CN114471733B - 一种改性海藻酸钠基光催化还原剂及其制备方法和应用 - Google Patents
一种改性海藻酸钠基光催化还原剂及其制备方法和应用 Download PDFInfo
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical class CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 50
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000017 hydrogel Substances 0.000 claims abstract description 32
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 23
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- 229960000282 metronidazole Drugs 0.000 claims abstract description 15
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Abstract
本发明公开了一种改性海藻酸钠基光催化还原剂及其制备方法和应用,涉及废水处理技术领域,以环氧氯丙烷为交联剂,将三乙烯四胺嫁接到海藻酸钠基体上,经过氯化钙和硝酸铁溶液进行固化,再置于冷冻干燥机中进行真空干燥,最终得到一种对六价铬和甲硝唑具备优良光催化性能的多孔水凝胶材料;本发明所制备的海藻酸钠基光催化剂,采用溶胶‑凝胶法,生产工艺简单,制备条件温和,可用于处理高浓度的六价铬和甲硝唑的制药废水中,在实际处理过程中具有操作简便,成本低廉,效率高的优点;此外,该发明所制备的光催化剂可延伸至用于处理含多种重金属离子、抗生素以及染料,拓宽有机光催化材料在实际工业生产中的多元化应用。
Description
技术领域
本发明涉及废水处理技术领域,具体涉及一种改性海藻酸钠基光催化还原剂及其制备方法和应用。
背景技术
在传统的制药生产过程中,会产生大量的含重金属离子和抗生素的医疗废水,而这些重金属离子和抗生素具有高溶性、难降解以及强毒性等特点,若处理不当排放到自然环境中,则会对人类和动植物的生存环境造成严重的威胁。目前,去除废水中的重金属离子和抗生素的方法主要包括吸附法、膜过滤法、化学沉淀法等。但这些方法中存在着许多不足之处,比如膜过滤法的处理成本高、化学沉淀法在处理过程中会产生大量污泥,从而造成二次污染等问题,而光催化作为一种有前途的环境修复方法,近些年来受到很多研究者的关注。目前用于光催化的材料主要是一些纳米金属化合物或者贵金属,原因是这些材料在光照条件下可以在很大程度上降低电荷转移阻力,有利于光照产生的电子-空穴的迁移,但是这些催化剂对Cr(Ⅵ)和MNZ的降解仅局限于低浓度的溶液中,主要原因是无机材料对Cr(VI)离子和MNZ没有明显的吸附作用,而光催化反应往往发生在光催化剂和处理目标的界面上。相比与传统的无机材料,生物质材料本身具有大量的活性官能团,经改性后可以显著提高其对重金属离子和有机污染物的吸附效果,同时由于部分的生物质材料具有较好的导电能力,可以尝试用于重金属离子和有机污染物的光催化降解中。
海藻酸钠作为一种天然多糖,广泛的分布于褐藻等藻类植物中,其分子链上含有丰富的羟基和羧基官能团,对重金属离子和抗生素具有较高的亲和力,可以为重金属离子和有机污染物的吸附提供良好的吸附位点。目前以海藻酸钠作为基底材料,通过三乙烯四胺和环氧氯丙烷进行化学改性,并在紫外光的条件下用于处理高浓度的Cr(VI)和MNZ废水,目前尚未见相关文献报道。
发明内容
本发明的目的就在于解决上述背景技术的问题,而提出一种改性海藻酸钠基光催化还原剂及其制备方法和应用,采用溶胶-凝胶法,生产工艺简单,制备条件温和,可用于处理高浓度的六价铬和甲硝唑的制药废水中,在实际处理过程中具有操作简便,成本低廉,效率高的优点;此外,该发明所制备的光催化剂可延伸至用于处理含多种重金属离子、抗生素以及染料,拓宽有机光催化材料在实际工业生产中的多元化应用。
本发明的目的可以通过以下技术方案实现:
一种改性海藻酸钠基光催化还原剂的制备方法,包括以下步骤:
S1:将氢氧化钠溶解在去离子水中,加入环氧氯丙烷和三乙烯四胺,升温至70℃,恒温震荡2h,得到接枝的中间体;
S2:向步骤S1得到的中间体中加入海藻酸钠,降低温度至60℃,搅拌均匀,恒温震荡8h,得到复合水凝胶;
S3:将步骤S2得到的水凝胶加入到氯化钙溶液中固化1h,然后转移到硝酸铁溶液中固化23h,得到复合水凝胶球;
S4:将步骤S3得到的复合水凝胶球用去离子水清洗5-6次,然后置于冷冻干燥机中冷冻干燥,即得到改性海藻酸钠基光催化还原剂。
作为本发明进一步的方案:在S1中,氢氧化钠的质量分数为1.5-2.5%;环氧氯丙烷和三乙烯四胺的体积比为1:1.5-1:2。
作为本发明进一步的方案:在S2中,海藻酸钠和中间体溶液的固液比1g:28mL-1g:32mL。
作为本发明进一步的方案:在S3中,氯化钙溶液质量分数为1-3%,硝酸铁溶液质量分数为3-5%。
作为本发明进一步的方案:在S4中,冷冻温度为-75至-85℃。
一种改性海藻酸钠基光催化还原剂,由上述的改性海藻酸钠基光催化还原剂的制备方法而得到的。
一种改性海藻酸钠基光催化还原剂在混合六价铬和甲硝唑制药废水中的应用。
作为本发明进一步的方案:将六价铬阴离子化合物和甲硝唑有机污染物吸附到改性海藻酸钠基光催化还原剂上,然后在紫外光的照射下使得六价铬还原为三价,将甲硝唑氧化成小分子有机物。
作为本发明进一步的方案:改性海藻酸钠基光催化还原剂在还原六价铬的同时协同促进甲硝唑的氧化。
本发明的有益效果:
本发明使用三乙烯四胺和环氧氯丙烷对海藻酸钠进行改性,并在氯化钙和硝酸铁溶液中进行固化,制备出一种催化效果好,便于回收的海藻酸钠基光催化剂,在紫外光照射的情况下可用于降解制药厂产生的高浓度六价铬和甲硝唑的制药废水;
本发明使用冷冻干燥机对改性海藻酸钠水凝胶球进行真空干燥,制备出一种比表面积大,孔径分布均匀的凝胶颗粒,对六价铬和甲硝唑具有良好的吸附性能。
本发明通过改性引入大量的氨基官能团,在酸性条件下,可以质子化与阴离子形态的六价铬发生静电吸引,增大对六价铬的吸附作用。将三价铁与海藻酸钠基体上的羧基络合,在紫外光的照射下,可以加强光生电子-空穴的迁移,降低电子-空穴的复合速率,进而加快六价铬和甲硝唑的降解速率。此外,在六价铬和甲硝唑共存的条件下,六价铬还原成三价铬的同时会促进甲硝唑的氧化降解。
附图说明
下面结合附图对本发明作进一步的说明。
图1为实施例中反应前改性海藻酸钠基光催化还原剂的扫描电镜图;
图2为实施例中反应后改性海藻酸钠基光催化还原剂的扫描电镜图;
图3为实施例中改性海藻酸钠基光催化还原剂的截面扫描电镜图;
图4为本发明中改性海藻酸钠基光催化还原剂和海藻酸钠的光致发光光谱图;
图5为本发明中改性海藻酸钠基光催化还原剂和海藻酸钠的紫外可见漫反射光谱图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
本发明为一种改性海藻酸钠基光催化还原剂的制备方法,包括以下步骤:
S1:将氢氧化钠溶解在去离子水中,加入环氧氯丙烷和三乙烯四胺,升温至70℃,恒温震荡2h,得到接枝的中间体;其中,氢氧化钠质量分数为1.5%,环氧氯丙烷和三乙烯四胺的体积比为1:1.5;
S2:向步骤S1得到的中间体中加入海藻酸钠,降低温度至60℃,搅拌均匀,恒温震荡8h,得到复合水凝胶;其中,海藻酸钠和中间体溶液的固液比1g:28mL;
S3:将步骤S2得到的水凝胶加入到氯化钙溶液中固化1h,然后转移到硝酸铁溶液中固化23h,得到复合水凝胶球;其中,氯化钙溶液质量分数为1%,硝酸铁溶液质量分数为3%;
S4:将步骤S3得到的复合水凝胶球用去离子水清洗5-6次,然后置于冷冻干燥机中冷冻干燥,即得到改性海藻酸钠基光催化还原剂;其中,冷冻温度为-75℃,真空干燥至20℃。
实施例2
本发明为一种改性海藻酸钠基光催化还原剂的制备方法,包括以下步骤:
S1:将氢氧化钠溶解在去离子水中,加入环氧氯丙烷和三乙烯四胺,升温至70℃,恒温震荡2h,得到接枝的中间体;其中,氢氧化钠的质量分数为2%;环氧氯丙烷和三乙烯四胺的体积比为1:1.9;
S2:向步骤S1得到的中间体中加入海藻酸钠,降低温度至60℃,搅拌均匀,恒温震荡8h,得到复合水凝胶;其中,海藻酸钠和中间体溶液的固液比1g:30.8mL;
S3:将步骤S2得到的水凝胶加入到氯化钙溶液中固化1h,然后转移到硝酸铁溶液中固化23h,得到复合水凝胶球;其中,氯化钙溶液质量分数为2%,硝酸铁溶液质量分数为4%;
S4:将步骤S3得到的复合水凝胶球用去离子水清洗5-6次,然后置于冷冻干燥机中冷冻干燥,即得到改性海藻酸钠基光催化还原剂;其中,冷冻温度为-80℃,真空干燥至25℃。
实施例3
本发明为一种改性海藻酸钠基光催化还原剂的制备方法,包括以下步骤:
S1:将氢氧化钠溶解在去离子水中,加入环氧氯丙烷和三乙烯四胺,升温至70℃,恒温震荡2h,得到接枝的中间体;其中,氢氧化钠的质量分数为2.5%;环氧氯丙烷和三乙烯四胺的体积比为1:2;
S2:向步骤S1得到的中间体中加入海藻酸钠,降低温度至60℃,搅拌均匀,恒温震荡8h,得到复合水凝胶;其中,海藻酸钠和中间体溶液的固液比1g:32mL;
S3:将步骤S2得到的水凝胶加入到氯化钙溶液中固化1h,然后转移到硝酸铁溶液中固化23h,得到复合水凝胶球;其中,氯化钙溶液质量分数为3%,硝酸铁溶液质量分数为5%;
S4:将步骤S3得到的复合水凝胶球用去离子水清洗5-6次,然后置于冷冻干燥机中冷冻干燥,即得到改性海藻酸钠基光催化还原剂;其中,冷冻温度为-85℃,真空干燥至30℃。
试验例1
光催化试验:分别配置pH为1和4的Cr(Ⅵ)和MNZ标准溶液,浓度为50mg/L,取上述制备好的光催化剂30mg分别置于Cr(VI)和MNZ的标准液中,体积为30mL,在紫外光照射下进行光催化降解30min,然后取样测量Cr(VI)和MNZ的浓度,标号分别为a1/a2/a3/b1/b2/b3,实验结果如表1所示。
表1不同pH条件下的光催化实验后溶液中剩余的Cr(Ⅵ)和MNZ的浓度
由表1可知,三种不同配方制备的改性海藻酸钠基光催化还原剂,在紫外光照射30min后,在溶液pH为1时对Cr(Ⅵ)和MNZ的去除效果要比溶液pH为3时的效果好,这主要是因为在较强的酸性条件下,改性引入的氨基容易质子化,可以通过静电作用增强对Cr(Ⅵ)和MNZ的吸附作用,进而导致光催化效果得到提升,且通过对比可知实施例2的去除效果最佳,在后续过程中将实施例2作为最优选的制备方案。
对比实验:配置pH为1的Cr(Ⅵ)和MNZ的单一溶液和混合溶液,浓度为50mg/L,取上述制备好的光催化剂30mg置于Cr(Ⅵ)和MNZ的溶液中,体积为30mL,先在黑暗条件下吸附30min,然后在紫外光照射下进行吸附-光催化降解,每隔5min取样一次测量Cr(Ⅵ)和MNZ的浓度,标号分别为c1/c2/c3/c4/c5/c6/c7/d1/d2/d3/d4/d5/d6/d7,实验结果如表2所示。
表2单一/共存体系中吸附-光催化实验后溶液中剩余Cr(VI)和MNZ的浓度
实施例2/单一 | c1 | c2 | c3 | c4 | c5 | c6 | c7 |
Cr(Ⅵ)(mg/L) | 42.61 | 20.95 | 13.92 | 7.95 | 0.25 | 0.00 | 0.00 |
MNZ(mg/L) | 47.73 | 28.74 | 15.54 | 9.88 | 5.16 | 1.39 | 0.00 |
实施例2/共存 | d1 | d2 | d3 | d4 | d5 | d6 | d7 |
Cr(Ⅵ)(mg/L) | 41.37 | 20.32 | 13.13 | 7.90 | 0.00 | 0.00 | 0.00 |
MNZ(mg/L) | 46.66 | 24.97 | 12.71 | 6.12 | 2.33 | 0.00 | 0.00 |
由表2可知,本发明的实施例2改性海藻酸钠基光催化还原剂在单一的体系中,在紫外光照射25min时,可将Cr(Ⅵ)完全去除完,在紫外光照射30min时,可将溶液中的MNZ完全降解完。而在Cr(Ⅵ)和MNZ共存的情况下,约在紫外光照射20min时可将Cr(Ⅵ)完全去除,约在紫外光照射25min时,可将MNZ完全降解完。由此对比可知,Cr(Ⅵ)在被还原成Cr(Ⅲ)的同时,促进了MNZ的氧化降解。
检测分析:将制备好的光催化剂磨成粉末分别检测其光致发光光谱和对紫外光的吸收特性;将做完吸附-光催化实验后的Cr(VI)和MNZ标准液分别用紫外分光光度计检测溶液中剩余六价铬和MNZ的浓度;挑选形貌规整的吸附剂进行SEM分析。
图1、图2和图3为实施例2改性海藻酸钠基光催化材料的表面电镜图,通过对比可知,反应后的光催化材料仍保留了原有的形貌结构,为光催化剂的循环使用提供可行性,且经冷冻干燥得到的光催化剂具有良好的孔隙结构,有利于重金属离子和抗生素的吸附。
图4为海藻酸钠和实施实例的光致发光光谱图,通过比较可知改性海藻酸钠基光催化还原剂具有载流子分离能力强,光生电子-空穴复合率低,电子-空穴利用率高。图5为海藻酸钠和实施实例的紫外可见漫反射光谱图,通过对比可知,改性后的材料在波长200nm-380nm的紫外光波长范围内有较高的吸收峰,而在380nm-800nm的可见光范围内,对可见光的吸收率呈逐步下降的趋势,相比海藻酸钠,改性后的材料对紫外光的吸收能力得到了明显的提升。综上所述,本发明的材料具有较低的光生电子-空穴复合率,对紫外光具有较好的吸收能力,在紫外光照射下可以快速的实现对Cr(Ⅵ)和MNZ的氧化还原降解。
由以上试验结果可知,通过此方法制备的改性海藻酸钠基光催化还原剂对Cr(VI)和MNZ具备光催化降解性能,并且该复合材料具有良好的载流子分离能力和对紫外光的吸收特性,因此可通过光催化氧化还原法处理溶液中的高价态重金属离子和抗生素,在降低制药废水重金属和抗生素污染方面具有良好应用前景和意义。
以上对本发明的一个实施例进行了详细说明,但所述内容仅为本发明的较佳实施例,不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进等,均应仍归属于本发明的专利涵盖范围之内。
Claims (4)
1.一种改性海藻酸钠基光催化还原剂的应用,其特征在于,改性海藻酸钠基光催化还原剂应用在混合六价铬和甲硝唑制药废水中;
将六价铬阴离子化合物和甲硝唑有机污染物吸附到改性海藻酸钠基光催化还原剂上,然后在紫外光的照射下使得六价铬还原为三价,将甲硝唑氧化成小分子有机物;
改性海藻酸钠基光催化还原剂制备方法包括以下步骤:
S1:将氢氧化钠溶解在去离子水中,加入环氧氯丙烷和三乙烯四胺,升温至70℃,恒温震荡2h,得到接枝的中间体;
S2:向步骤S1得到的中间体中加入海藻酸钠,降低温度至60℃,搅拌均匀,恒温震荡8h,得到复合水凝胶;
S3:将步骤S2得到的水凝胶加入到氯化钙溶液中固化1h,然后转移到硝酸铁溶液中固化23h,得到复合水凝胶球;
S4:将步骤S3得到的复合水凝胶球用去离子水清洗5-6次,然后置于冷冻干燥机中冷冻干燥,即得到改性海藻酸钠基光催化还原剂;
在步骤S1中,氢氧化钠的质量分数为1.5-2.5%;环氧氯丙烷和三乙烯四胺的体积比为1:1.5-1:2;
在步骤S2中,海藻酸钠和中间体溶液的固液比1g:28mL-1g:32mL。
2.根据权利要求1所述的一种改性海藻酸钠基光催化还原剂的应用,其特征在于,在步骤S3中,氯化钙溶液质量分数为1-3%,硝酸铁溶液质量分数为3-5%。
3.根据权利要求1所述的一种改性海藻酸钠基光催化还原剂的应用,其特征在于,在步骤S4中,冷冻温度为-75至-85℃。
4.一种改性海藻酸钠基光催化还原剂,其特征在于,由权利要求1-3任一项所述的应用中改性海藻酸钠基光催化还原剂制备方法制备而成。
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