CN114906975B - 一种焦化废水零排放处理工艺 - Google Patents
一种焦化废水零排放处理工艺 Download PDFInfo
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- CN114906975B CN114906975B CN202210145096.5A CN202210145096A CN114906975B CN 114906975 B CN114906975 B CN 114906975B CN 202210145096 A CN202210145096 A CN 202210145096A CN 114906975 B CN114906975 B CN 114906975B
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本申请公开了一种焦化废水零排放处理工艺,包括生化处理,深度处理及分盐结晶,其中,深度处理包括废水预处理,反渗透浓缩以及污泥脱水。废水预处理包括预处理加药,高效澄清,多介质过滤,超滤,树脂软化,二氧化碳脱除以及有机物脱除,有机物脱除包括有吸附罐内吸附、吸附罐外脱附以及洗脱废液湿式氧化。本申请的技术方案针对焦化工厂的废水进行零排放处理,根据废水组成特点进行针对性处理,结合生化处理、深度处理及分盐结晶实现了酚氰废水的零排放。
Description
技术领域
本发明属于环保技术领域,具体为焦化废水零排放处理工艺。
背景技术
焦化工厂在生产过程中会产生大量废水,随着环境保护力度加大,废水的排放限制愈加严格,原本可进行循环利用的废水需要进行处理达标后排放,因此,需要针对焦化工厂产生的废水进行零排放处理。焦化工厂中产生的废水主要包括:蒸氨废水、工艺酚氰废水、生产生活化验废水、初期雨水、消防事故水以及脱盐水站产生的浓盐水,,需要提供适用的零排放处理工艺,以实现废水的零排放。
发明内容
针对现有技术的不足,本发明提供一种酚氰废水零排放处理工艺。
零排放采用分盐工艺,生产精盐满足氯化钠含量指标达到T/CCT 002-2019《煤化工副产工业氯化钠》标准中的工业干盐一级品指标要求,其它指标不低于合格品要求。硫酸钠含量指标达到T/CCT 001-2019《煤化工副产工业硫酸钠》标准中的A类一等品标准要求,其它指标不低于合格品要求。
为实现上述目的,本发明采用如下工艺:
一种焦化废水零排放处理工艺,包括生化处理,深度处理及分盐结晶,其中,焦化废水生化处理出水进行深度处理至达到零排效果,达标回用水作为循环水系统补充水;深度处理包括废水预处理,反渗透浓缩以及污泥脱水,其中,废水预处理包括预处理加药,高效澄清,多介质过滤,超滤,树脂软化,二氧化碳脱除以及有机物脱除,有机物脱除包括吸附罐内吸附、吸附罐外脱附以及洗脱废液湿式氧化。
进一步地,蒸氨废水先进入除油池除油,无压污水先进入格栅及污水提升井,消防事故水与除油后的废水及格栅过滤后的废水均进入调节池,调节池内的废水经气浮装置去除浮渣,经两级A/O工艺后进入三沉池,再经混凝反应、混凝沉淀后进入集水池,产生的污泥进行污泥浓缩和污泥脱水处理,生化出水总氮≤20mg/L。其中,无压污水包括生产生活化验废水、初期雨水等。
进一步地,吸附罐外脱附包括:酸清洗一,盐碱+有机清洗液清洗,盐碱清洗以及酸清洗二,酸清洗一为:采用(2-8)wt%的盐酸1.5-3BV,温度为52-58℃,分二步清洗,每步一半用量,第一步要浸泡,浸泡时间不少于1小时,浸泡过程中用压缩空气搅拌,然后用去离子水冲洗;
盐碱+有机清洗液清洗为:(2-5)wt%NaOH+(8-12)wt%NaCl+(20-30)wt%有机溶剂0.5BV,温度为52-58℃,浸泡2小时,然后用去离子水冲洗。
可选地,有机清洗液为有机酸、有机醇或其组合;有机酸例如醋酸、草酸以及柠檬酸,有机醇例如甲醇、异丙醇等,可采用单一溶剂或其组合。
盐碱清洗为:(2-5)wt%NaOH+(8-12)wt%NaCl溶液2-4BV,温度为52-58℃,分三步清洗,前两步六分之一的用量,第一步中浸泡时间不少于2小时,然后用去离子水冲洗,排干;第二步中浸泡时间不少于2小时,浸泡过程中用压缩空气搅拌,浸泡结束后,用去离子水冲洗,排干;第三步三分之二的用量,然后用去离子水冲洗。
酸清洗二为:(2-3)wt%的盐酸0.5-1.5BV,常温,最后用去离子水冲洗。
进一步地,湿式氧化工艺为:将洗脱废液用硫酸将pH调整至2-4,按2-5%的浓度加入双氧水,混合均匀;将反应塔用蒸汽加温至145-150℃后,将配制好的原液送入反应塔,原液在反应塔内的有效停留时间为1.5-2h。
进一步地,分盐结晶包括浓水脱色及COD去除,分盐浓缩,其中分盐采用纳滤膜分离出氯化钠和硫酸钠,氯化钠纳滤过程进行两次纳滤分盐;硫酸钠纳滤浓水经冷冻结晶后的母液经湿式氧化处理、软化处理后与生化出水混合再次进行分盐结晶。
本发明与现有技术相比,优点在于:本申请的技术方案针对焦化工厂的废水进行零排放处理,根据废水组成特点进行针对性处理,结合生化处理、深度处理及分盐结晶实现了酚氰废水的零排放。其中,将现有技术中的树脂罐内吸附和脱附的过程改进为“体内吸附+体外脱附”的过程,显著改善了污染树脂的脱附效果,对于分盐结晶过程产生的母液进行湿式氧化及软化处理,使浓缩后的母液再次满足分盐结晶的条件,解决了母液难以处理的问题。对脱附废液及浓缩母液采用湿式催化氧化的工艺进行处理,脱附废液中的有机物去除率达到80%以及50%以上,最高可达92%,可实现有机物的高效去除,为工业废水的零排放提供了有力保障。
附图说明
图1为生化处理工艺流程图
图2为深度处理及分盐结晶工艺流程图
图3为有机物脱附装置结构示意图
图4为分盐及浓缩工艺流程图
图5为硫酸钠冷冻结晶工艺流程图
附图标记:
1、吸附罐一,2、吸附罐二,3、吸附罐三,4、脱附罐,5、湿式氧化装置,6、去离子水箱,7、酸脱附液箱,8、盐碱脱附液箱
具体实施方式
本发明中涉及的百分比均为质量百分比。
一种酚氰废水零排放处理工艺,包括生化处理,深度处理及分盐结晶,其中,焦化废水生化处理出水进行深度处理至达到零排效果,达标回用水作为循环水系统补充水;深度处理包括废水预处理,反渗透浓缩以及污泥脱水,其中,废水预处理包括预处理加药,高效澄清,多介质过滤,超滤,树脂再软化,二氧化碳脱除以及有机物脱除,有机物脱除包括吸附罐内吸附、吸附罐外脱附以及洗脱废液湿式氧化。
如图1所示,蒸氨废水先进入除油池除油,无压污水,如生产生活化验废水、初期雨水先进入格栅及污水提升井,消防事故水与除油后的废水及格栅过滤后的废水均进入调节池,调节池内的废水经气浮装置去除浮渣,经两级A/O工艺后进入三沉池,再经混凝反应、混凝沉淀后进入集水池,产生的污泥进行污泥浓缩和污泥脱水处理,生化出水总氮≤20mg/L。
深度处理及分盐结晶采用图2所示的流程,其中,脱附液处理装置及超级氧化装置均为湿式氧化装置。预处理加药采用“石灰+纯碱”软化工艺,在去除硬度的同时控制氟在一定的范围内,另外为防止废水滋生细菌,还考虑在预处理设施中投加杀菌剂。通过化学软化处理出水硬度控制在100mg/l以下,COD去除10-15%。高效澄清步骤中,投加石灰、烧碱、纯碱、絮凝剂、助凝剂、次氯酸钠溶液药剂,经高效澄清沉淀后,不仅可大幅降低悬浮物胶体物质,也可起到除硬除氟的作用,产水自流入清水池;反应沉淀池排泥排入污泥浓缩池后通过污泥给料泵提升至污泥脱水机间脱水,泥饼外运。多介质过滤步骤中,滤料采用无烟煤和石英砂双层滤料,主要是去除水中的悬浮物、胶体,控制藻类的繁殖,稳定供水水质,在水质发生大的波动时起到保护后级系统的作用。多介质过滤器采用气水联合反洗方式,水反洗强度:8-10L/m2.s,气洗强度:15L/m2.s,气压≥5.8mH2O。超滤步骤中,采用陶氏高质量的PVDF材质中空纤维、外压式超滤膜元件。装置内部各单支膜元件进水、反洗布水均匀,单支膜进水膜通量不高于45L/m2.h。树脂再软化步骤中,虽然高效混凝沉淀去除了大部分的硬度,但对于零排放这样的系统中,其硬度去除率仍无法满足要求,即使是残留很少的硬度,也会对高浓缩倍率反渗透系统造成污堵,因此采用树脂软化去除残留的硬度,将反渗透进水硬度控制在极低的水平,本实施例中树脂采用大孔弱酸阳树脂,其具有工交容量大,再生消耗低的优势。
优选地,采用图3中所示装置进行有机物脱除,吸附罐通过树脂转移管与脱附罐4连接,脱附罐4与湿式氧化装置5、去离子水箱6、酸脱附液箱7以及盐碱脱附液箱8连接,树脂转移装置将树脂从吸附罐输送至脱附罐4,脱附后将树脂输送回吸附罐。其中,树脂转移装置例如为泵。吸附罐上的树脂进料口通过树脂转移管与脱附罐4上的树脂出料口连接,吸附罐上的树脂出料口通过树脂转移管与脱附罐4上的树脂进料口连接。吸附罐设置三个,分别为吸附罐一1、吸附罐二2、吸附罐三3,其中两个交替工作,第三个备用。酸脱附液箱7内为(2-8)%的HCl,盐碱脱附液箱8内为(2-5)%NaOH+(8-12)%NaCl溶液和(2-5)%NaOH+(8-12)%NaCl+(20-30)%有机清洗液。
有机物脱附过程为:吸附罐一1进水,通过树脂吸附有机物;吸附罐一1达到工作交换容量后停止进水,对吸附罐内的树脂进行加气反洗,吸附罐二2进水并吸附,吸附罐一1内的树脂从出料口经树脂转移管进入脱附罐4,对脱附罐4内的树脂进行脱附;脱附罐4内的树脂脱附完毕后从出料口经树脂转移管进入吸附罐一1的进料口;吸附罐二2达到工作交换容量后停止进水,吸附罐一1进水并吸附,吸附罐二2内的树脂从出料口经树脂转移管进入脱附罐4,对脱附罐4内的树脂进行脱附;重复上述步骤。
脱附过程为:酸清洗一,盐碱+有机清洗液清洗,盐碱清洗以及酸清洗二,酸清洗一为:采用(2-8)wt%的盐酸1.5-3BV,温度为52-58℃,分二步清洗,每步一半用量,第一步要浸泡,浸泡时间不少于1小时,浸泡过程中用压缩空气搅拌,然后用去离子水冲洗;
盐碱+有机清洗液清洗为:(2-5)wt%NaOH+(8-12)wt%NaCl+(20-30)wt%有机清洗液0.5-1BV,温度为52-58℃,浸泡2小时,然后用去离子水冲洗;有机清洗液为有机酸、有机醇或其组合;有机酸例如醋酸、草酸以及柠檬酸,有机醇例如甲醇、异丙醇等,可采用单一清洗液或其组合。
盐碱清洗为:(2-5)wt%NaOH+(8-12)wt%NaCl溶液2-4BV,温度为52-58℃,分三步清洗,前两步六分之一的用量,第一步中浸泡时间不少于2小时,然后用去离子水冲洗,排干;第二步中浸泡时间不少于2小时,浸泡过程中用压缩空气搅拌,浸泡结束后,用去离子水冲洗,排干;第三步三分之二的用量,然后用去离子水冲洗。
酸清洗二为:(2-3)wt%的盐酸0.5-1.5BV,常温,最后用去离子水冲洗。其中,脱附各步均采用逆流的进液方式。
具体地,可采用表1中的具体步骤进行脱附。
表1
随着运行时间的延长,常规的罐内脱附方式在经过多次循环后,树脂的吸附性能通常会下降到初始吸附性能的80%以下,罐内脱附难以再将树脂的吸附性能提升,采用本申请中的脱附方法可显著提高树脂的脱附程度,采用表1中的具体步骤进行脱附后,树脂的吸附性能可由原始吸附性能的80%以下恢复至90%以上,脱附效果明显提升,从而可大幅降低树脂的使用成本。
优选地,反渗透包括原水反渗透,深度软化和浓水反渗透(CRO),其中,原水反渗透荐采用杜邦(原陶氏)FILMTECTMCR100超抗污染低能耗反渗透膜元件,浓水反渗透采用陶氏FILMTECTM富耐TMXC70/XC80反渗透膜。
优选地,污泥脱水装置与废水生化处理系统共用。
优选地,分盐结晶包括浓水脱色及COD去除,分盐浓缩,其中浓水脱色及COD去除采用多级活性炭吸附反应+沉淀工艺,通过吸附去除浓水中的COD及色度,脱色后的浓水再经超滤过滤得到清液。
分盐采用纳滤膜分离出氯化钠和硫酸钠,如图4所示,氯化钠纳滤过程进行两次纳滤分盐,其中,NaCl浓缩设置反渗透装置对组合分盐装置分离出来的氯化钠溶液进行浓缩处理,将氯化钠的浓度浓缩到80000mg/L左右,再去蒸发结晶。氯化钠蒸发结晶采用顺流三效强制循环蒸发结晶工艺;如图5所示,硫酸钠纳滤浓水经冷冻结晶后的母液经湿式氧化处理、软化处理后与生化出水混合再次进行分盐结晶。硫酸钠采用冷冻结晶出芒硝,芒硝反溶后采用二效强制循环顺流蒸发精制,洗脱液采用二效强制循环顺流蒸发结晶,最终母液采用刮板式蒸发结晶并干燥。
优选地,湿式氧化工艺为:将洗脱废液用硫酸将pH调整至2-4,按2-5%的浓度加入双氧水,混合均匀;将反应塔用蒸汽加温至145-150℃后,将配制好的原液送入反应塔,原液在反应塔内的有效停留时间为1.5-2h。
在本发明的描述中,需要理解的是,术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”“内”、“外”、“顺时针”、“逆时针”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系,仅是为了便于描述本发明和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本发明的限制。此外,限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中,除非另有说明,“多个”的含义是两个或两个以上。
在本发明的描述中,需要说明的是,除非另有明确的规定和限定,术语“安装”、“相连”、“连接”应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或一体地连接;可以是机械连接,也可以是电连接;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通。对于本领域的普通技术人员而言,可以具体情况理解上述术语在本发明中的具体含义。
在本发明的描述中,参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
尽管已经示出和描述了本发明的实施例,本领域的普通技术人员可以理解:在不脱离本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由权利要求及其等同物限定。
Claims (3)
1.一种焦化废水零排放处理工艺,其特征在于,包括生化处理,深度处理及分盐结晶,焦化废水生化处理出水进行深度处理至达到零排效果,达标回用水作为循环水系统补充水;其中,深度处理包括废水预处理,反渗透浓缩以及污泥脱水,其中,废水预处理包括预处理加药,高效澄清,多介质过滤,超滤,树脂软化,二氧化碳脱除以及有机物脱除,有机物脱除包括吸附罐内吸附、吸附罐外脱附以及洗脱废液湿式氧化;生化处理中,蒸氨废水先进入除油池除油,无压污水先进入格栅及污水提升井,消防事故水与除油后的废水及格栅过滤后的废水均进入调节池,调节池内的废水经气浮装置去除浮渣,经两级A/O工艺后进入三沉池,再经混凝反应、混凝沉淀后进入集水池,产生的污泥进行污泥浓缩和污泥脱水处理,生化出水总氮≤20mg/L;吸附罐外脱附包括:酸清洗一,盐碱+有机清洗液清洗,盐碱清洗以及酸清洗二,酸清洗一为:采用(2-8)wt%的盐酸1.5-3BV,温度为52-58℃,分二步清洗,每步一半用量,第一步要浸泡,浸泡时间不少于1小时,浸泡过程中用压缩空气搅拌,然后用去离子水冲洗;盐碱+有机清洗液清洗为:(2-5)wt%NaOH+(8-12)wt%NaCl+(20-30)wt%有机清洗液0.5BV,温度为52-58℃,浸泡2小时,然后用去离子水冲洗;盐碱清洗为:(2-5)wt%NaOH+(8-12)wt%NaCl溶液2-4BV,温度为52-58℃,分三步清洗,前两步六分之一的用量,第一步中浸泡时间不少于2小时,然后用去离子水冲洗,排干;第二步中浸泡时间不少于2小时,浸泡过程中用压缩空气搅拌,浸泡结束后,用去离子水冲洗,排干;第三步三分之二的用量,然后用去离子水冲洗;酸清洗二为:(2-3)wt%的盐酸0.5-1.5BV,常温,最后用去离子水冲洗;有机清洗液为有机酸、有机醇或其组合;分盐结晶包括浓水脱色及COD去除,分盐浓缩,其中分盐采用纳滤膜分离出氯化钠和硫酸钠,氯化钠纳滤过程进行两次纳滤分盐;硫酸钠纳滤浓水经冷冻结晶后的母液经湿式氧化处理、软化处理后与生化出水混合再次进行分盐结晶。
2.根据权利要求1所述的工艺,其特征在于,有机酸包括醋酸、草酸以及柠檬酸中的一种或多种,有机醇包括甲醇、异丙醇或其组合。
3.根据权利要求1所述的工艺,其特征在于,湿式氧化工艺为:将洗脱废液用硫酸将pH调整至2-4,按2-5%的浓度加入双氧水,混合均匀;将反应塔用蒸汽加温至145-150℃后,将配制好的原液送入反应塔,原液在反应塔内的有效停留时间为1.5-2h。
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