CN113846219B - 一种从废旧锂电池中提取锂的方法 - Google Patents
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002699 waste material Substances 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 27
- 238000002386 leaching Methods 0.000 claims abstract description 27
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical group [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 12
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- 229910017052 cobalt Inorganic materials 0.000 abstract description 9
- 239000010941 cobalt Substances 0.000 abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- -1 finally Chemical compound 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 3
- 238000005507 spraying Methods 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 238000011084 recovery Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000002893 slag Substances 0.000 description 4
- 239000010926 waste battery Substances 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 3
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
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- 230000001376 precipitating effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
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- C—CHEMISTRY; METALLURGY
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- C22B23/04—Obtaining nickel or cobalt by wet processes
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- C22B23/043—Sulfurated acids or salts thereof
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- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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Abstract
本发明公开了一种从废旧锂电池中提取锂的方法,将废旧锂电池的正极粉置于盐酸中进行浸出,过滤得浸出液,浸出液除去铜和铁,再通入硫化氢气体进行反应,固液分离得到第一滤渣和第一滤液,向第一滤液中加入高锰酸钾,固液分离得到第二滤渣和第二滤液,对第二滤液进行喷雾热解,得到固体颗粒,对固体颗粒进行水洗得到洗液,喷雾热解产生的尾气经水淋收集后与洗液混合得到锂盐溶液。本发明通过盐酸浸出正极粉,获得盐酸浸出液,再依次去除浸出液中的铜、铁杂质后,采用硫化氢沉淀镍钴,加入高锰酸钾,使锰离子沉淀,生成二氧化锰,最后经喷雾热解使溶液中的铝镁转化为氧化物,并分离出锂盐,整个反应过程,无需有机溶剂萃取,降低了锂的损失。
Description
技术领域
本发明属于锂电池回收技术领域,具体涉及一种从废旧锂电池中提取锂的方法。
背景技术
三元锂离子电池由于其安全性好、能量密度高、环保和良好的电化学性能等特点,广泛应用在电子产品、移动电源以及新能源汽车领域。然而其经过多次循环充放电后,电池中的活性物质就会失去活性,导致电池的容量下降而使电池报废。随着锂离子电池的广泛使用势必带来大量的废旧电池,如若对其随意丢弃不仅会对环境造成严重污染,同时正极材料中含有多种贵重及稀缺金属比如镍、钴、锂等。其中,Ni和Co元素是价值较高的有色金属,Ni元素的价格最高时可达40万元/吨,钴价也水涨船高达到37万元/吨,可以说废旧锂离子电池回收不仅仅绿色环保,还有丰厚的回报。因此,从环境保护和资源回收利用的角度来看,选择合适的方法处理废电池至关重要。
目前,针对废旧锂离子电池中有价金属的回收已经做了很多研究,较为传统的回收办法是采用酸浸工艺,首先需要对废旧锂离子电池进行拆解获取正极粉末,然后利用强酸浸出有价金属,利用氧化剂如H2O2,还原剂Na2SO3进行处理,再对溶液进行纯化后,利用溶液萃取的工艺获取纯的Ni、Co和Mn盐溶液。最后,通过元素分离回收金属或按比例加入一定量的硫酸镍、硫酸钴和硫酸锰溶液,组成再生正极材料前驱体的母液。虽然该方法工艺简单,但是效率却非常低,并且会产生大量的废水,对环境造成污染,还存在Li回收率低的问题。另一方面,电池材料对杂质含量要求很高,废锂离子电池中含有铁、铝、铜、镁等元素,在回收电池中的有价金属过程中需对浸出液进行净化。目前,多采用逐一分离回收金属的方法,流程较长、成本高,且萃取剂对锂都有萃取能力,进而降低了锂的回收率。若浸出液直接去做正极材料前驱体,则不能考虑锂的回收。因此,在保证镍、钴、锰完全回收的前提下,需要同时提高锂的回收率。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种从废旧锂电池中提取锂的方法。
根据本发明的一个方面,提出了一种从废旧锂电池中提取锂的方法,包括以下步骤:
S1:将废旧锂电池的正极粉置于盐酸中进行浸出,过滤得浸出液;
S2:所述浸出液除去铜和铁,再通入硫化氢气体进行反应,固液分离得到第一滤渣和第一滤液;
S3:向所述第一滤液中加入高锰酸钾,固液分离得到第二滤渣和第二滤液;
S4:对所述第二滤液进行喷雾热解,得到固体颗粒,对所述固体颗粒进行水洗得到洗液,喷雾热解产生的尾气经水淋收集后与所述洗液混合得到锂盐溶液。
在本发明的一些实施方式中,步骤S1中,所述盐酸的浓度为1.0-6.0mol/L,正极粉与盐酸的固液比为100-250g/L。
在本发明的一些实施方式中,步骤S1中,还加入过氧化氢参与浸出。可以提高浸出率。
在本发明的一些实施方式中,步骤S2中,所述除去铜和铁的过程为:向浸出液中加入铁粉进行置换反应,待反应结束后加入氧化剂并调节pH至3.5-4.0,固液分离除去铜铁渣。
在本发明的一些优选的实施方式中,步骤S2中,所述铁粉的加入量与浸出液中铜离子的含量的摩尔比为(1.0-1.1):1。
在本发明的一些优选的实施方式中,步骤S2中,所述调节pH采用碳酸钙。碳酸钙价格便宜,调节pH的同时还可以除去氟离子和磷酸根。
在本发明的一些优选的实施方式中,步骤S2中,所述氧化剂为氯气、过氧化氢或硝酸中的一种或多种。
在本发明的一些实施方式中,步骤S2中,所述硫化氢的压力为200-300kPa;优选的,通入硫化氢气体进行反应的温度为65-125℃。
在本发明的一些实施方式中,步骤S2中,所述第一滤渣为硫化镍钴沉淀,硫化镍钴沉淀经硫酸溶解后可得硫酸镍和硫酸钴溶液,可作为前驱体溶液。
在本发明的一些实施方式中,步骤S3中,所述高锰酸钾采用滴定的方式加入,直至不再产生沉淀。
在本发明的一些实施方式中,步骤S4中,所述喷雾热解的温度为600-1350℃,载气压力为0.1-0.3MPa。
在本发明的一些实施方式中,步骤S4中,向所述锂盐溶液中加入碳酸盐进行反应,得到碳酸锂沉淀;优选地,所述反应的温度为80-95℃。碳酸锂作为正极材料的锂源使用。进一步地,碳酸锂沉淀还进行精制提纯。
根据本发明的一种优选的实施方式,至少具有以下有益效果:
1、本发明通过盐酸浸出废旧电池正极粉,获得盐酸浸出液,再依次去除浸出液中的铜、铁杂质后,采用硫化氢沉淀镍钴,再加入高锰酸钾,使锰离子沉淀,生成二氧化锰,最后经喷雾热解使溶液中的铝镁转化为氧化物,并分离出锂盐,整个反应过程,无需有机溶剂萃取,降低了锂的损失。为保证后续喷雾热解的顺利进行,本发明选用盐酸浸出正极粉,由于浸出液中含有镁、铝,一般的有机萃取剂无法进行分离,故选用硫化氢沉淀镍钴,高锰酸钾氧化锰离子制备二氧化锰,最后采用喷雾热解,利用氯化氢和氯化锂易挥发的特点,氯化铝、氯化镁则热分解为氧化物从而分离出来。
2、本发明工艺流程短、生产成本低,省去了有机溶剂的萃取工艺,避免了锂的损耗,提升了浸出液中锂的收率。
附图说明
下面结合附图和实施例对本发明做进一步的说明,其中:
图1为本发明实施例1的工艺流程示意图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
一种从废旧锂电池中提取锂的方法,参照图1,具体过程为:
(1)浸出:将100g废旧锂电池正极粉放入1L浓度为6.0mol/L盐酸中,并加入100mL的过氧化氢浸出5h,反应完成后,过滤得到浸出液和炭黑渣;
检测浸出液:
(2)还原置换:向步骤(1)所得浸出液中加入铁粉,铁粉的加入量与浸出液中铜离子的含量的摩尔比为1.1:1;
(3)氧化水解:步骤(2)反应结束后,加入氯气并加入碳酸钙调节pH为3.5-4.0,固液分离后,得到铜铁渣和滤液;
(4)镍钴沉降:在温度为65-70℃下,向步骤(3)所得滤液中通入压力为200kPa的硫化氢气体至镍钴完全沉淀,固液分离后,分别制得硫化镍钴沉淀和富锂滤液;
(5)氧化滴定:向步骤(4)所得富锂滤液中滴定加入高锰酸钾,直至不再产生沉淀(即搅拌后溶液不再变为无色),分离出二氧化锰沉淀;
(6)喷雾热解:将步骤(5)剩余的滤液进行喷雾热解,控制喷雾热解温度为600-700℃,载气压力为0.1MPa,制得氧化物固体颗粒;
(7)水沉收锂:将步骤(6)喷雾热解产生的氧化物进行水洗得到洗液,喷雾热解产生的尾气经水淋收集后与洗液混合制得锂盐溶液;
(8)在温度为80-95℃下,向锂盐溶液中加入碳酸盐,分离得到的沉淀即为碳酸锂。碳酸锂经过精制提纯后可以得到纯净的碳酸锂。
称量精制后碳酸锂的质量为31.50g,计算得到锂的收率为98.47%。
实施例2
一种从废旧锂电池中提取锂的方法,具体过程为:
(1)浸出:将100g废旧锂电池正极粉放入0.5L浓度为3.0mol/L盐酸中,并加入800mL的过氧化氢浸出6h,反应完成后,过滤得到浸出液和炭黑渣;
检测浸出液:
(2)还原置换:向步骤(1)所得浸出液中加入铁粉,铁粉的加入量与浸出液中铜离子的含量的摩尔比为1.05:1;
(3)氧化水解:步骤(2)反应结束后,加入过氧化氢并加入碳酸钙调节pH为3.5-4.0,固液分离后,得到铜铁渣和滤液;
(4)镍钴沉降:在温度为80-90℃下,向步骤(3)所得滤液中通入压力为300kPa的硫化氢气体至镍钴完全沉淀,固液分离后,分别制得硫化镍钴沉淀和富锂滤液;
(5)氧化滴定:向步骤(4)所得富锂滤液中滴定加入高锰酸钾,直至不再产生沉淀(即搅拌后溶液不再变为无色),分离出二氧化锰沉淀;
(6)喷雾热解:将步骤(5)剩余的滤液进行喷雾热解,控制喷雾热解温度为800-900℃,载气压力为0.2MPa,制得氧化物固体颗粒;
(7)水沉收锂:将步骤(6)喷雾热解产生的氧化物进行水洗得到洗液,喷雾热解产生的尾气经水淋收集后与洗液混合制得锂盐溶液;
(8)在温度为80-95℃下,向锂盐溶液中加入碳酸盐,分离得到的沉淀即为碳酸锂。碳酸锂经过精制提纯后可以得到纯净的碳酸锂。
称量碳酸锂的质量为31.93g,计算得到锂的收率为98.18%。
实施例3
一种从废旧锂电池中提取锂的方法,具体过程为:
(1)浸出:将100g废旧锂电池正极粉放入0.8L浓度为1.0mol/L盐酸中,并加入120mL的过氧化氢浸出5h,反应完成后,过滤得到浸出液和炭黑渣;
检测浸出液:
(2)还原置换:向步骤(1)所得浸出液中加入铁粉,铁粉的加入量与浸出液中铜离子的含量的摩尔比为1.1:1;
(3)氧化水解:步骤(2)反应结束后,加入硝酸并加入碳酸钙调节pH为3.5-4.0,固液分离后,得到铜铁渣和滤液;
(4)镍钴沉降:在温度为85-95℃下,向步骤(3)所得滤液中通入压力为250kPa的硫化氢气体至镍钴完全沉淀,固液分离后,分别制得硫化镍钴沉淀和富锂滤液;
(5)氧化滴定:向步骤(4)所得富锂滤液中滴定加入高锰酸钾,直至不再产生沉淀(即搅拌后溶液不再变为无色),分离出二氧化锰沉淀;
(6)喷雾热解:将步骤(5)剩余的滤液进行喷雾热解,控制喷雾热解温度为950-1350℃,载气压力为0.1MPa,制得氧化物固体颗粒;
(7)水沉收锂:将步骤(6)喷雾热解产生的氧化物进行水洗得到洗液,喷雾热解产生的尾气经水淋收集后与洗液混合制得锂盐溶液;
(8)在温度为80-95℃下,向锂盐溶液中加入碳酸盐,分离得到的沉淀即为碳酸锂。碳酸锂经过精制提纯后可以得到纯净的碳酸锂。
称量碳酸锂的质量为31.61g,计算得到锂的收率为97.52%。
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (6)
1.一种从废旧锂电池中提取锂的方法,其特征在于,包括以下步骤:
S1:将废旧锂电池的正极粉置于盐酸中进行浸出,过滤得浸出液;所述盐酸的浓度为1.0-6.0mol/L,正极粉与盐酸的固液比为100-250g/L;
S2:所述浸出液除去铜和铁,再通入硫化氢气体进行反应,固液分离得到第一滤渣和第一滤液;所述除去铜和铁的过程为:向浸出液中加入铁粉进行置换反应,待反应结束后加入氧化剂并调节pH至3.5-4.0,固液分离除去铜铁渣;所述硫化氢的压力为200-300kPa;通入硫化氢气体进行反应的温度为65-125℃;
S3:向所述第一滤液中加入高锰酸钾,固液分离得到第二滤渣和第二滤液;
S4:对所述第二滤液进行喷雾热解,得到固体颗粒,对所述固体颗粒进行水洗得到洗液,喷雾热解产生的尾气经水淋收集后与所述洗液混合得到锂盐溶液;所述喷雾热解的温度为600-1350℃,载气压力为0.1-0.3MPa。
2.根据权利要求1所述的方法,其特征在于,步骤S2中,所述铁粉的加入量与浸出液中铜离子的含量的摩尔比为(1.0-1.1):1。
3.根据权利要求1所述的方法,其特征在于,步骤S2中,所述调节pH采用碳酸钙。
4.根据权利要求1所述的方法,其特征在于,步骤S2中,所述第一滤渣为硫化镍钴沉淀,硫化镍钴沉淀经硫酸溶解后可得硫酸镍和硫酸钴溶液。
5.根据权利要求1所述的方法,其特征在于,步骤S3中,所述高锰酸钾采用滴定的方式加入,直至不再产生沉淀。
6.根据权利要求1所述的方法,其特征在于,步骤S4中,向所述锂盐溶液中加入碳酸盐进行反应,得到碳酸锂沉淀;所述反应的温度为80-95℃。
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