CN114392745A - 一种制备Fe-过渡金属-Al复合金属氧化物的方法及其应用 - Google Patents
一种制备Fe-过渡金属-Al复合金属氧化物的方法及其应用 Download PDFInfo
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Abstract
本发明属于无机催化材料技术领域,具体涉及一种制备Fe‑过渡金属‑Al复合金属氧化物的方法与应用。采用共沉淀法制备了Fe‑过渡金属‑Al复合金属氧化物催化剂,通过滴加碱液生成前驱体,然后老化、抽滤、干燥、煅烧和研磨得到复合Fe‑过渡金属‑Al复合金属氧化物催化材料。本发明方法制备工艺简单,催化材料性能稳定、孔径大、可催化双氧水高效氧化降解苯酚和氯酚废水,重复循环利用5次后,COD去除率仍在80%以上。本发明制备的催化材料可广泛用于酚类工业废水的深度氧化处理。
Description
技术领域
本发明属于无机催化材料技术领域,具体涉及一种制备Fe-过渡金属-Al复合金属氧化物的方法与应用。
背景技术
酚类物质在许多行业都有生产或消费,如炼油厂、焦化厂、化学合成厂、制药厂、塑料工业、纺织制造业以及电子等领域。由于工业、农业和家庭活动,大量有毒有害污染物排放到环境中。氯酚是有毒工业化合物中最丰富的一类,它们能抵抗生物降解并在环境中长期存在,对水生环境造成相当大的损害,对大多数水生生物的毒性在10-100 ppm之间
在水和废水处理的各种催化氧化技术中,过氧化氢和铁离子参与的Fenton反应是一种非常流行的反应。这种反应遵循一种特殊的氧化途径,通常是由于在Fe2+离子存在下形成羟基自由基而引发的。这些羟基自由基具有极高的反应活性,可将有机污染物氧化成无害的最终产品。pH值限制、二次污染的可能性、催化剂的大量消耗和额外的循环过程都限制了均相Fenton的应用。为了克服这些缺点,提高催化效率,开发了固体催化剂,并被用作非均相Fenton中的铁源来代替均相Fenton法中的亚铁离子。采用非均相Fenton法,可以调节污泥的产率。污泥的产生取决于催化剂的金属浸出,随着浸出率的增加而增加。由于浸出性能很低,消耗的铁物种较少。在Fenton法中,催化剂很容易分离。非均相Fenton法不需要进一步的污泥处理。
当前所报道的固相催化剂多为将铁源负载于不同的载体上。潘嘉敏等人设计了Fe0-CNTs-Cu的新型材料,在pH=1.8时,反应60 min对2,4-DCP的降解率为92.3%;殷楠等人采用水热法合成了MoO3/g-C3N4复合光催化剂,240 min 内对亚甲基蓝(MB)溶液的降解率达95.7%;张晓等人采用醇助水热法制备了新型生物质炭修饰的α-FeOOH类芬顿催化剂,在pH中性条件下,反应120 min,对罗丹明B降解率达90%。由此可知,目前的类芬顿催化剂催化降解有机污染物存在催化剂制备条件严苛,适用pH低,反应时间长且不能彻底去除污染物等问题,综上所述需要实现非均相类芬顿催化剂的制备及应用在实际生活中的普及。
发明内容
本发明目的是克服上述已有技术的不足,提供一种制备Fe-过渡金属-Al复合金属氧化物的方法与应用 。
为实现上述目的,本发明采用技术方案为:
一种制备Fe-过渡金属-Al复合金属氧化物的方法及其应用,
1)前驱体的制备:以含铁、铝和一种或几种的过渡金属盐混合获得金属盐的混合溶液,而后向混合金属溶液中滴加pH为10~13的碱液,以共沉淀法获得前驱体,待用;
2)Fe-过渡金属-Al复合金属氧化物的制备:将前驱体在400-900 ℃ (优选为500~700 ℃)下煅烧2-5 h 后(优选为3~4 h),获得以共沉淀法实现的Fe-过渡金属-Al复合金属氧化物。
所述步骤1)中将含铁、铝和一种或几种的过渡金属盐混合,混合后溶解在去离子水中,超声分散,得到金属盐的混合溶液;而后向混合溶液中滴加pH为10~13(优选为pH为11~12)的碱液,以共沉淀法获得棕褐色乳状混合溶液,即Fe-过渡金属-Al的前驱体溶液;
其中,金属盐的混合溶液中总金属离子浓度为1.0~1.5 mol/L,金属盐的混合溶液与碱液的体积比为1:1-3。
上述碱液在磁力搅拌状态下,将其加热至50~70 ℃,而后逐滴加至金属盐混合溶液中,20~40 min 内加完,优选为25 min。
所述Fe-过渡金属-Al的前驱体溶液在微波反应器中继续反应1~4 h(优选为2 h),之后抽滤,干燥,研磨,得到粉末状前驱体,待用。
所述含铁盐为Fe(NO3)3、FeCl3、Fe2(SO4)3,或上述盐中带有结晶水的铁盐。
含铝盐为Al(NO3)3或其带有结晶水的硝酸铝盐;
所述过渡金属盐为Ce、Ni、Co、Mn、Ir、Bi一种或几种过渡金属的硝酸盐;
所述混合液中金属元素的Fe: 过渡金属:Al质量比为1:0.25:0.6-1:4:0.6。
所述碱液为Na2CO3和/或NaOH经水配置碱液;碱液中Na2CO3和/或NaOH的浓度为1-2mol/L。
优选,碱基为Na2CO3和NaOH加入至去离子水中,得到碱液,其中,Na2CO3和NaOH的摩尔比为1:3。
一种Fe-过渡金属-Al复合金属氧化物,所述制备方法获得团聚成纳米颗粒Fe-过渡金属-Al复合催化氧化剂。
一种Fe-过渡金属-Al复合金属氧化物的应用,所述Fe-过渡金属-Al复合金属氧化物可用作活化双氧水的催化剂,应用于催化双氧水高效分解产生羟基反应。
所述Fe-过渡金属-Al复合金属氧化物可作为非均相芬顿反应催化剂用于酚类废水的深度氧化处理。
在待处理样品中,常压下,50~70 ℃、pH=2~7下进行;样品体系内加入H2O2和上述催化剂;其中,所述的H2O2加入量为50~70 mmol/L、催化剂的加入量0.1~4 g/L。
本发明方法与已有技术相比优点为:
本发明采用共沉淀法,在较宽泛的条件下制备Fe-过渡金属-Al复合金属氧化物,避免采用浸渍法制备相同类型催化材料在煅烧处理过程中带来的NOx大气污染问题,同时使获得的复合金属氧化物有较好的结晶度,减少了金属活性组分的流失,提高了催化剂的循环稳定性;进而使所得催化剂解决了传统均相Fenton处理方法带来的产生大量铁泥,催化剂不能循环利用,降解反应适用pH窄等问题;本发明催化剂提出在Fe-Al复合材料中加入特定过渡金属元素,制成三元复合金属氧化物,在提高催化剂结晶度同时,提高催化剂稳定性,并提高催化剂的催化活性,本发明所得催化剂具有适用pH范围宽泛,反应时间短,催化活性高等优势,节约酚类废水的处理成本,有利于进一步实现非均相类芬顿催化剂的制备及应用在实际生活中的普及;具体为:
1.该催化剂在常压下即可进行,反应设备简单,节约处理成本;
2.该催化剂催化氧化活性高,在pH=2~7时能够氧化降解氯酚类污染物,pH=2~5时能够完全降解5 mM 的氯酚类污染物,且具有高的COD去除率;
3.该催化剂反应过程中金属离子溶出少,大大减少铁泥的生成,性能稳定,能循环使用4次以上;
4.该催化剂缩短了反应降解时间,降低了污水处理成本,提高污水处理效率并且具有更好的生产和实用价值。
附图说明
图1是本发明制备的Fe-Ce-Al复合催化氧化剂的电镜图;
图2是本发明制备的不同催化氧化剂的XRD谱图;
图3是本发明实施例制备所得不同催化剂对2,4-DCP催化氧化降解的影响;
图4是本发明实施例制备所得不同催化剂降解有机废水对COD去除率的影响;
图5是本发明实施例制备所得Fe-Ce-Al复合催化氧化剂降解实际工业废水结果。
具体实施方式
以下实施例是对本发明的进一步说明,但本发明不限于此。
本发明提供在常压下对氯酚类化合物样品进行多相催化氧化降解的方法,首先在圆底烧瓶中加入氯酚废水,加入复合催化氧化剂,将溶液加热到40~70 ℃,慢慢加入H2O2,在pH=2~7条件下对氯酚类化合物进行催化氧化降解。
实施例1,制备的不同催化氧化剂,催化剂中过渡金属可为Ni、Co、Mn、Ir、Bi或Ce,以Ce为例,具体为:
称取9.32 g Fe(NO3)3·9H2O、20.04 g Ce(NO3)3·6H2O、7.78 g Al(NO3)3·9H2O溶于60 mL 去离子水,超声10 min,获得金属盐溶液;称取7.22 g NaOH、6.38 g Na2CO3溶于120 mL 去离子水,超声5 min,将碱液加热到50 ℃ 后,慢慢滴加上述金属盐溶液,滴加时间控制在20 min 以内,滴加完后在于50℃恒温下继续搅拌80 min,而后转移至微波反应器在60 ℃老化2 h,老化后经水洗涤、抽滤、干燥和研磨成粉末,制成Fe-Ce-Al复合金属氧化物前驱体。将干燥好的前驱体放入马弗炉中500 ℃ 煅烧4 h,制得Fe-Ce-Al复合金属氧化物(参见图1和图2)。
按照上述记载的制备方法,将金属盐溶液中各金属量进行调配即获得含有不同量的Fe-Ce-Al复合金属氧化物,同时将金属盐溶液中过渡金属进行替换,例如Ni、Co、Mn、Ir、Bi,即可获得不同三元复合催化氧化剂(参见图2)。
由图1和图2可见,本发明所制备的催化剂表面形貌为由小颗粒堆积成的大颗粒,且形成了孔径较大的空隙。图2说明成功制备了不同复合金属氧化物催化氧化剂。
实施例2,不同复合催化氧化剂在降解苯酚废水中的应用
(1)、取100 mL 三口烧瓶,加入60 mL、5 mmol/L 的苯酚废水(COD值为1190 mg/L),2 g/L 的上述实施例制备获得不同催化剂,pH=4条件下,加热到50 ℃,慢慢滴加70mmol/L 的H2O2,反应降解60 min后,测定其降解率,而后离心(一般,4000转,5分钟),取上层清液,测试COD值。
(2)、将反应溶液离心,过滤,用剩余催化剂重复实施例2(1)中的操作步骤,研究催化剂稳定性,同时进一步以Fe-Ce-Al(1:2:0.6)复合催化氧化剂降解苯酚循环利用的影响;具体结果见表1、表2。
(3)、并且以按照实施例1的相同制备步骤,只改变金属溶液成分为9.32 g Fe(NO3)3·9H2O、7.78 g Al(NO3)3·9H2O的方法,制备获得Fe-Al作为对照。
表1 不同催化剂对苯酚氧化降解的影响
表2 Fe-Ce-Al(1:2:0.6)复合催化氧化剂降解苯酚循环利用的影响
由上述表1和2可见,以本发明所述方法制备的Fe-过渡金属-Al复合催化氧化剂有较高的催化活性,并且有良好的循环稳定性。
实施例3,Fe-Ce-Al复合催化氧化剂在降解2,4-DCP废水中的应用
(1)、取100 mL 三口烧瓶,加入60 mL、5 mmol/L 的2,4-DCP废水(COD值为897 mg/L),2 g/L的上述实施例获得Fe-Ce-Al(1:2:0.6)复合催化剂,不同pH条件下,加热到70 ℃,慢慢滴加70 mmol/L 的H2O2,反应降解60 min 后,测定其降解率,而后离心,取上层清液,测试COD值为138.66 mg/L。
(2)、按实施例2(2)中的步骤研究催化剂的循环利用性能,催化剂可重复至少四次,苯酚降解率为100%,COD去除率为84.45%。具体结果见表3。
表3 Fe-Ce-Al复合催化氧化剂不同pH对2,4-DCP氧化降解的影响
由上述表3可见,本发明所制备的催化剂在较宽pH范围(2~7)内都有较高催化活性。
实施例4,Fe-Ce-Al(1:2:0.6)复合催化氧化剂与传统均相催化剂比较实验
向100mL三口圆底烧瓶中加入60mL、5mM的2,4-DCP废水,分别加入0.37g的FeSO4·7H2O、或0.12g的上述实施例制备获得Fe-Ce-Al(1:2:0.6)复合催化氧化剂,分别在pH=4条件下,70 ℃ 反应,逐滴滴加70 mmol/L的H2O2,反应降解一定时间后,测定其不同反应时间下的降解率,而后离心,取上层清液,测试COD值(参见图3和4)。
由图3和4可见,本发明所制备的催化剂与均相Fe2+催化剂在60 min内均能彻底降解2,4-DCP,但是反应60 min后,Fe-Ce-Al(1:2:0.6)与Fe2+的COD去除率分别为86.18%、46.05%,近似Fe2+的两倍。由此可知,本发明所制备的催化剂有相较于传统均相Fe2+更高的催化活性。
实施例5,Fe-Ce-Al(1:2:0.6)复合催化氧化剂在降解实际工业废水中的应用
在100 mL 三口烧瓶中加入60 mL 工业废水(COD=1828.3mg/L),4 g/L 的催化剂,pH=4条件下,70 ℃ 反应,滴加0.2 mol/L 的H2O2,反应60 min,测定其不同反应时间下的降解率,而后离心,取上层清液,测试COD值为338.05 mg/L(参见图5)。
上述工业废水中2-CP、4-CP和2,4-DCP的初始含量依次为10%、10%、80%;
经过添加催化剂处理后,对于高浓度氯酚废水采用本发明催化剂2-CP、4-CP和2,4-DCP在30分钟后各污染物的降解率即可达到为100%, COD去除率为95%。
综上所述,本发明所制备的Fe-过渡金属-Al复合金属氧化物具有较高的催化活性,适用pH广泛,COD去除率高,大大降低了工业废水中氯酚类污染物的生物难降解性,且在催化活性比传统均相芬顿高的基础上,能够循环使用至少4次,在提高降解效果的基础上,节约了废水处理成本,具有更实际、广泛的应用。
Claims (9)
1.一种制备Fe-过渡金属-Al复合金属氧化物的方法及其应用,其特征在于:
1)前驱体的制备:以含铁、铝和一种或几种的过渡金属盐混合获得金属盐的混合溶液,而后向混合金属溶液中滴加pH为10~13的碱液,以共沉淀法获得前驱体,待用;
2)Fe-过渡金属-Al复合金属氧化物的制备:将前驱体在400-900 ℃ 下煅烧2-5 h 后,获得以共沉淀法实现的Fe-过渡金属-Al复合金属氧化物。
2.按权利要求1所述的制备Fe-过渡金属-Al复合金属氧化物的方法,其特征在于:所述步骤1)中将含铁、铝和一种或几种的过渡金属盐混合,混合后溶解在去离子水中,超声分散,得到金属盐的混合溶液;而后向混合溶液中滴加pH为10~13的碱液,以共沉淀法获得棕褐色乳状混合溶液,即Fe-过渡金属-Al的前驱体溶液;
其中,金属盐的混合溶液中总金属离子浓度为1.0~1.5 mol/L,金属盐的混合溶液与碱液的体积比为1:1-3。
3.按权利要求2所述的制备Fe-过渡金属-Al复合金属氧化物的方法,其特征在于:所述Fe-过渡金属-Al的前驱体溶液在微波反应器中继续反应1~4 h,之后抽滤,干燥,研磨,得到粉末状前驱体,待用。
4.按权利要求1-3所述的制备Fe-过渡金属-Al复合金属氧化物的方法,其特征在于:所述含铁盐为Fe(NO3)3、FeCl3、Fe2(SO4)3;
含铝盐为Al(NO3)3;
所述过渡金属盐为Ce、Ni、Co、Mn、Ir、Bi一种或几种过渡金属的硝酸盐;
所述混合液中金属元素的Fe:过渡金属:Al质量比为1:0.25:0.6-1:4:0.6。
5.按权利要求1-3所述的制备Fe-过渡金属-Al复合催化氧化剂的方法,其特征在于:所述碱液为Na2CO3和/或NaOH经水配制碱液;碱液中Na2CO3和/或NaOH的浓度为1-2 mol/L。
6.一种权利要求1所述方法制备获得Fe-过渡金属-Al复合金属氧化物,其特征在于:所述权利要求1制备方法获得团聚成纳米颗粒的Fe-过渡金属-Al复合催化氧化剂。
7.一种权利要求6所述的Fe-过渡金属-Al复合金属氧化物的应用,其特征在于:所述Fe-过渡金属-Al复合金属氧化物可用作活化双氧水的催化剂,应用于催化双氧水高效分解产生羟基自由基反应。
8.按权利要求7所述的应用,其特征在于:所述Fe-过渡金属-Al复合金属氧化物可作为非均相芬顿反应催化剂用于酚类废水的深度氧化处理。
9.按权利要求8所述的应用,其特征在于:在待处理样品中,常压下,50~70 ℃、pH=2~7下进行;样品体系内加入H2O2和上述催化剂;其中,所述的H2O2加入量为50~70 mmol/L、催化剂的加入量0.1~4 g/L。
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