CN113117749B - 一种催化去除煤化工高含盐废水中cod复合催化膜的制备方法及其应用 - Google Patents
一种催化去除煤化工高含盐废水中cod复合催化膜的制备方法及其应用 Download PDFInfo
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Abstract
本发明涉及一种去除煤化工高含盐废水中COD复合催化膜的制备方法,尤其是涉及一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,该复合膜由LDH纳米片和纳米Fe3O4‑MoS2催化剂层层堆叠形成,具体方法:首先称取LDH纳米片超声分散于去离子水中,再称取纳米Fe3O4‑MoS2催化剂超声分散于去离子水中,然后逐滴加至上述LDH纳米片分散液中,超声后用真空抽滤装置将混合分散液抽滤负载至PVDF薄膜上,干燥后即可制成Fe3O4‑MoS2/LDH/PVDF复合催化膜;本发明的复合催化膜采用压力自组装法制备,具有操作简单、成本低廉、可重复使用、不产生二次污染等特点。将本发明制得的复合催化膜应用于煤化工高含盐废水中COD的去除,COD去除率为96~98%。
Description
技术领域
本发明涉及一种去除煤化工高含盐废水中COD复合催化膜的制备方法及应用,尤其是涉及一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法以及该复合催化膜在去除高含盐废水COD中的应用。
背景技术
2015年,我国环境保护部曾经针对煤化工产业出台了《现代煤化工建设项目环境准入条件(试行)》,其中明确提出了所有煤化工的项目以后都要在其产生废水的处理技术、方案以及产物的利用与处置这方面有应对措施,煤化工行业要在整个化工产业中承担废水处理的示范任务。煤化工高盐废水是生产过程中最终工段汇集成的一类水,主要由循环水的排污水、脱盐水的离子交换酸碱水及其它工艺装置排污水(废碱液装置排水、煤气化装置煤气洗涤废水等)。水源的主要特点有:(1)高含盐量:含盐量为5000mg/L-6000mg/L;(2)水质波动大:废水由多股废水组成、水质差异较大,水量波动也较大;(3)污染物种类多:有机物、细菌、氨氮、无机盐、Ca2+、Mg2+、Ba2+、SO4 2-、SiO2、F-等,特别是污水中有机物含量高;(4)可生化性差,含有酚类化合物、稠环芳烃、萘、吡咯、联苯、油等有毒有害难降解有机物。这类废水如果未经处理就排放会造成水环境污染物的富集,对生态环境造成危害。因此,从受污染的水***中有效地去除各类污染物已经成为了当前的研究趋势。迄今为止,废水处理已经有了包括物理/生物吸附、化学沉淀、膜过滤和结晶在内的许多方法。在这些方法中,膜过滤技术因其高分离效率、低能耗、工艺简单、节省空间和对环境无污染而被认为是最受欢迎的水处理技术之一。但是,在煤化工高含盐废水分质提盐工艺中高COD会影响盐的纯度和色泽,达不到工业盐的标准,所以,如何降低含盐废水中COD含量非常重要。目前常用于去除废水中COD技术有生物法、物化法等,其中高级化学氧化技术是克服了普通化学氧化法存在氧化能力不强、选择性低且一次性投资大等不足,具有处理效率高、反应迅速、二次污染小等特点。利用Fe2+活化过氧化氢的体系能够产生强氧化性的羟基自由基并用于有机污染物的降解。尽管芬顿体系具有操作简单和氧化能力强等优点,但其仍严重受限于诸多缺陷,如pH适用范围窄(2.5-3.5)、形成大量铁泥、Fe3+/Fe2+循环受阻及羟基自由基半衰期短等。目前还没有更好的解决上述缺陷的方法。
发明内容
本发明的目的是克服现有技术的不足,提供一种制作方法独特、操作简单、成本低廉、可重复使用、不产生二次污染等特点且催化剂活性组分多、高度分散的一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法。
本发明的另一个目的是利用制备的复合催化膜解决现有技术中含盐废水中COD过高、催化剂稳定性差、盐离子易导致羟基自由基失活等问题的复合催化膜在去除高含盐废水COD中的应用。
本发明通过如下方式实现:
一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,其特征在于:该复合膜由LDH纳米片和纳米Fe3O4-MoS2催化剂层层堆叠形成,具体方法:首先称取LDH纳米片超声分散于去离子水中,再称取纳米Fe3O4-MoS2催化剂超声分散于去离子水中,然后逐滴加至上述LDH纳米片分散液中,超声后用真空抽滤装置将混合分散液抽滤负载至PVDF薄膜上,干燥后即可制成Fe3O4-MoS2/LDH/PVDF复合催化膜;
所述纳米Fe3O4-MoS2催化剂的制备方法为按照二硫化钼和七水合硫酸亚铁的摩尔比为1:2.5~3.5称取5~7mmol二硫化钼和12~25mmol七水合硫酸亚铁溶于80~120mL去离子水中,用稀氢氧化钠溶液调节pH值为10.5~11.5,将溶液倒入反应器中,在一定条件下进行共沉淀反应,反应结束后用去离子水和甲醇交替洗涤2~4次,55~65℃下干燥10-14小时,得到纳米Fe3O4-MoS2催化剂;
所述共沉淀反应条件为:在氮气气氛下,水浴85~95℃加热并搅拌3~5小时;
所述LDH纳米片的制备方法为:按照九水合硝酸铝和六水合硝酸镁的摩尔比为1:3.5~4.5称取7~13mmol九水合硝酸铝和25~55mmol六水合硝酸镁,溶于80~120mL去离子水中,用稀氢氧化钠溶液调节pH值至9.5~10.5,将溶液装入反应器中,进行共沉淀反应,反应结束后用去离子水和甲醇交替洗涤2~4次,55~65℃下干燥10-14小时,得到LDH纳米片;
所述共沉淀反应条件为:水浴75~85℃加热并搅拌10~20分钟;
称取30~50mg的所述LDH纳米片溶于40~60mL去离子水中,超声分散,再称取与所述LDH纳米片的质量比为1:1.5~2的纳米Fe3O4-MoS2催化剂,超声分散于50~80mL去离子水中,然后加至LDH纳米片分散液中,超声1~2小时,形成共混体系,然后用真空抽滤装置将分散液抽滤过基底膜,使复合材料通过压力负载在基底膜上,制成Fe3O4-MoS2/LDH/PVDF复合催化膜,在55~65℃干燥16~20小时后保存,所述用真空抽滤装置将分散液抽滤过基底膜是将直径为50mm、厚度为100μm、平均孔径为0.22μm的PVDF薄膜浸入100~120mL乙醇和去离子水的混合溶液中活化;
所述LDH纳米片的厚度为130~170nm,比表面积为6~12m2/g;
所述纳米Fe3O4-MoS2催化剂粒径为50~150nm,比表面积为24~34m2/g;
所述Fe3O4-MoS2/LDH/PVDF复合催化膜厚度为250~550μm;
将所述方法制备的复合催化膜用于去除煤化工高含盐废水中的COD,其特征在于:去除煤化工高含盐废水中的COD中的方法为将复合催化膜装入膜设备,加入含盐量为5000~6000mg/L、COD含量为2800~3200mg/L的煤化工高含盐废水,再加入2~4mL/L的30%过氧化氢,在压力0.2~0.4MPa、室温下反应80~120分钟,取滤液测定COD值。
本发明有如下效果:
1)制作方法独特:本发明提供的复合膜由LDH纳米片和纳米Fe3O4-MoS2催化剂层层堆叠形成,具体方法:首先称取LDH纳米片超声分散于去离子水中,再称取纳米Fe3O4-MoS2催化剂超声分散于去离子水中,然后逐滴加至LDH纳米片分散液中,超声后用真空抽滤装置将混合分散液抽滤负载至PVDF薄膜上,干燥后即可制成Fe3O4-MoS2/LDH/PVDF复合催化膜。
2)加工成本低:本发明提供复合催化膜包括基底部分和活性部分,其中基底部分为聚偏氟乙烯(PVDF)薄膜,活性部分为水滑石纳米片(LDH)和铁钼复合催化剂(Fe3O4-MoS2),制作原料为PVDF薄膜、乙醇、去离子水等,利用真空抽滤装置、干燥得到等方式,无论是材料还是装置,简单易获得,成本低。
3)去除方法简单易操作:利用本发明制备的复合催化膜去除高含盐废水COD,去除方法为将复合催化膜装入膜设备,加入含盐量为5000~6000mg/L、COD含量为2800~3200mg/L的煤化工高含盐废水,再加入2~4mL/L的30%过氧化氢,在压力0.2~0.4MPa、室温下反应80~120分钟,取滤液测定COD值即可
4)去除效果好,去除率高,且稳定性好,催化剂易于回收:本发明提供的一种以PVDF薄膜作为基底部分、以LDH纳米片和纳米Fe3O4-MoS2催化剂作为活性部分的复合催化膜,将膜过滤技术和高级催化氧化技术的优点结合,解决了催化反应易形成铁泥、羟基自由基半衰期短、利用效率不高的问题,将其应用于煤化工高含盐废水中COD的去除,去除效果好,且稳定性好,催化剂易于回收。因此,在去除工业含盐废水COD方面有着很好的应用前景。
5)形成限域催化效应,提高催化性能:本发明通过压力自组装法制备出的复合催化膜,在保持良好通量的基础上,可进一步提升催化剂的分散度,形成限域催化效应,提高催化性能,因此本发明提供的复合催化膜可以实现对工业高含盐废水中COD的有效去除。
6)操作易控:本发明所制备的复合催化膜以LDH纳米片和纳米Fe3O4-MoS2催化剂作为活性部分,制备条件便于调控。
具体实施方式
下面结合具体实施方案对本发明做进一步详细说明,但本发明不受其限制。下列实施例中未表明具体条件的试验方法,通常按照常规条件。
实施例1:一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,该制备方法为:称取5.2mmol二硫化钼和16mmol七水合硫酸亚铁,溶于80mL去离子水中;用稀氢氧化钠溶液调节pH值为10.6,将溶液倒入反应器中,在氮气气氛下,85℃水浴加热并搅拌反应3小时。反应结束后用去离子水和甲醇交替洗涤2次,65℃干燥10小时,得到纳米Fe3O4-MoS2催化剂。称取9mmol九水合硝酸铝和37mmol六水合硝酸镁,溶于100mL去离子水中,用稀氢氧化钠溶液调pH值至9.8,然后将溶液装入反应器中,85℃水浴加热并搅拌反应10分钟。反应结束后用去离子水和甲醇交替洗涤2次,65℃干燥10小时,得到LDH纳米片。将PVDF薄膜用乙醇和去离子水的混合溶液中活化后,65℃干燥16小时。称取34mg LDH纳米片超声分散于40mL去离子水中;再称取66mg纳米Fe3O4-MoS2催化剂超声分散于60mL去离子水中,然后逐滴加至LDH纳米片分散液中,超声1.5小时。用真空抽滤装置将混合分散液抽滤负载至PVDF薄膜上,55℃干燥16小时,制成Fe3O4-MoS2/LDH/PVDF复合催化膜。
以煤化工高含盐废水中的COD作为去除对象,将复合催化膜装入膜设备,然后加入含盐量为5120mg/L、COD含量为3050mg/L的煤化工高含盐废水,再加入3mL/L的30%过氧化氢,在压力0.3MPa、室温下反应100分钟,取滤液测定COD值。COD的去除率为97%。
实施例2:一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,该制备方法:称取5.5mmol二硫化钼和16.5mmol七水合硫酸亚铁,溶于90mL去离子水中;用稀氢氧化钠溶液调pH值为10.9,然后将溶液倒入反应器中,在氮气气氛下,90℃水浴加热并搅拌反应4小时。反应结束后用去离子水和甲醇交替洗涤3次,60℃下干燥12小时,得到纳米Fe3O4-MoS2催化剂。称取8mmol九水合硝酸铝和33mmol六水合硝酸镁,溶于90mL去离子水中,用稀氢氧化钠溶液调pH值为9.9,然后将溶液装入反应器中,85℃水浴加热并搅拌反应13分钟。反应结束后用去离子水和甲醇交替洗涤3次,60℃干燥12小时,得到LDH纳米片。将PVDF薄膜用乙醇和去离子水的混合溶液中活化后60℃干燥14小时。称取32mg LDH纳米片超声分散于40mL去离子水中;再称取55mg纳米Fe3O4-MoS2催化剂超声分散于55mL去离子水中,然后逐滴加至LDH纳米片分散液中,超声1小时。用真空抽滤装置将混合分散液抽滤负载于PVDF薄膜上,60℃干燥17小时,制成Fe3O4-MoS2/LDH/PVDF复合催化膜。
以煤化工高含盐废水中的COD作为去除对象,将复合催化膜装入膜设备,然后加入含盐量为5430mg/L、COD含量为3120mg/L的煤化工高含盐废水,再加入3.5mL/L的30%过氧化氢,在压力0.3MPa、室温下反应110分钟,取滤液测定COD值。COD的去除率为96.5%。
实施例3:一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,该制备方法为:称取6mmol二硫化钼和20mmol七水合硫酸亚铁,溶于100mL去离子水中;用稀氢氧化钠溶液调pH值为11.1,然后将溶液倒入反应器中,在氮气气氛下,95℃水浴加热并搅拌反应4小时。反应结束后用去离子水和甲醇交替洗涤3次,60℃干燥13小时,得到纳米Fe3O4-MoS2催化剂。称取10mmol九水合硝酸铝和42mmol六水合硝酸镁,溶于100mL去离子水中,用稀氢氧化钠溶液调pH值为10,然后将溶液装入反应器中,80℃水浴加热并磁力搅拌反应15分钟。反应结束后用去离子水和甲醇交替洗涤3次,60℃干燥13小时,得到LDH纳米片。将PVDF薄膜用乙醇和去离子水的混合溶液中活化后,60℃干燥13小时。称取39mg LDH纳米片超声分散于50mL去离子水中;再称取74mg纳米Fe3O4-MoS2催化剂超声分散于70mL去离子水中,然后逐滴加至LDH纳米片分散液中,超声2小时。用真空抽滤装置将混合分散液抽滤负载至PVDF薄膜上,60℃干燥18小时,制成Fe3O4-MoS2/LDH/PVDF复合催化膜。
以煤化工高含盐废水中的COD作为去除对象,将复合催化膜装入膜设备,然后加入含盐量为5770mg/L、COD含量为3180mg/L的煤化工高含盐废水,再加入4mL/L的30%过氧化氢,在压力0.4MPa、室温下反应120分钟,取滤液测定COD值。COD的去除率为96%。
实施例4:一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,该制备方法为:称取6.2mmol二硫化钼和18.2mmol七水合硫酸亚铁,溶于110mL去离子水中;用稀氢氧化钠溶液调pH值为10.8,然后将溶液倒入反应器中,在氮气气氛下,85℃水浴加热并搅拌反应5小时。反应结束后用去离子水和甲醇交替洗涤4次,55℃干燥14小时,得到纳米Fe3O4-MoS2催化剂。称取11mmol九水合硝酸铝和40mmol六水合硝酸镁,溶于110mL去离子水中,用稀氢氧化钠溶液调pH值为9.9,然后将溶液装入反应器中,75℃水浴加热并搅拌反应20分钟。反应结束后用去离子水和甲醇交替洗涤4次,55℃干燥14小时,得到LDH纳米片。将PVDF薄膜用乙醇和去离子水的混合溶液中活化后,55℃干燥16小时。称取46mg LDH纳米片超声分散于60mL去离子水中;再称取70mg纳米Fe3O4-MoS2催化剂超声分散于70mL去离子水中,然后逐滴加至LDH纳米片分散液中,超声1小时。用真空抽滤装置将混合分散液抽滤负载至PVDF薄膜上,55℃干燥20小时,制成Fe3O4-MoS2/LDH/PVDF复合催化膜。
以煤化工高含盐废水中的COD作为去除对象,将复合催化膜装入膜设备,然后加入含盐量为5610mg/L、COD含量为2840mg/L的煤化工高含盐废水,再加入2mL/L的30%过氧化氢,在压力0.3MPa、室温下反应90分钟,取滤液测定COD值。COD的去除率为97%。
实施例5:一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,该制备方法为:称取7mmol二硫化钼和22mmol七水合硫酸亚铁,溶于120mL去离子水中,用稀氢氧化钠溶液调pH值为11.5,然后将溶液倒入反应器中,在氮气气氛下,95℃水浴加热并搅拌反应5小时。反应结束后用去离子水和甲醇交替洗涤4次,65℃干燥12小时,得到纳米Fe3O4-MoS2催化剂。称取12mmol九水合硝酸铝和52mmol六水合硝酸镁,溶于120mL去离子水中,用稀氢氧化钠溶液调pH值为10.2,然后将溶液装入反应器中,85℃水浴加热并搅拌反应18分钟。反应结束后用去离子水和甲醇交替洗涤4次,65℃干燥12小时,得到LDH纳米片。将PVDF薄膜用乙醇和去离子水的混合溶液中活化后,65℃干燥14小时。称取33mg LDH纳米片超声分散于去50mL离子水中;再称取58mg纳米Fe3O4-MoS2催化剂超声分散于60mL去离子水中,然后逐滴加至LDH纳米片分散液中,超声2小时。用真空抽滤装置将混合分散液抽滤负载至PVDF薄膜上,65℃干燥17小时,制成Fe3O4-MoS2/LDH/PVDF复合催化膜。
以煤化工高含盐废水中的COD作为去除对象,将复合催化膜装入膜设备,然后加入含盐量为5320mg/L、COD含量为2840mg/L的煤化工高含盐废水,再加入3.5mL/L的30%过氧化氢,在压力0.3MPa、室温下反应100分钟,取滤液测定COD值。COD的去除率为98%。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,其特征在于:该复合膜由LDH纳米片和纳米Fe3O4-MoS2催化剂层层堆叠形成,具体方法:首先称取LDH纳米片超声分散于去离子水中,再称取纳米Fe3O4-MoS2催化剂超声分散于去离子水中,然后逐滴加至上述LDH纳米片分散液中,超声后用真空抽滤装置将混合分散液抽滤负载至PVDF薄膜上,干燥后即制成Fe3O4-MoS2/LDH/PVDF复合催化膜;所述纳米Fe3O4-MoS2催化剂的制备方法为按照二硫化钼和七水合硫酸亚铁的摩尔比为1:2.5~3.5称取5~7mmol二硫化钼和12~25mmol七水合硫酸亚铁溶于80~120mL去离子水中,用稀氢氧化钠溶液调节pH值为10.5~11.5,将溶液倒入反应器中,在一定条件下进行共沉淀反应,反应结束后用去离子水和甲醇交替洗涤2~4次,55~65℃下干燥10-14小时,得到纳米Fe3O4-MoS2催化剂,所述LDH纳米片的制备方法为:按照九水合硝酸铝和六水合硝酸镁的摩尔比为1:3.5~4.5称取7~13mmol九水合硝酸铝和25~55mmol六水合硝酸镁,溶于80~120mL去离子水中,用稀氢氧化钠溶液调节pH值至9.5~10.5,将溶液装入反应器中,进行共沉淀反应,反应结束后用去离子水和甲醇交替洗涤2~4次,55~65℃下干燥10-14小时,得到LDH纳米片。
2.如权利要求1所述的一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,其特征在于:所述共沉淀反应条件为:在氮气气氛下,水浴85~95℃加热并搅拌3~5小时。
3.如权利要求1所述的一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,其特征在于:所述共沉淀反应条件为:水浴75~85℃加热并搅拌10~20分钟。
4.如权利要求1所述的一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,其特征在于:称取30~50mg的所述LDH纳米片溶于40~60mL去离子水中,超声分散,再称取与所述LDH纳米片的质量比为1:1.5~2的纳米Fe3O4-MoS2催化剂,超声分散于50~80mL去离子水中,然后加至LDH纳米片分散液中,超声1~2小时,形成共混体系,然后用真空抽滤装置将分散液抽滤过基底膜,使复合材料通过压力负载在基底膜上,制成Fe3O4-MoS2/LDH/PVDF复合催化膜,在55~65℃干燥16~20小时后保存,所述用真空抽滤装置将分散液抽滤过基底膜是将直径为50mm、厚度为100μm、平均孔径为0.22μm的PVDF薄膜浸入100~120mL乙醇和去离子水的混合溶液中活化。
5.如权利要求1所述的一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,其特征在于:所述LDH纳米片的厚度为130~170nm,比表面积为6~12m2/g。
6.如权利要求1所述的一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,其特征在于:所述纳米Fe3O4-MoS2催化剂粒径为50~150nm,比表面积为24~34m2/g。
7.如权利要求1所述的一种催化去除煤化工高含盐废水中COD复合催化膜的制备方法,其特征在于:所述Fe3O4-MoS2/LDH/PVDF复合催化膜厚度为250~550μm。
8.将权利要求1所述方法制备的复合催化膜用于去除煤化工高含盐废水中的COD,其特征在于:去除煤化工高含盐废水中的COD中的方法为将复合催化膜装入膜设备,加入含盐量为5000~6000mg/L、COD含量为2800~3200mg/L的煤化工高含盐废水,再加入2~4mL/L的30%过氧化氢,在压力0.2~0.4MPa、室温下反应80~120分钟,取滤液测定COD值。
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CN111559760A (zh) * | 2020-06-16 | 2020-08-21 | 北京化工大学 | 一种磁性水滑石及其制备方法和应用 |
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