CN108439673A - 一种光催化降解染料废水的处理工艺 - Google Patents
一种光催化降解染料废水的处理工艺 Download PDFInfo
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Abstract
本发明提出了一种光催化降解染料废水的处理工艺,其采用的可见光催化剂为离子液体修饰的钙钛矿包裹类水滑石光催化剂。该催化剂以具有光催化活性的钙钛矿包裹类水滑石为基底,修饰能够提高基底对可见光利用率以及能够提高其光催化活性的离子液体,所述离子液体为1‑甲基‑3氨丙基六氟磷酸盐。本发明解决了现有技术中染料废水降解效率低的问题,适用于降解污染水体中的有机染料。
Description
技术领域
本发明涉及一种光催化降解染料废水的处理工艺,采用离子液体修饰的钙钛矿包裹类水滑石光催化剂,该处理工艺具有操作简单、成本低廉、降解效率高等优点。
背景技术
工业发展离不开染料的使用,染料广泛地应用于纺织、造纸、印刷、食品、制药、复印和打印等许多领域。全世界工业染料约有10万种,每年约有100万吨的产量。由染料产生的工业废水是当前水体的主要污染之一,全世界每年随废水排放到环境中的染料约6万吨。我国是染料生产和出口大国,生产量、出口量均占世界第一。在染料生产和纺织品印染过程中,工业染料的排放,改变了天然水的性质和组分,使水体受到生理、物理、化学、生物性污染,不仅对环境和生产造成了危害,更重要的是危害到人类身体的健康。
水是人类生活最重要的组成部分,水的问题将直接影响国民经济和社会的发展,基于染料废水的种种危害,对染料废水的处理势在必行。染料废水具有组成复杂、水量及水质变化大、高色度、高含盐量、可生化性差等特点,是难处理的工业废水之一。传统的处理方法往往达不到满意的去除效果,近年来臭氧氧化法、高温深度氧化法、光催化氧化法、超声波降解法等物化技术不断出现,尤其是光催化氧化技术的使用备受关注。目前使用最普遍的光催化剂是TiO2,但其对太阳能利用率不高。因此,研制可提高太阳能利用率的新型光催化剂成为新的焦点。
钙钛矿型复合氧化物(ABO3)以其稳定的晶体结构与良好的催化活性已成为光催化领域的热点之一。当A与B离子被半径相近的金属离子取代后,引入了能提高催化活性的点缺陷,而晶型没有发生根本改变,但是提高了此类氧化物的催化活性。近年来对ABO3及其掺杂型化合物光催化降解染料废水的研究报道越来越多。
水滑石(LDHs)是一种阴离子型层状化合物,其主体一般由两种金属的氢氧化物构成,因此又称为层状双羟基复合金属氧化物。水滑石的组成可以通过不同方式来调变,层间的阴离子也可以被许多其他阴离子所取代,层间距的大小取决于层间阴离子以及层与阴离子间静电作用的状态,改性后的水滑石一般被称为类水滑石材料。以水滑石和类水滑石为载体或部分载体的催化剂已有不少研究。
离子液体是指含有离子的液体。它们是液态盐,不需要溶于溶剂。一般而言,当一种盐在100℃以下是以液态形式存在时,就称之为离子液体。烷基咪唑、吡啶、铵和磷离子是典型的阳离子。离子的大小和对称性可以防止形成较强的晶体晶格,也就是说仅仅少量的热能即可克服晶格能,并且能够破坏其固态晶体结构。目前已有离子液体能够增强催化剂光解水制氢活性的研究,但将离子液体负载于适宜的载体上用于制备具有优异光催化降解染料废水的催化剂则鲜有报道。
发明内容
为了克服上述现有技术的缺点,本发明的目的在于提供一种降解染料废水的催化剂、制备方法及其处理工艺,其采用可见光催化的方式降解其中的染料,采用的光催化剂为离子液体修饰的钙钛矿包裹类水滑石光催化剂。
该可见光降解染料废水的处理工艺,包括如下步骤:
取一定量的染料废水,经过絮凝去除其中的颗粒物,其中染料的浓度为5mg/L~20mg/L,向其中加入一定量的离子液体修饰的钙钛矿包裹类水滑石光催化剂,暗光下进行超声分散30min,使得催化剂吸附完全,然后在400-600W滤除紫外光的氙灯光源下进行常温可见光催化反应0.5-3h,所述光催化剂与染料废水的用量比为20~40g:100L,氙灯与所述染料废水的液面距离为18cm~22cm,完成对染料的降解。
所述染料为刚果红、酸性红A或酸性红G中的一种或多种。
所述离子液体修饰的钙钛矿包裹类水滑石催化剂以具有光催化活性的钙钛矿包裹类水滑石为基底,修饰能够提高基底对可见光利用率以及能够提高其光催化活性的离子液体,所述离子液体为1-甲基-3氨丙基六氟磷酸盐。
钙钛矿包裹类水滑石基底的制备,首先合成类水滑石基复合氧化物,如MgO-Al2O3;其次,利用类水滑石基复合氧化物的“重构效应”在其上引入钙钛矿氧化物的主要组分;再次将所得样品进行煅烧后形成具有核壳结构的钙钛矿包裹类水滑石基氧化物。具体包括如下步骤:
a、配制Mg(NO3)2和Al(NO3)3的混合水溶液,其中Mg与Al的摩尔比为1-4,其中混合水溶液的浓度为0.2-2mol/L;
b、在强烈搅拌的条件下,向Na2CO3水溶液中滴加步骤a配制的混合水溶液,待滴加完毕后再用Na2CO3水溶液将体系pH值调到8.5-11,并维持在40-80℃下老化1-24h,优选6-20小时;
其中所述强烈搅拌条件为150-300 rpm/min,优选180-240 rpm/min,所述Na2CO3水溶液的浓度为0.2-2mol/L,在滴加过程中,Na2CO3水溶液和步骤a配制的混合水溶液的体积比为(2-8):(8-32),整个滴加过程中,控制滴加速度以使步骤a配制的混合水溶液在0.5-3h内滴加完毕。
c、将经过步骤b制备所得的沉淀抽滤,洗涤干燥后,在400-800℃中煅烧4-10h,再将所得粉体压制成颗粒。
具体而言,将经过步骤b所得的沉淀抽滤,去离子水充分洗涤并于真空或空气气氛中于80-120℃干燥6-24h,得到类水滑石前驱体;经干燥后的类水滑石前驱体在400-800℃于空气或Ar或N2气氛中煅烧4-10h,升温速率0.5-20℃/min,优选1-10℃/min,煅烧所得粉体压制成颗粒,即MgO-Al2O3颗粒。
d、将所得MgO-Al2O3颗粒浸泡于混合Co(NO3)3和La(NO3)3的混合水溶液中进行重构,其中Co与La的摩尔比为1-2。
所述步骤d中的重构,应用类水滑石基氧化物的“重构效应”在上引入钙钛矿主要组分La和Co。重构条件直接影响形成的壳结构的厚度,可选择在室温20-80℃下浸泡至少0.5小时,优选0.5-3小时。
e、将经过步骤d重构的产物抽滤洗涤干燥后,在700-1200℃煅烧3-12小时后,优选在800-1000℃煅烧4-8h,即得到钙钛矿包裹类水滑石基底。
离子液体的制备包括如下步骤:将3-溴丙胺氢溴酸盐溶于无水乙腈,加入1-甲基咪唑,升温至45-75℃反应,开始升温到反应结束的时间为24h,移除溶剂,以体积比1:1的甲醇和乙醚混合溶液洗涤,旋转蒸发移除甲醇和乙醚后,将剩余物溶于甲醇,滴加饱和NaOH甲醇溶液至溶液的pH值至8-9,旋转蒸发移除甲醇,离心分离无机盐后与六氟磷酸铵反应1h,以硅胶柱色谱分离得橘红色1-甲基-3氨丙基咪唑六氟磷酸盐离子液体,4℃保存备用。
其中,3-溴丙胺氢溴酸盐、1-甲基咪唑、六氟磷酸铵加入量的摩尔比为(2-8):1:(1-5)。
离子液体修饰的方法包括如下步骤:
f、在冰浴、氮气氛围下,取一定量橘红色1-甲基-3氨丙基咪唑六氟磷酸盐离子液体的甲醇溶液,然后向其中加入钙钛矿包裹类水滑石基底,搅拌反应2h。反应产物旋转蒸发移除溶剂,得浅黄色粉末,即为离子液体修饰的钙钛矿包裹类水滑石催化剂。
其中1-甲基-3氨丙基咪唑六氟磷酸盐离子液体与钙钛矿包裹类水滑石基底的质量比为1:(20-30)。
与现有技术相比,本发明具有以下优点:
1、与现有技术相比,本发明的处理方法操作简单,反应条件容易控制、成本低廉、净化效率高,具有潜在的工业化应用前景;
2、本发明的光催化剂结合了两大类复合金属氧化物,即钙钛矿型氧化物和类水滑石氧化物,利用类水滑石的“重构效应”,在层状类水滑石氧化物的表面引入具有光催化活性的La、Co基钙钛矿型氧化物,由此构成的核壳结构提高了光生电子在基底上的传导,利于光生电子和空穴的有效分离,并且该结构还有助于光催化降解过程中的传质和传热效率,提高了光催化剂的活性;
3、离子液体1-甲基-3氨丙基六氟磷酸盐的修饰,拓宽了钙钛矿对可见光的响应范围,提高了催化剂对于可见光的利用率,极大地提高了催化剂对于染料废水的光催化降解活性。
具体实施方式
下面结合具体实施例对本发明作进一步阐述本发明的方案。
实施例1 钙钛矿包裹类水滑石基底的制备
具体包括如下步骤:
a、配制Mg(NO3)2和Al(NO3)3的混合水溶液,其中Mg与Al的摩尔比为:3,其中混合水溶液的浓度为0.4mol/L;
b、在150-300 rpm/min搅拌条件下,向Na2CO3水溶液中滴加步骤a配制的混合水溶液,1h滴完,滴加过程中,Na2CO3水溶液和步骤a配制的混合水溶液的体积比为1:4,待滴加完毕后再用Na2CO3水溶液将体系pH值调到10,并维持在80℃下老化12h;
c、将经过步骤b制备所得的沉淀抽滤,去离子水洗涤,然后在100℃干燥6h后,在800℃空气气氛中煅烧6h,再将所得粉体压制成MgO-Al2O3颗粒。
d、40℃下将所得MgO-Al2O3颗粒浸泡于Co(NO3)3和La(NO3)3的混合水溶液中进行重构2h,其中Co与La的摩尔比为2。
e、将经过步骤d重构的产物抽滤洗涤干燥后,在800℃煅烧6小时后,即得到钙钛矿包裹类水滑石基底。
实施例2 离子液体的制备
将3-溴丙胺氢溴酸盐溶于无水乙腈,加入1-甲基咪唑,升温至55℃反应,开始升温到反应结束的时间为24h,移除溶剂,以体积比1:1的甲醇和乙醚混合溶液洗涤,旋转蒸发移除甲醇和乙醚后,将剩余物溶于甲醇,滴加饱和NaOH甲醇溶液至溶液的pH值至8.5,旋转蒸发移除甲醇,离心分离无机盐后与六氟磷酸铵反应1h,以硅胶柱色谱分离得橘红色1-甲基-3氨丙基咪唑六氟磷酸盐离子液体,4℃保存备用。其中,3-溴丙胺氢溴酸盐、1-甲基咪唑、六氟磷酸铵加入量的摩尔比为4:1:3。
实施例3离子液体修饰的钙钛矿包裹类水滑石光催化剂
f、在冰浴、氮气氛围下,取一定量橘红色1-甲基-3氨丙基咪唑六氟磷酸盐离子液体的甲醇溶液,然后向其中加入钙钛矿包裹类水滑石基底,搅拌反应2h。反应产物旋转蒸发移除溶剂,得浅黄色粉末,即为离子液体修饰的钙钛矿包裹类水滑石催化剂。其中1-甲基-3氨丙基咪唑六氟磷酸盐离子液体与钙钛矿包裹类水滑石基底的质量比为1:25。
对比例1 采用硬脂酸溶胶凝胶法制备LaCoO3钙钛矿氧化物
取一定量的硬脂酸加热,使其呈熔融状态,依次加入硝酸钴和硝酸镧,恒温搅拌,待完全溶解后,将其与苯共沸蒸馏,去除溶胶中的水,室温下冷却得到凝胶,即制得复合氧化物的前驱体。充分研磨后,将其置于马弗炉中,800℃煅烧6h,得到LaCoO3钙钛矿氧化物。
实施例4 光催化降解染料(以刚果红为染料模型分子)废水
配制三份10mg/L的刚果红溶液100mL作为反应污染物,分别向其中加入0.03g 对比例1制得的LaCoO3钙钛矿氧化物、实施例1制得的钙钛矿包裹类水滑石和实施例3制得的离子液体修饰的钙钛矿包裹类水滑石光催化剂。暗光下超声分散30min,然后在400W滤除紫外光的氙灯光源下进行常温可见光催化反应2.5h,保持氙灯与染料废水的液面距离为20cm,每隔30min取样分析样液中刚果红的浓度,从而考察不同时间催化剂的降解活性,具体数据参见下表1:
表1. 不同样品的光催化活性测试
由表1中的数据分析可知,相比硬脂酸溶胶凝胶法制备LaCoO3钙钛矿氧化物,在类水滑石氧化物上引入La、Co形成钙钛矿核壳材料后,其降解刚果红的效率有了不小的提升,这是由于核壳结构的行程增强了光生电子及空穴的分离,同时还强化了基底材料的传质和传热,提高了光催化活性;而再修饰离子液体后,由于离子液体对于可见光响应范围的拓宽,催化剂对于刚果红的降解效率有了更大的提升,由此可见,本发明制备的钙钛矿复合光催化剂具有优异的染料废水降解效果。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (7)
1.一种可见光降解染料废水的处理工艺,其特征在于,取一定量的染料废水,经过絮凝去除其中的颗粒物,其中染料的浓度为5mg/L~20mg/L,向其中加入一定量的离子液体修饰的钙钛矿包裹类水滑石光催化剂,暗光下进行超声分散30min,使得催化剂吸附完全,然后在400-600W滤除紫外光的氙灯光源下进行常温可见光催化反应0.5-3h,所述光催化剂与染料废水的用量比为20~40g:100L,氙灯与所述染料废水的液面距离为18cm~22cm,完成对染料的降解;
所述催化剂以具有光催化活性的钙钛矿包裹类水滑石为基底,修饰的离子液体为1-甲基-3氨丙基六氟磷酸盐,其制备包括如下步骤:
a、配制Mg(NO3)2和Al(NO3)3的混合水溶液,其中Mg与Al的摩尔比为1-4,其中混合水溶液的浓度为0.2-2mol/L;
b、在强烈搅拌的条件下,向Na2CO3水溶液中滴加步骤a配制的混合水溶液,待滴加完毕后再用Na2CO3水溶液将体系pH值调到8.5-11,并维持在40-80℃下老化1-24h;
c、将经过步骤b制备所得的沉淀抽滤,洗涤干燥后,在400-800℃中煅烧4-10h,再将所得粉体压制成颗粒;
d、将所得MgO-Al2O3颗粒浸泡于混合Co(NO3)3和La(NO3)3的混合水溶液中进行重构,其中Co与La的摩尔比为1-2;
e、将经过步骤d重构的产物抽滤洗涤干燥后,在700-1200℃煅烧3-12小时后,优选在800-1000℃煅烧4-8h,即得到钙钛矿包裹类水滑石基底。
2.如权利要求1所述的处理工艺,其特征在于,催化剂的制备还包括子液体的制备:将3-溴丙胺氢溴酸盐溶于无水乙腈,加入1-甲基咪唑,升温至45-75℃反应,开始升温到反应结束的时间为24h,移除溶剂,以体积比1:1的甲醇和乙醚混合溶液洗涤,旋转蒸发移除甲醇和乙醚后,将剩余物溶于甲醇,滴加饱和NaOH甲醇溶液至溶液的pH值至8-9,旋转蒸发移除甲醇,离心分离无机盐后与六氟磷酸铵反应1h,以硅胶柱色谱分离得橘红色1-甲基-3氨丙基咪唑六氟磷酸盐离子液体,4℃保存备用;其中,3-溴丙胺氢溴酸盐、1-甲基咪唑、六氟磷酸铵加入量的摩尔比为(2-8):1:(1-5)。
3.如权利要求2所述的处理工艺,其特征在于,离子液体修饰的方法包括如下步骤:f、在冰浴、氮气氛围下,取一定量橘红色1-甲基-3氨丙基咪唑六氟磷酸盐离子液体的甲醇溶液,然后向其中加入钙钛矿包裹类水滑石基底,搅拌反应2h,反应产物旋转蒸发移除溶剂,得浅黄色粉末,即为离子液体修饰的钙钛矿包裹类水滑石催化剂;其中1-甲基-3氨丙基咪唑六氟磷酸盐离子液体与钙钛矿包裹类水滑石基底的质量比为1:(20-30)。
4.如权利要求1-3任一项所述的处理工艺,其特征在于,所述染料为刚果红、酸性红A或酸性红G中的一种或多种。
5.如权利要求1-3任一项所述的处理工艺,其特征在于,步骤b的老化时间为6-20h,所述强烈搅拌条件为150-300 rpm/min,优选180-240 rpm/min,所述Na2CO3水溶液的浓度为0.2-2mol/L,在滴加过程中,Na2CO3水溶液和步骤a配制的混合水溶液的体积比为(2-8):(8-32),整个滴加过程中,控制滴加速度以使步骤a配制的混合水溶液在0.5-3h内滴加完毕。
6.如权利要求1-3任一项所述的处理工艺,其特征在于,将经过步骤b所得的沉淀抽滤,去离子水充分洗涤并于真空或空气气氛中于80-120℃干燥6-24h,得到类水滑石前驱体;经干燥后的类水滑石前驱体在400-800℃于空气或Ar或N2气氛中煅烧4-10h,升温速率0.5-20℃/min,优选1-10℃/min,煅烧所得粉体压制成颗粒,即MgO-Al2O3颗粒。
7.如权利要求1-3任一项所述的处理工艺,其特征在于,所述的浸泡为在室温20-80℃下浸泡至少0.5小时,优选0.5-3小时。
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CN109603832A (zh) * | 2018-12-28 | 2019-04-12 | 陕西师范大学 | 一种快速制备大量花状钴基双金属氢氧化物的方法 |
CN110404503A (zh) * | 2019-09-25 | 2019-11-05 | 长沙华时捷环保科技发展股份有限公司 | 一种氟改性水滑石除磷药剂及其制备方法和应用 |
CN116371464A (zh) * | 2023-02-10 | 2023-07-04 | 华东师范大学 | 一种聚离子液体-水滑石复合材料及制备方法和催化应用 |
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CN103111302A (zh) * | 2013-01-12 | 2013-05-22 | 天津大学 | 壳—核型钙钛矿包裹类水滑石基氧化物重整制氢催化剂的制备和应用 |
CN107337644A (zh) * | 2017-06-27 | 2017-11-10 | 中南民族大学 | 基于一种新型离子液体的功能化钙钛矿材料及其在太阳能电池制备中的应用 |
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CN103111302A (zh) * | 2013-01-12 | 2013-05-22 | 天津大学 | 壳—核型钙钛矿包裹类水滑石基氧化物重整制氢催化剂的制备和应用 |
CN107337644A (zh) * | 2017-06-27 | 2017-11-10 | 中南民族大学 | 基于一种新型离子液体的功能化钙钛矿材料及其在太阳能电池制备中的应用 |
Cited By (5)
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CN109603832A (zh) * | 2018-12-28 | 2019-04-12 | 陕西师范大学 | 一种快速制备大量花状钴基双金属氢氧化物的方法 |
CN109603832B (zh) * | 2018-12-28 | 2021-06-15 | 陕西师范大学 | 一种快速制备大量花状钴基双金属氢氧化物的方法 |
CN110404503A (zh) * | 2019-09-25 | 2019-11-05 | 长沙华时捷环保科技发展股份有限公司 | 一种氟改性水滑石除磷药剂及其制备方法和应用 |
CN116371464A (zh) * | 2023-02-10 | 2023-07-04 | 华东师范大学 | 一种聚离子液体-水滑石复合材料及制备方法和催化应用 |
CN116371464B (zh) * | 2023-02-10 | 2024-05-17 | 华东师范大学 | 一种聚离子液体-水滑石复合材料及制备方法和催化应用 |
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