WO2016029613A1 - 一种脱硫铅膏滤液的净化方法及装置 - Google Patents

一种脱硫铅膏滤液的净化方法及装置 Download PDF

Info

Publication number
WO2016029613A1
WO2016029613A1 PCT/CN2014/095967 CN2014095967W WO2016029613A1 WO 2016029613 A1 WO2016029613 A1 WO 2016029613A1 CN 2014095967 W CN2014095967 W CN 2014095967W WO 2016029613 A1 WO2016029613 A1 WO 2016029613A1
Authority
WO
WIPO (PCT)
Prior art keywords
filtrate
tank
iron
stage purification
purification tank
Prior art date
Application number
PCT/CN2014/095967
Other languages
English (en)
French (fr)
Inventor
曹靖
吴光辉
王振云
范伟
张俊丰
Original Assignee
湖南江冶机电科技股份有限公司
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 湖南江冶机电科技股份有限公司 filed Critical 湖南江冶机电科技股份有限公司
Publication of WO2016029613A1 publication Critical patent/WO2016029613A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/06—Preparation of sulfates by double decomposition

Definitions

  • the invention belongs to a resource recovery and utilization process, and particularly relates to a method and a device for purifying a desulfurization lead paste filtrate, which are used for recovering lead from a waste lead-acid battery.
  • Lead sulfate is a major component of lead-acid battery lead paste, and sodium sulfate can also be used in the manufacture of lead-acid batteries. Wet desulfurization-fire smelting is one of the important technical processes for recovering lead in waste lead-acid batteries.
  • U.S. Patent 4,769,116 reports that sodium carbonate is added to lead-acid battery lead paste to convert lead sulfate into lead carbonate, and desulfurization after reaction.
  • the lead paste filter press filtrate is directly purified by activated carbon, and the method of preparing sodium sulfate by evaporation and crystallization is carried out.
  • the desulfurization lead paste filter press filtrate contains a certain amount of sodium carbonate, which needs to be neutralized.
  • the filtrate can be partially purified by the activated carbon treatment, the sodium sulfate obtained by evaporating the filtrate is low in quality and cannot meet the quality requirements of sodium sulfate in the manufacture of lead acid batteries. The filtrate is further purified.
  • the desulfurization lead paste filter press filtrate is not pure because the waste lead-acid battery will inevitably mix some substances such as oil on the outer casing during the crushing process, which will cause the filtrate to yellow; and the lead sulfate paste is added with sodium carbonate. It turns into lead carbonate with less solubility, but there are always some dissolved lead ions in the solution, as well as heavy metal impurity ions such as copper and cadmium. If the desulfurization lead paste filter press filtrate is not purified, these impurities will inevitably remain in the sodium sulphate product which is subsequently crystallized, resulting in poor quality of the sodium sulfate product and failing to meet the requirements for reuse.
  • Activated carbon must be regenerated, which will greatly increase the processing cost and increase equipment investment. Therefore, it is necessary to design a process technology for purifying the desulfurization lead paste filter press filtrate which is more in line with resource recycling and clean production requirements, especially the technology and process for completely decomposing and removing impurities in the desulfurization lead paste filter press filtrate.
  • Iron-carbon micro-electrolysis technology is an emerging technology for treating wastewater: when iron filings and carbon particles are immersed in acidic wastewater, numerous micro-primary cells are formed in the wastewater due to the electrode potential difference between iron and carbon. These fine batteries are made of iron having a low potential as an anode, and carbon having a high potential as a cathode, and electrochemically reacting in an aqueous solution containing an acidic electrolyte. Micro-electrolysis has a significant effect on the removal of solution color, and it can also remove some heavy metals due to the reducing properties of iron and the flocculation of iron hydroxide colloid. Therefore, since the birth of micro-electrolytic wastewater, it has attracted more and more attention from environmental researchers at home and abroad due to its more thorough decomposition and removal of pollutants by electrochemical methods.
  • a method for purifying a desulfurized lead paste filtrate comprises the following steps:
  • Adjusting the pH value of the filtrate adding the diluted sulfuric acid to the filtrate, controlling the pH value of the filtrate to 3-6, converting the sodium carbonate in the filtrate into sodium sulfate, and providing a suitable pH for the iron-carbon microelectrolysis in the subsequent first-stage purification tank. surroundings;
  • the solution obtained in the step (1) is sent to the iron-carbon bed of the first-stage purification tank, and the residence time is controlled to be 0.5 to 2.5 hours, the pH is adjusted to neutral, and then aerated for 5 to 30 minutes. filter;
  • the filtrate obtained in the step (2) is sent to a second-stage purification tank, and a trace amount of heavy metal ions and other ions in the filtrate are removed by cation exchange to obtain a purified desulfurization lead paste filtrate.
  • the solution temperature is maintained at 35 to 65 ° C in the above three steps.
  • the iron-carbon molar ratio of the iron carbon bed in the step (2) is 0.01 to 2.
  • the dilute sulfuric acid is a sulfuric acid solution having a mass fraction of less than 70.4%.
  • a purification device for the above purification method comprising a filtrate storage tank, a pH adjustment tank, a first-stage purification tank, an aeration tank and a second-stage purification tank which are sequentially connected by a pipeline or a conveyor belt;
  • the pH adjustment tank is provided with a stirrer, the first stage purification tank is provided with an iron carbon bed, and the second stage purification tank is provided with a cation exchange tower;
  • a filtering device is disposed between the aeration tank and the second-stage purification tank, and the filtering device is a pipeline filter or a filter press, and the filtering method is online filtering or offline filtering.
  • the iron-carbon microelectrolysis used in the present invention can better remove organic impurities.
  • the purified crystallization process of the desulfurized lead paste filtrate of the present invention can recover a high quality sodium sulfate product.
  • Figure 1 is a block flow diagram of the apparatus of the present invention.
  • 300L of the filtrate in the filtrate storage tank is sent to the pH adjustment tank, and the filtrate is added with dilute sulfuric acid to control the pH value of the filtrate to 3.0.
  • the obtained solution enters the iron carbon bed of the first-stage purification tank, and the residence time is controlled for 1.5 hours.
  • the pH is adjusted to neutral, then aerated for 30 minutes, filtered, and the filtrate is sent to an ion exchange column in the second-stage purification tank for ion exchange to obtain a purified desulfurized lead paste filtrate.
  • the filtrate of the 200L filtrate storage tank is sent to the pH adjustment tank, and the filtrate is added with dilute sulfuric acid to control the pH value of the filtrate to 4.0.
  • the obtained solution enters the iron carbon bed of the first-stage purification tank, and the residence time is controlled for 2.5 hours.
  • the pH is adjusted to neutral, then aerated for 20 minutes, filtered, and the filtrate is sent to an ion exchange column in the second-stage purification tank for ion exchange to obtain a purified desulfurized lead paste filtrate.
  • 200L of the filtrate in the filtrate storage tank is sent to the pH adjusting tank, and the filtrate is added with dilute sulfuric acid to control the pH value of the filtrate to 3.5.
  • the obtained solution enters the iron carbon bed of the first-stage purification tank, and the residence time is controlled for 2 hours.
  • the pH is adjusted to neutral, then aerated for 20 minutes, filtered, and the filtrate is sent to an ion exchange column in the second-stage purification tank for ion exchange to obtain a purified desulfurized lead paste filtrate.
  • the method and device for purifying the desulfurization lead paste filtrate of the invention are used for the process of recovering lead from the waste lead-acid battery, and the purified desulfurization lead paste filtrate can be used for the subsequent crystallization process to recover the high quality sodium sulfate product, the process Simple and easy to implement industrial applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

提供一种脱硫铅膏滤液的净化方法及装置。该方法包括调节滤液pH值、铁碳微电解去除部分重金属和脱色、离子交换进一步去除高价阳离子步骤。该装置包括滤液储罐、pH调节池、第一级净化池、曝气池和第二级净化池。该方法对脱硫铅膏滤液进行深度净化，将滤液中的有色物质、重金属离子和其它高价离子去除，保证了后续滤液结晶获得高品质的硫酸钠。

Description

一种脱硫铅膏滤液的净化方法及装置 技术领域
本发明属于资源回收和利用工艺，特别涉及一种脱硫铅膏滤液的净化方法及装置，用于从废铅酸蓄电池回收再生铅的工艺过程。
背景技术
硫酸铅是废铅酸蓄电池铅膏的主要组成部分，硫酸钠也可用到铅酸电池制造中。湿法脱硫-火法冶炼是回收废铅酸蓄电池中铅的重要技术工艺之一，美国专利US4769116报道了废铅酸蓄电池铅膏中加入碳酸钠，使硫酸铅转变为碳酸铅，反应后的脱硫铅膏压滤滤液直接经活性炭净化，蒸发结晶制备硫酸钠的方法。在实际工业应用中为了提高硫酸铅的转化率，通常采用添加过量碳酸钠的方法。因此，脱硫铅膏压滤滤液含有一定的碳酸钠，需要进行中和处理。虽然通过活性炭处理中和后的滤液可部分纯化滤液，但只采用这种简单处理方法最后将滤液蒸发得到的硫酸钠品质较低，不能满足铅酸电池制造中对硫酸钠的品质要求，所以需要对滤液进行进一步净化处理。
脱硫铅膏压滤滤液不纯净是因为废铅酸电池在破碎处理过程中会有一些物质如外壳上的油污等不可避免的混入，这些会造成滤液发黄；还有硫酸铅膏虽然加碳酸钠转变成溶解度更小的碳酸铅，但溶液中总还有部分溶解的铅离子，以及铜、镉等重金属杂质离子存在。脱硫铅膏压滤滤液如不经过净化处理，这些杂质必然会残留在后续结晶出来的硫酸钠产品中，造成硫酸钠产品质量低劣，达不到回用的要求。
目前，净化脱硫铅膏压滤滤液的方法，主要有两种，一是前面提到的活性碳直接吸附法；另外一种如专利CN200810047091中描述的先用活性碳吸附，再用阳离子交换处理的方法。第一种方法显然不能满足最终结晶硫酸钠产品的品质要求；第二种方法是对前一种方法的改进，增加了离子交换处理步骤，可较大地提升结晶硫酸钠产品的品质，但活性碳吸附是一种物理吸附，杂质会不停累积，造成活性炭吸附能力下降并最终失活，活性碳必须再生处理，这将大大提高处理费用增加设备投资。因此，有必要设计一种更加符合资源回收利用和清洁生产要求的脱硫铅膏压滤滤液的净化的工艺技术，特别是能彻底分解和去除脱硫铅膏压滤滤液中杂质的技术和工艺。
铁碳微电解技术是一种处理废水的新兴技术：当将铁屑和碳颗粒浸没在酸性废水中时，由于铁和碳之间的电极电位差，废水中会形成无数个微原电池。这些细微电池是以电位低的铁做为阳极,电位高的碳做阴极,在含有酸性电解质的水溶液中发生电化学反应的。微电解对溶液色度去除有明显的效果，且由于铁的还原性质及氢氧化铁胶体的絮凝还可起到去除部分重金属的作用。因此，微电解处理废水自诞生以来，由于其利用电化学方法更彻底地分解和去除污染物，引起国内外环保研究学者的关注。
技术问题
现有的“离子交换+活性碳”工艺吸附处理时，存在活性碳失效可能性比较大、再生活性碳的工艺处理复杂等问题。
技术解决方案
本发明解决上述技术问题的技术方案为：
一种脱硫铅膏滤液的净化方法，包括如下步骤：
(1)调节滤液pH值：以稀硫酸加入滤液中，控制滤液pH值3～6，将滤液中的碳酸钠转换成硫酸钠，同时为后续第一级净化池中铁碳微电解提供合适的pH环境；
(2)铁碳微电解：将步骤(1)所得溶液送入第一级净化池的铁碳床，控制其停留时间0.5～2.5小时，调节pH至中性，然后曝气5～30分钟，过滤；
(3)离子交换：将步骤(2)所得的滤液送入第二级净化池中，通过阳离子交换，去除滤液中的微量重金属离子和其它离子，得净化的脱硫铅膏滤液。
上述的脱硫铅膏滤液的净化方法，所述的三个步骤中溶液温度均保持在35～65℃。
上述的脱硫铅膏滤液的净化方法，所述步骤(2)铁碳床的铁碳摩尔比为0.01～2。
上述的脱硫铅膏滤液的净化方法，所述的稀硫酸为质量分数小于70.4％的硫酸溶液。
一种用于上述净化方法的净化装置，包括通过管道或输送带依次连接的滤液储罐、pH调节池、第一级净化池、曝气池和第二级净化池；
pH调节池中设有搅拌器，第一级净化池中设有铁碳床，第二级净化池中设有阳离子交换塔；
曝气池和第二级净化池之间设置过滤装置，所述过滤装置为管道过滤器或压滤机，其过滤方式为在线过滤或者离线过滤方式。
有益效果
本发明的有益效果在于：
(1)本发明所采用的铁碳微电解能够更好去除有机杂质。
(2)本发明净化后的脱硫铅膏滤液后续结晶工艺可回收高品质的硫酸钠产品。
附图说明
图1是本发明的设备流程框图。
本发明的最佳实施方式
如图1所示，滤液储罐的300L滤液送入pH调节池，以稀硫酸加入滤液中，控制滤液pH值3.0，所得溶液进入第一级净化池的铁碳床，控制其停留时间1.5小时，调节pH至中性，然后曝气30分钟，过滤，滤液送入第二级净化池中的离子交换塔进行离子交换，得净化的脱硫铅膏滤液。
本发明的实施方式
实施例1
如图1所示，200L滤液储罐的滤液送入pH调节池，以稀硫酸加入滤液中，控制滤液pH值4.0，所得溶液进入第一级净化池的铁碳床，控制其停留时间2.5小时，调节pH至中性，然后曝气20分钟，过滤，滤液送入第二级净化池中的离子交换塔进行离子交换，得净化的脱硫铅膏滤液。
实施例2
如图1所示，滤液储罐的200L滤液送入pH调节池，以稀硫酸加入滤液中，控制滤液pH值3.5，所得溶液进入第一级净化池的铁碳床，控制其停留时间2小时，调节pH至中性，然后曝气20分钟，过滤，滤液送入第二级净化池中的离子交换塔进行离子交换，得净化的脱硫铅膏滤液。
工业实用性
本发明的脱硫铅膏滤液的净化方法及其装置，用于从废铅酸蓄电池回收再生铅的工艺过程，净化后的脱硫铅膏滤液可用于后续结晶工艺回收高品质的硫酸钠产品，处理过程简单，易于实现工业化应用。

Claims (5)

  1. 一种脱硫铅膏滤液的净化方法，包括如下步骤：
    (1)调节滤液pH值：以稀硫酸加入滤液中，控制滤液pH值3～6，将滤液中的碳酸钠转换成硫酸钠；
    (2)铁碳微电解：将步骤(1)所得溶液送入第一级净化池的铁碳床，控制其停留时间0.5～2.5小时，调节pH至中性，然后曝气5～30分钟，过滤；
    (3)离子交换：将步骤(2)所得的滤液送入第二级净化池中，通过阳离子交换，得净化的脱硫铅膏滤液。
  2. 根据权利要求1所述的脱硫铅膏滤液的净化方法，所述三个步骤中的溶液温度均保持在35～65℃。
  3. 根据权利要求1所述的脱硫铅膏滤液的净化方法，所述步骤(2)铁碳床的铁碳摩尔比为0.01～2。
  4. 一种用于权利要求1至3任一项所述的净化方法的净化装置，包括通过管道或输送带依次连接的滤液储罐、pH调节池、第一级净化池、曝气池和第二级净化池；
    pH调节池中设有搅拌器，第一级净化池中设有铁碳床，第二级净化池中设有阳离子交换塔；曝气池和第二级净化池之间装有过滤装置。
  5. 根据权利要求4所述的净化装置，所述过滤装置为管道过滤器或压滤机，其过滤方式为在线过滤或者离线过滤方式。
PCT/CN2014/095967 2014-08-25 2014-12-31 一种脱硫铅膏滤液的净化方法及装置 WO2016029613A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410417931.1 2014-08-25
CN201410417931.1A CN104192869A (zh) 2014-08-25 2014-08-25 一种脱硫铅膏滤液的净化方法及装置

Publications (1)

Publication Number Publication Date
WO2016029613A1 true WO2016029613A1 (zh) 2016-03-03

Family

ID=52078292

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/095967 WO2016029613A1 (zh) 2014-08-25 2014-12-31 一种脱硫铅膏滤液的净化方法及装置

Country Status (2)

Country Link
CN (1) CN104192869A (zh)
WO (1) WO2016029613A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109911990A (zh) * 2019-03-04 2019-06-21 中国科学院过程工程研究所 一种高活性铁碳微电解填料的制备方法
CN110669924A (zh) * 2019-10-31 2020-01-10 湘潭大学 一种基于co2循环利用的铅膏脱硫方法
CN112915743A (zh) * 2021-01-25 2021-06-08 中山大学 一种有机废气多相催化氧化处理系统

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104192869A (zh) * 2014-08-25 2014-12-10 湖南江冶机电科技股份有限公司 一种脱硫铅膏滤液的净化方法及装置
CN106337112A (zh) * 2016-08-25 2017-01-18 安徽华铂再生资源科技有限公司 一种湿法、低液固比废铅酸蓄电池铅膏脱硫工艺
CN111170359A (zh) * 2018-11-13 2020-05-19 湖南省金翼有色金属综合回收有限公司 一种脱硫铅制备红丹的装置及其工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2564554Y (zh) * 2002-08-29 2003-08-06 詹伯君 铁碳微电解流化床设备
CN101244831A (zh) * 2008-03-18 2008-08-20 华中科技大学 从脱硫铅膏滤液中回收无水硫酸钠的方法及其装置
CN103496828A (zh) * 2013-10-18 2014-01-08 红板（江西）有限公司 印制线路板高浓度有机废液及酸性废液处理工艺
CN203728620U (zh) * 2014-01-17 2014-07-23 浙江东发环保工程有限公司 一种高色度高有机物废水预处理系统
CN104192869A (zh) * 2014-08-25 2014-12-10 湖南江冶机电科技股份有限公司 一种脱硫铅膏滤液的净化方法及装置

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456637A (zh) * 2008-11-25 2009-06-17 天津大学 综合电镀废水的处理工艺及方法
CN202016933U (zh) * 2011-03-25 2011-10-26 青岛赛尔环境保护有限公司 污水处理器
CN102381789A (zh) * 2011-10-08 2012-03-21 昆明理工大学 一种含重金属冶炼废水的处理方法
CN103540741B (zh) * 2013-11-05 2015-11-04 湖南江冶机电科技股份有限公司 一种铅膏湿法强制脱硫工艺

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2564554Y (zh) * 2002-08-29 2003-08-06 詹伯君 铁碳微电解流化床设备
CN101244831A (zh) * 2008-03-18 2008-08-20 华中科技大学 从脱硫铅膏滤液中回收无水硫酸钠的方法及其装置
CN103496828A (zh) * 2013-10-18 2014-01-08 红板（江西）有限公司 印制线路板高浓度有机废液及酸性废液处理工艺
CN203728620U (zh) * 2014-01-17 2014-07-23 浙江东发环保工程有限公司 一种高色度高有机物废水预处理系统
CN104192869A (zh) * 2014-08-25 2014-12-10 湖南江冶机电科技股份有限公司 一种脱硫铅膏滤液的净化方法及装置

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109911990A (zh) * 2019-03-04 2019-06-21 中国科学院过程工程研究所 一种高活性铁碳微电解填料的制备方法
CN109911990B (zh) * 2019-03-04 2020-12-11 中国科学院过程工程研究所 一种高活性铁碳微电解填料的制备方法
CN110669924A (zh) * 2019-10-31 2020-01-10 湘潭大学 一种基于co2循环利用的铅膏脱硫方法
CN112915743A (zh) * 2021-01-25 2021-06-08 中山大学 一种有机废气多相催化氧化处理系统

Also Published As

Publication number Publication date
CN104192869A (zh) 2014-12-10

Similar Documents

Publication Publication Date Title
WO2016029613A1 (zh) 一种脱硫铅膏滤液的净化方法及装置
JP4947640B2 (ja) 廃酸液の処理方法
CN113772692A (zh) 一种废盐处理和回收利用的方法
CN106315947B (zh) 一种含重金属工业污水的处理系统及处理工艺
CN110950474A (zh) 一种酚氰废水资源化零排放方法及工艺
CN108396158A (zh) 一种电解锰过程的复盐结晶物的处理方法
CN105130854A (zh) 一种改进的h酸生产工艺
CN103848513A (zh) 一种基于芬顿氧化反应的含氟废水处理方法及其装置
CN110590034A (zh) 一种锂电池正极材料铁锂废水工艺处理方法
CN113354177A (zh) 一种磷酸铁含氨氮废水全元素资源化处理的系统及方法
JP2020020016A (ja) リチウムの精製方法
CN106698790B (zh) 一种石墨生产废水综合回用方法
US20110293506A1 (en) Method for processing waste water containing fluorine and silicon, method for producing calcium fluoride, and facility for processing fluorine-containing waste water
CN116462347A (zh) 磷酸铁生产废水的处理方法
CN108341514B (zh) 石墨酸法提纯过程中产生的废水的处理方法
CN203269712U (zh) 重金属废水零排放处理装置
CN103588345A (zh) 一种化学回收处理电极箔生产中含磷废水的方法
CN105923815A (zh) 一种废水的净化处理方法
CN116314991A (zh) 一种基于酸性富钒液的钒电解液及其制备方法
CN114409157B (zh) 一种废盐水电解制氯碱资源化方法
CN212403800U (zh) 一种燃煤电厂脱硫废水综合型处理系统
CN101713025B (zh) 一种含镍、锌混合溶液湿法分离方法
TWI486312B (zh) 自含銅廢液回收銅之方法
CN114262089A (zh) 含磷酸、硫酸的铝阳极氧化废水回用处理方法
CN103007588A (zh) 一种烧结烟气氨法脱硫工艺产生的硫铵母液净化的方法

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: 14900619

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: 14900619

Country of ref document: EP

Kind code of ref document: A1