CN113058544A - 一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂及其制备方法和应用 - Google Patents
一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂及其制备方法和应用,所述吸附剂的制备方法为:将Mg(NO3)2·6H2O、Al(NO3)3·9H2O和尿素加入水中搅拌得到透明溶液,然后加入ZnO超声分散得到混合液,混合液置于聚四氟乙烯高压反应釜中,于130‑150℃烘箱中反应20‑30 h,反应结束后的固体产物依次用乙醇和水洗数次,即得到所述吸附剂产物。本发明的吸附剂对含有机染料的水体进行处理时,吸附剂采用了先富集污染物、再降解的“二段式”新型效率提升机制,能够体现“二段式”处理工艺的效果,吸附饱和后的吸附剂材料暴露在阳光下,通过光催化降解吸附剂材料中的污染物,使得污染物中吸附位点重新暴露,达到吸附剂的再生和循环利用的目的。
Description
技术领域
本发明属于材料制备技术领域,尤其涉及一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂及其制备方法和应用。
背景技术
水体有机污染控制是当前面临的主要环境难题之一。吸附法作为一种高效便捷的方法,广泛应用于各种水处理工艺中。但现有的吸附剂普遍存在去除有机污染物的能力有限,再生循环能耗高,污染大,重复利用率低等技术难点。且容易造成能源浪费和二次污染。因此,开发一种遵循新型“二段式”速率提升机制的可光助再生非碳基吸附剂,可同时实现污染物的高效去除及吸附剂的再生,是值得探索的研究方向。其可以在不添加任何有毒有害化学物质的情况下,仅利用太阳光的情况下氧化降解(矿化)水中有机污染物。
中国专利109847786A公开的一种Z型光催化剂MgAl LDH/CN-H的方法中,首先制备g-C3N4对其酸化改性后制得CN-H;其次以硝酸镁、硝酸铝、柠檬酸、尿素为原料,在醇水混合体系中水热反应制备MgAlLDH;最后通过带正电荷的MgAl LDH和带负电荷的CN-H之间的静电引力作用组装形成Z型光催化剂MgAl LDH/CN-H。制得的光催化剂在模拟太阳光照射下表现出优异的光催化性能。该方法克服了“由于g-C3N4表面积非常小,可见光吸收能力不足以及光生载流子的分离率低限制了它的光催化活性”的难题。
发明内容
针对现有技术中存在的上述问题,本发明的目的在于提供一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂及其制备方法和应用,本发明的吸附剂既对有机染料具有较高的吸附容量,而且仅通过太阳光辐照实现污染物的降解和自身吸附能力的再生,解决了吸附再生循环过程中,吸附效率受限于过慢的再生动力学这个关键技术难点。
本发明公开的一种遵循新型“二段式”速率提升机制的可光助再生非碳基吸附剂,其特征在于以镁铝-层状双氢氧化物MgAl-LDH为基底,以ZnO为光催化剂,ZnO颗粒负载在镁铝-层状双氢氧化物MgAl-LDH基底上,形成ZnO/LDH非碳基吸附剂。
所述的一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂的制备方法,其特征在于所述吸收剂包括镁铝-层状双氢氧化物MgAl-LDH及负载于镁铝-层状双氢氧化物MgAl-LDH上的ZnO成分,其制备方法包括以下步骤:
1)在室温下,将Mg(NO3)2·6H2O、Al(NO3)3·9H2O和尿素加入去离子水中,搅拌溶解得到透明溶液;
2)在步骤1)得到的透明溶液中加入ZnO,超声分散得到混合液,再将所得的混合液置于聚四氟乙烯高压反应釜中,于130-150℃烘箱中进行尿素水解水热反应20-30h,反应结束后的固体产物依次用乙醇和水洗数次,即得到所述吸附剂产物。
所述的一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂的制备方法,其特征在于步骤1)中,Mg(NO3)2·6H2O、Al(NO3)3·9H2O和尿素的投料质量比为1:0.7-0.75:1.05-1.1,优选为1:0.73:1.09。
所述的一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂的制备方法,其特征在于在烘箱中反应的温度为140℃,反应时间24h。
按照上述方法制备的遵循“二段式”速率提升机制的可光助再生非碳基吸附剂。
所述的遵循“二段式”速率提升机制的可光助再生非碳基吸附剂在降解水体中有机染料中的应用。
所述的遵循“二段式”速率提升机制的可光助再生非碳基吸附剂在降解水体中有机染料中的应用,其特征在于所述有机染料为甲基橙、亚甲基蓝中的至少一种。
所述的遵循“二段式”速率提升机制的可光助再生非碳基吸附剂在降解水体中有机染料中的应用,其特征在于将吸附剂投入含有机染料的水体中,于避光条件下吸附饱和后,通过太阳光辐射实现有机染料的去除和吸附剂的再生。
通过采用上述技术,与现有技术相比,本发明具有如下有益效果:
1)本发明为了同时实现污染物的去除及吸附剂的再生,采用ZnO作为光催化剂,将具有抗氧化能力、高吸附容量和快速吸附动力学的镁铝-层状双氢氧化物MgAl-LDH吸附剂作为基底,采用尿素水解水热法将ZnO负载到LDH基底材料上,制备出氧化锌/层状双氢氧化物吸附剂ZnO/LDH,其吸附效率较传统碳基吸附剂提升2-3个数量级,具有高效的吸附性能,没有涉及传统光催化过程所掺杂的金属元素,降低了生产成本,减少了材料因金属渗出而造成的环境风险。
2)本发明得到的吸附剂产物不仅对水体中有机染料具有较高的吸附容量,也在太阳光辐射后实现污染物的降解同时实现自身吸附能力的再生,克服了吸附效率受限于过慢的再生动力学的影响。实验研究发现,对甲基橙的吸附量为323.8mg/g,在5h循环再生后仍具有91.3%的再生率;对亚甲基蓝的吸附量为169.2mg/g,在5h循环再生后仍具有85.0%的再生率。由于该遵循新型“二段式”速率提升机制的可光助再生非碳基吸附剂能高效削减水中多种污染物和高效的光助再生能力的特点,工业应用具有广阔的前景和环境应用具有巨大的潜力。
附图说明
图1为实施例1制得的ZnO/LDH材料在3微米下的扫描透射电镜图;
图2为实施例1制得的ZnO/LDH材料在20微米下的扫描透射电镜图。
具体实施方式
下面结合具体实施例对本发明作进一步说明,但本发明的保护范围并不限于此。本发明中试剂或材料,若无特殊说明,均为市售产品。
实施例1:
本实施例中,制备氧化锌/层状双氢氧化物(ZnO/LDH)非碳基吸附剂的具体步骤如下:
(1)在室温下,将1.20g Mg(NO3)2·6H2O、0.88gAl(NO3)3·9H2O和1.31g尿素在70ml去离子水中溶解,搅拌30min形成透明溶液;
(2)将步骤(1)所得的透明溶液中加入0.09gZnO超声分散1h,得混合液;
(3)将制得的混合液置于100ml聚四氟乙烯高压反应釜中,于140℃烘箱中反应24h后,依次用乙醇和水洗数次烘干得到ZnO/LDH粉末。
将实施例1的步骤(1)得到的透明溶液置于100ml聚四氟乙烯高压反应釜中,于140℃烘箱中反应24h后,依次用乙醇和水洗数次后,烘干得到LDH粉末。
将上述制备的LDH粉末,作为对照物和产物ZnO/LDH粉末进行对比。
实施例2:
本实施例中,制备氧化锌/层状双氢氧化物(ZnO/LDH)非碳基复合材料的具体步骤如下:
(1)在室温下,将0.60g Mg(NO3)2·6H2O、0.44gAl(NO3)3·9H2O和0.66g尿素在70ml去离子水中溶解,搅拌30min形成透明溶液;
(2)在步骤(1)的透明溶液中加入0.045gZnO超声分散1h;
(3)将制得的混合溶液置于100ml聚四氟乙烯高压反应釜中,于140℃烘箱中反应24h后,依次用乙醇和水洗数次后,烘干得到ZnO/LDH粉末。
实施例3:
本实施例中,制备氧化锌/层状双氢氧化物(ZnO/LDH)非碳基吸附剂的具体步骤如下:
(1)在室温下,将0.30g Mg(NO3)2·6H2O、0.22gAl(NO3)3·9H2O和0.33g尿素在70ml去离子水中溶解,搅拌30min形成透明溶液;
(2)在步骤(1)的透明溶液中加入0.023gZnO超声分散1h。
(3)将制得的混合溶液置于100ml聚四氟乙烯高压反应釜中,于140℃烘箱中反应24h后,依次用乙醇和水洗数次后,烘干得到ZnO/LDH粉末。
实施例4:
本实施例中,制备氧化锌/层状双氢氧化物(ZnO/LDH)非碳基吸附剂的具体步骤如下:
(1)在室温下,将0.15g Mg(NO3)2·6H2O、0.11gAl(NO3)3·9H2O和0.17g尿素在70ml去离子水中溶解,搅拌30min形成透明溶液。
(2)在步骤(1)的透明溶液中加入0.012gZnO超声分散1h。
(3)将制得的混合溶液置于100ml聚四氟乙烯高压反应釜中,于140℃烘箱中反应20h后,依次用乙醇和水洗数次后,烘干得到ZnO/LDH粉末。
实施例5:
本实施例中,制备氧化锌/层状双氢氧化物(ZnO/LDH)非碳基吸附剂的具体步骤如下:
(1)在室温下,将0.13gMg(NO3)2·6H2O、0.06gAl(NO3)3·9H2O和0.09g尿素在70ml去离子水中溶解,搅拌30min形成透明溶液。
(2)在步骤(1)的透明溶液中加入0.006gZnO超声分散1h;
(3)将制得的混合溶液置于100ml聚四氟乙烯高压反应釜中,于140℃烘箱中反应30h后,依次用乙醇和水洗数次后,烘干得到ZnO/LDH粉末。
对实施例1所得的ZnO/LDH粉末进行透射电镜扫描,其在3微米及20微米下的扫描透射电镜图分别如图1和图2所示。从图1图2中可以看出,ZnO在LDH(即层状镁铝双氢氧化物)上成功负载,且ZnO/LDH粉末保留了LDH的层状结构。
应用实施例1:
实施例1所得ZnO/LDH对亚甲基蓝的吸附实验过程:在25℃下,将6份具塞锥形瓶中分别加入1.0mg的吸附剂,然后分别加入浓度为0、4、8、12、16、20mg/L的亚甲基蓝水溶液100ml,分别置于25℃避光恒温摇床中以120r/min振荡吸附。4h后取样,通过微孔滤膜后,用双光束紫外可见分光光度计(Persee T6-1650E)测量吸附后溶液中亚甲基蓝的残留浓度Ct。
实施例1所得ZnO/LDH对甲基橙的吸附实验过程:在25℃下,将7份具塞锥形瓶中分别加入1.0mg的吸附剂,然后分别加入浓度为0、10、20、30、40、50、60mg/L的甲基橙水溶液100ml,分别置于25℃避光恒温摇床中以120r/min振荡吸附。4h后取样,通过微孔滤膜后,用双光束紫外可见分光光度计(Persee T6-1650E)测量吸附后溶液中甲基橙的残留浓度Ct。
在上述实验过程中,实施例1所得ZnO/LDH材料吸附甲基橙和亚甲基蓝时,分别采用Langmuir和Freundlich等温吸附模型进行拟合,拟合的参数结果如表1所示。
表1 ZnO/LDH对有机染料的Freundlich和Langumuir等温吸附参数
其中表1中,qm为吸附剂对有机染料的理论饱和吸附量,单位是mg/g;KL为Langmuir模型的吸附常数;Kf和n均为Freundlich模型的吸附常数;R2为Langmuir模型或Freundlich模型的相关系数。
从表1中可以看出:实施例1所得ZnO/LDH材料吸附甲基橙和亚甲基蓝时,Langmuir吸附模型拟合的相关系数均高于Freundlich吸附模型,表明ZnO/LDH非碳基吸附剂对有机染料的吸附倾向于单层而非多层吸附。ZnO/LDH非碳基吸附剂对带负电的甲基橙的吸附量(323.8mg/g)比带正电的亚甲基蓝的吸附量(169.2mg/g)高得多。相比于其他碳基吸附剂对有机染料的吸附量,ZnO/LDH展现出优异的吸附性能:例如,参见文献1“杨岳,陈珊媛,关成立,等.活性炭纤维ACF对甲基橙染料的吸附动力学研究[J].广州化工,2020,(1):66-68”公开的技术内容中,活性碳纤维对甲基橙的理论饱和吸附量qm=294.12mg/g;参见文献2“时文.兰炭的改性及其对废水中染料的吸附性能研究[D].合肥:合肥工业大学,2016”公开的技术内容中,兰炭材料对亚甲基蓝的理论饱和吸附量qm=40.8mg/g)。
应用实施例2:
实施例1所得ZnO/LDH对亚甲基蓝进行动力学吸附实验:量取100ml5mg/L的亚甲基蓝溶液于250ml具塞锥形瓶中,再准确称量1.0mg的吸附剂加入锥形瓶中,置于25℃避光恒温摇床中以120r/min振荡吸附。在间隔15min取样,通过微孔滤膜后,测量溶液中染料的残留浓度Ct。
实施例1所得ZnO/LDH对甲基橙进行动力学吸附实验:量取100ml的20mg/L甲基橙溶液于250ml具塞锥形瓶中,再准确称量1.0mg的吸附剂加入锥形瓶中,置于25℃避光恒温摇床中以120r/min振荡吸附。在间隔15min取样,通过微孔滤膜后,测量溶液中染料的残留浓度Ct。
通过拟一级和拟二级动力学模型对ZnO/LDH非碳基吸附剂吸附甲基橙和亚甲基蓝的过程分别进行拟合,实验结果如表2所示。在表2中,k1为拟一级速率常数,单位是1/s;k2为拟二级速率常数,单位是g/(mg·s);qe为平衡吸附量,mg/g。
表2 ZnO/LDH对有机染料的吸附动力学参数
从表2可以看出:拟二级动力学方程对LDH和TiO2/LDH材料吸附两种有机染料的相关性系数均大于拟一级动力学方程,这意味着两种污染物的吸附机制可能相同。
应用实施例3:
利用实施例1所得吸附剂进行光助再生实验实验。实验过程:将15mg预吸附材料(预吸附材料为对亚甲基蓝吸附饱和的ZnO/LDH材料,或者是对甲基橙吸附饱和的ZnO/LDH材料)分散在15ml去离子水中,用磁力搅拌器搅拌,通过低压汞灯(16mW/cm2)辐射样品溶液。在一定时间取出定量悬浊液,用15ml浓度为1mol/L的盐酸酸化解析悬浊液样品中残留的染料(酸化后对LDH的溶解度可以忽略不计)。通过微孔滤膜后,检测上清液中染料的浓度,通过获得不同辐照时间后复合材料吸附中染料的残留量来估算通过光催化降解后可用吸附位点百分比,评估复合材料的光助再生动力学。实验结果如表3所示,表3为ZnO/LDH对有机染料的再生动力学参数实验结果。其中亚甲基蓝吸附饱和的材料在5h内完成了80%以上的再生,在7h后达到了再生饱和,亚甲基蓝吸附饱和的ZnO/LDH材料第一轮再生率为87.3%。甲基橙吸附饱和的ZnO/LDH材料在3h内完成80%以上的再生,在7h后同样达到再生饱和,甲基橙吸附饱和的TiO2/LDH材料第一轮再生率为92.9%。
表3 ZnO/LDH对有机染料的再生动力学参数
本发明实施例2-4的ZnO/LDH产物与实施例1的ZnO/LDH产物具有类似的技术效果,即是对甲基橙均能够达到300mg/g以上的吸附量,在5h循环再生后仍具有90%以上的再生率;对亚甲基蓝均能够达到160mg/g以上的吸附量,在5h循环再生后仍具有80%以上的再生率。
本方法寻找了一种合成过程更加简单,而且耗时较短,利用水热合成法一步合成LDHs,而且克服了CN-H由于通过静电合成,导致的可能存在结构松散的问题,可同时实现污染物的去除及吸附剂的再生的非碳基吸附剂。对有机染料具有较高的吸附容量,且由于材料的抗氧化能力和透光性可以避免光催化过程中材料受活性氧攻击和基底的光吸收导致光量子效率的下降,具有高效的光助再生能力,并且该工艺过程将吸附过程从光催化中独立出来,不仅能发挥吸附的快速动力学之势,而且当吸附位点被耗尽时,可将材料暴露在阳光下以足够时间进行再生,再生动力学不再限制材料将污染物从水中去除的效率,是一种高效节能减排的方式。
本发明将ZnO颗粒负载在镁铝-层状双氢氧化物(MgAl-LDH)上,用于吸附及光助再生循环去除水中两种代表性的有机污染物:甲基橙(有机阴离子染料)和亚甲基蓝(有机阳离子染料)。本发明的吸附剂对含有机染料的水体进行处理时,首先通过吸附剂材料的吸附作用富集水中的污染物,吸附饱和后将吸附剂材料暴露在阳光下,通过光催化降解吸附剂材料中的污染物,使得污染物中吸附位点重新暴露,达到吸附剂的再生和循环利用的目的。该工艺过程将吸附过程从光催化中独立出来,不仅能发挥吸附的快速动力学之势,而且当吸附位点被耗尽时,可将材料暴露在阳光下以足够时间进行再生,再生动力学不再限制材料将污染物从水中去除的效率,是一种高效节能减排的方式。根据上述性质,采用新型“二段式”速率提升机制的可光助再生ZnO/LDH非碳基吸附剂对有机染料具有较高的吸附容量,不仅发挥了高效的吸附性能,同时解决了再生循环过程中,吸附效率受限于过慢的再生动力学这个关键技术难点,成本低廉,过程简单、低能耗,可用于环保、化工等领域。
本说明书所述的内容仅仅是对发明构思实现形式的列举,本发明的保护范围不应当被视为仅限于实施例所陈述的具体形式。
Claims (7)
1.一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂的制备方法,其特征在于所述吸收剂包括镁铝-层状双氢氧化物MgAl-LDH及负载于镁铝-层状双氢氧化物MgAl-LDH上的ZnO成分,其制备方法包括以下步骤:
1)在室温下,将Mg(NO3)2·6H2O、Al(NO3)3·9H2O和尿素加入去离子水中,搅拌溶解得到透明溶液;
2)在步骤1)得到的透明溶液中加入ZnO,超声分散得到混合液,再将所得的混合液置于聚四氟乙烯高压反应釜中,于130-150℃烘箱中进行尿素水解水热反应20-30 h,反应结束后的固体产物依次用乙醇和水洗数次,即得到所述吸附剂产物。
2.如权利要求1所述的一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂的制备方法,其特征在于步骤1)中,Mg(NO3)2·6H2O、Al(NO3)3·9H2O和尿素的投料质量比为1:0.7-0.75:1.05-1.1,优选为1:0.73:1.09。
3.如权利要求1所述的一种遵循“二段式”速率提升机制的可光助再生非碳基吸附剂的制备方法,其特征在于在烘箱中反应的温度为140℃,反应时间24h。
4.如权利要求1~3任一所述方法制备的遵循“二段式”速率提升机制的可光助再生非碳基吸附剂。
5.如权利要求4所述的遵循“二段式”速率提升机制的可光助再生非碳基吸附剂在降解水体中有机染料中的应用。
6.如权利要求5所述的应用,其特征在于所述有机染料为甲基橙、亚甲基蓝中的至少一种。
7.如权利要求5所述的应用,其特征在于将吸附剂投入含有机染料的水体中,于避光条件下吸附饱和后,通过太阳光辐射实现有机染料的去除和吸附剂的再生。
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