CN109647378B - 一种用于去除异味硫化氢的纳米片自组装微米球光催化材料的制备方法 - Google Patents
一种用于去除异味硫化氢的纳米片自组装微米球光催化材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种WO3·H2O纳米片自组装微米球光催化剂的水热制备方法,其特征在于制备的步骤为:1)WO3·H2O的前驱物的制备:将一定量的Na2WO4·2H2O溶于一定量的去离子水中,在搅拌下加入一定量的全氟丁基磺酸钾和柠檬酸,充分搅拌后加入稀盐酸,充分搅拌。2)在温度为60‑150℃,前驱物水热反应4‑50 h。然后将产物离心、水洗、于60℃下空气中干燥。本发明获得了WO3·H2O纳米片自组装而成的微米球催化剂材料,该光催化剂具备高效稳定的光催化性能用于去除异味硫化氢。
Description
技术领域
本发明属于光催化材料技术领域,具体涉及一种用于去除异味硫化氢的WO3·H2O纳米片自组装微米球光催化材料的制备方法。
背景技术
硫化氢(H2S)是高度腐蚀性和刺激性的有毒害气体, 往往很低浓度的H2S就可对人身健康和自然界造成严重的危害,是许多工业生产中的副产品。 例如,石油精炼、天然气净化、皮革制造、橡胶合成、煤气制取、造纸、石油化工、化肥、制药、污水处理和垃圾处理等等过程中都会产生大量硫化氢恶臭气体,不仅严重影响人们的日常生活,危害人体健康,同时也污染环境。H2S在空气中的最高容许浓度 10mg/m3,对人体健康的危害主要是通过呼吸道吸入或皮肤侵入。我国对环境大气、车间空气及工业废气中的硫化氢浓度已有严格的规定。居民区环境大气中硫化氢的浓度最高不得超过0.01mg/m3;国家规定的环境恶臭污染物控制标准中硫化氢的厂界一级标准值为小于0.03mg/m3;车间工作地点空气中硫化氢的浓度最高不得超过10mg/m3;城市煤气中硫化氢的浓度不得超过20mg/m3;油品炼厂废气中硫化氢的浓度要求净化至10~20mg/m3。硫化氢是强烈的神经毒物,当高浓度时可直接抑制呼吸中枢,引起迅速窒息而致死亡。随着人类对环境的要求越来越严格,对排气中硫化物浓度也提出了更严格的要求,因此, 硫化氢去除问题日显突出。
目前,国内外越来越重视去除H2S方法的研究。处理H2S的传统方法主要有三种,物理法只适宜处理低浓度、范围小的恶臭,且成本较高;化学法除臭不持久,除臭设施投资和运行费用高;生物法虽成本低廉,效果好,但菌种的筛选培养较为困难,见效稍慢。光催化氧化反应是一种高级的氧化过程(Advanced Oxidation process,简称AOP),与传统方法相比较,由于光催化方法反应条件温和、能耗低、无二次污染、可以在常温常压下氧化分解结构稳定的化合物、材料本身在反应过程中并不消耗、在正常气压下操作、可重复使用等优点,光催化技术逐渐成为备受瞩目的一种恶臭气体治理方法。
光催化氧化去除H2S的核心关键是开发有效的光催化剂。中国专利CN106732818A公开了一种TiO2@MIL-100双层中空材料对硫化氢气体有着很好的光催化效果,但其材料的合成分三步进行,且需要聚苯乙烯纳米球为模板,高温煅烧等苛刻条件;中国专利CN101927173A公开了一种原子比为Zn : Cd =7:3的光催化剂ZnIn2S4-CdIn2S4在高压汞灯光照下可以光催化分解硫化氢,众所周知,高压汞灯光源存在高耗能、危险性高等缺点;中国专利CN102671537A公开了锐钛矿型的改性负载光催化剂ACF/Fe/Ce/TiO2可以将低浓度的硫化氢气体在光催化反应器中15~30w紫外灯下进行吸附光解,但其应用局限于低浓度(1ppm)的H2S气体吸附光解;中国专利CN101760272A公开了TiO2负载在过渡金属改性MCM-41分子筛表面制得催化剂在可见光下将空气和沼气的混合气通入到光催化反应器中,将混合气中的硫化氢光催化氧化为硫酸盐沉积在催化床上,此方法只是将硫化氢转换为硫酸盐沉积,未能在光降解H2S的同时产生氢气等能源气体;中国专利CN101623646公开了一种丝光沸石负载型CdS光催化剂可以可见光分解硫化氢;中国专利CN101293632公开了一种贵金属担载的Cd1-yZnyS光催化剂在可见光下分解硫化氢, 但以上两种材料都属于硫化物,其本身在光催化应用中都存在着易光腐蚀,催化剂不稳定等缺点,此外催化剂中所含Cd元素属于重金属,毒性大,对于人体以及环境都有较大伤害,并不适合大规模投入使用。
发明内容
针对现有技术的不足,本发明的目的在于提供一种WO3·H2O纳米片自组装的微米球的光催化材料的制备方法,用于去除硫化氢气体,其光催化效率高,合成方法简单易行,安全低耗,无毒无害,绿色环保,可大规模使用。
为达此目的,本发明采用以下技术方案 :
一种基于纳米片自组装成微米球WO3·H2O材料的制备方法,包括以下步骤:
1)将Na2WO4·2H2O溶于去离子水中,充分搅拌使之完全溶解。
2)将一定量的全氟丁基磺酸钾加入步骤1)所得溶液中,搅拌5-30min。
3)将一定量的柠檬酸加入步骤2)所得溶液中,搅拌5-60min。
4)将一定量的盐酸溶液逐滴加入到步骤3)所得溶液中,于室温下充分搅拌0.5-1h。
5)将上述步骤所得溶液转移至100ml反应釜中,在一定温度下水热反应一段时间,将所得沉淀产物进行离心、洗涤、烘干,得到由纳米片自组装的微米球的WO3·H2O。
按上述方案,步骤1)所述的Na2WO4·2H2O为0.25-2mmol。
按上述方案,步骤2)所述的全氟丁基磺酸钾为0-5mmol。
按上述方案,步骤3)所述的柠檬酸为1-10mmol。
按上述方案,步骤4)所述的盐酸浓度为1-5mol/L,加入量为1-10mL。
按上述方案, 步骤 5) 所述的水热反应温度为60-150℃,水热反应时间为4-50h。
本发明提出在表面活性剂(全氟丁基磺酸钾)和柠檬酸的作用下,在一步水热反应中WO3·H2O结晶形成纳米片,进而自发组装为微米球。
WO3·H2O纳米片自组装微米球的光催化材料的光催化活性是通过在紫外灯照射下对硫化氢气体进行吸附光解来进行测试的。
WO3· H2O纳米片自组装微米球的光催化材料的物理性能表征方法:用X射线衍射(XRD)光谱分析产物物质组成及结构情况,用场发射扫描电镜(FESEM)观察产物的形貌。
本发明的优点在于:本发明所述的纳米片自组装微米球的WO3·H2O光催化材料的制备方法简便易行,水热反应条件温和,不需高温、高压、强酸等苛刻的合成条件,通过一步水热即可得到形貌均匀的WO3·H2O纳米片自组装微米球光催化材料。
与现有技术相比,本发明的有益效果为:
本发明通过简单的一步水热法制备的WO3·H2O纳米片自组装微米球光催化材料,形貌均一,性能稳定,用于硫化氢气体降解,光催化效率高,催化剂在254nm光照下均具有良好的光催化降解硫化氢的效果,紫外可见光吸收性能好,适合广泛应用于有毒及污染化学物质降解及洗消领域。
附图说明
图1为实例1合成方法所制得产物的XRD谱图。
图2为实例1合成方法所制得产物的SEM照片。
图3为实例1所得催化剂的光催化分解硫化氢气体两次循环实验的效果图。
图4为实例1光催化分解硫化氢气体实验装置示意图。
附图标记如下:
1-支架;2-氨浓度监测仪;3-流量计;4-风扇;5-紫外灯;6-催化剂;7-硫化氢钢瓶。
具体实施方式
下面结合实施例进一步说明本发明,该实例只用于说明本发明,并不限制本发明。
实施例一
纳米球的制备,具体步骤如下:
将0.5mmol Na2WO4·2H2O加入至70mL 去离子水中,搅拌至溶解,再加入0.5mmol全氟丁基磺酸钾,搅拌5min 后加入2mmol 柠檬酸,使混合溶液充分搅拌15min后缓慢滴入5mL 3mol/L的盐酸溶液,于室温下充分搅拌30min,随后将其移入100mL聚四氟乙烯内村,密封置于高压反应釜钢套中,于烘箱中恒温100℃保持8小时,水热结束使其自然降温。将合成好的样品,用去离子水和乙醇离心洗涤3次,将得到的催化剂60℃恒温干燥10h,充分研磨即得催化剂。用这种方法合成的催化剂具有较高的结晶度,且与WO3·H2O标准卡片PDF#43-0679完全吻合(如图1)。其形貌均一,是由50-100nm厚度的纳米片组装而成的微米球,直径约为2-3μm。
实施例二
硫化氢气体的光催化降解实验,具体步骤如下:
本发明的光催化降解硫化氢气体性能实验中的实验装置如图4所示。光催化实验测试在25℃温度,50%RH湿度下的环境测试舱内进行,环境测试舱内的尺寸为3立方米。光催化实验装置的测试舱内包括从上至下依次设置的风扇4、紫外灯5、催化剂6、支架1,所述光催化装置的一端连接有硫化氢气体钢瓶,另一端与所述硫化氢浓度监测仪2连接,其中,硫化氢气体流量通过流量计3控制,通入硫化氢的量为80mL/min,90s催化剂的用量为3g,以分散粉体的形式喷撒在面积为15cm*35cm的玻璃纤维载体上,厚度为1.0 mm。所用光源为直型波长254nm紫外灯。硫化氢的流量采用北京七星华创电子股份有限公司生产的D07系列型硫化氢气体流量计控制。硫化氢的浓度测试采用东莞市威拓仪器有限公司生产的HYCA-1硫化氢检测仪,检测限为:0-100ppm,灵敏度为0.01ppm。
实验过程:调节测试舱的温度为25℃,湿度为50%RH,关闭测试舱与外界联通的阀门,使之成为一个密闭体系,往测试舱内注入硫化氢,控制在6ppm左右,再进行相应的测试。
在图4的光催化反应装置中的两次循环实验结果如图3所示,经过四个小时的光催化反应,舱内H2S的浓度可由5.25ppm降低至0ppm附近,显示出较为突出的光催化降解H2S性能,并且经过两次循环实验,降解效果基本保持不变,可见本发明的催化剂具备高效且稳定的光催化降解H2S的效果。
Claims (3)
1.一种用于去除异味硫化氢的WO3·H2O纳米片自组装微米球光催化材料的制备方法,其特征在于:包括以下依次步骤:
1)将一定量的Na2WO4·2H2O溶于去离子水中,充分搅拌使之溶解;
2)将一定量的全氟丁基磺酸钾在搅拌下加入步骤1)所得溶液中,继续搅拌;
3)向步骤2)所得溶液中加入一定量的柠檬酸,然后充分搅拌;
4)将步骤3)中所得溶液中加入一定量稀盐酸,然后搅拌0.5-1 h;
5)将步骤4)所得浊液转移至100 mL反应釜中,在一定温度下水热反应一段时间,所得沉淀物经离心、洗涤、干燥,得到WO3·H2O纳米片自组装微米球;
所述Na2WO4·2H2O 为0.25-2 mmol,全氟丁基磺酸钾为0.5-5 mmol,柠檬酸为1-10mmol,去离子水为70 mL。
2.根据权利要求1所述的WO3·H2O纳米片自组装微米球光催化材料的制备方法,其特征在于:步骤4)所述稀盐酸浓度为1-5mol/L,加入量为1-10mL。
3.根据权利要求1所述的WO3·H2O纳米片自组装微米球光催化材料的制备方法,其特征在于:步骤5)所述水热反应温度为60-150 ℃,反应时间为4-24 h。
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