WO2021138960A1 - 一种同步实现有机磷废水处理和资源化利用的电化学方法 - Google Patents
一种同步实现有机磷废水处理和资源化利用的电化学方法 Download PDFInfo
- Publication number
- WO2021138960A1 WO2021138960A1 PCT/CN2020/075372 CN2020075372W WO2021138960A1 WO 2021138960 A1 WO2021138960 A1 WO 2021138960A1 CN 2020075372 W CN2020075372 W CN 2020075372W WO 2021138960 A1 WO2021138960 A1 WO 2021138960A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wastewater
- organic phosphorus
- treatment
- phosphorus
- resource utilization
- Prior art date
Links
Images
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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F2101/30—Organic compounds
Definitions
- This application relates to the field of wastewater treatment, and in particular to an electrochemical method for simultaneously realizing the treatment and resource utilization of organophosphorus wastewater.
- organophosphorus pesticides With the widespread use of organophosphorus pesticides in agriculture and forestry, the environmental pollution caused by them is becoming more and more serious. How to eliminate residual organophosphorus pesticides in the environment has become a research hotspot in countries all over the world, with broad application prospects and great application value .
- the common methods of organic phosphorus degradation include photodegradation, microbial degradation, and chemical degradation.
- the advanced electrochemical oxidation technology in recent years has used its degrading
- the advantages of high efficiency, universality and thoroughness have received widespread attention in the field of water treatment.
- this application provides an electrochemical method for simultaneously realizing the treatment and resource utilization of organophosphorus wastewater, and establishes an electrochemical reaction system of "anodic oxidation-cathode enrichment", which produces a large amount of strong oxidation on the anode surface Hydroxyl radicals rapidly degrade organophosphorus pollutants into inorganic phosphate ions, and at the same time induce the concentration of inorganic phosphate ions and calcium hardness ions on the cathode surface under the local strong alkaline atmosphere on the cathode surface, thereby solving the problem of organic phosphorus The problem of resource recycling of pollutants.
- the technical solution of the present application is to utilize the local strong alkaline atmosphere generated by the electrolysis water reaction on the cathode surface to induce and strengthen the inorganic phosphate ions and calcium hardness ions generated by the rapid oxidation of the organic phosphorus pollutants by the anode on the cathode surface. Collect, form phosphate minerals that can be recycled and reused, and realize the removal and resource utilization of organic phosphorus pollutants in wastewater. .
- the cathode is titanium mesh/plate, steel mesh/plate, etc.
- the anodes are BDD electrodes, DSA electrodes, tin antimony electrodes, ruthenium iridium electrodes, iridium tantalum electrodes, PbO 2 electrodes and the like.
- the distance between the anode and cathode electrodes in the electrochemical reaction system is 0-500 mm, and the current density is 0.1-50 mA/cm 2 .
- the molar concentration ratio of hardness ions to total phosphorus in the organic phosphorus wastewater is 0.5:1-20:1.
- the anodic oxidation mechanism takes BDD electrode as an example.
- Typical materials BDD inactive anode electrode, its high oxygen overpotential, ⁇ OH can produce more electrolyzed water on its surface.
- the mechanism is as formula (1,2):
- the local strong alkaline atmosphere on the surface of the cathode is used to induce the enrichment of calcium hydroxyphosphate without adding acid and alkali, which greatly reduces the amount of chemicals.
- the cathode itself is used as the enrichment carrier to fix the calcium hydroxyphosphate, which solves the problem of insufficient sedimentation performance and does not require an additional solid-liquid separation process.
- Figure 1 shows the change of (a) total phosphorus concentration and (b) inorganic phosphorus concentration over time during the 180min treatment of organic phosphorus wastewater with an organic phosphorus concentration of 10 mg/L using the method of this application. It can be seen from Figure 1 that after 180 minutes, the electrochemical anode can oxidize and degrade almost 100% of the organic phosphorus pollutants into inorganic phosphorus, while the electrochemical cathode can enrich 86% of the inorganic phosphorus ions on the cathode plate.
- Fig. 2 shows the change of total phosphorus concentration over time during the process of 180min treatment of organic phosphorus wastewater with an organic phosphorus concentration of 10 mg/L using different current densities in the method of the present application. It can be seen from Figure 2 that the recycling rate of total phosphorus is positively correlated with the current density.
Abstract
一种同步实现有机磷废水处理和资源化利用的电化学方法,电化学阳极用于有机磷污染物向无机磷的快速氧化,而阴极表面因电解水反应可产生局域强碱性氛围,进而诱导并强化无机磷酸根离子与钙硬度离子在阴极表面富集,形成可资源化回收利用的磷酸盐矿物,实现废水中有机磷污染物的去除和磷的资源化利用。
Description
本申请涉及废水处理领域,特别涉及一种同步实现有机磷废水处理和资源化利用的电化学方法。
随着有机磷农药在农林业上的广泛使用,其引发的环境污染问题日益严重,如何消除环境中的残留有机磷农药已成为世界各国的一个研究热点,具有广阔的应用前景和重大的应用价值。目前,有机磷降解的常见方法包括光降解、微生物降解和化学降解,但是由于有机磷废水处理难度大、生化处理装置负荷重、处理能耗高,故而近年来电化学高级氧化技术以其降解有机物的高效性、普遍性和彻底性等优势在水处理领域受到广泛关注。然而,尽管目前已有一些关注通过电化学高级氧化技术处理有机磷废水的研究,但是这些研究只是实现了有机磷向无机磷的氧化转化,并未实现水体中磷的彻底脱除及资源化利用。
作为一种应用广阔、不可或缺、但暂无替代品种的不可再生资源,磷矿石的全球储备量逐年大幅下降很有可能在未来引发潜在的磷资源短缺危机,这使得如何在有机磷废水中实现磷的资源化利用变得至关重要。大多数情况下,无机磷酸根离子可以通过生成难溶或不溶的磷酸盐沉淀去除。由于羟基磷酸钙可作为化肥行业的优质原料,且多数水体中通常含有钙硬度离子,所以利用钙硬度离子实现有机磷资源化回收利用的方法具有较好的发展前景。但是这种方法所生成的羟基磷酸钙沉淀的沉降性能不足,需要额外的固液分离过程,且处理后废水的高pH值不能满足排放要求,故而在实际应用上仍存在一定的局限性。
发明内容
根据以上现有技术的不足,本申请提供一种同步实现有机磷废水处理和资源化利用的电化学方法,建立“阳极氧化-阴极富集”的电化学反应体系,在阳极表面产生大量强氧化性的羟基自由基将有机磷污染物快速降解为无机磷酸根离子,同时在阴极表面的局域强碱性氛围下诱导无机磷酸根离子与钙硬度离子在阴极表面富集,从而解决了有机磷污染物资源化回收利用的难题。
本申请的技术方案是:利用阴极表面由于电解水反应产生的局域强碱性氛围,诱导并强化因有机磷污染物被阳极快速氧化所生成的无机磷酸根离子与钙硬度离子在阴极表面富集,形成可资源化回收利用的磷酸盐矿物,实现废水中有机磷污染物的去除和资源化利用。。
其中,优选方案如下:
所述的阴极为钛网/板、钢网/板等。
所述的阳极为BDD电极、DSA电极、锡锑电极、钌铱电极、铱钽电极、PbO
2电极等。
所述的电化学反应体系内阳阴极电极间距为0-500mm,电流密度为0.1-50mA/cm
2。
所述的有机磷废水中硬度离子与总磷的摩尔浓度比为0.5:1-20:1。
发明的原理:
阳极氧化机理以BDD电极为例。BDD电极是非活性阳极的典型材料,以其较高的析氧过电位,可以在其表面电解水产生较多的
·OH。机理如公式(1,2):
BDD+H
2O→BDD(
·OH)+H
++e
- (1)
BDD(
·OH)+有机物→BDD+CO
2+H
2O+无机离子 (2)
阴极电解水反应生成大量OH
-,OH
-一方面通过使阴极表面产生局域强碱性氛围来诱导磷酸盐矿物富集,一方面与无机磷酸根离子和钙硬度离子一同生成羟基磷酸钙沉淀。机理如公式(3,4):
H
2O+e
-→OH
-+H
2↑ (3)
PO
4
3-+Ca
2++OH
-→Ca
10(PO
4)
6(OH)
2↓ (4)
本申请所具有的优点在于:
(1)利用阴极表面的局域强碱性氛围诱导羟基磷酸钙富集,无需额外投加酸碱,大大减少了化学品的用量。
(2)利用阴极自身作为富集载体将羟基磷酸钙固定,解决了沉淀物沉降性能不足的问题,无需额外的固液分离过程。
(3)合理利用阴、阳极的不同机理,通过二者的协同作用,同步实现了有机磷废水的处理和资源化利用。
图1是使用本申请方法对有机磷浓度为10mg/L的有机磷废水进行180min处理的过程中(a)总磷浓度和(b)无机磷浓度随时间的变化情况。由图1可看出,180min后电化学阳极可将几乎100%的有机磷污染物氧化降解为无机磷,电化学阴极则可将其中86%的无机磷离子富集在阴极板上。
图2是在本申请方法中使用不同电流密度对有机磷浓度为10mg/L的有机磷废水进行180min处理的过程中总磷浓度随时间的变化情况。由图2可看出,总磷的资源化回收率与电流密度呈正相关关系。
为使本申请实施例的目的、技术方案和优点更加清楚,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得 的所有其他实施例,都属于本申请保护的范围。
实施例1:
在有机磷浓度为10mg/L的废水溶液中,加入50mg/L的Ca
2+和0.1M的无水硫酸钠,再加入硫酸将pH值调节至6.0,常温常压下以电流密度为20mA/cm
2进行处理即可。180min处理后的废水中总磷浓度为1.41mg/L,无机磷浓度为1.30mg/L,如图1所示。
实施例2:
在有机磷浓度为10mg/L的废水溶液中,加入50mg/L的Ca
2+和0.1M的无水硫酸钠,再加入硫酸将pH值调节至6,常温常压下以电流密度分别为0mA/cm
2、5mA/cm
2、10mA/cm
2、20mA/cm
2、30mA/cm
2进行处理即可。180min处理后的废水中总磷浓度分别降低至10.48mg/L、5.97mg/L、3.80mg/L、1.42mg/L、1.01mg/L,如图2所示。
对比实施例1:
在有机磷浓度为10mg/L的废水溶液中,加入0.1M的无水硫酸钠,再加入硫酸将pH值调节至6.0,常温常压下以电流密度为20mA/cm
2进行处理即可。180min处理后的废水中总磷浓度为10.52mg/L,无机磷浓度为10.25mg/L,如图1所示。
尽管上面已经示出和描述了本申请的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本申请的限制,本领域的普通技术人员在不脱离本申请的原理和宗旨的情况下在本申请的范围内可以对上述实施例进行变化、修改、替换和变型。
Claims (5)
- 一种同步实现有机磷废水处理和资源化利用的电化学方法,其特征在于:电化学阳极用于有机磷污染物向无机磷的快速氧化,而阴极表面因电解水反应可产生局域强碱性氛围,进而诱导并强化无机磷酸根离子与钙硬度离子在阴极表面富集,形成可资源化回收利用的磷酸盐矿物,实现废水中有机磷污染物的去除和磷的资源化利用。
- 根据权利1要求所述的一种同步实现有机磷废水处理和资源化利用的电化学方法,其特征在于:所述的阴极为钛网/板、钢网/板等。
- 根据权利1要求所述的一种同步实现有机磷废水处理和资源化利用的电化学方法,其特征在于:所述的阳极为BDD电极、DSA电极、锡锑电极、钌铱电极、铱钽电极、PbO 2电极等。
- 根据权利1要求所述的一种同步实现有机磷废水处理和资源化利用的电化学方法,其特征在于:所述的电化学反应体系内阳阴极电极间距为0-500mm,电流密度为0.1-50mA/cm 2。
- 根据权利1要求所述的一种同步实现有机磷废水处理和资源化利用的电化学方法,其特征在于:所述的有机磷废水中硬度离子与总磷的摩尔浓度比为0.5:1-20:1。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010023098.8A CN111186882A (zh) | 2020-01-09 | 2020-01-09 | 一种同步实现有机磷废水处理和资源化利用的电化学方法 |
CN202010023098.8 | 2020-01-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021138960A1 true WO2021138960A1 (zh) | 2021-07-15 |
Family
ID=70705225
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2020/075372 WO2021138960A1 (zh) | 2020-01-09 | 2020-02-14 | 一种同步实现有机磷废水处理和资源化利用的电化学方法 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN111186882A (zh) |
WO (1) | WO2021138960A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111847602A (zh) * | 2020-06-12 | 2020-10-30 | 中国科学院生态环境研究中心 | 一种电化学调控钙质矿物材料除磷的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6471873B1 (en) * | 2000-01-26 | 2002-10-29 | Bernard Greenberg | Electrolytic process and apparatus for purifying contaminated aqueous solutions and method for using same to remediate soil |
CN1457322A (zh) * | 2001-02-28 | 2003-11-19 | 三洋电机株式会社 | 排水处理方法、排水处理装置及排水处理系统 |
CN103058330A (zh) * | 2012-12-04 | 2013-04-24 | 江苏丰山集团有限公司 | 一种掺硼金刚石膜电极处理高浓度有机磷废水工艺 |
CN104591336A (zh) * | 2015-01-26 | 2015-05-06 | 重庆文理学院 | 一种从含磷霉素废水中回收磷的方法 |
CN206051636U (zh) * | 2016-08-12 | 2017-03-29 | 四川悦承环保节能科技有限公司 | 一种电解除磷装置 |
CN106915802A (zh) * | 2017-04-12 | 2017-07-04 | 哈尔滨工业大学 | 难降解有机废水处理的一体式电化学反应装置及处理方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4696178B1 (ja) * | 2010-09-16 | 2011-06-08 | 吉昭 小池 | 水素含有水の製造方法 |
-
2020
- 2020-01-09 CN CN202010023098.8A patent/CN111186882A/zh active Pending
- 2020-02-14 WO PCT/CN2020/075372 patent/WO2021138960A1/zh active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6471873B1 (en) * | 2000-01-26 | 2002-10-29 | Bernard Greenberg | Electrolytic process and apparatus for purifying contaminated aqueous solutions and method for using same to remediate soil |
CN1457322A (zh) * | 2001-02-28 | 2003-11-19 | 三洋电机株式会社 | 排水处理方法、排水处理装置及排水处理系统 |
CN103058330A (zh) * | 2012-12-04 | 2013-04-24 | 江苏丰山集团有限公司 | 一种掺硼金刚石膜电极处理高浓度有机磷废水工艺 |
CN104591336A (zh) * | 2015-01-26 | 2015-05-06 | 重庆文理学院 | 一种从含磷霉素废水中回收磷的方法 |
CN206051636U (zh) * | 2016-08-12 | 2017-03-29 | 四川悦承环保节能科技有限公司 | 一种电解除磷装置 |
CN106915802A (zh) * | 2017-04-12 | 2017-07-04 | 哈尔滨工业大学 | 难降解有机废水处理的一体式电化学反应装置及处理方法 |
Also Published As
Publication number | Publication date |
---|---|
CN111186882A (zh) | 2020-05-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10718055B2 (en) | Carbon dioxide capture and storage electrolytic methods | |
CN104152905A (zh) | 酸性氯化铜蚀刻液电解再生循环及铜板回收装置及方法 | |
Ren et al. | Effective treatment of spacer tube reverse osmosis membrane concentrated leachate from an incineration power plant using coagulation coupled with electrochemical treatment processes | |
CN208279439U (zh) | 一种高盐有机氨氮废水电解处理装置 | |
CN103771633A (zh) | 一种高盐度稀土湿法冶炼废水中有机污染物的电解处理工艺 | |
CN110639937A (zh) | 一种无害稳定化电解锰渣的综合处理方法 | |
CN110902895A (zh) | 一种垃圾渗滤液中氨氮去除与回收的电化学膜分离方法 | |
CN104911596A (zh) | 一种蚀刻液循环再生及提铜装置及方法 | |
CN109761412A (zh) | 一种高盐度稀土湿法冶炼废水中低含量有机污染物的电解处理工艺及装置 | |
CN103951017B (zh) | 一种电解处理含氰含铜电镀废水并回收铜的方法 | |
WO2015165234A1 (zh) | 一种离子交换树脂脱附液的无害化处置与资源化利用方法 | |
CN105329988A (zh) | Fenton法结合双极膜技术处理高盐工业废水电解槽 | |
CN111170526A (zh) | 一种钨冶炼废水中的氨氮、磷、砷的处理方法 | |
WO2021138960A1 (zh) | 一种同步实现有机磷废水处理和资源化利用的电化学方法 | |
CN203976921U (zh) | 酸性氯化铜蚀刻液电解再生循环及铜板回收装置 | |
CN101391846A (zh) | 一种将油田产出水处理成配聚水的电化学方法 | |
CN110668614B (zh) | 电催化氧化结合电磁复合材料处理蚀刻废液的方法 | |
KR101373486B1 (ko) | 고염도 폐수의 전기화학적 처리 및 재활용 방법 | |
CN111087047A (zh) | 一种含溴有机废水的处理方法 | |
CN109179801B (zh) | 一种三价铬电镀废液的处理方法 | |
CN105293642A (zh) | 一种处理高盐工业废水的多电极多隔膜电解槽 | |
CN101058447A (zh) | 兼具絮凝与消毒效能的水处理药剂的电化学制备反应器 | |
CN205204884U (zh) | 一种处理高盐工业废水的多电极多隔膜电解槽 | |
CN107215988B (zh) | 一种焦化废水深度处理方法 | |
CN111333152A (zh) | 一种电解氧化处理高浓度含镍含磷有机废液的方法 |
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: 20912478 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 11/11/2022) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 20912478 Country of ref document: EP Kind code of ref document: A1 |