroxide and lithium sulfate monohydrate using hydrogen depolarized anode |
| CN105347364A (zh) * | 2015-10-30 | 2016-02-24 | 华陆工程科技有限责任公司 | 一种碳酸锂生产中沉锂母液闭环回收的方法 |
| FI128092B (en) | 2016-06-01 | 2019-09-13 | Keliber Oy | Process for the preparation of non-conductive lithium metal phosphates |
| CA2940509A1 (en) | 2016-08-26 | 2018-02-26 | Nemaska Lithium Inc. | Processes for treating aqueous compositions comprising lithium sulfate and sulfuric acid |
| CN107777712A (zh) * | 2016-08-27 | 2018-03-09 | 湖南金源新材料股份有限公司 | 用粗制氟化锂制取工业级碳酸锂的方法及碳酸锂产品 |
| KR20190072667A (ko) | 2016-11-14 | 2019-06-25 | 리락 솔루션즈, 인크. | 코팅된 이온 교환 입자를 이용한 리튬 추출 |
| CN106892443B (zh) * | 2017-03-30 | 2019-03-15 | 山西北斗星新材料有限公司 | 利用离子交换法制取高纯碳酸锂的工艺方法 |
| EP3661619A4 (en) | 2017-08-02 | 2021-05-05 | Lilac Solutions, Inc. | LITHIUM EXTRACTION WITH POROUS ION EXCHANGE BEADS |
| CA3083136C (en) | 2017-11-22 | 2022-04-12 | Nemaska Lithium Inc. | Processes for preparing hydroxides and oxides of various metals and derivatives thereof |
| JP7427598B2 (ja) | 2018-02-28 | 2024-02-05 | ライラック ソリューションズ，インク． | リチウム抽出用の粒子トラップを備えたイオン交換反応器 |
| KR20220119166A (ko) | 2020-01-09 | 2022-08-26 | 리락 솔루션즈, 인크. | 바람직하지 않은 금속의 분리 방법 |
| EP4090461A1 (en) * | 2020-01-17 | 2022-11-23 | BL Technologies, Inc. | Ion exchange system and method for conversion of aqueous lithium solution |
| EP4162087A1 (en) | 2020-06-09 | 2023-04-12 | Lilac Solutions, Inc. | Lithium extraction in the presence of scalants |
| CA3199218A1 (en) | 2020-11-20 | 2022-05-27 | David Henry SNYDACKER | Lithium production with volatile acid |
| CN112717468A (zh) * | 2020-12-09 | 2021-04-30 | 西安蓝晓科技新材料股份有限公司 | 一种用于沉锂母液中锂回收的方法 |
| WO2022226219A1 (en) | 2021-04-23 | 2022-10-27 | Lilac Solutions, Inc. | Ion exchange devices for lithium extraction |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5419819A (en) * | 1994-03-17 | 1995-05-30 | The United States Of America As Represented By The United States Department Of Energy | Self-regenerating column chromatography |
| CN1172462A (zh) * | 1995-09-01 | 1998-02-04 | 水泽化学工业株式会社 | 碱金属铝配合氢氧化物碳酸盐、和生产该盐的方法及其应用 |
| WO1999029624A1 (en) * | 1997-12-09 | 1999-06-17 | Limtech | Process for the purification of lithium carbonate |
| US6120927A (en) * | 1998-03-17 | 2000-09-19 | Kabushiki Kaisha Toshiba | Method of recovering lithium from batteries |
| US6592832B1 (en) * | 1998-03-05 | 2003-07-15 | Basf Aktiengesellschaft | Method for producing highly pure lithium salts |
| CN1686805A (zh) * | 2005-06-22 | 2005-10-26 | 广州锐鑫锂能新材料科技有限公司 | 工业级氢氧化锂生产高纯高清氢氧化锂的提纯生产技术 |
| CN101177288A (zh) * | 2007-10-30 | 2008-05-14 | 中国科学院青海盐湖研究所 | 一种利用盐湖锂资源制取高纯碳酸锂的工艺方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5451383A (en) * | 1993-12-23 | 1995-09-19 | Praxair Technology, Inc. | Lithium recovery |
| FR2743798B1 (fr) * | 1996-01-18 | 1998-02-27 | Air Liquide | Procede de purification d'une solution de sels de lithium contaminee par des cations metalliques et utilisation de ce procede dans la fabrication de zeolites echangees au lithium |
| CN1124985C (zh) | 2000-03-13 | 2003-10-22 | 南京大学 | 2－羟基－3－萘甲酸生产废水的治理和资源回收利用方法 |
| US6514414B1 (en) * | 2000-09-08 | 2003-02-04 | Clariant Finance (Bvi) Limited | Process for separation and removal of iron ions from basic zinc solution |
| RU2243157C2 (ru) * | 2003-02-11 | 2004-12-27 | Открытое акционерное общество "Новосибирский завод химконцентратов" | Способ получения особочистого карбоната лития |
-
2009
- 2009-03-11 FI FI20090090A patent/FI121785B/fi active IP Right Grant
-
2010
- 2010-03-01 PT PT2010050158A patent/PT2010103173W/pt unknown
- 2010-03-01 EA EA201190148A patent/EA019279B9/ru not_active IP Right Cessation
- 2010-03-01 BR BRPI1009523-3A patent/BRPI1009523B1/pt active IP Right Grant
- 2010-03-01 ES ES201150014A patent/ES2379423B1/es active Active
- 2010-03-01 CA CA2755123A patent/CA2755123C/en active Active
- 2010-03-01 AU AU2010223194A patent/AU2010223194B2/en active Active
- 2010-03-01 CN CN201080011083.4A patent/CN102348817B/zh active Active
- 2010-03-01 WO PCT/FI2010/050158 patent/WO2010103173A1/en active Application Filing
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- 2010-03-10 AR ARP100100727A patent/AR075734A1/es active IP Right Grant
-
2011
- 2011-09-09 CL CL2011002230A patent/CL2011002230A1/es unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5419819A (en) * | 1994-03-17 | 1995-05-30 | The United States Of America As Represented By The United States Department Of Energy | Self-regenerating column chromatography |
| CN1172462A (zh) * | 1995-09-01 | 1998-02-04 | 水泽化学工业株式会社 | 碱金属铝配合氢氧化物碳酸盐、和生产该盐的方法及其应用 |
| WO1999029624A1 (en) * | 1997-12-09 | 1999-06-17 | Limtech | Process for the purification of lithium carbonate |
| US6592832B1 (en) * | 1998-03-05 | 2003-07-15 | Basf Aktiengesellschaft | Method for producing highly pure lithium salts |
| US6120927A (en) * | 1998-03-17 | 2000-09-19 | Kabushiki Kaisha Toshiba | Method of recovering lithium from batteries |
| CN1686805A (zh) * | 2005-06-22 | 2005-10-26 | 广州锐鑫锂能新材料科技有限公司 | 工业级氢氧化锂生产高纯高清氢氧化锂的提纯生产技术 |
| CN101177288A (zh) * | 2007-10-30 | 2008-05-14 | 中国科学院青海盐湖研究所 | 一种利用盐湖锂资源制取高纯碳酸锂的工艺方法 |
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| ES2379423B1 (es) | 2013-01-24 |
| BRPI1009523A2 (pt) | 2016-03-15 |
| CA2755123C (en) | 2016-08-23 |
| EA201190148A1 (ru) | 2012-03-30 |
| BRPI1009523B1 (pt) | 2017-08-01 |
| FI20090090A0 (fi) | 2009-03-11 |
| US20110318253A1 (en) | 2011-12-29 |
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| ES2379423A1 (es) | 2012-04-26 |
| CL2011002230A1 (es) | 2012-02-17 |
| FI20090090A (fi) | 2010-09-12 |
| EA019279B9 (ru) | 2014-06-30 |
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| FI121785B (fi) | 2011-04-15 |
| PT2010103173W (pt) | 2014-08-11 |
| AU2010223194A1 (en) | 2011-09-08 |
| EA019279B1 (ru) | 2014-02-28 |
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| AR075734A1 (es) | 2011-04-20 |
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