CN114807609B - 一种高效回收废水中镍的方法 - Google Patents
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Abstract
一种高效回收废水中镍的方法,是调节含镍废水pH为3‑9,采用磷酸二异辛酯(P204)和2‑溴癸酸(2‑BDA)作为复合萃取剂,置于含镍废水中,常温下搅拌反应10‑20min,然后采用硫酸解吸获得富集液后进行电沉积处理。本发明中以磷酸二异辛酯和2‑溴癸酸在特定比例下作为复合萃取剂,以较少的萃取剂实现了高效的释放镍离子,废水中镍离子的去除率达到了91.72%,且达到去除平衡的时间仅仅为10min左右,镍离子的回收率达到99.4%。
Description
技术领域
本发明涉及工业废水处理技术领域,具体涉及一种高效回收废水中镍的方法。
背景技术
电镀作为全球应用领域最广泛的技术,受到越来越多人的关注。电镀生产给各工业产品附上包覆膜,但同时给全球生态环境和自然资源带来了严重的威胁。化学镀镍过程中会持续发生氧化还原反应,镀液逐渐被消耗,一定生命周期后镀液被迫报废。化学镀镍槽液中的报废液初始废水中除了含有大量重金属镍离子外,还存在磷(H2PO2-、HPO3 2-、PO4 3-)、络合剂、乳酸、醋酸钠以及苹果酸等,它们会与镍离子形成稳定的络合物,使得回收重金属之前要先破络合,导致回收难度大大提高。如果废液直接排放至生态环境中,不仅会破坏生态平衡,还对人类生命造成严重危害。因此,化学镀镍废水在排放之前必须进行净化处理。
常见的重金属废水处理方法有化学沉淀法、膜分离法、离子交换法等。然而它们或多或少存在很多弊端,如化学沉淀法在沉淀的过程中会产生金属污泥,增加处理难度和成本;膜分离法存在膜污染问题,易造成二次污染;离子交换树脂存在强度低、易氧化实效、且再生频繁、操作费用高等缺点,大大限制了他们在重金属废水处理方面的应用,因此我们考虑使用萃取法对镍离子进行破络合去除。
磷酸二异辛酯(P204)对于镍的萃取去除具有较好的效果,但是在实际电镀含镍废水中使用时,需要极大的使用量,但是P204价格较为昂贵(约140元/500mL),导致投入的经济成本极高。因而需求更适合的萃取剂来降低经济成本的投入。
发明内容
基于上述技术问题,本发明目的在于提供一种回收废水中镍的方法。
本发明目的通过如下技术方案实现:
一种高效回收废水中镍的方法,其特征在于:调节含镍废水pH为3-9,采用磷酸二异辛酯(P204)和2-溴癸酸(2-BDA)作为复合萃取剂,置于废水中,常温下搅拌反应10-20min,然后采用硫酸解吸获得富集液后进行电沉积处理,其中2-BDA占复合萃取剂体积的6.5-12.5%。
进一步,上述复合萃取剂与含镍废水体积比为1:9-12,废水中镍的浓度为6-8g/L。
在采用P204作为萃取剂对镍的络合物进行破络合过程中发现,当P204的投加量与含镍废水体积比为1:1时,对于镍离子的去除率是最好的,但是P204价格较为昂贵,因此若按照该体积进行使用,造成投入的经济成本极大。而在研究时发现将本身对于镍离子去除效果不好的2-溴葵酸(2-BDA)作为辅助萃取剂,少量的与P204复合后,在大量降低萃取剂使用量的情况下,对于镍离子的去除率不仅没有下降,反而呈现上升的趋势,且缩短了去除平衡时间,同时拓宽了萃取时适宜的pH环境,使得萃取性能更为稳定。
优选的,上述含镍废水的pH调节至4-8。
优选的,复合萃取剂与含镍废水体积比为1:10,2-BDA占复合萃取剂体积的10%,废水中镍的浓度为6.5g/L。
进一步,硫酸解吸是将反应结束后,取反应结束后的上清液与等体积浓度为1mol/L的硫酸,解吸15-25min,获得富集液。
进一步,上述电沉积处理的阳极是钌钛网,阴极是不锈钢,电流为2-3A,电压为32-35V。
最具体的,一种高效回收废水中镍的方法,其特征在于,按如下步骤进行:
步骤(1)萃取
将含有镍的废水pH调节到3-9,采用磷酸二异辛酯(P204)和2-溴葵酸(2-BDA)混合作为复合萃取剂投入含镍废水中,在常温下搅拌反应10-20min,复合催化剂与含镍废水的体积比为1:9 -12,其中2-BDA的体积占复合催化剂总量的6.5-12.5%,含镍废水中镍的浓度为6-8g/L;
步骤(2)解吸
反应结束后,去上清液与等体积的浓度为1mol/L的硫酸混合,反应15-25min,获得富集液;
步骤(3)电沉积
以钌钛网为阳极,不锈钢为阴极,在电流为2-3A、电压为32-35V下对富集液进行电沉积10-20min。
本发明具有如下技术效果:
本发明中以磷酸二异辛酯和2-溴癸酸在特定比例下作为复合萃取剂,以较少的萃取剂对化学镀镍废水中镍实现了突出的破络合效果,实现了高效的释放镍离子,且在pH为4-8的弱酸性、中心和弱碱性环境下具有优异的去除效果,且稳定性优异,从而达到高效去除回收废水中的镍离子,废水中镍离子的去除率达到了91.72%,且达到去除平衡的时间仅仅为10min左右,镍离子的回收率达到99.4%,实现了镍离子的循环利用,同时有效降低了回收镍的经济成本。
附图说明
图1:不同萃取剂在与含镍废水体积比为1:1时对于镍离子的去除率曲线图。
图2:复合萃取剂中2-BDA的体积占比对于镍离子去除率的影响曲线图。
图3:pH变化对不同萃取剂去除镍离子的影响曲线图。
图4:萃取剂的添加量对于镍离子去除率的影响曲线图。
具体实施方式
下面通过实施例对本发明进行具体的描述,有必要在此指出的是,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术人员可以根据上述本发明内容对本发明作出一些非本质的改进和调整。
实施例1
一种高效回收废水中镍的方法,按如下步骤进行:
步骤(1)萃取
将含有镍的废水pH调节到6,采用磷酸二异辛酯(P204)和2-溴葵酸(2-BDA)混合作为复合萃取剂投入含镍废水中,在常温下搅拌反应15min,复合催化剂与含镍废水的体积比为1:10,其中2-BDA的体积占复合催化剂总量的10%,含镍废水中镍的浓度为6.5g/L;
步骤(2)解吸
反应结束后,去上清液与等体积的浓度为1mol/L的硫酸混合,反应20min,获得富集液;
步骤(3)电沉积
以钌钛网为阳极,不锈钢为阴极,在电流为2A、电压为35V下对富集液进行电沉积15min。
在研究对于镍离子的回收过程中,由于在真实的电镀废水中,其环境较实验室模拟废水更为复杂,化学镀镍槽液中的报废液初始水中除了含有大量重金属镍离子外,还存在磷(H2PO2-、HPO3 2-、PO4 3-)、络合剂、乳酸、醋酸钠以及苹果酸等,它们会与镍离子形成稳定的络合物,使得回收重金属之前要先破络合,导致回收难度大大提高。在研究过程中,我们尝试了大量的萃取剂,如图1所示,P204对镍的络合物进行破络合,对于镍离子的去除率最高,达到76.43%,且达到平衡吸附的时间最短,为20min左右,而其他萃取剂达到平衡萃取的时间较长,且对于镍离子的破络合去除率均较低,其中最低的是2-溴葵酸(2-BDA)仅仅为20.74%,但是当将2-BDA与P204按照特定比例(2-BDA占复合萃取剂体积的10%)复合后,其对于镍离子的去除率得到了显著的提高,从单一的P204去除率为76.4%上升至91.72%,且平衡萃取时间缩短至10min。
本实施例萃取、解吸进行电沉积,对镍离子进一步回收,回收率达到99.4%。
在研究P204中加入2-BDA,复合后对于镍离子去除率的影响发现,2-BDA的占比对于镍离子的去除率影响较大,具体如图2所示:在萃取剂与浓度为6.5g/L的含镍废水体积比为1:1时,单独的P204对于镍离子的最高去除率达到76.43%,随着2-BDA的加入,取代部分P204,镍离子的去除率呈下降趋势,当2-BDA在复合萃取剂中体积占比达到5%后,镍离子的去除率开始成上升趋势,当2-BDA在复合萃取剂中的体积占比达到10%左右时,镍离子的去除率达到最高91.72%,之后再持续增加2-BDA,镍离子去除率又开始降低。因此,2-BDA在该复合萃取剂中占比较少,仅仅作为辅助萃取剂,促进P204的催取效率的提高。
P204和2-BDA对于含镍废水不同pH环境下,对于镍离子的去除率情况如图3所示,二者均是在pH为6-8的环境下对镍离子具有较高的去除率,且去除率趋于稳定,在pH低于6的环境下,对于镍离子的去除率均是呈明显的下降趋势,而二者按照特定比例(2-BDA占复合萃取剂体积的10%)复合后,其适宜的pH为4-8,且在该范围内其对于镍离子的去除率达到稳定的状态,即复合后的萃取剂适宜的pH范围变宽。
按照镍离子浓度为6.5g/L的含镍废水体积为100mL,分别向其中添加不同体积的P204、2-BDA和复合萃取剂,随萃取剂添加量变化,镍离子去除率的变化如图4所示:三种萃取剂均是与含镍废水体积比为1:1时,萃取剂与含镍废水体积比为1:10时,对于镍离子的去除率最高,但是将P204和2-BDA复合后,其去除率的到显著提高,最高达到了91.72%,且在萃取剂与含镍废水体积比为1:1下降至1:10时,而P204对镍离子的去除率已经从76.4%下降至38.89%,2-BDA从20.74%下降至9.91%,而本发明去除率均维持在较高水平,为88.36%,随着萃取剂投加量的下降,本发明到达1:12时,去除率有略微下降,之后再持续降低萃取剂的投加量,镍离子的去除率成剧烈下降,因此本发明中选择复合萃取剂与含镍废水的体积比为1:9-12,最优的选择是1:10。
实施例2
一种回收废水中镍的方法,按如下步骤进行:
步骤(1)萃取
将含有镍的废水pH调节到3,采用磷酸二异辛酯(P204)和2-溴葵酸(2-BDA)混合作为复合萃取剂投入含镍废水中,在常温下搅拌反应20min,复合催化剂与含镍废水的体积比为1:12,其中2-BDA的体积占复合催化剂总量的12.5%,含镍废水中镍的浓度为8g/L;
步骤(2)解吸
反应结束后,去上清液与等体积的浓度为1mol/L的硫酸混合,反应15min,获得富集液;
步骤(3)电沉积
以钌钛网为阳极,不锈钢为阴极,在电流为3A、电压为32V下对富集液进行电沉积30min。
本实施例中对于镍离子的去除率达到88.2%,镍离子回收率达到99.1%。
实施例3
一种高效回收废水中镍的方法,按如下步骤进行:
步骤(1)萃取
将含有镍的废水pH调节到9,采用磷酸二异辛酯(P204)和2-溴葵酸(2-BDA)混合作为复合萃取剂投入含镍废水中,在常温下搅拌反应10min,复合催化剂与含镍废水的体积比为1: 9,其中2-BDA的体积占复合催化剂总量的6.5%,含镍废水中镍的浓度为6g/L;
步骤(2)解吸
反应结束后,去上清液与等体积的浓度为1mol/L的硫酸混合,反应25min,获得富集液;
步骤(3)电沉积
以钌钛网为阳极,不锈钢为阴极,在电流为2A、电压为32V下对富集液进行电沉积10min。
本实施例中对于镍离子的去除率达到86.4%,镍离子回收率达到99.6%。
Claims (5)
1.一种高效回收废水中镍的方法,其特征在于:调节废水pH为3-9,采用磷酸二异辛酯(P204)和2-溴癸酸(2-BDA)作为复合萃取剂,置于废水中,常温下搅拌反应10-20min,然后采用硫酸解吸获得富集液后进行电沉积处理,其中2-BDA占复合萃取剂体积的6.5-12.5%。
2.如权利要求1所述的一种高效回收废水中镍的方法,其特征在于:所述复合萃取剂与含镍废水体积比为1:9-12,废水中镍的浓度为6-8g/L。
3.如权利要求1或2所述的一种高效回收废水中镍的方法,其特征在于:所述硫酸解吸是将反应结束后,取反应结束后的上清液与等体积浓度为1mol/L的硫酸,解吸15-25min,获得富集液。
4.如权利要求1-3任一项所述的一种高效回收废水中镍的方法,其特征在于:所述电沉积处理的阳极是钌钛网,阴极是不锈钢,电流为2-3A,电压为32-35V。
5.一种高效回收废水中镍的方法,其特征在于,按如下步骤进行:
步骤(1)萃取
将含有镍的废水pH调节到4-8,采用磷酸二异辛酯(P204)和2-溴葵酸(2-BDA)混合作为复合萃取剂投入含镍废水中,在常温下搅拌反应10-20min,复合催化剂与含镍废水的体积比为1:9 -12,其中2-BDA的体积占复合催化剂总量的6.5-12.5%,含镍废水中镍的浓度为6-8g/L;
步骤(2)解吸
反应结束后,去上清液与等体积的浓度为1mol/L的硫酸混合,反应15-25min,获得富集液;
步骤(3)电沉积
以钌钛网为阳极,不锈钢为阴极,在电流为2-3A、电压为32-35V下对富集液进行电沉积10-20min。
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Publication number | Priority date | Publication date | Assignee | Title |
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SU581158A1 (ru) * | 1975-02-21 | 1977-11-25 | Норильский Ордена Ленина Горно-Металлургический Комбинат Им. А.П.Завенягина | Способ окислительного автоклавного выщелачивани сульфидов цветных металлов |
SU726031A1 (ru) * | 1972-12-28 | 1980-04-05 | Научно-Исследовательский Институт Сланцев | Способ биохимической очистки сточных вод от органических соединений |
CN106046374A (zh) * | 2016-05-31 | 2016-10-26 | 重庆交通大学 | 一种新型多孔吸附材料的制备方法 |
CN106521164A (zh) * | 2016-11-07 | 2017-03-22 | 清华大学 | 一种复合萃取剂及其从化学镀镍废液中回收镍的方法 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU726031A1 (ru) * | 1972-12-28 | 1980-04-05 | Научно-Исследовательский Институт Сланцев | Способ биохимической очистки сточных вод от органических соединений |
SU581158A1 (ru) * | 1975-02-21 | 1977-11-25 | Норильский Ордена Ленина Горно-Металлургический Комбинат Им. А.П.Завенягина | Способ окислительного автоклавного выщелачивани сульфидов цветных металлов |
CN106046374A (zh) * | 2016-05-31 | 2016-10-26 | 重庆交通大学 | 一种新型多孔吸附材料的制备方法 |
CN106521164A (zh) * | 2016-11-07 | 2017-03-22 | 清华大学 | 一种复合萃取剂及其从化学镀镍废液中回收镍的方法 |
Non-Patent Citations (2)
Title |
---|
Volkan Eyupoglu a, Recep Ali Kumbasar .Extraction of Ni(II) from spent Cr–Ni electroplating bath solutions using LIX 63 and 2BDA as carriers by emulsion liquid membrane technique.《Journal of Industrial and Engineering Chemistry Volume 21, 25 January 2015, Pages 303-310 Journal of Industrial and Engineering Chemistry》.2015,第25卷 303-310. * |
刘静源 ; 张旭 ; 郑治龙 ; 张瑜林 ; .用P204从鼓风炉烟尘浸出液中萃取铟的试验研究.湿法冶金.2007,(第04期), * |
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