CN112316955A - 一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法 - Google Patents
一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂及其制备方法。该制备方法首先通过溶剂热法制备二氧化钛微球,并在二氧化钛上原位负载硫化镉,构筑二氧化钛/硫化镉异质结,然后进一步通过超声以及热处理将二氧化钛/硫化镉异质结与壳聚糖凝胶进行复合,最终制得了二氧化钛/硫化镉/壳聚糖光催化剂。本发明所制备的二氧化钛/硫化镉/壳聚糖光催化剂具有优异的降解印染污水能力,并且其原料便宜易得、制备方法简单,可重现性高,易实现产业化生产。
Description
技术领域
本发明涉及污水处理和光催化技术领域,特别是涉及一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法。
背景技术
我国是世界上最大的纺织品服装生产国,据国家环保总局统计,纺织业的印染污水排放量居全国制造业排放总量的第5位,60%以上的行业污水排放来自印染行业。印染行业的污水水量大、浊度高、色度高、污染物浓度高,其主要含有染料、浆料、酸碱、表面活性剂、纤维碎屑以及酶类等污染物,不仅降解困难、易产生二次污染、回收利用成本昂贵,还消耗大量的资源与能源。所以,在一定程度上实现印染污水的有效净化,将对资源利用和环境保护展现出巨大的经济效益。现今对印染污水的处理大多是以好氧或厌氧工艺的生物方法处理为主,混凝、电解和化学氧化等工艺处理为辅。但通过此类工艺处理纺织印染污水,其设备昂贵、工艺操作复杂,且污水最多只能达到低级排放标准。因此,人们急需找到一种可全面、高效处理印染污水的方式来解决印染污水处理的难题。而光催化技术作为一项绿色技术,具有安全高效、节约能源、适应范围广和氧化性强等优点,充分利用了紫外-可见光源来激发催化剂,驱动氧化-还原反应,可有效地降解有毒有害的气体和污水中难以降解的有机物。综上所述,本发明提供一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法。
发明内容
本发明主要目的是提供一种成本低廉、绿色环保、性质稳定的高效二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,这对于印染污水的处理具有十分重大的现实意义。
所述的一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,其技术方案包括以下步骤:
步骤1:将乙二醇和醋酸混合均匀,加入模板剂二乙烯三胺,在磁力搅拌下逐滴滴加四氯化钛,然后将其转移到反应釜中,在160-200℃下反应12-24h,待自然冷却后,将产物洗涤、干燥,既得到由纳米棒分级自组装的二氧化钛微球;
步骤2:将镉源与去离子水和少量稀硝酸混合,pH≤7时,即可配置成镉溶液,然后在磁力搅拌下加入硫代乙酰胺,匀速搅拌10min,加入步骤1所制备的二氧化钛微球,超声20min,再匀速搅拌10min,然后加入1mol/L的盐酸,调节pH至3-6,然后将其转移到反应釜中,在200℃下反应12-24h,将产物洗涤、离心、真空干燥,即得到二氧化钛/硫化镉复合物;
步骤3:将壳聚糖与2%浓度的醋酸液混合,配置成壳聚糖胶状液,加入步骤2所制备的二氧化钛/硫化隔复合物,混合均匀,超声20min,将产物洗涤、离心、真空干燥,然后转移到马弗炉中,在250-500℃下煅烧1-6h,即得到二氧化钛/硫化镉/壳聚糖复合材料。
作为上述技术方案的优选,本发明提供的一种用于污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法进一步包括下列技术特征的部分或全部:
优选地,步骤1中所述的乙二醇、醋酸、二乙烯三胺和四氯化钛的体积比50:(1-5):(0.02-0.2):(1-5)。
优选地,步骤2中所述的镉源为氯化镉、硝酸镉四水合物、醋酸镉四水合物或硫酸镉八水合物的一种。
优选地,步骤2中所述的镉溶液浓度为(0.01-0.2)mol/L。
优选地,步骤2中所述的镉源、硫代乙酰胺和二氧化钛微球的摩尔比为(1-2):(1-2):(1-4)。
优选地,步骤3中所述的壳聚糖胶状液质量浓度为(0.01-0.04)g/mL。
优选地,步骤3中所述的壳聚糖胶状液和二氧化钛/硫化隔复合物的质量体积比为20mL:(0.4-2)g。
与现有技术相比,本发明的技术方案具有如下有益效果:
(1)本发明所制备的二氧化钛/硫化镉/壳聚糖光催化剂是由二氧化钛、硫化镉和壳聚糖共同组成的复合材料。一方面,二氧化钛和硫化镉是十分具有发展前景的光催化剂,两者利用协同效应,增强了材料在紫外-可见光吸收范围内的光响应范围,有效的提高了光生电子-空穴对的分离效率。不仅可以利用电子和空穴获取的能量将大分子有机污染物直接分解,还可以利用光生空穴与水分子反应产生的羟基自由基来分解有机污染物。另一方面,壳聚糖结构中含有大量自由的羟基、氨基官能团,其与污水中的负电荷微粒结合,进一步通过络合及离子交换作用将印染污水中的有机染料、酶等难处理的大分子污染物降解,这对印染废水的处理起到了良好的水质净化作用。
(2)本发明制备的二氧化钛/硫化镉/壳聚糖光催化剂具有优异的光催化降解印染污水能力。印染污水经光催化处理后,其色度降解87-89%,浊度降解70%-83%,COD下降86%-88%,BOD下降77%-87%,达到了一级的排放标准,甚至还可以作为循环水参与部分工艺流程,实现资源的合理化利用。
具体实施方式
为能进一步了解本发明的发明内容、特征及其优点,通过以下实施例以及对比例来进一步阐述。
实施例1
一种具有优异降解印染污水性能的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法以及光降解印染废水性能测试方法,具体步骤如下:
(1)制备分级结构的二氧化钛:将50mL乙二醇和2mL醋酸混合均匀,加入100μL二乙烯三胺,在磁力搅拌下逐滴滴加4mL四氯化钛,然后将其转移到反应釜中,在200℃下反应12h,待反应釜自然冷却后,将产物用去离子水和无水乙醇分别洗涤、离心、真空干燥;
(2)制备二氧化钛/硫化镉复合物:将2.2g硝酸镉和50mL去离子水混合,当有少量沉淀产生时,加入1mol/L的稀硝酸调节pH至7时,加入0.6g硫代乙酰胺,在磁力搅拌下匀速搅拌10min,然后加入1g步骤1所制备的二氧化钛微球,超声20min,再匀速搅拌10min,然后加入1mol/L的盐酸,调节pH至5,然后将其转移到反应釜中,在200℃下反应12h,将产物洗涤、离心、真空干燥。
(3)制备二氧化钛/硫化镉/壳聚糖复合材料:将0.4g壳聚糖与20mL 2%浓度的醋酸液混合,配置成壳聚糖胶状液,然后加入0.4g步骤2所制备的二氧化钛/硫化隔复合物,混合均匀,超声20min,将产物洗涤、离心、真空干燥,然后转移到马弗炉中,在350℃下煅烧3h;
(4)光催化降解印染污水性能测试:采用实施例1所制备的二氧化钛/硫化镉/壳聚糖复合材料作为光催化剂,取1L印染废水和0.5g二氧化钛/硫化镉/壳聚糖光催化剂于一用锡纸包裹起来的烧杯中,超声10min,再置于设有氙灯光源装置的磁力搅拌器下,匀速搅拌,0.5h后抽取两毫升污水并离心、取上清液,作为待检测样品S1;待第一次取点结束后,将氙灯打开,继续匀速搅拌,1h后抽取两毫升污水并离心、取上清液,作为待检测样品S2;待第二次取点结束后,继续匀速搅拌,1h后抽取两毫升污水并离心、取上清液,作为待检测样品S3;待第三次取点结束后,继续匀速搅拌,1h后抽取两毫升污水并离心、取上清液,作为待检测样品S4;待第四次取点结束后,继续匀速搅拌,1h后抽取两毫升污水并离心、取上清液,作为待检测样品S5。
实施例2
一种具有优异降解印染污水性能的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法以及光降解印染废水性能测试方法,具体步骤如下:
(1)制备分级结构的二氧化钛:将50mL乙二醇和2mL醋酸混合均匀,加入100μL二乙烯三胺,在磁力搅拌下逐滴滴加4mL四氯化钛,然后将其转移到反应釜中,在200℃下反应12h,待反应釜自然冷却后,将产物用去离子水和无水乙醇分别洗涤、离心、真空干燥;
(2)制备二氧化钛/硫化镉复合物:将2.2g硝酸镉和50mL去离子水混合,当有少量沉淀产生时,加入1mol/L的稀硝酸调节pH至7时,加入0.6g硫代乙酰胺,在磁力搅拌下匀速搅拌10min,然后加入1g步骤1所制备的二氧化钛微球,超声20min,再匀速搅拌10min,然后加入1mol/L的盐酸,调节pH至5,然后将其转移到反应釜中,在200℃下反应12h,将产物洗涤、离心、真空干燥;
(3)制备二氧化钛/硫化镉/壳聚糖复合材料:将0.4g壳聚糖与20mL 2%浓度的醋酸液混合,配置成壳聚糖胶状液,然后加入1g步骤2所制备的二氧化钛/硫化隔复合物,混合均匀,超声20min,将产物洗涤、离心、真空干燥,然后转移到马弗炉中,在350℃下煅烧3h;
(4)光催化降解印染污水性能测试:采用实施例2所制备的二氧化钛/硫化镉/壳聚糖复合材料作为光催化剂,取1L印染废水和0.5g二氧化钛/硫化镉/壳聚糖光催化剂于一用锡纸包裹起来的烧杯中,超声10min,再置于设有氙灯光源装置的磁力搅拌器下,匀速搅拌,0.5h后将氙灯打开,继续匀速搅拌,4h后抽取两毫升污水并离心、取上清液,作为待检测样品。
实施例3
一种具有优异降解印染污水性能的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法以及光降解印染废水性能测试方法,具体步骤如下:
(1)制备分级结构的二氧化钛:将50mL乙二醇和2mL醋酸混合均匀,加入100μL二乙烯三胺,在磁力搅拌下逐滴滴加4mL四氯化钛,然后将其转移到反应釜中,在200℃下反应12h,待反应釜自然冷却后,将产物用去离子水和无水乙醇分别洗涤、离心、真空干燥;
(2)制备二氧化钛/硫化镉复合物:将2.2g硝酸镉和50mL去离子水混合,当有少量沉淀产生时,加入1mol/L的稀硝酸调节pH至7时,加入0.6g硫代乙酰胺,在磁力搅拌下匀速搅拌10min,然后加入1g步骤1所制备的二氧化钛微球,超声20min,再匀速搅拌10min,然后加入1mol/L的盐酸,调节pH至5,然后将其转移到反应釜中,在200℃下反应12h,将产物洗涤、离心、真空干燥;
(3)制备二氧化钛/硫化镉/壳聚糖复合材料:将0.4g壳聚糖与20mL 2%浓度的醋酸液混合,配置成壳聚糖胶状液,然后加入2g步骤2所制备的二氧化钛/硫化隔复合物,混合均匀,超声20min,将产物洗涤、离心、真空干燥,然后转移到马弗炉中,在350℃下煅烧3h;
(4)光催化降解印染污水性能测试:采用实施例3所制备的二氧化钛/硫化镉/壳聚糖复合材料作为光催化剂,取1L印染废水和0.5g二氧化钛/硫化镉/壳聚糖光催化剂于一用锡纸包裹起来的烧杯中,超声10min,再置于设有氙灯光源装置的磁力搅拌器下,匀速搅拌,0.5h后将氙灯打开,继续匀速搅拌,4h后抽取两毫升污水并离心、取上清液,作为待检测样品。
对比例1
与实施例1-3相比,对比例1的区别在于制备过程中未加入硫化镉和壳聚糖,具体步骤如下:
(1)制备分级结构的二氧化钛:将50mL乙二醇和2mL醋酸混合均匀,加入100μL二乙烯三胺,在磁力搅拌下逐滴滴加4mL四氯化钛,然后将其转移到反应釜中,在200℃下反应12h,待反应釜自然冷却后,将产物用去离子水和无水乙醇分别洗涤、离心、真空干燥;
(2)光催化降解印染污水性能测试:采用对比例1所制备的二氧化钛/硫化镉/壳聚糖复合材料作为光催化剂,取1L印染废水和0.5g二氧化钛/硫化镉/壳聚糖光催化剂于一用锡纸包裹起来的烧杯中,超声10min,再置于设有氙灯光源装置的磁力搅拌器下,匀速搅拌,0.5h后将氙灯打开,继续匀速搅拌,4h后抽取两毫升污水并离心、取上清液,作为待检测样品。
对比例2
与实施例1-3相比,对比例2的区别在于制备过程中未加入壳聚糖,具体步骤如下:
(1)制备分级结构的二氧化钛:将50mL乙二醇和2mL醋酸混合均匀,加入100μL二乙烯三胺,在磁力搅拌下逐滴滴加4mL四氯化钛,然后将其转移到反应釜中,在200℃下反应12h,待反应釜自然冷却后,将产物用去离子水和无水乙醇分别洗涤、离心、真空干燥;
(2)制备二氧化钛/硫化镉复合物:将2.2g硝酸镉和50mL去离子水混合,当有少量沉淀产生时,加入1mol/L的稀硝酸调节pH至7时,加入0.6g硫代乙酰胺,在磁力搅拌下匀速搅拌10min,然后加入1g步骤1所制备的二氧化钛微球,超声20min,再匀速搅拌10min,然后加入1mol/L的盐酸,调节pH至5,然后将其转移到反应釜中,在200℃下反应12h,将产物洗涤、离心、真空干燥;
(3)光催化降解印染污水性能测试:采用对比例2所制备的二氧化钛/硫化镉复合物作为光催化剂,取1L印染废水和0.5g二氧化钛/硫化镉/壳聚糖光催化剂于一用锡纸包裹起来的烧杯中,超声10min,再置于设有氙灯光源装置的磁力搅拌器下,匀速搅拌,0.5h后将氙灯打开,继续匀速搅拌,4h后抽取两毫升污水并离心、取上清液,作为待检测样品。
本发明所述的印染污水来源于天津田歌纺织有限公司纺织品染色以及退浆后的清洗污水。
在对该印染污水进行水质净化处理之前,先参照CJ/T 51-2004城市污水水质检验方法标准,对其进行水质检测分析,具体数据如表1所示。
表1:天津田歌纺织有限公司印染污水的水质检测数据
本发明所述实施例1在不同时间段里对印染污水处理的水质参数如表2所示。
表2:实施例1在4.5h内对印染污水处理的水质检测数据
由上表可以观察到,本发明实施例1所制备的二氧化钛/硫化镉/壳聚糖光催化剂在4.5h内对印染污水处理的水质情况随着光催化降解时间产生变化。在0.5h的暗处理中,S1样品经过物理吸附,对印染污水起到了一定的净化作用;在0.5h暗处理后,进行连续4小时的光催化降解实验,可检测到S2-S5样品的水质检测数据大幅度下降,这说明采用光催化技术对印染废水降解起到了良好的效果;并且还发现S4样品与S5样品对印染废水降解的数据相差不大,这说明该催化剂在经过0.5h的暗处理以及3小时的光催化实验后,对印染废水的降解逐渐趋于稳定。
本发明实施例1-3和对比例1-2所制备的光催化剂对印染废水处理后,均达到了GB4287-1992纺织染整工业水污染物排放标准,其对印染污水处理后的水质参数具体如表3所示。
表3:实施例1-3和对比例1-2对印染污水处理4.5h后的水质检测数据
由上表可以观察到,本发明实施例1-3所制备的二氧化钛/硫化镉/壳聚糖光催化剂对印染废水降解的各参数高于对比例2,对比例2所制备的二氧化钛/硫化镉光催化剂对印染废水降解的各参数高于对比例1。上述结果表明,本发明实施例1-3所制备的二氧化钛/硫化镉/壳聚糖光催化剂具有优异的光降解印染废水性能,其中壳聚糖的添加和二氧化钛/硫化镉的复合结构的构筑对印染废水的降解起到了很关键的作用。
本发明所列举的各种原料,以及本发明各原料的上下区间取值,以及工艺参数(如温度、时间等)的上下区间取值都能实现本发明,在此不一一列举实施例。以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些都属于本发明的保护范围。这些改进和变动也视为本发明的保护范围。
Claims (7)
1.一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,其特征在于,所述制备方法包括如下步骤:
步骤1:将乙二醇和醋酸混合均匀,加入模板剂二乙烯三胺,在磁力搅拌下逐滴滴加四氯化钛,然后将其转移到反应釜中,在160-200℃下反应12-24h,待自然冷却后,将产物洗涤、干燥,既得到由纳米棒分级自组装的二氧化钛微球;
步骤2:将镉源与去离子水和少量稀硝酸混合,pH≤7时,即可配置成镉溶液,然后在磁力搅拌下加入硫代乙酰胺,匀速搅拌10min,加入步骤1所制备的二氧化钛微球,超声20min,再匀速搅拌10min,然后加入1mol/L的盐酸,调节pH至3-6,然后将其转移到反应釜中,在200℃下反应12-24h,将产物洗涤、真空干燥,即得到二氧化钛/硫化镉复合物;
步骤3:将壳聚糖与2%浓度的醋酸液混合,配置成壳聚糖胶状液,加入步骤2所制备的二氧化钛/硫化隔复合物,混合均匀,超声20min,将产物洗涤、离心、真空干燥,然后转移到马弗炉中,在250-500℃下煅烧1-6h,即得到二氧化钛/硫化镉/壳聚糖复合材料。
2.根据权利要求1所述的一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,其特征在于,步骤1所述的乙二醇、醋酸、二乙烯三胺和四氯化钛的体积比50:(1-5):(0.02-0.2):(1-5)。
3.根据权利要求1所述的一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,其特征在于,步骤2所述的镉源为氯化镉、硝酸镉四水合物、醋酸镉四水合物或硫酸镉八水合物的一种。
4.根据权利要求1所述的一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,其特征在于,步骤2所述的镉溶液浓度为(0.01-0.2)mol/L。
5.根据权利要求1所述的一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,其特征在于,步骤2所述的镉源、硫代乙酰胺和二氧化钛微球的摩尔比为(1-2):(1-2):(1-4)。
6.根据权利要求1所述的一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,其特征在于,步骤3所述的壳聚糖胶状液质量浓度为(0.01-0.04)g/mL。
7.根据权利要求1所述的一种用于印染污水处理的二氧化钛/硫化镉/壳聚糖光催化剂的制备方法,其特征在于,步骤3所述的壳聚糖胶状液和二氧化钛/硫化隔复合物的质量体积比为20mL:(0.4-2)g。
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