CN107902835A - 一种处理高固含量高盐废水的装置 - Google Patents
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Abstract
本发明公开一种处理高固含量高盐废水的装置,包括通过管道依次连接的臭氧气浮池、电催化氧化池、MVR蒸发器、电加热反应釜、A/O生化池、BAF和反渗透装置,所述臭氧气浮池的进口与高固含量高盐废水进口连接,反渗透装置的出口与废水排出口连接;所述电催化氧化装置的电极为金属电极或石墨电极,电流密度在30mA/cm2以下,电压在工业用电电压以下。本发明中组合了多种废水处理工艺,对高固含量高盐废水深度处理,使得最终处理出水COD<50mg/L、色度<10,达到国家排放一级标准;同时本发明在废水处理过程中,产生的固体废物含量较少,MVR蒸发器的结焦现象有明显的减轻作用,从而降低了废水处理成本,减轻了企业维护经济压力。
Description
技术领域
本发明涉及一种废水处理工艺,具体是一种处理高固含量、高含盐量难以生化降解的废水处理装置。
背景技术
精细化工产业不断发展的同时,化工产周围的水体也不断受到污染,此类废水高色度、高COD、高含盐量、COD中的重组分含量高。不仅难以使用传统的生化方法进行处理,在蒸发环节还会容易导致蒸发器发生结焦堵塞情况。此类废水若不经过处理直接排放到自然水体当中,会严重污染水源而导致生态失衡,最后总威胁人类生存。
目前对于高固含量高盐废水的处理主要方法有以下的几种:最常用的吸附法是活性炭法,通过活性炭分子与污染物分子之间的范德华力吸附有机物,或者通过化学键化学吸附。絮凝法:絮凝也是常见的处理手段,许多有机废水用絮凝可得到不错的出水效果。生物法:生物法是利用微生物代谢实现污染物减量化、无害化的理想手段,可以有效的去除污水中的COD。化学氧化法:常用的化学氧化法有Fenton法、次氯酸钠氧化法等。
但是上述的废水处理方法仍然有着各自的不足,尤其是对于高固含量高含盐量的废水处理,一般常用的处理方法很难能够处理达标。比如用活性炭吸附法,水体中的各类污染物并不能完全被吸附,而且使用后的活性炭不能够再生,需被当作危险废物处理,处理效果不达标的同时又极大的怎加了运行成本;絮凝法本质上并没有将污染物质切底降解,而是将水中的污染物转移为固体污染物,而且并不能完全絮凝出水中的污染物质,絮凝剂的使用成本较高,不适合大规模的使用;传统的生物法对水体环境要求极为敏感,此类高含盐量的废水会导致微生物发生脱水死亡的情况;化学氧化法并不能完全氧化有机物使其矿化为CO2、N2之类的无机物,而且需使用大量的化学原料,成本极高。
发明内容
发明目的:本发明目的在于针对目前传统技术上的不足,提供一种多种废水处理技术组合的工艺,并在个别工艺上进行了改进,针对精细化工行业高固含量高含盐量难生化降解废水的装置,确保排放水质达到国家相关排放标准的同时,解决了MVR蒸发器容易发生结焦堵塞的问题。
技术方案:本发明所述处理高固含量高含盐量的装置,包括通过管道依次连接的臭氧气浮池、电催化氧化池、MVR蒸发器、电加热反应釜、A/O生化池、BAF和反渗透装置,所述臭氧气浮池的进口与高固含量高盐废水进口连接,反渗透装置的出口与废水排出口连接;所述电催化氧化装置的电极为金属电极或石墨电极,电流密度在30mA/cm2以下,电压为工业用电电压以下。
本发明进一步优选地技术方案为,所述电催化氧化装置的阳极为金属电极或石墨电极,阴极为与阳极等面积的不锈钢。
优选地,所述所述的蒸发单元,其特征在于,所述电加热反应釜用于处理MVR蒸发器的浓缩母液,蒸发气体与MVR蒸发气体汇合冷凝,含盐固体浓缩冷却。
本发明中应用上述装置处理高固含量高含盐量的废水的方法,包括如下步骤:
(1)预处理:将高固含量高含盐量的废水排入臭氧气浮池,并向臭氧气浮池内加入混凝剂进行气浮处理;经过混凝剂和臭氧气浮的处理水样的固体废物较原水降低很多,并且由于臭氧的氧化作用,废水中未能分离的水溶性有机物得到一定的氧化分解。使得水中的COD有效降低并减轻后续蒸发结焦程度;
(2)电催化氧化:将经过预处理的废水排入电催化氧化池,通电后电极表面产生强氧化物质,将轻组分的COD有效降解,降解率达到50%,重组分转化为轻组分,转化率达到30%。有效的减轻了后续蒸发结焦程度。在电催化氧化过程中,无需添加额外的化学试剂,减轻了运行成本的同时也避免了二次污染。与一般的高电压电催化氧化设备相比,本发明所用电催化氧化设备为低电压高电流,保证了处理效果的同时提高了安全系数,避免人员操作时发生危险。反应时控制水力停留时间60~100min,电流密度在30mA/cm2以下,电压为工业用电电压以下;
(3)MVR蒸发:将经过步骤(2)处理后的废水进行过滤,随后对其进行蒸发,分离出废液内的盐分;MVR蒸发器相对于传统的多效蒸发器节能,蒸发一吨水能耗约在传统多效蒸发器的1/6到1/5。运行过程中不需要消耗蒸汽,所以无需业主提供蒸汽。将经过步骤(2)处理后的水样进入蒸发器进行处理,废水中的盐分被分离出来,得到白色的盐,控制母液浓度随后通入后续的电加热反应釜继续浓缩,避免MVR蒸发器换热器的有机物结焦问题,而蒸发液进行后续处理;
(4)电加热反应釜:将经过步骤(3)处理后的浓缩母液通过保温管道排入电加热反应釜。由于母液的浓度较高,反应釜中加入搅拌功能。蒸汽与步骤(3)MVR蒸发器产生的蒸汽合并冷凝排入后续工艺段。完全浓缩的半固态母液排出冷却。此段工艺很大程度降低了MVR蒸发器的结焦堵塞现象,降低维护成本;
(5)A/O工艺:对步骤(4)处理后的废水进行生化处理,将废水内的大分子有机物水解为小分子有机物,降低废水的COD以及氨氮含量;A段工艺主要起着脱除氮元素的作用,而O段工艺则主要用于降解水中的有机物,本工艺段对步骤(4)处理后的废水进行生化处理,将废水内的大分子有机物水解为小分子有机物并彻底降解,由于采用了A/O工艺,降低废水的COD同时可以有效降低废水中氨氮含量;
(6)BAF工艺:对步骤(5)处理后的废水进行深度处理,进一步降低COD和有机氮,截留悬浮固体,为后续工艺减轻负担。污水进入第一级BAF-C/N滤池,绝大部分COD、BOD在此进行降解,部分氨氮进行硝化(或反硝化)接着污水进入第二级BAF-N滤池,进行氨氮的彻底硝化及COD、BOD地进一步降解,以保证出水总磷≤0.5mg/L,NH3-N≤5mg/L,TN≤10mg/L;
(7)反渗透工艺:对步骤(6)处理后的废水进行深度处理,进一步降低COD和有机氮,截留悬浮固体,使出水达到国家一级标准。废水进入后,对膜的一侧施加压力,在膜的低压侧得到透过的溶剂即渗透液,高压侧得到浓缩液。渗透液可以直接排放,渗透液回流至步骤(5)的A/O池中再处理。
优选地,步骤(1)中所述臭氧气浮池所用气体为高压溶解臭氧气体气浮。
优选地,步骤(2)中所述电催化氧化装置的阳极为金属电极或石墨电极,阴极为与阳极等面积的不锈钢。反应时控制水力停留时间60~100min,电流密度在30mA/cm2以下,电压为工业用电电压以下。
优选地,步骤(3)中所述特征在于,所述MVR蒸发器母液排入电加热反应釜用于处理MVR蒸发器的浓缩母液,蒸发气体与MVR蒸发气体汇合冷凝,含盐固体浓缩冷却。
本发中处理高固含量高含盐量的废水的装置及方法,所应用的原理包括:
臭氧气浮该技术是将融入臭氧的污水在高压下制成的臭氧水通过微气泡发生装置流入气浮池,可以有效去除有机物、磷化物,脱臭、脱色、降低浑浊度,提高废水可生化性。
电催化氧化主要是指,通过外加电场的作用,电极表面生成一系列强氧化性物质(如、O2 -、HO2 - 、ROO-等),使在生化中难以被处理的物质被降解。
MVR蒸发用于将含盐废水进行浓缩,回收其中的盐分,母液排入电加热反应釜蒸发,而蒸发液进行后续处理。
上述原理在废水处理领域已经有一定应用,但是在本发明中重点要解决的是如何有效的结合几种废水处理工艺,在确保排放的废水达到国家相关直排标准的同时,保证MVR蒸发器能够长期运行不会发生结焦堵塞。
以下详细说明本发明的具体工作过程:
首先,加入混凝剂进行预处理,可在高固含量高含盐量的废水中直接加入混凝剂进行混凝,将经过混凝后的水样,通入溶解臭氧气体的水气浮,固液分离后的废水排入电催化氧化池中;
在电催化氧化工序中,电催化氧化反应器产生大量的,电极电势达到2.8V(),可以将部分轻组分COD直接氧化为H2O和CO2,将一部分难降解并会导致MVR蒸发器结焦堵塞的重组分氧化为轻组分,降低了出水COD,减轻了后续工艺负担,处理效果较好。
电催化氧化出水排入MVR蒸发器中进行蒸发浓缩,部分盐分被提取出,可继续回用至生产当中。母液不再回流,直接排入电加热反应釜中;
母液在保温管排入电加热反应釜中后,在其中搅拌加热,蒸汽和MVR蒸汽汇合冷凝,冷凝液排入A/O生化池中继续处理。母液被继续浓缩至半固态时排出冷却,转化为固体废物;
A/O工艺中,A段工艺主要起着脱除氮元素的作用,而O段工艺则主要用于降解水中的有机物。将废水内的大分子有机物水解为小分子有机物并彻底降解,由于采用了A/O工艺,降低废水的COD同时可以有效降低废水中氨氮含量;
A/O工艺的还未能将有机污染物完全降解,使用BAF工艺废水进行深度处理,进一步降低COD和有机氮,截留悬浮固体。污水进入第一级BAF-C/N滤池,绝大部分COD、BOD在此进行降解,部分氨氮进行硝化(或反硝化)接着污水进入第二级BAF-N滤池,进行氨氮的彻底硝化及COD、BOD进一步降解;
BAF出水各项指标都已达到较低的数值,使用反渗透膜进一步深度处理,对膜的一侧施加压力,在膜的低压侧得到透过的溶剂即渗透液,高压侧得到浓缩液。渗透液可以直接排放,渗透液回流至A/O池中再处理。
有益效果:(1)本发明中有机结合多种废水处理工艺,对碱性染料废水进行深度处理,使得废水的COD<50mg/L、色度<10,确保最终排出的废水达到国家排放标准;同时本发明在处理过程中,中间添加的化学物质极少,部分盐分可以被回收利用,同时蒸发器不易产生结焦堵塞,能够减少废水处理成本,设备运行维护成本,减轻企业经济压力;
(2)采用电加热反应釜处理MVR蒸发器母液,可以使MVR蒸发器始终保持较低的固含量,保证换热器的换热效率,节约了MVR的长期运行成本,避免发生结焦堵塞现象。
(3)本电催化氧化采用高电压低电流方案,电流密度在30mA/cm2以下,电压为工业用电电压以下,保证了处理效果的同时也减少了防护设备的投资。采用电极不存在腐蚀、钝化问题,具有高效、长寿命特点。不需要添加化学药剂,无二次污染产生;有机物在反应过程中可以被迅速降解,水力停留时间较短,所需的设备体积小。
附图说明
图1为本发明所述处理高固含量高盐废水的装置的结构示意图;
图2为本发明所述处理高固含量高盐废水的装置的废水处理流程图。
具体实施方式
下面通过附图对本发明技术方案进行详细说明,但是本发明的保护范围不局限于所述实施例。
实施例:一种处理高固含量高盐废水的装置,包括通过管道依次连接的臭氧气浮池、电催化氧化池、MVR蒸发器、电加热反应釜、A/O生化池、BAF和反渗透装置,所述臭氧气浮池的进口与高固含量高盐废水进口连接,反渗透装置的出口与废水排出口连接。
所述的处理高固含量高盐废水的装置,其特征在于,所述臭氧气浮池所用气体为高压溶解臭氧气体气浮。
所述电催化氧化装置的阳极为金属电极或石墨电极,阴极为与阳极等面积的不锈钢,电流密度在30mA/cm2以下,电压为工业用电电压以下。
所述的处理高固含量高盐废水的装置,其特征在于,所述电加热反应釜用于处理MVR蒸发器的浓缩母液,蒸发气体与MVR蒸发气体汇合冷凝,含盐固体浓缩冷却。
一种应用该装置处理高固含量高盐废水的方法,包括如下步骤:
向上述废水中加入3‰用量的絮凝剂后进行臭氧气浮,原水的颜色变淡,产生了大量固体浮渣,色度下降了约35%,COD去除率为7.5%。
将经过臭氧气浮后的废水进入电催化氧化反应器进行反应100min后,出水色度控制在50以下,色度去除率86%,COD去除率20%。
将上述废水通过MVR蒸发器浓缩,将其中的部分盐分分理出进行回用,蒸汽冷凝液无色透明,进行生化处理。母液排入电加热反应釜中继续蒸发。COD去除率95%。
母液进入电加热反应釜后继续加热搅拌蒸发,蒸汽与MVR的蒸汽汇合冷凝,母液进一步浓缩至半固态后排出凝固。
冷凝液进行A/O工艺处理,废水经过处理之后,COD的去除率达到80%,约为700mg/L;最后进入BAF系统进行处理,COD去除率72%;最后通入反渗透系统COD去除率75%,最终出水COD低于50mg/L。
如上所述,尽管参照特定的优选实施例已经表示和表述了本发明,但其不得解释为对本发明自身的限制。在不脱离所附权利要求定义的本发明的精神和范围前提下,可对其在形式上和细节上作出各种变化。
Claims (4)
1.一种处理高固含量高盐废水的装置,其特征在于,包括通过管道依次;连接的臭氧气浮池、电催化氧化池、MVR蒸发器、电加热反应釜、A/O生化池、BAF装置和RO装置,所述的臭氧气浮池的进口与高固含量高盐废水进口连接,RO装置的出口与废水排出口连接;所述电催化氧化装置的电极为金属电极或石墨电极,电流密度在30mA/cm2以下,电压在工业用电电压以下。
2.根据权利要求1所述的处理高固含量高盐废水的装置,其特征在于,所述臭氧气浮池所用气体为高压溶解臭氧气体气浮。
3.根据权利要求1所述的处理高固含量高盐废水的装置,其特征在于,所述电催化氧化装置的阳极为金属电极或石墨电极,阴极为与阳极等面积的不锈钢,电流密度在30mA/cm2以下,电压为工业用电电压以下。
4.根据权利要求1所述的处理高固含量高盐废水的装置,其特征在于,所述电加热反应釜用于处理MVR蒸发器的浓缩母液,蒸发气体与MVR蒸发气体汇合冷凝,含盐固体浓缩冷却。
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