CN105731691A - 一种酸性废水与焚烧灰耦合稳定化处理方法 - Google Patents
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Abstract
本发明公开了一种酸性废水与焚烧灰耦合稳定化处理方法,(1)常温常压下,搅拌过程中向酸性废水中加入焚烧灰调节pH至6~8,然后加入稳定药剂,搅拌混合后静置沉降,所述酸性废水为钢铁行业酸洗废水或电镀行业酸洗废水;(2)将步骤(1)静置沉降后的混合液进行固液分离,得废液和污泥,所得滤液经重金属含量测定后进行达标排放或返回步骤(1)中循环处理,所得污泥进行安全填埋或回收利用。本发明利用焚烧灰的弱碱性,对行业酸性废水进行中和预处理。将pH调节近中性,并通过加入重金属稳定药剂进行深度处理,实现对酸性废水和焚烧灰稳定化处理的工艺,处理方法简单、效果好。
Description
技术领域
本发明涉及环境化学领域,具体涉及一种酸性废水与焚烧飞灰耦合稳定化共处置方法。
背景技术
生活垃圾焚烧可有效减量可燃物质,但对其中所含的重金属物质而言,通常在其焚烧后大部分重金属会富集分布在焚烧飞灰中。文献表明,飞灰中含有能被水浸出的较高浓度的Cd、Pb、Zn等多种有害重金属物质和少量有机污染物。
目前主要的处理处置手段为固化填埋和水泥厂资源化利用。固化填埋是目前焚烧飞灰的常规处理手段,固化后的飞灰重金属浸出达到填埋标准,但飞灰固化后增容较大,填埋场容量与飞灰快速增长之间的矛盾日益凸现。飞灰与水泥生料组分相近,但飞灰中的重金属和氯元素会导致水泥窑的结圈和堵塞。因此,资源化利用前,需要对飞灰进行预处理,目前北京建工、上海城投、南方水泥等企业对飞灰水泥窑协同处置都有相关研究,但鲜有成功报道。
例如,公开号为CN103170488A的中国发明专利申请文献公开了一种垃圾焚烧飞灰固化剂及垃圾焚烧飞灰的处理方法,垃圾焚烧飞灰固化剂包括轻烧氧化镁粉;垃圾焚烧飞灰的处理方法包括:将待处理的垃圾焚烧飞灰与垃圾焚烧飞灰固化剂和水混合,得到液固混合物,然后将液固混合物进行固化,得到固化体。
行业酸性废水是在生产工艺过程中,对钢铁或金属表面采用强酸进行表面处理后产生的工业废水。该类废水主要含大量金属离子、重金属离子,同时pH变化较大,多为偏酸性,直接排入水体会造成严重污染,水生动植物死亡。通常采用加碱中和的办法进行处理,处理后的污泥含有大量的重金属,属于危险废物。
例如,公开号为CN105314764A的中国发明专利申请公开了一种含铜酸性废水的处理工艺,将含铜酸性废水经混合池混合后流入硫化反应罐,向罐内同时加入工业硫化钠和粉煤灰,搅拌30-40min,经硫化反应后,将出水流入斜板沉淀池沉淀50-60min,沉淀后的出水经设置在沉淀池中的脱气装置,吹脱H2S气体,然后与浓缩池中的上清液、过滤后的滤液汇集在一起回用或外排。沉淀池的底泥进入浓缩池,浓缩后的滤渣回用。
但是现有的处理方法都存在处理工序繁多、处理成本高或处理不彻底等问题。
发明内容
本发明提供了一种酸性废水与焚烧灰耦合稳定化处理方法,利用焚烧灰的弱碱性,对行业酸性废水进行中和预处理。将pH调节近中性,并通过加入重金属稳定药剂进行深度处理,实现对酸性废水和焚烧灰稳定化处理的工艺,处理方法简单、效果好。
一种酸性废水与焚烧灰耦合稳定化处理方法,包括如下步骤:
(1)常温常压下,搅拌过程中向酸性废水中加入焚烧灰调节pH至6~8,然后加入稳定药剂,搅拌混合后静置沉降,所述酸性废水为钢铁行业酸洗废水或电镀行业酸洗废水;
(2)将步骤(1)静置沉降后的混合液进行固液分离,得废液和污泥,所得滤液经重金属含量测定后进行达标排放或返回步骤(1)中循环处理,所得污泥进行安全填埋或回收利用。
本发明利用焚烧灰的碱性条件对行业酸性废水进行中和预处理。将酸性废水和焚烧灰的pH调节近中性,并加入重金属稳定化药剂,通过化学反应,生成稳定的重金属矿物质盐类,实现对酸性废水和焚烧灰中重金属的稳定化。本工艺降低了行业酸性废水和焚烧灰单独处理的成本,且在实现废物无害化的同时,达到废物少增容或不增容,从而提高危险废物处理处置的总体效率和经济性。
优选地,所述酸性废水中所含重金属元素为Zn、Cd、Mn和Pb中的至少一种。进一步地,所述酸性废水中的污染物指标如下:
最优选地,所述酸性废水中的污染物指标如下:
焚烧灰为白色或微黄色细小粉末,优选地,所述焚烧灰为生活垃圾焚烧炉产生的焚烧灰,重金属元素为Zn、Cd、Cr和Pb中的至少一种。进一步优选地,所述焚烧灰的基本成分(%)如下:
最优选地,所述焚烧灰的基本成分(%)如下:
优选地,所述稳定药剂为磷酸二氢钠和/或磷酸二氢钾。
优选地,步骤(1)中搅拌速度为50~150转/min,最优选为100转/min。
优选地,步骤(1)中静置沉降时间为15-20min,最优选为20min。
优选地,步骤(1)中酸性废水、焚烧灰和稳定药剂的体积质量比为1L:(15~25)g:(1~2)g。
进一步优选地,步骤(1)中酸性废水、焚烧灰和稳定药剂的体积质量比为1L:20g:1.5g。
与现有技术相比,本发明具有如下有益效果:
本发明利用垃圾焚烧飞灰的弱碱性,对行业酸性废水进行中和预处理。将pH调节近中性,并通过深度处理,同时解决了行业酸性废水和垃圾焚烧飞灰两种危险废物的无害化、稳定化处理问题。
附图说明
图1是本发明酸性废水与焚烧灰共处置技术工艺路线图。
图2是本发明飞灰加入量与废水pH值变化图。
具体实施方式
实施例1
1、行业酸性废水指标测定
浙江某企业酸性废水为浅褐色透明液体,酸性,且含有大量金属,主要有Pb、Zn、Cd、Mn、Fe等。由表1可知,酸性废水污染物指标中Pb、Zn、Cd三种重金属超标,pH值为2.33。
表1浙江某企业酸性废水污染物指标
2、焚烧灰指标测定
表2飞灰的基本成分(%)
焚烧灰为白色或微黄色细小粉末。本发明所用的焚烧灰取自杭州市某垃圾焚烧厂,基本成分如表2所示。其主要元素以Ca、Cl、K、S和Si为主,挥发性元素如Cl、Pb、Cd、Zn等化合物及单体富集物含量高,重金属以Pb、Zn、等为主。
3、投加比例参数设计
酸性废水初始pH为2.33,通过加入垃圾焚烧灰,pH不断上升,在pH为3-4附近上升缓慢,直到投加量大于15g以上,pH继续升高,投加量达到24g时pH为10.4,之后逐步趋于平稳,最终pH约为11。其中,pH在3-4附近并未随着投加量的增加而线性增加,是因为废水中Fe3+被沉淀为Fe(OH)3时,大量消耗OH-,从而在一定范围内,保持废水中的pH值无较大变化。由图可知,当pH接近7时,飞灰的投加量约为20g,因此确定酸性废水与焚烧飞灰的质量比为50:1。
4、稳定药剂投加量
根据磷酸根离子与两种污染物中的重金属摩尔配比可知,1L废水与20g飞灰混合物,需要添加稳定药剂理论值为2.5g。药剂添加量为1.0g时,重金属Pb和Cd浓度降低至0.58mg/L和0.096mg/L,满足排放标准;药剂添加量为1.5g时,重金属Zn浓度为3.86mg/L,满足5mg/L的排放标准。重金属稳定药剂添加量达到1.5g以后,各类重金属基本达到排放标准浓度以下。
因此,确定实验室工艺参数为矿山酸性废水:焚烧飞灰:稳定药剂=1L:20g:1.5g。
实施例2
1、酸性废水耦合处理结果
表3处理后的酸性废水重金属浓度(mg/L)
注:废水排放标准为《污水综合排放标准》(GB8978-1996)。
酸性废水经垃圾焚烧灰耦合处理后,pH调节至中性,并加入重金属螯合稳定药剂后,对其重金属浓度进行测定。其中,Cu、Pb、Zn、Cd、Mn、Fe、As等金属浓度均有一定幅度的下降,去除率分别为58.5%、88.1%、93.7%、76.1%、49.8%、63.1%、100%。各类重金属相对处理前形成了较稳定的重金属磷酸盐类,从液相转变为固相沉淀,经测定,各种重金属均满足废水综合排放标准。
2、焚烧灰耦合处理结果
表4飞灰处理前后的TCLP数据
垃圾焚烧灰经酸性废水耦合处理后,重金属浸出浓度均有不同程度的降低。其中,Cr的稳定化处理效果一般,浸出浓度降低了28%,Pb、Zn和Cd分别降低了92.1%、73.4%和95.2%。
处理后的垃圾焚烧灰可满足《危险废物鉴别标准-浸出毒性鉴别》(GB5085.3-2007)要求,可作为资源化利用的预处理产物或安全填埋。
Claims (8)
1.一种酸性废水与焚烧灰耦合稳定化处理方法,其特征在于,包括如下步骤:
(1)常温常压下,在搅拌过程中向酸性废水中加入焚烧灰调节废水的pH至6~8,然后加入稳定药剂,搅拌混合后静置沉降,所述酸性废水为钢铁行业酸洗废水或电镀行业酸洗废水;
(2)将步骤(1)静置沉降后的混合液进行固液分离,得废液和污泥,所得滤液经重金属含量测定后进行达标排放或返回步骤(1)中循环处理,所得污泥进行安全填埋或回收利用。
2.根据权利要求1所述酸性废水与焚烧灰耦合稳定化处理方法,其特征在于,所述酸性废水中所含重金属元素为Zn、Cd、Mn和Pb中的至少一种。
3.根据权利要求1所述酸性废水与焚烧灰耦合稳定化处理方法,其特征在于,所述焚烧灰为生活垃圾焚烧炉产生的焚烧灰,重金属元素为Zn、Cd、Cr和Pb中的至少一种。
4.根据权利要求1所述酸性废水与焚烧灰耦合稳定化处理方法,其特征在于,所述稳定药剂为磷酸二氢钠和/或磷酸二氢钾。
5.根据权利要求1所述酸性废水与焚烧灰耦合稳定化处理方法,其特征在于,步骤(1)中搅拌速度为50~150转/min。
6.根据权利要求1所述酸性废水与焚烧灰耦合稳定化处理方法,其特征在于,步骤(1)中静置沉降时间为15-25min。
7.根据权利要求1所述酸性废水与焚烧灰耦合稳定化处理方法,其特征在于,步骤(1)中酸性废水、焚烧灰和稳定药剂的体积质量比为1L:(15~25)g:(1~2)g。
8.根据权利要求1所述酸性废水与焚烧灰耦合稳定化处理方法,其特征在于,步骤(1)中酸性废水、焚烧灰和稳定药剂的体积质量比为1L:20g:1.5g。
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