CN107416942A - 一种微波辅助快速降解染料废水的方法 - Google Patents
一种微波辅助快速降解染料废水的方法 Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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Abstract
本发明公开了一种微波辅助快速降解有机染料废水的方法,在有机染料废水中,加入双功能负载型ZnFe2O4/SiC催化剂,采用微波加热辅助处理实现有机废水快速降解,其中,微波的功率为100‑400W,反应时间为20‑60s。本发明利用载体的强吸波特性,实现在微波中与催化剂诱导催化的协同作用,具有降解速度快,降解效率高,无二次污染的特点,可以在较短的时间内实现有机废水,尤其是常规方法难以降解的偶氮型有机废水的快速降解,在纺织印染等工业废水处理的应用方面有着广阔的前景。
Description
技术领域
本发明属于有机废水处理技术领域,涉及一种微波辅助快速降解染料废水的方法。
背景技术
染料工业是我国国民经济中的重要行业,染料的产量和贸易额都居世界第一位。染料在生产和处理过程中会排放出大量废水,其中有机物含量大,一般都具有复杂的芳香环结构,对环境和自然水体有极强污染性。其中的偶氮类染料,有一定致癌作用,极难降解(Journal of Hazardous Materials,177,781-791;Applied Catalysis A General,2009,359,25-40)。目前国内外对染料废水的处理方法主要有物理法、化学法及生物法。
其中物理法主要包括吸附法和膜分离技术。使用较多的吸附法有活性炭吸附(Mahmoodi N M,Salehi R,Arami M.Binary system dye removal from colored textilewastewater using activated carbon:Kinetic and isotherm studies[J].Desalination,2011,272(1):187-195.)、矿物吸附(Vimonses V,Lei S M,Jin B,etal.Kinetic study and equilibrium isotherm analysis of Congo Red adsorption byclay materials.[J].Chemical Engineering Journal,2009,148(2–3):354-364.)、固体废弃物吸附(Cui L,Guiping W U,Deng K.Adsorption performance and mechanism ofbinding of dye by protonated coke waste[J].Journal of Chemical Industry&Engineering,2007,58(5):1290-1295.)、改性生物质吸附(Ping L I,Gong L.AdsorptionTreatment of Dyeing Wastewater Using Fallen Leaves as Adsorbent[J].Journal ofQingdao University of Science&Technology,2012.)等。该类方法存在的主要问题有吸附剂再生性差,吸附量小。膜分离技术主要有超滤和纳滤(Cong W,Xiang H,Zhang G L,etal.DYEING WASTEWATER TREATMENT AND REUTILIZATION THROUGH ULTRAFILTRATION ANDNANOFILTRATION INTEGRATED MEMBRANE PROCESSES[J].Technology of WaterTreatment,2008.)、反渗透技术(Fan L L,Ren-Wu L U,Chen W P.Test Study of DyeingWastewater Treatment by Reverse Osmosis Technology[J].Environmental Science&Technology,2009.)。膜分离过程中膜容易堵塞且费用高昂。此外,物理法处理不能达到对废水中的污染物进行降解,容易造成二次污染。
常用的化学法主要有电化学法和高级氧化法。电化学法包括电化学还原及电化学氧化(A,Y,Koparal AS,et al.Carbon sponge as a new cathode materialfor the electro-Fenton process:Comparison with carbon felt cathode andapplication to degradation of synthetic dye basic blue 3in aqueous medium[J].Journal of Electroanalytical Chemistry,2008,616(1–2):71-78.)和电凝胶电气浮法(Balla W,Essadki A H,Gourich B,et al.Electrocoagulation/electroflotation ofreactive,disperse and mixture dyes in an external-loop airlift reactor[J].Journal of Hazardous Materials,2010,184(1-3):710.)。而该类化学处理法存在以下问题:单位电耗大,成本过高以及电极材料制备复杂。高级氧化法包括光催化氧化法(Sun JH,Dong S Y,Wang Y K,et al.Preparation and photocatalytic property of a noveldumbbell-shaped ZnO microcrystal photocatalyst.[J].Journal of HazardousMaterials,2009,172(2–3):1520-1526.),Fenton及类Fenton氧化法(Sun S P,Li C J,SunJ H,et al.Decolorization of an azo dye Orange G in aqueous solution by Fentonoxidation process:effect of system parameters and kinetic study.[J].Journalof Hazardous Materials,2009,161(2):1052-1057.)和O3氧化法(Khadhraoui M,Trabelsi H,Ksibi M,et al.Discoloration and detoxicification of a Congo reddye solution by means of ozone treatment for a possible water reuse[J].Journal of Hazardous Materials,2009,161(2–3):974-981.),此方法局限于催化剂价格贵、光能利用率低、反应器复杂、工艺条件苛刻、运转费用高产生污泥较多等。
常用的生物法有微生物处理法、好氧法、厌氧法及厌氧-好氧联合法。微生物处理法主要利用真菌、细菌和藻类等产生的酶进行降解。该方法对有机废水的降解不足有处理时间长、效果不稳定及抗冲击能力差,而且还会产生大量二次污染物,同时酶对环境的适应性差,成本高也制约了该方法的使用。
非均相Fenton催化氧化是比较有效的处理难降解有机污染物的方法,而铁基非均相Fenton催化剂具有较高磁性,可以容易利用外加磁场将其从溶液中分离。为了提高铁基催化剂的活性和稳定性,可以通过掺杂金属、非金属等方式对其进行改性,目前已有一些新颖的二元金属氧化物如铁酸盐等非均相Fenton催化剂用于有机废水处理的报道。本发明利用铁酸锌的高效催化性,并将其负载于具有高效微波吸收性的碳化硅载体上,制备出高效、稳定的双功能催化剂/微波吸收剂,将其用于微波辅助的有机废水处理,可以实现有机废水的快速降解。
发明内容
发明目的:本发明的目的是提供一种微波辅助快速降解有机染料废水的方法,可以实现微波辅助条件下快速高效降解有机废水。
技术方案:为了实现上述发明目的,本发明采用的技术方案为:
一种微波辅助快速降解有机染料废水的方法:在有机染料废水中,加入双功能负载型ZnFe2O4/SiC催化剂,采用微波加热辅助处理实现有机废水快速降解,其中,微波的功率为100-400W,反应时间为20-60s。
所述双功能负载型ZnFe2O4/SiC催化剂与有机染料的质量比为12.5:1~75。
所述微波的功率300W,反应60s。
所述双功能负载型ZnFe2O4/SiC催化剂是将ZnFe2O4及SiC按照1:1的比例通过溶胶凝胶法制备而成。
所述溶胶凝胶法,具体过程如下:
1)取摩尔比至少为2:1的Fe(NO3)3·9H2O和Zn(NO3)2·6H2O溶于去离子水中,在55~65℃条件下,加热搅拌30-40min;
2)取柠檬酸,加入到步骤1)的混合溶液中,在80-90℃加热条件下,继续搅拌反应2-3h;
3)加入SiC粉末,再搅拌反应4-6h,反应结束后,经旋蒸除水,然后将混合物放入烘箱中,100~120℃烘干过夜,得到催化剂前体;
4)经400~900℃氮气保护煅烧2-4h,最终得到催化剂ZnFe2O4/SiC;
其中,SiC占催化剂总质量的50%。
步骤1)中,60℃下搅拌30min。
步骤2)中,柠檬酸的摩尔加入量为锌的3-6倍,搅拌反应2h。
步骤3)中,碳化硅加入后搅拌反应4h。
步骤4)中,煅烧温度600℃,煅烧时间2h。
所述有机废水中的有机模型物为甲基橙、亚甲基蓝、结晶紫、罗丹明B。
有益效果:与现有的技术相比,本发明的优点包括:本发明采用溶胶凝胶法制备出新型的双功能负载型ZnFe2O4/SiC催化剂,在微波作用下,表面会形成高温热点,均匀的分布于ZnFe2O4/SiC催化剂的表面,促进催化剂表面的活性位点和电子空穴的产生,可以和氧气以及水反应形成多种活性成分,如羟基自由基和超氧负离子自由基等,从而实现甲基橙的快速氧化降解。经试验,在ZnFe2O4催化协同作用下,经微波辅助可在短时间内实现有机废水快速降解,具有催化降解效率高,降解速度快,无二次污染等优点,是一种快速处理有机废水的新方法。
附图说明
图1是ZnFe2O4/SiC催化剂的扫描电子显微镜图;
图2是ZnFe2O4/SiC催化剂的透射电子显微镜图;
图3是ZnFe2O4/SiC催化剂的红外图谱;
图4是催化剂对甲基橙的降解效果图;
图5是催化剂对亚甲基蓝的降解效果图;
图6是催化剂对结晶紫的降解效果图;
图7是催化剂对罗丹明B的降解效果图。
具体实施方式
下面结合具体实施例对本发明的具体实施方式做详细的说明。
以下实施例中采用的分析方法为:利用紫外-可见光分光光度计在465nm处对溶液的吸光值进行测定。配置不同浓度的甲基橙标准溶液,绘制甲基橙溶液的标准曲线,根据公式(1)计算出甲基橙的降解率:
公式中C0代表了初始甲基橙浓度,Ct代表了反应时间t分钟后,溶液中甲基橙的浓度。
所制备的ZnFe2O4/SiC用于有机染料废水的降解:
实施例1双功能负载催化剂ZnFe2O4/SiC的制备
催化剂ZnFe2O4-SiC的制备采用凝胶溶胶法。称取质量摩尔比为2:1的Fe(NO3)3·9H2O和Zn(NO3)2·6H2O溶于100mL的去离子水中,在60℃条件下,加热搅拌30min。之后称取柠檬酸(与Zn(NO3)2·6H2O的摩尔比为6:1),加入到混合溶液中,在80℃加热条件下,继续搅拌反应2h。反应时间到后,加入碳化硅粉末,再搅拌反应4h,反应结束后,经旋蒸除水后,将混合物放入烘箱中,120℃烘干过夜,得到催化剂前体,再在700℃氮气保护煅烧2h,最终得到ZnFe2O4/SiC催化剂,放入干燥器,备用,在ZnFe2O4/SiC催化剂中,SiC的质量占50%。
对ZnFe2O4/SiC催化剂进行表征,扫描电子显微镜图如图1所示,从图中可以看出:该催化剂是粒径分布均匀的球状颗粒,分散相对比较均匀且颗粒间空隙较小;但由于该催化剂本身的强磁性导致催化剂有一定的聚集现象。透射电子显微镜图如图2所示,从图中可以观察到:ZnFe2O4负载在立方晶SiC表面,大量填充在ZnFe2O4-SiC内部。上述结果表明,ZnFe2O4成功负载到SiC表面,SiC作为载体,使得ZnFe2O4-SiC表面孔增加。红外图谱如图3所示,从图中可以看出:在3400cm-1处的吸收峰是羟基的伸缩振动特征峰;在1620cm-1有很强的吸收峰,这是由于催化剂表面吸附的水分子的O-H伸缩振动引起的;在1400cm-1处的吸收峰是由N-O键的伸缩振动引起的;在550m-1和474-1处的两个吸收峰,分别对应于四面体和八面体位置的固有伸缩振动,进一步表明形成铁氧体,催化剂表面吸附的水分子更容易产生活性粒子,如羟基自由基,使得催化剂催化活性增强。
实施例2
微波降解实验使用的反应装置为Milestone Ethos A微波消解仪,过程如下:
准确量取20mL甲基橙(MO)水溶液(40mg/L)转移到聚四氟乙烯反应管中,在溶液中加入60mg的催化剂ZnFe2O4/SiC(实施例1制备),并加入搅拌磁子。关紧反应管,放入微波反应器(Milestone Ethos A)中,在300W的功率下加热60s,反应结束冷却至室温取出,经离心分离后,取上层清液,用紫外-可见光分光光度计测其吸光值,检测结果如图4显示在其最大吸收波长465nm处的吸光值为0,并计算出MO的降解产率为100%。
实施例3
微波降解实验使用的反应装置为Milestone Ethos A微波消解仪,过程如下:
准确量取20mL亚甲基蓝(MB)水溶液(40mg/L)转移到聚四氟乙烯反应釜中,在溶液中加入60mg的催化剂ZnFe2O4/SiC(实施例1制备)。关紧反应釜,放入微波反应器中,在300W的功率下加热60s,反应结束冷却至室温取出,经离心分离后,取上层清液,用紫外-可见光分光光度计测其吸光值,检测结果如图5显示在其最大吸收波长662nm处的吸光值为0。
实施例4
微波降解实验使用的反应装置为Milestone Ethos A微波消解仪,过程如下:
准确量取20mL结晶紫(CV)水溶液(40mg/L)转移到聚四氟乙烯反应釜中,在溶液中加入60mg的催化剂ZnFe2O4/SiC(实施例1制备)。关紧反应釜,放入微波反应器中,在300W的功率下加热60s,反应结束冷却至室温取出,经离心分离后,取上层清液,用紫外-可见光分光光度计测其吸光值,检测结果如图6显示在其最大吸收波长590nm处的吸光值为0。
实施例5
微波降解实验使用的反应装置为Milestone Ethos A微波消解仪,过程如下:
准确量取20mL罗丹明B(Rhodamine B)水溶液(40mg/L)转移到聚四氟乙烯反应釜中,在溶液中加入60mg的催化剂ZnFe2O4/SiC(实施例1制备)。关紧反应釜,放入微波反应器中,在300W的功率下加热60s,反应结束冷却至室温取出,经离心分离后,取上层清液,用紫外-可见光分光光度计测其吸光值,检测结果如图7显示在其最大吸收波长554nm处的吸光值为0。
实施例6
分别称取60mg实施例1制备的催化剂ZnFe2O4/SiC放入到两个50mL圆底烧瓶中,各加入20mL的甲基橙溶液,采用油浴或微波分别加热反应,反应结束冷却至室温取出,经离心分离后,取上层清液,用紫外-可见光分光光度计测其吸光值,结果如表1所示。
表1两种不同的加热方式对甲基橙有机废水的降解效果对比
时间(min) | 温度(℃) | 降解率(%) | |
油浴加热 | 110 | 80 | 100 |
微波加热 | 1 | 78 | 100 |
表1的结果表明:在微波条件下,降解时间大大缩短,反应速度大幅度加快是传统条件(油浴)下降解速度的100多倍,微波可有效促进有机废物的降解反应。
Claims (10)
1.一种微波辅助快速降解有机染料废水的方法,其特征在于:在有机染料废水中,加入双功能负载型ZnFe2O4/SiC催化剂,采用微波加热辅助处理实现有机废水快速降解,其中,微波的功率为100-400W,反应时间为20-60s。
2.根据权利要求1所述的微波辅助快速降解有机染料废水的方法,其特征在于:所述双功能负载型ZnFe2O4/SiC催化剂与有机染料的质量比为12.5:1~75。
3.根据权利要求1所述的微波辅助快速降解有机染料废水的方法,其特征在于:所述微波的功率300W,反应60s。
4.根据权利要求1所述的微波辅助快速降解有机染料废水的方法,其特征在于:所述双功能负载型ZnFe2O4/SiC催化剂是将ZnFe2O4及SiC按照1:1的比例通过溶胶凝胶法制备而成。
5.根据权利要求4所述的微波辅助快速降解有机染料废水的方法,其特征在于:所述溶胶凝胶法,具体过程如下:
1)取摩尔比至少为2:1的Fe(NO3)3•9H2O和Zn(NO3)2•6H2O溶于去离子水中,在55~65℃条件下,加热搅拌30-40min;
2)取柠檬酸,加入到步骤1)的混合溶液中,在80-90℃加热条件下,继续搅拌反应2-3h;
3)加入SiC粉末,再搅拌反应4-6h,反应结束后,经旋蒸除水,然后将混合物放入烘箱中,100~120℃烘干过夜,得到催化剂前体;
4)经400~900℃氮气保护煅烧2-4h,最终得到催化剂ZnFe2O4/SiC;
其中,SiC占催化剂总质量的50%。
6.根据权利要求5所述的微波辅助快速降解有机染料废水的方法,其特征在于:步骤1)中,60℃下搅拌30min。
7.根据权利要求5所述的微波辅助快速降解有机染料废水的方法,其特征在于:步骤2)中,柠檬酸的摩尔加入量为锌的3-6倍,搅拌反应2h。
8.根据权利要求5所述的微波辅助快速降解有机染料废水的方法,其特征在于:步骤3)中,碳化硅加入后搅拌反应4h。
9.根据权利要求5所述的微波辅助快速降解有机染料废水的方法,其特征在于:步骤4)中,煅烧温度600℃,煅烧时间2h。
10.根据权利要求1所述的微波辅助快速降解有机染料废水的方法,其特征在于:所述有机废水中的有机模型物为甲基橙、亚甲基蓝、结晶紫、罗丹明B。
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