WO2017121343A1 - Process for recovering lithium from industrial wastewater - Google Patents

Process for recovering lithium from industrial wastewater Download PDF

Info

Publication number
WO2017121343A1
WO2017121343A1 PCT/CN2017/070932 CN2017070932W WO2017121343A1 WO 2017121343 A1 WO2017121343 A1 WO 2017121343A1 CN 2017070932 W CN2017070932 W CN 2017070932W WO 2017121343 A1 WO2017121343 A1 WO 2017121343A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
lithium
extract
mixed
industrial wastewater
Prior art date
Application number
PCT/CN2017/070932
Other languages
French (fr)
Chinese (zh)
Inventor
曹乃珍
高洁
樊平
肇巍
张炳元
杜明泽
赵莉
Original Assignee
天齐锂业股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 天齐锂业股份有限公司 filed Critical 天齐锂业股份有限公司
Publication of WO2017121343A1 publication Critical patent/WO2017121343A1/en

Links

Classifications

    • 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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • 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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C02F1/265—Desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds

Definitions

  • the invention relates to a method for recovering lithium by an extraction method, in particular to a process for extracting lithium from industrial wastewater by an extraction method.
  • Chinese patent CN1781847 discloses a method for producing lithium chloride by using lithium-containing waste liquid, which separates lithium-containing waste liquid generated in the production process of alkyl lithium by oil-water phase, and then uses water phase neutralization to filter and remove impurities.
  • the precipitant BaCl 2 and ammonium oxalate are added to precipitate Ca 2+ and SO 4 2- in the solution as a precipitate.
  • the liquid is filtered through a filter tank and then enters the intermediate tank, and the pH is adjusted to 6 with hydrochloric acid. 8; Finally, by granulation by spraying and drying, lithium chloride particles are obtained.
  • the process introduces new impurities during impurity removal, and the recycling process is complicated and difficult to control.
  • Chinese patent CN1211546 is to separate the lithium-containing waste liquid by oil and water, adjust the pH value twice with hydrochloric acid and filter, add sodium carbonate, precipitate lithium to obtain lithium carbonate product, the product is centrifugally dehydrated, and then convert lithium carbonate with hydrochloric acid. The lithium chloride solution is finally centrifuged to obtain lithium chloride crystals.
  • the disadvantage of this method is that the hydrochloric acid reaction is used multiple times, and more impurities such as iron and magnesium are introduced; at the same time, the cost is increased due to the addition of sodium carbonate, and the running cost is high.
  • the present invention provides a process for recovering lithium from industrial wastewater.
  • the extractant, the co-extractant and the diluent are mixed to obtain an extract, and the extract and the wastewater are mixed in a volume ratio of 1 to 3:1 to 3, placed in a separatory funnel, and extracted for 1 to 30 minutes to obtain an organic phase;
  • the organic phase obtained in the first step and the stripping acid are mixed in a volume ratio of 1 to 3:1, placed in a separatory funnel, and subjected to back extraction.
  • the back extraction time is 3 to 30 minutes, and the aqueous phase is collected.
  • the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
  • the extracting agent in the first step is one of tributyl phosphate, dibutyl butyl phosphate and trioctylphosphine oxide;
  • the co-extracting agent is ferric chloride;
  • the diluent is ethanol, n-octanol, n-butanol, isooctanol, n-hexane, cyclohexane, cyclohexanone, kerosene 200 # a # 260 sulfonated kerosene.
  • the extracting agent is 30% to 60%
  • the co-extracting agent is 3% to 10%
  • the diluent is 30% to 60%
  • the concentration of the co-extracting agent is 0.01 mol. /L ⁇ 5mol / L.
  • the stripping acid in the second step is at least one of formic acid, acetic acid, nitric acid, hydrochloric acid, and sulfuric acid, and the stripping acid concentration is 0.1 mol/L to 2 mol/L.
  • the extract and the wastewater are mixed at a volume ratio of 3:1 and extracted for 10 minutes.
  • the stripping acid is hydrochloric acid having a substance concentration of 1 mol/L
  • the organic phase is mixed with hydrochloric acid at a volume ratio of 1:1 and extracted for 30 minutes.
  • the process of the present invention is simple in operation, strong in controllability, and requires no additional energy supply, thereby saving energy and environmental protection; (2) the extract in the process of the present invention can be reused, thereby greatly reducing production cost. (3) The process of the present invention has a high recovery rate of lithium in wastewater.
  • a process for recovering lithium from industrial wastewater comprising the steps of:
  • the extractant, the co-extractant and the diluent are mixed to obtain an extract, and the extract and the wastewater are mixed at a volume ratio of 1:1, placed in a separatory funnel, and extracted for 30 minutes to obtain an organic phase;
  • the organic phase obtained in the first step and the stripping acid are mixed at a volume ratio of 3:1, placed in a separatory funnel, subjected to back extraction, the stripping time is 3 min, and the aqueous phase is collected to obtain the wastewater.
  • the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
  • the extracting agent in the extract in the first step is tributyl phosphate
  • the co-extracting agent is ferric chloride
  • the diluent is ethanol
  • the extracting agent is 33% by mass fraction
  • the co-extracting agent is 7 %
  • the diluent is 60%
  • the concentration of the co-extractant is 0.01 mol/L.
  • the stripping acid has a stripping acid concentration of 0.1 mol/L.
  • a process for recovering lithium from industrial wastewater comprising the steps of:
  • the extractant, the co-extractant and the diluent are mixed to obtain an extract, and the extract and the wastewater are mixed at a volume ratio of 3:1, placed in a separatory funnel, and extracted for 10 minutes to obtain an organic phase;
  • the organic phase obtained in the first step and the stripping acid are mixed in a volume ratio of 1:1, placed in a separating funnel, and subjected to back extraction, the stripping time is 30 min, and the aqueous phase is collected to obtain the wastewater.
  • the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
  • the extractant in the extract in the first step is dibutyl butyl phosphate; the co-extractant is ferric chloride; the diluent is n-hexane; and the extractant is 42% by mass fraction, and the extract is The agent is 6%, the diluent is 52%, and the concentration of the co-extractant is 3 mol / L.
  • the stripping acid is a mixed solution of hydrochloric acid, and the stripping acid concentration is 1 mol/L.
  • a process for recovering lithium from industrial wastewater comprising the steps of:
  • the extractant, the co-extractant and the diluent are mixed to obtain an extract, and the extract and the wastewater are mixed at a volume ratio of 2:1, placed in a separatory funnel, and extracted for 10 minutes to obtain an organic phase;
  • the organic phase obtained in the first step and the stripping acid are mixed at a volume ratio of 2:1, placed in a separatory funnel, and subjected to back extraction, the stripping time is 10 min, and the aqueous phase is collected to obtain the wastewater.
  • the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
  • the extracting agent in the first step is trioctylphosphine oxide
  • the co-extracting agent is ferric chloride
  • the diluent is 200 # kerosene; and according to the mass fraction, the extracting agent is 60%, and the co-extracting agent is 3%.
  • the diluent is 37% and the concentration of the co-extractant is 5 mol/L.
  • the stripping acid is a mixture of formic acid and sulfuric acid, and the stripping acid concentration is 2 mol/L.

Abstract

A process for recovering lithium from an industrial wastewater, comprising three procedures: extraction, back extraction, and rinsing. Compared with the prior art, the process offers the following advantages: (1) the process has simple operations and strong controllability, requires no extra energy supply, and is therefore energy saving and environmentally friendly; (2) the extraction liquid in the process can be reused, thereby greatly reducing production cost; (3) the process achieves a high recovery rate of lithium from wastewater.

Description

一种从工业废水中回收锂的工艺Process for recovering lithium from industrial wastewater 技术领域Technical field
本发明涉及一种萃取法回收锂的方法，尤其涉及一种萃取法从工业废水中回收锂的工艺。The invention relates to a method for recovering lithium by an extraction method, in particular to a process for extracting lithium from industrial wastewater by an extraction method.
背景技术Background technique
随着温室效应越来越受到全球关注，低碳经济和新能源产业的发展给电池级碳酸锂行业带来了巨大机遇，同时也对电池级碳酸锂的品质提出了更高要求。目前，电池级碳酸锂产品标准中，钙、镁含量是个很重要的指标，故要求在生产碳酸锂时，通过降低原料中的钙、镁含量来降低碳酸锂中的钙、镁含量。通过离子交换树脂来吸附原料中的钙、镁离子是目前比较常用的方法，但离子交换树脂在吸附钙、镁离子的同时，也会对锂离子进行吸附，在对离子交换树脂进行酸洗时，随钙、镁离子一起洗脱下来，进入到废水***中，造成锂离子的损失。传统工艺对该部分废水进行的处理包括中和除杂、蒸发浓缩回收，也有直接将其排放至环境中，上述现有技术中，中和除杂存在着引入其它杂质的不足；蒸发浓缩回收则存在能耗高、设备易腐蚀等缺陷，而直接排放至环境中则易带来严重的环境污染问题。As the greenhouse effect is increasingly receiving global attention, the development of low-carbon economy and new energy industry has brought great opportunities to the battery-grade lithium carbonate industry, and also puts higher requirements on the quality of battery-grade lithium carbonate. At present, calcium and magnesium contents are important indexes in battery-grade lithium carbonate product standards. Therefore, it is required to reduce the calcium and magnesium contents in lithium carbonate by reducing the calcium and magnesium contents in the raw materials when producing lithium carbonate. It is a common method to adsorb calcium and magnesium ions in raw materials by ion exchange resin, but ion exchange resin adsorbs calcium and magnesium ions and also adsorbs lithium ions. When pickling ion exchange resin It elutes with calcium and magnesium ions and enters the wastewater system, causing the loss of lithium ions. The traditional process of treating some of the wastewater includes neutralization and impurity removal, evaporation and concentration recovery, and direct discharge to the environment. In the prior art, neutralization and impurity removal have the disadvantage of introducing other impurities; There are defects such as high energy consumption and corrosion of equipment, and direct discharge into the environment is likely to cause serious environmental pollution problems.
中国专利CN1781847公开了一种利用含锂废液生产氯化锂的方法，该方法将烷基锂生产过程中产生的含锂废液经油水相分离后，采用水相中和过滤除杂，在除杂的过程中加入沉淀剂BaCl2和草酸铵，使溶液中的Ca2+、SO4 2-以沉淀形式析出，料液经过滤槽过滤后进入中间罐，用盐酸调pH值至6～8；最后通过喷射造粒及干燥，得到氯化锂颗粒。该工艺在除杂时引入了新的杂质，且回收工艺复杂，难控制。Chinese patent CN1781847 discloses a method for producing lithium chloride by using lithium-containing waste liquid, which separates lithium-containing waste liquid generated in the production process of alkyl lithium by oil-water phase, and then uses water phase neutralization to filter and remove impurities. In the process of removing impurities, the precipitant BaCl 2 and ammonium oxalate are added to precipitate Ca 2+ and SO 4 2- in the solution as a precipitate. The liquid is filtered through a filter tank and then enters the intermediate tank, and the pH is adjusted to 6 with hydrochloric acid. 8; Finally, by granulation by spraying and drying, lithium chloride particles are obtained. The process introduces new impurities during impurity removal, and the recycling process is complicated and difficult to control.
中国专利CN1211546是将含锂废液经油水分离后，以盐酸两次调节pH值和过滤后，加入碳酸钠，沉淀锂得到碳酸锂产品，所得产品经离心脱水，并再次以盐酸转化碳酸锂为氯化锂溶液，最后经离心甩干，得到氯化锂晶体。该方法的缺点是：多次使用盐酸反应，引入较多的铁、镁等杂质；同时，由于加入碳酸钠导致成本上升，且运行成本较高。Chinese patent CN1211546 is to separate the lithium-containing waste liquid by oil and water, adjust the pH value twice with hydrochloric acid and filter, add sodium carbonate, precipitate lithium to obtain lithium carbonate product, the product is centrifugally dehydrated, and then convert lithium carbonate with hydrochloric acid. The lithium chloride solution is finally centrifuged to obtain lithium chloride crystals. The disadvantage of this method is that the hydrochloric acid reaction is used multiple times, and more impurities such as iron and magnesium are introduced; at the same time, the cost is increased due to the addition of sodium carbonate, and the running cost is high.
发明内容Summary of the invention
解决的技术问题：为了获得一种对工业废水中锂回收效率高、原料重复利用、生产成本低、操作可行性强的回收方法，本发明提供了一种从工业废水中回收锂的工艺。Technical Problem to be Solved: In order to obtain a recovery method for high efficiency of lithium recovery, reuse of raw materials, low production cost, and high operational feasibility in industrial wastewater, the present invention provides a process for recovering lithium from industrial wastewater.
技术方案：一种从工业废水中回收锂的工艺，包含以下步骤：Technical Solution: A process for recovering lithium from industrial wastewater, comprising the following steps:
第1步、将萃取剂、共萃剂和稀释剂混合得萃取液，将萃取液与废水按体积比1～3:1～3混合，置于分液漏斗中，萃取1～30min，取有机相；In the first step, the extractant, the co-extractant and the diluent are mixed to obtain an extract, and the extract and the wastewater are mixed in a volume ratio of 1 to 3:1 to 3, placed in a separatory funnel, and extracted for 1 to 30 minutes to obtain an organic phase;
第2步、将第1步获得的有机相与反萃酸按体积比1～3:1混合，置于分液漏斗中，进行反萃取，反萃取时间为3～30min，收集水相，即可获得废水中的锂离子；In the second step, the organic phase obtained in the first step and the stripping acid are mixed in a volume ratio of 1 to 3:1, placed in a separatory funnel, and subjected to back extraction. The back extraction time is 3 to 30 minutes, and the aqueous phase is collected. Obtaining lithium ions in wastewater;
第3步、将第2步反萃取后的有机相与纯水混合，进行水洗，得到可循环利用的萃取液。In the third step, the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
其中，第1步中所述萃取剂为磷酸三丁酯、丁基磷酸二丁酯、三辛基氧化膦中的一种；共萃剂为氯化铁；稀释剂为乙醇、正辛醇、正丁醇、异辛醇、正己烷、环己烷、环己酮、200# 煤油、260#磺化煤油中的一种。Wherein, the extracting agent in the first step is one of tributyl phosphate, dibutyl butyl phosphate and trioctylphosphine oxide; the co-extracting agent is ferric chloride; the diluent is ethanol, n-octanol, n-butanol, isooctanol, n-hexane, cyclohexane, cyclohexanone, kerosene 200 # a # 260 sulfonated kerosene.
优选的，所述萃取液中，按质量分数计，萃取剂为30％～60％，共萃剂为3％～10％，稀释剂为30％～60％，其中共萃剂浓度为0.01mol/L～5mol/L。Preferably, in the extract, according to the mass fraction, the extracting agent is 30% to 60%, the co-extracting agent is 3% to 10%, the diluent is 30% to 60%, and the concentration of the co-extracting agent is 0.01 mol. /L ~ 5mol / L.
优选的，第2步中所述反萃酸为甲酸、醋酸、硝酸、盐酸、硫酸中的至少一种，反萃酸浓度为0.1mol/L～2mol/L。Preferably, the stripping acid in the second step is at least one of formic acid, acetic acid, nitric acid, hydrochloric acid, and sulfuric acid, and the stripping acid concentration is 0.1 mol/L to 2 mol/L.
优选的，第1步中，所述萃取液与废水按体积比3:1混合，萃取10min。Preferably, in the first step, the extract and the wastewater are mixed at a volume ratio of 3:1 and extracted for 10 minutes.
优选的，第2步中，所述反萃酸是物质的量浓度为1mol/L的盐酸，有机相与盐酸按体积比1:1混合，萃取30min。Preferably, in the second step, the stripping acid is hydrochloric acid having a substance concentration of 1 mol/L, and the organic phase is mixed with hydrochloric acid at a volume ratio of 1:1 and extracted for 30 minutes.
有益效果：(1)本发明所述工艺操作简便、可控性强，无需额外提供能量，因而节能环保；(2)本发明所述工艺中的萃取液可重复利用，因而可以大大降低生产成本；(3)本发明所述工艺对废水中的锂回收率高。Advantageous Effects: (1) The process of the present invention is simple in operation, strong in controllability, and requires no additional energy supply, thereby saving energy and environmental protection; (2) the extract in the process of the present invention can be reused, thereby greatly reducing production cost. (3) The process of the present invention has a high recovery rate of lithium in wastewater.
具体实施方式detailed description
以下实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。The following examples are intended to further illustrate the invention, but are not to be construed as limiting the invention. Modifications and substitutions of the methods, steps or conditions of the invention are intended to be included within the scope of the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise specified.
实施例1Example 1
一种从工业废水中回收锂的工艺，包含以下步骤：A process for recovering lithium from industrial wastewater, comprising the steps of:
第1步、将萃取剂、共萃剂和稀释剂混合得萃取液，将萃取液与废水按体积比1:1混合，置于分液漏斗中，萃取30min，取有机相；In the first step, the extractant, the co-extractant and the diluent are mixed to obtain an extract, and the extract and the wastewater are mixed at a volume ratio of 1:1, placed in a separatory funnel, and extracted for 30 minutes to obtain an organic phase;
第2步、将第1步获得的有机相与反萃酸按体积比3:1混合，置于分液漏斗中，进行反萃取，反萃取时间为3min，收集水相，即可获得废水中的锂离子；In the second step, the organic phase obtained in the first step and the stripping acid are mixed at a volume ratio of 3:1, placed in a separatory funnel, subjected to back extraction, the stripping time is 3 min, and the aqueous phase is collected to obtain the wastewater. Lithium ion
第3步、将第2步反萃取后的有机相与纯水混合，进行水洗，得到可循环利用的萃取液。In the third step, the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
其中，第1步中所述萃取液中的萃取剂为磷酸三丁酯，共萃剂为氯化铁，稀释剂为乙醇；且按质量分数计，萃取剂为33％，共萃剂为7％，稀释剂为60％，共萃剂浓度为0.01mol/L。Wherein, the extracting agent in the extract in the first step is tributyl phosphate, the co-extracting agent is ferric chloride, the diluent is ethanol; and the extracting agent is 33% by mass fraction, and the co-extracting agent is 7 %, the diluent is 60%, and the concentration of the co-extractant is 0.01 mol/L.
所述反萃酸盐酸，反萃酸浓度为0.1mol/L。The stripping acid has a stripping acid concentration of 0.1 mol/L.
对经上述实施例处理后的工业废水进行检测，锂的回收率为82.1％。The industrial wastewater treated by the above examples was tested, and the recovery rate of lithium was 82.1%.
实施例2Example 2
一种从工业废水中回收锂的工艺，包含以下步骤：A process for recovering lithium from industrial wastewater, comprising the steps of:
第1步、将萃取剂、共萃剂和稀释剂混合得萃取液，将萃取液与废水按体积比3:1混合，置于分液漏斗中，萃取10min，取有机相；In the first step, the extractant, the co-extractant and the diluent are mixed to obtain an extract, and the extract and the wastewater are mixed at a volume ratio of 3:1, placed in a separatory funnel, and extracted for 10 minutes to obtain an organic phase;
第2步、将第1步获得的有机相与反萃酸按体积比1:1混合，置于分液漏斗中，进行反萃取，反萃取时间为30min，收集水相，即可获得废水中的锂离子；In the second step, the organic phase obtained in the first step and the stripping acid are mixed in a volume ratio of 1:1, placed in a separating funnel, and subjected to back extraction, the stripping time is 30 min, and the aqueous phase is collected to obtain the wastewater. Lithium ion
第3步、将第2步反萃取后的有机相与纯水混合，进行水洗，得到可循环利用的萃取液。In the third step, the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
其中，第1步中所述萃取液中的萃取剂为丁基磷酸二丁酯；共萃剂为氯化铁；稀释剂为正己烷；且按质量分数计，萃取剂为42％，共萃剂为6％，稀释剂为52％，共萃剂浓度为 3mol/L。Wherein, the extractant in the extract in the first step is dibutyl butyl phosphate; the co-extractant is ferric chloride; the diluent is n-hexane; and the extractant is 42% by mass fraction, and the extract is The agent is 6%, the diluent is 52%, and the concentration of the co-extractant is 3 mol / L.
所述反萃酸为盐酸的混合液，反萃酸浓度为1mol/L。The stripping acid is a mixed solution of hydrochloric acid, and the stripping acid concentration is 1 mol/L.
对经上述实施例处理后的工业废水进行检测，锂的回收率为92.3％。The industrial wastewater treated by the above examples was examined, and the recovery rate of lithium was 92.3%.
实施例3Example 3
一种从工业废水中回收锂的工艺，包含以下步骤：A process for recovering lithium from industrial wastewater, comprising the steps of:
第1步、将萃取剂、共萃剂和稀释剂混合得萃取液，将萃取液与废水按体积比2:1混合，置于分液漏斗中，萃取10min，取有机相；In the first step, the extractant, the co-extractant and the diluent are mixed to obtain an extract, and the extract and the wastewater are mixed at a volume ratio of 2:1, placed in a separatory funnel, and extracted for 10 minutes to obtain an organic phase;
第2步、将第1步获得的有机相与反萃酸按体积比2:1混合，置于分液漏斗中，进行反萃取，反萃取时间为10min，收集水相，即可获得废水中的锂离子；In the second step, the organic phase obtained in the first step and the stripping acid are mixed at a volume ratio of 2:1, placed in a separatory funnel, and subjected to back extraction, the stripping time is 10 min, and the aqueous phase is collected to obtain the wastewater. Lithium ion
第3步、将第2步反萃取后的有机相与纯水混合，进行水洗，得到可循环利用的萃取液。In the third step, the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
其中，第1步中所述萃取剂为三辛基氧化膦，共萃剂为氯化铁，稀释剂为200#煤油；且按质量分数计，萃取剂为60％，共萃剂为3％，稀释剂为37％，共萃剂浓度为5mol/L。Wherein, the extracting agent in the first step is trioctylphosphine oxide, the co-extracting agent is ferric chloride, and the diluent is 200 # kerosene; and according to the mass fraction, the extracting agent is 60%, and the co-extracting agent is 3%. The diluent is 37% and the concentration of the co-extractant is 5 mol/L.
所述反萃酸为甲酸与硫酸的混合液，反萃酸浓度为2mol/L。The stripping acid is a mixture of formic acid and sulfuric acid, and the stripping acid concentration is 2 mol/L.
对经上述实施例处理后的工业废水进行检测，锂的回收率为86.5％。 The industrial wastewater treated by the above examples was tested, and the recovery rate of lithium was 86.5%.

Claims (5)

  1. 一种从工业废水中回收锂的工艺，其特征在于，包含以下步骤：A process for recovering lithium from industrial wastewater, characterized by comprising the steps of:
    第1步、将萃取剂、共萃剂和稀释剂混合得萃取液，所述萃取剂为磷酸三丁酯、丁基磷酸二丁酯、三辛基氧化膦中的一种；共萃剂为氯化铁；稀释剂为乙醇、正辛醇、正丁醇、异辛醇、正己烷、环己烷、环己酮、200#煤油、260#磺化煤油中的一种，将萃取液与废水按体积比1～3:1～3混合，置于分液漏斗中，萃取1～30min，取有机相；In the first step, the extracting agent, the co-extracting agent and the diluent are mixed to obtain an extracting liquid, the extracting agent is one of tributyl phosphate, dibutyl butyl phosphate and trioctylphosphine oxide; the co-extracting agent is ferric chloride; diluent is ethanol, n-octanol, n-butanol, isooctanol, n-hexane, cyclohexane, cyclohexanone, kerosene 200 # a # 260 sulfonated kerosene, and the extract The wastewater is mixed in a volume ratio of 1 to 3:1 to 3, placed in a separatory funnel, and extracted for 1 to 30 minutes to obtain an organic phase;
    第2步、将第1步获得的有机相与反萃酸按体积比1～3:1混合，置于分液漏斗中，进行反萃取，反萃取时间为3～30min，收集水相，即可获得废水中的锂离子；In the second step, the organic phase obtained in the first step and the stripping acid are mixed in a volume ratio of 1 to 3:1, placed in a separatory funnel, and subjected to back extraction. The back extraction time is 3 to 30 minutes, and the aqueous phase is collected. Obtaining lithium ions in wastewater;
    第3步、将第2步反萃取后的有机相与纯水混合，进行水洗，得到可循环利用的萃取液。In the third step, the organic phase after the second step of back extraction is mixed with pure water and washed with water to obtain a recyclable extract.
  2. 根据权利要求1所述的一种从工业废水中回收锂的工艺，其特征在于，所述萃取液中，按质量分数计，萃取剂为30％～60％，共萃剂为3％～10％，稀释剂为30％～60％，其中共萃剂浓度为0.01mol/L～5mol/L。The process for recovering lithium from industrial wastewater according to claim 1, wherein in the extract, the extractant is 30% to 60% by mass fraction, and the co-extractant is 3% to 10%. %, the diluent is 30% to 60%, wherein the concentration of the co-extractant is from 0.01 mol/L to 5 mol/L.
  3. 根据权利要求1所述的一种从工业废水中回收锂的工艺，其特征在于，第2步中所述反萃酸为甲酸、醋酸、硝酸、盐酸、硫酸中的至少一种，反萃酸浓度为0.1mol/L～2mol/L。The process for recovering lithium from industrial wastewater according to claim 1, wherein the stripping acid in the second step is at least one of formic acid, acetic acid, nitric acid, hydrochloric acid and sulfuric acid, and the stripping acid is The concentration is from 0.1 mol/L to 2 mol/L.
  4. 根据权利要求1所述的一种从工业废水中回收锂的工艺，其特征在于，第1步中，所述萃取液与废水按体积比3:1混合，萃取10min。A process for recovering lithium from industrial wastewater according to claim 1, wherein in the first step, the extract and the wastewater are mixed at a volume ratio of 3:1 and extracted for 10 minutes.
  5. 根据权利要求1所述的一种从工业废水中回收锂的工艺，其特征在于，第2步中，所述反萃酸是物质的量浓度为1mol/L的盐酸，有机相与盐酸按体积比1:1混合，萃取30min。 The process for recovering lithium from industrial wastewater according to claim 1, wherein in the second step, the stripping acid is hydrochloric acid having a concentration of the substance of 1 mol/L, and the volume of the organic phase and hydrochloric acid is volume. Mix 1:1 and extract for 30 min.
PCT/CN2017/070932 2016-01-12 2017-01-11 Process for recovering lithium from industrial wastewater WO2017121343A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610016200.5 2016-01-12
CN201610016200.5A CN105502551A (en) 2016-01-12 2016-01-12 Technology for recycling lithium from industrial wastewater

Publications (1)

Publication Number Publication Date
WO2017121343A1 true WO2017121343A1 (en) 2017-07-20

Family

ID=55710937

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/070932 WO2017121343A1 (en) 2016-01-12 2017-01-11 Process for recovering lithium from industrial wastewater

Country Status (2)

Country Link
CN (1) CN105502551A (en)
WO (1) WO2017121343A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111945017A (en) * 2020-07-31 2020-11-17 湖南邦普循环科技有限公司 Method for recovering lithium from lithium-containing wastewater
CN114804275A (en) * 2022-04-02 2022-07-29 南京工业大学 Chloride ion removal extracting agent and preparation method thereof
CN114804410A (en) * 2022-04-13 2022-07-29 南京工业大学 Method for extracting chloride ions from wet flue gas desulfurization wastewater

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105502551A (en) * 2016-01-12 2016-04-20 四川天齐锂业股份有限公司 Technology for recycling lithium from industrial wastewater
CN106191445B (en) * 2016-06-30 2018-07-27 江西环锂新能源科技有限公司 The separation method of lithium ion in a kind of lithium ion battery leachate
CN115528338A (en) * 2022-09-16 2022-12-27 广东邦普循环科技有限公司 Method for recovering lithium from lithium ion battery electrolyte

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010036176A (en) * 2008-08-01 2010-02-18 Kosuke Ota Method of collecting lithium, strontium and manganese from waste hot spring
CN101698488A (en) * 2009-11-04 2010-04-28 中国科学院青海盐湖研究所 Method for preparing lithium carbonate by using salt lake brine with high magnesium-to-lithium ratio
CN101767804A (en) * 2009-12-25 2010-07-07 江南大学 Method for extracting lithium from salt lake brine
CN102001692A (en) * 2010-12-03 2011-04-06 中国科学院青海盐湖研究所 Coordinate extracting system for extracting lithium from salt lake brine with extraction method
CN104388677A (en) * 2014-12-02 2015-03-04 中国科学院青海盐湖研究所 Regeneration method of lithium extraction system
CN105502551A (en) * 2016-01-12 2016-04-20 四川天齐锂业股份有限公司 Technology for recycling lithium from industrial wastewater

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3537813A (en) * 1968-04-25 1970-11-03 Lithium Corp Recovery of lithium from bitterns
CN1005145B (en) * 1987-05-07 1989-09-13 中国科学院青海盐湖研究所 Process for extracting absolute lithium chloride from brine containing chloride
CN102992358A (en) * 2012-02-24 2013-03-27 中国科学院青海盐湖研究所 Method for extracting lithium salt from lithium brine
CN103233134B (en) * 2013-05-10 2014-04-23 桃江瑞龙金属新材料有限责任公司 Recycling method of organic phase used for extracting scandium
CN103849902A (en) * 2014-03-25 2014-06-11 金隆铜业有限公司 Recovery process of stibium and bismuth in copper electrolyte
CN104120258B (en) * 2014-07-25 2016-05-18 广西师范大学 A kind of method that separates LREE without saponifiable extraction

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010036176A (en) * 2008-08-01 2010-02-18 Kosuke Ota Method of collecting lithium, strontium and manganese from waste hot spring
CN101698488A (en) * 2009-11-04 2010-04-28 中国科学院青海盐湖研究所 Method for preparing lithium carbonate by using salt lake brine with high magnesium-to-lithium ratio
CN101767804A (en) * 2009-12-25 2010-07-07 江南大学 Method for extracting lithium from salt lake brine
CN102001692A (en) * 2010-12-03 2011-04-06 中国科学院青海盐湖研究所 Coordinate extracting system for extracting lithium from salt lake brine with extraction method
CN104388677A (en) * 2014-12-02 2015-03-04 中国科学院青海盐湖研究所 Regeneration method of lithium extraction system
CN105502551A (en) * 2016-01-12 2016-04-20 四川天齐锂业股份有限公司 Technology for recycling lithium from industrial wastewater

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FAN: "Li3li2zi1 de cui4qu3 he2 fan3cui4 yan2jui1", JOURNAL OF HENAN SCIENCE AND TECHNOLOGY, no. 8, 31 December 2014 (2014-12-31), ISSN: 1003-5168 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111945017A (en) * 2020-07-31 2020-11-17 湖南邦普循环科技有限公司 Method for recovering lithium from lithium-containing wastewater
CN111945017B (en) * 2020-07-31 2023-03-07 湖南邦普循环科技有限公司 Method for recovering lithium from lithium-containing wastewater
CN114804275A (en) * 2022-04-02 2022-07-29 南京工业大学 Chloride ion removal extracting agent and preparation method thereof
CN114804275B (en) * 2022-04-02 2023-11-17 南京工业大学 Chloride ion removal extractant and preparation method thereof
CN114804410A (en) * 2022-04-13 2022-07-29 南京工业大学 Method for extracting chloride ions from wet flue gas desulfurization wastewater

Also Published As

Publication number Publication date
CN105502551A (en) 2016-04-20

Similar Documents

Publication Publication Date Title
WO2017121343A1 (en) Process for recovering lithium from industrial wastewater
WO2015161660A1 (en) Method for preparing low-silicon vanadium pentoxide from solution containing vanadium, chromium and silicon
CN102557085B (en) Method for extracting sodium salt in cesium salt and rubidium salt production process
CN109881012B (en) Treatment method for recycling tungsten from tungsten metallurgy dephosphorization residues
CN103991898B (en) A kind of catalytic coal gasifaction lime-ash utilize method
CN106630313A (en) Reduction circulation process method for recycling zinc elements in iron-containing waste acid
CN103614560B (en) Method of recycling scandium in titanium white waste acid
CN103964445B (en) A kind of quartz sand pickling circulation comprehensive utilizes processing method
CN108950249A (en) A kind of vanadium aluminum separation method of vanadium-containing shale pickle liquor
CN111020196B (en) Method for separating thorium and enriching rare earth from radioactive waste residue leachate based on POAA
CN114572949A (en) Production process of lithium dihydrogen phosphate
CN105420521B (en) A kind of organic extractant phase Rare Earth Separation technique
US10822241B2 (en) Recycling of nuclear liquid waste with boron control
CN112342407B (en) Back extraction method of lithium extraction liquid
CN104003910B (en) The method extracting 5-sodium sulfo isophthalate waste water is produced from three monomers
CN115403018B (en) Method for preparing ferric phosphate by high-impurity phosphoric acid and preparation method of positive electrode material
CN111348633A (en) Wet phosphoric acid purifying process and its extraction liquid regenerating method
CN107758719B (en) A kind of environmentally friendly extracting process of high-purity ceria
CN106892479B (en) Method for recovering oxalic acid and hydrochloric acid from rare earth oxalic acid precipitation wastewater
CN214829053U (en) Salt lake brine adsorbs and carries lithium device
CN105331834A (en) Method for removing iron and aluminum continuously from yttrium-rich feed liquid through N235
CN209872557U (en) System for separating acid and salt in wastewater
CN103274923A (en) Method for recycling dehydropregnenolone acetate waste liquor
CN108164069B (en) Treatment method of tetraethylammonium tetrafluoroborate production wastewater
CN109293049A (en) A method of oxalic acid and hydrochloric acid are recycled from oxalic acid precipitation RE waste water

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17738157

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17738157

Country of ref document: EP

Kind code of ref document: A1