CN114643058A - 一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂及其制备方法 - Google Patents
一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂及其制备方法 Download PDFInfo
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- CN114643058A CN114643058A CN202210437239.XA CN202210437239A CN114643058A CN 114643058 A CN114643058 A CN 114643058A CN 202210437239 A CN202210437239 A CN 202210437239A CN 114643058 A CN114643058 A CN 114643058A
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- hydroxyl radicals
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- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
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- 230000009286 beneficial effect Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于水污染处理技术领域，具体涉及一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂及其制备方法。本催化剂以多孔材料作为载体，含铁镍元素纳米合金颗粒的活性物前驱体浸渍液，在含H2还原气氛中，通过浸渍‑高温还原两步法合成具有高活性、长寿命、低成本的催化剂。本发明的催化剂充分利用纳米合金元素间的协同作用，生成的纳米合金颗粒具有高催化活性、高化学稳定性、金属离子溶出率低、反复催化活性较好、适用范围广等优点。
Description
技术领域
本发明属于污水处理技术领域，具体涉及一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂及其制备方法。
背景技术
自从芬顿催化氧化技术发现后，由于降解能力强，被广泛应用于医药废水、工业废水和农业废水等的处理工程中。但是，由于其在反应过程对溶液pH要求高且产生大量铁泥，增加了水处理工艺设备及成本。目前仍有较大量的均相芬顿催化技术应用于废水处理工程中，开发类芬顿有机物降解技术具有重大的现实意义。
为克服均相芬顿技术存在的缺点，人们对多相类芬顿降解技术进行了大量的研究与开发工作，近期取得了取得不少成果，尤其在催化剂制备技术的研究领域。多相类芬顿催化氧化过程中与其催化剂自身形态结构、固液微界面的性质以及反应体系的pH值、溶液性质等因素相关。在多相类芬顿催化体系中，H2O2与催化剂表面的活性位点发生界面反应，同时从催化剂中溶出的过渡金属离子反应进而产生羟基自由基(·OH)。多相类芬顿催化剂对H2O2的高效利用，则主要通过催化剂表面的氧化还原反应促使界面电子进行转移，进而使H2O2分解形成羟基自由基(·OH)和超氧自由基等这些含氧自由基团的高氧化性能，对水中难降解的有机污染物实现高效去除。多相类芬顿催化反应中H2O2反应机制，其无效分解主要是发生在金属离子的还原过程，因而具有高还原性能催化剂的研究开发至关重要。
发明内容
为了解决现有多相类芬顿催化反应中，H2O2在金属离子还原过程中的无效分解产生氧气，造成羟基自由基生成量降低、H2O2有效利用率减小，使得化学稳定性和催化活性较低、催化寿命较短、反复催化活性较低等问题，本发明提供了一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂及其制备方法。
为解决上述问题，本发明采用了如下方案：
一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂，该催化剂由多孔性载体、含铁镍元素纳米合金颗粒的活性物前驱体浸渍液、含H2还原气氛制得。
进一步的，所述多孔性载体为陶瓷材料、碳基载体、沸石、堇青石、Al2O3、多孔分子筛、泡沫金属材料中的任意一种。
进一步的，所述碳基载体为：煤质活性炭、椰壳活性炭、合成材料活性炭、碳纤维、碳棒、碳纳米管、碳毡、碳纸或碳布任意一种。
进一步的，所述活性物前驱体浸渍液是含铁盐、镍盐、第三种金属元素盐的溶液；所述铁盐与镍盐的摩尔比为1:0.2～100，所述铁盐和镍盐的总摩尔与第三种金属元素盐的摩尔比为1:0.01～0.2。
进一步的，所述铁盐为氯化铁、硫酸铁、硝酸铁及醋酸铁中的一种或几种；所述镍盐为氯化镍、硫酸镍及硝酸镍中的一种或几种；所述第三种金属元素盐为含有Co、Cu、Mn、Sn、Mo、Ce、Pt、W其中一种金属元素的氯化盐、硫酸盐及硝酸盐中的一种或几种。
进一步的，所述含H2还原气氛为单一H2或者H2与惰性气体组成的混合气；所述混合气中H2与惰性气体总摩尔的摩尔比为1:0.01～24；所述惰性气体为N2、Ar、He中的一种或几种。
一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂的制备方法，其包括以下步骤：
步骤1：配制活性物前驱体浸渍液，将铁盐、镍盐、第三种金属元素盐与去离子水按比例混合，在室温下搅拌20～60min，制得活性物前驱体浸渍液；
步骤2：浸渍和干燥，将多孔性载体置入活性物前驱体浸渍液中，在25℃～80℃条件下浸渍2～24h，然后将载体捞出置于60～90℃条件下，在空气中干燥4h～12h，制得催化剂半成品；
步骤3：高温煅烧，将催化剂半成品置于250℃～850℃的煅烧炉内，在还原气氛中煅烧1h～12h，在煅烧过程中高温煅烧炉的升温速率为1～20℃/min，降温速率为1～15℃/min；冷却后即得催化剂。
与现有技术相比，本发明的有益效果是：
(1)本发明采用浸渍-高温煅烧还原法制得的催化剂，煅烧过程通过还原形成纳米金属颗粒，纳米合金球结构稳定、耐酸性介质腐蚀，催化活性较高、不易被氧化，适用范围广，在水处理过程中避免材料表面碳的沉积，防止材料失活增加催化剂寿命，不会造成二次污染。
(2)本发明通过浸渍-高温分解还原两步法制得催化剂，制备工艺简单，原料价廉易得，生产成本低。
(3)本发明在催化剂制备过程中通过还原气氛形成纳米金属颗粒，利用金属间的协同作用，改变晶格结构，产生大量氧空位，促进催化剂表面金属离子价态转换，提高H2O2分解生成足量羟基自由基的速率，羟基自由基将污水样中的有机物充分氧化成CO2与H2O以达到降解目的。
附图说明
图1为实施例1制备完成的铁镍钴三元合金催化剂的XRD结果图；
图2为实施例1制备完成的铁镍钴三元合金催化剂的XPS结果图。
具体实施方式
为更好的理解本发明所述的技术方案，下面结合附图和实施例对本发明作进一步详细说明，但是本发明的实施方式不局限于此，本发明要求保护的范围也不局限于实施例表示的范围。
实施例1：
按照摩尔比为8:1:1称取一定量的硝酸铁、硝酸镍及硝酸钴，溶于100mL去离子水中，室温下搅拌60min得到均一的活性物前驱体浸渍液；在活性物前驱体浸渍液中加入15g的活性炭基体，于25℃下搅拌24h，让活性炭在金属盐溶液中充分浸渍；将浸渍结束的活性炭基体捞出，置于40℃条件下，在空气中干燥12h，制得催化剂半成品；将催化剂半成品置于650℃高温煅烧炉内，在摩尔比为H2/Ar＝1/8的还原气氛中煅烧4h，在煅烧过程中高温煅烧炉的升温速率为5℃/min，降温速率为15℃/min，冷却后即得催化剂。
实施例2：
按照摩尔比为20:4:1称取一定量的氯化铁、氯化镍及硫酸铜，溶于100ml去离子水中，室温下搅拌20min得到均一的活性物前驱体浸渍液；在活性物前驱体浸渍液中加入10g分子筛ZSM-11载体，于60℃下搅拌浸渍18h；将浸渍结束的分子筛ZSM-11载体捞出，置于70℃条件下，在空气中干燥8h，制得催化剂半成品；将催化剂半成品置于250℃高温煅烧炉内，在摩尔比为H2/He＝1/10的还原气氛中煅烧12h，在煅烧过程中高温煅烧炉的升温速率为1℃/min，降温速率为3℃/min，冷却后即得催化剂。
实施例3：
按照摩尔比为13:6:2称取一定量的硫酸铁、硫酸镍及氯化锡，溶于100ml去离子水中，室温下搅拌40min得到均一的活性物前驱体浸渍液；在活性物前驱体浸渍液中加入5g堇青石基体，于80℃下浸渍2h；将浸渍结束的堇青石基体取出，置于90℃条件下，在空气中干燥4h，制得催化剂半成品；将催化剂半成品置于500℃高温煅烧炉，在摩尔比为H2/N2＝1/2的还原气氛中煅烧8h，在煅烧过程中高温煅烧炉的升温速率为3℃/min，降温速率为1℃/min，冷却后即得催化剂。
实施例4：
按照摩尔比为10:3:1称取一定量的氯化铁、氯化镍及氯化锰，溶于100ml去离子水中，室温下搅拌50min得到均一的活性物前驱体浸渍液；在活性物前驱体浸渍液中加入50g固体Al2O3基体，于50℃下浸渍12h；将浸渍结束的固体Al2O3基体取出，置于70℃条件下，在空气中干燥8h，制得催化剂半成品；将催化剂半成品置于850℃高温煅烧炉，在摩尔比为H2/N2/He＝1/3/9的还原气氛中煅烧1h，在煅烧过程中高温煅烧炉的升温速率为10℃/min，降温速率为4℃/min，冷却后即得催化剂。
实施例5：
按照摩尔比为20:7:2称取一定量的硝酸铁、硝酸镍及氯化锑，溶于100ml去离子水中，室温下搅拌35min得到均一的活性物前驱体浸渍液；在活性物前驱体浸渍液中加入35g椰壳活性炭基体，于40℃下浸渍10h；将浸渍结束的椰壳活性炭基体取出，置于50℃条件下，在空气中干燥7h，制得催化剂半成品；将催化剂半成品置于600℃高温煅烧炉，在摩尔比为H2/N2/Ar/He＝1/9/2/4的还原气氛中煅烧6h，在煅烧过程中高温煅烧炉的升温速率为20℃/min，降温速率为5℃/min，冷却后即得催化剂。
图1和图2分别是实施例1中制得催化材料的XRD图谱和XPS图谱，结合图谱可以明显看出主要的衍射峰分别对应铁镍合金及铁钴合金，证实该催化材料活性组分以合金纳米颗粒负载于催化剂上。
将实施例1-5制得的催化剂进行降解效果对比测试评价，评价方式如下：催化剂反应温度为室温，使用H2O2作为氧化剂，H2O2用量为200mg/L，采用浓度为500mg/L某焦化厂二沉池出水作为待降解溶液；实验量取50ml水样加入1g催化剂，不断搅拌持续反应60min，待反应结束，将剩余溶液倒掉重新加入新的待降解溶液继续催化降解实验，其中催化剂不变，并重复该实验10次，记录每次水样的COD降解率。
对实施例1-5制得的催化剂采用某焦化厂废水进行降解效果测试结果如表1。从表中可以看出催化剂具有高活性及稳定性优秀性能，同时不同制备工艺条件对催化材料的性能有很大影响。经过降解反应，催化剂对待降解水样的COD去除率能达到80％以上，经过10次反应，催化剂对水样的降解率仍能达到65％以上，其高稳定性即对水样的降解下降不超过20％，再次证实该材料金属离子溶出率低且反复催化活性较好，能够广泛应用于工业化生产。
表1
Claims (7)
1.一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂，其特征在于，该催化剂由多孔性载体、含铁镍元素纳米合金颗粒的活性物前驱体浸渍液、含H2还原气氛制得。
2.根据权利要求1所述的一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂，其特征在于，所述多孔性载体为陶瓷材料、碳基载体、沸石、堇青石、Al2O3、多孔分子筛、泡沫金属材料中的任意一种。
3.根据权利要求2所述的一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂，其特征在于，所述碳基载体为：煤质活性炭、椰壳活性炭、合成材料活性炭、碳纤维、碳棒、碳纳米管、碳毡、碳纸或碳布任意一种。
4.根据权利要求1所述的一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂，其特征在于，所述活性物前驱体浸渍液是含铁盐、镍盐、第三种金属元素盐的溶液；所述铁盐与镍盐的摩尔比为1:0.2～100，所述铁盐和镍盐的总摩尔与第三种金属元素盐的摩尔比为1:0.01～0.2。
5.根据权利要求4所述的一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂，其特征在于，所述铁盐为氯化铁、硫酸铁、硝酸铁及醋酸铁中的一种或几种；所述镍盐为氯化镍、硫酸镍及硝酸镍中的一种或几种；所述第三种金属元素盐为含有Co、Cu、Mn、Sn、Mo、Ce、Pt、W其中一种金属元素的氯化盐、硫酸盐及硝酸盐中的一种或几种。
6.根据权利要求1所述的一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂，其特征在于，所述含H2还原气氛为单一H2或者H2与惰性气体组成的混合气；所述混合气中H2与惰性气体总摩尔的摩尔比为1:0.01～24；所述惰性气体为N2、Ar、He中的一种或几种。
7.根据权利要求1至6任意一项所述的一种用于双氧水分解生成羟基自由基降解有机废水的三元纳米合金催化剂的制备方法，其特征在于，其包括以下步骤：
步骤1：配制活性物前驱体浸渍液，将铁盐、镍盐、第三种金属元素盐和去离子水按比例混合，在室温下搅拌20～60min，制得活性物前驱体浸渍液；
步骤2：浸渍和干燥，将多孔性载体置入活性物前驱体浸渍液中，在25℃～80℃条件下浸渍2～24h，然后将载体捞出置于60～90℃条件下，在空气中干燥4h～12h，制得催化剂半成品；
步骤3：高温煅烧，将催化剂半成品置于250℃～850℃的煅烧炉内，在还原气氛中煅烧1h～12h，在煅烧过程中高温煅烧炉的升温速率为1～20℃/min，降温速率为1～15℃/min；冷却后即得催化剂。
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