CN115007190A - 一种基于生成单线态氧降解磺胺类药物催化剂的制备方法及其应用 - Google Patents
一种基于生成单线态氧降解磺胺类药物催化剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开一种基于生成单线态氧降解磺胺类药物催化剂的制备方法及其应用。在水溶液中催化剂与过硫酸盐形成单线态氧活性物质参与降解磺胺类抗生素的过程。按下列步骤进行:A1、催化剂制备:取铁盐、氮源和镁盐为原料采用一步热解法合成即得;A2、磺胺类药物降解:将合成得到的催化剂加入磺胺类药物废水中,通过添加过一硫酸盐形成反应体系,通过催化氧化反应降解磺胺类药物。催化剂可高效活化过一硫酸盐产生单线态氧,以单线态氧非自由基途径有效降解废水中磺胺类药物,40分钟内降解效率即可达到100%。本发明的催化剂对废水中磺胺类药物具有高效降解、抗干扰能力强,环境友好且成本低廉。
Description
技术领域
本发明属于功能材料制备催化氧化处理环境水污染技术领域,具体涉及一种基于生成单线态氧降解磺胺类药物催化剂制备方法及其应用。
背景技术
磺胺甲恶唑(SMX)作为一种典型的磺胺类抗生素,在所有结构相似的类似物中消耗速度最快,但在代谢过程中伴有肝损伤。磺胺类抗生素及其次级代谢产物的滥用在水生生态系统中会抑制微生物的活动,进一步导致抗生素抗性基因的产生。因此,开发一种高效、无二次污染的SMX去除方法势在必行。
基于羟基自由基、硫酸根自由基的过硫酸盐高级氧化技术得到了快速发展,并且对磺胺类抗生素表现出展现良好的降解效率,但仍存许多问题和不足,例如,专利号202111522306 .X公开了一种木材海绵协同热活化过硫酸盐降解磺胺甲恶唑的方法,该方法将木材海绵与过硫酸盐混合,在pH为3-9之间,温度在30-60℃加热条件下,进行磺胺甲恶唑的降解。该方法虽然降解效率高,但处理时间相对较长,材料制作复杂,能耗大。专利号202111008075 .0公开了一种利用生物炭激活过氧碳酸氢盐降解磺胺甲恶唑的方法,该方法法采用生物炭激活过氧碳酸氢盐对磺胺甲恶唑进行处理。该方法虽然充分利用生物炭本身的优势进行催化剂合成,但合成条件严格,处理时间过长。在实际水体中自由基易被环境中的干扰因素而淬灭。而非自由基能克服上述缺点。其次催化剂性能不高和无法回收利用等日渐突出。所以设计一种活化过硫酸盐高效转化为非自由基途径,且具有绿色无污染、可回收性强的催化剂对磺胺类药物降解有重要环境意义。
单线态氧是一种非自由基途径中的高反应性氧化剂,在水处理系统中具有很大的应用潜力。同时,单线态氧也是一种重要的氧化剂、适中的半衰期和不同的氧化机制。其具备高选择性而被广泛用于难降解污染物的降解。迄今为止,大多数产生单线态氧催化生成方法都通过活化过氧硫酸盐产生。因此,制备一种稳定产生单线态氧氧化物的催化剂用于快速高效处理水体中难降解有机污染物具有广泛的研究和应用意义。
目前,在活化过硫酸盐材料中,碳纳米管封装金属纳米粒子技术具有良好的催化能力和稳定性,能够提高碳材料的催化性能,同时减少金属溶出,减少二次污染,提高回收利用。
发明内容
针对上述问题,本发明着眼于绿色环保材料制备及其对水中有机物的降解,将铁盐、氮源和镁盐为原料采用一步热解法制备氮掺杂碳纳米管包裹铁镁氧化物催化剂,协同活化过硫酸盐产生单线态氧,相比于传统自由基途径,具有更强的抗干扰能力,更高效降解磺胺类抗生素,在降低金属溶出和二次污染的同时,增强催化能力,和对pH、各种离子、腐殖酸等的抗干扰能力,能保持较高效率的有机物氧化能力且回收方便。
为此,本发明提出一种基于生成单线态氧降解磺胺类药物催化剂制备方法及其应用,实现以单线态氧为主要活性氧化物来降解磺胺类药物,具有适用pH值范围广、环境友好且成本低廉的特点。
为实现上述目的,本发明提供一种基于生成单线态氧降解磺胺类药物催化剂制备方法,具体包括以下步骤:
A01、取铁盐、氮源和镁盐混合后溶解于乙醇中,形成混合溶液;
A02、将步骤A01中制得的混合溶混合溶液置于烘箱干燥温度为50-80℃,干燥的时间为8-14 h,得到混合固体;
A03、将步骤A02中制得的混合固体以2-5℃/min的升温速率升温至600-1000℃温度下煅烧2-5 h,然后用酸浸泡,得到降解磺胺类药物催化剂;所述铁盐、氮源和镁盐的摩尔比为(0.1-10.0):1 :(0.1-10.0)。
本发明的催化剂制备方法简单高效,降解过程可通过催化剂本身磁性回收循环利用,循环使用仍具有较高的催化活性,并且具有包裹性,防止金属溶出。因此,具有环境友好且成本低廉的优点。
根据本发明的一些实施方式,其特征在于,A01所述铁盐为氯化铁水合物;优选地,所述铁盐为六水合氯化铁。
根据本发明的一些实施方式,其特征在于,A01所述氮源为三聚氰胺;优选地,所述氮源为三聚氰胺。
根据本发明的一些实施方式,其特征在于,A01所述镁盐为氯化镁水合物;优选地,所述镁盐为氯化镁。
根据本发明的一些实施方式,步骤A02中所述干燥的温度为50-80℃,干燥的时间为8-14 h。
优选地,步骤A02中所述干燥的温度为60℃,干燥的时间为12 h。
根据本发明的一些实施方式,步骤A03中所述煅烧的升温速率为2-5℃/min。
优选地,步骤A03中所述煅烧的升温速率为5℃/min。
根据本发明的一些实施方式,步骤A03中所述煅烧的温度为600-1000℃温度下煅烧2-5 h。
优选地,步骤A03中所述煅烧的温度为800℃,时间为2h。
根据本发明的一些实施方式,步骤A01中所述铁盐、氮源和镁盐的摩尔比为(0.1-10.0):1 :(0.1-10.0)。优选地,所述铁盐、氮源和镁盐的摩尔比为1:1:5。
本发明因而提供所述的方法制备得到的催化剂。
本发明进而提供上述催化剂的应用,即一种磺胺类药物的降解方法,其特征在于,将所述的催化剂加入磺胺类药物废水中,通过添加过一硫酸盐形成反应体系,通过催化氧化反应降解磺胺类药物。
优选地,所述反应体系的pH为3-11;优选地,所述催化剂的使用量为0 .1 g/L -0.3 g/L,优选地,所述催化剂的使用量为0.2 g/L;所述过一硫酸盐的使用量为0.1 -2.0 g/L,优选地,所述过一硫酸盐的使用量为0.6 g/L。
根据本发明的一些实施方式,所述催化剂与所述过一硫酸盐的质量比例为0.1:(0.1-5);优选地,所述催化剂与所述过一硫酸盐的比例为1:3。
附图说明
图1是本发明制备的催化剂扫描电镜照片。
图2是本发明制备的催化剂对磺胺甲恶唑的降解效果。实验条件:[FeMg@NCNTs] =5mg,[过一硫酸盐] = 15mg,温度:25℃。
图3是本发明制备的催化剂在不同pH条件下对磺胺甲恶唑的降解效果。实验条件:[FeMg@NCNTs] = 5mg,[过一硫酸盐] = 15mg,温度:25℃。
图4是本发明制备的催化剂在无机阴离子和腐殖酸的干扰下对磺胺甲恶唑降解的影响。实验条件:[FeMg@NCNTs] = 5mg,[过一硫酸盐] = 15mg,温度:25℃。
图5是本发明制备的催化剂的回收再利用。实验条件:[FeMg@NCNTs] = 5mg,[过一硫酸盐] = 15mg,温度:25℃。
具体实施方式
下面详细描述本发明的实施例,但以下所述内容仅用于解释本
发明,并不用于限定本发明保护范围。
实施例1:
本实施例制备基于生成单线态氧催化剂(FeMg@NCNTs)的方法,具体步骤如下:
(1)室温下,5.4 g FeCl3· 6H2O,称取12.6 g 三聚氰胺,9.5 g MgCl2于20 mL 乙醇中,超声分散,随后磁力搅拌使其完全溶解并形成黄色溶液。
(2)将步骤(1)所得混合溶液转移至60℃的烘箱中干燥12 h以蒸干乙醇使混合物呈黄褐色固体状。
(3)用研钵将步骤(2)中所得黄褐色固体研磨成粉末后置于通氮气的管式炉中进行煅烧,煅烧温度为800℃,升温速率为5℃/min,煅烧维持2 h。煅烧后的样品用浓盐酸浸泡以去除杂质,洗涤后可得FeMg@NCNTs催化剂。催化剂的电镜图如附图1所示,催化剂以碳纳米管状形式存在,金属纳米颗粒被碳纳米管牢固包裹,不易造成离子的流失,可提高催化剂的电子传输能力和可回收性。
实施例2:
FeMg@NCNTs降解磺胺甲恶唑
取50 mL 5mg/L磺胺甲恶唑废水,称取5mg FeMg@NCNTs催化剂加入到溶液中,再加入15mg过一硫酸盐,启动氧化反应。分别在5,10,20,30,40,60,80,120 min取样,利用高效液相色谱检测样品中的磺胺甲恶唑:其中流动相为乙腈和0 .1%甲酸水(体积比2:3),流速为0 .6 mL/min,柱温35 ℃,检测波长254 nm。结果如图2所示,结果表明,FeMg@NCNTs能够在30 min内超过95%磺胺甲恶唑被降解,60分钟到达完全降解的效果。说明催化剂具有良好的催化性能。
实施例3:
分别量取50 mL5mg/L磺胺甲恶唑废水,加入5mg FeMg@NCNTs催化剂,分别用H2SO4或NaOH将pH调为3、5、7、9、11,加入15mg过一硫酸盐以启动氧化反应。在5,10,20,30,40,60,80,120 min时刻进行取样,利用高效液相色谱检测样品中的磺胺甲恶唑浓度。图3的结果表明,FeMg@NCNTs能够在不同的pH条件下快速、完全降解磺胺甲恶唑。pH在3-11之间30 min内去除率分别为95.9%,96.2%,96.6%,94.6%,89.5%,120min除pH=11去除率为99.1,其余所有都达到100%去除,这说明催化剂具有广泛的适用范围。
实施例4:
分别量取50 mL 5mg/L的磺胺甲恶唑废水,加入5mg FeMg@NCNTs催化剂,分别加入氯化钠(10mmol/L)、硝酸钠(10mmol/L)、硫酸钠(10 mmol/L)和腐殖酸钠(10 mg/L), 再加入15mg过一硫酸盐以启动氧化反应。在5,10,20,30,40,60,80,120 min时刻进行取样,利用高效液相色谱检测样品中的磺胺甲恶唑浓度。图4的结果表明,FeMg@NCNTs能够在不同阴离子和有机质存在的情况下完全降解磺胺甲恶唑。加入氯化钠30min内100%降解,出现加速情况。除腐殖酸以外,加入硝酸钠和硫酸钠降解效率依旧超过95%,在120min依旧能够100%清除。说明催化剂具有良好的抗干扰能力和活化性能。
实施例5:
将实施例2反应液静置,使用普通磁铁进行固液分离,倒出上清液,回收反应后的FeMg@NCNTs,并利用回收后的FeMg@NCNTs作为催化剂处理磺胺甲恶唑废水,其余操作均与实施例2相同。图5的结果表明,第一次循环降解磺胺甲恶唑达100%,第二次循环降解达98.7%,第三次循环达87.2%,第四次循环降解达75.9%,第五次循环达60.6%。FeMg@NCNTs能够在循环5次的情况下,仍能降解超过60%的磺胺甲恶唑,说明催化剂具有良好的重用性能。
上述实施例仅用于对本发明经行说明,并不构成对权利要求范围的限制,本领域的技术人员可以想到其他替代手段,均在本发明权利要求范围内。
Claims (10)
1.一种基于生成单线态氧降解磺胺类药物催化剂的制备方法,包括以下步骤:
A01、取铁盐、氮源和镁盐混合后溶解于乙醇中,形成混合溶液;
A02、将步骤A01中制得的混合溶液置于烘箱中干燥,得到混合固体;
A03、将步骤A02中制得的混合固体以2-5℃/min的升温速率升温至600-1000℃温度下煅烧2-5 h,然后用酸浸泡,得到高效降解磺胺类药物催化剂;
所述铁盐、氮源和镁盐的摩尔比为(0.1-10.0):1 :(0.1-10.0),优选地,步骤A03中所述铁盐、氮源和镁盐的摩尔比为1:1:5。
2.根据权利要求1所述的方法,其特征在于,步骤A01所述铁盐为硫酸铁、硝酸铁、氯化铁中的至少一种。
3.根据权利要求1所述的方法,其特征在于,步骤A01所述氮源为三聚氰胺、二氰二胺、尿素中的至少一种。
4.根据权利要求1所述的方法,其特征在于,步骤A01所述镁盐为硫酸镁、硝酸镁、氯化镁中的至少一种。
5.根据权利要求1所述的方法,其特征在于,步骤A02所述中过一硫酸盐为过一硫酸钠、过一硫酸钾以和过硫酸氢钾复合盐中的至少一种。
6.根据权利要求2所述的方法,其特征在于,步骤A02中所述干燥的温度为50-80℃;所述干燥的时间为8-14 h;优选地,步骤A02中所述干燥的温度为60℃,干燥的时间为12 h。
7.根据权利要求2所述的方法,其特征在于,步骤A03中所述煅烧的温度为700-900℃;所述煅烧的升温速率为2-5℃/min,更优选地,所述煅烧的升温速率为5℃/min;进一步优选,步骤A03中所述煅烧的温度为600-1000℃温度下煅烧2-5 h;优选地,步骤A03中所述煅烧的温度为800℃,时间为2h。
8.根据权利要求1至7任一项所述的方法制备得到的催化剂。
9.一种磺胺类药物的降解方法,其特征在于,将如权利要求8所述的催化剂加入磺胺类药物废水中,通过添加过一硫酸盐形成反应体系,通过催化氧化反应降解磺胺类药物。
10.根据权利要求9所述的方法,其特征在于,所述反应体系的pH为3-11;优选地,所述催化剂的使用量为0 .1 g/L -0 .3 g/L;所述过一硫酸盐的使用量为0 .1 -2.0 g/L。
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