CN115180716A - 一种基于硫循环的含砷废水处理方法 - Google Patents
一种基于硫循环的含砷废水处理方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/284—Anaerobic digestion processes using anaerobic baffled reactors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2806—Anaerobic processes using solid supports for microorganisms
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/2853—Anaerobic digestion processes using anaerobic membrane bioreactors
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/103—Arsenic compounds
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- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
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- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C02F2303/06—Sludge reduction, e.g. by lysis
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Abstract
一种基于硫循环的含砷废水处理方法,它涉及一种基于硫循环的含砷废水处理方法。本发明是要解决现有含砷废水处理过程中效率低,处理成本高的问题。本发明通过驯化培养的厌氧活性污泥,将厌氧活性污泥添加到厌氧折流板反应器中,用于生物去除砷,酸性条件下,污泥中铁粉及铁的化合物提高了对砷的去除效果,在最后一个厌氧反应池中放置膜组件,反应用于固液分离,实现泥水分离,减少砷沉淀随水的流出,防止了砷的溶出,降低了出水中砷的含量。污泥中还添加有铁电气石颗粒,能够吸附砷离子及加快砷的价态的改变,铁电气石表面吸附砷离子提高了局部范围内砷的浓度,有利于砷离子生成硫化物沉淀去除,提高了处理效率。本发明用于含砷废水处理。
Description
技术领域
本发明涉及一种基于硫循环的含砷废水处理方法。
背景技术
砷广泛存在于自然界中,含砷矿物主要是硫化物和氧化物,砷的存在和应用几乎均以无机和有机化合物出现,而这些化合物均有毒性,其中某些化合物,如砒霜(三氧化二砷)是剧毒物质。砷可通过与蛋白和酶的巯基的相互作用(使蛋白质和酶在细胞内变性)以及增加细胞内的活性氧簇引起细胞损伤而产生毒性。砷被广泛用于硬化合金和生产半导体、杀虫剂、除草剂、木材防腐剂、半导体材料以及饲料添加剂等,这些人为活动将大量的砷引入到环境中,国内外都有关于地方性砷引发疾病的报道。不同价态和形态的砷,理化性质不一样,毒性也各异。砷单质不溶于水,而且进入人体后几乎不被吸收,直接能排除体外,所以单质砷一般对人体无害。但所有的砷化合物均有毒性。在自然水体中,根据水中氧的含量差异不同形态不同,厌氧情况下一般以亚砷酸盐As(III)存在,好氧情况下一般以砷酸盐As(V)存在;另外水的pH值大小对水中砷价态和存在形式也有较大影响。
为了防止砷中毒,目前各国规定饮用水中的最大含砷浓度为5.0×10-8~1.5×10-7,世界卫生组织所规定的饮用水标准为2.0×10-8。在工厂空气中被允许的最高含砷浓度为0.3mg/m3。为了使大气和饮用水中的含砷量达到标准以下,必需采用一定的技术来除砷。目前国内外除砷技术主要可概括为生物法、硫化法、混凝法、离子交换法、高分子粘合剂和滤膜技术、直接沉淀法、光催化氧化法等,这些除砷技术和方法有着各自的优缺点和适用围,部分除砷方法只能应用于实验室中除砷,其中几种除砷技术和方法已用于工业生产和废水中除砷。
化学沉淀法是一种较为传统的水处理方法,其发展时间较长,技术较为成熟。化学沉淀法一般可分为两类:一类是将砷沉淀为较为稳定的化合物后存放,这种方法是目前较为普遍的处理较高浓度的工业含砷废水;另一类是将砷沉淀为某种中间产物,然后再将它转化为砷产品出售,该方法较第一种方法能避免因为含砷沉淀物长期存放所可能带来的二次污染。较理想的除砷方法,从技术上讲,不仅必须确保处理后外排水达到环保要求,而且所得砷沉淀物也应具有较高的稳定性,适宜长期存放。
电化学方法主要包括电凝法和电渗析法。电凝除砷有以下两方面机理:一方面是阳极板电离出的金属离子(Fe3+、Al3+)直接与As(V)反应形成难溶性砷酸盐,另一方面是电解产物所形成的氢氧化物胶体可吸附废水中带负电荷的砷,氢氧化物沉淀可与难溶性砷酸盐形成共沉淀,从而有效去除废水中的砷。电渗析工作机理是利用交替排列着的阴膜和阳膜将废水分隔成小水室。当含砷原水进入这些小室时,在直流电场的作用下,溶液中的离子就作定向迁移。阳膜只允许阳离子通过而把砷酸根离子和亚砷酸酸根离子截留下来;阴膜只允许阴离子通过而把阳离子截留下来。从而使离子得到了分离和浓缩,污水便得到了净化。
吸附法除砷是利用吸附剂从废水中捕集砷,然后再用少量的酸、碱或盐溶液从含砷饱和的吸附剂中把砷洗脱出来,同时使吸附剂获得再生。常用的吸附剂有活性炭、活性铝土矿、沸石、磺化煤、赤泥(生产氧化铝的废料)、粉煤灰、赤铁矿、长石、硅灰石等。但是吸附法存在许多尚待解决的问题,如大多数吸附剂只能有效地吸附As(V),对As(Ⅲ)却不能有效地脱除,这样就使得处理砷的工艺变得复杂。另外,吸附剂与As(V)之间的强吸附作用会造成吸附剂再生、回收上的问题。而且在每次循环操作以后,吸附剂对砷的吸附量会下降5%~10%。当溶液中的磷酸盐、硫酸盐、硅酸、硒及氯化物含量较大时,由于这些物质容易与砷竞争吸附位点,所以也会导致对砷的吸附效率下降。
生物法除砷的原理是用菌种在培养基上培养,产生一种类似于活性污泥的物质,这种物质起絮凝作用,与砷结合进行絮凝沉降,然后分离达到除砷效果。李雅芹等用生物法处理某铅锌矿的浮选精矿使砷脱除,其砷的含量可以达到冶炼标准。
生物法是近年来处理工业含砷废水发展较快的一种方法,它利用活性污泥对砷的选择性表面吸附和细胞内吸收等作用对废水中的砷进行去除,从而降低水体内砷的浓度,使之达到除砷的目的。砷对于大部分生物来说,是一种有的毒的物质,但是它在某些特定情况下能被一些微生物、植物、动物,吸收、富集、浓缩甚至转化,利用生物的这种特有的性质,可以很好的解决水体砷污染问题。另外,砷也会被这些生物体氧化、甲基化,使砷化合物的毒性得到一定程度的降低,起到降毒、脱毒的作用。有些研究表明:活性污泥与As(V)的作用极为迅速,对低浓度砷的去除效率明显大于对高浓度砷的去除效率。但生物处理法对废水的砷浓度范围有一定要求,且对进水各项指标要求较高,仅适合于处理低浓度的含砷废水。
发明内容
本发明是要解决现有含砷废水处理过程中效率低,处理成本高的问题,而提供一种基于硫循环的含砷废水处理方法。
一种基于硫循环的含砷废水处理方法具体是按以下步骤进行:
一、将驯化培养的厌氧活性污泥放置于厌氧折流板反应器中,驯化培养的厌氧活性污泥中含有铁电气石颗粒,厌氧折流板内部装有1/4体积的聚氨酯多孔填料,最后一级厌氧折流板内设置有膜组件;
二、向厌氧折流板反应器内通入含砷废水同时投加葡萄糖和硫酸钠;含砷废水中砷含量不超过10mg/L;
三、开启膜组件控制器,采用高启低停的运行方式进行废水处理,即完成含砷废水处理。
本发明的有益效果是:
本发明通过驯化培养的厌氧活性污泥,将厌氧活性污泥添加到厌氧折流板反应器中,用于生物去除砷,酸性条件下(3.5-4.2),污泥中铁粉及铁的化合物提高了对砷的去除效果,在最后一个厌氧反应池中放置膜组件,反应用于固液分离,实现泥水分离,减少砷沉淀随水的流出,防止了砷的溶出,降低了出水中砷的含量。
厌氧活性污泥中还添加有铁电气石颗粒,铁电气石颗粒能够吸附砷离子及加快砷的价态的改变,铁电气石表面吸附砷离子提高了局部范围内砷的浓度,有利于砷离子生成硫化物沉淀去除,提高了处理效率。本发明进水为酸性3.5-4.2;经处理后的含砷废水中砷含量低于0.2mg/L。能够实现反应器能够连续运行,操作简单,污泥产量小。避免了pH的大范围调节,减少了化学药剂的使用量,处理成本低,运行成本低于1.0元/吨。
附图说明
图1为本发明污染物去除模式图;
图2为实施例1中去除砷效果的变化曲线;
图3为实施例1中出水pH的变化曲线;
图4为实施例2中去除砷效果的变化曲线;
图5为实施例2中出水pH的变化曲线。
具体实施方式
具体实施方式一:本实施方式一种基于硫循环的含砷废水处理方法具体是按以下步骤进行:
一、将驯化培养的厌氧活性污泥放置于厌氧折流板反应器中,驯化培养的厌氧活性污泥中含有铁电气石颗粒,厌氧折流板内部装有1/4体积的聚氨酯多孔填料,最后一级厌氧折流板内设置有膜组件;
二、向厌氧折流板反应器内通入含砷废水同时投加葡萄糖和硫酸钠;含砷废水中砷含量不超过10mg/L;
三、开启膜组件控制器,采用高启低停的运行方式进行废水处理,即完成含砷废水处理。
本实施方式在厌氧折流板反应器中使用了新型生物填料来提高微生物对重金属镉的耐受能力,利用多级厌氧处理提高了对重金属砷的去除能力,通过膜组件实现了泥水分离及砷盐沉淀的截留,防止了砷的氧化溶出,提高了出水水质。本发明减少了化学药剂的使用且使用的为安全无毒的常规药品,降低了处理成本。
本实施方式步骤三中所述高启低停是水位低时真空泵自动关闭,水位高时自动开启。
具体实施方式二:本实施方式与具体实施方式一不同的是:步骤一中所述驯化培养的厌氧活性污泥是经活性污泥驯化培养液处理的厌氧活性污泥;所述活性污泥驯化培养液由以下物质组成:葡萄糖100g/L、无水硫酸钠30g/L、尿素0.5g/L,磷酸氢二钾0.5g/L、乳酸钠10g/L、砷酸钠0.3g/L、硫酸亚铁2g/L、硫酸镁0.1g/L。其他与具体实施方式一相同。
具体实施方式三:本实施方式与具体实施方式二不同的是:步骤一中所述驯化培养的厌氧活性污泥的具体驯化过程按以下步骤进行:
①、配制活性污泥驯化培养液;
②、取生活污水处理厂活性污泥,将污泥放于塑料桶或污泥池中,加硫酸调节pH为3.5~4.2,向污泥中添加活性污泥驯化培养液;污泥与活性污泥驯化培养液的体积比为10:1;
③、然后向污泥中加入铁粉,搅拌均匀后密封隔绝氧气,静置培养10~15d,即获得驯化培养的厌氧活性污泥;所述铁粉的添加量为0.2g/L。其他与具体实施方式二相同。
本实施方式中如果所取活性污泥为干污泥则需要加水稀释。
具体实施方式四:本实施方式与具体实施方式一不同的是:步骤一中驯化培养的厌氧活性污泥的体积为厌氧折流板反应器有效体积的1/3~1/2。其他与具体实施方式一相同。
具体实施方式五:本实施方式与具体实施方式一不同的是:步骤一中所述铁电气石颗粒的直径为1~2mm。其他与具体实施方式一相同。
具体实施方式六:本实施方式与具体实施方式一不同的是:步骤二中通入含砷废水是通过蠕动泵或污水泵。其他与具体实施方式一相同。
具体实施方式七:本实施方式与具体实施方式一不同的是:步骤二中葡萄糖的投加量为100~300mg/L,硫酸钠的投加量为200mg/L。其他与具体实施方式一相同。
具体实施方式八:本实施方式与具体实施方式一不同的是:步骤三中所述废水处理的水力停留时间为6h。其他与具体实施方式一相同。
具体实施方式九:本实施方式与具体实施方式一不同的是:基于硫循环的含砷废水处理方法还包括向厌氧折流板反应器中投加生物增强剂;所述生物增强剂为纳米氧化锌、纳米纤维素或碳纳米管;所述生物增强剂的投加量按每公斤污泥投加0.02~0.05克的生物增强剂。其他与具体实施方式一相同。
具体实施方式十:本实施方式与具体实施方式一不同的是:基于硫循环的含砷废水处理方法还包括定期排泥并补充部分污泥。其他与具体实施方式一相同。
通过以下实施例验证本发明的有益效果:
实施例1:将驯化培养后的厌氧活性泥与聚氨酯生物填料混合均匀后放置于厌氧折流板反应器中,通过蠕动泵将配制的砷含量约为10mg/L,葡萄糖含量为200mg/L,硫酸钠含量为150mg/L,pH为4.0的含砷废水通入厌氧折流板反应器中,HRT为6h,厌氧折流板反应器膜出水中砷含量如图2所示。
配水实验过程中反应器出水砷含量如图2所示,厌氧折流板反应器出水中砷含量为0.08~0.15mg/L,出水pH升高到6.1~6.3,能够达到《电镀污染物排放标准》(GB21900-2008)中的处理要求。
实施案例2:
将进水改为某厂冶金废水,其中砷含量约为2.5mg/L,pH为3.9~4.1,在冶金废水中加入150mg/L的葡萄糖,150mg/L的硫酸钠,其余条件和实施案例1相同。测得沉淀出水中砷的浓度为0.08mg/L。
冶金废水处理过程中反应器出水砷含量如图4所示,厌氧折流板反应器出水中砷含量为0.08~0.15mg/L,出水为6.1~6.3,能够达到《电镀污染物排放标准》(GB21900-2008)中的处理要求。
Claims (10)
1.一种基于硫循环的含砷废水处理方法,其特征在于基于硫循环的含砷废水处理方法具体是按以下步骤进行:
一、将驯化培养的厌氧活性污泥放置于厌氧折流板反应器中,驯化培养的厌氧活性污泥中含有铁电气石颗粒,厌氧折流板内部装有1/4体积的聚氨酯多孔填料,最后一级厌氧折流板内设置有膜组件;
二、向厌氧折流板反应器内通入含砷废水同时投加葡萄糖和硫酸钠;含砷废水中砷含量不超过10mg/L;
三、开启膜组件控制器,采用高启低停的运行方式进行废水处理,即完成含砷废水处理。
2.根据权利要求1所述的一种基于硫循环的含砷废水处理方法,其特征在于步骤一中所述驯化培养的厌氧活性污泥是经活性污泥驯化培养液处理的厌氧活性污泥;所述活性污泥驯化培养液由以下物质组成:葡萄糖100g/L、无水硫酸钠30g/L、尿素0.5g/L,磷酸氢二钾0.5g/L、乳酸钠10g/L、砷酸钠0.3g/L、硫酸亚铁2g/L、硫酸镁0.1g/L。
3.根据权利要求2所述的一种基于硫循环的含砷废水处理方法,其特征在于步骤一中所述驯化培养的厌氧活性污泥的具体驯化过程按以下步骤进行:
①、配制活性污泥驯化培养液;
②、取生活污水处理厂活性污泥,将污泥放于塑料桶或污泥池中,加硫酸调节pH为3.5~4.2,向污泥中添加活性污泥驯化培养液;污泥与活性污泥驯化培养液的体积比为10:1;
③、然后向污泥中加入铁粉,搅拌均匀后密封隔绝氧气,静置培养10~15d,即获得驯化培养的厌氧活性污泥;所述铁粉的添加量为0.2g/L。
4.根据权利要求1所述的一种基于硫循环的含砷废水处理方法,其特征在于步骤一中驯化培养的厌氧活性污泥的体积为厌氧折流板反应器有效体积的1/3~1/2。
5.根据权利要求1所述的一种基于硫循环的含砷废水处理方法,其特征在于步骤一中所述铁电气石颗粒的直径为1~2mm。
6.根据权利要求1所述的一种基于硫循环的含砷废水处理方法,其特征在于步骤二中通入含砷废水是通过蠕动泵或污水泵。
7.根据权利要求1所述的一种基于硫循环的含砷废水处理方法,其特征在于步骤二中葡萄糖的投加量为100~300mg/L,硫酸钠的投加量为200mg/L。
8.根据权利要求1所述的一种基于硫循环的含砷废水处理方法,其特征在于步骤三中所述废水处理的水力停留时间为6h。
9.根据权利要求1所述的一种基于硫循环的含砷废水处理方法,其特征在于基于硫循环的含砷废水处理方法还包括向厌氧折流板反应器中投加生物增强剂;所述生物增强剂为纳米氧化锌、纳米纤维素或碳纳米管;所述生物增强剂的投加量按每公斤污泥投加0.02~0.05克的生物增强剂。
10.根据权利要求1所述的一种基于硫循环的含砷废水处理方法,其特征在于基于硫循环的含砷废水处理方法还包括定期排泥并补充部分污泥。
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