WO2019010835A1 - Procédé d'élimination complète d'ions métalliques lourds dans les eaux usées d'une usine de piles au moyen d'un système de mousse à base d'eau - Google Patents

Procédé d'élimination complète d'ions métalliques lourds dans les eaux usées d'une usine de piles au moyen d'un système de mousse à base d'eau Download PDF

Info

Publication number
WO2019010835A1
WO2019010835A1 PCT/CN2017/104317 CN2017104317W WO2019010835A1 WO 2019010835 A1 WO2019010835 A1 WO 2019010835A1 CN 2017104317 W CN2017104317 W CN 2017104317W WO 2019010835 A1 WO2019010835 A1 WO 2019010835A1
Authority
WO
WIPO (PCT)
Prior art keywords
heavy metal
wastewater
metal ions
surfactant
water
Prior art date
Application number
PCT/CN2017/104317
Other languages
English (en)
Chinese (zh)
Inventor
李英
张凯
Original Assignee
山东大学
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 山东大学 filed Critical 山东大学
Publication of WO2019010835A1 publication Critical patent/WO2019010835A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Definitions

  • the invention relates to a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system, and belongs to the technical field of environmental chemistry.
  • the treatment measures for heavy metal pollution in water can be mainly divided into physical methods, chemical methods, biological methods, etc. according to their mechanism of action.
  • the physical method includes extraction method, adsorption method, ion exchange method, membrane separation, etc., adsorption, concentration and separation without changing the chemical form of heavy metal ions in the wastewater; the method has high efficiency, but has high input cost and large engineering quantity. It is easy to introduce secondary pollution sources and other shortcomings.
  • the biological method mainly removes heavy metal ions in polluted water by the absorption and enrichment of plants and microorganisms. However, due to its long action period and small amount of treatment, plants treated with heavy metal ions are difficult to handle, and the recovery rate of metal ions is low. Short boards also restrict their promotion in industrial applications.
  • the chemical method generally removes heavy metal ions by oxidation, reduction, precipitation, adsorption and inhibition of additives and heavy metal ions.
  • the precipitation method has become the most widely used treatment method in battery plant wastewater treatment because of its good economy and wide application range.
  • the addition of hydroxides, sulfides and chelating agents or complexes which strongly bind to heavy metal ions forms a water-insoluble precipitate with heavy metal ions, thereby purifying the water body.
  • the operation is complicated, the efficiency is not high, and the treatment of precipitates is difficult. If it is not handled properly, it will be easily reactivated, which will cause secondary pollution and it is difficult to meet national emission standards.
  • the present invention provides a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system.
  • the invention adopts a green environmentally-friendly specific surfactant to form a water-based foam, and the selected surfactant has electrical interaction or complexation with heavy metal ions such as Pb 2+ and Zn 2+ , and the surfactant molecules are closely related to the metal cation.
  • the amphiphilic adsorption of the surfactant is carried out at the gas-liquid interface, and the heavy metal ions are carried out of the polluted water body by the floating bubbles.
  • the invention has the advantages of simple operation, low cost, low concentration of surfactant, strong adaptability to the complexity of the wastewater of the battery factory, high removal efficiency, suitable for removal of various heavy metal ions, and ensuring by using a green environmentally-friendly surfactant. There is no secondary pollution to the environment.
  • a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system including the following steps:
  • the surfactant described in the step (1) is a surfactant having at least one negatively charged polar hydrophilic group and a hydrophobic base carbon chain having a length of from 8 to 24, which is negative.
  • the electrodepositive hydrophilic group is a sulfate group, a sulfonic acid group or a carboxylic acid group.
  • the surfactant further contains an EO, carbonyl or amide group.
  • the surfactant is one or more selected from the group consisting of an alkyl sulfate, a fatty alcohol polyoxyethylene ether sulfate, an alkyl carboxylate or an alkyl polyether carboxylate. mixing.
  • the sulfate group-containing surfactant is sodium lauryl sulfate or a fatty alcohol polyoxyethylene ether sulfate.
  • the carboxylic acid group-containing surfactant is sodium lauryl carboxylate or sodium tridecyl polyether-4-carboxylate.
  • the molar ratio of the surfactant to the total moles of all heavy metal ions in the wastewater in the step (1) is (1 to 30): 1, preferably, the total moles of all heavy metal ions in the surfactant and the wastewater.
  • the molar ratio is (3-15): 1, and most preferably, the molar ratio of the surfactant to the total moles of all heavy metal ions in the wastewater is (5-7):1.
  • the pH of the wastewater in step (1) is 5-11.
  • the flow rate of the blowing gas in the step (2) is 0.1 to 0.7 L/min, and more preferably, the flow rate of the blowing gas is 0.2 to 0.6 L/min.
  • the blowing gas in step (2) is N 2 or air.
  • the bottom of the foam processor in step (2) is filled with a porous medium quartz sand having a porosity of 35-45%, an average pore throat radius of 0.1-10 ⁇ m, and a filling height of 4-7 mm. .
  • the wastewater can be pretreated before the foam separation, that is, the pH of the wastewater is adjusted to weak acid or neutral by adding an appropriate amount of alkali solution, and The resulting precipitate was filtered. If the wastewater does not have the above characteristics, no pretreatment is required. After the treatment, the flame atomic spectrophotometer is used. The remaining water body is subjected to measurement of heavy metal ion concentration, and the removal efficiency of heavy metal ions is calculated.
  • the invention adopts a specific surfactant which interacts with heavy metal ions such as Pb 2+ , Zn 2+ , the surfactant molecule and the metal cation are tightly combined in the aqueous solution, and the gas is introduced into the solution, due to the parents of the surfactant The property will be adsorbed on the gas-liquid interface of the bubble, and the foam will be formed by the difference in density, and the heavy metal ions will be carried out of the polluted water body.
  • heavy metal ions such as Pb 2+ , Zn 2+
  • the method of the invention can completely remove the heavy metal ions such as Pb 2+ and Zn 2+ enriched in the wastewater of the battery plant, and has the advantages of rapid and high efficiency, low input, low energy consumption and simple operation.
  • the method of the invention is applied to the treatment of wastewater of a battery factory contaminated by heavy metal ions such as Pb 2+ , Zn 2+ , the amount of surfactant is small, the removal efficiency of heavy metal ions is high, and the Pb 2+ and Zn 2+ in the wastewater are high.
  • the removal efficiency can reach more than 99.8%, which does not cause secondary pollution to the water body, and achieves the effect of completely removing heavy metal ions.
  • the method of the invention can be directly applied to various battery plant wastewaters polluted by heavy metal ions to achieve an ideal removal efficiency and meet national emission standards.
  • the method of the present invention which is detached from the foam of the aqueous phase, can be recovered after treatment, and the surfactant can also be recycled.
  • the removal efficiency was calculated by measuring the concentration of heavy metal ions in the water before and after the treatment.
  • the removal efficiency ⁇ (C 1 - C 2 ) / C 1 , where C 1 is the concentration of heavy metal ions before treatment, and C 2 is the concentration of residual heavy metal ions after the end of foaming.
  • Factors influencing the removal efficiency include the type of hydrophilic group of the surfactant, the molar ratio of surfactant to metal ion, the gas flow rate, the concentration of the surfactant solution, and the bulk pH.
  • Figure 1 is a graph showing the effect of gas flow rate on the removal efficiency of Pb 2+ and Zn 2+ .
  • a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system wherein the concentration of Pb 2+ in the wastewater to be treated is 0.5 mmol/L, the solution is weakly acidic, and the pH is 4, and the steps are as follows:
  • the wastewater is weakly acidic and does not require pretreatment.
  • Sodium dodecyl sulfate is dissolved in water to prepare a solution of sodium lauryl sulfate, which is added to the wastewater.
  • the overall concentration of sodium lauryl sulfate in the wastewater is 3.5 mmol. / L, the molar ratio of sodium lauryl sulfate to Pb 2+ is 7:1;
  • the mixture obtained in the step (1) is introduced into a foam processor filled with porous media quartz sand, and N 2 is introduced into the bottom of the foam processor at a gas flow rate of 0.1 L/min, and foaming is continued until it cannot be produced.
  • the foam is introduced into the foam collector through a pipe at the top of the treatment column for use as a surfactant and heavy metal ion recovery.
  • the wastewater is neutral, no pretreatment is required, and the sodium tridecyl polyether-4-carboxylate is dissolved in water to prepare a solution of sodium tridecyl polyether-4-carboxylate, which is added to the wastewater and mixed uniformly in the wastewater.
  • the overall concentration of sodium tridecyl polyether-4-carboxylate is 2.5 mmol/L, and the molar ratio of sodium tridecyl polyether-4-carboxylate to the total moles of Pb 2+ and Zn 2+ is 5: 1;
  • the mixture obtained in the step (1) is introduced into a foam processor filled with a porous medium quartz sand, and N 2 is introduced into the bottom of the foam processor at a gas flow rate of 0.2 L/min, and foaming is continued until it cannot be produced.
  • the foam is introduced into the foam collector through a pipe at the top of the treatment column for use as a surfactant and heavy metal ion recovery.
  • the results show that the method removes Pb 2+ and Zn 2+ . The efficiency can reach more than 99.9%.
  • a method for thoroughly removing heavy metal ions in battery plant wastewater by using a water-based foam system wherein the concentration of Pb 2+ and Zn 2+ after dilution of the treated wastewater is 0.3 mmol/L, 0.7 mmol/L, the solution is weakly acidic, and the pH is 5, the steps are as follows:
  • the wastewater is weakly acidic, no pretreatment is required, and the sodium tridecyl polyether-4-carboxylate is dissolved in water to prepare a solution of sodium tridecyl polyether-4-carboxylate, which is added to the wastewater, and uniformly mixed in the wastewater.
  • the overall concentration of sodium tridecyl polyether-4-carboxylate is 5 mmol/L, and the molar ratio of sodium tridecyl polyether-4-carboxylate to the total moles of Pb 2+ and Zn 2+ is 5:1. ;
  • the mixture obtained in the step (1) is introduced into a foam processor filled with a porous medium quartz sand, and N 2 is introduced into the bottom of the foam processor at a gas flow rate of 0.2 L/min, and foaming is continued until it cannot be produced.
  • the foam is introduced into the foam collector through a pipe at the top of the treatment column for use as a surfactant and heavy metal ion recovery.
  • a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system wherein the concentrations of Pb 2+ and Zn 2+ in the wastewater to be treated are 1.0 mmol/L and 1.5 mmol/L, respectively, and the solution is strongly acidic and has a pH of 1.2. Proceed as follows:
  • the wastewater is strongly acidic.
  • the wastewater from the battery plant is pretreated, 1mmol/L sodium hydroxide solution is prepared, the wastewater is added to the wastewater to adjust the wastewater to neutrality, the pH is 7, the precipitate is filtered, and the filtrate is retained to measure the heavy metal ions again.
  • the mixture obtained in the step (1) is introduced into a foam processor filled with a porous medium quartz sand, and N 2 is introduced into the bottom of the foam processor at a gas flow rate of 0.3 L/min, and foaming is continued until it cannot be produced.
  • the foam is introduced into the foam collector through a pipe at the top of the treatment column for use as a surfactant and heavy metal ion recovery.
  • Comparative Example 1 The gas flow rate was 0.01 L/min.
  • Comparative Example 2 The gas flow rate was 0.05 L/min.
  • Comparative Example 4 The gas flow rate was 1.2 L/min.
  • Comparative Example 5 The gas flow rate was 1.4 L/min.
  • Comparative Example 6 The gas flow rate was 1.6 L/min.
  • Comparative Example 7 The gas flow rate was 2.0 L/min.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

L'invention concerne un procédé d'élimination complète d'ions de métaux lourds dans des eaux usées d'usine de piles au moyen d'un système de mousse à base d'eau, le procédé consistant : à ajuster la valeur de pH des eaux usées de 4 à 11, à ajouter une solution d'agent tensioactif aux eaux usées de telle sorte que le rapport molaire du nombre total de moles de l'agent tensioactif et de tous les ions de métaux lourds dans les eaux usées soit approprié, à agiter jusqu'à uniformité; à introduire le liquide mélangé dans un processeur de mousse, et à introduire un gaz moussant dans le fond du processeur de mousse à un certain débit de gaz au moyen d'un noyau en sable de quartz, ainsi qu'à introduire la mousse générée dans un collecteur de mousse au moyen d'un tuyau au sommet du processeur de mousse de façon à réaliser un traitement de démoussage et de récupération de métal lourd jusqu'à ce qu'il n'y ait plus de mousse. Le procédé présente une opération simple, est peu coûteux, et est approprié pour éliminer divers ions de métaux lourds.
PCT/CN2017/104317 2017-07-14 2017-09-29 Procédé d'élimination complète d'ions métalliques lourds dans les eaux usées d'une usine de piles au moyen d'un système de mousse à base d'eau WO2019010835A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710576845.9A CN107352680B (zh) 2017-07-14 2017-07-14 一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法
CN201710576845.9 2017-07-14

Publications (1)

Publication Number Publication Date
WO2019010835A1 true WO2019010835A1 (fr) 2019-01-17

Family

ID=60292971

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/104317 WO2019010835A1 (fr) 2017-07-14 2017-09-29 Procédé d'élimination complète d'ions métalliques lourds dans les eaux usées d'une usine de piles au moyen d'un système de mousse à base d'eau

Country Status (2)

Country Link
CN (1) CN107352680B (fr)
WO (1) WO2019010835A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108658204A (zh) * 2018-06-07 2018-10-16 厦门大学 无患子提取物在泡沫分离采收镍离子中的应用
CN109081393A (zh) * 2018-08-27 2018-12-25 北京中晟清源环保科技有限公司 一种新型气浮助剂及制备方法
CN109721147B (zh) * 2019-02-27 2021-11-19 郑州大学 一种回收废水中金属离子并制备锂离子电池负极材料的方法
CN109809518A (zh) * 2019-03-06 2019-05-28 广州大学 一种泡沫浮选法处理含铊废水的装置
CN112427451A (zh) * 2020-11-20 2021-03-02 山东大学 同时去除土壤中重金属和有机污染物的水基泡沫体系及方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6635182B1 (en) * 2001-05-04 2003-10-21 Industrial Waste Water Services, Llp Floatation process for removal of heavy metal waste and associated apparatus
CN1843963A (zh) * 2006-04-30 2006-10-11 湖南大学 中空纤维超滤膜强化超滤和泡沫气浮处理含镉废水的方法
KR20120069895A (ko) * 2010-12-21 2012-06-29 재단법인 포항산업과학연구원 중금속을 함유한 폐수 처리방법 및 그 처리장치
CN107055666A (zh) * 2017-06-06 2017-08-18 陕西理工大学 一种高效处理废水中多种重金属离子的装置与方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106587273A (zh) * 2017-01-05 2017-04-26 扬州大学 一种生物表面活性剂胶团强化超滤处理重金属废水的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6635182B1 (en) * 2001-05-04 2003-10-21 Industrial Waste Water Services, Llp Floatation process for removal of heavy metal waste and associated apparatus
CN1843963A (zh) * 2006-04-30 2006-10-11 湖南大学 中空纤维超滤膜强化超滤和泡沫气浮处理含镉废水的方法
KR20120069895A (ko) * 2010-12-21 2012-06-29 재단법인 포항산업과학연구원 중금속을 함유한 폐수 처리방법 및 그 처리장치
CN107055666A (zh) * 2017-06-06 2017-08-18 陕西理工大学 一种高效处理废水中多种重金属离子的装置与方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG ET AL.: "An experimental study on waste water containing Cr of continuous foam separation", CHINESE JOURNAL OF HEALTH LABORATORY TECHNOLOGY, 31 December 2008 (2008-12-31) *

Also Published As

Publication number Publication date
CN107352680A (zh) 2017-11-17
CN107352680B (zh) 2020-04-21

Similar Documents

Publication Publication Date Title
WO2019010835A1 (fr) Procédé d'élimination complète d'ions métalliques lourds dans les eaux usées d'une usine de piles au moyen d'un système de mousse à base d'eau
CN100390081C (zh) 含硝基苯、苯胺污染物废水的处理方法
CN104843934B (zh) 一种抗生素生产废水的处理方法
CN107473466B (zh) 一种选矿废水的处理方法
CN108002580A (zh) 一种酸性烟气洗涤废水处理方法及其用途
CN103951114B (zh) 一种重金属废水三级处理与深度净化回用工艺
CN104437389B (zh) 一种处理含铅废水吸附剂的制备方法及应用
CN107162298A (zh) 一种高盐有机废水的近零排放处理方法
CN208471815U (zh) 一种ao工艺与芬顿系统配套的高浓度污水处理系统
CN204714549U (zh) 一种煤化工废水二氧化碳气浮处理系统
CN106186559A (zh) 高硫酸盐高有机物工业废水的处理方法
CN106809939B (zh) 保持铁锰氧化物催化氧化去除地表水中氨氮活性的方法
CN104761039A (zh) 一种处理含镉废水的复合螯合剂及其应用方法
CN204325076U (zh) 一种畜禽养殖废水脱氮除磷处理系统
CN113562830B (zh) 一种铜冶炼污酸沉砷剂的制备方法
CN110092498A (zh) 一种废水的芬顿氧化处理方法
CN108793505A (zh) 同时处理浮选硫化铜废水和酸性有机废水的方法
CN101665289B (zh) 一种油田聚合物驱采出水的处理方法
CN104445715B (zh) 一种脱除高浓度含镍电镀废水的处理方法
CN107032536A (zh) 一种串级一体式气浮去除柑橘废水中cod的方法
CN107473316A (zh) 固态重金属废水处理剂
CN103449671A (zh) 一种煤矿酸性矿井水的处理系统及其处理工艺
CN209081624U (zh) 一种微电解联合催化氧化的污水处理系统
CN102757103B (zh) 一种新型环保炼油废水除臭剂及其应用
CN208648942U (zh) 一种基于过硫酸盐处理脱硫废水的装置

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: 17917674

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: 17917674

Country of ref document: EP

Kind code of ref document: A1