CN111841659A - 一种磁性悬浮态3d微球的制备及其催化臭氧矿化难降解有机物上的应用 - Google Patents
一种磁性悬浮态3d微球的制备及其催化臭氧矿化难降解有机物上的应用 Download PDFInfo
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- CN111841659A CN111841659A CN202010737857.7A CN202010737857A CN111841659A CN 111841659 A CN111841659 A CN 111841659A CN 202010737857 A CN202010737857 A CN 202010737857A CN 111841659 A CN111841659 A CN 111841659A
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Abstract
本发明属于污水处理技术领域,具体涉及一种磁性悬浮态3D微球的制备及其催化臭氧矿化难降解有机物上的应用。以SA、PVDF、Fe3O4纳米粒子和桐油等为原料,采用反相悬浮法制备了磁性悬浮态微球载体,再与Ce、Mn、Co通过化学螯合作用交联形成三维网状结构,达到固定催化活性组分,延长微球生命周期的目的。本发明所制备的磁性悬浮态3D微球在自然状态下稳定悬浮于反应体系,随O3微气泡匀速转动,可有效促进微球表面O3分解,提高O3利用率,实现对难降解有机物的高效降解和高度矿化,具有良好的抗盐度、抗水硬度性能;同时可以快速实现原位再生,循环利用后仍然具有良好的废水处理性能。
Description
技术领域
本发明属于污水处理技术领域,具体涉及一种磁性悬浮态3D微球的制备及其催化O3矿化难降解有机物上的应用。
背景技术
高盐废水是指总含盐质量分数大于1%的含盐废水,其主要来自印染、生产腌制类食物及石油和天然气的采集加工等。这类废水具有盐分含量高、成分复杂、可生化性差等特点,经二级生化处理后,残留高浓度难降解有机物,其中有些有机物具有致癌、致畸和致突变作用,这些物质若不经治理而肆意排放,势必严重污染环境,威胁人类身体健康。环保部门从可持续发展及节能减排角度倡导企业自行处理实现再生回用以降低企业生产成本、提高经济和环境效益。
高盐废水的有机物根据生产过程不同,所含有机物的种类及化学性质差异较大,但所含盐类物质多为Cl-、SO4 2-、Na+、Ca2+等。常见的去除高盐废水中难降解有机物的方法有物化法、化学法和生物法。物化法主要有活性炭吸附、化学沉淀、离子交换、膜渗析、汽提及湿式氧化法等,考虑到操作难度和运行成本等问题,活性炭吸附是较好的选择,但当吸附饱和时需进行更换,频繁更换势必导致较高的处理成本,且难以实现持续净化修复的效果。传统化学法处理效果虽好,但处理费用高、对盐分也不能有效去除,且在处理过程中需投加化学药剂,易造成二次污染。生物法是利用微生物的新陈代谢功能将污水中呈溶解或胶体状态的有机物降解为稳定无机物,使污水得到净化,但高盐会抑制微生物的生长甚至成为微生物的毒害剂,其处理效果也不佳。
高级氧化技术(AOPs)是近年来水处理领域兴起的新技术,其反应机理在于利用光、电、催化剂、氧化剂等在反应中产生活性极强的自由基(如羟基自由基·OH,氧化还原标准电位E0=2.80V),将大分子难降解有机污染物氧化为低毒或无毒小分子中间产物,甚至直接矿化为CO2和H2O,达到高度净化的效果。非均相臭氧催化氧化与传统的高级氧化相比具有操作简单、非均相臭氧催化剂易与水体分离,能重复利用的优点,在实际污水处理中被广泛应用。
专利申请201910027161.2(公开号:CN 109663589A,公开日:2019.04.23)公开了铈钛氧化物介孔毫米球臭氧催化剂及其制备方法与应用,通过将铈钛氢氧化物分散于海藻酸钠水凝胶,固化后采用两段式煅烧成型法制备所述催化剂。所述催化剂克服了凝胶化后导入金属氧化物前驱体不得不使用昂贵娇气的有机金属醇盐原料的缺陷,兼具高催化活性、优良的流体力学特性、适宜的孔结构、抗压机械强度和稳定性,可显著提高臭氧氧化降解有机污染物的矿化率,但是该发明中的催化剂只在中性条件下对毒害有机污染物的臭氧氧化降解具有较高的催化活性,pH应用范围较窄;并且该催化剂含有铈钛复合氧化物,在酸性条件下易浸出金属元素成分,造成资源浪费和二次污染。
根据目前臭氧催化氧化技术的运行情况,臭氧催化剂对于高盐废水中有机物去除率低于30%,效果普遍不佳。究其原因可能是高盐废水中盐分含量高,占据活性位点,易堵塞难降解有机物进入臭氧催化剂孔道的“路径”,从而影响了高盐废水中难降解有机物与臭氧催化剂表面的自由基的接触几率和接触时间,进而影响到自由基去除难降解有机物的效率。
发明内容
本发明的目的在于提供一种磁性悬浮态3D微球的制备及其催化臭氧矿化高盐废水中难降解有机物上的应用。本发明所制备的磁性悬浮态3D微球臭氧催化剂富含羟基和Lewis酸性位,具有较高的亲水性和催化活性,利用其表面特性实现对难降解有机物和O3的有效吸附,在自然状态下稳定悬浮于反应体系,随O3微气泡匀速转动,有效促进了微球表面O3分解,提高了O3利用率,实现了对难降解有机物的高效降解和高度矿化,具有良好的抗盐度、抗水硬度性能;同时可以快速实现原位再生,循环利用后仍然具有良好的废水处理性能。
为实现上述目的,本发明采用如下技术方案:
一种磁性悬浮态3D微球的制备,具体是以SA、PVDF、Fe3O4纳米粒子和桐油等为原料,采用反相悬浮法制备了磁性悬浮态微球载体,再与Ce、Mn、Co金属离子通过化学螯合作用交联形成三维网状结构、富含羟基和Lewis酸性位的磁性悬浮态3D微球,达到固定催化活性成分、延长微球生命周期、提高高活性自由基物种(如·OH或超氧自由基·O2 -)产生量的目的。
所述催化活性组分选自至少一种镧系的金属组分、至少一种VIIB族的金属组分和至少一种VIII族的金属组分的组合。
所述磁性悬浮态3D微球的制备方法,具体步骤包括:
(1)称取一定量的SA溶于3.0wt% PVA溶液得2.0wt%淡黄色凝胶A;将15.0g PVDF粉末溶于100mL DMAC,再加入5.0g PVP,60℃机械搅拌1d,静置脱泡得铸膜液B;将1L 4mM氨水溶液匀速滴入由0.1M FeCl3.6H2O 10mL和0.05M FeSO4·7H2O 10mL组成的混合溶液中,匀速搅拌得磁性Fe3O4纳米粒子;将凝胶A、铸膜液B、Fe3O4纳米粒子和桐油按一定比例复合,超声反应得塑性浆料,静置脱泡,备用;
(2)在缓慢搅拌下将100g配制好的步骤(1)的塑性浆料缓慢加入到由40mL氯仿、60mL正己烷和1mL 吐温80组成的有机相中,常温下充分搅拌15min,再加入2.0wt%的戊二醛溶液30mL,常温搅拌,转速保持在150~400r/min,化学交联6~12h,过滤固体样品,用去离子水和无水乙醇反复洗涤,60℃烘干得磁性悬浮态微球载体;
(3)将步骤(2)获得的磁性悬浮态微球载体置于3wt%CaCl2溶液中固化3h,取出用去离子水反复冲洗至溶液中检测不出Ca2+;随后置于-60℃真空冷冻干燥机中冷冻干燥3~5h;接着置于含硝酸铈、硝酸锰和硝酸钴的多元金属混合液中,间歇性搅拌状态下浸泡6h,取出用去离子水反复洗涤至溶液中检测不出金属离子;最后置于70~80℃的真空干燥箱中干燥2h,得磁性悬浮态3D微球。
进一步地,步骤(1)所述凝胶A、溶液B、Fe3O4磁性纳米粒子和桐油的质量比为(2~8):(4.5~7.5):(1~4):(2~3)。
进一步地,步骤(1)所述超声反应中,超声波频率为40~60HZ,超声反应时间为30min~5h。
进一步地,以所述载体的重量为基准计,催化活性成分Ce、Mn、Co的含量比为(1~2)wt%:(6~10)wt%:(5~8)wt%。
进一步地,步骤(3)所述间歇搅拌,具体为每次搅拌30min,停止30min,交替进行,搅拌速度保持在150~400r/min。
进一步地,本发明所制备的微球大小、直径范围为12~50μm,孔径为10~200nm,比表面积为188~237m2/g,表面酸性位点密度为1.1~3.5mmol/g,球形颗粒抗压机械强度>5N。
本发明的显著优点在于:
(1)本发明制备的磁性悬浮态3D微球的催化活性组分(Ce、Mn、Co)是通过化学螯合的形式与SA上活泼的羧基进行配位而被固定的,能有效防止活性组分的流失,延长微球(臭氧催化剂)的生命周期。高度分散的高密度金属位点就是活性中心,完全暴露在微球表面或孔道的金属离子可提供100%的利用率,在长期或反复使用过程中催化性能基本保持稳定。此外包埋Fe3O4磁性纳米粒子的悬浮态3D微球可以很好地通过磁分离进行回收,提高重复利用率,降低使用成本。
(2)行业人士普遍认为,比表面积太小,反应物和活性组分接触面积小,催化活性低;比表面积太大,孔径就会相应变小,孔径小内扩散阻力增加,易堵塞不利于反应;而本发明所制备的磁性悬浮态3D微球比表面积和孔隙率适中,孔隙尺寸较大,内扩散阻力较小,利于催化反应的顺利进行。
(3)本发明采用PVDF和桐油对SA进行共混改性,促进SA固化成膜,赋予其耐热、酸、碱、污染等优点,所制备的磁性悬浮态3D微球,机械强度(硬度、抗冲击性、柔韧性和拉伸强度等)和耐氧化性得到了较大的提高,在反应器内堆积承重或碰撞条件下不易发生破碎;在·OH、·O2 -和O3强氧化环境中自身结构和性能不发生明显改变。
(4)本发明中PVA和SA富含羟基,金属离子(Ce/Mn/Co)与SA上的活泼羧基通过化学螯合作用交联成三维网状结构而均匀分布于微球中,形成富含羟基和Lewis酸性位的磁性悬浮态3D微球。该微球在O3微气泡的推动下匀速转动,利于难降解有机物和O3分子附着于亲水性微球表面,提高O3攻击有机物产生臭氧化产物(有机中间体)的传质效率;Lewis酸性位的Ce、Co具有优良的电子转移效率,在催化反应过程中起电子穿梭作用,与Mn、Fe、Ca产生协同效应活化O3快速分解为·OH和·O2 -,降解吸附于微球表面的有机中间体,转化为CO2和H2O,达到高度矿化的效果。
附图说明
图1为实施例1微球的透射电镜图;
图2为实施例1微球的氮气吸脱附等温线;
图3为微球催化臭氧降解高盐生化废水的工艺装置示意图;
1-臭氧发生器,2-臭氧浓度分析仪,3-固定床或流化床反应器,4-高盐生化废水,5-蠕动泵,6-取样口,7-O3微气泡,8-微球,9-多孔板,10-臭氧破坏器,11-储液池,12-尾气;
图4为Fe-C微电解对高盐生化废水中COD和NH4 +-N的去除效果;
图5高盐生化废水的紫外光谱图;
图6为实施例1微球/O3对高盐生化废水中COD和NH4 +-N的循环去除效果。
具体实施方式
为进一步公开而不是限制本发明,以下结合实例对本发明作进一步的详细说明。
实施例1
一种磁性悬浮态3D微球的制备方法,具体步骤包括:
(1)称取一定量的SA溶于3.0wt% PVA溶液得2.0wt%淡黄色凝胶A;将15.0g PVDF粉末溶于100mL DMAC,再加入5.0g PVP,60℃机械搅拌1d,静置脱泡得铸膜液B;将1L 4mM氨水溶液匀速滴入由0.1M FeCl3溶液10mL和0.05M FeSO4溶液10mL组成的混合溶液中,匀速搅拌得磁性Fe3O4纳米粒子;将凝胶A、铸膜液B、Fe3O4纳米粒子和桐油按5:6:2.5:2.5的质量比例复合,超声反应3h得塑性浆料,静置脱泡,备用;
(2)在缓慢搅拌下将100g配制好的步骤(1)的塑性浆料缓慢加入到由40mL氯仿、60mL正己烷和1mL 吐温80组成的有机相中,常温下充分搅拌15min,再加入2.0wt%的戊二醛溶液30mL,常温搅拌,转速保持在150~400r/min,化学交联6~12h,过滤固体样品,用去离子水和无水乙醇反复洗涤,60℃烘干得磁性悬浮态微球载体;
(3)将步骤(2)获得的磁性悬浮态微球载体置于3wt%CaCl2溶液中固化3h,取出用去离子水反复洗涤至溶液中检测不出Ca2+;随后置于-60℃真空冷冻干燥机中冷冻干燥3~5h;按固液质量比为1:1取出100g微球载体置于含硝酸铈、硝酸锰和硝酸钴的多元金属混合液(0.5 g/mL硝酸铈2.8mL,0.5 g/mL硝酸锰15mL,0.5 g/mL硝酸钴12.2mL,加去离子水定容至100mL)中浸泡(间歇性搅拌30min,停止30min,交替进行,搅拌速度保持在150~400r/min),化学交联6h,取出用去离子水反复洗涤至溶液中检测不出金属离子;最后置于70~80℃的真空干燥箱中干燥2h,得磁性悬浮态3D微球。
实施例2
一种磁性悬浮态3D微球的制备方法,具体步骤包括:
(1)称取一定量的SA溶于3.0wt% PVA溶液得2.0wt%淡黄色凝胶A;将15.0g PVDF粉末溶于100mL DMAC,再加入5.0g PVP,60℃机械搅拌1d,静置脱泡得铸膜液B;将1L 4mM氨水溶液匀速滴入由0.1M FeCl3溶液10mL和0.05M FeSO4溶液10mL组成的混合溶液中,匀速搅拌得磁性Fe3O4纳米粒子;将凝胶A、铸膜液B、Fe3O4纳米粒子和桐油按8:7.5:4:3的质量比例复合,超声反应3h得塑性浆料,静置脱泡,备用;
(2)在缓慢搅拌下将100g配制好的步骤(1)的塑性浆料缓慢加入到由40mL氯仿、60mL正己烷和1mL 吐温80组成的有机相中,常温下充分搅拌15min,再加入2.0wt%的戊二醛溶液30mL,常温搅拌,转速保持在150~400 r/min,化学交联6~12h,过滤固体样品,用去离子水和无水乙醇反复洗涤,60℃烘干得磁性悬浮态微球载体;
(3)将步骤(2)获得的磁性悬浮态微球载体置于3wt%CaCl2溶液中固化3h,取出用去离子水反复洗涤至溶液中检测不出Ca2+;随后置于-60℃真空冷冻干燥机中冷冻干燥3~5h;按固液质量比为1:1取出100g微球载体置于含硝酸铈、硝酸锰和硝酸钴的多元金属混合液(0.5 g/mL硝酸铈3mL,0.5 g/mL硝酸锰15mL,0.5 g/mL硝酸钴12mL,加去离子水定容至100mL)中浸泡(间歇性搅拌30min,停止30min,交替进行,搅拌速度保持在150~400 r/min),化学交联6h,取出用去离子水反复洗涤至溶液中检测不出金属离子;最后置于70~80℃的真空干燥箱中干燥2h,得磁性悬浮态3D微球。
实施例3
一种磁性悬浮态3D微球的制备方法,具体步骤包括:
(1)称取一定量的SA溶于3.0wt% PVA溶液得2.0wt%淡黄色凝胶A;将15.0g PVDF粉末溶于100mL DMAC,再加入5.0g PVP,60℃机械搅拌1d,静置脱泡得铸膜液B;将1L 4mM氨水溶液匀速滴入由0.1M FeCl3.6H2O 10mL和0.05M FeSO4·7H2O 10mL组成的混合溶液中,匀速搅拌得磁性Fe3O4纳米粒子;将凝胶A、铸膜液B、Fe3O4纳米粒子和桐油按2:4.5:1:2的质量比例复合,超声反应3h得塑性浆料,静置脱泡,备用;
(2)在缓慢搅拌下将100g配制好的步骤(1)的塑性浆料缓慢加入到由40mL氯仿、60mL正己烷和1mL 吐温80组成的有机相中,常温下充分搅拌15min,再加入2.0wt%的戊二醛溶液30mL,常温搅拌,转速保持在150~400r/min,化学交联6~12h,过滤固体样品,用去离子水和无水乙醇反复洗涤,60℃烘干得磁性悬浮态微球载体;
(3)将步骤(2)获得的磁性悬浮态微球载体置于3wt%CaCl2溶液中固化3h,取出用去离子水反复洗涤至溶液中检测不出Ca2+;随后置于-60℃真空冷冻干燥机中冷冻干燥3~5h;按固液质量比为1:1取出100g微球载体置于含硝酸铈、硝酸锰和硝酸钴的多元金属混合液(0.5 g/mL硝酸铈2.5mL,0.5 g/mL硝酸锰15mL,0.5 g/mL硝酸钴12.5mL,加去离子水定容至100mL)中浸泡(间歇性搅拌30min,停止30min,交替进行,搅拌速度保持在150~400 r/min),化学交联6h,取出用去离子水反复洗涤至溶液中检测不出金属离子;最后置于70~80℃的真空干燥箱中干燥2h,得磁性悬浮态3D微球。
对比例1
一种悬浮态3D微球的制备方法,具体步骤包括:
(1)称取一定量的SA溶于3.0wt% PVA溶液得2.0wt%淡黄色凝胶A;将15.0g PVDF粉末溶于100mL DMAC,再加入5.0g PVP,60℃机械搅拌1d,静置脱泡得铸膜液B;将凝胶A、铸膜液B和桐油按5:6:2.5的质量比例复合,超声反应3h得塑性浆料,静置脱泡,备用;
(2)在缓慢搅拌下将100g配制好的步骤(1)的塑性浆料缓慢加入到由40mL氯仿、60mL正己烷和1mL 吐温80组成的有机相中,常温下充分搅拌15min,再加入2.0wt%的戊二醛溶液30mL,常温搅拌,转速保持在150~400r/min,化学交联6~12h,过滤固体样品,用去离子水和无水乙醇反复洗涤,60℃烘干得悬浮态微球载体;
(3)将步骤(2)获得的悬浮态微球载体置于3wt%CaCl2溶液中固化3h,取出用去离子水反复洗涤至溶液中检测不出Ca2+;随后置于-60℃真空冷冻干燥机中冷冻干燥3~5h;按固液质量比为1:1取出100g微球载体置于含硝酸铈、硝酸锰和硝酸钴的多元金属混合液(0.5 g/mL硝酸铈2.8mL,0.5 g/mL硝酸锰15mL,0.5 g/mL硝酸钴12.2mL,加去离子水定容至100mL)中浸泡(间歇性搅拌30min,停止30min,交替进行,搅拌速度保持在150~400r/min),化学交联6h,取出用去离子水反复洗涤至溶液中检测不出金属离子;最后置于70~80℃的真空干燥箱中干燥2h,得悬浮态3D微球。
对比例2
一种磁性悬浮态3D微球的制备方法,具体步骤包括:
(1)称取一定量的SA溶于3.0wt% PVA溶液得2.0wt%淡黄色凝胶A;将15.0g PVDF粉末溶于100mL DMAC,再加入5.0g PVP,60℃机械搅拌1d,静置脱泡得铸膜液B;将1L 4mM氨水溶液匀速滴入由0.1M FeCl3.6H2O 10mL和0.05M FeSO4·7H2O 10mL组成的混合溶液中,匀速搅拌得磁性Fe3O4纳米粒子;将凝胶A、铸膜液B和Fe3O4纳米粒子按5:6:2.5的质量比例复合,超声反应3h得塑性浆料,静置脱泡,备用;
(2)在缓慢搅拌下将100g配制好的步骤(1)的塑性浆料缓慢加入到由40mL氯仿、60mL正己烷和1mL 吐温80组成的有机相中,常温下充分搅拌15min,再加入2.0wt%的戊二醛溶液30mL,常温搅拌,转速保持在150~400r/min,化学交联6~12h,过滤固体样品,用去离子水和无水乙醇反复洗涤,60℃烘干得磁性悬浮态微球载体;
(3)将步骤(2)获得的磁性悬浮态微球载体置于3wt%CaCl2溶液中固化3h,取出用去离子水反复洗涤至溶液中检测不出Ca2+;随后置于-60℃真空冷冻干燥机中冷冻干燥3~5h;按固液比为1:1取出100g微球载体置于含硝酸铈、硝酸锰和硝酸钴的多元金属混合液(0.5 g/mL硝酸铈2.8mL,0.5 g/mL硝酸锰15mL,0.5 g/mL硝酸钴12.2mL,加去离子水定容至100mL)中浸泡(间歇性搅拌30min,停止30min,交替进行,搅拌速度保持在150~400r/min),化学交联6h,取出用去离子水反复洗涤至溶液中检测不出金属离子;最后置于70~80℃的真空干燥箱中干燥2h,得磁性悬浮态3D微球。
对比例3
一种Ce、Mn、Co负载活性氧化铝微球的制备方法,具体步骤包括:采用等体积浸渍法,将活性氧化铝100g加入至含有硝酸铈、硝酸锰和硝酸钴的混合溶液(0.5g/mL硝酸铈2.8mL,0.5g/mL硝酸锰15mL,0.5g/mL硝酸钴12.2mL,加去离子水定容至100mL)中浸渍6h(间歇性搅拌30min,停止30min,交替进行,搅拌速度保持在150~400r/min),取出用去离子水和无水乙醇反复洗涤至溶液中检测不出金属离子;随后置于真空干燥箱中70~80℃条件下干燥2h;最后置于马弗炉中500℃煅烧3h,得Ce、Mn、Co负载活性氧化铝微球。
图1显示微球内部有大量的孔道分布,孔径介于10~200nm之间,孔道结构可能是因为微球在真空冷冻干燥过程中,温度从20℃急剧下降到-60℃,微球内的水分子凝结为固体,随后冻干过程引起冰的升华而形成的。图2等温线属IUPAC分类中的Ⅴ型,H3滞后环。在低压(0.0-0.1)段吸附量平缓增加,表明微孔数量较少;中压(0.3-0.8)段滞后环两侧吸附支和脱附支几乎平行,表明介孔孔道类型为两端开口,孔径分布均匀。高压(0.9-1.0)段吸附量有一突增,说明大孔数量较多。以上数据进一步证明本发明所制备的磁性悬浮态3D微球同时含有介、大孔,孔隙尺寸较大,内扩散阻力较小,利于催化反应的顺利进行。
应用实验:
一种磁性悬浮态3D微球在催化O3矿化高盐生化废水中难降解有机物上的应用,具体步骤为:
步骤a:高盐生化废水取自福建省某固废处置有限公司(常年填埋工业盐和焚烧医疗垃圾)的MBR出水,残留高浓度难降解有机物,其水质如表1所示,COD和NH4 +-N值远高于《城市污水再生利用工业用水水质》(GB /T 19923- 2005)表1敞开式循环冷却水系统补充水标准。
步骤b:向固定床或流化床反应器中加入本发明制备的微球为臭氧催化剂,填充率为10~50%;
步骤c:将高盐生化废水连续或批量经蠕动泵通入上述反应器,反应器采用上向流形式,底部进水,上部出水;启动臭氧发生器将O3连续或间歇通入废水中,O3浓度为10~50mg/L,O3从反应器底部进入,经多孔板在反应器内与微球、废水充分接触促使高活性自由基(·OH和/或·O2 -)大量产生,降解废水中的难降解有机污染物。
步骤d:废水连续或间歇排出反应器,微球依靠磁分离或网孔筛分装置与废水分离而留在反应器内,完成对废水的处理。
表1 高盐生化废水基本理化性质
表2 臭氧催化氧化降解高盐生化废水
在自然pH条件下,当微球(臭氧催化剂)填充率为25%,O3浓度为30mg/L,反应时间为20min时,各实施例和对比例对高盐生化废水的处理效果如表2所示。仅实施例1的COD和NH4 +-N浓度分别降为54mg/L和7.5mg/L,达《城市污水再生利用工业用水水质》(GB/T 19923-2005)表1敞开式循环冷却水系统补充水标准(60mg/L和10mg/L),此时去除率分别为84.4%和86.3%;而采用目前应用较为广泛的Fe-C微电解技术处理该废水(图4),反应4h,出水COD和NH4 +-N浓度分别降为190mg/L和26mg/L,去除率仅为45%和53%,未达《城市污水再生利用工业用水水质》(GB/T 19923-2005)表1敞开式循环冷却水系统补充水标准。由此说明本发明实施例1所制备的磁性悬浮态3D微球在高盐废水的处理中表现出优良的性能。这是因为该微球臭氧催化剂在反应体系随O3微气泡匀速转动,既保证了废水、O3和微球的充分混合接触,促进O3分解为高活性自由基(·OH和·O2 -),提高了O3的传质和转化效率,又防止了微球被污泥、悬浮物或盐分等包裹或堵塞而影响矿化效果。
为了进一步研究臭氧氧化和臭氧催化氧化两者之间的矿化差异,对两种工艺处理的废水进行紫外检测,得到对应的紫外光谱图(图5)。由图5可知,高盐生化废水的光吸收主要集中在280~340nm,结合废水的来源,推测高盐生化废水的主要成分是芳香化合物,经臭氧氧化后废水中对应的紫外吸收峰明显降低,说明各类有机物均有不同程度的降解,芳香度逐渐降低。这是由于O3通过Criegge机理和芳香环上的C〓C反应,造成芳香环开环,难降解有机物被氧化,可生化性提高(BOD5/COD由原水的0.068提升至0.175)。与臭氧氧化相比,经臭氧催化氧化后,废水中对应的紫外吸收峰进一步降低,说明废水中难降解有机物被进一步矿化,可生化性得到提高(BOD5/COD由0.175大幅提升至0.352),在废水降解过程中臭氧催化氧化起主要作用。
稳定性实验:
实施例1的磁性悬浮态3D微球经六次重复使用后,高盐生化废水的COD和NH4 +-N去除率没有明显下降(图6),仅下降1.07%和1.39%,此时两者的浓度分别为57.1mg/L和8.2mg/L,出水未检测到Ce、Mn、Co、Ca和Fe等离子,符合《城市污水再生利用工业用水水质》(GB/T19923-2005)表1敞开式循环冷却水系统补充水标准(60mg/L和10mg/L)。上述结果表明本发明提供的磁性悬浮态3D微球可以快速实现原位再生,吸附的有机中间体(有机碳)或Cl-会在臭氧催化氧化过程进一步分解或氧化,使得催化活性中心得以再生,再生后的微球凭借“结构记忆”效应重复“吸附-降解”过程,整个催化反应过程活性组分没有流失,催化活性持久高效、重复使用稳定性好。
成本估算
该公司进水量80m3/d,每天运行10h,处理量为8 m3/h。成本主要为催化剂(本发明实施例1)、电费和设备费,其中氧化塔和氧气源臭氧发生器的配电功率分别为3kw和6kw,5年电费則为9kw*10h*0.65元/(kw.h)*365*5=10.676万元。本发明的磁性悬浮态3D微球在整个处理过程均不存在催化活性成分流失与破碎现象,不需额外补充。微球(臭氧催化剂)、氧化塔、蠕动泵可保证运行5年,经估算,使用本发明的工艺年造价+运行费用为3.455万元,污水处理价约为34550元/(365d*80 m3/d)=1.183元/m3(表3)。王兵等采用“酸化曝气+Fenton氧化+臭氧氧化”处理工艺处理天然气净化厂检修污水,成本主要为药剂费和电费,处理费用为36.6元/m3,其中酸化曝气、Fenton氧化和臭氧氧化单元的处理成本分别为0.50元/m3、10.15元/m3和25.95元/m3。由此可见,本发明的处理费用远远小于Fenton或臭氧氧化工艺,具有显著的经济优势。
表3 造价和运行成本估算
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (9)
1.一种磁性悬浮态3D微球,其特征在于:采用反相悬浮法以聚乙烯醇PVA、海藻酸钠SA、磁性Fe3O4纳米粒子和桐油为原料制备微球载体,然后利用载体上活泼的羧基,与催化活性组分通过化学螯合作用交联形成具有三维孔道结构、富含羟基和Lewis酸性位的磁性悬浮态海藻酸钠微球。
2.根据权利要求1所述的一种磁性悬浮态3D微球,其特征在于:所述催化活性组分选自至少一种镧系的金属组分、至少一种VIIB族的金属组分和至少一种VIII族的金属组分的组合。
3.根据权利要求2所述的一种磁性悬浮态3D微球,其特征在于:所述催化活性组分为铈Ce、锰Mn、钴Co。
4.根据权利要求1~3任一项所述的一种磁性悬浮态3D微球的制备方法,其特征在于:具体步骤包括:
(1)称取一定量的SA溶于3.0wt% PVA溶液得2.0wt%淡黄色凝胶A;将15.0g聚偏氟乙烯PVDF粉末溶于100mL N、N-二甲基乙酰胺DMAC,再加入5.0g聚乙烯吡咯烷酮PVP,60℃机械搅拌1d,静置脱泡得铸膜液B;将1L 4mM氨水溶液匀速滴入由0.1M FeCl3.6H2O 10mL和0.05MFeSO4·7H2O 10mL组成的混合溶液中,匀速搅拌得磁性Fe3O4纳米粒子;将凝胶A、铸膜液B、Fe3O4纳米粒子和桐油按一定比例复合,超声反应得塑性浆料,静置脱泡,备用;
(2)在缓慢搅拌下将100g配制好的步骤(1)的塑性浆料缓慢加入到由40mL氯仿、60mL正己烷和1mL 吐温80组成的有机相中,常温下充分搅拌15min,再加入2.0wt%戊二醛溶液30mL,常温搅拌,转速保持在150~400r/min,化学交联6~12h,过滤固体样品,用去离子水和无水乙醇反复洗涤,60℃烘干得磁性悬浮态微球载体;
(3)将步骤(2)获得的磁性悬浮态微球载体置于3wt%CaCl2溶液中固化3h,取出用去离子水反复洗涤至溶液中检测不出Ca2+;随后置于-60℃真空冷冻干燥机中冷冻干燥3~5h;接着置于含硝酸铈、硝酸锰和硝酸钴的多元金属混合液中,间歇搅拌状态下浸泡6h,取出用去离子水反复洗涤至溶液中检测不出金属离子;最后置于70~80℃的真空干燥箱中干燥2h,得磁性悬浮态3D微球。
5.根据权利要求4所述的制备方法,其特征在于:步骤(1)所述凝胶A、
铸膜液B、Fe3O4纳米粒子和桐油的质量比为(2~8):(4.5~7.5):(1~4):(2~3)。
6.根据权利要求4所述的制备方法,其特征在于:步骤(1)所述超声反应中,超声波频率为40~60HZ,超声反应时间为30min~5h。
7.根据权利要求4所述的制备方法,其特征在于:步骤(3)所述间歇搅拌,具体为每次搅拌30min,停止30min,交替进行,搅拌速度保持在150~400r/min。
8.根据权利要求4所述的制备方法,其特征在于:以所述载体的重量为基准计,催化活性组分Ce、Mn和Co的含量比为(1~2)wt%:(6~10)wt%:(5~8)wt%。
9.一种如权利要求1所述磁性悬浮态3D微球在催化臭氧O3矿化难降解有机物上的应用。
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