CN107118477B - 一种碳包覆金属纳米颗粒负载pvdf膜及其制备方法和应用 - Google Patents
一种碳包覆金属纳米颗粒负载pvdf膜及其制备方法和应用 Download PDFInfo
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- CN107118477B CN107118477B CN201710334553.4A CN201710334553A CN107118477B CN 107118477 B CN107118477 B CN 107118477B CN 201710334553 A CN201710334553 A CN 201710334553A CN 107118477 B CN107118477 B CN 107118477B
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- organic pollutant
- pvdf membrane
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
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- 229940043267 rhodamine b Drugs 0.000 claims description 5
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
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- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 2
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
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- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 1
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种碳包覆金属纳米颗粒负载PVDF膜及其制备方法和应用，其是首先合成碳包覆金属纳米颗粒，然后将其与聚偏氟乙烯粉末、有机添加剂和分散介质混合、搅拌得到铸膜液，再经溶液相转化法获得目标产物。本发明的碳包覆金属纳米颗粒负载PVDF膜可高效矿化水体中的有毒有机污染物，降解率高；构建催化膜反应器进行催化降解有机污染物反应，基于膜孔结构的微纳分离作用，阻断大分子有机污染物透过，起到截留作用，提高降解的转化率和选择性，解决了金属纳米颗粒易团聚、流失的技术问题，避免对水体造成潜在的二次污染；且制备方法具有成本较低、工艺简单、结构可控、可操作性强、易于产业化应用等优点。
Description
技术领域
本发明涉及无机催化剂制备的技术领域，具体涉及一种碳包覆金属纳米颗粒负载PVDF膜及其降解有机污染物的方法。
背景技术
化学工业所排放出的废水大部分是成分复杂、可生化性差、难生物降解的物质，给生态环境和人类健康带来了巨大危害。高级氧化技术因其可高效矿化水体中的有毒有机污染物而成为污水处理领域的研究热点。在各种高级氧化技术中，通过金属纳米粒子M(M：Fe、Cu、Co、Mn、Zn、Ni等)激活强氧化剂产生高活性自由基的类Fenton催化机制因其反应体系简单、所需条件温和、能耗较低、无需外加热源和光源且对后续的生化处理无毒害作用等优点而受到了广泛的关注，但反应过程中的淤泥和金属离子浸出仍然是此类活化机制体系中的最大缺陷。
随着纳米技术的发展，碳包覆金属纳米颗粒复合材料已经成为复合材料、纳米材料领域研究的热点。包覆结构通过给活性金属纳米颗粒穿上碳纳米层，避免金属纳米颗粒被毒化，极大的提高了催化剂的稳定性。然而，包覆结构复合材料依然存在金属离子浸出、易产生二次污染、金属颗粒易团聚失活及不易回收等技术问题。近来，为了克服金属纳米颗粒的团聚、流失、水解及产生二次污染等缺陷，将金属纳米颗粒填充、沉积或包裹于聚合物膜材料中成为复合材料领域的研究热点。
聚偏氟乙烯(PVDF)多孔膜是一种新兴且综合性能优良的膜材料，其高的比表面积和大量的通孔结构使其成为理想的纳米粒子载体，将金属纳米粒子负载到膜孔中，金属纳米粒子将会有更大的活性位点与反应物分子接触反应，提高反应活性；与此同时，生成物将会更容易从纳米粒子表面离开，大大降低对活性位点的包覆，提高反应效率，克服了金属纳米颗粒的聚集和流失缺陷，避免失活金属纳米颗粒对水体产生二次污染。同时，金属纳米粒子加入到膜的基体中，可作为成孔剂促进形成多孔结构，赋予聚合膜亲水性、催化活性等新的功能特性。CN103638827A通过化学还原制备负载贵金属纳米粒子的PVDF杂化膜，用于降解水体中的有机氯代物，其方法合成的金属单质易被毒化及水解，产生相当的金属离子浸出，且制备成本较高，重复利用性能较低；Ganesh K等(Water.Res.,2009,43(10):3086-3094)通过化学沉积制备负载单质Fe/Ni的聚合物膜，用于三氯乙烯的脱氯降解，此方法的操作条件比较苛刻，制备工艺过于繁琐，制备的膜需储存在无氧条件下，且产生较大的离子浸出，限制了它的应用；CN104984668A采用热致相转化法制备纳米粒子掺杂聚偏氟乙烯催化膜，该方法制备过程能耗较高，且纳米粒子易自团聚而分散不够均匀，制约纳米粒子发挥出应有的功效，局限了其实际应用；CN103611436B通过化学还原制备负载双金属纳米粒子的PVDF杂化膜用于降解含氯有机物，复合膜所负载的金属纳米粒子只负载于膜的表面而未进入到膜孔中，造成相当的离子浸出，且金属纳米粒子由于缺少保护易被氧化及水解，重复利用性能较低，孔径不可控，成本高，限制了其实际应用。
这些已报道的制备方法通常存在以下问题：步骤繁多、需要比较苛刻的实验条件、制备成本及能耗较高、孔径不可控、重复利用性能较低；负载的金属纳米粒子由于缺少保护而易被毒化、氧化，制约其在催化反应中的活性，限制了其在实际过程中的应用；负载于聚合膜的金属纳米粒子易团聚及流失，产生相当的离子浸出。
发明内容
本发明旨在提供一种碳包覆金属纳米颗粒负载PVDF膜的制备方法以及降解有机污染物的方法，所要解决的问题是制膜过程步骤繁琐、实验条件苛刻、制膜工艺成本高、能耗高、金属纳米粒子易团聚、流失、不能规模化生产等技术问题。
为了解决上述技术问题，本发明采用如下技术方案：
本发明碳包覆金属纳米颗粒负载PVDF膜的制备方法，是按如下步骤进行：
(1)将水溶性金属二价盐、氰胺类化合物和含氮、含硫或含硼的非金属化合物在温度为50℃的甲醇溶液中混合并搅拌均匀，然后蒸发干燥、研磨，获得均相粉末；在高纯氮气或氩气的保护下，将所述均相粉末在700～750℃恒温煅烧2～4小时，获得热解产物；
(2)将步骤(1)中的所述热解产物与PVDF粉末、聚乙烯吡咯烷酮在N,N-二甲基甲酰胺中混合，然后在65～75℃下持续搅拌10～12小时，得到均匀的铸膜液；将所述铸膜液在20～30℃条件下恒温静置脱泡12～14小时，然后刮膜，再在凝固浴中浸泡1～24小时胶凝，即制得碳包覆金属纳米颗粒负载PVDF膜。
步骤(1)中，所述的水溶性金属二价盐为过渡金属Fe、Co或Ni的可溶性二价盐中的一种，所述的氰胺类化合物为尿素、三聚氰胺、双氰氨、环氰氨或六亚甲基四氨，所述的含氮、含硫或含硼的非金属化合物分别为硫酸铵盐、硫代硫酸盐、硼酸铵盐。
步骤(1)中水溶性金属二价盐、氰胺类化合物和含氮、含硼或含硫的非金属化合物的用量比为1～3g：2～7g：1～3g。
步骤(2)中热解产物、PVDF粉末、聚乙烯吡咯烷酮、N,N-二甲基甲酰胺的用量比为0.01～0.1g：0.3～0.7g：0.1～0.4g：4～6mL。
步骤(2)中所用的凝固浴为40～60％(质量分数)的乙醇溶液，所述凝固浴的温度为20～30℃。
本发明按上述制备方法所获得的碳包覆金属纳米颗粒负载PVDF膜，平均孔径为2～500nm、膜通道的内径为2～100nm。
本发明的碳包覆金属纳米颗粒负载PVDF膜可用于构建催化膜反应器装置，以降解有机污染物。利用本发明的碳包覆金属纳米颗粒负载PVDF膜与氧化剂结合降解有机污染物的方法如下：
构建催化膜反应器装置，所述反应器装置包括有机玻璃筒体，在所述有机玻璃筒体内固定有所述碳包覆金属纳米颗粒负载PVDF膜，在所述有机玻璃筒体的上、下端分别设置有进液口和出液口；
在有机污染物溶液中加入氧化剂，然后通过自吸泵从进液口泵入催化膜反应器装置中，经所述碳包覆金属纳米颗粒负载PVDF膜降解后，从出液口流出；
所述有机污染物为金橙II、亚甲蓝、罗丹明B、甲基紫或甲基橙。所述氧化剂为过—硫酸氢盐、双氧水或过二硫酸钾。所述有机污染物溶液中有机污染物的浓度为1-200mg/L，所加入的氧化剂的浓度为0.1～1g/L。
本发明的碳包覆金属纳米颗粒负载PVDF膜能激活氧化剂产生具有催化活性的自由基，而高活性自由基能够使有机污染物发生降解反应，矿化为CO2和H2O。
与已有技术相比，本发明的有益效果体现在：
1、本发明的碳包覆金属纳米颗粒负载PVDF膜可高效矿化水体中的有毒有机污染物，降解率高；构建催化膜反应器进行催化降解有机污染物反应，基于膜孔结构的微纳分离作用，阻断大分子有机污染物透过，起到截留作用，提高降解的转化率和选择性，解决了金属纳米颗粒易团聚、流失的技术问题，避免对水体造成潜在的二次污染；且制备方法具有成本较低、工艺简单、结构可控、可操作性强、易于产业化应用等优点。
2、本发明的制备方法解决了金属纳米颗粒易团聚、降解能力不理想及其直接用于环境治理时纳米颗粒易流失和堵塞的问题；金属纳米粒子加入到膜的基体中，作为成孔剂可以促进形成多孔结构，在保证高截留率的同时又有可控的膜通量，提高复合膜的强度及尺寸稳定性，同时赋予聚合膜亲水性、催化活性等新的功能特性，使其在催化领域具有潜在的应用价值。
3、本发明制备的碳包覆金属纳米颗粒表面具有大量的亲水性官能团，其在制膜过程中起到交联剂的作用，与PVDF交联形成稳定的多孔网络结构，提高PVDF和碳包覆金属纳米粒子的相容性，解决金属纳米粒子与PVDF无法结合的难题，克服金属纳米粒子的流失缺陷，保证了膜结构的稳定性、持久性。
4、本发明通过溶液相转化法将纳米催化与PVDF膜耦合构成膜反应器，利用金属纳米粒子的成孔作用构筑多级高效传质催化孔道，水体中的有毒有机污染物通过膜孔实现微尺度分散，与活性位点充分接触，使污染物被高效矿化；同时有效实现金属纳米颗粒的原位分离，避免对水体造成毒化及潜在的二次污染；且本发明的有机污染物处理过程具有工艺简单、运行成本低、易回收、催化活性高、再生性好等优点，在降解水体中有毒有机污染物方面有广阔的应用价值。
附图说明
图1是本发明实施例1所制备的碳包覆铁纳米颗粒的XRD图；
图2是本发明实施例1所制备的碳包覆铁纳米颗粒的TEM图；
图3是本发明实施例1所制备的碳包覆铁纳米颗粒负载PVDF膜复合材料的表面SEM图；
图4是本发明实施例1所制备的碳包覆铁纳米颗粒负载PVDF膜复合材料的断面SEM图。
具体实施方式
下面通过具体的实施例对本发明作进一步的详细描述，以下实施例可以使专业技术人员更全面的了解本发明，但不以任何方式限制本发明。
实施例1
本实施例首先按如下步骤制备碳包覆铁纳米颗粒负载PVDF膜催化剂：
(1)称取2g(10.06mmol)四水合氯化亚铁(FeCl2·4H2O)、5g(59.47mmol)二氰二氨(C2H4N4)和2g(12.66mmol)硫代硫酸钠(Na2S2O3)在200mL、50℃的甲醇溶液中混合并搅拌均匀，然后蒸发干燥、研磨，获得均相粉末；将均相粉末置于石英管中，把石英管置于管式电阻炉的均温区，在流率为0.2mL/min的高纯氮气气氛中以10℃/min的速率升温至700℃，恒温煅烧2小时；待反应结束后，将石英管在高纯氮气气氛中冷却至室温，得热解产物碳包覆铁纳米颗粒；
(2)称取步骤(1)中的热解产物碳包覆铁纳米颗粒50mg与0.5g聚偏氟乙烯粉末(PVDF)、0.25g聚乙烯吡咯烷酮(PVP)在5mL的N,N-二甲基甲酰胺(DMF)中混合，然后在70℃下持续搅拌10小时，得到均匀的铸膜液；将铸膜液在25℃恒温静置脱泡12小时，之后用1000μL移液枪每次取1mL铸膜液刮膜，再于25℃置于200mL质量分数为50％的乙醇溶液中5小时胶凝，再将聚合物膜多次水洗后，储存于去离子水中，即获得目标产物碳包覆铁纳米颗粒负载PVDF膜复合材料，铁的负载量为5％。
图1和图2是本实施例所制备的碳包覆铁纳米颗粒的XRD图和TEM图，从图1中可以看出产物具有较高的纯度，从图2中可以看出该产物具有包覆结构。
图3和图4是本实施例所制备的碳包覆铁纳米颗粒负载PVDF膜复合材料的表面SEM图和断面SEM图，可以看出该复合材料具有多孔结构。
利用本实施例的碳包覆金属纳米颗粒负载PVDF膜降解有机污染物的方法如下：
构建催化膜反应器装置：反应器装置包括有机玻璃筒体，在有机玻璃筒体内固定有碳包覆金属纳米颗粒负载PVDF膜，在有机玻璃筒体的上、下端分别设置有进液口和出液口；反应器有效容积为1L，核心部件为PVDF膜(膜平均孔径为40nm，膜通道的内径为30nm，有效表面积为24cm2)。
配制20mg/L的金橙II溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg，用自吸泵(压力为0.1MPa)将有机污染物溶液从进液口泵入催化膜反应器装置中，通过碳包覆金属纳米颗粒负载PVDF膜进行降解，采用空气泵(压力为0.2MPa)维持反应器内的压力恒定，产物从出液口流出。经测试，有机污染物降解率达到100％。
实施例2
本实施例以与实施例1相同的碳包覆铁纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的亚甲蓝溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例3
本实施例以与实施例1相同的碳包覆铁纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的罗丹明B溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例4
本实施例以与实施例1相同的碳包覆铁纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的甲基紫溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例5
本实施例以与实施例1相同的碳包覆铁纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的甲基橙溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例6
本实施例首先按与实施例1相同的方法制备碳包覆镍纳米颗粒负载PVDF膜催化剂，区别仅在于：选用2.93g(10.06mmol)六水合硝酸镍(Ni(NO3)2·6H2O)来代替2g(10.06mmol)四水合氯化亚铁(FeCl2·4H2O)，制得目标产物碳包覆镍纳米颗粒负载PVDF膜复合材料。
本实施例以碳包覆镍纳米颗粒负载PVDF膜构建与实施例1相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的金橙II溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg，采用催化膜反应器装置进行降解实验。经测试，有机污染物降解率可达到100％。
实施例7
本实施例以与实施例6相同的碳包覆镍纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的亚甲蓝溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例8
本实施例以与实施例6相同的碳包覆镍纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的罗丹明B溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例9
本实施例以与实施例6相同的碳包覆镍纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的甲基紫溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例10
本实施例首先按与实施例1相同的方法制备碳包覆钴纳米颗粒负载PVDF膜催化剂，区别仅在于：选用2.93g(10.06mmol)六水合硝酸钴(Co(NO3)2·6H2O)来代替2g(10.06mmol)四水合氯化亚铁(FeCl2·4H2O)，制得目标产物碳包覆钴纳米颗粒负载PVDF膜复合材料。
本实施例以碳包覆钴纳米颗粒负载PVDF膜构建与实施例1相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的金橙II溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg，采用催化膜反应器装置进行降解实验。经测试，有机污染物降解率可达到100％。
实施例11
本实施例以与实施例10相同的碳包覆钴纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的亚甲蓝溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例12
本实施例以与实施例10相同的碳包覆钴纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的罗丹明B溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
实施例13
本实施例以与实施例10相同的碳包覆钴纳米颗粒负载PVDF膜催化剂构建相同的催化膜反应器装置，处理如下有机污染物溶液：配制20mg/L的甲基橙溶液模拟有机污染物废水(V＝250mL)，同时加入氧化剂过一硫酸氢盐(PMS)150mg。
经测试，有机污染物降解率达到100％。
以上仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.一种碳包覆金属纳米颗粒负载PVDF膜的制备方法，其特征在于，是按如下步骤进行：
(1)将水溶性金属二价盐、氰胺类化合物和含氮、含硫或含硼的非金属化合物在温度为50℃的甲醇溶液中混合并搅拌均匀，然后蒸发干燥、研磨，获得均相粉末；在高纯氮气或氩气的保护下，将所述均相粉末在700～750℃恒温煅烧2～4小时，获得热解产物；
所述的水溶性金属二价盐为过渡金属Fe、Co或Ni的可溶性二价盐中的一种，所述的氰胺类化合物为尿素、三聚氰胺、双氰氨、环氰氨或六亚甲基四氨，所述的含氮、含硫或含硼的非金属化合物分别为硫酸铵盐、硫代硫酸盐、硼酸铵盐；
水溶性金属二价盐、氰胺类化合物和含氮、含硼或含硫的非金属化合物的用量比为1～3g：2～7g：1～3g；
(2)将步骤(1)中的所述热解产物与PVDF粉末、聚乙烯吡咯烷酮在N,N-二甲基甲酰胺中混合，然后在65～75℃下持续搅拌10～12小时，得到均匀的铸膜液；将所述铸膜液在20～30℃条件下恒温静置脱泡12～14小时，然后刮膜，再在凝固浴中浸泡1～24小时胶凝，即制得碳包覆金属纳米颗粒负载PVDF膜。
2.根据权利要求1所述的方法，其特征在于：步骤(2)中热解产物、PVDF粉末、聚乙烯吡咯烷酮、N,N-二甲基甲酰胺的用量比为0.01～0.1g：0.3～0.7g：0.1～0.4g：4～6mL。
3.一种权利要求1～2中任意一项所述制备方法所获得的碳包覆金属纳米颗粒负载PVDF膜。
4.根据权利要求3所述的碳包覆金属纳米颗粒负载PVDF膜，其特征在于：所述碳包覆金属纳米颗粒负载PVDF膜的平均孔径为2～500nm、膜通道的内径为2～100nm。
5.一种权利要求3或4所述的碳包覆金属纳米颗粒负载PVDF膜的应用，其特征在于：用于构建催化膜反应器装置，以降解有机污染物；具体是在有机污染物溶液中加入氧化剂，然后泵入催化膜反应器装置中，经所述碳包覆金属纳米颗粒负载PVDF膜降解后流出；
所述有机污染物为金橙II、亚甲蓝、罗丹明B、甲基紫或甲基橙。
6.根据权利要求5所述的应用，其特征在于：所述氧化剂为过一硫酸氢盐、双氧水或过二硫酸钾。
7.根据权利要求6所述的应用，其特征在于：所述有机污染物溶液中有机污染物的浓度为1-200mg/L，所加入的氧化剂的浓度为0.1～1g/L。
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