CN105970598B - 一种染料废水处理用纤维膜的制造方法 - Google Patents
一种染料废水处理用纤维膜的制造方法 Download PDFInfo
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- CN105970598B CN105970598B CN201610343241.5A CN201610343241A CN105970598B CN 105970598 B CN105970598 B CN 105970598B CN 201610343241 A CN201610343241 A CN 201610343241A CN 105970598 B CN105970598 B CN 105970598B
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- tunica fibrosa
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- deionized water
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
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Abstract
本发明公开了纤维膜制造技术领域的可催化氧化剂快速高效氧化分解多种染料纤维膜的制造方法,该制造方法首先采用沉淀聚合工艺合成具有优异静电纺可纺性的共聚物,随后静电纺制备纤维膜,并进行离子交联,最后在可溶性亚铁盐水溶液中完成络合物纤维膜的制备,使其具备催化氧化剂氧化分解染料的特性。与Fenton试剂中具有催化功能的粉末状或颗粒状组分相比,具有催化活性高、染料处理速度快、易从水体中回收、不易造成二次污染、可反复使用等优点,还作为过滤媒介对含H2O2、O3等氧化剂的染料废水进行净化处理,一步完成污染物截留以及氧化分解过程;而与已有的复合Fenton催化膜相比,具有制备流程短、成本低、耗能小等优点,因此,更加满足工业实用性要求。
Description
技术领域
本发明涉及一种纤维膜的制造技术,具体为一种可催化氧化剂快速高效氧化分解多种染料纤维膜的制造方法,该制造方法利用了沉淀聚合、静电纺丝、离子交联以及络合铁离子等技术,所得纤维膜可用于染料废水处理。
背景技术
随染料生产和印染行业的发展,染料工业废水的排放量急剧增多,据调查,中国每年约有1.6亿立方米的染料废水排放进入水环境中。染料废水具有色度大、有机污染物含量高、组分复杂、水质变化和生物毒性大以及难生化降解等特性,并朝着抗光解、抗氧化等方向发展,使染料废水的处理难度进一步加大(任南琪,周显娇,郭婉茜,杨珊珊,染料废水处理技术研究进展,化工学报,2013,64(1):85-64)。染料废水中的有机物多以苯、萘、蒽、醌等芳香基团为母体而存在,颜色很深,色度高达50-500万,具有极强的污染性,由于有些原料和副产品含有卤化物、硝基物、氨基物、苯胺酚等有机物,染料废水同时还有很高的毒性。基于以上几点,染料废水已成为国内外难处理的工业废水之一,我国也已将染料废水的治理列为环境保护工作的重点。
目前,工业上普遍采用物理化学(如吸附、絮凝)和生物等方法处理染料等有机污染物(孙赛楠,于飞,刘凡,韩生,马杰,石墨烯及其复合材料对水中有机物和重金属的吸附研究,现代化工,2015,35(11):32-36;邱并生,脱水污泥中脱色偶氮染料功能菌,微生物学通报,2016,43(2):465-466)。物理化学方法具有设备简单、操作简便等优点,但此类方法通常仅是将染料等有机物从液相转移到固相(如活性碳吸附),并没有完全消除有机污染物,而且会带来大量的固体废弃物和再生废水,因此,在去除效果和二次污染等方面均存在一定的缺陷(马留可,詹福如,活性炭对水中亚甲基蓝的吸附性能研究,化学工程,2016,44(1):28-32;阮超,周文婷,林怡汝,胡善爽,泥质活性炭在污水处理中的应用,再生资源与循环经济,2016,9(1):31-33)。生物法具有运行费用低等优点,但存在处理周期长、设备占用面积大,染料等有机污染物对生物的毒性作用会引起去除效果不佳等问题,在厌氧的条件下还可能生成致癌的芳香胺类化合物(Huma Hayat,Qaisar Mahmood,Arshid Pervez,Comparative decolorization of dyes in textile wastewater using biological andchemical treatment,Separation and Purification Technology,2015,154,149-153),因此,生物法应用受到了限制。催化分解法能够弥补上述物理化学、生物法所存在的缺陷,是目前处理染料废水比较理想的方法之一,因此,研制和开发新型可催化分解染料的材料在治理染料废水污染方面具有重要的现实意义。
目前,已出现可催化分解染料的材料,例如,①高活性二氧化钛基光催化材料,但二氧化钛光响应范围较窄,只能吸收太阳光中的紫外光,同时其量子效率偏低,阻碍了其实际应用和商业化发展(向全军,二氧化钛基光催化材料的微结构调控与性能增强,2012,武汉理工大学博士学位论文;Alexandru R.Biris,Dana Toloman,Adriana Popa,Synthesisof Tunable core-shell nanostructures based on TiO2-graphene architectures andtheir application in the photodegradation of rhodamine dyes,Physica E:Low-dimensional Systems and Nanostructures,2016,81,326-333);②氧化锌、石墨烯、二氧化钛三元复合纳米催化剂,这种催化剂具有良好的可见光催化活性,能高效处理染料废水,但制作复杂,容易失活,且分离和回收困难,因此应用受到限制(Prawit Nuengmatcha,Saksit Chanthai,Ratana Mahachai,Visible light-driven photocatalyticdegradation of rhodamine B and industrial dyes(texbrite BAC-L and texbriteNFW-L)by ZnO-graphene-TiO2composite,Journal of Environmental ChemicalEngineering,2016,4(2):2170-2177);③载银氧化锌微纳米球,作为光催化剂,在分解某些染料时具有很好的光催化活性,但其量子产率低,极大地降低了光催化效率,因此,其应用受到限制(张振飞,刘海瑞,张华,刘旭光等,ZnO/Ag微米球的合成与光催化性能,高等学校化学学报,2013,34(12):2827-2833);④三氧化钨光催化材料,这种材料表现出较高的催化活性和目标产物的选择性,但活性钨组分容易从载体上脱落,不能重复使用,因此,其应用受到限制(祝全敬,新型含钨纳米材料的合成及其在绿色选择氧化反应中的应用研究,复旦大学博士学位论文,2013;Maria Hepel,Sandra Hazelton,Photoelectrocatalyticdegradation of diazo dyes on nanostructured WO3electrodes,ElectrochimicaActa,2005,5278-5291);⑤Fenton试剂,其实质是H2O2、O3等氧化剂在Fe2+的催化作用下生成具有高反应活性的羟基自由基(·OH),·OH可与大多数有机物作用使其降解(王帅军,赵朝成,刘其友,张勇,Fe-Ce/ZSM-5类Fenton催化剂降解甲基橙废水的影响因素研究,石油炼制与化工,2016,47(1):17-21;Haiyan Song,Chunxia Chen,Han Zhang,Jie Huang,Rapiddecolorization of dyes in heterogeneous Fenton-like oxidation catalyzed byFe-incorporated Ti-HMS molecular sieves,Journal of Environmental ChemicalEngineering,2016,4(1):460-467;Sergi Garcia-Segura,Enric Brillas,Combustion oftextile monoazo,diazo and triazo dyes by solar photoelectro-Fenton:Decolorization,kinetics and degradation routes,Applied Catalysis B:Environmental,2016,181,681-691;Lie Wang,Yuyuan Yao’,Zhanhao Zhang,Lijie Sun,Activated carbon fibers as an excellent partner of Fenton catalyst for dyesdecolorization by combination of adsorption and oxidation,ChemicalEngineering Journal,2014,251,348-354),Fenton试剂与上述其他催化材料相比,具有反应时间短、速度快、效率高、反应过程易于控制、能氧化分解多种染料,在处理难降解染料等有机污染物时具有独特的优势,是一种很有应用前景的染料废水处理方法。尽管如此,目前Fenton试剂中具有催化功能的组分多为粉末状或颗粒状物质,形态单一,使用后难以与水分离,极易造成二次污染,其应用受到了限制,因此,将Fenton试剂中具有催化功能的组分纤维化,实现使用后与水直接分离的目的,在催化氧化剂氧化分解染料,进而治理染料废水方面具有重要实际意义。众所周知,静电纺丝是获得微纳米纤维的有效途径之一,静电纺丝法纤维具有极细的直径,因此具有极大的比表面积,可快速高效地亲和多种物质,且成形时以非织造布形式存在,整体性极好,使用极其便利,在染料废水处理领域具有极佳的应用前景。若将Fenton反应催化功能赋予静电纺纤维,静电纺纤维则可在染料废水治理领域发挥革命性作用,但关键是选用何种聚合物来静电纺丝,这种聚合物一方面要具有优异的络合铁离子能力,以保证可催化Fenton反应;另一方面又要具有良好的静电纺可纺性,以便形成期待的纤维非织造布材料,这就要求从大分子结构上设计和合成新型聚合物。
含羧酸基聚合物,如聚丙烯酸(PAA),具有无毒、可络合金属离子等特点,但采用溶液聚合法合成PAA时,AA单体极易爆聚,且作为聚电解质,难以将PAA通过静电纺丝技术纺制成纤维。含羟基甲基丙烯酸酯单体,如甲基丙烯酸羟乙酯(HEMA),分子内兼有可聚合乙烯基和活性羟基,是一种亲水性功能单体,其与含羧酸基单体(如丙烯酸)共聚可制得侧链含有活性羟基和羧酸基的共聚物,共聚物不仅具有优异的络合金属离子功能,而且与常规含羧酸基聚合物如PAA相比,静电纺可纺性得到了有效改善。以水为反应介质的沉淀聚合,污染小、易实施,为常用合成聚合物的方法,为含羟基甲基丙烯酸酯-含羧酸基单体共聚物的制备提供了便利。针对上述情况,本发明基于单体的选择,从大分子结构设计角度出发合成了新型聚合物,即含羟基甲基丙烯酸酯-含羧酸基单体共聚物,该共聚物具有优异的静电纺可纺性,同时具有络合金属离子的能力,这种情况下,本发明以该共聚物为原料,可溶性碱水溶液为溶剂,采用静电纺丝工艺制备了由超细纤维组成的纤维膜,随后将所得纤维膜置于可溶性金属盐水溶液中进行离子交联以提高纤维膜的耐水性能,再经洗涤工艺以除去纤维膜表面附着的金属盐,赋予纤维膜大比表面积,为快速高效络合铁离子提供便利,适度干燥后将纤维膜置于可溶性亚铁盐水溶液中,纤维膜富含的羧酸基、羟基与亚铁离子之间发生络合作用,使亚铁离子牢固地结合于纤维膜表面及内部,制得络合物纤维膜,纤维膜具备了催化氧化剂氧化分解染料的特性,成为Fenton试剂中具有催化功能的组分,且为非织造布形态,与Fenton试剂中具有催化功能的粉末状或颗粒状组分相比,用后可直接从水体中取出,不易造成二次污染,也可多次重复使用,特别是可以作为过滤媒介对含H2O2、O3等氧化剂的染料废水进行净化处理,一步完成污染物截留以及氧化分解过程,更富有先进性,与已有的复合Fenton催化膜相比,具有制备流程短、成本低、耗能小等优点,在染料废水处理领域拥有更为广阔的应用空间。
发明内容
针对现有技术的不熟,本发明拟解决的技术问题是,提供一种可催化氧化剂快速高效氧化分解多种染料纤维膜的制造方法。该制造方法首先采用沉淀聚合工艺使含羧酸基单体和含羟基甲基丙烯酸酯单体共聚,生成具有优异静电纺可纺性的共聚物,干燥后将所得共聚物溶于可溶性碱水溶液中,配制成综合性能较适宜的纺丝液,然后通过调控溶液组成、加工参数和环境温湿度条件,采用静电纺丝技术制备纤维膜,接着在适宜的可溶性金属盐水溶液中进行离子交联,以增强纤维膜的耐水性能,洗涤除去纤维膜表面附着的金属盐,以便提高络合铁离子的能力,与现有可络合铁离子聚合物基材料相比,交联后的纤维膜络合铁离子的能力更强、络合牢度更高,最后将交联后的纤维膜置于可溶性亚铁盐水溶液中,纤维膜富含的羧酸基、羟基与亚铁离子之间发生络合作用,使亚铁离子牢固地结合于纤维膜表面及内部,制得络合物纤维膜,纤维膜具备了催化氧化剂氧化分解染料的特性,成为Fenton试剂中具有催化功能的组分。这种纤维膜实质上为非织造布,其中超细纤维交错不定向排列形成多孔性三维立体网络结构,与Fenton试剂中具有催化功能的粉末状或颗粒状组分相比,具有催化活性高、染料处理速度快、易从水体中分离、回收方便,不易造成二次污染、可反复使用等优点,特别是可以作为过滤媒介对含H2O2、O3等氧化剂的染料废水进行净化处理,一步完成污染物截留以及氧化分解过程,更富有先进性;而与已有的复合Fenton催化膜相比,具有制备流程短、成本低、耗能小等优点,因此,更加满足工业实用性要求。
本发明解决所述技术问题的技术方案是:设计一种可催化氧化剂快速高效氧化分解多种染料纤维膜的制造方法,其工艺过程如下:
(1)沉淀聚合工艺:称取一定质量的单体1,将其置于适宜的烧杯中,称取单体2,使其与单体1的质量之比为1∶9~9∶1,将单体2加入上述烧杯中,称取占单体1和单体2总质量0.2~2%的引发剂,并将其加入到上述烧杯中,搅拌直至引发剂完全溶解于单体中,停止搅拌;称取去离子水,使其质量与单体1和单体2总质量之比为1∶2~1∶0.5,将其加入到上述烧杯中,搅拌使其混合均匀,随后将单体、引发剂和去离子水形成的混合体系移至聚合釜中,开启搅拌,通入氮气以排净聚合釜中残留的空气,将聚合釜升温至70~95℃,并开始计时,反应1~4h后,取出胶状产物,用去离子水洗涤一次以上,除去未反应的单体以及低聚物,以防聚合产物着色,于真空干燥机中40~80℃条件下干燥48~96h后,于高速粉碎机中充分粉碎,制得淡黄色粉末状聚合物;
所述单体1为丙烯酸、甲基丙烯酸、顺丁烯二酸酐中的一种;
所述单体2为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中的一种;
所述引发剂为过氧化苯甲酰、偶氮二异丁腈、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二异丙苯、过氧化二叔丁基中的一种;
(2)纺丝液配制工艺:称取一定质量去离子水,将其置于适宜的烧杯中,称取一定质量可溶性碱,使可溶性碱与去离子水的质量之比为0.5∶9.5~9.5∶0.5,将其加入到上述去离子水中,搅拌至可溶性碱完全溶解,即为溶剂;称取一定质量步骤(1)中制得的聚合物粉末,使聚合物与上述溶剂的质量之比为0.1∶10~3∶10,将其加入到上述溶剂中,在40~80℃条件下磁力搅拌直至形成均匀溶液,即为纺丝液;
所述可溶性碱为氢氧化钠、氢氧化锂、氢氧化钾、氢氧化钡中的一种;
(3)静电纺丝工艺:将上述纺丝液吸入静电纺丝用注射器中,将注射器上端向上置于支架上,并保持上端口开启,将支架置于真空干燥机中在25~95℃以及-0.07~-0.1MPa条件下脱泡,时间为0~60min,将平头针头小心地装在含有纺丝液的注射器上,并将注射器置于注射泵上,使针头高度与接收板的中心高度相等,调节注射泵的挤出速度为0~2ml/h,调整针头到接收板的距离为10~40cm,设定接收板的转速为50~2000r/min,将高压电源的高压输出端连接在针头上,地线连接到接收板上,然后在接收板上包裹一层锡纸,使接收板旋转起来,启动高压电源,调节直流电压为5~40kv,启动注射泵,在温度为20~50℃、湿度为10~50%条件下开始纺丝,待1~300h后停止纺丝,将锡纸剥离后,可获得纤维膜;
(4)离子交联工艺:称取一定质量去离子水,将其置于适宜的烧杯中,称取一定质量可溶性金属盐,使可溶性金属盐与去离子水的质量之比为0.1∶10~10∶0.1,将其加入到上述去离子水中,搅拌至可溶性金属盐完全溶解,即为交联溶液,将交联溶液置于处理槽中,称取一定质量步骤(3)中制得的纤维膜,使纤维膜与上述交联溶液的质量之比为1∶10~1∶100,并将纤维膜放入处理槽中,浸没于交联溶液中,开始计时,对纤维膜进行离子交联处理,交联时间为0.01~5h,达交联时间后,将纤维膜立即从处理槽中取出,制得交联纤维膜;
所述可溶性金属盐为氯化钙、氯化镁、氯化铝、氯化钡中的一种;
(5)洗涤、干燥工艺:称取一定质量去离子水,将其置于洗涤槽中,称取一定质量步骤(4)中制得的交联纤维膜,使交联纤维膜与去离子水的质量之比为0.01∶100~100∶0.01,将其放入到上述洗涤槽中洗涤,将洗涤后的纤维膜置于真空干燥箱中,在20~50℃条件下干燥1~3h,获得初生纤维膜;
(6)络合工艺:称取一定质量的去离子水,将其置于适宜烧杯中,称取一定质量的可溶性亚铁盐,使去离子水与亚铁盐的质量比为0.01∶10~10∶0.01,将其加入到上述去离子水中,搅拌至可溶性亚铁盐完全溶解,即为亚铁盐水溶液,并将其置于处理槽中,称取一定质量步骤(5)中制得的纤维膜,使纤维膜与上述亚铁盐水溶液质量之比为1∶100~1∶10,并将纤维膜放入处理槽中,浸没于亚铁盐水溶液中,开始计时,纤维膜与铁离子进行络合,络合时间为0.01~300min,达络合时间后,将纤维膜立即从处理槽中取出,并置于真空干燥箱中,在20~50℃条件下干燥1~3h,制得可催化氧化剂快速高效氧化分解多种染料的络合物纤维膜;
所述可溶性亚铁盐为氯化亚铁、硫酸亚铁、硝酸亚铁中的一种。
与现有技术产品相比,首先,本发明所得络合物纤维膜在形态上具有突出优势,现有Fenton试剂中具有催化功能的组分多为粉末状或颗粒状物质,形态单一,在处理流动的染料废水时,存在诸多操作不便的缺陷,难以回收,极易残留于水中造成二次污染,本发明所得络合物纤维膜整体性好,易于漂浮于水体表面,在处理静态或动态染料废水时,可直接将其投到废水中完成对染料的催化氧化分解,催化完成后可轻易打捞回收,而不会遗留在水中造成二次污染,使用极其方便;其次,在制造技术上本发明同样富有创新性,本发明从聚合物合成、非织造布一步成型这一思路出发,将沉淀聚合与静电纺丝技术结合起来用于制备初生纤维膜,即非织造布,特别是静电纺丝技术的选择,使聚合物纺丝成形、成膜过程融为一体,在一台设备上同时实现了纺丝和成膜,一步获得了非织造布产品,而现有的同类型湿法纺丝法纤维,必须再次在非织造布设备上进行加工,才能获得具有实际使用价值的产品,因此,本发明设计的工艺流程更为简化,生产成本相对更低;再次,本发明所得初生纤维膜的比表面积相对更大,在快速高效络合金属离子方面具有更为突出的优势,本发明所得初生纤维膜由微纳米纤维交错不定向排列组合而成,超细纤维本身具有极大的比表面积,使初生纤维膜的比表面积提高,而超细纤维彼此构建的众多孔洞结构进一步提高了初生纤维膜的比表面积,在大比表面积的影响下,初生纤维膜与现有的同类型湿法纺丝法纤维相比,可以更为快速高效地络合金属离子,进而可高效率地制备络合物纤维膜,在染料废水治理领域可发挥更为积极的作用;此外,在催化H2O2、O3等氧化剂氧化分解染料时,本发明所得络合物纤维膜可多次使用,而染料去除效率不会大幅下降,经多次使用后,纤维膜还可以继续络合铁离子,而使其催化活性恢复至初,之后继续多次使用,如此反复,实现了循环利用,应用前景更为突出;最后,在申请人检索的范围内,尚未见到采用本发明所述工艺制造可催化氧化剂快速高效氧化分解多种染料的络合物纤维膜的相关文献报道。
具体实施方式
下面结合实施例进一步叙述本发明:本发明设计的可催化氧化剂快速高效氧化分解多种染料络合物纤维膜的制造方法(以下简称制造方法)涉及沉淀聚合、静电纺丝、离子交联、洗涤、干燥和络合等工艺技术的综合应用,旨在解决现有Fenton试剂中具有催化功能的粉末状或颗粒状组分在处理染料废水时存在的形态单一、难以回收再利用等问题,为染料污染物治理创造一种新的材料,其工艺过程或步骤如下:
(1)沉淀聚合工艺:称取一定质量的单体1,将其置于适宜的烧杯中,称取单体2,使其与单体1的质量之比为1∶9~9∶1,将单体2加入上述烧杯中,称取占单体1和单体2总质量0.2~2%的引发剂,并将其加入到上述烧杯中,搅拌直至引发剂完全溶解于单体中,停止搅拌;称取去离子水,使其质量与单体1和单体2总质量之比为1∶2~1∶0.5,将其加入到上述烧杯中,搅拌使其混合均匀,随后将单体、引发剂和去离子水形成的混合体系移至聚合釜中,开启搅拌,通入氮气以排净聚合釜中残留的空气,将聚合釜升温至70~95℃,并开始计时,反应1~4h后,取出胶状产物,用去离子水洗涤一次以上,除去未反应的单体以及低聚物,以防聚合产物着色,于真空干燥机中40~80℃条件下干燥48~96h后,于高速粉碎机中充分粉碎,制得淡黄色粉末状聚合物;
(2)纺丝液配制工艺:称取一定质量去离子水,将其置于适宜的烧杯中,称取一定质量可溶性碱,使可溶性碱与去离子水的质量之比为0.5∶9.5~9.5∶0.5,将其加入到上述去离子水中,搅拌至可溶性碱完全溶解,即为溶剂;称取一定质量步骤(1)中制得的聚合物粉末,使聚合物与上述溶剂的质量之比为0.1∶10~3∶10,将其加入到上述溶剂中,在40~80℃条件下磁力搅拌直至形成均匀溶液,即为纺丝液;
(3)静电纺丝工艺:将上述纺丝液吸入静电纺丝用注射器中,将注射器上端向上置于支架上,并保持上端口开启,将支架置于真空干燥机中在25~95℃以及-0.07~-0.1MPa条件下脱泡,时间为0~60min,将平头针头小心地装在含有纺丝液的注射器上,并将注射器置于注射泵上,使针头高度与接收板的中心高度相等,调节注射泵的挤出速度为0~2ml/h,调整针头到接收板的距离为10~40cm,设定接收板的转速为50~2000r/min,将高压电源的高压输出端连接在针头上,地线连接到接收板上,然后在接收板上包裹一层锡纸,使接收板旋转起来,启动高压电源,调节直流电压为5~40kv,启动注射泵,在温度为20~50℃、湿度为10~50%条件下开始纺丝,待1~300h后停止纺丝,将锡纸剥离后,可获得纤维膜;
(4)离子交联工艺:称取一定质量去离子水,将其置于适宜的烧杯中,称取一定质量可溶性金属盐,使可溶性金属盐与去离子水的质量之比为0.1∶10~10∶0.1,将其加入到上述去离子水中,搅拌至可溶性金属盐完全溶解,即为交联溶液,将交联溶液置于处理槽中,称取一定质量步骤(3)中制得的纤维膜,使纤维膜与上述交联溶液的质量之比为1∶10~1∶100,并将纤维膜放入处理槽中,浸没于交联溶液中,开始计时,对纤维膜进行离子交联处理,交联时间为0.01~5h,达交联时间后,将纤维膜立即从处理槽中取出,制得交联纤维膜;
(5)洗涤、干燥工艺:称取一定质量去离子水,将其置于洗涤槽中,称取一定质量步骤(4)中制得的交联纤维膜,使交联纤维膜与去离子水的质量之比为0.01∶100~100∶0.01,将其放入到上述洗涤槽中洗涤,将洗涤后的纤维膜置于真空干燥箱中,在20~50℃条件下干燥1~3h,获得初生纤维膜;
(6)络合工艺:称取一定质量的去离子水,将其置于适宜烧杯中,称取一定质量的可溶性亚铁盐,使去离子水与亚铁盐的质量比为0.01∶10~10∶0.01,将其加入到上述去离子水中,搅拌至可溶性亚铁盐完全溶解,即为亚铁盐水溶液,并将其置于处理槽中,称取一定质量步骤(5)中制得的纤维膜,使纤维膜与上述亚铁盐水溶液质量之比为1∶100~1∶10,并将纤维膜放入处理槽中,浸没于亚铁盐水溶液中,开始计时,纤维膜与铁离子进行络合,络合时间为0.01~300min,达络合时间后,将纤维膜立即从处理槽中取出,并置于真空干燥箱中,在20~50℃条件下干燥1~3h,制得可催化氧化剂快速高效氧化分解多种染料的络合物纤维膜。
本发明制造方法所述的单体1为丙烯酸、甲基丙烯酸、顺丁烯二酸酐中的一种,由单体1聚合生成的聚合物含有大量羧酸基,可在水中电离成带负电的羧酸阴离子,进而与亚铁离子进行络合,使亚铁离子牢固地结合于纤维表面及内部,因此,本发明制造方法中所述的单体1是用来保障所合成聚合物具有络合亚铁离子功能的,进而将催化氧化剂氧化分解染料性能赋予所得纤维膜。
本发明制造方法所述的单体1优选丙烯酸,原因如下:①丙烯酸是最简单的不饱和羧酸,也是聚合速度非常快的乙烯类单体;②甲基丙烯酸受热分解时会产生有毒气体,这种气体能与空气形成爆炸混合物;③顺丁烯二酸酐有强烈的刺激气味,而且有毒,能刺激皮肤及黏膜,严重时导致视力减退甚至失明;基于上述三方面原因,本发明制造方法所述的单体1优选丙烯酸。
本发明制造方法所述的单体2为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中的一种,只用单体1进行聚合,聚合过程中体系粘度会急剧增大,甚至产生爆聚,难以获得分子量和分子量分布适宜的可纺丝聚合产物,即使获得了单体1的均聚物,该均聚物溶于水,但其水溶液为强聚电解质溶液,给静电纺丝成形带来了极大困难,由此,单体2一方面是用来改善体系的聚合温和程度,另一方面是用来改善所得聚合物的静电纺可纺性。
本发明制造方法所述的单体2优选甲基丙烯酸羟乙酯,原因如下:与甲基丙烯酸羟丙酯相比,甲基丙烯酸羟乙酯是无毒化学品,广泛用作牙科、骨科、隐形眼镜等医用材料。
本发明制造方法所述的引发剂为过氧化苯甲酰、偶氮二异丁腈、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二异丙苯、过氧化二叔丁基中的一种,选择引发剂的原则包括:①根据聚合温度选择半衰期适当的引发剂,使聚合时间适中,以聚合釜的传热能力为基础,在保证温度控制和避免爆聚的前提下,应尽可能选用高活性的引发剂,即半衰期较短的引发剂,以提高聚合速率,缩短聚合时间,同时可降低聚合温度和减少引发剂用量;②还应该考虑引发剂对聚合物质量有无影响、引发剂有无毒性、使用和贮存过程中是否安全等问题。众所周知,过氧化二叔丁基在100℃时的半衰期为218h,过氧化二异丙苯在115℃时的半衰期为12.3h,叔丁基过氧化氢在154.5℃时的半衰期为44.8h,异丙苯过氧化氢在125℃时的半衰期为21h,偶氮二异丁腈在100℃时的半衰期为0.1h,过氧化苯甲酰在125℃时的半衰期为0.42h,且温度降低半衰期延长,温度升高半衰期缩短。本发明涉及的聚合反应温度范围为70~95℃,时间为1~4h,针对上述温度区间及要求的反应时间,过氧化苯甲酰的半衰期均较为合适,可保证在涉及的聚合时间内就能达到理想的聚合程度,且由于过氧化苯甲酰属低毒化学品,使用和贮存相对安全,故本发明优选的引发剂为过氧化苯甲酰。
本发明制造方法所述的可溶性碱为氢氧化钠、氢氧化锂、氢氧化钾、氢氧化钡中的一种,本发明制造方法所述的可溶性碱优选氢氧化钠,原因如下:①与氢氧化锂、氢氧化钾相比,氢氧化钠价格低廉、易得,更利于工业实施;②与氢氧化钡相比,在溶剂制备以及溶解聚合物过程中,氢氧化钠虽与空气中的二氧化碳反应,但生成物是水溶性的,不易残留在纤维膜上,而氢氧化钡与空气中二氧化碳反应生成物不溶于水,极易残留在纤维膜上,对其后续应用造成影响;基于上述两方面原因,本发明制造方法所述的可溶性碱优选氢氧化钠。
本发明制造方法所述的可溶性金属盐为氯化钙、氯化镁、氯化铝、氯化钡中的一种。本发明制造方法所述的可溶性金属盐优选氯化钙,原因如下:①与氯化镁相比,氯化钙水溶液的碱性稍差,交联后纤维膜的碱性也相对较差,有利于染料废水处理后的再利用,经过洗涤更容易除去纤维膜表面的无机物,进而避免无机物对染料氧化分解的影响;②与氯化铝相比,在交联溶液制备过程中氯化钙比较稳定,而氯化铝在去离子水中会部分水解生成氯化氢气体,对操作环境造成污染;③与氯化钡相比,氯化钙无毒、价格便宜;基于上述原因,本发明制造方法所述的可溶性金属盐优选氯化钙。
本发明制造方法所述的可溶性亚铁盐为氯化亚铁、硫酸亚铁、硝酸亚铁中的一种,本发明制造方法所述的可溶性亚铁盐优选氯化亚铁,原因如下:与硫酸亚铁、硝酸亚铁相比,氯化亚铁水溶性更好、更稳定,更利于工业实施,基于上述原因,本发明制造方法所述的可溶性亚铁盐优选氯化亚铁。
下面给出具体实施例,以进一步详细描述本发明,但本申请权利要求保护范围不受具体实施例的限制。
实施例1
称取70g丙烯酸,将其置于适宜的烧杯中,称取30g甲基丙烯酸羟乙酯,并将其加入到上述烧杯中,称取0.5g过氧化苯甲酰,并将其加入到上述烧杯中,用玻璃棒搅拌,直至过氧化苯甲酰完全溶解于丙烯酸和甲基丙烯酸羟乙酯混合溶液中,此后,称取100g去离子水,将其加入到上述丙烯酸、甲基丙烯酸羟乙酯、过氧化苯甲酰形成的溶液中,并搅拌使其混合均匀,随后将上述溶液移至聚合釜中,开启搅拌,通入氮气以排净聚合釜中残留的空气,将聚合釜升温至85℃时开始计时,反应2.5h后,取出胶状产物,用去离子水洗涤三次,除去未反应的单体以及低聚物,以防聚合产物着色,于真空干燥机中80℃条件下干燥96h后,于高速粉碎机中充分粉碎;称取40g去离子水,将其置于适宜的烧杯中,称取7.5g氢氧化钠,将其加入到上述去离子水中,搅拌至氢氧化钠完全溶解,即为溶剂,称取2.5g上述制得的聚合物粉末,将其加入到上述溶剂中,在80℃条件下磁力搅拌直至形成均匀溶液;将上述溶液吸入静电纺丝用注射器中,将注射器上端向上置于支架上,并保持上端口开启,将支架置于真空干燥机中在40℃以及-0.09MPa条件下脱泡,时间为30min;将平头针头小心地装在含有纺丝液的注射器上,并将注射器置于注射泵上,使针头高度与接收板的中心高度相等,调节注射泵的挤出速度为0.8ml/h,调整针头到接收板的距离为15cm,设定接收板的转速为250r/min,将高压电源的高压输出端连接在针头上,地线连接到接收板上,然后在接收板上包裹一层锡纸,使接收板旋转起来,启动高压电源,调节直流电压为18kv,启动注射泵,在温度为30℃、湿度为40%条件下开始纺丝,待24h后停止纺丝,将锡纸剥离后,可获得纤维膜;称取90g去离子水,将其置于适宜的烧杯中,称取10g氯化钙,将其加入到上述去离子水中,搅拌至氯化钙完全溶解,即为交联溶液,将其置于处理槽中;称取1g纤维膜,并将纤维膜放入处理槽中,浸没于交联溶液中,开始计时,纤维膜进行交联,交联时间为30min,达交联时间后,将纤维膜立即从处理槽中取出,制得力学强度得到改善的交联纤维膜;称取100g去离子水,将其置于洗涤槽中,称取1g所得交联纤维膜,将其放入到上述洗涤槽中洗涤,将洗涤后的纤维膜置于真空干燥箱中,在30℃条件下干燥2h,获得初生纤维膜;称取90g去离子水,将其置于适宜的烧杯中,称取10g氯化亚铁,将其加入到上述去离子水中,磁力搅拌至氯化亚铁完全溶解,即为亚铁盐水溶液,将其置于处理槽中;称取1g初生纤维膜,并将纤维膜放入处理槽中,浸没于亚铁盐水溶液中,将处理槽温度升高至25℃,开始计时,纤维膜与铁离子进行络合,络合时间为2s,达络合时间后,将纤维膜立即从处理槽中取出,并置于真空干燥箱中,在30℃条件下干燥1h,制得可催化氧化剂快速高效氧化分解多种染料的络合物纤维膜。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,60分钟后亚甲基蓝染料的去除效率达100%。
实施例2
本实施例工艺过程及参数与实施例1相同,仅去离子水与氯化亚铁的比例有改变,去离子水由实施例1中的90g变为70g,氯化亚铁由实施例1中的10g变为30g。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,10分钟后亚甲基蓝染料的去除效率达100%。
实施例3
本实施例工艺过程及参数与实施例1相同,仅去离子水与氯化亚铁的比例有改变,去离子水由实施例1中的90g变为95g,氯化亚铁由实施例1中的10g变为5g。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,90分钟后亚甲基蓝染料的去除效率达50%。
实施例4
本实施例工艺过程及参数与实施例1相同,仅纤维膜与铁离子的络合时间有改变,络合时间由实施例1中的2s变为1min。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,60分钟后亚甲基蓝染料的去除效率达100%。
实施例5
本实施例工艺过程及参数与实施例1相同,仅纤维膜与铁离子的络合时间有改变,络合时间由实施例1中的2s变为3min。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,60分钟后亚甲基蓝染料的去除效率达100%。
实施例6
本实施例工艺过程及参数与实施例1相同,仅纤维膜与铁离子的络合时间有改变,络合时间由实施例1中的2s变为5min。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,20分钟后亚甲基蓝染料的去除效率达100%。
实施例7
本实施例工艺过程及参数与实施例1相同,仅纤维膜与铁离子的络合时间有改变,络合时间由实施例1中的2s变为30min。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,10分钟后亚甲基蓝染料的去除效率达100%。
实施例8
本实施例工艺过程及参数与实施例1相同,仅纤维膜的交联时间有改变,交联时间由实施例1中的30min变为5min。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,10分钟后亚甲基蓝染料的去除效率达100%。
实施例9
本实施例工艺过程及参数与实施例1相同,仅纤维膜的交联时间有改变,交联时间由实施例1中的30min变为15min。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,60分钟后亚甲基蓝染料的去除效率达100%。
实施例10
本实施例工艺过程及参数与实施例1相同,仅纤维膜的交联时间有改变,交联时间由实施例1中的30min变为1h。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,80分钟后亚甲基蓝染料的去除效率达100%。
实施例11
本实施例工艺过程及参数与实施例1相同,仅去离子水与氯化钙的比例有改变,去离子水由实施例1中的90g变为80g,氯化钙由实施例1中的10g变为20g。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,70分钟后亚甲基蓝染料的去除效率达100%。
实施例12
本实施例工艺过程及参数与实施例1相同,仅去离子水与氯化钙的比例有改变,去离子水由实施例1中的90g变为70g,氯化钙由实施例1中的10g变为30g。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后亚甲基蓝染料的去除效率为8%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维膜置于上述溶液中,90分钟后亚甲基蓝染料的去除效率达90%。
Claims (6)
1.一种染料废水处理用纤维膜的制造方法,其特征在于工艺过程如下:
(1)沉淀聚合工艺:称取一定质量的单体1,将其置于适宜的烧杯中,称取单体2,使其与单体1的质量之比为1∶9~9∶1,将单体2加入上述烧杯中,称取占单体1和单体2总质量0.2~2%的引发剂,并将其加入到上述烧杯中,搅拌直至引发剂完全溶解于单体中,停止搅拌;称取去离子水,使其质量与单体1和单体2总质量之比为1∶2~1∶0.5,将其加入到上述烧杯中,搅拌使其混合均匀,随后将单体、引发剂和去离子水形成的混合体系移至聚合釜中,开启搅拌,通入氮气以排净聚合釜中残留的空气,将聚合釜升温至70~95℃,并开始计时,反应1~4h后,取出胶状产物,用去离子水洗涤一次以上,除去未反应的单体以及低聚物,以防聚合产物着色,于真空干燥机中40~80℃条件下干燥48~96h后,于高速粉碎机中充分粉碎,制得淡黄色粉末状聚合物;
所述单体1为丙烯酸、甲基丙烯酸、顺丁烯二酸酐中的一种,所述单体2为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中的一种;
(2)纺丝液配制工艺:称取一定质量去离子水,将其置于适宜的烧杯中,称取一定质量可溶性碱,使可溶性碱与去离子水的质量之比为0.5∶9.5~9.5∶0.5,将其加入到上述去离子水中,搅拌至可溶性碱完全溶解,即为溶剂;称取一定质量步骤(1)中制得的聚合物粉末,使聚合物与上述溶剂的质量之比为0.1∶10~3∶10,将其加入到上述溶剂中,在40~80℃条件下磁力搅拌直至形成均匀溶液,即为纺丝液;
(3)静电纺丝工艺:将上述纺丝液吸入静电纺丝用注射器中,将注射器上端向上置于支架上,并保持上端口开启,将支架置于真空干燥机中在25~95℃以及-0.07~-0.1MPa条件下脱泡,时间为0~60min,将平头针头小心地装在含有纺丝液的注射器上,并将注射器置于注射泵上,使针头高度与接收板的中心高度相等,调节注射泵的挤出速度为0~2ml/h,调整针头到接收板的距离为10~40cm,设定接收板的转速为50~2000r/min,将高压电源的高压输出端连接在针头上,地线连接到接收板上,然后在接收板上包裹一层锡纸,使接收板旋转起来,启动高压电源,调节直流电压为5~40kv,启动注射泵,在温度为20~50℃、湿度为10~50%条件下开始纺丝,待1~300h后停止纺丝,将锡纸剥离后,可获得纤维膜;
(4)离子交联工艺:称取一定质量去离子水,将其置于适宜的烧杯中,称取一定质量可溶性金属盐,使可溶性金属盐与去离子水的质量之比为0.1∶10~10∶0.1,将其加入到上述去离子水中,搅拌至可溶性金属盐完全溶解,即为交联溶液,将交联溶液置于处理槽中,称取一定质量步骤(3)中制得的纤维膜,使纤维膜与上述交联溶液的质量之比为1∶10~1∶100,并将纤维膜放入处理槽中,浸没于交联溶液中,开始计时,对纤维膜进行离子交联处理,交联时间为0.01~5h,达交联时间后,将纤维膜立即从处理槽中取出,制得交联纤维膜;
(5)洗涤、干燥工艺:称取一定质量去离子水,将其置于洗涤槽中,称取一定质量步骤(4)中制得的交联纤维膜,使交联纤维膜与去离子水的质量之比为0.01∶100~100∶0.01,将其放入到上述洗涤槽中洗涤,将洗涤后的纤维膜置于真空干燥箱中,在20~50℃条件下干燥1~3h,获得初生纤维膜;
(6)络合工艺:称取一定质量的去离子水,将其置于适宜烧杯中,称取一定质量的可溶性亚铁盐,使去离子水与亚铁盐的质量比为0.01∶10~10∶0.01,将其加入到上述去离子水中,搅拌至可溶性亚铁盐完全溶解,即为亚铁盐水溶液,并将其置于处理槽中,称取一定质量步骤(5)中制得的纤维膜,使纤维膜与上述亚铁盐水溶液质量之比为1∶100~1∶10,并将纤维膜放入处理槽中,浸没于亚铁盐水溶液中,开始计时,纤维膜与铁离子进行络合,络合时间为0.01~300min,达络合时间后,将纤维膜立即从处理槽中取出,并置于真空干燥箱中,在20~50℃条件下干燥1~3h,制得可催化氧化剂快速高效氧化分解多种染料的络合物纤维膜。
2.根据权利要求1所述的一种染料废水处理用纤维膜的制造方法,其特征在于所述的引发剂为过氧化苯甲酰、偶氮二异丁腈、异丙苯过氧化氢、叔丁基过氧化氢、过氧化二异丙苯、过氧化二叔丁基中的一种。
3.根据权利要求1所述的一种染料废水处理用纤维膜的制造方法,其特征在于所述的可溶性碱为氢氧化钠、氢氧化锂、氢氧化钾、氢氧化钡中的一种。
4.根据权利要求1所述的一种染料废水处理用纤维膜的制造方法,其特征在于所述的可溶性金属盐为氯化钙、氯化镁、氯化铝、氯化钡中的一种。
5.根据权利要求1所述的一种染料废水处理用纤维膜的制造方法,其特征在于所述的可溶性亚铁盐为氯化亚铁、硫酸亚铁、硝酸亚铁中的一种。
6.根据权利要求1~5中任一项所述的一种染料废水处理用纤维膜的制造方法,其特征在于所述的单体1为丙烯酸;所述的单体2为甲基丙烯酸羟乙酯;所述的引发剂为过氧化苯甲酰;所述的可溶性碱为氢氧化钠;所述的可溶性金属盐为氯化钙;所述的可溶性亚铁盐为氯化亚铁。
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JP2006026588A (ja) * | 2004-07-20 | 2006-02-02 | Japan Atom Energy Res Inst | 温泉水に溶存する有用・有害金属を回収および除去する方法 |
CN100393935C (zh) * | 2005-09-30 | 2008-06-11 | 中国石油化工股份有限公司 | 高吸水纤维及其制造方法 |
CN104264373B (zh) * | 2014-09-09 | 2017-02-15 | 天津工业大学 | 一种吸油纤维膜的制造方法 |
CN104313796B (zh) * | 2014-09-09 | 2016-05-11 | 天津工业大学 | 一种油水分离用纤维膜的制造方法 |
CN104264453B (zh) * | 2014-09-09 | 2017-02-15 | 天津工业大学 | 一种吸附阳离子纤维膜的制造方法 |
CN105195223B (zh) * | 2015-09-16 | 2018-10-16 | 天津工业大学 | 一种蚕丝纤维铁配合物光催化剂及其制备方法 |
CN105126633B (zh) * | 2015-09-18 | 2017-04-26 | 东南大学 | 一种高压静电纺丝法制备阴离子交换膜的方法 |
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