CN113786804A - 一种用于吸附重金属的磁性多孔复合材料的制备方法及应用 - Google Patents
一种用于吸附重金属的磁性多孔复合材料的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种用于吸附重金属的磁性多孔复合材料的制备方法及应用。本方法将芬顿污泥及粉煤灰干燥研磨过筛,加入尿素、碳酸钾及水超声分散,后转移至磁力搅拌器中搅拌,将样品自然干燥后研磨并转移到石英舟中,后置于管式炉中焙烧,自然冷却至室温,用水离心洗涤多次,到近中性为止,然后用乙醇离心洗涤,自然晾干即得。采用该方法制备而得到磁性多孔复合材料对水中Cr(Ⅵ)有良好的吸附性能和吸附容量,本发明多利用固废等制备多孔复合材料有利于芬顿污泥的减量化、资源化、无害化的实现。
Description
技术领域
本发明属于固体废弃物资源化利用技术领域,具体涉及一种用于吸附重金属的磁性多孔复合材料的制备方法及应用。
背景技术
铬及其化合物在制革、纺织、电镀、染料、燃料、木材防腐等方面应用十分广泛,随着科学技术的进步,应用重金属能极大促进世界工业化的快速发展,但也不可避免地造成了一系列的污染。铬及其化合物的应用但在带动经济快速增长的同时,也带来了剧毒副产物——含铬废水。
自然水生环境中铬的存在形式分为Cr(Ⅲ)和Cr(Ⅵ)两种。Cr(Ⅲ)是一种痕量元素,它会影响哺乳动物的新陈代谢作用。Cr(Ⅵ)是一种具有高毒性和高迁移率的代表性污染物,它也是国际公认的三种致癌金属之一,会诱发腹泻、肺癌和其他疾病,它具有强氧化性,非常容易溶于水中,它的致癌原理是能够通过细胞膜穿透细胞来氧化活细胞,从而使细胞发现癌变。美国环境保护署的一项调查表明,长期暴露于Cr(Ⅵ)环境会增加人类得肺癌的风险。向环境中排放含Cr(Ⅵ)废水会危害水体、土壤,会严重影响生态环境和人类健康。根据我国生态环境部的要求,含铬废水必须经过处理再排放,不能直接排放,因为即使少量Cr(Ⅵ)对生物也有剧毒、致突变和致癌作用,主要威胁水生生物和人类健康,因此非常有必要去除。
去除Cr(Ⅵ)常见方法为吸附法、还原法、沉淀法和离子交换法。因为吸附法初始成本低、设计简单且易于操作,目前已成为一种高效且经济的解决方案。通常用于去除重金属的吸附剂包括工业废料、农业废料、生物材料和活性炭。碳材料是目前应用最多的吸附材料,其优点为、疏松多孔、比表面积大、高吸附率等。常见的含碳材料有生物质碳和活性炭。活性炭表面含有许多活性基团(如酚羟基、酸酐、-COOH等),全世界目前生产的50%以上的活性炭都被用于水处理。在各种吸附材料中,碳材料由于原料多样化及成本低的优势备受青睐,被认为是去除重金属最具有潜力的材料。
但传统的活性炭合成利用含碳丰富的原料进行无氧碳化,而多孔复合材料利用重复碳热再生铁化合物和含碳化合物。高成本、环境风险问题限制了传统方法的发展,而目前多孔复合材料以其低成本、环保的优势成为处理含铬废水的研究重点。
本发明对粉煤灰和芬顿污泥两种废弃物进行合理利用制备多孔复合材料来对含铬废水进行吸附。其中粉煤灰是燃煤火力发电过程中各种有机和无机组分在1200~1700℃燃烧后产生的工业固体废弃物,其成分复杂,处理不当会造成水土污染,对环境及生态产生危害。但全球能源需求的增长、煤炭成本低以及自然资源替代品开发不稳定,因此,煤炭作为主要能源的模式在很长一段时间内不会改变。全球每年粉煤灰的产量约为4.5亿t,粉煤灰在我国年产量在1亿吨左右。芬顿污泥是芬顿工艺生产的危险废物,需要被妥善处理。其缺点在于易结垢,保强水性,普通机械脱水无法达到预期效果、具有有机污染物,会带来一系列的环境问题。利用上述多孔复合材料吸附含铬废水实现以废治废的目标。
发明内容
本发明的目的在于提供一种用于吸附重金属的磁性多孔复合材料的制备方法,并将其应用在废水重金属的吸附中。
基于上述目的,本发明采取的技术方案如下:
一种用于吸附重金属的磁性多孔复合材料的制备方法,步骤如下:
(1)将芬顿污泥及粉煤灰进行干燥得到固体状的芬顿污泥及粉煤灰;将固体状的芬顿污泥和粉煤灰分别敲碎并研磨过筛得到芬顿污泥粉末和粉煤灰粉末,将制备好的芬顿污泥粉末和粉煤灰粉末分别放入干燥皿中备用;
(2)取芬顿污泥粉末、粉煤灰粉末、尿素、碳酸钾和水加入容器中超声使其颗粒分散,然后转移至磁力搅拌器中进行搅拌,最后将搅拌好的样品自然干燥;
(3)干燥后样品研磨并转移到石英舟中,后置于管式炉中,在氮气氛围下升温500℃保温2h,再升温到800℃保温2h,自然冷却至室温,取出后用水离心洗涤多次,到中性为止,然后用乙醇离心洗涤,再自然晾干即得磁性多孔复合材料。
进一步的,步骤(1)中,干燥温度为105℃,干燥时间为48h,研磨得到的芬顿污泥粉末和粉煤灰粉末均小于等于200目。
进一步的,步骤(2)中芬顿污泥粉末、粉煤灰粉末、尿素和碳酸钾的质量比为1-2:1-2:0-2:1-2。
进一步的,步骤(2)中磁力搅拌器转速为500rpm,搅拌时长为2h。
进一步的,步骤(3)中将干燥后的样品研磨至小于等于200目。
进一步的,步骤(3)中通入20min氮气,升温至500℃保温2h,再升温至800℃保温2h,其中氮气流速为30mL/min,升温速率为5℃/min,离心洗涤是在离心机10000转的条件下进行离心洗涤。
基于上述制备方法制得基于芬顿污泥和粉煤灰的磁性多孔复合材料,可应用于水中重金属离子,尤其是Cr(Ⅵ)。
本发明的工作原理:本发明选择芬顿污泥、粉煤灰为主要原料,用粉煤灰与芬顿污泥制备一种磁性多孔复合材料的方法来吸附废水中Cr(Ⅵ)。将一定比例的粉煤灰与芬顿污泥研磨,再将其充分混合后高温焙烧,再进行二次氧化增加表面官能团,再经过干燥冷却后制备为多孔吸附材料,利用此材料吸附废水中Cr(Ⅵ)。既可以减少芬顿污泥和粉煤灰对环境的污染,又可以对含铬废水进行Cr(Ⅵ)的去除,也能达到以废治废的目标。
本发明的有益效果:
(1)本发明利用芬顿污泥与粉煤灰制备的磁性多孔复合材料吸附废水中的重金属铬,实现以废治废的目标;
(2)本发明制备了以介孔为主磁性多孔复合材料,其表面上形成大量含氧官能团,可提供大量活性位点,因此对Cr(Ⅵ)吸附容量较大,有助于高效去除Cr(Ⅵ);
(3)本发明具有较高的应用价值,不仅适用于含铬废水的处理,也适用于其他需要进行重金属吸附的溶液处理。
附图说明
图1为本发明制备用于吸附重金属的磁性多孔复合材料的流程图;
图2为本发明制备的四种不同样品的吸附率示意图;
图3是本发明实施例4制备磁性多孔复合材料NMC-2的扫描电镜示意图;图(a)的标尺为200nm,图(b)的标尺为1μm,图(c)和图(d)的标尺为5μm;
图4是本发明实施例4中制备磁性多孔复合材料NMC-2的XRD示意图;
图5是本发明实施例4中制备磁性多孔复合材料NMC-2的红外示意图;
图6是本发明实施例4中磁性多孔复合材料NMC-2的吸附剂氮气吸附-脱附曲线;
图7是本发明实施例4中磁性多孔复合材料NMC-2的孔径分布图;
图8是本发明实施例4中磁性多孔复合材料NMC-2性能评价:时间对磁性多孔复合材料Cr(Ⅵ)去除率的影响。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
本发明中将来源于广州市某污水处理厂废水处理工艺中的芬顿高级氧化处理工段的芬顿污泥浆用真空抽滤装置过滤,收集滤渣,置于烘箱中,在105℃的条件下保持48h,得块状红褐色固体。接着用研钵小锤敲碎,置于研钵研磨至200目,得到红褐色固体粉末,得到原始芬顿污泥粉末,备用。将粉煤灰置于烘箱中,在105℃的条件下保持48h,得到黑色固体,再用研钵小锤敲碎,置于研钵研磨至200目,得到原始粉煤灰泥粉,备用。
实施例1
取1g芬顿污泥粉末于100mL三颈圆底烧瓶中,加入1g粉煤灰粉末、1g尿素和1g碳酸钾及50mL蒸馏水先超声使其颗粒分散,按照如图1所示的流程进行多孔复合材料的制备,再以500rpm磁力搅拌2h,后以105℃烘干24h,烘干后的固体用研钵研磨后过200目筛,将筛下物装至刚玉方舟中,后置于管式炉中,先通20min氮气,然后于N2流速30mL/min、5℃/min升温速度,500℃保温2h,再升温到800℃保温2h,自然冷却至室温后取出,取出后离心洗涤,先用蒸馏水洗涤至中性,再用无水乙醇洗涤2~3次,后于105℃烘箱中烘干,得到的磁性多孔复合材料记为NMC-1。
实施例2
取1g芬顿污泥粉末于100mL三颈圆底烧瓶中,加入1g粉煤灰粉末、0g尿素和1g碳酸钾及50mL蒸馏水先超声使其颗粒分散,再以500rpm磁力搅拌2h,后以105℃烘干24h,烘干后的固体用研钵研磨后过200目筛,将筛下物装至刚玉方舟中,后置于管式炉中,先通20min氮气,然后于N2流速30mL/min、5℃/min升温速度,500℃保温2h,再升温到800℃保温2h,自然冷却至室温后取出,取出后离心洗涤,先用蒸馏水洗涤至中性,再用无水乙醇洗涤2~3次,后于105℃烘箱中烘干,得到的磁性多孔复合材料记为MC-1。
实施例3
取0.5g芬顿污泥粉末于100mL三颈圆底烧瓶中,加入1g粉煤灰粉末、1g尿素和1g碳酸钾及50mL蒸馏水先超声使其颗粒分散,再以500rpm磁力搅拌2h,后以105℃烘干24h,烘干后的固体用研钵研磨后过200目筛,将筛下物装至刚玉方舟中,后置于管式炉中,先通20min氮气,然后于N2流速30mL/min、5℃/min升温速度,500℃保温2h,再升温到800℃保温2h,自然冷却至室温后取出,取出后离心洗涤,先用蒸馏水洗涤至中性,再用无水乙醇洗涤2~3次,后于105℃烘箱中烘干,得到的磁性多孔复合材料记为NMC-0.5。
实施例4
取2g芬顿污泥泥粉于100mL三颈圆底烧瓶中,加入1g粉煤灰、1g碳酸钾、1g尿素及50mL蒸馏水先超声使其颗粒分散,再以500rpm磁力搅拌2h,后以105℃烘干24h,烘干后的固体用研钵研磨后过200目筛,将筛下物装至刚玉方舟中,后置于管式炉中,先通20min氮气,然后于N2流速30mL/min、5℃/min升温速度,500℃保温2h,再升温到800℃保温2h,自然冷却至室温后取出,取出后离心洗涤,先用蒸馏水洗涤至中性,再用无水乙醇洗涤2~3次,后于105℃烘箱中烘干,得到的磁性多孔复合材料记为NMC-2。
用pH计将K2Cr2O7配制的Cr6+溶液用1mol/L HCl和1mol/L NaOH溶液调节到pH=8,分别将MC-1、NMC-0.5、NMC-1、NMC-2四个样品(每个样品6mg)与30mL50mg/LK2Cr2O7配制的Cr6+溶液加入棕色小瓶中,在pH=8、T=298K条件下,摇床250rpm振摇吸附20h,吸附后将悬浮液用外部磁体分离,取上清液用0.45μm孔径注射滤膜过滤,洗涤分离的固体,并保存以再生。用紫外分光光度计测定Cr6+的浓度,结果如图2所示,通过MC-1和NMC-1Cr6+去除率对比可知,NMC-1中加入了1g尿素,其Cr6+去除率为48.8%;MC-1中,没有加入尿素,其Cr6+去除率为17.8%,在本实验的研究范围内说明投加尿素对Cr6+的去除具有促进作用。通过NMC-0.5、NMC-1、NMC-2Cr6+去除率对比可知,NMC-0.5中芬顿污泥投加量为0.5g,其Cr6+去除率为33.3%;NMC-1中芬顿污泥投加量为1g,其Cr6+去除率为48.8%;NMC-2中芬顿污泥投加量为2g,其Cr6+去除率为64.3%;说明材料对Cr6+的吸附与芬顿污泥投加量有关,芬顿污泥投加量越高,吸附效率越高,即NMC-2的吸附效果较好。
上述制得的磁性多孔复合材料NMC-2外观为黑色固体粉末,用扫描电镜SEM观察如图3所示,复合材料呈球状且表面不光滑,有较多的毛绒状纤维结构,纤维排列松散,无规律,由图可以看出复合材料铁炭化合物组成,铁炭化合物分布的非常均匀,XRD结果也证明了这一点。所示NMC-2表面有较多孔隙产生,这可能是由于芬顿污泥、粉煤灰在焙烧过程中产生的二氧化碳和其他气体形成的孔洞,这些孔洞可以提供很多活性位点,红外光谱结果也证明这一点。
图4显示了NMC-2复合材料在吸附前的XRD图谱。从该图谱可以看出宽衍射NMC-2的峰值出现在41.1、44.6、47.9、65.0、82.3。Fe的特征峰出现在44.6、65.0、82.3,C的特征峰出现在41.1、82.3,Fe7C3的特征峰出现在42.5、44.8、47.9、69.6、82.3,Fe2C的特征峰出现在41.1、43.2,FeC的特征峰出现在42.6、44.9、69.6、82.4。对比以上标准卡片可以得知41.1、44.6、47.9、65.0、82.3出现的峰为Fe、C、Fe7C3、Fe2C、FeC的峰。可以表明在碳化过程中形成了铁炭复合材料。在实验过程中发现材料具有磁性,是因为含有Fe、Fe7C3、Fe2C、FeC。
由红外光谱图5分析可以分析出材料表面官能团类型、化学键。图像3440cm-1宽、强的吸收峰是因为-OH的伸缩振动引起的,有大量的-OH存在于材料的表面;1640cm-1出现的峰为-COOH。表征发现-OH吸收峰较宽。此外,1390cm-1和1000cm-1的吸收归属为由于醇类和酚类的-OH振动弯曲和C-O的伸缩振动,以上结果表明NMC-2表面含有大量的含氧官能团,而这些官能团可以为去除Cr(VI)提供许多活性位点。
进行BET测试来探究NMC-2吸附剂的比表面积等参数,从图6吸附剂氮气吸附-脱附曲线可知,这是第Ⅳ类曲线,在中压端观察到H3型滞后环的出现,H3常见于层状结构的聚集体,产生狭缝的介孔或大孔材料,这表示N2在孔道内冷凝积聚,而这些现象证明NMC-2为多孔材料。图7是根据BJH计算方法得到吸附剂NMC-2的孔径分布图,从图中可以看出孔径分布不均匀范围,大部分集中在20nm以下,同时根据表1,芬顿污泥和粉煤灰原样比表面积分别为124.08m2/g和3.79m2/g,NMC-2比表面积为228.65m2/g,芬顿污泥和粉煤灰原样孔容分别为0.18cm3/g和0.006cm3/g,而NMC-2的孔容为0.24cm3/g,芬顿污泥和粉煤灰原样孔径分别为5.72nm和6.70nm,NMC-2的孔径为4.22nm。以上数据说明合成材料比起原样比表面积、孔容增大。由于介孔材料的孔径为2~50nm。NMC-2是以介孔为主的多孔材料。得益于介孔所提供的大比表面积,使得材料拥有大量的活性位点,另外介孔可以存储更多的Cr(VI)离子[94],有助于NMC-2高效去除Cr(VI)。
表1NMC-2的BJH吸附累积总孔内比表面积、孔容、孔径
用pH计将K2Cr2O7配制的Cr6+溶液用1mol/L HCl和1mol/L NaOH溶液调节到pH=10,取30mL 100mg/L的Cr6+溶液和6mg NMC-2加入棕色小瓶中,在指定的时间段t=0、5、10、30、60、120、240、360、480、720、960、1200min、T=298K、pH=10、摇床250rpm振摇吸附。吸附后将悬浮液用外部磁体分离,取上清液用0.45μm孔径注射滤膜过滤,洗涤分离的固体,并保存以再生。用紫外分光光度计测定Cr6+的浓度,探究时间值Cr(Ⅵ)吸附的影响,结果如图8显示选择出研究范围内在时间为何值条件下NMC-2对Cr(Ⅵ)吸附效果较好。在本实验研究范围内发现Cr6+去除率在5min时已经达到25.93%,随后在最初的60min内增加迅速,在360min的时候,Cr6+去除率达75.84%,之后开始减慢下降,随时间进行,Cr6+去除率缓慢增加,直至1200min时达到平衡状态,此时Cr6+去除率较高,能达到80.36%。
将NMC-2与其他吸附剂进行比较,结果如下表2所示:
表2NMC-2与其他吸附剂吸附效果对比
由表2可知,本实施例中制备的磁性多孔复合材料NMC-2的吸附效果最好,1g NMC-2最多可吸附390.83mg的Cr6+,吸附水平远高于其他吸附剂。
Claims (7)
1.一种用于吸附重金属的磁性多孔复合材料的制备方法,其特征在于,步骤如下:
(1)将芬顿污泥及粉煤灰进行干燥得到固体状的芬顿污泥及粉煤灰;将固体状的芬顿污泥和粉煤灰分别敲碎并研磨过筛得到芬顿污泥粉末和粉煤灰粉末,将制备好的芬顿污泥粉末和粉煤灰粉末分别放入干燥皿中备用;
(2)取芬顿污泥粉末、粉煤灰粉末、尿素、碳酸钾和水加入容器中超声使其颗粒分散,然后转移至磁力搅拌器中进行搅拌,最后将搅拌好的样品自然干燥;
(3)干燥后样品研磨并转移到石英舟中,后置于管式炉中,在氮气氛围下升温500℃保温2h,再升温到800℃保温2h,自然冷却至室温,取出后用水离心洗涤多次,到中性为止,然后用乙醇离心洗涤,再自然晾干即得磁性多孔复合材料。
2.根据权利要求1所述的用于吸附重金属的的磁性多孔复合材料的制备方法,其特征在于,所述步骤(1)中,干燥温度为105℃,干燥时间为48h,研磨得到的芬顿污泥粉末和粉煤灰粉末均小于等于200目。
3.根据权利要求1所述的用于吸附重金属的的磁性多孔复合材料的制备方法,其特征在于,所述步骤(2)中芬顿污泥粉末、粉煤灰粉末、尿素和碳酸钾的质量比为1-2:1-2:0-2:1-2。
4.根据权利要求1所述的用于吸附重金属的的磁性多孔复合材料的制备方法,其特征在于,所述步骤(2)中磁力搅拌器转速为500rpm,搅拌时长为2h。
5.根据权利要求1所述的用于吸附重金属的的磁性多孔复合材料的制备方法,其特征在于,所述步骤(3)中将干燥后的样品研磨至小于等于200目。
6.根据权利要求1所述的用于吸附重金属的的磁性多孔复合材料的制备方法,其特征在于,所述步骤(3)中通入20min氮气,升温至500℃保温2h,再升温至800℃保温2h,其中氮气流速为30mL/min,升温速率为5℃/min。
7.将权利要求1-6中任意一项所述的磁性多孔复合材料应用于水中重金属离子的吸附,其特征在于,所吸附的重金属离子为Cr(Ⅵ)。
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CN114213146A (zh) * | 2022-01-18 | 2022-03-22 | 中国建筑材料工业地质勘查中心宁夏总队 | 一种采用煤泥作为原料制备吸附co2用路面铺设绿色建筑材料关键技术 |
CN114213146B (zh) * | 2022-01-18 | 2023-08-11 | 中国建筑材料工业地质勘查中心宁夏总队 | 一种采用煤泥作为原料制备吸附co2用路面铺设绿色建筑材料的制备方法 |
CN114768760A (zh) * | 2022-04-14 | 2022-07-22 | 昆明理工大学 | 一种利用尾菜叶提取腐殖酸钾并制备铁碳复合材料的方法及应用 |
CN114773128A (zh) * | 2022-04-14 | 2022-07-22 | 昆明理工大学 | 一种废弃尾菜叶的资源化利用方法 |
CN114773128B (zh) * | 2022-04-14 | 2023-06-20 | 昆明理工大学 | 一种废弃尾菜叶的资源化利用方法 |
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