CN105803557B - 一种染料废水处理用纤维的制造方法 - Google Patents
一种染料废水处理用纤维的制造方法 Download PDFInfo
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- CN105803557B CN105803557B CN201610343242.XA CN201610343242A CN105803557B CN 105803557 B CN105803557 B CN 105803557B CN 201610343242 A CN201610343242 A CN 201610343242A CN 105803557 B CN105803557 B CN 105803557B
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Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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Abstract
本发明公开了纤维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的制造方法,所得纤维可用于染料废水处理,该制造方法首先采用沉淀聚合法合成含特殊官能团的聚合物,随后以可溶性碱水溶液为溶剂、无机酸水溶液为凝固介质,采用湿法纺丝技术纺制纤维,洗涤、干燥后,在可溶性亚铁盐水溶液中,纤维富含的羧酸基、羟基与亚铁离子之间发生络合作用,制得络合物纤维,纤维具备了催化氧化剂氧化分解染料的特性。所得纤维与现有粉末状或颗粒状Fenton反应催化剂相比,除具有可重复使用、处理效率高、染料去除率高、应用成本低等优点外,还具有可非织造或纺织加工、整体性好、使用方便、易回收等优点,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的制造方法,该制造方法利用了沉淀聚合、湿法纺丝以及络合铁离子等技术,所得纤维可用于染料废水处理。
背景技术
水是人类及一切生物赖以生存的重要物质,是工农业生产、经济发展和环境改善过程中不可替代的宝贵资源。众所周知,我们地球上淡水资源有限,由于人口增长速度过快,水资源短缺问题日益突出,并逐渐成为制约经济发展、影响人们生活的主要问题之一。近年来,由于经济快速发展的缘故,工业废水污染日趋严重,造成水资源水质恶化。全世界染料工业每年大约消耗和生产80000吨染料,其中有10000吨用于商业染料工业(GuangweiZhang,Idzumi Okajima,Takeshi Sako,Decomposition and decoloration of dyeingwastewater by hydrothermal oxidation,The Journal of Supercritical Fluids,2016,112,136-142;Lee J W,Choi S P,Thiruvenkatachari R,Evaluation of theperformance of adsorption and coagulation processes for the maximum removalof reactive dyes,Dyes and Pigments,2006,69(3):196-203),这些染料主要用于纺织、印染、造纸、制革、油漆等产业,而上述产业产生的废水大概有10%-15%没有经过处理而直接排放,因此,染料工业排放的染料废水已成为工业废水的主要来源之一。在这些染料废水中,染料成分复杂,浓度和色度较高,大多数难生物降解,而且还含有多种具有生物毒性或具有致癌、致畸和致突变的有机物,因此,染料废水处理已变得十分迫切(Jin Wu,LumingMa,Yunlu Chen,Catalytic ozonation of organic pollutants from bio-treateddyeing and finishing wastewater using recycled waste iron shavings as acatalyst:Removal and pathways,Water Research,2016,92,140-48)。
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,Visiblelight-driven photocatalyticdegradation of rhodamine B and industrial dyes(texbrite BAC-L and texbriteNFW-L)by ZnO-graphene-TiO2 composite,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 WO3 electrodes,ElectrochimicaActa,2005,5278-5291);⑤Fenton反应催化剂,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,Rapid decolorization of dyes in heterogeneous Fenton-like oxidation catalyzedby Fe-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反应催化剂与上述其他催化材料相比,具有反应时间短、催化速度快、催化效率高、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材料。尽管如此,目前制得的Fenton反应催化剂多为粉末状或颗粒状,形态单一,使用后难以与水直接分离,需借助过滤或离心等手段,极大地增加了应用成本,其应用受到了限制,因此,研究和开发纤维状Fenton反应催化剂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。
在上述技术背景下,本发明旨在以常规可溶性亚铁盐为络合对象,新型聚合物为成纤基质,采用湿法纺丝和络合工艺制备用后可直接与水分离的纤维状Fenton反应催化剂,以拓展Fenton反应催化剂在染料废水治理领域的应用。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,且由于凝固困难等问题,难以直接将PAA通过湿法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,溶液纺丝时,易于凝固,纺丝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。含羟基甲基丙烯酸酯-含羧酸基单体共聚物可溶于可溶性碱水溶液,该共聚物与可溶性碱水溶液组成的溶液体系可在无机酸水溶液中快速凝固,故可采用湿法纺丝法将共聚物纺制成纤维。湿法纺丝成形的纤维中存在发达的微孔结构,为纤维比表面积的提高创造了便利,而随后的洗涤工艺则可除去纤维表面附着的无机酸盐,极大地提高了纤维的络合能力,经适度干燥即可获得兼具大比表面积和络合金属离子功能的纤维。在可溶性亚铁盐水溶液中,纤维富含的羧酸基、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表面及内部,制得络合物纤维,纤维具备了催化氧化剂氧化分解染料的特性。将上述络合物纤维引入染料废水体系,并引入氧化剂,如H2O2、O3等,染料分解结束后,直接将纤维从水体中取出,此时的纤维富含氧化铁,在紫外光照射下,氧化铁中的三价铁与水中氢氧根离子的复合离子可以直接产生羟基自由基和二价铁离子,二价铁离子可与H2O2、O3等进一步反应生成羟基自由基,即可光催化分解废水中的染料,此时的纤维也可继续络合亚铁离子,由此进行多次使用;此外,染料分解结束后,水体会出现泛黄现象,这是亚铁离子氧化生成铁离子所致,经含羟基甲基丙烯酸酯-含羧酸基单体共聚物纤维进一步络合,可使水体变得澄清,络合后的纤维可作为类Fenton反应催化剂继续在染料废水处理中发挥作用,由此可见,与粉末状或颗粒状Fenton反应催化剂相比,本发明设计的络合物纤维可多次循环使用,具有极佳的可重复使用性,还可纺织或非织造加工制成多种形态产品,进而满足不同应用领域对产品形态的要求。
发明内容
针对现有技术的不足,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的制造方法。该制造方法首先采用沉淀聚合法合成含特殊官能团的聚合物,随后以可溶性碱水溶液为溶剂、无机酸水溶液为凝固介质,采用湿法纺丝技术将所合成聚合物纺制成纤维,再经洗涤、干燥等工艺获得兼具大比表面积和络合金属离子功能的纤维材料,最后,在可溶性亚铁盐水溶液中,纤维富含的羧酸基、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表面及内部,制得络合物纤维,纤维具备了催化氧化剂氧化分解染料的特性。所得纤维与现有粉末状或颗粒状Fenton反应催化剂相比,除具有可重复使用、处理效率高、染料去除率高、应用成本低等优点外,还具有可非织造或纺织加工、整体性好、使用方便、易回收等优点,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)湿法纺丝工艺:量取一定体积的去离子水,将其置于凝固浴中,量取一定体积的无机酸,使无机酸与去离子水的体积之比为0.2∶9.8~9.8∶0.2,将其缓慢、小心地倒入上述凝固浴中,搅拌使其混合均匀,自然冷却至室温,即为凝固介质;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,待温度降至室温后,将纺丝液倒入湿法纺丝用盛液器中,随后将盛液器置于真空干燥机中在40℃以及-0.09MPa条件下脱泡,时间为30min;将聚四氟乙烯喷丝组件浸没于凝固浴液中,利用蠕动泵将上述盛液器中的纺丝液以0.1~1.0ml/min的速度输送到聚四氟乙烯喷丝板中,纺丝液经喷丝板上的喷丝孔进入到凝固浴,待凝固浴中的溶液细流凝固成丝后,收丝,即可获得附着有无机酸盐的纤维;
所述无机酸为硫酸、硝酸、盐酸、磷酸中的一种;
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)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(2)中制得的纤维,使纤维与去离子水的质量之比为0.1∶100~10∶100,将其放入到上述洗涤槽中洗涤,将洗涤后的纤维置于鼓风干燥箱中于10~40℃条件下干燥24~96h,获得初生纤维;
(4)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0.5∶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;称取一定质量的纤维,使纤维与上述亚铁盐水溶液质量之比为1∶100~1∶10,并将纤维放入处理槽中,浸没于亚铁盐水溶液中,将处理槽温度升高至10~90℃,开始计时,纤维与铁离子进行络合,络合时间为1~300min,达络合时间后,将纤维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;
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,本发明所得纤维在形态上具有突出优势,现有Fenton反应催化剂多为粉末状或颗粒状,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,本发明所得纤维可非织造或纺织加工,整体性好,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,本发明所得纤维具有大比表面积和络合金属离子两大特性,大比表面积来自于湿法纺丝中所形成的疏松多孔结构,而络合金属离子功能则是由纤维本身所具有的众多活性基团导致的,结果使本发明所得络合物纤维具有现有Fenton反应催化剂的所有功能,显现出处理效率高、染料去除率高等优势,使用后的纤维可在紫外光照射下继续光催化分解废水中的染料,还可继续络合亚铁离子,由此进行多次使用,应用成本显著降低,应用前景更为突出;再次,现有的可催化氧化剂氧化分解染料无机材料多由单一无机物或多种无机物制成,所需原料价格均较高,成型后催化材料的价格更为昂贵,而本发明所得纤维以常规无机物和有机物为原料制得,主体原料为含羧酸基单体和含羟基甲基丙烯酸酯单体,辅助原料为可溶性亚铁盐,且用量极少,原料成本较低,成形后纤维的价格也较低,为其规模应用提供了便利;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络合物纤维的相关文献报道。
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纤维的制造方法(以下简称制造方法)涉及沉淀聚合、湿法纺丝、洗涤、干燥和络合等工艺技术的综合应用,旨在解决现有粉末状或颗粒状Fenton反应催化剂在处理染料废水时存在的形态单一(粉末状或颗粒状)、回收时因需借助过滤、离心等技术手段而成本极高、很难多次使用等问题,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)湿法纺丝工艺:量取一定体积的去离子水,将其置于凝固浴中,量取一定体积的无机酸,使无机酸与去离子水的体积之比为0.2∶9.8~9.8∶0.2,将其缓慢、小心地倒入上述凝固浴中,搅拌使其混合均匀,自然冷却至室温,即为凝固介质;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,待温度降至室温后,将纺丝液倒入湿法纺丝用盛液器中,随后将盛液器置于真空干燥机中在40℃以及-0.09MPa条件下脱泡,时间为30min;将聚四氟乙烯喷丝组件浸没于凝固浴液中,利用蠕动泵将上述盛液器中的纺丝液以0.1~1.0ml/min的速度输送到聚四氟乙烯喷丝板中,纺丝液经喷丝板上的喷丝孔进入到凝固浴,待凝固浴中的溶液细流凝固成丝后,收丝,即可获得附着有无机酸盐的纤维;
(3)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(2)中制得的纤维,使纤维与去离子水的质量之比为0.1∶100~10∶100,将其放入到上述洗涤槽中洗涤,将洗涤后的纤维置于鼓风干燥箱中于10~40℃条件下干燥24~96h,获得初生纤维;
(4)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0.5∶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;称取一定质量的纤维,使纤维与上述亚铁盐水溶液质量之比为1∶100~1∶10,并将纤维放入处理槽中,浸没于亚铁盐水溶液中,将处理槽温度升高至10~90℃,开始计时,纤维与铁离子进行络合,络合时间为1~300min,达络合时间后,将纤维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。
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。
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,但其水溶液难以凝固,给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纺丝可纺性。
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无机酸为硫酸、硝酸、盐酸、磷酸中的一种,本发明制造方法所述的无机酸优选硫酸,原因如下:①与硝酸、盐酸、磷酸相比,硫酸性质稳定,不会见光分解,不易挥发,不会潮解,无刺激性气味,更利于工业实施;②与硝酸、盐酸、磷酸相比,本发明制得的聚合物溶液在硫酸凝固浴中凝固成纤所用时间短,而且成纤性最好,收丝极为容易,故本发明制造方法所述的无机酸优选硫酸。
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;量取800ml去离子水,将其置于适宜的凝固浴中,量取200ml浓硫酸,将其缓慢的、小心的倒入上述凝固浴中,搅拌使其混合均匀,使其自然冷却至室温,即为凝固浴液;称取40g去离子水,将其置于适宜的烧杯中,称取10g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,即为纺丝液,待温度降至室温将纺丝液倒入湿法纺丝用盛液器中,随后将盛液器置于真空干燥机中在40℃以及-0.09MPa条件下脱泡,时间为30min;将聚四氟乙烯喷丝组件浸没于凝固浴液中,利用蠕动泵将上述盛液器中的纺丝液以0.5ml/h的速度输送到聚四氟乙烯喷丝板中,纺丝液经喷丝板上的喷丝孔进入凝固浴,待凝固浴中的溶液细流凝固成丝,收丝,即可获得附着有无机酸盐的纤维;称取100g去离子水,将其置于洗涤槽中,称取1g所得纤维,将其放入上述去离子水中洗涤,将洗涤后纤维置于鼓风干燥箱中于25℃条件下干燥72h,获得初生纤维;称取70g去离子水,将其置于适宜的烧杯中,称取30g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纤维,并将纤维放入处理槽中,浸没于亚铁盐水溶液中,将处理槽温度升高至25℃(室温),开始计时,纤维与铁离子进行络合,络合时间为1h,达络合时间后,将纤维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。
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纤维置于上述溶液中,30分钟后亚甲基蓝染料的去除效率达100%。
取10ml浓度为20mg/L的阳离子蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后阳离子蓝染料的去除效率为30%;取10ml浓度为20mg/L的阳离子蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维置于上述溶液中,90分钟后阳离子蓝染料的去除效率达100%。取10ml浓度为20mg/L的阳离子翠兰水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后阳离子翠兰染料的去除效率为19%;取10ml浓度为20mg/L的阳离子翠兰水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维置于上述溶液中,90分钟后阳离子翠兰染料的去除效率达100%。取10ml浓度为20mg/L的阳离子艳蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后阳离子艳蓝染料的去除效率为18%;取10ml浓度为20mg/L的阳离子艳蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维置于上述溶液中,90分钟后阳离子艳蓝染料的去除效率达100%。取10ml浓度为20mg/L的阳离子艳红水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后阳离子艳红染料的去除效率为15%;取10ml浓度为20mg/L的阳离子艳红水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维置于上述溶液中,90分钟后阳离子艳红染料的去除效率达100%。取10ml浓度为20mg/L的碱性艳蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后碱性艳蓝染料的去除效率为16%;取10ml浓度为20mg/L的碱性艳蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维置于上述溶液中,90分钟后碱性艳蓝染料的去除效率达100%。取10ml浓度为20mg/L的弱酸性艳蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后弱酸性艳蓝染料的去除效率为13%;取10ml浓度为20mg/L的弱酸性艳蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维置于上述溶液中,90分钟后弱酸性艳蓝染料的去除效率达100%。取10ml浓度为20mg/L的酸性湖蓝水溶液,加入0.5ml双氧水,通入1min臭氧,90分钟后酸性湖蓝染料的去除效率为12%;取10ml浓度为20mg/L的酸性湖蓝水溶液,加入0.5ml双氧水,通入1min臭氧,将0.002g纤维置于上述溶液中,90分钟后酸性湖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70g变为80g,氯化亚铁由实施例1中的30g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纤维置于上述溶液中,50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70g变为50g,氯化亚铁由实施例1中的30g变为50g。
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4
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70g变为40g,氯化亚铁由实施例1中的30g变为60g。
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5
本实施例工艺过程及参数与实施例1相同,仅纤维与铁离子的络合时间有改变,络合时间由实施例1中的1h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纤维置于上述溶液中,90分钟后亚甲基蓝染料的去除效率达30%。
实施例6
本实施例工艺过程及参数与实施例1相同,仅纤维与铁离子的络合时间有改变,络合时间由实施例1中的1h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纤维置于上述溶液中,50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,仅纤维与铁离子的络合时间有改变,络合时间由实施例1中的1h变为2h。
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8
本实施例工艺过程及参数与实施例1相同,仅处理槽温度有改变,处理槽温度由实施例1中的25℃变为60℃。
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纤维置于上述溶液中,30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,仅处理槽温度有改变,处理槽温度由实施例1中的25℃变为80℃。
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纤维置于上述溶液中,30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,仅丙烯酸与甲基丙烯酸羟乙酯单体比例有改变,丙烯酸由实施例1中的70g变为50g,甲基丙烯酸羟乙酯由实施例1中的30g变为50g。
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纤维置于上述溶液中,50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,仅丙烯酸与甲基丙烯酸羟乙酯单体比例有改变,丙烯酸由实施例1中的70g变为30g,甲基丙烯酸羟乙酯由实施例1中的30g变为70g。
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纤维置于上述溶液中,90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。
取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.02ml双氧水,通入30min臭氧,将0.002g纤维置于上述溶液中,1分钟后亚甲基蓝染料的去除效率为87%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.02ml双氧水,通入30min臭氧,将上面完成第一次催化后的纤维置于上述溶液中,4分钟后亚甲基蓝染料的去除效率达88%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.02ml双氧水,通入30min臭氧,将上面完成第二次催化后的纤维置于上述溶液中,7分钟后亚甲基蓝染料的去除效率达80%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.02ml双氧水,通入30min臭氧,将上面完成第三次催化后的纤维置于上述溶液中,90分钟后亚甲基蓝染料的去除效率达80%;取10ml浓度为20mg/L的亚甲基蓝水溶液,加入0.02ml双氧水,通入30min臭氧,将上面完成第四次催化后的纤维置于上述溶液中,90分钟后亚甲基蓝染料的去除效率达10%。
Claims (6)
1.一种染料废水处理用纤维的制造方法,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)湿法纺丝工艺:量取一定体积的去离子水,将其置于凝固浴中,量取一定体积的无机酸,使无机酸与去离子水的体积之比为0.2∶9.8~9.8∶0.2,将其缓慢、小心地倒入上述凝固浴中,搅拌使其混合均匀,自然冷却至室温,即为凝固介质;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,待温度降至室温后,将纺丝液倒入湿法纺丝用盛液器中,随后将盛液器置于真空干燥机中在40℃以及-0.09MPa条件下脱泡,时间为30min;将聚四氟乙烯喷丝组件浸没于凝固浴液中,利用蠕动泵将上述盛液器中的纺丝液以0.1~1.0ml/min的速度输送到聚四氟乙烯喷丝板中,纺丝液经喷丝板上的喷丝孔进入到凝固浴,待凝固浴中的溶液细流凝固成丝后,收丝,即可获得附着有无机酸盐的纤维;
(3)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(2)中制得的纤维,使纤维与去离子水的质量之比为0.1∶100~10∶100,将其放入到上述洗涤槽中洗涤,将洗涤后的纤维置于鼓风干燥箱中于10~40℃条件下干燥24~96h,获得初生纤维;
(4)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0.5∶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;称取一定质量的纤维,使纤维与上述亚铁盐水溶液质量之比为1∶100~1∶10,并将纤维放入处理槽中,浸没于亚铁盐水溶液中,将处理槽温度升高至10~90℃,开始计时,纤维与铁离子进行络合,络合时间为1~300min,达络合时间后,将纤维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。
2.根据权利要求1所述的一种染料废水处理用纤维的制造方法,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的制造方法,其特征在于所述的无机酸为硫酸、硝酸、盐酸、磷酸中的一种。
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。
5.根据权利要求1所述的一种染料废水处理用纤维的制造方法,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,所述的无机酸为硫酸,所述的可溶性碱为氢氧化钠,所述的可溶性亚铁盐为氯化亚铁。
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