CN109225242B - 一种复合型纳米凹凸棒土陶粒臭氧催化剂及其制备方法和应用 - Google Patents
一种复合型纳米凹凸棒土陶粒臭氧催化剂及其制备方法和应用 Download PDFInfo
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- CN109225242B CN109225242B CN201811202810.XA CN201811202810A CN109225242B CN 109225242 B CN109225242 B CN 109225242B CN 201811202810 A CN201811202810 A CN 201811202810A CN 109225242 B CN109225242 B CN 109225242B
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- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 claims abstract description 13
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Abstract
本发明公开了一种复合型纳米凹凸棒土陶粒臭氧催化剂及其制备方法和应用,该催化剂由颗粒凹凸棒土陶粒及负载在颗粒凹凸棒土陶粒表面的掺杂Sb元素的TiO2固溶体复合催化剂构成。其制备方法包括以下步骤:(1)研磨成型;(2)干燥烧结;(3)浸渍水热纳米化:将烧结完成的凹凸棒土陶粒置于一定Ti、Sb摩尔比的混合溶胶溶液中,并在一定温度条件下进行震荡浸渍,运行结束后滤去浸渍液进行干燥;(4)焙烧活化;(5)重复处理:重复第三步和第四步即可得到复合型纳米凹凸棒土陶粒臭氧催化剂。本发明制备的催化剂应用于三维电极反应器中可以高效的处理氯霉素废水,降解效果彻底。
Description
技术领域
本发明属于环保领域,涉及一种复合型纳米凹凸棒土陶粒臭氧催化剂及其制备方法和应用。
背景技术
抗生素被广泛用于人类和动物传染性疾病的预防、治疗以及作为动物的生长促进剂。随着全球抗生素使用量的不断增长,抗生素在为人类及动物健康发展作出巨大贡献的同时,也带来了日益严重的环境问题。由于这些物质的大部分都难以被动物完全吸收,剩余物以母体化合物等形式排出,进而进入到环境中。这些残留于环境中的抗生素可以通过饮用水、畜禽产品等途径进入食物链,且微量抗生素即可能引起微生物的耐药性,将对人类健康和生态系统造成重大威胁。
抗生素废水中有机物氨氮和硫酸盐等含量高,且含有抗生素等生物抑制性物质,成分复杂,可生化性差,盐度高,毒性大,COD高,色度深,处理难度大。由于抗生素废水具有生物毒性大,含有抑菌物质等特点,传统的二级生化处理技术难以满足排放要求。由此,高级氧化技术应运而生,并得到迅速发展。三维电催化氧化作为一种高级氧化水处理技术,是通过电极和外加催化剂的作用产生羟基自由基等活性基团,将水中难降解有机污染物氧化降解为易生化处理的小分子物质,不仅操作简便、降解速度快,而且具有易建立密闭循环和无二次污染等优点,是一种极具产业前景的清洁净化方法。
三维粒子电极是三维电催化氧化反应体系中的重要组成部分,现有粒子电极主要以负载型γ-A12O3、负载型分子筛、负载型陶瓷、涂膜活性炭、负载催化剂的活性炭为主,但以上粒子电极仍存在以下问题:1、废水适用性差,如中国专利CN201610033469.4将Mn、Co和Ce负载在颗粒活性炭上制得粒子电极,但由于其两性特征,耐酸碱性较差,因此不适用于在强酸性强碱性的废水中使用;2、催化活性差,如中国专利CN1669942将活性炭和过渡金属通过粘结烧结后作为粒子电极催化剂,虽然提高了羟基自由基的产生量,但处理后的活性炭粒子电极比表面积大幅减少,降低了粒子电极的催化氧化能力;3、电流效率低,如中国专利CN200610161243.9以活性炭作为填料,通过对活性炭进行酸碱改性和负载金属离子改性等方式制得涂膜活性炭,该涂膜活性炭在三维电极体系中容易出现短路电流,从而降低了三维电极的电流效率。
发明内容
针对现有技术存在的上述不足,本发明解决三维粒子电极存在的废水适用性差、催化活性差、电流效率低等问题,提供一种具有催化氧化能力强、电流效率高、能耗低、稳定性好等优点的纳米臭氧催化剂的制备方法。
解决上述技术问题,本发明采用如下技术方案来实现:一种复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,包括以下步骤:
一种复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,包括以下步骤:
第一步,研磨成型:将一定质量的凹凸棒土和辅料充分混合后研磨至粉末状,按投加量为10~40mL水/100g凹凸棒土添加去离子水,混合均匀成浆状混合物并制成粒径为3-5mm的球形颗粒;所述辅料包括骨料添加剂、造孔剂、活性催化组分A以及粘结剂;所述的骨料添加剂为高岭土、石脂、蒙脱石、伊来石、水铝英石或蛭石中的一种或其组合,其与凹凸棒土的质量比为骨料添加剂:凹凸棒土=(1~45):100;所述的造孔剂为碳酸氢铵、碳酸钠、碳酸氢钠、粉煤灰、碳粉、木屑、尿素或碳酸铵中的一种或其组合,其与凹凸棒土的质量比为造孔剂:凹凸棒土=(0.01~5):100;所述的粘结剂为硅酸钠、糊精、石膏、磷酸钙、磷酸二氢钠、纤维素钠、壳聚糖、淀粉或长石中的一种或其组合,其与凹凸棒土的质量比为粘结剂:凹凸棒土=(0.1~10):100;所述的活性催化组分A为硝酸铁、氯化铁、硝酸锰、氯化锰、硝酸钴、硝酸镍、硝酸钼、硝酸锌、四氯化钛、钛酸丁酯、硝酸镍、硝酸铜、硝酸银、氯化金、硝酸铂、钨酸钠中的一种或多种金属盐与其中一种或多种金属盐的纳米颗粒的混合物,其与凹凸棒土的质量比为金属盐:金属盐纳米颗粒:凹凸棒土=(0.01~5):(1~5):100;
第二步,干燥烧结:将第一步制得的球形颗粒置于105℃±5℃恒温烘箱内干燥处理;将干燥处理后的球形颗粒用瓷坩埚盛装并置于马弗炉内进行预热、烧结,烧结完成后炉内自然冷却至常温即得凹凸棒土陶粒;
第三步,浸渍水热纳米化:在添加适量助溶剂的情况下,配制一定浓度的活性组分B无水乙醇溶液,并加入稳定剂,并在快速搅拌下添加去离子水,摇匀后形成透明稳定的混合溶胶溶液;将上述配制的混合溶胶溶液加入已放置一定量凹凸棒土陶粒的锥形瓶中,并将锥形瓶置于25-60℃恒温水浴摇床中震荡4.0~20.0h,并滴加碱性溶液,并辅以超声波震荡,运行结束后倾倒出上清液,置于105℃±5℃恒温烘箱内烘干;其中,所述的助溶剂为盐酸、硝酸、磷酸、钛酸丁酯、醋酸、草酸、柠檬酸、酒石酸中的任意一种;所述助溶剂添加体积为无水乙醇体积的(5~10)‰,其中无水乙醇与上述第一步中所投加的凹凸棒土质量比为(300~800)g:100g;所述的稳定剂为甲酸、乙酸、醋酸、酒石酸或丙二酸中的一种或其组合;所述稳定剂添加体积为无水乙醇体积的(0.5~2.0)‰;所述的活性组分B选自一种或多种含有Fe2+(如FeSO4、FeCl2等)、Sb3+(如SbCl3等)、Mn2+(如MnCl2等)、Co2+(如CoSO4、CoCl2等)、Ni2+(如NiSO4、NiCO3等)、Mo6+(如Na2MoO4等)、Zn2+(如ZnCl2、ZnBr2等)、Ti4+(如TiCl4等)、Ni2+(如NiSO4、NiCl2等)、Cu2+(如CuSO4、CuCl2等)、Ag+(如AgCl、AgNO3等)、Au3+(如AuCl3等)、W6+(如WCl6、WBr6等)的盐,活性组分B在无水乙醇溶液中的含量为0.5~5mol/L;所述去离子水投加比例为每100mL无水乙醇溶液添加(2~5)mL去离子水;所述碱性溶液投加比例为每100mL无水乙醇溶液添加(0.5~1.0)mL碱性溶液。
第四步,焙烧活化:将第三步经浸渍水热纳米化后的凹凸棒土陶粒用瓷坩埚盛装并置于马弗炉内进行焙烧,焙烧完成后炉内自然冷却至室温;
第五步,重复处理:上一步冷却后的凹凸棒土陶粒加入第三步的上清液中,辅以超声波震荡,运行结束后倾倒出上清液,凹凸棒土陶粒置于105℃±5℃恒温烘箱内烘干,并重复第四步即可得到复合型纳米凹凸棒土陶粒臭氧催化剂。
本发明上述的制备方法中,其进一步的技术方案是第一步中所述的凹凸棒土是莫氏强度为2.5~3.0,比重为2.20~2.30的天然粘土矿物。
本发明上述的制备方法中,其进一步的技术方案还可以是第二步中所述的一种纳米臭氧催化剂的制备方法,其特征在于,所述第二步中的干燥处理时间为1~3h。
本发明上述的制备方法中,其进一步的技术方案还可以是第二步中所述的升温程序为在预热温度为500~600℃下预热30~20min,在烧结温度为500~1200℃下烧结30~100min;所述马弗炉升温速率为10℃/min。
更进一步地,本发明上述的制备方法中,其技术方案还可以是第三步中所述的碱性溶液为氢氧化钠、磷酸钠或磷酸氢钠的溶液,浓度为0.2~4mol/L,滴加速率为50-300滴/min,持续时间为4.0~10.0h。
更进一步地,本发明上述的制备方法中,其技术方案还可以是第三步中所述的助溶剂优选盐酸,盐酸浓度优选5.0mol/L;稳定剂优选甲酸或乙酸,甲酸或乙酸浓度优选2.0mol/L;所述的去离子水与无水乙醇的体积比为1:30~70。
更进一步地,本发明上述的制备方法中,其技术方案还可以是第三步中所述的超声波功率为50-1000w,持续时间为4.0-20.0h。
更进一步地,本发明上述的制备方法中,其技术方案还可以是第四步中所述的升温程序为在450~800℃温度下焙烧3.0~2.0h。所述马弗炉升温速率为10℃/min。
更进一步地,本发明上述的制备方法中,其技术方案还可以是第五步中所述的重复处理重复第三步和第四步的次数为1~4次。
更进一步地,本发明上述的制备方法中,其技术方案还可以是所述的一种复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法的复合型纳米Ti-Sb/凹凸棒土陶粒臭氧催化剂用于降解抗生素废水的应用、抗生素废水为氯霉素废水、青霉素废水、红霉素废水、链霉素废水、万古霉素废水或吡哌酸废水。
本发明与现有技术相比,具有以下优点及突出性的技术效果:①经活性组分负载后,凹凸棒土陶粒表面呈现平整且致密的结构特征,原有的孔道被遮盖,纳米臭氧催化剂比表面积得到大幅提高;②经活性组分负载后,金属Ti晶粒数量显著增加,且新生长的方锑矿Sb2O3的晶粒尺寸较小,粒子电极表面催化活性得到大幅提高,羟基自由基产生量高,因此保证了负载型三维粒子电极具备较高的结构稳定性、催化剂流失量低和催化活性高的特点;③本发明用多次浸渍、煅烧法制备一种作为负载型三维粒子电极催化剂,制备的粒子电极多孔,比表面积大、吸附性能强、导电性能和催化性能良好,是一种新型的粒子电极,大大增加了电极的面体比和电流利用效率,提高了电极的反应速度,可高效的降解抗生素类废水;④本发明制备的纳米臭氧催化剂应用于三维电极反应器中可以高效的处理氯霉素废水,降解效果彻底;⑤本发明制备方法简单,未使用贵金属催化剂,所用原材料来源广泛,制造成本低廉,无二次污染。
附图说明
图1为本发明实施例1的Ti-Sb/凹凸棒土陶粒表面SEM图。由图可知,空白凹凸棒土陶粒表观结构是均匀有序的,且晶型较好,晶体间中有较多的聚集体存在,这些鳞片状晶束在三维空间呈松散交错的排列结构,即晶束间间隔大,这表明Ti-Sb/凹凸棒土陶粒的显微结构松散,同时验证了其比表面积较大的特征。
图2为本发明实施例1的复合型纳米凹凸棒土臭氧催化剂表面SEM图。经活性组分负载后,复合型纳米凹凸棒土臭氧催化剂表面呈现平整且致密的结构特征,原有的孔道被遮盖,使其粗糙度及表面积均增大,这符合催化剂多孔的要求。此外,可以观察到许多粒径在2μm~5μm范围内的金属颗粒负载在凹凸棒土陶粒涂层表面,且分散度较高。而颗粒直径不等,可能是由于催化剂在制备过程中产生了团聚所致。综上,活性催化组分的颗粒均匀分散在凹凸棒土陶粒载体的表面,达到了负载活性组分的目的。
图3为本发明实施例1的复合型纳米凹凸棒土臭氧催化剂EDS图。复合型纳米凹凸棒土臭氧催化剂表面中含有Ti、Si、Al以及Na等金属元素,同时微量的金属Sb元素亦被检测到,标志着复合型纳米凹凸棒土臭氧催化剂制备成功。
图4为本发明实施例1的复合型纳米凹凸棒土臭氧催化剂XRD图。(a)和(b)分别表示凹凸棒土陶粒和负载Ti-Sb的复合型纳米凹凸棒土臭氧催化剂的XRD谱图,对比负载Ti-Sb活性催化组分前后的XRD谱图,可以发现2θ位于25°~30°范围内的尖强峰在负载后被弱干中等强度峰替代,由此说明原有的凹凸棒土陶粒表面结构被破坏。特别地,负载活性组分后,在此范围内出现了金红石型TiO2的衍射峰,同时其余四处锐钛矿TiO2衍射峰强度均有不同程度的提高,表明对应的金属Ti晶粒数量大幅增加,有助于提高电催化反应活性位点。负载后黄锑矿SbO2以及方锑矿Sb2O3的出现,证实了金属Sb已被顺利引入粒子电极表面结构中,其中2θ位于46.165°处的衍射峰宽度较大,说明新生长的方锑矿Sb2O3的晶粒尺寸较小,这有利于提高粒子电极的表面催化活性。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明。
实施例1:
一种复合型纳米凹凸棒土臭氧催化剂的制备方法,包括以下步骤:
第一步,研磨成型:选取莫氏强度为2.5,比重为2.20的凹凸棒土50g作为凹凸棒土陶粒原材料;关于辅料,骨料添加剂选取高岭土,造孔剂选取粉煤灰,粘结剂选取硅酸钠,质量投加比例为凹凸棒土:高岭土:粉煤灰:硅酸钠=10:1.2:0.5:0.6;活性催化组分A选取硝酸铁和硝酸铁纳米颗粒的混合物,质量投加比例为硝酸铁:硝酸铁纳米颗粒:凹凸棒土=0.02:1.2:100;混合上述材料并研磨至粉末状;按投加量为25mL/100g添加12.5mL去离子水,混合均匀成浆状混合物后制成粒径为4mm的球形颗粒;
第二步,干燥烧结:将第一步制得的球形颗粒置于105℃恒温烘箱内干燥处理1h;将干燥处理后的球形颗粒用50mL瓷坩埚盛装并置于升温速率为10℃/min的程序升温马弗炉内;控制升温程序为在预热温度为500℃下预热30min,在烧结温度为1000℃下烧结30min进行煅烧;烧结完成后炉内自然冷却至常温即得凹凸棒土陶粒;
第三步,浸渍水热纳米化:助溶剂选取盐酸,稳定剂选取乙酸,活性组分B选取三氯化锑和钛酸丁酯;称取45.64g三氯化锑溶于200mL无水乙醇溶液中,并加入10mL浓度为5.0mol/L的盐酸助溶,即配制了活性组分Sb元素含量为1.0mol/L的三氯化锑无水乙醇溶液200mL;向上述配制完成的三氯化锑无水乙醇溶液中加入浓度为2.0mol/L的乙酸溶液人0.1mL作为稳定剂,充分摇匀后按摩尔比为n(Sb):n(Ti)=1.0:10投加钛酸丁酯,并在快速搅拌下缓慢滴加去离子水4.0mL,摇匀后形成透明稳定的混合溶胶溶液;将上述配制完成的混合溶胶溶液分2次利用玻璃杯导流进入已放置25g凹凸棒土陶粒的500mL锥形瓶中,每次100mL;将锥形瓶置于25℃恒温水浴摇床中震荡4.0h,震荡开始即以滴加速率为80滴/min向锥形瓶内滴加浓度为0.2moL/L的氢氧化钠溶液1.2mL;运行结束后倾倒出上清液,置于105℃恒温烘箱内烘干;
第四步,焙烧活化:将第三步经浸渍陈化后的凹凸棒土陶粒用50mL瓷坩埚盛装并置于升温速率为10℃/min的程序升温马弗炉内;控制升温程序为在600℃温度下焙烧2.0h进行煅烧,煅烧完成后炉内自然冷却至室温;
第五步,重复处理:上一步冷却后的凹凸棒土陶粒加入第三步的上清液中,辅以超声波震荡,运行结束后倾倒出上清液,凹凸棒土陶粒置于105℃±5℃恒温烘箱内烘干,并重复第四步即可得到复合型纳米凹凸棒土陶粒臭氧催化剂。
空白凹凸棒土陶粒及复合型纳米凹凸棒土臭氧催化剂的扫描电子显微镜(SEM)和能量色散谱仪(EDS)分析通过扫描电镜(Quanta200)完成;空白凹凸棒土陶粒及复合型纳米凹凸棒土臭氧催化剂的X射线衍射(XRD)分析通过X射线衍射仪(Smartlab TM 9KW)完成。
以下为所制备复合型纳米凹凸棒土臭氧催化剂应用于三维粒子电极法处理各种抗生素废水的研究结果:
(1)氯霉素废水
以铱钽/钛板、石墨板分别为阳极和阴极,按粒子填充比为50.0%向有效容积为300mL的三维电催化氧化反应器中投加上述实施例中制备的复合型纳米凹凸棒土陶粒臭氧催化剂。在电解反应前进行预吸附试验以排除吸附作用的影响。试验在电流密度为20mA·cm-2,极板间距为3cm,初始pH值为1,电导率为5000μS/cm,空气流量为3.0L·min-1条件下,通电电解300ml浓度为100mg/L氯霉素溶液270min。将降解时间与氯霉素去除率的结果列于表1,由表1可知处理270min后氯霉素去除率高达73.70%。
表1实施例1所得的复合型纳米凹凸棒土陶粒臭氧催化剂对氯霉素的去除率结果
时间/min | 30 | 60 | 90 | 120 | 150 | 180 | 210 | 240 | 270 |
去除率/% | 15.21 | 26.67 | 35.52 | 46.21 | 57.59 | 63.23 | 69.26 | 72.29 | 73.70 |
(2)青霉素废水
以铱钽/钛板、石墨板分别为阳极和阴极,按粒子填充比为50.0%向有效容积为300mL的三维电催化氧化反应器中投加上述实施例中制备的复合型纳米凹凸棒土陶粒臭氧催化剂。在电解反应前进行预吸附试验以排除吸附作用的影响。试验在电流密度为20mA·cm-2,极板间距为3cm,初始pH值为2,电导率为6000μS/cm,空气流量为2.0L·min-1条件下,通电电解300ml浓度为100mg/L青霉素溶液270min。将降解时间与青霉素去除率的结果列于表2,由表2可知处理270min后青霉素去除率高达68.20%。
表2实施例1所得的复合型纳米凹凸棒土陶粒臭氧催化剂对青霉素的去除率结果
时间/min | 30 | 60 | 90 | 120 | 150 | 180 | 210 | 240 | 270 |
去除率/% | 16.22 | 27.24 | 36.52 | 47.11 | 56.80 | 62.21 | 65.10 | 67.41 | 68.20 |
(3)红霉素废水
以铱钽/钛板、石墨板分别为阳极和阴极,按粒子填充比为50.0%向有效容积为300mL的三维电催化氧化反应器中投加上述实施例中制备的复合型纳米凹凸棒土陶粒臭氧催化剂。在电解反应前进行预吸附试验以排除吸附作用的影响。试验在电流密度为30mA·cm-2,极板间距为3.5cm,初始pH值为1,电导率为4500μS/cm,空气流量为3.0L·min-1条件下,通电电解300ml浓度为100mg/L红霉素溶液270min。将降解时间与红霉素去除率的结果列于表3,由表3可知处理270min后红霉素去除率高达71.48%。
表3实施例1所得的复合型纳米凹凸棒土陶粒臭氧催化剂对红霉素的去除率结果
时间/min | 30 | 60 | 90 | 120 | 150 | 180 | 210 | 240 | 270 |
去除率/% | 14.97 | 21.44 | 31.68 | 44.50 | 55.27 | 61.80 | 67.32 | 70.04 | 71.48 |
实施例2:
一种复合型纳米凹凸棒土臭氧催化剂的制备方法,包括以下步骤:
第一步,研磨成型:选取莫氏强度为2.7,比重为2.25的凹凸棒土60g作为凹凸棒土陶粒原材料;关于辅料,骨料添加剂选取蒙脱石,造孔剂选取碳酸氢钠,粘结剂选取纤维素钠,质量投加比例为凹凸棒土:蒙脱石:碳酸氢钠:纤维素钠=10:1.0:1.0:2.0;活性催化组分A选取四氯化钛和四氯化钛纳米颗粒的混合物,质量投加比例为四氯化钛:四氯化钛纳米颗粒:凹凸棒土=0.05:1.5:100;混合上述材料并研磨至粉末状;按投加量为25mL/100g添加15.0mL去离子水,混合均匀成浆状混合物后制成粒径为3.0mm的球形颗粒;
第二步,干燥烧结:将第一步制得的球形颗粒置于105℃恒温烘箱内干燥处理1.5h;将干燥处理后的球形颗粒用50mL瓷坩埚盛装并置于升温速率为10℃/min的程序升温马弗炉内;控制升温程序为在预热温度为550℃下预热25min,在烧结温度为800℃下烧结50min进行煅烧;烧结完成后炉内自然冷却至常温即得凹凸棒土陶粒;
第三步,浸渍水热纳米化:助溶剂选取硝酸,稳定剂选取甲酸,活性组分B选取三氯化锑和钛酸丁酯;称取54.75g三氯化锑溶于200mL无水乙醇溶液中,并加入5mL浓度为5.0mol/L的硝酸助溶,即配制了活性组分Sb元素含量为1.2mol/L的三氯化锑无水乙醇溶液200mL;向上述配制完成的三氯化锑无水乙醇溶液中加入浓度为2.0mol/L的乙酸溶液人0.5mL作为稳定剂,充分摇匀后按摩尔比为n(Sb):n(Ti)=1.0:5.5投加钛酸丁酯,并在快速搅拌下缓慢滴加去离子水5.0mL,摇匀后形成透明稳定的混合溶胶溶液;将上述配制完成的混合溶胶溶液分2次利用玻璃杯导流进入已放置30g凹凸棒土陶粒的500mL锥形瓶中,每次100mL;将锥形瓶置于25℃恒温水浴摇床中震荡4.0h,震荡开始即以滴加速率为100滴/min向锥形瓶内滴加浓度为0.5moL/L的氢氧化钠溶液1.0mL;运行结束后倾倒出上清液,置于105℃恒温烘箱内烘干;
第四步,焙烧活化:将第三步经浸渍陈化后的凹凸棒土陶粒用50mL瓷坩埚盛装并置于升温速率为10℃/min的程序升温马弗炉内;控制升温程序为在600℃温度下焙烧2.5h进行煅烧,煅烧完成后炉内自然冷却至室温;
第五步,重复处理:上一步冷却后的凹凸棒土陶粒加入第三步的上清液中,辅以超声波震荡,运行结束后倾倒出上清液,凹凸棒土陶粒置于105℃±5℃恒温烘箱内烘干,并重复第四步即可得到复合型纳米凹凸棒土陶粒臭氧催化剂。
按照实施例1中记载的方法处理300ml浓度为100mg/L氯霉素溶液270min,氯霉素去除率高达72.50%;处理浓度为100mg/L青霉素溶液270min,青霉素去除率高达69.42%;处理浓度为100mg/L红霉素溶液270min,红霉素去除率高达73.22%。
实施例3:
一种复合型纳米凹凸棒土臭氧催化剂的制备方法,包括以下步骤:
第一步,研磨成型:选取莫氏强度为3.0,比重为2.20的凹凸棒土40g作为凹凸棒土陶粒原材料;关于辅料,骨料添加剂选取伊来石,造孔剂选取碳酸铵,粘结剂选取磷酸钙,质量投加比例为凹凸棒土:伊来石:碳酸铵:磷酸钙=10:1.2:0.8:1.0;活性催化组分A选取硝酸镍和硝酸镍纳米颗粒的混合物,质量投加比例为硝酸镍:硝酸镍纳米颗粒:凹凸棒土=0.5:2.0:100;混合上述材料并研磨至粉末状;按投加量为20mL/100g添加8.0mL去离子水,混合均匀成浆状混合物后制成粒径为3.5mm的球形颗粒;
第二步,干燥烧结:将第一步制得的球形颗粒置于105℃恒温烘箱内干燥处理1.2h;将干燥处理后的球形颗粒用50mL瓷坩埚盛装并置于升温速率为10℃/min的程序升温马弗炉内;控制升温程序为在预热温度为600℃下预热20min,在烧结温度为1100℃下烧结30min进行煅烧;烧结完成后炉内自然冷却至常温即得凹凸棒土陶粒;
第三步,浸渍水热纳米化:助溶剂选取磷酸,稳定剂选取醋酸,活性组分B选取三氯化锑和钛酸丁酯;称取36.50g三氯化锑溶于200mL无水乙醇溶液中,并加入10mL浓度为5.0mol/L的磷酸助溶,即配制了活性组分Sb元素含量为0.8mol/L的三氯化锑无水乙醇溶液200mL;向上述配制完成的三氯化锑无水乙醇溶液中加入浓度为2.0mol/L的醋酸溶液人0.2mL作为稳定剂,充分摇匀后按摩尔比为n(Sb):n(Ti)=1.0:2.5投加钛酸丁酯,并在快速搅拌下缓慢滴加去离子水4.0mL,摇匀后形成透明稳定的混合溶胶溶液;将上述配制完成的混合溶胶溶液分2次利用玻璃杯导流进入已放置20g凹凸棒土陶粒的500mL锥形瓶中,每次100mL;将锥形瓶置于25℃恒温水浴摇床中震荡4.0h,震荡开始即以滴加速率为60滴/min向锥形瓶内滴加浓度为0.2moL/L的磷酸钠溶液1.5mL;运行结束后倾倒出上清液,置于105℃恒温烘箱内烘干;
第四步,焙烧活化:将第三步经浸渍陈化后的凹凸棒土陶粒用50mL瓷坩埚盛装并置于升温速率为10℃/min的程序升温马弗炉内;控制升温程序为在800℃温度下焙烧2.0h进行煅烧,煅烧完成后炉内自然冷却至室温;
第五步,重复处理:上一步冷却后的凹凸棒土陶粒加入第三步的上清液中,辅以超声波震荡,运行结束后倾倒出上清液,凹凸棒土陶粒置于105℃±5℃恒温烘箱内烘干,并重复第四步即可得到复合型纳米凹凸棒土陶粒臭氧催化剂。
按照实施例1中记载的方法处理300ml浓度为100mg/L氯霉素溶液270min,氯霉素去除率高达69.71%;处理浓度为100mg/L青霉素溶液270min,青霉素去除率高达68.40%;处理浓度为100mg/L红霉素溶液270min,红霉素去除率高达70.22%。
Claims (12)
1.一种复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,包括以下步骤:
第一步,研磨成型:将一定质量的凹凸棒土和辅料充分混合后研磨至粉末状,按投加量为10~40mL水/100g凹凸棒土添加去离子水,混合均匀成浆状混合物并制成粒径为3~5mm的球形颗粒;所述辅料包括骨料添加剂、造孔剂、活性催化组分A以及粘结剂;所述的骨料添加剂为高岭土、石脂、蒙脱石、伊来石、水铝英石或蛭石中的一种或几种的组合,其与凹凸棒土的质量比为骨料添加剂:凹凸棒土=(1~45):100;所述的造孔剂为碳酸氢铵、碳酸钠、碳酸氢钠、粉煤灰、碳粉、木屑、尿素或碳酸铵中的一种或几种的组合,其与凹凸棒土的质量比为造孔剂:凹凸棒土=(0.01~5):100;所述的粘结剂为硅酸钠、糊精、石膏、磷酸钙、磷酸二氢钠、纤维素钠、壳聚糖、淀粉或长石中的一种或几种的组合,其与凹凸棒土的质量比为粘结剂:凹凸棒土=(0.1~10):100;所述的活性催化组分A为硝酸铁、氯化铁、硝酸锰、氯化锰、硝酸钴、硝酸镍、硝酸钼、硝酸锌、四氯化钛、钛酸丁酯、硝酸镍、硝酸铜、硝酸银、氯化金、硝酸铂、钨酸钠中的一种或多种与该金属盐的纳米颗粒的混合物,其与凹凸棒土的质量比为金属盐:金属盐纳米颗粒:凹凸棒土=(0.01~5):(1~5):100;
第二步,干燥烧结:将第一步制得的球形颗粒置于105℃±5℃恒温烘箱内干燥处理;将干燥处理后的球形颗粒用瓷坩埚盛装并置于马弗炉内进行预热、烧结,烧结完成后炉内自然冷却至常温即得凹凸棒土陶粒;
第三步,浸渍水热纳米化:在添加适量助溶剂的情况下,配制一定浓度的活性组分B无水乙醇溶液,并加入稳定剂,添加去离子水,摇匀后形成透明稳定的混合溶胶溶液;将上述配制的混合溶胶溶液加入已放置一定量凹凸棒土陶粒的容器中,并将容器置于25-60℃恒温水浴摇床中震荡4.0-20.0h,并滴加碱性溶液,并辅以超声波震荡,运行结束后倾倒出上清液,置于105℃±5℃恒温烘箱内烘干;其中,所述的助溶剂为盐酸、硝酸、磷酸、钛酸丁酯、醋酸、草酸、柠檬酸、酒石酸中的任意一种;所述助溶剂添加体积为无水乙醇体积的(5~10)‰,其中无水乙醇与上述第一步中所投加的凹凸棒土质量比为(300-800)g:100g;所述的稳定剂为甲酸、乙酸、醋酸、酒石酸或丙二酸中的一种或多种的组合;所述稳定剂添加体积为无水乙醇体积的(0.5~2.0)‰;所述的活性组分B选自一种或多种含有Fe2+、Sb3+、Mn2+、Co2+、Ni2+、Mo6+、Zn2+、Ti4+、Ni2+、Cu2+、Ag+、Au3+、W6+的盐,活性组分B在无水乙醇溶液中的含量为(0.5~12)mol/L;所述去离子水投加比例为每100mL无水乙醇溶液添加(2~5)mL去离子水;所述碱性溶液投加比例为每100mL无水乙醇溶液添加(0.5~1.0)mL碱性溶液;
第四步,焙烧活化:将第三步经浸渍水热纳米化后的凹凸棒土陶粒用瓷坩埚盛装并置于马弗炉内进行焙烧,焙烧完成后炉内自然冷却至室温;
第五步,重复处理:上一步冷却后的凹凸棒土陶粒加入第三步的上清液中,辅以超声波震荡,运行结束后倾倒出上清液,凹凸棒土陶粒置于105℃±5℃恒温烘箱内烘干,并重复第四步即可得到复合型纳米凹凸棒土陶粒臭氧催化剂。
2.根据权利要求1所述的复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,所述第一步中的凹凸棒土是莫氏强度为2.5~3.0,比重为2.20~2.30的天然粘土矿物。
3.根据权利要求1所述的复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,所述第二步中的干燥处理时间为1~3h。
4.根据权利要求1所述的复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,所述第二步中的将干燥处理后的球形颗粒用瓷坩埚盛装并置于马弗炉内,以10℃/min的程序升温进行预热、烧结,预热温度为500~600℃,预热时间为30~20min,烧结温度为500~1200℃,烧结时间为30~100min。
5.根据权利要求1所述的复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,所述第三步中的碱性溶液为氢氧化钠、磷酸钠、磷酸氢钠的溶液,浓度为0.2~4mol/L,滴加速率为50-300滴/min,持续时间为4.0~10.0h。
6.根据权利要求1所述的复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,所述第三步中的超声波功率为50~1000w,持续时间为4.0~20.0h。
7.根据权利要求1所述的复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,所述第三步中含有Fe2+的盐选自FeSO4、FeCl2,含有Sb3+的盐选自SbCl3,含有Mn2+的盐选自MnCl2,含有Co2+的盐选自CoSO4、CoCl2,含有Ni2+的盐选自NiSO4、NiCO3,含有Mo6+的盐选自Na2MoO4,含有Zn2+的盐选自ZnCl2、ZnBr2,含有Ti4+的盐选自TiCl4,含有Ni2+的盐选自NiSO4、NiCl2,含有Cu2+的盐选自CuSO4、CuCl2,含有Ag+的盐选自AgCl、AgNO3,含有Au3+的盐选自AuCl3,含有W6+的盐选自WCl6、WBr6。
8.根据权利要求1所述的复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,所述第四步中的焙烧为以10℃/min的程序升温至450~800℃温度下焙烧3.0~2.0h。
9.根据权利要求1所述的复合型纳米凹凸棒土陶粒臭氧催化剂的制备方法,其特征在于,所述第五步中的重复处理重复第三步和第四步的次数为1~4次。
10.按照权利要求1~9中任一项所述的制备方法制备得到的复合型纳米凹凸棒土陶粒臭氧催化剂。
11.权利要求10所述的复合型纳米凹凸棒土陶粒臭氧催化剂用于降解抗生素废水的应用。
12.根据权利要求11所述的应用,其特征在于所述的抗生素废水选自氯霉素废水、青霉素废水、红霉素废水、链霉素废水、万古霉素废水或吡哌酸废水。
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