CN111992250A - 一种植物基催化柱的制备方法及其在水处理中的应用 - Google Patents
一种植物基催化柱的制备方法及其在水处理中的应用 Download PDFInfo
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Abstract
本发明提供一种植物基催化柱的制备方法,包括以下步骤:S1:将植物部分器官从植物体上收割下来,剥去外皮,切割成所需形状,将其置于80‑100℃热水中浸泡20‑300min,再用清水清洗后,通风阴凉处风干,得到植物原料;S2:配制0.01‑10mol/L的金属离子溶液,将植物原料置于上述金属离子溶液中,一并置于太阳光下晾晒后,用清水清洗,在自然条件下风干,得到负载有纳米催化剂的植物基催化剂;S3:将负载有纳米催化剂的植物基催化剂以直接放入、挤压成型或推积成型的方式放入外柱内,制得直径为1cm‑100cm的催化柱。本发明制得的催化柱可实现对水中污染物的高效、连续催化降解,并解决纳米催化剂难以回收再利用问题。
Description
技术领域
本发明涉及一种植物基催化柱的制备方法及其在水处理中的应用,属于环境功能材料技术领域。
背景技术
催化剂是化学反应工程中必不可少的一种助剂,它能大大缩短反应进行的时间,提高生产效率。纳米催化剂是具有纳米级外观尺寸和较高比表面积的催化剂,具有良好的催化性能。但纳米催化剂由于自身特点,在使用过程中易团聚、反应结束后通常需要靠离心和过滤等操作与产物进行分离。此外,在催化降解水中污染物时,纳米材料还易对水体造成二次污染,其对水生动物和人体亦存在潜在污染,限制了纳米材料的单独使用范围。负载型催化剂是把催化剂固定在合适载体上的一类催化剂。在催化反应时,催化剂连同载体与反应物和产物并存,反应结束后更易与产物分离、解决了上述非负载型催化剂存在的问题。
催化膜是目前为较新型的载体型催化剂之一,膜作为催化剂的载体,其存在的类指状孔、类海绵孔等多孔结构为催化剂的负载提供了较大的空间,并为反应物与催化剂的接触提供了较多的活性位点和较为充足的反应时间。但催化膜所需的膜材料多为以聚偏氟乙烯、聚四氟乙烯、聚氯乙烯、聚丙烯酸、聚砜、聚醚砜、聚乙烯醇和聚乳酸为原料的有机膜或以氧化铝、氧化钛、氧化锆、碳化硅等为原料的无机陶瓷膜。前者的原料成本高昂,后者需要高温烧结制备工艺大大的增加了能耗成本,因此研究开发一种新型、价格低廉的催化剂载体做为两类主流材料的替代品势在必行。
植物基材料是以植物的某个器官为原料的一种天然多孔材料,无需人工制造孔隙结构、主要利用植物在成长过程中水、养分及无机盐运输通道经自然风干后形成天然多孔结构。此外,该材料在一定程度上具有耐酸、耐碱和耐盐的性能,长期使用后还可以在天然条件下进行降解、降低了载体材料对环境造成的影响。因此,植物基材料是一种理想的新型催化载体。近年来,采用植物体部分器官制成生物质碳再制备成负载型催化剂已成为研究者们研究的新热点。中国专利CN201911022690.X公开了一种用于水处理的生物质碳基双金属催化剂的制备方法及应用,该专利将海藻酸钠凝胶滴入Cu(NO3)2与FeCl2的混合溶液中形成凝胶珠,对其进行酸洗后再冷冻干燥、再于高温下进行焙烧碳化,最终制得碳-气凝胶双金属催化剂。中国专利CN201911424475.2公开了一种以生物质活性炭为载体的金纳米花的催化剂及其制备方法和应用,该专利以废弃柚子皮制备成多孔活性炭载体,以金纳米花为催化活性组分,抗坏血酸为还原剂将活性组分前驱体溶液还原成金纳米花胶体溶液,并将多孔活性炭载体浸渍于活性组分胶体溶液中,经干燥得到重整制氢催化剂。上述专利均需要焙烧碳化、外加还原剂辅助等复杂的制备工艺,与节能低碳的环保主流趋势不符。因此,研发出一种普适性强、可室温条件下制备,无需外加还原剂制备植物基催化柱的方法,有望解决上述问题且可能在水处理领域得到推广应用。
发明内容
针对现有技术存在的不足,本发明的第一目的在于提供一种植物基催化柱的制备方法。
本发明的第二目的在于提供上述方法制备的植物基催化柱在水处理中的应用。
为了实现上述第一目的,本发明是通过如下的技术方案来实现:一种植物基催化柱的制备方法,包括以下步骤:
S1:植物原料的预处理
S1.1:将植物部分器官从植物体上收割下来,剥去外皮,切割成所需形状;
S1.2:将其置于热水中浸泡一段时间,再用清水清洗后,通风阴凉处风干,得到植物原料;
S2:催化剂的负载
配制一定浓度的金属离子溶液,将S1制备的植物原料置于上述金属离子溶液中,一并置于太阳光下晾晒一段时间后,用清水清洗,在自然条件下风干,得到负载有纳米催化剂的植物基催化剂;
S3:植物基催化柱的制备
将S2制得的负载有纳米催化剂的植物基催化剂以直接放入、挤压成型或推积成型的方式放入一定尺寸的外柱内,制得催化柱。
采用上述技术方案,将植物原料与金属离子溶液一并置于太阳光下晾晒,利用太阳光作为光源加速植物基材料内木质素与金属离子间的氧化还原反应,得到纳米催化剂。
优选的,S1.2所述的植物原料为向日葵杆芯髄、玉米杆芯、莲叶杆芯、灯芯草芯髄、高粱杆芯、芝麻杆芯、甘蔗杆芯、大豆杆芯、芦苇杆芯、玉米芯内芯、一年生香椿杆芯、麻杆芯、竹子杆、椴木、松木、杨木、柳木、巴沙木、姜、丝瓜络、麦麸皮、柚子皮、橘子皮、冬瓜内瓤中的一种或几种。
优选的,S1.1所述的形状为长方体、正方体、圆柱体或薄片状,有效厚度为0.5cm-4.5cm。
优选的,S1.1所述的形状还包括粉末状,所粉末为花生外壳粉、椰子壳粉、碧根果壳粉、核桃壳粉、杏仁外壳粉、李子壳粉、桃核粉、栗子壳粉、山楂种子外壳粉、开心果果壳粉、白果果壳粉、油茶果壳粉、竹子杆粉、小麦秸秆粉、花生秸秆粉、水稻秸秆粉、玉米芯粉、松木粉、石松粉、莲蓬粉、棉花秸秆粉、茅草纤维粉、剑麻纤维粉、地瓜秧粉、油菜秸秆粉、杨柳柳絮、香蒲粉、荷叶粉和青竹竹叶粉中的一种或几种,粒径20-200目。
优选的,S1.2具体为:将其置于80-100℃热水中浸泡20-300min,再用清水清洗后,通风阴凉处进行风干处理,得到植物原料。
优选的,S2中所述的金属离子溶液为AgNO3、AuCl3·HCl·4H2O、Cu(NO3)2、PdCl2、Zn(Ac)2·2H2O、FeCl2、(NH4)2TiF6、BiCl3、InCl3、NbCl5中的一种或几种。
优选的,S2中所述的金属离子溶液的浓度为0.01-10mol/L。
优选的,S2中的负载方式为原位负载,以植物原料内木质素作为还原剂直接对金属离子进行原位还原,无需外加还原剂得到纳米催化剂,并利用太阳光作为光源加速以其与金属离子间的氧化还原反应。
优选的,S3中所述的直接放入方式:其外柱内设有垫圈防止料液侧漏;所述挤压成型方式:负载有纳米催化剂的植物基催化剂的根数为1-300根,压缩率在1%-75%;所述堆积成型方式:负载有纳米催化剂的植物基催化剂的厚度为0.5cm-4.5cm。
优选的,S3中所述的外柱是聚四氟乙烯柱、不锈钢柱、聚丙烯柱、聚氯乙烯柱或聚甲基丙烯酸甲酯柱,有效内径为2-250cm。
优选的,S3制得的催化柱的外部结构为上端有进料口,下端有出料口,进行单向垂直催化。
优选的,S3制得的催化柱的直径为1cm-100cm。
为了实现上述第二目的,本发明是通过如下的技术方案来实现:一种植物基催化柱在水处理中的应用,包括以下步骤:
S1:配制降解溶液
将降解目标物以及一定量配制的NaBH4水溶液配制成一定浓度的降解溶液(光催化降解时无需添加NaBH4水溶液);
S2:催化柱降解目标物
将一定体积的降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将大量的降解溶液连续地注入植物基催化柱内(光催化反应还需增加紫外光源辅助),在一定温度下收集催化降解后的水样,置于相应仪器中测定其浓度,计算催化转化率和表观反应速率常数。
优选的,S1中所述的降解目标物为染料废水、对硝基苯酚和有机氯化物中的一种或几种。
优选的,所述染料废水中染料浓度为1mg/L-1000mg/L,pH为3.5-10。
优选的,所述染料为曙红Y、苋菜红、活性红195、罗丹明B、落日黄、甲基橙、酸性黄36、固绿FCF、亚甲基蓝、直接蓝15、结晶紫和实际印染废水中的一种或几种。
优选的,所述有机氯化物为一氯醋酸、二氯苯酚、三氯乙烯、四氯甲烷、多氯联苯中的一种或几种。
优选的,所述降解溶液的体积为2-5000mL。
优选的,所述一定温度是催化反应温度为15-45℃。
优选的,所述紫外光源是发出波长为254nm、302nm或365nm中一种的紫外线高压汞灯。
优选的,所述相应仪器为紫外可见分光光度计或气相色谱仪。
本发明的有益效果:
(1)本发明可室温条件下在植物基材料上负载纳米金属或金属氧化物催化剂,并根据植物材料特点以合适的成型方式制成催化柱。该催化柱可实现对水中污染物的高效、连续催化降解,并解决纳米催化剂难以回收再利用问题。
(2)植物材料为基底材料:本发明采用植物材料为基底材料,来源广泛、天然无污染。
(3)绿色制备过程:本发明的无需人工制孔,可利用植物材料自身的理化性质获得天然多孔结构及化合物。室温条件下可实施对纳米催化剂的负载及固定,不需高温碳化。
(4)可负载的催化剂种类多样:本发明可负载单金属、双金属、金属氧化物等多种类型的催化剂,可对多类别水中污染物实现催化降解。
(5)可循环使用:本发明制备的催化柱具有良好的催化性能,还可以多次循环使用,解决非负载型催化剂难以回收利用的问题。
附图说明
通过阅读参照以下附图对非限制性实施例所作的详细描述,本发明的其它特征、目的和优点将会变得更明显:
图1为本发明的纳米催化柱对对硝基苯酚还原反应的活化能图。
图2为本发明实施例12中灯芯草髓负载纳米催化剂前后对比图(左图为负载前实物图,右图为负载后实物图)。
具体实施方式
为使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施方式,进一步阐述本发明。
实施例1
(1)催化柱的制备
将甘蔗杆从甘蔗植株上收割下来,剥去外皮,切割成薄片状。将其置于95℃热水中浸泡300min,再用清水清洗,通风阴凉处进行风干陈置。配制0.05mol/L的AgNO3溶液,将预处理后的植物原料放在AgNO3溶液中,一并置于阳光充足的室外进行晾晒,加速氧化还原反应过程。2h过后,用清水进行清洗,在自然条件下风干,制得Ag纳米催化剂的植物基催化剂。将上述厚度为0.8cm的1片原位负载型催化剂以直接放入的方式置于有效直径为3.5cm的聚丙烯外柱内,制得催化柱。
(2)植物基催化柱在水处理中的应用
将0.03g亚甲基蓝以及50mM NaBH4溶于1L水中配制成30mg/L的降解溶液。取30mL上述降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将降解溶液连续地注入催化柱内,在25℃下收集催化降解后的水样,置于紫外可见分光光度计中,在664nm处测定其最大吸光度,再换算成对应的浓度,计算催化转化率和表观反应速率常数。
实施例2
(1)催化柱的制备
将高粱杆从高粱植株上收割下来,剥去外皮,切割成薄片状。将其置于100℃热水中浸泡240min,再用清水清洗,通风阴凉处进行风干陈置。配制0.01mol/L的PdCl2溶液,将预处理后的植物原料放在PdCl2溶液中,一并置于阳光充足的室外进行晾晒,2h过后,用清水进行清洗,在自然条件下风干,制得原位负载型Pd纳米催化剂的植物基催化剂。将上述厚度为1cm的1片原位负载型催化剂以直接放入方式置于有效直径为1.5cm的聚甲基丙烯酸甲酯外柱内,制得催化柱。
(2)植物基催化柱在水处理中的应用
同实施例1。
实施例3
(1)催化柱的制备
将椴木树枝从树干上砍伐割下来,剥去外皮,切割成薄片状。将其置于100℃热水中浸泡240min,再用清水清洗,通风阴凉处进行风干陈置。配制0.02mol/L的AuCl3溶液,将预处理后的植物原料放在AuCl3溶液中,一并置于阳光充足的室外进行晾晒,2h过后,用清水进行清洗,在自然条件下风干,制得原位负载型Au纳米催化剂的植物基催化剂。将上述厚度为0.8cm的1片原位负载型催化剂以直接放入方式置于有效直径为2.5cm的聚丙烯外柱内,制得催化柱。
(2)植物基催化柱在水处理中的应用
同实施例1。
实施例4
(1)催化柱的制备
将芦苇杆从芦苇植株上收割下来,剥去外皮,切割成薄片状。将其置于100℃热水中浸泡240min,再用清水清洗,通风阴凉处进行风干陈置。配制pH5.5的0.015mol/L FeCl2溶液,将预处理后的植物原料放在FeCl2溶液中,一并置于阳光充足的室外进行晾晒,4h过后,用清水进行清洗,并将负载有Fe0的植物基材料浸泡在含PdCl2的0.015mol/L乙醇和水(体积比9:1)的混合液中,再在阳光充足的室外进行晾晒30min。在自然条件下风干,制得原位负载型Fe/Pd双金属纳米催化剂的植物基催化剂。将上述厚度为1.4cm的1片原位负载型催化剂以直接放入方式置于有效直径为1.5cm的聚丙烯外柱内,制得催化柱。
(2)植物基催化柱在水处理中的应用
将0.03g三氯乙烯溶于1L水中配制成30mg/L的需降解溶液(pH=7)。取30mL上述需降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将需降解溶液连续地注入催化柱内,在25℃下进行催化反应,收集催化降解后的水样。用正己烷对其进行萃取,再置于气相色谱仪中测试其浓度,计算催化转化率和表观反应速率常数。
实施例5
将玉米杆从玉米植株上切割下来,剥去外皮,切割成薄片状。将其置于100℃热水中浸泡240min,再用清水清洗,通风阴凉处进行风干陈置。预先浸泡在0.3M的H3BO3溶液中预处理2min,再将其转移到新鲜配制的pH 3.87((NH4)2TiF6+H3BO3)的混合溶液中继续浸泡,一并置于阳光充足的室外进行晾晒,液相沉积反应1h后,用清水进行清洗,在自然条件下风干,制得原位负载型TiO2纳米催化剂的植物基光催化剂。将上述厚度为1.8cm的1片原位负载型催化剂以直接放入方式置于有效直径为2cm的聚丙烯外柱内,制得光催化柱。
(2)植物基催化柱在水处理中的应用:
将0.03g亚甲基蓝溶于1L水中配制成30mg/L的需降解溶液。取30mL上述需降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将需降解溶液连续地注入催化柱内,在25℃下进行光催化反应。紫外线高压汞灯的发射波长为365nm,收集催化降解后的水样,置于紫外可见分光光度计中在664nm处测定其最大吸光度,再换算成对应的浓度,计算催化转化率和表观反应速率常数。
实施例6
(1)催化柱的制备
同实施例1。
(2)植物基催化柱在水处理中的应用
将0.01g对硝基苯酚以及50mM NaBH4溶于1L水中配制成10mg/L的需降解溶液。取30mL上述需降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将需降解溶液连续地注入催化柱内,在25℃下进行催化反应,收集催化降解后的水样,置于紫外可见分光光度计中在400nm处测定其最大吸光度,再换算成对应的浓度,计算催化转化率和表观反应速率常数。
实施例7
(1)催化柱的制备
同实施例1。
(2)植物基催化柱在水处理中的应用:
将0.02g对硝基苯酚以及50mM NaBH4溶于1L水中配制成20mg/L的需降解溶液。取30mL上述需降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将需降解溶液连续地注入催化柱内,在25℃下进行催化反应,收集催化降解后的水样,置于紫外可见分光光度计中在400nm处测定其最大吸光度,再换算成对应的浓度,计算催化转化率和表观反应速率常数。
实施例8
(1)催化柱的制备
同实施例1。
(2)植物基催化柱在水处理中的应用
将0.03g对硝基苯酚以及50mM NaBH4溶于1L水中配制成30mg/L的需降解溶液(pH=10)。取30mL上述需降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将需降解溶液连续地注入催化柱内,在25℃下进行催化反应,收集催化降解后的水样,置于紫外可见分光光度计中在400nm处测定其最大吸光度,再换算成对应的浓度,计算催化转化率和表观反应速率常数。
实施例9
(1)催化柱的制备
同实施例1。
(2)植物基催化柱在水处理中的应用:
将0.03g对硝基苯酚以及50mM NaBH4溶于1L水中配制成30mg/L的需降解溶液(pH=10)。取30mL上述需降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将需降解溶液连续地注入催化柱内,在15℃下进行催化反应,收集催化降解后的水样,置于紫外可见分光光度计中在400nm处测定其最大吸光度,再换算成对应的浓度,计算催化转化率和表观反应速率常数。
实施例10
(1)催化柱的制备
同实施例1。
(2)植物基催化柱在水处理中的应用
将0.03g对硝基苯酚以及50mM NaBH4溶于1L水中配制成30mg/L的需降解溶液(pH=10)。取30mL上述需降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将需降解溶液连续地注入催化柱内,在30℃下进行催化反应,收集催化降解后的水样,置于紫外可见分光光度计中在400nm处测定其最大吸光度,再换算成对应的浓度,计算催化转化率和表观反应速率常数。
实施例11
(1)催化柱的制备
同实施例1。
(2)植物基催化柱在水处理中的应用
将0.03g对硝基苯酚以及50mM NaBH4溶于1L水中配制成30mg/L的需降解溶液(pH=10)。取30mL上述需降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将需降解溶液连续地注入催化柱内,在41℃下进行催化反应,收集催化降解后的水样,置于紫外可见分光光度计中在400nm处测定其最大吸光度,再换算成对应的浓度,计算催化转化率和表观反应速率常数。
实施例12
(1)催化柱的制备
将灯芯草茎从灯芯草植株上收割下来,在阳光充足的室外进行自然晾晒,再放置阴凉通风处进行风干处理,最后将灯芯草髓与外皮进行剥离,切割成有效长度7cm,平均直径为2.5mm的海绵状材料。将其置于95℃热水中浸泡300min,再用清水清洗,通风阴凉处进行风干陈置。配制0.05mol/L的AgNO3溶液,将预处理后的植物原料放在AgNO3溶液中,一并置于阳光充足的室外进行晾晒,加速氧化还原反应过程。2h过后,用清水进行清洗,在自然条件下风干,制得Ag纳米催化剂的植物基催化剂。将2500根原位负载型催化剂扎成柱状,并逐渐压缩成密实紧凑的圆柱状,压缩率为55.2%。以压缩成型的方式置于有效直径为20cm的聚丙烯外柱内,制得中等催化截面的催化柱。
(2)植物基催化柱在水处理中的应用
同实施例1。
实施例13
(1)催化柱的制备
将花生壳用水清洗干净,进行二次晒干。再将其置于超微研磨机内进行粉碎及研磨,得到粉末状材料,过1000目筛网待用。将其置于95℃热水中浸泡300min,再用清水清洗,通风阴凉处进行风干陈置。配制0.05mol/L的AgNO3溶液,将预处理后的植物原料放在AgNO3溶液中,一并置于阳光充足的室外进行晾晒,加速氧化还原反应过程。2h过后,用清水进行清洗,在自然条件下风干,制得Ag纳米催化剂的植物基催化剂。将上述原位负载型催化剂以堆积成型的方式置于有效直径为80cm的聚丙烯外柱内,制得较大催化截面的催化柱。
(2)植物基催化柱在水处理中的应用
同实施例1。
试验例1同一植物基催化柱处理不同浓度的降解溶液
对照组:为未负载有纳米催化剂的植物基柱。
实施例6-8所涉及的降解溶液的浓度依次为10mg/L、20mg/L、30mg/L,其催化转化率和表观反应速率常数见表1。
表1同一植物基催化柱处理不同浓度的降解溶液的转化率和表观反应速率常数
由表1可知,相同反应时间内,未负载纳米催化剂的植物基柱对降解溶液基本没有降解作用。但负载有纳米催化剂的催化柱对不同浓度降解溶液的催化转化率均接近100%,且随着降解溶液浓度的增加,表观反应速率常数呈现出先降低后趋向于稳定的趋势。这表明此催化柱可在极短时间内对低浓度降解溶液进行降解,随着降解溶液浓度的增大反应速率常数保持恒定,便于研究其他因素对反应结果的影响。因此后续研究均选择30mg/L的溶液作为催化降解过程的研究对象。
试验例2不同反应温度对催化转化率的影响
实施例8-11所涉及的反应温度依次为25℃、15℃、30℃、41℃,其催化转化率和表观反应速率常数见表2。
表2同一植物基催化柱在不同温度下的转化率和表观反应速率常数
由表2可知,相同反应温度和时间内,未负载纳米催化剂的植物基柱对降解溶液基本没有降解作用。在实施例8-11中,反应温度对降解溶液的催化转化率影响较小,转化率均达到了99.9%。随着反应温度的升高,其表观反应速率常数逐渐增大,表明反应速率逐渐加快,催化反应所需的时间缩短。
由Arrhenius公式可知,对反应速率常数(Kobs)取-ln计算后作Y轴,反应的热力学温度的倒数作X轴,再进行作图,如图1所示,拟合后可从图中得到直线的斜率求出表观活化能Ea。通过计算得知,本发明实施例8-11中使用的纳米催化柱对对硝基苯酚还原反应的活化能为18.80KJ/mol,说明该反应速率的控制步骤是受扩散控制的。
试验例3
实施例1-11以直接放入的方式制得的催化柱直径为1-5cm,而实施例12通过挤压成型的方式将催化柱直径扩大至5-50cm,得到中等催化截面的催化柱,最后实施例13通过对粉末状催化剂的推积成型将催化柱直径扩大至30-100cm,得到较大催化截面的催化柱,更有望进行大规模的催化反应应用。无论哪种成型方式制得的催化柱,纳米催化剂均牢牢地被固定在各种载体上,均无需催化剂回收这一工艺流程,真正有效解决纳米催化剂难以回收再利用这一难题。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点,对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
Claims (10)
1.一种植物基催化柱的制备方法,其特征在于,包括以下步骤:
S1:植物原料的预处理
S1.1:将植物部分器官从植物体上收割下来,剥去外皮,切割成所需形状;
S1.2:将其置于80-100℃热水中浸泡20-300min,再用清水清洗后,通风阴凉处风干,得到植物原料;
S2:催化剂的负载
配制0.01-10mol/L的金属离子溶液,将S1制备的植物原料置于上述金属离子溶液中,一并置于太阳光下晾晒后,用清水清洗,在自然条件下风干,得到负载有纳米催化剂的植物基催化剂;
S3:植物基催化柱的制备
将S2制得的负载有纳米催化剂的植物基催化剂以直接放入、挤压成型或推积成型的方式放入外柱内,制得直径为1cm-100cm的催化柱。
2.如权利要求1所述的一种植物基催化柱的制备方法,其特征在于,S1.2所述的植物原料为向日葵杆芯髄、玉米杆芯、莲叶杆芯、灯芯草芯髄、高粱杆芯、芝麻杆芯、甘蔗杆芯、大豆杆芯、芦苇杆芯、玉米芯内芯、一年生香椿杆芯、麻杆芯、竹子杆、椴木、松木、杨木、柳木、巴沙木、姜、丝瓜络、麦麸皮、柚子皮、橘子皮、冬瓜内瓤中的一种或几种。
3.如权利要求1或2所述的一种植物基催化柱的制备方法,其特征在于,S1.1所述的形状为长方体、正方体、圆柱体或薄片状,有效厚度为0.5cm-4.5cm。
4.如权利要求3所述的一种植物基催化柱的制备方法,其特征在于,S1.1所述的形状还包括粉末状,所述粉末为花生外壳粉、椰子壳粉、碧根果壳粉、核桃壳粉、杏仁外壳粉、李子壳粉、桃核粉、栗子壳粉、山楂种子外壳粉、开心果果壳粉、白果果壳粉、油茶果壳粉、竹子杆粉、小麦秸秆粉、花生秸秆粉、水稻秸秆粉、玉米芯粉、松木粉、石松粉、莲蓬粉、棉花秸秆粉、茅草纤维粉、剑麻纤维粉、地瓜秧粉、油菜秸秆粉、杨柳柳絮、香蒲粉、荷叶粉和青竹竹叶粉中的一种或几种,粒径20-200目。
5.如权利要求4所述的一种植物基催化柱的制备方法,其特征在于,S2中所述的金属离子溶液为AgNO3、AuCl3·HCl·4H2O、Cu(NO3)2、PdCl2、Zn(Ac)2·2H2O、FeCl2、(NH4)2TiF6、BiCl3、InCl3、NbCl5中的一种或几种。
6.如权利要求5所述的一种植物基催化柱的制备方法,其特征在于,S2中的负载方式为原位负载。
7.一种如权利要求6所述的方法制备的植物基催化柱在水处理中的应用,其特征在于,包括以下步骤:
S1:配制降解溶液
将降解目标物以及NaBH4水溶液配制成30mg/L的降解溶液;
S2:催化柱降解目标物
将体积为2-5000mL的降解溶液滴加到植物基催化柱内,经润湿、吸附饱和后,再将大量的降解溶液连续地注入植物基催化柱内,在14-45℃下收集催化降解后的水样,置于紫外可见分光光度计或气相色谱仪中测定其浓度,计算催化转化率和表观反应速率常数。
8.如权利要求7所述的一种植物基催化柱在水处理中的应用,其特征在于,S1中不添加NaBH4水溶液;S2中增加紫外光源。
9.如权利要求8所述的一种植物基催化柱在水处理中的应用,其特征在于,S1中所述的降解目标物为染料废水、对硝基苯酚和有机氯化物中的一种或几种;所述染料废水中染料浓度为1mg/L-1000mg/L,pH为3.5-10。
10.如权利要求9所述的一种植物基催化柱在水处理中的应用,其特征在于,所述染料为曙红Y、苋菜红、活性红195、罗丹明B、落日黄、甲基橙、酸性黄36、固绿FCF、亚甲基蓝、直接蓝15、结晶紫和实际印染废水中的一种或几种;所述有机氯化物为一氯醋酸、二氯苯酚、三氯乙烯、四氯甲烷、多氯联苯中的一种或几种。
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