CN113976117A - 一种用于催化过硫酸盐氧化有机物的零价铝/含铁粘土复合材料的制法及应用 - Google Patents
一种用于催化过硫酸盐氧化有机物的零价铝/含铁粘土复合材料的制法及应用 Download PDFInfo
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Abstract
本发明涉及一种用于催化过硫酸盐氧化有机物的零价铝/含铁粘土复合材料的制法及应用,属于水环境处理领域。含铁粘土材料与零价铝经过简单球磨法制备新型催化剂,以达到活化过硫酸盐高效氧化降解水中难降解有机物的效果,本发明的催化剂制备方法和操作工艺简单,相比化学合成法二次污染小,合成时间短,产量大,成本低。采用的改性材料是天然含铁粘土材料,其来源广泛,无毒,且作为非均相催化剂性质稳定。零价铝/含铁粘土复合催化剂对PS活化效果良好,且使用pH范围较宽,在3–9内均可应用。本发明的零价铝/含铁粘土复合催化剂可以活化PS对不同的难降解有机物氧化去除,具有较宽的应用范围。
Description
技术领域
本发明涉及含铁粘土材料与零价铝经过简单球磨法制备新型催化剂,以达到活化过硫酸盐高效氧化降解水中难降解有机物的效果,属于水环境处理领域。
背景技术
近年来,杀虫剂、消毒副产物、药物及个人护理品等难降解有机物对于水体的污染破坏了生态系统的稳定性,影响了工农业发展。大部分难降解有机物很难被生物降解,具有高毒性,并且采用传统的处理方法去除效率低。高级氧化法作为一种能够彻底矿化污染物的方法,能够有效减小污染物毒性,增加其生物可降解性,受到了越来越广泛的关注。目前,基于过硫酸盐(PS)活化产生硫酸根自由基用于降解污染物的技术正在成为一种可代替传统Fenton技术的新型高级氧化技术。
零价金属材料(ZVMs)由于其较强的还原性,来源广泛性以及可重复利用性,被应用于污废水处理、地下水修复、土壤修复等领域。对于ZVMs的研究较集中于对零价铁(ZVI),零价锌(ZVZ)以及零价铜(ZVC)的应用研究,近年来,零价铝(ZVAl)因其具有比其他ZVMs更低的氧化还原电位(E0(Al3+/Al0))=-1.662V,以及其两性性质(反应pH可以拓展到碱性)而逐渐受到关注。目前环境领域关于ZVAl的研究主要集中于两类:以零价铝/氧化剂体系为核心的氧化体系和以零价铝/无氧体系为核心的还原体系。然而,由于ZVAl活泼的性质,在空气中能迅速生成一层致密的表面氧化膜,导致其在pH 4–9条件下性质稳定,影响Al0表面的暴露和电子传递。因此,其还原性利用pH范围较窄,为了拓宽其适用pH范围,许多学者提出采用一系列辅助方法,例如外加能源、酸洗预处理、添加化学试剂、材料改性等来改善它的氧化体系的效率。这些改进方法的核心都是以破坏氧化膜来增加电子的传递效率,其中近年来,有学者借鉴铝-水产氢反应中采用机械球磨活化铝粉的方法,将球磨铝粉应用于环境领域,提高了其还原活性。
一些天然的粘土矿物材料含有S,Mn,Fe等元素,使得它们具有较好的氧化还原活性,并且能影响元素在自然界中的生物化学循环以及污染物的迁移。其中,含铁粘土矿物中Fe(III)/Fe(II)氧化还原电对在自然界中的循环起到了氧化还原缓冲的作用,能够随着周围氧化还原环境的变化而改变。粘土矿物中的结构Fe常以Fe(III)的形式存在,利用生物或者化学还原的方法可以将其还原为结构Fe(II),使其具有还原重金属离子、放射性元素、硝酸盐,活化氧气、过氧化氢、过一硫酸盐产生自由基氧化有机污染物的能力。此外,粘土矿物材料属于超细粉末,具有较大的比表面积,稳定的骨架结构和绿色无毒的特点,因此它是一种具有潜力的环境修复功能材料。
已有研究利用表明过硫酸盐PS够加速纳米零价铝材料的(nZVAl)表面电化学腐蚀,从而使得nZVAl/PS体系在较宽的pH范围内高效降解污染物。然而,微米级零价铝(mZVAl)相比于nZVAl更加廉价易得和环境友好,然而其具有比nZVAl更低的比表面积,使得其活化PS效率低下。
发明内容
本发明的目的是提供微米零价铝与天然含铁粘土矿物材料用简单球磨方法合成新型复合催化剂及其制法,成本低,无污染,在污水中应用以达到高效活化PS氧化难降解有机物的效果。
为了解决本发明的技术问题,所提出的技术方案如下:一种零价铝/含铁粘土复合材料的制备方法,由微米零价铝、天然含铁粘土矿物材料球磨混合制得的一种复合催化剂;
所述的微米零价铝粒径大小为100-200目(75-150μm);
所述的天然含铁粘土矿物材料为绿脱石、蒙脱石、凹凸棒或膨润土,
具体制备方法如下:
将微米零价铝与所述含铁粘土以质量比为1:2–8:1混合,置于玛瑙球磨罐中,加入球料质量比为20:1–50:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨,球磨时间控制在0.5–4小时,行星式球磨旋转速率控制在200–800rpm,球磨结束后将混合粉末放入手套箱烘干,得到零价铝/含铁粘土复合材料。
优选的,微米零价铝与所述含铁粘土以质量比为1:1。
优选的,所述的天然含铁粘土矿物材料为绿脱石。
为了解决本发明的技术问题,所提出的另一技术方案如下:所述的零价铝/含铁粘土复合材料的用于去除难降解有机物的方法,包括以下步骤:
向有机污染物溶液中依次加入0.2g/L–1.5g/L的零价铝/含铁粘土复合材料和119mg/L–1904mg/L的过硫酸盐,零价铝/含铁粘土复合材料pH为3.00–9.00之间能够活化过硫酸盐去除难降解的有机污染物。
优选的,所述的有机污染物为4-氯酚、苯甲酸、硝基苯、苯酚或氧氟沙星溶液。
优选的,所述的零价铝/含铁粘土复合材料的用于去除难降解有机物的方法,零价铝/含铁粘土复合材料在pH为3活化过硫酸盐去除难降解的有机污染物。
优选的,将微米零价铝(约75μm)与所述绿脱石以质量比为1:1的比例混合,置于50mL玛瑙球磨罐中,加入球料质量比为20:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨,球磨时间控制为1.0小时,行星式球磨旋转速率控制在600rpm,球磨结束后将混合粉末放入手套箱烘干,得到零价铝/绿脱石含铁粘土复合材料,向含有浓度为20.0mg/L 4-氯酚的废水200mL中加入100mg零价铝/绿脱石复合催化剂和476mg/L过硫酸盐反应1h。
相比现有技术,本发明的有益效果如下:
(1)本发明采用简单球磨法制得零价铝/含铁粘土复合催化剂,制备方法和操作工艺简单,相比化学合成法二次污染小,合成时间短,产量大,成本低。
(2)本发明采用的改性材料是天然含铁粘土材料,其来源广泛,无毒,且作为非均相催化剂性质稳定。
(3)本发明的零价铝/含铁粘土复合催化剂对PS活化效果良好,且使用pH范围较宽,在3–9内均可应用。
(4)本发明的零价铝/含铁粘土复合催化剂可以活化PS对不同的难降解有机物氧化去除,具有较宽的应用范围。
(5)本发明采用零价铝与含铁粘土球磨的方法,既破坏了零价铝的氧化膜增加了其活性,又利用零价铝的强还原性促进含铁粘土中Fe元素的循环,增强其复合物对过硫酸盐的活化能力。
(6)微米零价铝与所述含铁粘土以质量比为1:1。以不同零价铝/绿脱石质量比复合的催化剂对4-氯酚的去除率对比,随着质量比的增加,零价铝/绿脱石复合催化剂对4-氯酚的去除率先上升后下降,在投料比为1:1时达到最优效果。
(7)所述的天然含铁粘土矿物材料为绿脱石,其与零价铝复合材料活化过硫酸盐的效果优于蒙脱石、凹凸棒和膨润土,可能是因为它们含铁量以及粘土中结构铁的占位差异而造成的。
(8)零价铝/绿脱石复合材料在pH为3.00–9.00之间能够高效活化PS降解4-氯酚,且随着pH降低,催化活性升高,可能是因为酸性条件下促进了零价铝的腐蚀,使得其对绿脱石中Fe元素循环的促进作用增强。
附图说明
图1为零价铝、含铁粘土、零价铝/含铁粘土复合催化剂的粒度分布图。
图2为零价铝、含铁粘土、零价铝/含铁粘土复合催化剂的XRD图。
图3为零价铝、含铁粘土、零价铝/含铁粘土复合催化剂的扫描电镜图。
图4为不同体系对一种难降解有机物:4-氯酚的降解动力学曲线。
图5为零价铝/含铁粘土复合催化剂在pH为3.00–10.00下对一种难降解有机物:4-氯酚的降解动力学曲线。
具体实施方式
以下通过实施例进一步说明本发明。
实施例1:
一种零价铝/含铁粘土复合材料的制备方法
将微米零价铝(约110μm)与绿脱石以质量比为1:1混合,置于50mL玛瑙球磨罐中,加入球料质量比为20:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨。球磨时间控制为1.0小时,行星式球磨旋转速率控制在600rpm。球磨结束后将混合粉末放入手套箱烘干,得到零价铝/含铁粘土复合材料。图1是零价铝、绿脱石、零价铝/绿脱石复合催化剂的粒度分布图,零价铝和绿脱石的中位粒径分别为111.75μm和0.60μm,而零价铝/绿脱石复合催化剂的中位粒径为15.44μm,说明两者复合后零价铝颗粒发生断裂或破碎导致粒径减小。图2中零价铝的晶体结构特征峰强度减小,说明其晶粒尺寸和晶型有序度有所下降,也和氧化膜破坏有关。图3电镜照片也显示,新生成的复合材料的粒径相比零价铝有所降低,且表面更加粗糙,可能是粘土颗粒与零价铝碎片相互掺杂复合压实所造成的。通过XPS表征,发现含铁粘土中的铁元素都为Fe(III),与零价铝球磨复合后,其中47.0%的Fe都被还原为Fe(II),而Fe(II)对过硫酸盐有较强的活化效果。
以一种不含铁粘土:合成锂蒙脱石替换绿脱石,采用实施例1中相同方法合成得到零价铝/不含铁粘土复合材料作为对比。图4是以含有一种难降解有机物:4-氯酚的废水为实验室模拟水样的降解效果对比图。模拟废水初始4-氯酚浓度为20mg/L,在200mL的4-氯酚溶液中分别加入100mg零价铝/含铁粘土复合催化剂、100mg零价铝/不含铁粘土复合催化剂、50mg零价铝、50mg绿脱石含铁粘土,过硫酸盐浓度为476mg/L。本工艺通过液相色谱仪检测体系中4-氯酚的剩余含量(Ct/C0),从图4中可以看出,零价铝、绿脱石以及复合催化剂对4-氯酚没有降解效果,且前两者对过硫酸盐没有活化降解4-氯酚的能力;零价铝/不含铁粘土复合催化剂活化过硫酸盐1h后对4-CP的去除率只有16.2%,而零价铝/绿脱石复合催化剂能够高效活化过硫酸盐降解4-氯酚污染物,达到100%去除率。
实施例2:
一种由实施例1制备得到的零价铝/绿脱石复合材料高效活化过硫酸盐(PS)应用于去除难降解有机物,包括以下步骤:
(1)配制20.0mg/L的4-氯酚废水为实验室模拟水样;
(2)量取5份200mL(1)中的实验室模拟水样于5个锥形瓶,将溶液pH分别调至3.00、5.00、7.00、9.00、10.00,向每个锥形瓶中加入100mg零价铝/绿脱石土复合材料和浓度为476mg/L的过硫酸盐,在不同的反应时间点用注射器取样,通过液相色谱仪检测体系中4-氯酚的剩余含量(Ct/C0),相关结果如图5所示。由图5可知,零价铝/绿脱石复合材料在pH为3.00–9.00之间能够高效活化PS降解4-氯酚,且随着pH降低,催化活性升高。
实施例3:
一种零价铝/含铁粘土复合材料的制备方法
将微米零价铝(约75μm)与上述绿脱石以质量比分别为1:2、1:1、2:1、4:1、8:1的比例混合,置于50mL玛瑙球磨罐中,加入球料质量比为20:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨。球磨时间控制为1.0小时,行星式球磨旋转速率控制在600rpm。球磨结束后将混合粉末放入手套箱烘干,得到零价铝/含铁粘土复合材料。
含有4-氯酚的废水200mL为实验室模拟水样,模拟废水初始4-氯酚浓度为20.0mg/L,加入100mg复合催化剂和476mg/L过硫酸盐反应1h。本工艺通过液相色谱仪检测产品实际降解4-氯酚的效果,表1为以不同零价铝/绿脱石质量比复合的催化剂对4-氯酚的去除率对比,随着质量比的增加,零价铝/绿脱石复合催化剂对硝基苯的去除率先上升后下降,在投料比为1:1时达到最优效果。
表1实施例3中不同零价铝/绿脱石质量比复合的催化剂对4-氯酚去除率的对比
实施例4:
一种零价铝/含铁粘土复合材料的制备方法
将微米零价铝(约150μm)与蒙脱石以质量比分别为1:1的比例混合,置于50mL玛瑙球磨罐中,加入球料质量比为20:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨。球磨时间控制为1.0小时,行星式球磨旋转速率控制在600rpm。球磨结束后将混合粉末放入手套箱烘干,得到零价铝/蒙脱石复合材料。
含有苯甲酸的废水200mL为实验室模拟水样,模拟废水初始苯甲酸浓度为12.2mg/L,加入0.2g/L–1.5g/L的复合催化剂和476mg/L过硫酸盐反应1h。本工艺通过液相色谱仪检测产品实际降解硝基苯的效果。当复合催化剂投加量在0.5g/L时,达到最佳的苯甲酸降解效果,去除率为54.0%。
实施例5:
一种零价铝/含铁粘土复合材料的制备方法
将微米零价铝(约90μm)与凹凸棒以质量比分别为1:1的比例混合,置于50mL玛瑙球磨罐中,加入球料质量比为20:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨。球磨时间控制为1.0小时,行星式球磨旋转速率控制在600rpm。球磨结束后将混合粉末放入手套箱烘干,得到零价铝/蒙脱石复合材料。
含有苯酚的废水200mL为实验室模拟水样,模拟废水初始苯酚浓度为9.14mg/L,加入0.5g/L的复合催化剂和119mg/L–1904mg/L的过硫酸盐反应1h。本工艺通过液相色谱仪检测产品实际降解苯酚的效果。随着过硫酸盐投加量的增加,苯酚的降解效果越好,最高去除率可达67.2%。
实施例6:
一种零价铝/含铁粘土复合材料的制备方法
将微米零价铝(约130μm)与上述膨润土以质量比为1:1的比例混合,置于50mL玛瑙球磨罐中,加入球料质量比为20:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨。球磨时间控制为1.0小时,行星式球磨旋转速率控制在600rpm。球磨结束后将混合粉末放入手套箱烘干,得到零价铝/膨润土复合材料。
含有氧氟沙星的废水200mL为实验室模拟水样,模拟废水初始氧氟沙星浓度为36.1mg/L,加入0.5g/L的复合催化剂和476mg/L的过硫酸盐反应1h。本工艺通过液相色谱仪检测产品实际降解氧氟沙星的效果。
实施例7:
一种零价铝/含铁粘土复合材料的制备方法
将微米零价铝(约130μm)分别与绿脱石、蒙脱石、凹凸棒以质量比为1:1的比例混合,置于50mL玛瑙球磨罐中,加入球料质量比为20:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨。球磨时间控制为1.0小时,行星式球磨旋转速率控制在600rpm。球磨结束后将混合粉末放入手套箱烘干,分别得到零价铝/绿脱石、零价铝/蒙脱石、零价铝/凹凸棒复合材料。
含有4-氯酚的废水200mL为实验室模拟水样,模拟废水初始4-氯酚浓度为20.0mg/L,加入100mg上述3种复合催化剂和476mg/L过硫酸盐反应1h。本工艺通过液相色谱仪检测产品实际降解4-氯酚的效果,表2为不同零价铝/含铁粘土复合催化剂对4-氯酚的去除率的对比,零价铝/绿脱石对4-氯酚有最好的降解效果,去除率达100%,而零价铝/凹凸棒效果最差,只有30.7%。
表2实施例7中不同零价铝/含铁粘土复合催化剂对4-氯酚的去除率的对比
本发明的不局限于上述实施例所述的具体技术方案,凡采用等同替换形成的技术方案均为本发明要求的保护范围。
Claims (7)
1.一种零价铝/含铁粘土复合材料的制备方法,其特征在于:由微米零价铝、天然含铁粘土矿物材料球磨混合制得的一种复合催化剂;
所述的微米零价铝粒径大小为100-200目(75-150μm);
所述的天然含铁粘土矿物材料为绿脱石、蒙脱石、凹凸棒或膨润土,具体制备方法如下:
将微米零价铝与所述含铁粘土以质量比为1:2–8:1混合,置于玛瑙球磨罐中,加入球料质量比为20:1–50:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨,球磨时间控制在0.5–4小时,行星式球磨旋转速率控制在200–800rpm,球磨结束后将混合粉末放入手套箱烘干,得到零价铝/含铁粘土复合材料。
2.根据权利要求1所述的零价铝/含铁粘土复合材料的制备方法,其特征在于:微米零价铝与所述含铁粘土以质量比为1:1。
3.根据权利要求1所述的零价铝/含铁粘土复合材料的制备方法,其特征在于:所述的天然含铁粘土矿物材料为绿脱石。
4.根据权利要求1-3任一所述的零价铝/含铁粘土复合材料的用于去除难降解有机物的方法,其特征在于:包括以下步骤:
向有机污染物溶液中依次加入0.2g/L–1.5g/L的零价铝/含铁粘土复合材料和119mg/L–1904mg/L的过硫酸盐,零价铝/含铁粘土复合材料pH为3.00–9.00之间能够活化过硫酸盐去除难降解的有机污染物。
5.根据权利要求1-3任一所述的零价铝/含铁粘土复合材料的用于去除难降解有机物的方法,其特征在于:所述的有机污染物为4-氯酚、苯甲酸、硝基苯、苯酚或氧氟沙星溶液。
6.根据权利要求1-3任一所述的零价铝/含铁粘土复合材料的用于去除难降解有机物的方法,其特征在于:零价铝/含铁粘土复合材料在pH为3活化过硫酸盐去除难降解的有机污染物。
7.根据权利要求1-3任一所述的零价铝/含铁粘土复合材料的用于去除难降解有机物的方法,其特征在于:将微米零价铝(约75μm)与所述绿脱石以质量比为1:1的比例混合,置于50mL玛瑙球磨罐中,加入球料质量比为20:1的玛瑙球,将玛瑙罐放入真空套抽真空后开始球磨,球磨时间控制为1.0小时,行星式球磨旋转速率控制在600rpm,球磨结束后将混合粉末放入手套箱烘干,得到零价铝/绿脱石含铁粘土复合材料,向含有浓度为20.0mg/L 4-氯酚的废水200mL中加入100mg零价铝/绿脱石复合催化剂和476mg/L过硫酸盐反应1h。
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