CN108722425A - 一种利用剩余污泥制备污泥基Fe-Zn三维粒子催化剂的方法 - Google Patents
一种利用剩余污泥制备污泥基Fe-Zn三维粒子催化剂的方法 Download PDFInfo
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Abstract
本发明公开了一种利用剩余污泥制备污泥基Fe‑Zn三维粒子催化剂的方法,以污水处理厂经过聚铁絮凝调理的剩余污泥为原料,将脱水后的剩余污泥经过烘干、破碎、过筛、成型、活化、造粒、碳化、清洗和干燥步骤,制备污泥基Fe‑Zn三维粒子催化剂。制备的催化剂填充于三维电极反应器中正负电极板之间的有效空间内,用于催化污水的电催化氧化。本发明以污泥碳为骨架,利用聚铁絮凝剂中的铁元素和活化剂氯化锌中的锌元素,制备Fe‑Zn结构污泥基催化剂。本发明制备工艺流程简单,操作方便;遵循可持续发展的原则,变废为宝,并高效催化降解污染物,达到污泥资源化利用和难降解废水高效去除的双重目的,具有良好的环境效益和经济效益。
Description
技术领域
本发明属于固体废弃物资源化利用和污水处理技术领域。涉及一种利用剩余污泥制备污泥基Fe-Zn三维粒子催化剂的方法。
背景技术
污水处理污泥作为一种具有巨大环境污染危害的废弃物,其合理科学的处理处置问题一直是环境领域亟待解决的重大课题。目前我国污泥处理的四大主要方式,填埋、堆肥、自然干化和焚烧所占比大致分别为 65%,15%,6%和3%。卫生填埋耗费土地资源且极易污染生态环境; 堆肥可实现污泥资源化利用,但是污泥中重金属成为限制资源化的瓶颈;焚烧及干化能耗太大,且焚烧易造成空气污染。因此污泥资源化利用大势所趋且势在必行。
在污泥资源化利用中,人们利用污泥中含有大量的细菌菌体和有机物碎片作为碳源,将污泥制备成活性炭形式的催化剂,实现以废治废的目的。
专利CN106311202A 公开了一种污泥碳催化剂的制备方法及催化剂的应用,用于催化湿式氧化反应。以城市污水处理厂活性污泥为原料,利用其含有的金属元素作为活性成分,以聚阴离子纤维素、羟乙基纤维素或黄原胶作为成型助剂,污泥粉末与成型助剂充分混合后,经过混捏、挤压成型、烘干、碳化及活化后得到污泥碳催化剂。将污泥碳催化剂以酸溶液或碱溶液浸泡改性,制成表面改性的污泥碳催化剂;将污泥碳催化剂或表面改性的污泥碳催化剂等体积浸渍过渡金属盐溶液,煅烧,制备得到过渡金属改性的污泥碳催化剂。专利CN1923361A公开了一个利用剩余污泥制备氮氧化物催化剂的方法。将剩余污泥干燥、粉碎、筛滤成污泥颗粒,将此污泥颗粒与化学活化剂混合,浸渍、搅拌和活化烘干,所用活化剂为ZnCl2和Fe(NO3)3的混合溶液;惰性气体环境下热解,冷却。清洗,干燥。ZnCl2用于形成良好的碳骨架,使得有机物质在热解时保留更多的碳质成分,Fe(NO3)3催化氮氧化物还原。
上述两个专利的污泥碳骨架催化剂用于催化湿式氧化反应。专利CN106311202A利用污泥中固有的金属元素作为催化剂活性成分,但是金属的种类和数量随机性较大,所以活性成分数量有限且催化活性不稳定。专利CN1923361A以污泥碳颗粒为载体,负载Fe(NO3)3,催化氮氧化物还原。需要额外的污泥颗粒与Fe(NO3)3溶液混合、浸渍、搅拌和烘干步骤。
专利CN105218073A公开了一种剩余污泥基粒子电极载体的制备方法。以污泥干粉末和蒙脱石为原料,制得污泥基粒子电极载体,其上负载Sb-SnO2催化剂。专利CN106111142A 公开了一种电激发处理高浓度废水装置所用填料催化剂的制备方法,由脱水污泥经预处理,制成成型污泥活性炭填料,再经钙、铜、钒、锰、镍等金属活可溶性盐类的水溶液进行熏煮、烘干和焙烧。
上述两个专利均用于三维电化学的粒子电极或粒子催化剂。三维电化学技术是在传统的二维电化学反应器中填充粒子电极构成,具有处理效率高,水力停留时间短,占地面积少,废渣少,广谱适应性等优点。专利CN105218073A污泥干粉末需要配伍蒙脱石,制成的污泥基粒子电极载体还需要负载Sb-SnO2催化剂;专利CN106111142A成型的污泥活性炭填料需要经过钙、铜、钒、锰、镍等金属可溶性盐类的水溶液的熏煮、烘干和焙烧过程。
污泥中含有大量的有机物和金属元素,通过相关的物理、化学活化方法可以制备出污泥碳催化剂,将此催化剂应用于高级氧化污水处理体系中,可以提高有机物的去除率,实现以废治废的目的,实现污泥的资源化利用。
发明内容
本发明的目的是针对现有技术的不足而提供的一种高效、廉价、实现污泥资源化利用的污泥基Fe-Zn三维粒子催化剂的制备和应用。为实现上述目的,本发明采用以下技术方案:
一种利用剩余污泥制备污泥基Fe-Zn三维粒子催化剂的方法,特点是以污水处理厂剩余污泥为基质,经过烘干、破碎、筛分、成型、活化、造粒、碳化、清洗和干燥步骤,制备Fe-Zn三维粒子催化剂,其中:
所述剩余污泥在进行催化剂制备前,需要经过聚铁混凝剂调理后脱水处理,具体为板框压滤脱水或离心脱水;
所述污泥烘干步骤为:脱水污泥在90~120℃条件下烘干10~30h;
所述筛分步骤的筛网孔径为100~300目;
所述成型步骤为,经过筛分的污泥粉末添加成型助剂-羧甲基纤维素钠,混合均匀,添加量为质量分数0.3~3%;
所述活化步骤的活化剂为氯化锌溶液,质量浓度为1~10mol/L,投加量为质量分数20~60%,污泥粉末与活化剂混合均匀;
所述造粒步骤为,将与成型助剂-羧甲基纤维素钠和活化剂混合均匀的污泥基质进行充分的机械碾压,通过造粒机制成直径为5~30mm的实心球、空心球或直径1.5~10mm的圆柱体,并于90~120℃下烘干;
所述碳化步骤是以氮气为保护气,将制成的污泥球或棒置于碳化炉中,以10~20℃/min的升温速度加热到500~1000℃,热解50~150 min后冷却至室温;
所述清洗步骤是将经过碳化步骤的污泥球或棒浸泡在50~80℃水中0.5~3.5 h;
所述干燥步骤是将清洗后的污泥球或棒在105℃烘干。
一种上述Fe-Zn三维粒子催化剂的应用,特点是将所述催化剂填充于三维电极反应器中正负电极板之间的有效空间内,用于催化污水的电催化氧化还原反应。
本发明的有益效果
利用污水处理厂经过聚铁调理后的脱水污泥制备三维电极反应器的粒子催化剂,不需要添加其他元素或原料。制备工艺流程简单,操作方便。
所制备的粒子催化剂强度大,污染物去除效率高,降低了三维电极反应器的成本。
遵循可持续发展的原则,变废为宝,并高效催化降解污染物,达到污泥资源化利用和污染物去除的双重目的,具有良好的环境效益和经济效益。
附图说明
图1为本发明流程图;
图2~图5 为本发明实施例所制备的催化剂的形状和显微结构图;
图6为采用X射线光电子能谱方法分析本发明实施例的催化剂中的C,O,Fe,Zn的结合能示意图;
图7为本发明实施例制备的催化剂和商业颗粒活性炭分别作为三维电极粒子连续运行处理双酚A废水的效果图。
具体实施方式
以下结合说明书附图和具体实施例对本发明作进一步描述,但并不因此而限制本发明的保护范围。
参阅图1,取污水处理厂经过聚铁调理后的脱水污泥,于90~120℃条件下烘干10~30h,粉碎机打磨后过100~300目筛,得到污泥干粉;为污泥粉末添加质量分数0.3~3%的羧甲基纤维素钠,并充分混合均匀;以质量浓度为1~10mol/L的氯化锌溶液为活化剂,投加量为质量分数20~60%,污泥基与活化剂充分混合并机械碾压充分均匀后通过造粒机制成直径为5~30mm不等的实心球、空心球或直径1.5~10mm的圆柱体,并于90~120℃条件下烘干;以氮气为保护气,将制成的污泥球或棒置于坩埚中,放入碳化炉中,以10~20℃/min的升温速度加热到500~1000℃,热解50~150 min后冷却至室温;将经过炭化步骤的污泥炭球或棒浸泡在50~80℃水中0.5~3.5 h,至出水pH为7;将清洗步骤后的污泥炭球或棒在110℃烘干,即得所述污泥基三维粒子催化剂。制得的催化剂填充于三维电极反应器中正负电极板之间的有效空间内,用于催化污水的电化学氧化和还原反应。
实施例
取污水处理厂经过聚铁调理后的脱水污泥,于110℃条件下烘干24h,粉碎机打磨后过150目筛,得到污泥干粉;为污泥粉末添加质量分数1%的羧甲基纤维素钠,并充分混合均匀;以质量浓度为5mol/L的氯化锌溶液为活化剂进行活化,投加量为质量分数40%,污泥基与活化剂均匀混合后通过造粒机制成直径为8mm的实心球并于110℃条件下烘干;以氮气为保护气,将制成的污泥球置于碳化炉,以15℃/min的升温速度加热到600℃,热解120 min后冷却至室温;将经过炭化步骤的污泥炭球浸泡在90℃水中至出水pH为7;将清洗步骤后的污泥炭球在110℃下烘干,即得所述污泥基Fe-Zn三维粒子催化剂。图2 为所制备的污泥基Fe-Zn三维粒子催化剂形态图,图3为粒子电极扫描电镜微观结构图,图4 荧光分析显示 Fe在粒子电极上均匀分布,图5荧光分析显示 Zn在粒子电极上均匀分布。图6 XPS分析显示污泥基粒子催化剂中C,O,Fe,Zn的结合能。
以该污泥基催化剂作为粒子催化剂连续运行处理双酚A(BPA)废水为例。本实施例中采用的三维电化学反应装置的阳极钛基钌铱氧化物电极,阴极为纯钛板,电压强度为1V/cm,电解质为0.1 mol/L无水硫酸钠,连续进出水,水力停留时间为8 min,双酚A进水浓度为400 mg/L。连续运行14h后,双酚A去除效果如图7所示。稳定运行后,污泥基粒子催化剂对双酚A的去除率稳定在80~90%。污泥基Fe-Zn三维粒子催化剂与商业颗粒活性炭GAC相对照,处理双酚A废水的效果图见图7。
Claims (2)
1.一种利用剩余污泥制备污泥基Fe-Zn三维粒子催化剂的方法,其特征在于,以污水处理厂剩余污泥为基质,经过烘干、破碎、筛分、成型、活化、造粒、碳化、清洗和干燥步骤,制备Fe-Zn三维粒子催化剂,其中:
所述剩余污泥在进行催化剂制备前,需要经过聚铁混凝剂调理后脱水处理,具体为板框压滤脱水或离心脱水;
所述污泥烘干步骤为:脱水污泥在90~120℃条件下烘干10~30h;
所述筛分步骤的筛网孔径为100~300目;
所述成型步骤为,经过筛分的污泥粉末添加成型助剂-羧甲基纤维素钠,混合均匀,添加量为质量分数0.3~3%;
所述活化步骤的活化剂为氯化锌溶液,质量浓度为1~10mol/L,投加量为质量分数20~60%,污泥粉末与活化剂混合均匀;
所述造粒步骤为,将与成型助剂-羧甲基纤维素钠和活化剂混合均匀的污泥基质进行充分的机械碾压,通过造粒机制成直径为5~30mm的实心球、空心球或直径1.5~10mm的圆柱体,并于90~120℃下烘干;
所述碳化步骤是以氮气为保护气,将制成的污泥球或棒置于碳化炉中,以10~20℃/min的升温速度加热到500~1000℃,热解50~150 min后冷却至室温;
所述清洗步骤是将经过碳化步骤的污泥球或棒浸泡在50~80℃水中0.5~3.5 h;
所述干燥步骤是将清洗后的污泥球或棒在105℃烘干。
2.一种权利要求1所述Fe-Zn三维粒子催化剂的应用,其特征在于,将所述催化剂填充于三维电极反应器中正负电极板之间的有效空间内,用于催化污水的电催化氧化还原反应。
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