CN111841487A - 改性粉煤灰复合材料的制备工艺及其用途 - Google Patents
改性粉煤灰复合材料的制备工艺及其用途 Download PDFInfo
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Abstract
本发明公开改性粉煤灰复合材料的制备工艺及其用途,以粉煤灰为内核,依次原位沉积尖晶石型铁酸铜、硫化亚铜,得到粉煤灰基磁性异质结催化剂,包括以下步骤:S1:碱处理、热处理粉煤灰;S2:将Cu(NO3)2、Fe(NO3)3溶解于水中,再加入预处理后粉煤灰,超声分散后,在磁力搅拌条件下,滴加25%浓氨水调节至pH为10,于160~180℃水热反应3~6h;S3:将氯化亚铜、硫脲、PVP溶解于15~20%乙二胺溶液中,再加入负载磁性CuFe2O4的粉煤灰和乙二醇,130~160℃反应6~8h;其用于抗生素的降解。本发明制备出的改性粉煤灰材料兼具吸附、磁选、可见光催化的功能,能高效快速降解环境中残留抗生素,且易于磁分离、循环再利用,同时,实现了粉煤灰的资源化利用,变废为宝、绿色环保。
Description
技术领域
本发明属于固废资源化利用技术领域,还属于光催化剂材料制备技术领域,具体涉及改性粉煤灰复合材料的制备工艺及其用途。
背景技术
粉煤灰又称飞灰或烟灰,是煤燃烧过程中排出的烟气灰分中的细微固体颗粒物,其粒径一般为1~100μm。粉煤灰是煤粉进入1300~1500℃的炉膛后,在悬浮燃烧条件下经受热面吸热后冷却而形成的。由于表面张力作用,粉煤灰大部分呈球状,表面光滑,微孔较小;部分颗粒因在熔融状态下互相碰撞而粘连,成为表面粗糙、棱角较多的蜂窝状组合粒子。粉煤灰再生循环利用方向主要为制备建筑材料、造纸纸浆、吸附材料等,但其作为磁性可见光催化剂材料的应用还较为罕见。
随着抗生素在农、畜、渔、牧、林业生产中的大量使用,土壤和水体中抗生素的被不断积累,抗生素污染问题日益严峻化,由于抗生素普遍具有较高的毒性和稳定性,少量进入环境中即可破坏生态系统、危害人类健康。因此,如何高效快速降解抗生素一直是环境保护领域的重要课题和研究热点。
基于以上所述,本发明提供尖晶石型铁酸铜/纳米硫化亚铜改性粉煤灰复合材料,并将其用于抗生素的吸附、催化降解。
发明内容
针对现有技术的不足之处,本发明的目的在于提供改性粉煤灰复合材料的制备工艺及其用途。
本发明的技术方案概述如下:
改性粉煤灰复合材料的制备工艺,以粉煤灰为内核,依次原位沉积尖晶石型铁酸铜、硫化亚铜,得到粉煤灰基磁性异质结催化剂,包括以下步骤:
S1:预处理粉煤灰:将粉煤灰加入0.2~0.4mol/L NaOH溶液中,控制固液比为1g/2mL,浸渍处理1~3h,中和、过滤、干燥,300~380℃热处理6h后,即得到预处理后粉煤灰;
S2:沉积磁性铁酸铜:将Cu(NO3)2、Fe(NO3)3溶解于水中,再加入预处理后粉煤灰,控制Cu(NO3)2、Fe(NO3)3、预处理后粉煤灰、水的用量比为1mmol:2mmol:(2.5~5)g:(20~40)mL,超声分散后,在磁力搅拌条件下,滴加25%浓氨水调节至pH为10,再转移至反应釜中,于160~180℃水热反应3~6h,过滤、洗涤、干燥后,得到负载磁性CuFe2O4的粉煤灰;
S3:沉积硫化亚铜:将氯化亚铜、硫脲、聚乙烯吡咯烷酮溶解于15~20%乙二胺溶液中,再加入负载磁性CuFe2O4的粉煤灰,搅拌分散后,在磁力搅拌条件下,滴加乙二醇,控制氯化亚铜、硫脲、聚乙烯吡咯烷酮、负载磁性CuFe2O4的粉煤灰、15~20%乙二胺溶液、乙二醇的用量比为0.1g:(0.15~0.2)g:(0.08~0.1)g:(4~8)g:(30~50)mL:(2~4)mL,再转移至反应釜中,130~160℃反应6~8h,过滤、洗涤、干燥后,得到Cu2S/CuFe2O4改性粉煤灰复合材料。
改性粉煤灰复合材料的用途:该复合材料用于抗生素污染土壤的修复。
改性粉煤灰复合材料的用途:该复合材料用于抗生素污染水体的净化。
优选的是,所述抗生素包括四环素类抗生素、氨基糖苷类抗生素、糖肽类抗生素、磺胺类抗生素、大环内酯类抗生素中的一种或多种。本发明的有益效果:
1、本发明首次以粉煤灰为内核载体,依次原位沉积尖晶石型铁酸铜、纳米硫化亚铜,制备出的改性粉煤灰材料兼具吸附、磁选、可见光催化的功能,能高效快速降解环境中残留抗生素,且易于磁分离、循环再利用,同时,实现了粉煤灰的资源化利用,变废为宝、绿色环保。
2、本发明通过碱处理、热处理粉煤灰,提高其孔隙率和比表面积,进而提高其吸附和负载性能,碱处理使粉煤灰表面外壳被破坏而呈现松散裂解形貌,进而提高比表面积,同时,粉煤灰玻璃体表面可溶性物质能与碱反应生成胶凝物质,提高粉煤灰的絮凝沉淀能力,热处理直接破坏粉煤灰的玻璃网络结构,使粉煤灰疏松多孔,暴露出更多的活性位点,进一步提高粉煤灰的吸附和负载性能。
3、本发明先在粉煤灰原位生长磁性尖晶石型铁酸铜,铁酸铜的禁带宽度为2eV,吸收光谱遍及整个紫外和可见光区域,对400~760nm范围内的可见光有较大的吸收,具有很高的光催化活性,并进一步原位沉积纳米硫化亚铜,形成异质结结构,使光生电子与空穴在异质结界面向不同方向转移,抑制电子与空穴的复合,显著提高了光催化活性;此外,硫化亚铜的禁带宽度仅1.2eV,进一步提高复合材料对可见光的吸收效率和利用率,提高光催化降解性能。
4、本发明以乙二醇作为还原剂,防止Cu+在水热反应过程中被氧化成Cu2+,避免副反应的发生。
附图说明
图1为改性粉煤灰复合材料的制备工艺流程图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。
实施例1
改性粉煤灰复合材料的制备工艺,以粉煤灰为内核,依次原位沉积尖晶石型铁酸铜、硫化亚铜,得到粉煤灰基磁性异质结催化剂,包括以下步骤:
S1:预处理粉煤灰:将10g粉煤灰加入20mL的0.2mol/L NaOH溶液中(即固液比为1g/2mL),浸渍处理1h,中和、过滤、干燥,300℃热处理6h后,即得到预处理后粉煤灰;
S2:沉积磁性铁酸铜:将1mmol Cu(NO3)2、2mmol Fe(NO3)3溶解于40mL水中,再加入5g预处理后粉煤灰(即Cu(NO3)2、Fe(NO3)3、预处理后粉煤灰、水的用量比为1mmol:2mmol:5g:40mL),超声分散后,在磁力搅拌条件下,滴加25%浓氨水调节至pH为10,再转移至反应釜中,于160℃水热反应3h,过滤、洗涤、干燥后,得到负载磁性CuFe2O4的粉煤灰;
S3:沉积硫化亚铜:将0.05g氯化亚铜、0.075g硫脲、0.04g聚乙烯吡咯烷酮溶解于25mL的15%乙二胺溶液中,再加入4g负载磁性CuFe2O4的粉煤灰,搅拌分散后,在磁力搅拌条件下,滴加2mL乙二醇(即氯化亚铜、硫脲、聚乙烯吡咯烷酮、负载磁性CuFe2O4的粉煤灰、15%乙二胺溶液、乙二醇的用量比为0.1g:0.15g:0.08g:8g:50mL:4mL),再转移至反应釜中,140℃反应6h,过滤、洗涤、干燥后,得到Cu2S/CuFe2O4改性粉煤灰复合材料。
实施例2
改性粉煤灰复合材料的制备工艺,以粉煤灰为内核,依次原位沉积尖晶石型铁酸铜、硫化亚铜,得到粉煤灰基磁性异质结催化剂,包括以下步骤:
S1:预处理粉煤灰:将10g粉煤灰加入20mL的0.4mol/L NaOH溶液中(即固液比为1g/2mL),浸渍处理3h,中和、过滤、干燥,380℃热处理6h后,即得到预处理后粉煤灰;
S2:沉积磁性铁酸铜:将2mmol Cu(NO3)2、4mmol Fe(NO3)3溶解于40mL水中,再加入5.0g预处理后粉煤灰(即Cu(NO3)2、Fe(NO3)3、预处理后粉煤灰、水的用量比为1mmol:2mmol:2.5g:20mL),超声分散后,在磁力搅拌条件下,滴加25%浓氨水调节至pH为10,再转移至反应釜中,于180℃水热反应6h,过滤、洗涤、干燥后,得到负载磁性CuFe2O4的粉煤灰;再转移至反应釜中,
S3:沉积硫化亚铜:将0.1g氯化亚铜、0.2g硫脲、0.1g聚乙烯吡咯烷酮溶解于30mL的20%乙二胺溶液中,再加入4g负载磁性CuFe2O4的粉煤灰,搅拌分散后,在磁力搅拌条件下,滴加2mL乙二醇(即氯化亚铜、硫脲、聚乙烯吡咯烷酮、负载磁性CuFe2O4的粉煤灰、20%乙二胺溶液、乙二醇的用量比为0.1g:0.2g:0.1g:4g:30mL:2mL),再转移至反应釜中,160℃反应8h,过滤、洗涤、干燥后,得到Cu2S/CuFe2O4改性粉煤灰复合材料。
对比例1与实施例1相同,区别在于:无S2沉积磁性铁酸铜操作。
对比例2与实施例1相同,区别在于:无S3沉积硫化亚铜操作。
对比例3:原始粉煤灰。
验证试验:测定实施例1~2、对比例1~2制出的改性粉煤灰材料及对比例3原始粉煤灰对抗生素的降解性能:
称取实施例1~2、对比例1~2制出的改性粉煤灰材料及对比例3原始粉煤灰,各0.1g,分别加入5组200mL的10mg/L四环素模拟废水(pH值为6.0)中,在420nm以上的可见光下处理12h后,测定处理后水体中四环素含量,按照公式100%×(C0-C)/C0(C0为10mg/L)计算降解率,试验结果如下表所示:
实施例1 | 实施例2 | 对比例1 | 对比例2 | 对比例3 | |
<u>降解率/%</u> | 91.3 | 96.6 | 72.5 | 65.8 | 22.4 |
由上表可知,本发明改性粉煤灰材料对抗生素具有显著的催化降解作用,明显优于对比例1~3,对比例3原始粉煤灰也具有一定的抗生素去除作用,是由于粉煤灰颗粒具有微孔结构,赋予其吸附性能,但其对抗生素的去除作用取决于自身吸附容量,无法达到高效去除。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节。
Claims (4)
1.改性粉煤灰复合材料的制备工艺,其特征在于,以粉煤灰为内核,依次原位沉积尖晶石型铁酸铜、硫化亚铜,得到粉煤灰基磁性异质结催化剂,包括以下步骤:
S1:预处理粉煤灰:将粉煤灰加入0.2~0.4mol/L NaOH溶液中,控制固液比为1g/2mL,浸渍处理1~3h,中和、过滤、干燥,300~380℃热处理6h后,即得到预处理后粉煤灰;
S2:沉积磁性铁酸铜:将Cu(NO3)2、Fe(NO3)3溶解于水中,再加入预处理后粉煤灰,控制Cu2+、Fe3+、预处理后粉煤灰、水的用量比为1mmol:2mmol:(2.5~5)g:(20~40)mL,超声分散后,在磁力搅拌条件下,滴加25%浓氨水调节至pH为10,再转移至反应釜中,于160~180℃水热反应3~6h,过滤、洗涤、干燥后,得到负载磁性CuFe2O4的粉煤灰;
S3:沉积硫化亚铜:将氯化亚铜、硫脲、聚乙烯吡咯烷酮溶解于15~20%乙二胺溶液中,再加入负载磁性CuFe2O4的粉煤灰,搅拌分散后,在磁力搅拌条件下,滴加乙二醇,控制氯化亚铜、硫脲、聚乙烯吡咯烷酮、负载磁性CuFe2O4的粉煤灰、15~20%乙二胺溶液、乙二醇的用量比为0.1g:(0.15~0.2)g:(0.08~0.1)g:(4~8)g:(30~50)mL:(2~4)mL,再转移至反应釜中,130~160℃反应6~8h,过滤、洗涤、干燥后,得到Cu2S/CuFe2O4改性粉煤灰复合材料。
2.如权利要求1所述改性粉煤灰复合材料的用途,其特征在于:该复合材料用于抗生素污染土壤的修复。
3.如权利要求1所述改性粉煤灰复合材料的用途,其特征在于:该复合材料用于抗生素污染水体的净化。
4.根据权利要求2或3任一项所述改性粉煤灰复合材料的用途,其特征在于,所述抗生素包括四环素类抗生素、氨基糖苷类抗生素、糖肽类抗生素、磺胺类抗生素、大环内酯类抗生素中的一种或多种。
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