CN111003890A - 一种利用含锌废液协同处理高浓度废乳化液的方法 - Google Patents
一种利用含锌废液协同处理高浓度废乳化液的方法 Download PDFInfo
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Abstract
本发明关于一种利用含锌废液协同处理高浓度废乳化液的方法,包括步骤:(1)破乳:利用含锌废液对高浓度废乳化液进行破乳化;(2)气浮:采用两级气浮法,对废乳化液中经过破乳反应产生的游离油粒进行油水分离;(3)Fenton氧化:利用Fenton试剂的强氧化性去除废乳化液中部分有机组分或提高废乳化液的BOD5/CODCr值;(4)混凝沉淀:采用化学中和/或混凝沉淀方式去除含锌废液中金属锌离子,通过混、絮凝剂的吸附架桥作用去除废乳化液中部分有机组分;(5)生化处理:混凝沉淀后的废乳化液上清液引入生活污水,借助生活污水进行深度生化处理至达标排放。上述方法实现含锌废液及高浓度废乳化液的无害化处理,达到“以废治废”目的,节约处理成本避免环境污染。
Description
技术领域
本发明属于危险废物无害化处理技术领域,尤其涉及一种利用含锌废液协同处理高浓度废乳化液的方法。
背景技术
随着工业化的迅速发展,油品的使用量越来越大,但由于各种技术的限制和管理落后等原因,大量油品进入水体,形成污染。废乳化液的来源很多,石油工业的采油、炼油、贮油运输及化工工业都会产生废乳化液,油轮压舱水、洗舱水、机械工业的冷润滑液、轧钢水,及粮油加工、皮革、造纸、纺织、食品加工(含餐饮业)的废水中也都含有大量的油品。废乳化液是一种量大面广且危害严重的污染源,其处理的难易程度取决于油分的来源、成分以及存在形式。含油废水的分类、特征及其危害:1.油类在水体中的存在形态。根据废乳化液来源和油类在水中存在的形式不同,可分为浮油、分散油、乳化油和溶解油四类:(1)浮油:以连续相的油膜漂浮于水面,形成油膜或油层。油珠颗粒较大,一股大于l00um。(2)分散油:以微小油滴悬浮分散于水相中,不稳定,可聚集成较大的油珠转化为浮油,其油滴粒径一般为10~100um。(3)乳状油:由于表面活性剂的存在,油在水中呈乳状液,体系较稳定。油滴粒径极微小,一般小于l0um,大部分为0.1~2um。(4)溶解油:以分子状态分散于水体中形成油一水均相体系,非常稳定,一般低于5~15mg/L。油珠粒径非常小,有时可小到几纳米。2.废乳化液的特征。石油本身成分非常复杂,有烷烃、环烷烃、芳香烃及各种非烃组分如含硫化合物、含氮化合物等。而石油经过各种特殊用途的加工所产生的废乳化液成分更加复杂,如燕京石油化工总公司所属工厂排出废水用色谱-质谱联检出的有机物多达230多种,除油外,还有酚、腈、胺、有机氯化物、有机磷化物、有机酸、醛、酮等,含乳化油成分多,去除难度较大。3.废乳化液的危害。废乳化液的危害主要表现在:油类物质漂浮在水面,形成一层薄膜,能阻止空气中的氧溶解于水中,使水中的溶解氧减少,致使水体中浮游生物等因缺氧而死亡,也妨碍水生植物的光合作用,从而影响水体的自净作用,甚至使水质变臭,破坏水资源的利用价值。对于鱼、虾、贝类长期在含油污水中生活将导致其肉内含有油味,而不宜食用,严重时由于油膜蒙在鱼鳃上影响呼吸作用,导致窒息而死亡,而且在水体表面的聚结油还有可能燃烧产生安全问题。
目前,工业上对含锌废液处理工艺主要有中和法、混凝沉淀法等;针对高浓度废乳化液的处理工艺主要有破乳气浮分离法、电絮凝法等。专利号201711260221.2一种含锌废液处理工艺,包括:向含锌废液中加入中和剂以沉淀杂质形成废渣和富锌矿浆;采用超重力分级装置分离出富锌矿浆与废渣。根据本发明的含锌废液处理工艺,通过超重力分级装置能够分离出富锌矿浆与废渣,从而有利于回收含锌废液中的有价金属锌,操作方便。专利号201710205207.6一种机械加工含油废液预处理的方法,首先将机械加工含油废液经过格栅,去除大颗粒污染物;然后经过均质调节罐,实现油、水、砂三相分离;分离出的水相经过两级破乳破坏稳定的乳浊体系,并进行固液分离;将破乳后分离出的上清液,调节pH值,进行芬顿氧化;芬顿反应完成后,调节pH进行沉淀,出水进入生化***。本发明所公开的处理机械加工含油废液的方法,使高CODCr的机械加工废乳化液直接经过简单二级破乳和芬顿氧化过程,CODCr含量大幅度减少,浊度明显降低,B/C比明显提高,为生化处理创造条件。
本发明方法针对含锌废液和高浓度废乳化液处理的复杂特征,采用破乳-气浮-Fenton氧化-混凝沉淀-生化组合工艺协同处理,既无害化处理含锌废液,又实现了高浓度废乳化液无害化处理,最终废水达标排放,达到“以废治废”的目的,又节约了处理成本。
发明内容
针对以上问题,本发明的目的是提出一种利用含锌废液协同处理高浓度废乳化液的方法,采用破乳-气浮-Fenton氧化-混凝沉淀-生化组合工艺协同处理主要成分为高浓度废乳化液。主要解决目前存在的以下几个问题:(1)常规方法处理含锌废液成本高;(2)常规方法处理废乳化液成本高;(3)运行操作要求比较高,处理技术稳定性需要改善。
本发明的目的是通过以下技术方案实现的:一种利用含锌废液协同处理高浓度废乳化液的方法,针对主要含锌废液和高浓度废乳化液,即锌含量不低于1%(w%),油/乳化液含量不低于10%(w%),采用破乳-气浮-Fenton氧化-混凝沉淀-生化处理组合工艺路线,具体如下:
(1)破乳反应:利用厂内产生含锌废液对高浓度废乳化液进行破乳化。含锌废液中主要组分为废酸和金属锌离子,分别通过酸化和盐析双重作用对废乳化液进行破乳反应。废乳化液与含锌废液添加比例(v/v)控制在(4~10):1。经过破乳反应废乳化液油中油/乳化液组分脱除效率可达95%以上。
(2)气浮处理:分别采两级气浮处理,一级涡凹气浮对废乳化液中经过破乳反应产生的游离大油粒进行油水分离;二级全回流加压溶气气浮法对废乳化液中经过破乳反应产生的游离细小油粒进行油水分离。经过气浮反应废乳化液油中破乳后的油/乳化液组分脱除效率可达99%以上。
(3)Fenton反应:利用Fenton试剂的强氧化性去除废乳化液中部分有机组分或提高废乳化液的BOD5/CODCr值;Fenton试剂的添加比例(w/w):氧化剂:CODCr=(2~5):1;催化剂:(1~5)g/L。
(4)混凝沉淀处理:采用化学中和、混凝沉淀等方式去除含锌废液中金属锌离子,同时通过混、絮凝剂的吸附架桥作用去除废乳化液中部分有机组分;化学药剂的添加比例(w/w)参照:中和剂控制pH=7~11,混凝剂:(1~5)g/L,絮凝剂:(0.01~0.3)g/L。
(5)生化处理:混凝沉淀后的废乳化液上清液通过结合生活污水,提高可生化性,对其进行深度处理至达标排放。生化处理工艺采用A2/O处理工艺或类似工艺。
本发明处理效果是:本发明利用含锌废液协同处理高浓度废乳化液,采用破乳-气浮-Fenton氧化-混凝沉淀-生化处理组合工艺路线,具有运行稳定、管理方便、运行成本低、废水稳定达标等特点,在生产运用中可以大幅度减少含锌废液和高浓度废乳化液对环境的污染,达到“以废治废”目的,同时具备很好的环境效益和社会效益。
附图说明
图1是本发明具体工艺流程框图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
本发明提供的一种利用含锌废液协同处理高浓度废乳化液的方法,如图1所示,包括以下步骤:
(1)破乳反应:利用厂内产生含锌废液对高浓度废乳化液进行破乳化。含锌废液中主要组分为废酸和金属锌离子,分别通过酸化和盐析双重作用对废乳化液进行破乳反应。废乳化液与含锌废液添加比例(v/v)控制在(4~10):1。经过破乳反应废乳化液油中油/乳化液组分脱除效率可达95%以上。
(2)气浮处理:分别采两级气浮处理,一级涡凹气浮对废乳化液中经过破乳反应产生的游离大油粒进行油水分离;二级全回流加压溶气气浮法对废乳化液中经过破乳反应产生的游离细小油粒进行油水分离。经过气浮反应废乳化液油中破乳后的油/乳化液组分脱除效率可达99%以上。
(3)Fenton反应:利用Fenton试剂的强氧化性去除废乳化液中部分有机组分或提高废乳化液的BOD5/CODCr值;Fenton试剂的添加比例(w/w):氧化剂:CODCr=(2~5):1;催化剂:(1~5)g/L。
(4)混凝沉淀处理:采用化学中和、混凝沉淀等方式去除含锌废液中金属锌离子,同时通过混、絮凝剂的吸附架桥作用去除废乳化液中部分有机组分;化学药剂的添加比例(w/w)参照:中和剂控制pH=7~11,混凝剂:(1~5)g/L,絮凝剂:(0.01~0.3)g/L。
(5)生化处理:混凝沉淀后的废乳化液上清液通过引入生活污水,进一步提高废水可生化性,对废乳化液进行深度生化处理至达标排放,生化处理工艺采用A2/O处理工艺或类似工艺。
实施例1
取某油轮压舱水/洗舱水11.4t,经过分析原料液中废矿物油含量约11.05%(w%);厂内产生的含锌废液,锌离子含量约1.65%(w%),废硫酸含量约3.13%(w%),选择破乳-气浮-Fenton氧化-混凝沉淀-生化处理组合工艺路线处理。
经过破乳反应和两级气浮处理,油轮压舱水/洗舱水与含锌废液添加比例(v/v)采用8:1进行破乳,破乳后经过两级气浮处理,废矿物油含量约0.93%(w%),废矿物油去除率约91.5%。经过Fenton氧化和混凝沉淀后锌离子含量约4.1mg/L,废矿物油含量约3867mg/L。
实施例2
取某厂废切削液7.43t,经过分析原料液中废矿物油含量约8.23%(w%);厂内产生的含锌废液,锌离子含量约1.65%(w%),废硫酸含量约3.13%(w%),选择破乳-气浮-Fenton氧化-混凝沉淀-生化处理组合工艺路线处理。
经过破乳反应和两级气浮处理,废切削液与含锌废液添加比例(v/v)采用5.5:1进行破乳,破乳后经过两级气浮处理,废矿物油含量约0.69%(w%),废矿物油去除率约91.6%。经过Fenton氧化和混凝沉淀后锌离子含量约4.3mg/L,废矿物油含量约3593mg/L。
实施例3
取某生产企业废乳化液3.5t,经过分析原料液中废矿物油含量约12.47%(w%);厂内产生的含锌废液,锌离子含量约1.65%(w%),废硫酸含量约3.13%(w%),选择破乳-气浮-Fenton氧化-混凝沉淀-生化处理组合工艺路线处理。
经过破乳反应和两级气浮处理,废乳化液与含锌废液添加比例(v/v)采用8.5:1进行破乳,破乳后经过两级气浮处理,废矿物油含量约1.35%(w%),废矿物油去除率约89.1%。经过Fenton氧化和混凝沉淀后锌离子含量约5.3mg/L,废矿物油含量约4761mg/L。
本工艺方法与其他废乳化液处理方法对比如表1所示。
表1本方法与其他废乳化液处理方法对比
本工艺的核心创新在于利用含锌废液协同处理不同来源的高浓度废乳化液,分别消除危险废物含锌废液和废乳化液对环境的危害,实现“以废治废”的同时,降低了危废的处理处置成本。具有运行稳定、管理方便、运行成本低、废水达标率高等特点。大大降低含锌废液和废乳化液对环境的潜在风险。
上述实施例用来解释说明本发明,而不是对本发明进行限制,在本发明的精神和权利要求的保护范围内,对本发明作出的任何修改和改变,都落入本发明的保护范围。
Claims (5)
1.一种利用含锌废液协同处理高浓度废乳化液的方法,其特征在于,包括以下步骤:
(1)破乳:利用含锌废液对高浓度废乳化液进行破乳化;
(2)气浮:采用两级气浮法,对废乳化液中经过破乳反应产生的游离油粒进行油水分离;
(3)Fenton氧化:利用Fenton试剂的强氧化性去除废乳化液中部分有机组分或提高废乳化液的BOD5/CODCr值;
(4)混凝沉淀:采用化学中和和/或混凝沉淀方式去除含锌废液中金属锌离子,同时通过混、絮凝剂的吸附架桥作用去除废乳化液中部分有机组分;
(5)生化处理:混凝沉淀后的废乳化液上清液引入生活污水,借助生活污水进行深度生化处理至达标排放。
2.根据权利要求1所述的利用含锌废液协同处理高浓度废乳化液的方法,其特征在于,所述步骤(1)破乳工序中,高浓度废乳化液被送入反应釜后,含锌废液添加入反应釜,废乳化液与含锌废液添加比例(v/v)控制在(4~10):1。
3.根据权利要求1所述的利用含锌废液协同处理高浓度废乳化液的方法,其特征在于,所述步骤(2)气浮处理工序中,分别采两级气浮处理,一级涡凹气浮对废乳化液中经过破乳反应产生的游离大油粒进行油水分离;二级全回流加压溶气气浮法对废乳化液中经过破乳反应产生的游离细小油粒进行油水分离。
4.根据权利要求1所述的利用含锌废液协同处理高浓度废乳化液的方法,其特征在于,所述步骤(3)Fenton氧化处理工序中,Fenton试剂的添加比例(w/w)参照:氧化剂:CODCr=(2~5):1;催化剂:(1~5)g/L。
5.根据权利要求1所述的利用含锌废液协同处理高浓度废乳化液的方法,其特征在于,所述步骤(4)混凝沉淀处理工序中,化学药剂的添加比例(w/w)参照:中和剂控制pH=7~11,混凝剂:(1~5)g/L,絮凝剂:(0.01~0.3)g/L。
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