CN102285738A - Treatment method of high-salinity waste water in waste lithium battery recovering industry - Google Patents

Treatment method of high-salinity waste water in waste lithium battery recovering industry Download PDF

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Publication number
CN102285738A
CN102285738A CN2011102334874A CN201110233487A CN102285738A CN 102285738 A CN102285738 A CN 102285738A CN 2011102334874 A CN2011102334874 A CN 2011102334874A CN 201110233487 A CN201110233487 A CN 201110233487A CN 102285738 A CN102285738 A CN 102285738A
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Prior art keywords
salt wastewater
reclaims
lithium cell
waste lithium
salinity
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CN2011102334874A
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CN102285738B (en
Inventor
王皓
龙桂花
谭群英
李达飞
曾昭华
刘长根
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Hunan Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/138—Water desalination using renewable energy
    • Y02A20/141—Wind power
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment
    • Y02A20/208—Off-grid powered water treatment
    • Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/33—Wastewater or sewage treatment systems using renewable energies using wind energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)

Abstract

The invention discloses a treatment method of high-salinity waste water in a waste lithium battery recovering industry. According to the treatment method, purified water and concentrated water are obtained with a reverse osmosis process, wherein the purified water can be recycled, and the salt in the concentrated water is recovered. By utilizing the treatment method in the invention, the cyclic utilization of the high-salinity waste water in the waste lithium battery recovering industry can be realized, thereby the zero emission of the waste water is truly realized; and simultaneously, the salt in the waste water is recovered by fully utilizing natural energies such as solar energy, wind energy and the like, thereby energy consumption is obviously reduced and cost is saved, and the recovered salt has a larger economic benefit.

Description

A kind of waste lithium cell reclaims the treatment process of industry high-salt wastewater
Technical field
The present invention relates to a kind of wastewater treatment method, reclaim the treatment process of the high-salt wastewater that produces in the industry more specifically to a kind of waste lithium cell.
Background technology
Along with the fast development that waste lithium cell reclaims industry, the sector wastewater treatment generally receives publicity.Each waste lithium cell reclaims enterprise's recyclings of paying close attention to and studying valuable metal nickel, cobalt, lithium in the waste water more at present, and for a large amount of salinities that exist in the waste water, because it reclaims difficulty, processing cost is high, more each enterprise abandons reclaiming and takes direct discharging, so not only contaminate environment has also greatly caused the wasting of resources.
Reclaim the high-salt wastewater that produces in the industry for waste lithium cell at present and also do not have cost-effective processing means.How economical, handle waste lithium cell effectively and reclaim the high-salt wastewater that industry produces, become the obstacle that battery reclaims industry healthy development.
Summary of the invention
For overcoming the prior art defective, the invention provides a kind of waste lithium cell and reclaim industry high-salt wastewater treatment process, this treatment process is simple, economy and salinity rate of recovery height.
The treatment process that waste lithium cell of the present invention reclaims the industry high-salt wastewater as shown in Figure 1, its concrete scheme is: a kind of waste lithium cell reclaims the treatment process of industry high-salt wastewater, may further comprise the steps:
(1) reverse osmosis process is handled: described high-salt wastewater is handled through reverse osmosis process, be purified water and dense water, the recycling of purifying waste water;
(2) dense water treatment: the salinity crystallization in the dense water is separated out, reclaimed;
(3) mother liquor after the salinity crystallization is separated out in the dense water is selected to return dense water treatment steps or mix and return the reverse osmosis process treatment step in the high-salt wastewater according to salt concentration wherein.
Described high-salt wastewater is that the waste lithium cell after operations such as gac, alkaline chemical precipitation heavy metal, resin deep purifying are handled reclaims industry production waste water, and its pH is 6～9, and each heavy metal content is 70～100g/L less than 1mg/L, sodium sulfate concentration.
Adopt one-level syllogic reverse osmosis process in the described step (1), use the low high desalination complex reverse osmosis membrane that pollutes.The rate of recovery of purifying waste water in this step is 50～55%, and ratio of desalinization is greater than 95%.
The method that the salinity crystallization is separated out described in the described step (2) is the method for spontaneous evaporation or low temperature crystallization or multistage flash evaporation.Described spontaneous evaporation method is that dense water enters the pond spontaneous evaporation of saltouing when sun power or wind energy abundance; Described low temperature crystallization method is to utilize winter the solubility with temperature of salt to reduce and the character that significantly reduces, allows salinity separate out naturally; The method of described multistage flash evaporation is for when for rainy season or spring and autumn, and dense water is handled through multistage flash evaporation, and the slurry after concentrating is put to saltouing the pond naturally cooling, obtains product salt.
In the salinity rate of recovery described in the step (2) greater than 75%.
The pond of saltouing of using in step (2) is long to be 100m, and wide be 20m, and sudden and violent tracheae is installed in the pond in, at the bottom of the pond with apply anticorrosion, leak-proof coating all around, establish Automatic rain awning above the pond.
Disclosed waste lithium cell of the present invention reclaims industry high-salt wastewater treatment process, and this treatment process is simple, economy and waste water and salinity rate of recovery height.Utilize the present invention can make waste lithium cell reclaim in the industry high-salt wastewater 50～55% waste water and directly return production, the salinity 95% or more enters dense water to be separated with waste water, and 75% above salinity obtains recovery with product form.The present invention has realized the recycle that waste lithium cell reclaims the industry high-salt wastewater, really realizes wastewater zero discharge; The present invention simultaneously makes full use of the salinity in the natural energies recovery waste water such as sun power, wind energy, significantly cuts down the consumption of energy, and saves cost, and the salinity that reclaims has certain economic benefits.
Description of drawings
Fig. 1 is a high-salt wastewater treatment process process flow sheet of the present invention.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1:
Implementation condition: summer, ambient temperature height, sun power abundance
A high-salt wastewater 100m picks up the car 3, Na 2SO 4Concentration is 94.16g/L, and PH is 8.1.Above-mentioned waste water is handled through reverse osmosis process, and middle employing one-level syllogic reverse osmosis process uses the low high desalination complex reverse osmosis membrane that pollutes, and is purified water 51m 3, dense water 49m 3Purify waste water and return the workshop reuse, Na in the dense water 2SO 4Concentration is 187.58g/l; Above-mentioned dense water is put into the pond of saltouing, utilizes sun power spontaneous evaporation to salt to analyze, after carry out solid-liquid separation and get 15.8 tons of saltcake (Na 2SO 410H 2O) and 5.6m 3Mother liquor, Na in the mother liquor 2SO 4Concentration is 397.03g/L, returns dense water treatment.
The waste water reclamation rate is 51% in the present embodiment, and ratio of desalinization is 97.6%, and the salinity rate of recovery is 75.81%.
Embodiment 2:
Implementation condition: in winter, ambient temperature is low
A high-salt wastewater 100m picks up the car 3, Na 2SO 4Concentration is 80.16g/L, and PH is 8.8.Above-mentioned waste water is handled through reverse osmosis process, is purified water 51.7m 3, dense water 48.3m 3Purify waste water and return the workshop reuse, Na in the dense water 2SO 4Concentration is 158.43g/l; Above-mentioned dense water is put into the pond of saltouing by after the heat exchanger heats to 70 ℃ earlier, open pneumatic blending in the pond, cooling afterwards salt analyzes, after carry out solid-liquid separation and get 14.15 tons of saltcake and 26m 3Mother liquor, wherein Na 2SO 4Concentration is 54.08g/l, this mother liquor is heated to 20 ℃ after, return the reverse osmosis operation, 14m must purify waste water 3With dense water 12m 3, Na in the dense water 2SO 4Concentration is 112.33g/l; Above-mentioned dense water is heated to 70 ℃ puts into the pond of saltouing, carry out solid-liquid separation after the cooling, get 2.42 tons of saltcake and 5.3m 3Mother liquor, Na in the mother liquor 2SO 4Concentration is 52.97g/l, returns the reverse osmosis operation.Twice altogether 16.57 tons of saltcake.
Twice waste water reclamation rate is respectively 51.7%, 53.8% in the present embodiment, and ratio of desalinization is respectively 95.46%, 95.87%; The salinity rate of recovery is respectively 77.84%, 79.88%.
Embodiment 3:
Implementation condition: spring and autumn, rainy season
A high-salt wastewater 100m picks up the car 3, Na 2SO 4Concentration is 95.16g/L, and PH is 9.3.Above-mentioned waste water is handled through reverse osmosis process, and 50m must purify waste water 3With dense water 50m 3Purify waste water and return the workshop reuse, Na in the dense water 2SO 4Concentration is 186.58g/l; Above-mentioned dense water through the multistage flash evaporation art breading, is carried out concentration and evaporation, and solid-liquid separation is carried out in the slurry pond of going into to saltout after cooling, 17.2 tons of saltcake, 9m 3Mother liquor, wherein Na 2SO 4Concentration is 193.76g/l.This mother liquor mixes dense water and returns the multistage flash evaporation operation.
The waste water reclamation rate is 50% in the present embodiment, and ratio of desalinization is 98.03%, and the salinity rate of recovery is 79.7%.
In sum, but the present invention is not limited to above-mentioned embodiment, and persons skilled in the art are in the disclosed technical scope of the present invention, and the variation that can expect easily is all within protection scope of the present invention.

Claims (8)

1. a waste lithium cell reclaims the treatment process of industry high-salt wastewater, it is characterized in that may further comprise the steps:
(1) reverse osmosis process is handled: described high-salt wastewater is handled through reverse osmosis process, be purified water and dense water, the recycling of purifying waste water;
(2) dense water treatment: the salinity crystallization in the dense water is separated out, reclaimed;
(3) mother liquor after the salinity crystallization is separated out in the dense water is selected to return dense water treatment steps or mix and return the reverse osmosis process treatment step in the high-salt wastewater.
2. waste lithium cell as claimed in claim 1 reclaims the treatment process of industry high-salt wastewater, and it is characterized in that: described high-salt wastewater pH is 6～9, and each heavy metal content is 70～100g/L less than 1mg/L, sodium sulfate concentration.
3. waste lithium cell as claimed in claim 1 reclaims the treatment process of industry high-salt wastewater, it is characterized in that: adopt one-level syllogic reverse osmosis process in the step (1), use the low high desalination complex reverse osmosis membrane that pollutes.
4. waste lithium cell as claimed in claim 3 reclaims the treatment process of industry high-salt wastewater, and it is characterized in that: the described rate of recovery of purifying waste water is 50～55%, and ratio of desalinization is greater than 95%.
5. waste lithium cell as claimed in claim 1 reclaims the treatment process of industry high-salt wastewater, and it is characterized in that: the method that the salinity crystallization is separated out described in the step (2) is the method for spontaneous evaporation or low temperature crystallization or multistage flash evaporation.
6. waste lithium cell as claimed in claim 5 reclaims the treatment process of industry high-salt wastewater, it is characterized in that: described spontaneous evaporation method is that dense water enters the pond spontaneous evaporation of saltouing when sun power or wind energy abundance; Described low temperature crystallization method is to utilize winter the solubility with temperature of salt to reduce and the character that significantly reduces, allows salinity separate out naturally; The method of described multistage flash evaporation is for when for rainy season or spring and autumn, and dense water is handled through multistage flash evaporation, and the slurry after concentrating is put to saltouing the pond naturally cooling, obtains product salt.
7. waste lithium cell as claimed in claim 6 reclaims the treatment process of industry high-salt wastewater, and it is characterized in that: the described salinity rate of recovery is greater than 75%.
8. waste lithium cell as claimed in claim 6 reclaims the treatment process of industry high-salt wastewater, it is characterized in that: the described pond of saltouing is long to be 100m, and wide be 20m, and sudden and violent tracheae is installed in the pond in, at the bottom of the pond with apply anticorrosion, leak-proof coating all around, establish Automatic rain awning above the pond.
CN201110233487.4A 2011-08-15 2011-08-15 Treatment method of high-salinity waste water in waste lithium battery recovering industry Active CN102285738B (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103058305A (en) * 2013-01-15 2013-04-24 中国寰球工程公司 Evaporation pond and crystal recovering method of high-salt concentrated water
CN103373785A (en) * 2012-04-25 2013-10-30 郭朝军 Cooling concentration and reverse osmosis combined salt-containing water concentrating method and equipment
CN104628217A (en) * 2013-11-12 2015-05-20 天津卡特化工技术有限公司 Method for recovery treatment of waste-and-old lithium battery electrolyte and treatment of electrolyte wastewater
CN104903246A (en) * 2012-08-08 2015-09-09 苏舍化学技术有限公司 Apparatus, use of apparatus and process for desalination of water
CN106277518A (en) * 2016-08-25 2017-01-04 东莞珂洛赫慕电子材料科技有限公司 A kind of electronic waste reclaims the processing method of waste water
CN107768760A (en) * 2016-08-22 2018-03-06 万向二三股份公司 A kind of lithium resource and salt alkali reclaiming method
CN108558126A (en) * 2018-02-27 2018-09-21 广东莞绿环保工程有限公司 A kind of processing method of lithium battery wastewater zero discharge
CN109721110A (en) * 2018-12-30 2019-05-07 沈阳化工研究院有限公司 A method of obtaining nickel cobalt manganese hydroxide from the active material that waste lithium cell recycles
CN110217933A (en) * 2019-07-15 2019-09-10 中国恩菲工程技术有限公司 The processing method of high-salt wastewater
CN110282786A (en) * 2019-06-14 2019-09-27 江苏卓博环保科技有限公司 Recycle waste lithium cell positive electrode waste water reclaiming processing unit and method
CN112939309A (en) * 2021-01-19 2021-06-11 重庆神华薄膜太阳能科技有限公司 Method and system for treating wastewater generated by thin-film solar cell

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JP2001321768A (en) * 2000-05-15 2001-11-20 Kawasaki Heavy Ind Ltd Method and device for treating leachate from waste landfill site
CN101139151A (en) * 2007-08-09 2008-03-12 上海市工业用水技术中心 Desalting amd concentrating method of polyvinyl chloride technique wastewater
CN101624248A (en) * 2009-07-29 2010-01-13 深圳市天骄科技开发有限公司 Method for processing wastewater in production of nickel cobalt lithium manganate

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JP2001321768A (en) * 2000-05-15 2001-11-20 Kawasaki Heavy Ind Ltd Method and device for treating leachate from waste landfill site
CN101139151A (en) * 2007-08-09 2008-03-12 上海市工业用水技术中心 Desalting amd concentrating method of polyvinyl chloride technique wastewater
CN101624248A (en) * 2009-07-29 2010-01-13 深圳市天骄科技开发有限公司 Method for processing wastewater in production of nickel cobalt lithium manganate

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103373785A (en) * 2012-04-25 2013-10-30 郭朝军 Cooling concentration and reverse osmosis combined salt-containing water concentrating method and equipment
US10118836B2 (en) 2012-08-08 2018-11-06 Sulzer Chemtech Ag Apparatus, use of apparatus and process for desalination of water
CN104903246A (en) * 2012-08-08 2015-09-09 苏舍化学技术有限公司 Apparatus, use of apparatus and process for desalination of water
CN103058305A (en) * 2013-01-15 2013-04-24 中国寰球工程公司 Evaporation pond and crystal recovering method of high-salt concentrated water
CN103058305B (en) * 2013-01-15 2015-09-30 中国寰球工程公司 The crystallization recovery method of a kind of evaporation pond and the dense water of a kind of high saliferous
CN105541043B (en) * 2013-11-12 2019-05-31 天津卡特化工技术有限公司 Based on MBR and A2The waste lithium cell electrolyte of/O and the processing method of electrolyte waste water
CN104628217B (en) * 2013-11-12 2016-09-07 天津卡特化工技术有限公司 A kind of processing method recycling waste lithium cell electrolyte and electrolyte waste water
CN105541043A (en) * 2013-11-12 2016-05-04 天津卡特化工技术有限公司 MBR and A2/O based treatment method of waste lithium battery electrolyte and electrolyte waste water
CN104628217A (en) * 2013-11-12 2015-05-20 天津卡特化工技术有限公司 Method for recovery treatment of waste-and-old lithium battery electrolyte and treatment of electrolyte wastewater
CN107768760A (en) * 2016-08-22 2018-03-06 万向二三股份公司 A kind of lithium resource and salt alkali reclaiming method
CN107768760B (en) * 2016-08-22 2019-07-16 万向一二三股份公司 A kind of lithium resource and salt alkali reclaiming method
CN106277518A (en) * 2016-08-25 2017-01-04 东莞珂洛赫慕电子材料科技有限公司 A kind of electronic waste reclaims the processing method of waste water
CN108558126A (en) * 2018-02-27 2018-09-21 广东莞绿环保工程有限公司 A kind of processing method of lithium battery wastewater zero discharge
CN109721110A (en) * 2018-12-30 2019-05-07 沈阳化工研究院有限公司 A method of obtaining nickel cobalt manganese hydroxide from the active material that waste lithium cell recycles
CN110282786A (en) * 2019-06-14 2019-09-27 江苏卓博环保科技有限公司 Recycle waste lithium cell positive electrode waste water reclaiming processing unit and method
CN110217933A (en) * 2019-07-15 2019-09-10 中国恩菲工程技术有限公司 The processing method of high-salt wastewater
CN112939309A (en) * 2021-01-19 2021-06-11 重庆神华薄膜太阳能科技有限公司 Method and system for treating wastewater generated by thin-film solar cell

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