CN113860640A - 一种聚合物多元醇生产过程中高浓度有机废水的处理方法 - Google Patents
一种聚合物多元醇生产过程中高浓度有机废水的处理方法 Download PDFInfo
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Abstract
本发明公开了一种聚合物多元醇生产过程中高浓度有机废水的处理方法,包括如下步骤:(1)将废水收集池中的混合废水泵入铁碳微电解反应池中;将铁碳微电解反应池中废水的pH调节至酸性,废水在铁碳微电解反应池中进行氧化还原反应,反应后出水自流入催化氧化池;(2)往催化氧化池中加入双氧水同时进行曝气搅拌,在亚铁离子的催化下进行氧化反应,经催化氧化反应后的出水自流入混凝沉淀装置中;(3)调节混凝沉淀装置中废水的pH至8~9,然后往其中投加阴离子PAM,经絮凝沉淀反应后,进行固液分离;(4)固液分离后的液体进入A/O生化池中,同时在好氧池中投加营养剂;所述A/O生化池包括依次连接的缺氧池和好氧池;好氧池中投加有复合生物菌剂;(5)A/O生化池出水进入二沉池固液分离,固液分离后的上清液直接外排纳管。
Description
技术领域
本发明涉及一种聚合物多元醇生产过程中高浓度有机废水的处理方法。
背景技术
聚合物多元醇(POP)主要是以偶氮二异丁酸甲酯(AIBN)为引发剂,聚醚多元醇为母体,在一定温度下与丙烯腈(AN)、苯乙烯(SM)等单体接枝共聚而成,是聚醚多元醇、接枝聚醚多元醇、AN和SM的共聚物或自聚物等的混合物。聚合多元醇类产品生产过程中产生的有机废水,基本组分为聚醚多元醇、苯乙烯、丙烯腈等,具有污染物种类多、成分复杂、有机物浓度高、有毒有害物质多、水质波动较大、可生化性差等特点。废水中的苯乙烯是一种可致癌的环境激素物质,具有亲油脂、难分解、易蓄积、残留期长及可沿食物链逐级传递富集的特点。苯乙烯难生物降解且易于富集,目前处理方法无法使出水中苯乙烯浓度达到园区纳管标准。
发明内容
发明目的:本发明目的在于克服聚合多元醇产品生产过程中产生的高浓度含苯乙烯废水生物毒性大、苯乙烯浓度高、出水难以达标等问题,提供一种聚合物多元醇生产过程中高浓度有机废水的处理方法,该处理方法能够将出水中的苯乙烯浓度降至1mg/L以下。
技术方案:本发明所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,包括如下步骤:
(1)将废水收集池中的混合废水泵入铁碳微电解反应池中;将铁碳微电解反应池中废水的pH调节至酸性,废水在铁碳微电解反应池中进行氧化还原反应,反应后出水自流入催化氧化池;
(2)往催化氧化池中加入双氧水同时进行曝气搅拌,在亚铁离子的催化下双氧水形成氧化性更强的自由基,经催化氧化反应后的出水自流入混凝沉淀装置中;其中,催化剂就是Fe2+,催化剂是来自于铁碳微电解反应池;
(3)调节混凝沉淀装置中废水的pH至8~9,然后往其中投加阴离子PAM,经絮凝沉淀反应后,进行固液分离,固液分离的方式是自然沉降;
(4)固液分离后的液体进入A/O生化池中,同时在好氧池中投加营养剂;所述A/O生化池包括依次连接的缺氧池和好氧池;好氧池中投加有复合生物菌剂;
(5)A/O生化池出水进入二沉池固液分离,固液分离后的上清液直接外排纳管。
其中,步骤(1)中,混合废水包括预处理后的废水和含低浓度苯乙烯的生产废水,预处理后的废水与含低浓度苯乙烯的生产废水的混合比例是:50m3/d的预处理废水;450m3/d含低浓度苯乙烯的生产废水。含低浓度苯乙烯的生产废水主要来源于其他(POP、PPG、表面活性剂、农化生产)车间不含苯乙烯的生产废水;混合废水的COD≤5000mg/L,苯乙烯浓度≤20mg/L,盐分浓度≤15000mg/L。
其中,预处理后的废水在预处理前,废水中苯乙烯的浓度不高于205mg/L;废水预处理过程具体是指:(a)将聚合物多元醇生产车间排出的含苯乙烯废水泵入加药池中,加药池pH调节至6~8(pH调节的目的是便于后续的絮凝与催化氧化反应),往加药池中依次加入催化剂、氧化剂和絮凝剂,经过催化氧化反应和絮凝沉淀反应后,进入气浮设备中;催化剂为棕榈酸异辛酯(IOP),催化剂投加量为0.25~0.75kg/m3,即每立方米废水中催化剂的加入量为0.25~0.75kg;氧化剂为双氧水,氧化剂投加量为0.2~0.4kg/m3,即每立方米废水中双氧水的加入量为0.25~0.75kg;絮凝剂为阴离子PAM絮凝剂,阴离子絮凝剂用于中性或碱性的废水,絮凝剂投加量为0.002~0.0025kg/m3;(b)在气泡浮力作用下,絮体与气泡一起上升至液面,形成浮渣,浮渣由刮沫机刮至污泥区,实现固液分离;(c)固液分离后的污水通过集水管流至电催化氧化反应器中进行电催化反应,电催化反应后排出进入废水收集池中。
其中,所述电催化氧化反应中设有多对阴阳电极板,每块电极板间距10mm,阳极极板材料为钛铱钌材料(IrO2-RuO2/Ti)。在中性溶液中,钛铱钌(IrO2-RuO2/Ti)阳极析氯点位低,Cl2容易在阳极表面析出,其溶于水产生活性氯可以快速氧化溶液中的苯乙烯,有效提高苯乙烯的去除效率;同时钛铱钌材料(IrO2-RuO2/Ti)具有低的过电位特性,电极间表面及电极的气泡容易排除,可有效降低电解槽电压、节约能耗;电催化反应中,电流为10~20A,电压为4.5~6.0V。
预处理能够将含高浓度苯乙烯废水从初始浓度205mg/L降低至20mg/L以下,将COD初始浓度为接近10000mg/L降低至3000mg/L以下;具体机理为:废水中过氧化氢在催化剂(IOP)的催化作用下,利用催化质子反应机理,在分解过程中产生超氧化氢中间体,超氧化氢氧化性比过氧化氢强且含有更多的活性氧,因此超氧化氢与苯乙烯反应比过氧化氢更具优势,氧化性更强,氧化速率更快,可以直接一步氧化苯乙烯生成苯乙醛;气浮用于去除废水中表面活性剂、含油物质及絮凝沉淀物,从而提升后续电催化氧化的效率;经催化氧化后浓度较低的苯乙烯进入电催化氧化体系后,被体系内产生的氧化还原性物质:·OH、Cl-、ClO-、H·降解矿化,在电催化的过程中,IrO2-RuO2阳极析氯产生Cl2,其溶于水产生活性氯氧化溶液中的苯乙烯,进一步提高苯乙烯的去除效率。
其中,步骤(2)中,铁碳微电解反应池中含有铁碳填料,所述铁碳填料为铁和碳高温烧结的铁碳球填料,铁碳球填料中铁含量(质量百分含量)75±3%,碳含量(质量百分含量)15±3%,膨润土含量(质量百分含量)10±3%以及金属催化剂含量(质量百分含量)0.1%,铁碳球填料比表面积为1.2±0.2㎡/g,强度≥600kgf/cm2,堆积孔隙率≥65%,堆积密度1.4±0.1t/m3。铁碳填料优选Fe/C(质量比)不小于5:1,一方面Fe/C含量满足铁碳微电解反应过程中的电位差,另一方面较高的铁含量有助于释放出更多的Fe2+,为后续的催化氧化提供反应条件。
其中,铁碳微电解反应池中pH为2.5~3.5,气水比(体积比)为3.5:1。
其中,步骤(3)中,阴离子PAM的投加量是0.001~0.003kg/m3,即每立方米的废水中投加0.001~0.003kg的阴离子PAM。
其中,步骤(4)中,所述复合生物菌剂由以下单菌母液按体积百分比混合而成:21%~29%红游动菌、17%~21%蛭弧菌、10%~12%生丝微菌、8.0%~10%氢噬菌、7.5%~9.3%硝化螺旋菌、7.5%~8.4%芽单胞菌、4.8%~8.3%新鞘脂杆菌、4.8%~6.4%浮霉状菌和5.0%~5.6%苯基杆菌。复合生物菌剂能够有效降解生产废水中的COD。
其中,步骤(4)中,所述营养剂为氮、磷、硫、维生素、氨基酸、微量元素中的一种或者多种。
其中,步骤(4)中,好氧池中硝化液的回流比为100~200%。
其中,步骤(5)中,二沉池中混凝沉淀产生的沉渣及生物过程产生的剩余污泥由污泥提升泵抽入污泥浓缩池,经高压隔膜压滤机脱水后进入污泥干化设备,干化后外运处理。
本发明利用对铁炭微电解填料中Fe/C比例的控制,利用铁碳自身产生的电位差,在反应池内形成无数原电池,原电池以废水做电解质,在铁阳极形成Fe2+,阴极形成新生态的[·H]将苯乙烯的侧链氧化为醇,经电化学处理后的污水,在催化氧化池中加入H2O2与水中的Fe2+形成类芬顿效应,快速生成高活性的·OH自由基进一步强化电解效果,使废水中苯乙烯及其他有机物发生断链、开环,将大分子有机物(苯环类有机物)降解为利于微生物降解的小分子有机物,为后续生化处理创造良好的条件。通过电化学、氧化-还原、物理吸附以及混凝沉淀的共同对废水进行处理,使苯类开环断链,从而使难降解、高有机物浓度、高含盐量的废水中的COD和苯乙烯大幅度降低,提高废水的可生化性。
本发明好氧复合菌剂,主要用于直接对废水中COD进行降解;红游动菌利用有机化合物进行光合异养生长,去除有机物的同时还能脱氮,该菌能够将难降解的长链聚合物多元醇及聚醚等降解为容易降解的小分子聚合物,从而提供自身生长所需的碳源;蛭弧菌一方面能够降解小分子的聚合物,另一方面可以裂解老化细菌,为体系中其他微生物提供更加方便利用的碳源及胞外聚合物,促进各个微生物之间的共生;生丝微菌能利用甲醇、乙醇、甲胺、乙醇酸、乙酸盐等小分子有机物为生长能源,将其最终氧化为CO2和H2O,实现有机物的最终降解。氢噬菌是兼性嗜氢自养菌,以氧为末端电子受体的氢化型的糖代谢,能够消耗体系中微生物对有机物代谢产物酸中的氢,主要作用为调节体系的pH。硝化螺旋菌能将亚硝酸盐直接转化为硝酸盐,由于聚醚产品中有一部分有机氮在微生物的作用下氧化为氨氮,氨氮再进一步氧化为亚硝态氮,亚硝态氮对大部分微生物有抑制作用,因此硝化螺旋菌的存在能够减少污水处理过程中亚硝酸盐的积累,从而有效协同其他微生物的处理效率。Blastomonas是降解苯酚的主要细菌,主要可利用苯酚为碳源进行自身新陈代谢,辅助去除芳香族化合物。新鞘脂杆菌对芳香族化合物有极为广泛的代谢能力,能够将芳香族化合物分解为CO2和H2O,有效促进污水中苯乙烯的降解;苯基杆菌具有两方面的功能:一方面可将长链的烷基链断裂,有助于提高亲水性;另一方面对苯环进行开环,形成醛类、醇类等小分子产物。
有益效果:本发明方法能够有效解决聚合多元醇产品生产过程中产生的高浓度含苯乙烯废水生物毒性大、苯乙烯浓度高、出水难以达标排放这一技术问题,本发明方法能够将出水中的苯乙烯浓度降至1mg/L以下;此外,不仅能够有效降解废水中的苯乙烯,还能够有效降解废水中的其它有机物且副产物少,从而显著提高高浓度有机废水的可生化性。
附图说明
图1为本发明处理方法的流程图。
具体实施方式
以下结合具体实施例对本发明的技术方案做进一步说明。
本发明聚合物多元醇生产过程中高浓度有机废水的处理方法,应用于南京某化工企业的聚合物多元醇生产过程中高浓度有机废水处理站;包括如下步骤:
(1)对含高浓度苯乙烯的废水进行预处理,具体为:将聚合物多元醇生产车间排出的含高浓度苯乙烯废水泵入加药池中,加入过氧化氢0.4kg/m3和IOP0.75kg/m3;搅拌反应25min后,再加入阴离子絮凝剂PAM 0.002kg/m3絮凝15min;将絮凝后的混合液通入气浮池,控制容器罐压力表读数为3.4~5kg/cm2,停留时间20min;在气泡浮力作用下,絮体与气泡一起上升至液面,形成浮渣,浮渣由刮沫机刮至污泥区,实现固液分离;固液分离后的污水从设备底部集水管进入电催化氧化反应器中进行电催化氧化反应,控制电流强度为15A,电压恒定为5V,停留时间为1.5h,经电催化氧化处理后出水经电催化氧化反应器出水口排出至废水收集池中。加药池进水和电催化氧化出水口出水的指标见表1:
表1预处理前后COD及苯乙烯的去除情况
由表1可知,经预处理后含苯乙烯废水的COD去除率为75.6%,苯乙烯去除达96.6%,废水B/C比由0.01提升至0.38;该预处理方法反应速率快,IOP催化过氧化氢在分解过程中产生超氧化氢,从而提升了苯乙烯的氧化效率;针对初始浓度为205mg/L的含高浓度苯乙烯废水,化学氧化处理时间只需半小时;
(2)将预处理后的废水与含低浓度苯乙烯的生产废水在废水收集池中混匀,均质均量后由泵提升至铁碳微电解反应池中;将铁碳微电解反应池中废水的pH调节至酸性,同时曝气,铁碳微电解反应池中的有效停留时间为2h,废水在铁碳微电解反应池中进行氧化还原反应,反应后出水自流入催化氧化池;
(2)往催化氧化池中加入双氧水同时进行曝气搅拌,催化氧化有效停留时间为3.5h,在亚铁离子的催化下,双氧水形成氧化性更强的自由基,经催化氧化反应后的出水自流入混凝沉淀装置中;
(3)调节混凝沉淀装置中废水的pH至8~9,然后往其中投加阴离子PAM,混凝沉淀的表面负荷在0.75m3/(㎡·h),经絮凝沉淀反应后,进行固液分离;
(4)固液分离后的液体由泵打入A/O生化池的缺氧池中,同时在好氧池中投加营养剂;A/O生化池由串联的缺氧池和好氧池组成;好氧池中投加复合生物菌剂;缺氧池停留时间为40h,缺氧池为有效容积990m3,配有搅拌系统,好氧池停留时间为120h,有效容积2970m3,配有曝气系统;
(5)A/O生化池出水进入二沉池固液分离,固液分离后的上清液直接外排纳管;二沉池表面负荷0.22m3/(㎡·h),有效容积为475m3;二沉池中混凝沉淀产生的沉渣及生物过程产生的剩余污泥由污泥提升泵抽入污泥浓缩池,经高压隔膜压滤机脱水后进入污泥干化设备,干化后外运处理。
表2为本发明方法处理后废水的变化情况
Claims (10)
1.一种聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于,包括如下步骤:
(1)将废水收集池中的混合废水泵入铁碳微电解反应池中;将铁碳微电解反应池中废水的pH调节至酸性,废水在铁碳微电解反应池中进行氧化还原反应,反应后出水自流入催化氧化池;
(2)往催化氧化池中加入双氧水同时进行曝气搅拌,在亚铁离子的催化下进行氧化反应,经催化氧化反应后的出水自流入混凝沉淀装置中;
(3)调节混凝沉淀装置中废水的pH至8~9,然后往其中投加阴离子PAM,经絮凝沉淀反应后,进行固液分离;
(4)固液分离后的液体进入A/O生化池中,同时在好氧池中投加营养剂;所述A/O生化池包括依次连接的缺氧池和好氧池;好氧池中投加有复合生物菌剂;
(5)A/O生化池出水进入二沉池固液分离,固液分离后的上清液直接外排纳管。
2.根据权利要求1所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:步骤(1)中,混合废水包括预处理后的废水和含低浓度苯乙烯的生产废水,混合废水的COD≤5000mg/L,苯乙烯浓度≤20mg/L,盐分浓度≤15000mg/L。
3.根据权利要求2所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:预处理后的废水在预处理前,废水中苯乙烯的浓度为不高于205mg/L;废水预处理过程具体是指:(a)将聚合物多元醇生产车间排出的含苯乙烯废水泵入加药池中,加药池pH调节至6~8,往加药池中依次加入催化剂、氧化剂和絮凝剂,经过催化氧化反应和絮凝沉淀反应后,进入气浮设备中;(b)在气泡浮力作用下,絮体与气泡一起上升至液面,形成浮渣,浮渣由刮沫机刮至污泥区;实现固液分离;(c)固液分离后的污水通过集水管流至电催化氧化反应器中进行电催化反应,电催化反应后排出进入废水收集池中。
4.根据权利要求3所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:所述催化剂为棕榈酸异辛酯,催化剂投加量为0.25~0.75kg/m3;氧化剂为双氧水,氧化剂投加量为0.2~0.4kg/m3;絮凝剂为阴离子PAM絮凝剂,絮凝剂投加量为0.002~0.0025kg/m3。
5.根据权利要求3所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:所述电催化氧化反应中设有多对阴阳电极板,所述阳极极板材料为IrO2-RuO2/Ti;电催化反应中,反应电流为10~20A,反应电压为4.5~6.0V。
6.根据权利要求1所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:步骤(2)中,铁碳微电解反应池中含有铁碳填料,所述铁碳填料为铁和碳高温烧结的铁碳球填料,铁碳填料中铁与碳的质量比为不小于5:1。
7.根据权利要求6所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:铁碳微电解反应池中pH为2.5~3.5,气水比为3.5:1。
8.根据权利要求1所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:步骤(3)中,阴离子PAM的投加量是0.001~0.003kg/m3。
9.根据权利要求1所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:步骤(4)中,好氧池中硝化液的回流比为100~200%。
10.根据权利要求1所述的聚合物多元醇生产过程中高浓度有机废水的处理方法,其特征在于:步骤(5)中,二沉池中混凝沉淀产生的沉渣及生物过程产生的剩余污泥由污泥提升泵抽入污泥浓缩池,经高压隔膜压滤机脱水后进入污泥干化设备,干化后外运处理。
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