CN114906973A - 一种焦化污水深度处理零排放工艺 - Google Patents
一种焦化污水深度处理零排放工艺 Download PDFInfo
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- CN114906973A CN114906973A CN202110174102.5A CN202110174102A CN114906973A CN 114906973 A CN114906973 A CN 114906973A CN 202110174102 A CN202110174102 A CN 202110174102A CN 114906973 A CN114906973 A CN 114906973A
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Abstract
本发明涉及一种焦化污水深度处理零排放工艺,焦化污水进入调节池,经隔油池、溶气气浮池、电气浮池处理后,进入蒸氨系统、脱酚系统,进行蒸氨脱酚处理,然后进入铁碳微电解池、芬顿氧化池,进行强化预处理,芬顿氧化池出水进入中和沉淀池;然后依次进入厌氧池、两级(缺氧/好氧)A/O生化反应,再依次进入沉淀池、滤池,滤池出水依次进入超滤系统、反渗透系统进行深度处理。反渗透产出浓水进入结晶系统处理,达到焦化污水“零排放”,透过水作为工业回用水。本发明的目的在于焦化污水处理过程中,提高油处理效果,将高级氧化处理传统生化处理结合,提高处理效果,降低成本;同时保障后续深度处理的稳定,减少膜污染,降低处理成本,稳定处理效果。
Description
技术领域
本发明涉及焦化污水深度处理及回用领域,具体说是一种焦化污水深度处理零排放工艺。
背景技术
目前我国焦炭产量占全球产量的一半以上,是全球最大焦炭生产国。焦化行业在生产过程中产生大量高污染废水。焦化污水是一种典型的高浓度难降解有毒工业焦化有机污水,主要含有酚类、苯系物、喹啉、吡啶、胺类等难降解有机物以及氨、硫化物、氰化物和多种重金属离子等无机物,对环境产生危害的主要组分有COD、氨氮、酚、氰化物、硫物、及油分等,重点是有机污染物,由于焦化行业废水的成分复杂,所以焦化废水不经处理排放不仅污染环境,而且严重威胁人类健康。国内焦化行业废水处理始自上世纪,处理方法主要变化如下:初期主要是以机械处理方法为手段,以脱酚为主要目的;由于生化理论的发展,后期焦化污水在机械处理方法的基础上,结合生物处理方法,将焦化污水对环境污染程度大幅降低;《中华人民共和国环境保护法(试行)》颁布后,国内各大科研院所开始重视污水处理技术的研究,积极吸收国内外先进污水处理技术,并设计发展众多焦化废水处理装置;进入90年代,环境保护制度日益完善,相关焦化废水排放标准日益严格,焦化废水处理重点研究氮和COD的去除,A/O脱氮工艺在焦化污水处理领域得到广泛应用。为实现坚持可持续发展观,通过焦化污水深度处理零排放,能够更好地满足相关标准及规范要求。
目前,焦化污水处理中,污水含有大量酚类及油类物质,现有方法对油的去除效果不佳,焦化污水中的油污会污染高级氧化填料,高级氧化不能发挥作用,降低污水的可生化性,影响后续生化处理效果,增加生化处理成本,降低后续处理的稳定性;另外,单独的生化处理投资大,处理效果不佳;同时单独的高级氧化工艺处理虽然处理比较彻底,但系统运行成本高;处理效果不佳的生化处理污水中的油会加重分离膜的污堵,增加清洗频率,降低分离膜寿命;单一的处理系统稳定性差,处理成本高或投资巨大。
发明内容
本发明采用“调节池 +隔油池+蒸氨系统+脱酚系统+溶气气浮池+电气浮池+铁碳微电解池+芬顿氧化池+中和沉淀池+厌氧池+
一级缺氧池+一级好氧池+二级缺氧池+二级好氧池+沉淀池+滤池+超滤系统+反渗透系统+结晶系统”工艺。
本发明所涉及的原水为焦化污水,其水质为:CODCr=15000~30000mg/L,氨氮=3500~6000mg/L,SS=700~1000mg/L,pH=6~9,电导率=5000~9000μs/cm,油=450~600mg/L,挥发酚类=6000~12000mg/L。
本发明的铁碳微电解池可以将[0011]工艺段出水中的酚、喹啉、吡啶、吲哚、呋
喃、哌嗪、吖啶、咪唑、长链烷烃、环烷烃、苯、联苯、卤代烷烃及少量的醇、酸、酯等难降解有
机物分解成小分子有机物,打开苯环类物质的环结构,提高焦化污水的可生化性,焦化污水
的CODCr值有一定的增加,难降解有机物处理成易降解或可降解有机物的比率达到95%以上。
本发明芬顿氧化池可以有效将[0012]工艺段出水中的有机物进行分解:部分
有机物被完全分解为二氧化碳与水,部分有机物被分解为分子量更小、分子结构更简单的
有机物,保证后续焦化污水可生化性,同时,焦化污水COD的去除率达到60%至70%。
本发明的“一级缺氧池+一级好氧池+二级缺氧池+二级好氧池”
可以有效去除[0015]工艺段出水的总氮,同时去除污水中的有机物,总氮的去除率达到86%
以上,COD的去除率达到93%以上,同时污水中的二价铁离子被氧化为三价铁,在好氧池中,
生成三价铁的絮体,成为活性污泥的一部。
附图说明
附图1是本发明是一种焦化污水深度处理零排放的全流程工艺图。
具体实施方法
下面就本发明具体实施进行详细说明。
本发明是一种焦化污水深度处理零排放全流程工艺方案,处理步骤为:
来自生产车间的焦化污水进入调节池,由于生产产生污水的水质及生产环节
水质的周期性变化,调节池对焦化污水的水量及水质,进行调节,降低对后续处理环节
的冲击,在调节池内设置对角的进水槽,调节池内四周设置集水槽,根据水量及水
质变化周期,调节停留时间10-14h。
调节池出水进入隔油池,焦化污水中的浮油及分散油:比重比水大的下
沉,由池底的管道排除;比重比水小的上升,聚集池面,流入隔油池未端的集油槽,通过
排油管排除,通过隔油池的作用,浮油的去除率达到99%以上,分散油去除率达到30%以
上,以保障后续处理工艺的处理效果。
蒸氨系统采用间接蒸氨方法,经隔油池处理的焦化污水进入蒸氨系统的蒸氨塔,蒸氨碱液用泵送入蒸氨塔,在蒸氨塔内,焦化污水PH值调整至不小于10.5,
蒸氨塔底设间接加热装置,塔底加热温度在105℃-112℃,压力0.045Mpa,蒸氨塔底少部分
热废水用泵打入再沸器,用循环氨水加热后产生的蒸汽返回蒸氨塔内,大部分塔底废水用8
废水泵抽出经换热器后,进入脱酚系统。蒸氨塔顶设置分凝器温度100℃-103℃,压力
0.030Mpa,蒸氨塔顶氨气进入分凝器,用中温水冷却后,冷凝液进氨水冷却器,用低温水冷
却后进入氨水槽。
蒸氨系统处理的焦化污水进入脱酚系统,脱酚系统采用煤油萃取挥
发酚方法,根据相似相溶原理,进入脱酚系统的焦化污水内有部分与煤油性质相近的
有机物,同时也有部分沸点较高的有机物,与煤油性质相近的低沸点有机物表现出与煤油
作为萃取剂类似的现象,与煤油相溶,在高温的作用下,随煤油及挥发酚一同从焦化污水中
逸出,后经反萃取塔,回收作为萃取剂的煤油,萃取剂重新使用,通过这一过程,达到降低焦
化污水酚浓度的目的,为后期的生化处理提供保障,脱酚系统的萃取塔底部剩余的焦
化污水经管道排出。
脱酚系统出流的焦化污水中依然含有一定浓度的分散油及溶解油,焦化污水
设置溶气气浮池。采用水处理药剂PAC和PAM,分别设置PAC和PAM的溶药罐和储药罐,水
处理药剂PAC与水混合的配置浓度为2%,水处理药剂PAM与水混合的配置浓度为0.2%,PAC药
液通过加药计量泵通过混凝池,在搅拌机的作用下,与混凝池内的焦化污水充分混合,此过
程污水停留时间约2min,然后焦化污水流入絮凝池,PAM药液通过计量泵,打入絮凝池,并在
搅拌机的作用下与污水充分混合,焦化污水在通过加入PAC与PAM作用后,焦化污水中生成
大量的细小矾花,然后污水进入反应池,溶气罐内加压溶气水通入反应池。溶气罐压力设置
为0.4MPA,采用溶气气浮池部分出水回流加压溶气罐,既能保证处理效果,又不增加处
理水量,同时溶气气浮池出水的油浓度较低,减轻了对加压溶气罐设备的污堵。加压溶
汽水在反应池内,经常压释放,产生大量的微米级气泡,与絮体结合并上升产生溶气气浮
渣,浮渣在池面汇集,池面设置的刮渣板将浮渣收集到浮渣槽,由管道排放至浮渣池,溶气
气浮池内浮渣下层污水由管道排出。
由于溶气气浮池释放压力溶气的微小气泡的数量密度受限于溶气罐内的气
体溶解度,为了进一步将焦化污水中的油污去除,在溶气气浮池后设置电气浮池,
溶气气浮池与电气浮池两工艺的结合,既能保证油污的去除效率,又能降低处理
成本。
电气浮池是一种运用电化学方法去除固态颗粒、油污的废水处理装置,溶气
气浮池出流的焦化污水流入电气浮池,电气浮池内设置难腐蚀惰性石墨板,
作为阴、阳两极,并通入直流电,在两极附近发生电化学反应,由于水的电解和有机物的电
解氧化,在阴、阳两极表面上会有气体,如氢气、氧气、二氧化碳、氯气等微小气泡逸出,由于
溶气气浮池出流的焦化污水中有少量的未反应的水处理药剂PAC及PAM,在电气浮装置
内,发生混合、絮凝作用,产生矾花,与污水中的油污结合。同时电气产生的气体形成的微小
气泡在上升过程中,可粘附水中的杂质微粒和油类浮到水面,上浮的浮渣由池面设置的刮
渣板刮除,汇集到集渣槽;同时,由于电解氧化的作用,将污水中的难降解的复杂有机物氧
化,产生的氯气等强氧化性气体同污水中的有机物发生氧化还原反应,或改变复杂有机物
有结构,加强PAC、PAM的絮凝吸附效果,对焦化污水中的溶解油有去除率达到90%以上,达到
既降低污水油污浓度,又能降低污水COD。
电气浮出流的焦化污水由泵输送入铁碳微电解池,铁碳微电解池内加入
硫酸,调整PH值=3,在铁碳烧结填料中铁、碳组成的数量巨大的原电池及其微电场,阳极反
应生成大量的Fe2+进入废水,进而氧化生成Fe3+,形成具有较高吸附絮凝活性的絮凝剂,阴
极反应产生大量新生[H]和[O],焦化污水中的复杂有机物被断链降解,提高焦化污水的可
生化性。
铁碳微电解池出流的焦化污水流入芬顿氧化池,芬顿氧化池中设竖
轴式搅拌装置,同时向池中通入加酸管,双氧水投加管,硫酸亚铁溶液投加管,调整芬顿氧
化池的PH=3~4之间,池中双氧水与硫酸亚铁的投加摩尔比为5.5―2.5,芬顿氧化池中焦化污水的停留时间为0.5―1.5小时,通过反应将污水中的难降解有机物的复杂结
构打断,同时部分有机物被彻底氧化分解,降低焦化污水的COD,同时提高焦化污水的可生
化性,为后续的生化反应提供更好的保障。
从芬顿氧化池出流的焦化污水,进入中和沉淀池,在中和沉淀池中
设置熟石灰乳液加注管,池中心设置竖轴搅拌机,加入熟石灰,由于硫酸钙溶度积的限制,
通过加入熟石灰,焦化污水中将生成硫酸钙沉淀,降低了污水中的硫酸根离子的浓度,同时
中和污水中的氢离子,调节污水的PH=8,由于铁碳微电解池、芬顿氧化池中溶解到
污水中大量的Fe3+离子,及SO4+离子,通过中和沉淀池中投加熟石灰,生成大量的氢氧
化铁沉淀及硫酸钙沉淀,在中和沉淀池的斜板沉淀池中,通过设置间距为40mm的斜板,
将焦化污中的沉淀絮体去除,同时由于絮体的吸附作用,污水中的部分有机物会被絮体沉
淀吸附而去除,斜板上层跑水面10cm,池底设计排泥斗,斜板下层跑底部的泥斗距离为
1800cm,,同时在设置斜板沉淀池的冲洗水管,水管压力=0.32Mpa,用于后续检修期间斜板
沉淀池内斜板上沉淀污泥的清洗,斜板沉淀池中污水停留时间1.5h。
中和沉淀池出流焦化污水流入厌氧池,污水通过导流墙从厌氧池底
部进入,在厌氧池中,为维持池内活性污泥浓度,接后端沉淀池的污泥回流管,通
过回流包含厌氧菌的活性污泥,将池中的焦化污水中的难降解有机物,进一步厌氧分解,同
时将有机物机中有机氮进一步氨化得到NH3及NH4+。为了保持厌氧池的处理效率,在厌
氧池内设置组合填料,填料填充比为60%-80%,池内污泥浓度5500mg/L--7500mg/L,池
内污水停留时间20h—30h。
厌氧池出流的焦化污水流入一级缺氧池,一级缺氧池接入二级好氧
池的硝化液回流管,硝化液回流比200%-400%,污泥浓度维持在2500mg/L--3500mg/L,
在一级缺氧池中,设置竖轴搅拌机,搅拌功率15w/m3,一级缺氧池内污水停留时间
10h—15h,池内反硝化异养菌利用硝化液中的硝态氮,及厌氧池流入的焦化污水中的
有降解有机物,通过生化反应,硝态氮生成N2,同时有机物被氧化降解,为了保障缺氧池反
硝化作用的顺利进行,在一级缺氧池上设置增加池内BOD浓度的管道,如淀粉溶液或类
似淀粉作用的投加管道。
一级缺氧池出流的焦化污水流入一级好氧池,在一级好氧池内,通
过池内曝气管,维持池内好氧环境,溶解氧不小于2.0mg/L,好氧活性污泥浓度2500mg/L--
3500mg/L,池内污水停留时间18h—24h,在好氧池内,好氧异养菌将污水中的有机物氧化分
解为CO2、H2O,污水中的NH3及NH4+,被亚硝化菌氧化为亚硝态氮,亚硝态氮通过硝态菌氧化
生成硝态氮。为了减轻好氧池运行过程中产生的泡沫的影响,在一级好氧池上设置沉
淀池出水喷洒管。
一级好氧池流出的焦化污水流入二级缺氧池,二级缺氧池内不设置
充氧曝气装置,污泥浓度维持在2500mg/L--3500mg/L,在二级缺氧池中,设置竖轴搅拌
机,搅拌功率15w/m3,池内污水停留时间8h—12h,池内反硝化异养菌利用污水中的硝态氮,
及污水中的有机物,通过反硝化作用,硝态氮生成N2,同时有机物被氧化降解,同时二级缺
氧池中的兼氧菌,将污水中的有机物分解,有机物中的有机氮氨化为污水中的NH3及
NH4+。
二级缺氧池出流的焦化污水流入二级好氧池,在二级好氧池8内,通
过池内曝气管,维持池内好氧环境,溶解氧不小于2.0mg/L,好氧活性污泥浓度2500mg/L--
3500mg/L,池内污水停留时间12h—18h,在好氧池内,好氧异养菌将污水中的有机物氧化分
解为CO2、H2O,污水中的NH3及NH4+,被亚硝化菌氧化为亚硝态氮,亚硝态氮通过硝态菌氧化
生成硝态氮。二级好氧池末端内设置硝化液回流泵。为了减轻二级好氧池运行过
程中产生的泡沫的影响,在二级好氧池上设置沉淀池出水喷洒管。
二级好氧池流出的污水流入沉淀池,通过重力沉淀作用,达到泥水分离,
停留时间2h—4h,沉淀池下设污泥收集斗,通过污泥泵抽出污泥,通过管道将部分污泥
回流到前端厌氧池,污泥回流比50%-100%,剩余部分污泥外排到系统外处理。
滤池出流焦化污水COD含量≤80mg/L,NH3-N浓度≤5mg/L,SS≤10mg/L,滤池流出的焦化污水泵入超滤系统,超滤系统采用抗污染膜,超滤系统运行
压力0.03-0.07MPa,膜通量50-65L/h∙m2,自动反洗正洗周期为30min,其中反洗60秒,正洗
30秒,冲洗排水排至铁碳微电解池。为了清除超滤膜上短时间积累的污染物,系统在正
常运行过程中,采用正洗与反洗,正洗或反洗过程可以不使用或使用低浓度药剂,冲洗时间
短。为了将超滤膜通过长时间运行在膜表面积累的正洗或反洗不易清除的有机污泥及无机
盐垢等,系统采用化学清洗,通过在一定浓度的化学药剂中浸泡、循环清洗等手段,达到清
洁超滤膜表面,恢复超滤膜的膜能量,化学清洗周期120h--200h。清洗药剂采用次氯酸钠,
其加入量为1000mg/L;若无机垢污堵,采用碱洗,使用氢氧化钠将pH调至11,然后酸洗,采用
盐酸将pH调至2。在清洗过程中通过投加次氯酸钠杀菌,去除微生物污染物;氢氧化钠协助
去除生物粘泥,同时还对硅垢等有去除作用;盐酸酸洗可以去除大部分的无机盐垢。清洗需
要根据污染物的类型来确定使用何种药剂。如果各种污染物都有,通常采用先进行次氯酸
钠和火碱配合使用进行清洗,然后酸洗。如果污染很厉害,也可以先酸洗,再次氯酸钠和碱
洗,再酸洗。
超滤系统出流的焦化污水,经反渗透系统的5μm的保安过滤器用于进一
步截留水中≥5um颗粒等微小杂质,确保护反渗透装置安全、有效运行,本体材质为304不锈
钢,内装精度为5umPP熔喷滤芯。滤芯更换视进、出水压差情况而定,当出水压头损失超过
0.15MPa时须更换滤芯。
焦化污水经过反渗透系统的保安过滤器过滤后,经过高压泵送入反渗透系统的膜组件内,高压泵提供反渗透装置正常工作所需水量和压力,反渗透系统的高
压泵设计采用立式多级离心泵,扬程:90m—140m;材质:304不锈钢,反渗透系统的反渗
透膜元件通过以压力为推动力,进行膜分离除盐,同时可除去水中溶解性有机物等,反渗透
膜元件采用运行安全稳定,质量可靠的芳香族聚胺复合膜。压力膜组件使用不锈钢膜壳,该
膜壳内壁光滑、与膜元件吻合程度好,并不易滋生细菌。通过设计计算对膜元件采用合理的
排列方式,总回收率65%,脱盐率≥98%。反渗透系统配置就地仪表盘和操作盘,在仪表
盘上可读出反渗透系统的相关运行参数,如流量(浓水、产水);压力(进水、浓水、产
水)、电导等,在操作盘上可手动启、停高压泵。高压泵进、出口设置高低压保护开关,可确保
因供水压力不足而损坏高压泵,因压力过高而损坏膜元件。进水侧、浓水侧设置电动阀,可
自动定时对膜面进行低压冲洗,尽可能延长膜的清洗周期和提高膜的使用寿命。反渗透系
统运行一段时间后原水中少量污染物逐渐积累,导致组件压差升高产水量下降,脱盐
率下降等现象,须通过注入药液进行化学清洗恢复膜元件性能,一般化学清洗周期为4-6个
月。清洗用药剂可通过不同的污染情况注入相应药液,如钙、镁可调节PH后注入柠檬酸药
液,胶体有机物、微生物污染可注入EDTA四钠盐及三聚磷酸钠等药液,清洗系统设计采用PE
水箱、不锈钢保安滤器及不锈钢卧式离心泵,反渗透系统设置中间水箱、水泵贮存原
水、调节进水水量及增压供水,水箱设置液位控制器,发出高、中、低3个液位讯号与水泵相
联锁。
Claims (11)
1.一种焦化污水处理方法,其特征在于,采用“调节池+隔油池+蒸氨系统+脱酚系统+溶气气浮池+电气浮池+铁碳微电解池+芬顿氧化池+中和沉淀池+厌氧池+一级缺氧池+一级好氧池+二级缺氧池+二级好氧池+沉淀池+滤池+超滤系统+反渗透系统+结晶系统”;
焦化污水水质为:CODCr= 15000 ~ 30000mg/L,氨氮= 3500 ~ 6000mg/L,SS =700 ~ 1000mg/L,pH = 6 ~ 9,电导率= 5000 ~ 9000μs/cm,油= 450~600 mg/L,挥发酚=6000~10000mg/L;
5.以保障后续高级氧化工艺的稳定运行。
8.同时去除生成的沉淀。
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