CN107233891A - 一种处理苯酚废水的光催化剂制备方法及其处理方法 - Google Patents
一种处理苯酚废水的光催化剂制备方法及其处理方法 Download PDFInfo
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
本发明公开了一种处理苯酚废水的光催化剂制备方法。该方法是将钴盐、铁盐、镧盐,依次加入水中,再与钛酸四丁酯的乙醇溶液混合后加入柠檬酸,水浴条件下形成凝胶,干燥后煅烧,得到La掺杂CoFe2O4/TiO2复合光催化剂,其中Co:Ti:La:水:柠檬酸的摩尔比为(0.5‑0.8):1:(0.10‑0.18):(120‑200):(7‑10)的比例进行配比,其中Fe摩尔量为Co摩尔量的2倍。该方法制备得到的光催化剂将光相应波长从紫外光区扩大至可见光区,同时光催化性能得到显著提高,1.5h内苯酚的催化降解率可以达到73.59%‑84.27%,并且该复合光催化剂易于回收。
Description
技术领域
本发明属于环境材料制备领域领域,具体涉及一种用于降解含苯酚废水的的La掺杂CoFe2O4/TiO2复合光催化剂制备方法。
背景技术
酚是一类常用的化工原料,很难降解,且具有致癌、致畸、致变的潜在毒性,因而含酚废水来源十分广泛,对人类健康来带十分严重的危害。苯酚是含酚废水中常见的污染物,有效处理苯酚废水已经是环保方面的一个重要课题,光催化氧化降解苯酚具有高效、稳定和无二次污染等特点,已成为近年来环保领域一种新型污染治理技术。
利用半导体及复合半导体光催化降解有机污染物,近年来在环境污染治理中取得较好的研究效果。TiO2作为光催化剂,具有良好的化学稳定性、低成本、五毒、原料易获得,而且能直接利用太阳光中的可见光作为激发光源来进行催化氧化,无二次污染。但TiO2光催化剂量子效率低,且光谱响应范围在紫外光区,太阳光谱中可见光部分不能有效利用,限制了其工业应用。针对TiO2光催化氧化技术存在的不足,目前国内外相关文献主要对TiO2光催化剂进行两个方面的改性研究:一是通过掺杂改性;二是开发研究负载型光催化剂,使其在实际应用中得到更好地利用。
现有专利201410286125.5《一种漂浮型CoFe2O4/TiO2/漂珠复合光催化剂及其制备方法》公开了一种漂珠作为载体,在其上先后负载TiO2和CoFe2O4,但是该方法制备过程复杂,且需要对中间物质和最终产物分别进行煅烧,且煅烧条件相同,又同时要保证中间产物和最终产物的性质,因此两者兼顾情况下,很大程度上会影响最终产物的性质,并且对苯酚的降解率远远低于对亚甲基蓝的降解率,3h内降解率最高不超过80%。
专利200410089201.X《用于含苯酚废水处理的光催化剂及其制备方法》公开了由微孔磷酸镍VSB-1为载体,活性组分TiO2组装于孔道内,形成复合催化剂,但是对苯酚的降解率最高也仅仅只有64.51%。
专利201410764458.4《一种处理硝基苯酚废水的光催化剂的制备方法、一种硝基苯酚废水的处理方法》公开了将溶胶-凝胶法合成的纳米TiO2负载在改性的二次介孔分子筛(ZSM5),可以提高UV(紫外光)激发下产生硫酸根自由基协同·OH能发挥出更强的氧化能力,虽然降解率高,但得到的复合催化剂需要在硫酸亚铁、过硫酸钠提供硫酸根的基础上,在170W紫外线高压汞灯照射条件下才能显著催化氧化硝基苯酚。
发明内容
本发明的目的是针对上述缺陷,提供一种制备过程简单,苯酚催化降解率高的光催化剂制备方法。
为了实现本发明的目的,通过大量试验研究并不懈努力,最终获得如下技术方案:一种处理苯酚废水的光催化剂制备方法,包括如下步骤:
(1)取钴盐、铁盐、镧盐,依次加入水中,搅拌均匀,得到混合溶液A;
(2)将混合溶液A加入钛酸四丁酯的乙醇溶液中,再加入柠檬酸,得到混合溶液B;
(3)将混合溶液B在70-90℃下水浴加热,搅拌至形成凝胶;
(4)凝胶干燥后研磨,得到的干凝胶颗粒在150-220℃下焙烧2-3h,再在380-500℃下煅烧10-14h,得到La掺杂CoFe2O4/TiO2复合光催化剂;
上述步骤中按照Co:Ti:La:水:柠檬酸的摩尔比为(0.5-0.8):1:(0.10-0.18):(120-200):(7-10)的比例进行取样,其中Fe摩尔量为Co摩尔量的2倍。
优选地,如上所述处理苯酚废水的光催化剂制备方法,其中Co:Ti:La:柠檬酸的摩尔比为0.6:1:0.12:9。
优选地,所述镧盐为硝酸镧或者氯化镧。
优选地,所述钴盐为硝酸钴或氯化钴。
优选地,所述铁盐为硝酸铁、氯化铁和硫酸铁中任意一种。
所述水为蒸馏水或去离子水。
进一步,本发明还提供利用上述方法制备得到的La掺杂CoFe2O4/TiO2复合光催化剂处理含苯酚废水的方法,将所述La掺杂CoFe2O4/TiO2复合光催化剂悬浊于苯酚废水中进行处理。
如上所述处理含苯酚废水的方法,优选地,按0.5-5g/L的比例向废水中投加所述La掺杂CoFe2O4/TiO2复合光催化剂,然后常温搅拌处理1.5-2.5h。
本发明相对于现有技术,具有如下技术效果:
本发明La掺杂CoFe2O4/TiO2复合光催化剂制备方法简单易行,通过多种物质的复合,不但使得光相应波长从紫外光区扩大至可见光区,提高了光的利用率;且催化剂活性组分为Co、Fe、Ti,且掺杂适量La,整体光催化性能得到显著提高,1.5h内苯酚的催化降解率可以达到73.59%-84.27%;本发明中CoFe2O4不但作为催化剂活性成分,且具有磁性,得到的复合光催化剂易于回收。
具体实施方式
下面对本发明的具体实施方式作进一步说明。
实施例1
复合光催化剂的制备:
步骤1:称取4.26g六水合硝酸钴、11.82g九水硝酸铁、1.27g六水硝酸镧433,依次加入到63.3g水中,搅拌均匀,得到混合溶液A;
步骤2:将10ml钛酸四丁酯(2.927×10-2mol)溶于35ml乙醇,磁力搅拌,得到钛酸四丁酯的乙醇溶液;
步骤3:将混合溶液A加入钛酸四丁酯的乙醇溶液中,再向其中加入39.4g柠檬酸,得到混合溶液;
步骤4:将混合溶液在70℃水浴条件下加热,搅拌直至形成凝胶,将凝胶在40℃下进行干燥,干凝胶研磨成颗粒后,将其放入马弗炉中,首先在150℃下焙烧2h,再迅速升温至380℃,煅烧11h,得到La掺杂CoFe2O4/TiO2复合光催化剂。
实施例2
复合光催化剂的制备:
步骤1:称取5.11g六水合硝酸钴、14.19g九水硝酸铁、1.52g六水硝酸镧,依次加入到79.0g水中,搅拌均匀,得到混合溶液A;
步骤2:将10ml钛酸四丁酯(2.927×10-2mol)溶于35ml乙醇,磁力搅拌,得到钛酸四丁酯的乙醇溶液;
步骤3:将混合溶液A加入钛酸四丁酯的乙醇溶液中,再向其中加入50.61g柠檬酸,得到混合溶液;
步骤4:将混合溶液在80℃水浴条件下加热,搅拌直至形成凝胶,将凝胶在40℃下进行干燥,干凝胶研磨成颗粒后,将其放入马弗炉中,首先在180℃下焙烧3h,再迅速升温至450℃,煅烧12h,得到La掺杂CoFe2O4/TiO2复合光催化剂。
实施例3
复合光催化剂的制备:
步骤1:称取6.81g六水合硝酸钴、18.92g九水硝酸铁、2.28g六水硝酸镧,依次加入到105g水中,搅拌均匀,得到混合溶液A;
步骤2:将10ml钛酸四丁酯(2.927×10-2mol)溶于35ml乙醇,磁力搅拌,得到钛酸四丁酯的乙醇溶液;
步骤3:将混合溶液A加入到钛酸四丁酯的乙醇溶液中,再向其中加入56.2g柠檬酸,得到混合溶液;
步骤4:将混合溶液在90℃水浴条件下加热,搅拌直至形成凝胶,将凝胶在40℃下进行干燥,干凝胶研磨成颗粒后,将其放入马弗炉中,首先在220℃下焙烧3h,再迅速升温至500℃,煅烧14h,得到La掺杂CoFe2O4/TiO2复合光催化剂。
实施例4
苯酚含量的测定方法:采用分光光度法测定-苯酚溶液经4-铵基安替吡啉显色后,用分光光度计测定吸光度。苯酚类在pH=10.0±0.2和以铁氰化钾为氧化剂的溶液中,与4-氨基安替比林反应形成有色的安替比林染料。此染料的最大吸收波长在510nm处,颜色在30min内稳定。
苯酚初始吸光度的测量:取1.00g/L的苯酚溶液10mL于100mL的容量瓶中,再加水稀释至100mL,同时调节溶液PH=7~8,配制成100mg/L的苯酚溶液。于常温放置15min后,取5.0mL的100mg/L的苯酚溶液于另一100mL的容量瓶中,加少量水,再加2.0mL缓冲溶液及4.0mL4-氨基安替比林溶液,混匀;再加4.0mL铁氰化钾,混匀,定容至100mL,于常温放置15min后,在分光光度计上于510nm波长处用1cm比色皿以零浓度为参比测量吸光度,测得其吸光度A1=0.992。
降解液中苯酚吸光度的测量:降解后取样5.0mL在抽滤机上过滤掉固体后置于100mL的容量瓶中,加少量水,再加2.0mL缓冲溶液及4.0mL 4-氨基安替比林溶液,混匀;再加4.0mL铁氰化钾,混匀,定容至100mL,于常温放置15min后,在分光光度计上于510nm波长处用1cm比色皿以零浓度为参比测量吸光度,计算其降解率。
苯酚吸附效果检测:
称取实施例1-3得到的La掺杂CoFe2O4/TiO2复合光催化剂各0.05g,放入100ml锥形瓶,加入配制好的50ml 100mg/L的苯酚溶液,pH=5,将其在可见光催化反应器下进行降解实验,反应1.5h后将溶液过滤,随后将滤液用752型紫外-可见分光光度计在波长510nm处测其吸光度,按照吸光度-浓度工作曲线换算成吸附平衡时的苯酚溶液浓度,进而计算出苯酚的降解率η%。
η%={(A1-A2)/A1}×100%,其中A1—苯酚水溶液的初始吸光度值,A2—苯酚水溶液的末态吸光度值。
表1不同La掺杂CoFe2O4/TiO2复合光催化剂降解苯酚
实施例1 | 实施例2 | 实施例3 | |
A2 | 0.262 | 0.156 | 0.203 |
η(%) | 73.59 | 84.27 | 79.54 |
从表1可知,本发明制备得到的La掺杂CoFe2O4/TiO2对苯酚有显著的降解效果,且在1.5h内对苯酚的降解率高达73.59%以上,最高可以达到84.27%。
实施例5
取实施例1-3制备得到的催化剂,催化剂的加入量与实施例4中相同,改变搅拌时间分别为40min、1.5h、2.5h,考察苯酚降解率,得到如表2所示结果。
表2不同搅拌时间下苯酚降解率
从表2可知,当搅拌时间从40min至1.5h时,苯酚降解率增加显著,当从1.5h到2.5h时,苯酚降解率提高不明显,因此在实际处理时,选择催化剂加入苯酚后搅拌时间高于40min,搅拌时间在1.5h左右,不超过2.5h。
实施例6
称取实施例2得到的催化剂,将其加入苯酚溶液中,其它步骤与实施例4的相同,改变苯酚溶液浓度为25mg/L、50mg/L、75mg/L、100mg/L,考察其1h时降解率,得到如表3所示结果。
表3不同浓度苯酚溶液降解率(%)
从表3数据可知,本发明得到的La掺杂CoFe2O4/TiO2复合光催化剂对浓度低于100mg/L的苯酚废水处理效果均显著,降解率最高可以达到87.04%以上。
实施例7
步骤1:称取2.55g六水合硝酸钴、7.1g九水硝酸铁、0.88g六水硝酸镧,依次加入到63.3g水中,搅拌均匀;
步骤2:将10ml钛酸四丁酯(2.927×10-2mol)溶于35ml乙醇,磁力搅拌,得到钛酸四丁酯的乙醇溶液;
步骤3:将钛酸四丁酯的乙醇溶液加入步骤1的混合溶液中,再加入33.7g柠檬酸;
其余步骤如实施例2所示,制备得到复合光催化剂,称取0.05g得到的复合光催化剂,按实施例4所述处理过程加入到100mg/L苯酚溶液中,测得苯酚降解率为68.17%。
实施例8
步骤1:称取8.51g六水合硝酸钴、23.65g九水硝酸铁、2.53g六水硝酸镧,依次加入到79.0g水中,搅拌均匀;
步骤2:将10ml钛酸四丁酯(2.927×10-2mol)溶于35ml乙醇,磁力搅拌,得到钛酸四丁酯的乙醇溶液;
步骤3:将钛酸四丁酯的乙醇溶液加入步骤1的混合溶液中,再加入50.61g柠檬酸;
其余步骤如实施例2所示,得到复合光催化剂,称取0.05g得到的复合光催化剂,按实施例5所述处理过程加入到100mg/L苯酚溶液中,测得苯酚降解率为74.28%。
由实施例2和实施例7、8的降解率比较,可知,当反应物中活性物质的摩尔量比例在本发明公开的范围外时,对100mg/L苯酚溶液的降解率远低于本发明方法制备得到的La掺杂CoFe2O4/TiO2复合光催化剂。
对比例1
CoFe2O4/TiO2光催化剂的制备:
步骤1:取无水乙醇35ml、乙酸4ml、蒸馏水10ml,及3.5gCoFe2O4磁性微粒,搅拌形成悬浊液,CoFe2O4磁性微粒为现有技术,具体是以硝酸铁、硝酸钴为原料,柠檬酸为络合剂,采用溶胶-凝胶法制备得到;
步骤2:取无水乙醇35ml、钛酸四丁酯10ml加入另一烧杯,搅拌10mni后得到钛酸四丁酯的醇溶液,将钛酸四丁酯的醇溶液以15ml/min滴加到CoFe2O4悬浊液,持续剧烈搅拌悬浊液,滴加完毕后再搅拌30min,得到分散有CoFe2O4磁性微粒的溶胶,将溶胶在40℃恒温水浴2h后于105℃中烘干得到干凝胶,将干凝胶首先在220℃下焙烧3h,再迅速升温至480℃,煅烧12h,得到CoFe2O4/TiO2光催化剂。
取CoFe2O4/TiO2光催化剂0.5g,将其投加入到50ml 100mg/L的苯酚溶液,溶液pH=5,1.5h后测得滤液吸光度为0.475,苯酚降解率为52.12%。
对比例2
步骤1:将10ml钛酸四丁酯(2.927×10-2mol)溶于35ml乙醇,磁力搅拌,得到钛酸四丁酯的乙醇溶液;
步骤2:称取1.55g六水硝酸镧,溶于30ml水中,得到硝酸镧溶液;
步骤3:将硝酸镧溶液滴加至钛酸四丁酯的醇溶液中,继续搅拌直至形成溶胶,溶胶在60℃下恒温水浴2h,得到凝胶,将凝胶在烘箱中80℃下烘干,将干凝胶研磨后置于马弗炉中,先在200℃下焙烧3h,再迅速升温至480℃,煅烧12h,得到La掺杂TiO2复合光催化剂。
取0.5g制备得到的La掺杂TiO2复合光催化剂,投加到50ml 100mg/L的苯酚溶液中,溶液pH=5,1.5h后测得滤液吸光度为0.568,苯酚降解率为42.74%。
Claims (8)
1.一种处理苯酚废水的光催化剂制备方法,其特征在于包括如下步骤:
(1)取钴盐、铁盐、镧盐,依次加入水中,搅拌均匀,得到混合溶液A;
(2)将混合溶液A加入钛酸四丁酯的乙醇溶液中,再加入柠檬酸,得到混合溶液B;
(3)将混合溶液B在70-90℃下水浴加热,搅拌条件下形成凝胶;
(4)凝胶干燥后研磨,得到的干凝胶颗粒在150-220℃下焙烧2-3h,再在380-500℃下煅烧10-14h,得到La掺杂CoFe2O4/TiO2复合光催化剂;
上述步骤中按照Co:Ti:La:水:柠檬酸的摩尔比为(0.5-0.8):1:(0.10-0.18):(120-200):(7-10)的比例进行配比,其中Fe摩尔量为Co摩尔量的2倍。
2.根据权利要求1所述处理苯酚废水的光催化剂制备方法,其特征在于:Co:Ti:La:柠檬酸的摩尔比为0.6:1:0.12:9。
3.根据权利要求1所述处理苯酚废水的光催化剂制备方法,其特征在于:所述镧盐为硝酸镧或者氯化镧。
4.根据权利要求1所述处理苯酚废水的光催化剂制备方法,其特征在于:所述钴盐为硝酸钴或氯化钴。
5.根据权利要求1所述处理苯酚废水的光催化剂制备方法,其特征在于:所述铁盐为硝酸铁、氯化铁和硫酸铁中任意一种。
6.根据权利要求1所述处理苯酚废水的光催化剂制备方法,其特征在于:所述水为蒸馏水或去离子水。
7.一种权利要求1-6任一项所述处理苯酚废水的光催化剂处理苯酚废水的方法,其特征在于:将制备得到的La掺杂CoFe2O4/TiO2复合光催化剂悬浊于苯酚废水中进行处理。
8.根据权利要求7所述处理含苯酚废水的方法,其特征在于:按0.5-5g/L的比例向废水中投加所述La掺杂CoFe2O4/TiO2复合光催化剂,然后常温搅拌处理1.5-2.5h。
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