CN111499094B - 一种高浓度吡啶醇钠酸水的无害化处理方法 - Google Patents
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Abstract
本发明公开了一种高浓度吡啶醇钠酸水的无害化处理方法,包括以下步骤:(1)稀释:用水将废水稀释1‑10倍;(2)酸碱调节:用氢氧化钠调节废水的pH,控制废水的pH在6‑10,过滤得出废水I;(3)球状催化剂+一次臭氧催化氧化;(4)球状催化剂+二次臭氧催化氧化;(5)单效蒸发系统处理:将步骤四得到的废水通入单效蒸发系统蒸发,过滤得出废水III,COD=100‑500ppm,pH=6‑10,颜色无色;(6)污水生化系统处理:将废水III通入污水生化体系,再经中水回用系统可达到回用水标准,直接回用生产。本发明所述处理方法工艺流程简单,操作方便,易实现自动化,且可充分氧化废水,使出水达标排放,不产生二次污染,显著提高工厂的日处理废水量。
Description
技术领域
本发明属于农药行业高浓度废水处理领域,具体涉及一种高浓度吡啶醇钠酸水的无害化处理方法。
背景技术
生产农药产品的过程中,一般会产生较多的农药废水,均属于高浓度难降解的有机废水,包括氯苯、苯胺、吡啶醇、卤代吡啶、氨基吡啶等原料或产物。大部分的废水成分比较复杂,无机盐含量较多,难降解的物质多,颜色较深,使得废水处理难度加大,现有技术对该类废水的处理手段主要分为几种:(1)主要是以化学氧化处理为主,后续再进行生化工艺处理;(2)部分农药企业主要采用的是先物化预处理,再进行常规的生化处理;(3)也有部分企业采用的厌氧-好氧工艺进行处理;(4)针对吡啶含量高的废水,公开号为CN101074211A的中国发明专利文献公开了一种处理高浓度吡啶废水的方法,通过精馏,然后萃取回收吡啶;(5)公开号为CN102765850A的中国发明专利文献公开了一种三氯吡啶醇钠及毒死蜱生产废水的处理工艺,将废水蒸发脱盐后浓缩液焚烧、冷凝水生化处理。针对上述现有技术,存在以下问题:
1、化学氧化的成本高,能耗高,同时会产生的很多固体废弃物,会带来二次污染,给企业带来沉重的经济负担;
2、生化装置本身存在固有缺陷,需要对高浓度物料进行稀释大的倍数,会消耗大量的水资源,末端产生的废水量也会很多,给企业造成困扰;
3、厌氧处理技术对水质要求教高,耐冲击能力弱,反应速度较慢,反应周期较长,处理构筑物容积大;使得处理效率很低、设备投资大、末端废水排放量大,同时厌氧过程产生的气体有臭味,排放需要二次处理,使得厌氧工艺技术受到了很大限制;
4、专利CN101074211A所述方法针对医药吡啶废水,成分单一、回收价值高,但是萃取处理程序复杂,不利于大规模处置;
5、专利CN102765850A所述方法能耗大,蒸发出来的盐会夹带部分吡啶类有机物,需后处理或做固废处理,焚烧易产生二次污染,经济成本加大。
采用常规化学氧化处理工艺后,若保证处理出水水质满足好氧进水指标,药剂投加量大,并且产生大量的固体危险废弃物;同时,经酸碱反复调节后的处理出水,TDS也较高,给后续好氧生化带来不利影响。
发明内容
发明目的:本发明的目的是提供一种工艺流程简单、操作方便且不产生二次污染的高浓度醇钠酸水的无害化处理方法。
技术方案:本发明所述的一种高浓度吡啶醇钠酸水的无害化处理方法,包括以下步骤:
(1)稀释:用水将废水稀释1-10倍;
(2)酸碱调节:用氢氧化钠调节废水的pH,控制废水的pH在6-10,过滤得出废水I;
(3)球状催化剂+一次臭氧催化氧化:将调整pH后的废水I通入一级氧化塔中,电解反应总停留时间2-24h,过滤后得到废水II,COD=20000-60000ppm,pH=6-10,颜色黄色;
(4)球状催化剂+二次臭氧催化氧化:将球状催化剂微电解后的废水II通入二级氧化塔,氧化反应总停留时间2-24h,得到的废水COD=10000-30000ppm,pH=6-10,颜色淡黄色;
(5)单效蒸发系统处理:将步骤(4)处理后的废水通入单效蒸发系统,60℃-90℃下蒸发,过滤得出废水III,COD=100-500ppm,pH=6-10,颜色无色;
(6)污水生化系统处理:将步骤(5)得到的废水III通入污水生化体系,经污水生化系统处理后,再经中水回用系统处理可达到回用水标准,直接回用生产。
采用球状催化剂微电解法,利用金属腐蚀的原理,形成原电池对废水进行处理的良好工艺,其中利用填充在废水中的球状催化剂微电解材料自身产生的1.2V电位差对废水进行电解处理,达到降解废水中有机污染物的目的;其次,铁受腐蚀变成二价铁,有混凝作用,与污染物中带微弱负电荷的微粒异性相吸,形成稳定的絮凝物而去除,氧化还原反应还可以破坏染料中间体分子发色基团,使其脱色。
进一步的,所述球状催化剂中含有Al2O3、Pt、Pb和稀土元素,稀土元素多以稀土尾矿的形式加入。
进一步的,所述球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe45-55份,Pt 8-12份,Pb 8-12份,C 23-27份,稀土元素4-6份;组分B按质量份数计包括:Al2O318-22份,Pt 8-12份,C 65-75份;采用两种组分的球状催化剂,增加微电解效果,并且可以达到催化氧化效果。
进一步的,稀土元素可以以稀土氧化物的形式存在。
进一步的,步骤(3)中A、B组分的比例为(50-80):(20-50),步骤(4)中A、B组分的比例为(20-50):(50-80)。
进一步的,两级氧化塔的臭氧供应的量为24公斤/小时。
进一步的,步骤(2)的酸碱调节在中和反应釜中进行,完成后利用板框压滤机将絮凝沉淀过滤得到废水I。
有益效果:本发明所述处理方法利用新型球状催化剂微电解和臭氧氧化相结合的系统来处理高浓度农药废水,相比传统的技术,处理效果更稳定,重复性强,可利用性高;农药废水属于高含盐、难降解有机废水,处理难度极大,采用球状催化剂微电解与臭氧氧化相结合的方式,可提高该废水生化性,减轻其对厌氧菌的生物致毒性;球状催化剂的重复使用性稳定,显著降低了处理高浓度废水的成本;本发明所述处理方法是直接采用球状催化剂电解臭氧氧化处理工艺,没有额外增加化学氧化等预处理工艺,因此没有二次污染,没有危废产生,又由于没有酸碱反复调节等步骤,因此废水的TDS没有增加,从而有利于后续生化处理。所以,本发明所述方法工艺流程简单,操作方便,易实现自动化,可充分氧化,使出水达标排放,不产生二次污染,显著提高工厂的日处理废水量。
附图说明
图1本发明所述处理方法的工艺流程图;
图2本发明所述处理方法的具体示意图。
具体实施方式
为进一步了解本发明的内容,结合附图及实施例对本发明作详细描述。
实施例1
本实施例所述的一种高浓度吡啶醇钠酸水的无害化处理方法,工艺流程和具体示意图分别如图1和图2所示,包括以下步骤:
(1)稀释:用水将废水稀释5倍;
(2)酸碱调节:在中和反应釜1中进行,用氢氧化钠调节废水的pH,控制废水的pH在8,完成后利用板框压滤机3将絮凝沉淀2过滤得到废水I;
(3)球状催化剂+一次臭氧催化氧化:将调整pH后的废水I通入一级氧化塔4中,电解反应总停留时间10h,过滤后得到的废水II,COD=40000ppm,pH=8,颜色黄色;
其中,球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe50份,Pt10份,Pb10份,C25份,稀土元素5份;组分B按质量份数计为:Al2O3 20份,Pt10份,C70份;A和B的比例65:35;
(4)球状催化剂+二次臭氧催化氧化:将球状催化剂微电解后的废水II通入二级氧化塔5,氧化反应总停留时间10h,COD=20000ppm,pH=8,颜色淡黄色;
其中,球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe50份,Pt10份,Pb10份,C25份,稀土元素5份;组分B按质量份数计为:Al2O3 20份,Pt10份,C70份;A和B的比例35:65;
(5)单效蒸发系统6处理:将步骤(4)处理后的废水通入单效蒸发系统,70℃下蒸发,过滤得出废水III,COD=200ppm,pH=8,颜色无色;
(6)污水生化系统7处理:将步骤(5)得到的废水III通入污水生化体系,经污水生化系统处理后,再经中水回用系统(纳滤+RO)8可达到回用水标准,直接回用生产9。
实施例2
本实施例所述的一种高浓度吡啶醇钠酸水的无害化处理方法,包括以下步骤:
(1)稀释:用水将废水稀释10倍;
(2)酸碱调节:在中和反应釜中进行,用氢氧化钠调节废水的pH,控制废水的pH在10,完成后利用板框压滤机将絮凝沉淀过滤得到废水I;
(3)球状催化剂+一次臭氧催化氧化:将调整pH后的废水I通入一级氧化塔中,电解反应总停留时间2h,过滤后得到的废水II,COD=20000ppm,pH=10,颜色黄色;
其中,球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe45份,Pt8份,Pb12份,C27份,稀土元素6份;组分B按质量份数计为:Al2O3 18份,Pt8份,C75份;A和B的比例50:50;
(4)球状催化剂+二次臭氧催化氧化:将球状催化剂微电解后的废水II通入二级氧化塔,氧化反应总停留时间2h,COD=10000ppm,pH=8,颜色淡黄色;
其中,球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe45份,Pt8份,Pb12份,C27份,稀土元素6份;组分B按质量份数计为:Al2O3 18份,Pt8份,C75份;A和B的比例50:50;
(5)单效蒸发系统处理:将步骤(4)处理后的废水通入单效蒸发系统,60℃下蒸发,过滤得出废水III,COD=100ppm,pH=10,颜色无色;
(6)污水生化系统处理:将步骤(5)得到的废水III通入污水生化体系,经污水生化系统处理后,再经中水回用系统可达到回用水标准,直接回用生产。
实施例3
本实施例所述的一种高浓度吡啶醇钠酸水的无害化处理方法,包括以下步骤:
(1)稀释:用水将废水稀释1倍;
(2)酸碱调节:在中和反应釜中进行,用氢氧化钠调节废水的pH,控制废水的pH在6,完成后利用板框压滤机将絮凝沉淀过滤得到废水I;
(3)球状催化剂+一次臭氧催化氧化:将调整pH后的废水I通入一级氧化塔中,电解反应总停留时间24h,过滤后得到的废水II,COD=60000ppm,pH=6,颜色黄色;
其中,球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe55份,Pt12份,Pb8份,C23份,稀土元素4份;组分B按质量份数计为:Al2O3 22份,Pt12份,C65份;A和B的比例20:80;
(4)球状催化剂+二次臭氧催化氧化:将球状催化剂微电解后的废水II通入二级氧化塔,氧化反应总停留时间24h,COD=30000ppm,pH=6,颜色淡黄色;
其中,球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe55份,Pt12份,Pb8份,C23份,稀土元素4份;组分B按质量份数计为:Al2O3 22份,Pt12份,C65份;A和B的比例80:20;
(5)单效蒸发系统处理:将步骤(4)处理后的废水通入单效蒸发系统,90℃下蒸发,过滤得出废水III,COD=500ppm,pH=6,颜色无色;
(6)污水生化系统处理:将步骤(5)得到的废水III通入污水生化体系,经污水生化系统处理后,再经中水回用系统可达到回用水标准,直接回用生产。
Claims (1)
1.一种高浓度吡啶醇钠酸水的无害化处理方法,其特征在于,包括以下步骤:
(1)稀释:用水将废水稀释10倍;
(2)酸碱调节:在中和反应釜中进行,用氢氧化钠调节废水的pH,控制废水的pH在10,完成后利用板框压滤机将絮凝沉淀过滤得到废水I;
(3)球状催化剂+一次臭氧催化氧化:将调整pH后的废水I通入一级氧化塔中,电解反应总停留时间2h,过滤后得到的废水II,COD=20000ppm,pH=10,颜色黄色;
其中,球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe45份,Pt8份,Pb12份,C27份,稀土元素6份;组分B按质量份数计为:Al2O3 18份,Pt8份,C75份;A和B的比例50:50;
(4)球状催化剂+二次臭氧催化氧化:将球状催化剂微电解后的废水II通入二级氧化塔,氧化反应总停留时间2h,COD=10000ppm,pH=8,颜色淡黄色;
其中,球状催化剂为两种组分的球状催化剂,组分A按质量份数计为:Fe45份,Pt8份,Pb12份,C27份,稀土元素6份;组分B按质量份数计为:Al2O3 18份,Pt8份,C75份;A和B的比例50:50;
(5)单效蒸发系统处理:将步骤(4)处理后的废水通入单效蒸发系统,60℃下蒸发,过滤得出废水III,COD=100ppm,pH=10,颜色无色;
(6)污水生化系统处理:将步骤(5)得到的废水III通入污水生化体系,经污水生化系统处理后,再经中水回用系统可达到回用水标准,直接回用生产。
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