CN104445839A - 一种煤焦油废水的三级串联式光催化处理工艺 - Google Patents
一种煤焦油废水的三级串联式光催化处理工艺 Download PDFInfo
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Abstract
本发明采用厌氧好氧处理、预处理、光催化、臭氧氧化等一系列工艺对煤焦油废水进行处理。该发明不但工艺和设备制造简单,并且出水水质可达GB8978-1996《污水综合排放标准》中的一级排放标准。本发明效率高,成本低,操作方便,绿色环保无二次污染,适合用于煤焦油的废水的处理。
Description
技术领域
本发明涉及煤焦油污水处理工艺。
背景技术
煤焦油废水分类上属于焦化废水,但其污染物含量不同于常规焦炉废水。煤焦油废水焦油含量很高,难降解的有机物质(如酚类)含量较高,成分更为复杂。除了含有氨氮、氰化物、硫氰化物等物质外,还含有高浓度的酚类、萘、苯胺、吡啶、吲哚、喹啉等有机物质,其能够大量释放出来具有强致癌性的多环有机物,并且含有氮硫氧的杂环的有机化合物,具有毒性大色度大的特点,是一种处理起来较困难的废水。此类废水的有机物含量在20000-60000mg/L左右,氨氮含量大约2000-5000mg/L。
煤焦油废水的危害主要有:一,废水中含有高浓度的难降解及有毒有害的物质,消耗水中的溶解氧。二,氨氮使水体气味恶臭水质下降,极易导致水体的富营养化;氨氮对硝化菌的活性起到严重的抑制作用,在好氧情况下,氨氮极易变为致癌性亚硝酸盐。三,含有危害生物的剧毒致癌物,如氰化物及硫氰化物等。四,色度高,严重影响入射光线的量,对水生植物的光合作用和水生动物的生存带来严重危害。五,含有的表面活性剂将水体与空气隔绝,隔绝水体的表面复氧,造成水体自净能力的降低。六,内含的酚类物质是极强的神经性毒物并具有局部腐蚀性,对任何生物个体都能造成毒害作用。
鉴于煤焦油废水氨氮和COD浓度高,国内外几乎没有类似的处理经验可借鉴。由于煤焦油废水的性质与高浓度难生物降解废水有相似之处,可以选用国内外针对高浓度难生物降解废水的处理方法进行研究对比。
废水处理方法主要有物化法、生物法以及生化法三大类。
物化处理方法以混凝沉淀技术和活性炭吸附技术为主。物化处理方法投资成本较低,出水水质比较稳定,受外界条件影响较小,但运行成本较高(丑明和窦吉平 2001)。
生化法具有对COD及氨氮去除率高、工艺成熟、运行费用低等优点,因而被广泛应用于生活污水和工业废水的处理,但是对于煤焦油废水这种高有机物浓度、高毒性的难生物降解废水来说,单纯使用生化法的处理效果并不能实现废水的达标排放。
目前,国内外处理此类废水一般采用物化结合生化的方法进行处理。通过物化预处理降低废水毒性,提高其可生化性,然后用生物法进行后续处理(滕仕峰 2005)。但是此方法运行成本高,且易造成二次污染。
郝志明、郑伟等(2010)采用生化-吸附-混凝-过滤工艺处理该类废水,经该工艺处理后,使高污染浓度废水达到循环冷却补充水的水质标准,充分体现了废水再生利用的原则。但此方法也易造成二次污染。
总之,煤焦油废水现有处理工艺普遍存在工艺流程长、占地面积大,操作复杂,抗冲击能力差,投资及处理成本高,处理效果不稳定,出水COD、色度、氨氮等指标很难达标等问题。
我们所采用的主要是利用光催化等方法对煤焦油废水进行处理,光催化原理是一些半导体材料(如TiO2)在可见光或紫外线的照射下阶带电子会被激发到导带,从而产生具有很强反应活性的电子(e)空穴(h+)对,这些电子空穴对迁移到半导体表面后,在光催化作用下产生羟基(·OH) 和超氧化物离子,在不使用任何化学药物的情况下将水中的有机物、细菌、病毒以及其它致病体和完全氧化成二氧化碳、水和无机小分子,达到了净化、消毒和降解污染物的目的。
我们通过三级串联式光催化处理工艺对煤焦油废水进行处理,此工艺在处理的煤焦油废水时,加入以植物皮、膜或者光敏活性物为模板制备的介孔二氧化钛光催化剂作为预处理剂,此材料可高效、低成本的吸附煤焦油废水中的有机废弃物分子以及无机有害离子,从而达到降解污染物的目的。
鉴于煤焦油废水中含有大分子物质或者难降解的大分子物质,需要进行预热处理,将废水加热到50—100 oC,目的是为光催化反应中介孔二氧化钛光催化剂(如TiO2)的阶带电子被激发到导带提供一定的能量,从而产生具有很强反应活性的羟基(·OH) 和超氧化物离子,以便使光催化反应达到非常有效的结果。处理煤焦油废水首先通过厌氧好氧池、最后通过三级串联式光催化设备处理,使煤焦油废水里的大分子物质通过三级串联式光催化设备生成小分子进而以气体形式排出。即可达GB8978-1996《污水综合排放标准》中的一级排放标准。本发明技术不但成本低,工艺流程及操作简单,而且无需过多复杂的化学处理方法,便于实现工业化。
发明内容
本发明的目的是提供一种高效、低投资、操作方便的的煤焦油废水处理工艺,且不对环境造成二次污染。研究的水样取自云南省某化工厂,经处理后出水水质达标。本发明中涉及到三项已申请的专利:王家强,光催化真空气液固三相高效分离工艺处理高盐分高浓度有机废水 发明专利(申请号:201010039195.2), 以植物皮、膜为模板制备介孔二氧化钛光催化剂的方法(已授权:ZL200710065939.6)和以光敏活性物为模板的介孔晶体二氧化钛的制备方法,发明专利(已授权:ZL200710065747.5)。
本发明相比背景技术中的处理法,有如下优点:
1、成本低,工艺流程及操作简单,无需过多复杂的化学处理方法,便于实现工业化。
2、经过该工艺处理后,出水水质可达GB8978-1996《污水综合排放标准》中的一级排放标准。
本发明的技术方案是第一步,厌氧好氧处理;第二步,采用三级串联式光催化工艺对废水进行处理,其中的三级分别为一级预处理、二级光催化处理及三级深度处理。
厌氧好氧处理即在池中投加活性污泥,好氧处理加入曝气装置。
一级预处理中的预处理剂可为介孔二氧化钛光催化材料、氧化剂或絮凝剂,其与废水质量比为1:50—1:1000,并将废水加热到50-100oC。
二级光催化处理为在光催化装置内部涂上一层以植物皮、膜或光敏活性物为模版的介孔晶体二氧化钛并且接入一个40-1000W紫外光源。
三级深度处理中加入的氧化剂为O3或新生的二氧化锰、Fenton试剂、ClO2,达标排放的水从此排出。工艺流程见说明书附图图1。
现详细说明本发明技术方案:
第一步 厌氧好氧处理
首先,将煤焦油废水引入厌氧池,在池中投加活性污泥,反应15天后,将其引入好氧池,在池中投加活性污泥,加入曝气装置,反应15天。利用活性污泥中的微生物以有机物为食料迅速生长增殖,消耗有机物使废水得以净化。
第二步 采用三级串联式光催化工艺对废水进行处理
1、一级预处理
将煤焦油废水引入预处理池,通过池中格栅之后可去除较大颗粒的悬浮物,其目的是为了防止之后的工艺设备发生堵塞。然后加入介孔二氧化钛光催化剂或者絮凝剂,搅拌溶解即可。介孔材料与经典的微孔分子筛相比,介孔材料具有以下优点:
1)具有规则的孔道结构;
2)孔径分布窄,且孔径可在1.5-10 nm之间调节;
3)经过优化合成条件或处理后,具有很好的热稳定性和水热稳定性。
4)具有较高的比表面积(1000-1500 m2/g)
5)颗粒具有规则外形,且在纳米尺度内保持高度的孔道有序性。
由于有序的结构极为独特的优越性,可用作功能材料、吸附剂、催化剂及其载体,不仅弥补了微孔沸石分子筛的不足,还可以利用有序介孔作为纳米粒子的“微反应器”。因此在化学工业、能源与环境、生物技术、吸附分离、催化及光、电、磁等众多领域有广阔的发展前景。此材料可高效、低成本的吸附煤焦油废水中的有机废弃物分子以及无机有害离子,从而达到降解污染物的目的。然后进行预热处理,将废水加热到50—100 oC,目的是为光催化反应做好准备工作,加热的目的是将废水中的大分子有机物转化成小分子物质或者气体的形式;同时使细菌、病毒等失去活性,以便使光催化达到非常有效的结果。
2、二级光催化处理
光催化原理简单地说,就是一些半导体材料(如TiO2)在可见光或紫外线的照射下阶带电子会被激发到导带,从而产生具有很强反应活性的电子(e)空穴(h+)对,这些电子空穴对迁移到半导体表面后,在光催化作用下产生羟基(·OH) 和超氧化物离子,在不使用任何化学药物的情况下将水中的有机物、细菌、病毒以及其它致病体和完全氧化成二氧化碳、水和无机小分子,达到了净化、消毒和降解污染物的目的。在这些半导体催化剂中,TiO2化学性质稳定、难溶、无毒、成本低、催化效率高,对于难降解有机物非常有效。鉴于废水中化合物极为稳定的特点,我们提高光催化反应温度至微温条件下发生光催化反应,之后生成的CO2等以气体的形式连续排出,从而降解水中有机物和COD。总之,煤焦油废水在二级光催化处理后能够达到很好的脱色及降解效果。
3、三级深度处理
将经光催化处理后的废水引入深度处理器,加入O3、新生的二氧化锰或Fenton试剂、ClO2,反应后出水的有机物含量较低。出水水质可达GB8978-1996《污水综合排放标准》中的一级排放标准。
附图说明:
图1为深度处理工艺流程图。
具体实施例
实施例1:
将COD约为25000mg/L、NH3-N约为2000 mg/L、pH值为8-9的煤焦油废水通过池中格栅之后可去除较大颗粒的悬浮物,送入厌氧好氧池,之后将煤焦油废水送入预处理池,去除较大颗粒悬浮物后将加入1g介孔催化材料a,之后经过预热器,再连续送入光催化反应器,进行连续反应,送入深度处理装置并通入O3,经排出的水,最后污水的COD为70mg/L、NH3-N为5mg/L、pH值为7.5、色度小于50,达到GB8978-1996《污水综合排放标准》中的一级排放标准。
实施例2:
将COD约为25000mg/L、NH3-N约为2000 mg/L、pH值为8-9的煤焦油废水通过池中格栅之后可去除较大颗粒的悬浮物,送入厌氧好氧池,之后将煤焦油废水送入预处理池,去除较大颗粒悬浮物后将其加入1g介孔催化材料b,之后经过预热器,再连续送入光催化反应器,进行连续反应,送入深度处理装置并加入新生的二氧化锰,经排出的水,最后出水的COD为90mg/L、NH3-N为7mg/L、pH值为7.5、色度小于50,达到GB8978-1996《污水综合排放标准》中的一级排放标准。
实施例3:
将COD约为25000mg/L、NH3-N约为2000 mg/L、pH值为8-9的煤焦油废水通过池中格栅之后可去除较大颗粒的悬浮物,送入厌氧好氧池,之后将煤焦油废水送入预处理池,去除较大颗粒悬浮物后将其加入1g介孔催化材料c,之后经过预热器,再连续送入光催化反应器,进行连续反应,送入三级ClO2处理装置,经排出的水,最后出水的COD为72mg/L、NH3-N为8mg/L、pH值为7.5、色度小于50,达到GB8978-1996《污水综合排放标准》中的一级排放标准。
实施例4:
将COD约为25000mg/L、NH3-N约为2000 mg/L、pH值为8-9的煤焦油废水通过池中格栅之后可去除较大颗粒的悬浮物,送入厌氧好氧池,之后将煤焦油废水送入预处理池,去除较大颗粒悬浮物后将其加入2.0g介孔催化材料d后,再加0.5g铝盐和铁盐混合絮凝沉降,之后经过预热器,再连续送入光催化反应器,进行连续反应,送入深度处理装置并加入Fenton试剂,经排出的水,最后出水的COD为83mg/ L、NH3-N为9mg/ L、pH值为7.5、色度小于50,达到GB8978-1996《污水综合排放标准》中的一级排放标准。
Claims (5)
1.一种煤焦油废水的处理工艺,其特征在于处理步骤如下:第一步,厌氧好氧处理;第二步,采用三级串联式光催化工艺对废水进行处理,其中的三级分别为一级预处理、二级光催化处理及三级深度处理。
2.如权利要求1所述的煤焦油废水的处理工艺,其特征在于所述的厌氧好氧处理即在池中投加活性污泥,好氧处理阶段加入曝气装置。
3.如权利要求1所述的煤焦油废水的处理工艺,其特征在于所述的一级预处理中的预处理剂可为以植物皮、膜或光敏活性物为模版介孔催化材料、氧化剂、絮凝剂,其与废水的质量比为1:50—1:1000,并将废水加热到50-100oC。
4.如权利要求1所述的煤焦油废水的处理工艺,其特征在所述的二级光催化处理为在光催化装置内部涂上一层以介孔分子筛,并且接入一个40-1000W紫外光源。
5.如权利要求1所述的煤焦油废水的处理工艺,其特征在于所述的三级深度处理中加入的氧化剂为O3、新生的二氧化锰、Fenton试剂、ClO2的其中一种,达标排放的水从此排出的其中一种。
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