CN107376870B - 一种磁性聚合物染料吸附剂的制备方法 - Google Patents
一种磁性聚合物染料吸附剂的制备方法 Download PDFInfo
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- CN107376870B CN107376870B CN201710598541.2A CN201710598541A CN107376870B CN 107376870 B CN107376870 B CN 107376870B CN 201710598541 A CN201710598541 A CN 201710598541A CN 107376870 B CN107376870 B CN 107376870B
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- magnetic
- dye
- deionized water
- adsorption
- acrylic acid
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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Abstract
本发明涉及一种磁性聚合物染料吸附剂的制备方法,采用改良化学共沉淀法制备磁性纳米粒子,然后分别用γ‑氯丙基三甲氧基硅烷和聚乙烯亚胺对其进行表面改性,得到聚乙烯亚胺改性磁性纳米粒子,最后将聚乙烯亚胺改性磁性纳米粒子和功能性单体进行共聚,制备具有多层级交联结构和多种吸附基团的磁性聚合物染料吸附剂,饱和磁化强度为3.5~15.5 emu/g,剩磁和矫顽力均趋于零,具有顺磁性和磁响应性,对于初始浓度为100~1000mg/L染料水溶液,染料吸附容量达到50~600mg/g,60~150min达到吸附平衡,再生循环利用5次后的染料吸附容量超过第一次吸附容量的90%,可广泛应用于染料吸附分离以及染料废水污染治理等。
Description
一、技术领域
本发明涉及一种磁性聚合物染料吸附剂的制备方法,本发明制备的磁性聚合物染料吸附剂适用于染料的吸附分离,可广泛应用于染料吸附、染料分离提纯以及染料环境污染治理等。
二、背景技术
染料废水主要来源于染料及染料中间体生产行业和纺织,皮革,造纸,橡胶,塑料,化妆品,制药和食品等不同行业,具有组成复杂、水量和水质变化大、色度高、COD和BOD浓度高、悬浮物多、难生物降解物质多等特点,是较难处理的工业废水之一。另外,染料废水不仅有明显的色度,影响感官,并且废水中含对水体或人体有毒有害的污染物,染料废水若不经过处理直接排放,会引起水体生态环境的破坏,有毒有害物进入食物链,会影响人体的健康,因此环保高效处理染料废水已成为当今社会亟需解决的问题。
目前处理染料废水的方法主要有化学、生物、物理法等。沉淀絮凝法操作简单,成本低,但产生的大量污泥增加运营成本。电解法处理废水时消耗电和金属电极量大。光催化氧化只对低浓度染料废水效果好。生物法选择性较单一、且微生物对环境敏感。吸附法操作简单,成本低、效果好,吸附剂易于回收利用。常用的吸附剂有活性炭、矿物、树脂类吸附剂等。活性炭吸附力强,去除率高,但成本高,一般只用于浓度较低的印染废水处理或深度处理。矿物包括天然沸石、膨润土等,其离子交换能力和吸附性能较好,但活性低,再生困难。而树脂类吸附剂处理效率高,可在一定条件下再生,再生后仍可保持高效,适用于染料废水的处理。
传统的吸附剂如离子交换树脂、吸附树脂、炭质类吸附剂以及天然介孔矿物材料等,这些吸附材料吸附染料后只能通过离心、过滤、沉淀等传统方法分离,不但费时费力而且不节能环保,易破坏吸附材料的结构,对于吸附材料的再生利用带来影响。近年来,纳米材料和纳米技术的出现极大促进了染料处理技术的进步和发展,磁性纳米材料因其自身特有的大比表面积、丰富的活性点及高磁性等优点在染料吸附及去除领域展现出巨大的应用潜力。磁性纳米吸附剂可以吸附水体中的染料污染物,吸附完成后,在外部磁场的作用下通过磁性分离,实现吸附剂和母液的快速有效分离,并且成本低,操作简单,较好地解决了常规吸附剂固液分离难和回收分离难的问题。
Li等利用原位共沉淀法合成磁性聚(丙烯酸-丙烯酰胺-甲基丙烯酸丁酯)水凝胶,对阳离子染料结晶紫和碱性品红具有较好的吸附去除性能。Xu等采用溶剂热法合成氨基改性磁性纳米粒子,然后加入聚丙烯酸与氨基改性磁性纳米粒子进行化学接枝制备磁性聚合物吸附剂,对罗丹明R6G的吸附速率快,吸附容量55.8mg/g。He等首先合成超支化聚甘油包覆磁性Fe3O4纳米粒子,然后加入琥珀酰酐得到羧基化改性超支化包覆磁性Fe3O4纳米粒子,对阳离子染料吸附效率高、吸附速率快、可重复性好。Zhou等首先制备具有核壳结构的Fe3O4/SiO2纳米粒子,然后加入超支化聚合物进行表面改性,最后加入琥珀酰酐得到羧基化改性超支化包覆磁性Fe3O4/SiO2纳米粒子,罗丹明R6G和结晶紫吸附容量分别达到0.37mmol/g和0.60mmol/g。Chen等采用溶剂热法合成氨基改性Fe3O4纳米粒子,然后加入交联剂戊二醛和聚乙烯亚胺,生成具有三维网络结构的磁性聚乙烯亚胺吸附剂,酸性媒茜素红、甲基橙、亚甲基蓝、日落黄、核固红和茜素绿的吸附容量分别为145.7mg/g、127.5mg/g、137.0mg/g、118.3mg/g和126.8mg/g。
Wen等采用1,2-二溴乙烷交联聚乙烯亚胺合成聚乙烯亚胺纳米凝胶,然后采用原位沉淀法制备磁性聚乙烯亚胺纳米复合水凝胶,阴离子染料CR的去除率超过99%。Cheng等采用一步合成法合成磁性聚乙烯醇/氧化石墨烯水凝胶,亚甲基蓝和甲基紫吸附容量分别为231.12mg/g和204.74mg/g。Shanehsaz等采用氧化聚合法制备磁性聚吡咯吸附剂,活性蓝RB19吸附容量达到112.36mg/g。
Hosseinadeh等采用一锅合成法制备羧甲基纤维素和聚丙烯酸为基体的磁性纤维素/聚丙烯酸水凝胶,染料结晶紫吸附容量达到189mg/g。Beyki等以具有核壳式结构的磁性Fe3O4-纤维素作为基体,加入环氧氯丙烷和1-甲基咪唑制备磁性纤维素离子液体吸附剂,刚果红染料吸附容量达131mg/g。Luo等将γ-Fe2O3、纤维素和活性炭用环氧氯丙烷交联得到磁性纤维素/活性炭吸附剂,对甲基橙和亚甲基蓝的去除率均超过99%。Chang等将淀粉共价接枝多层碳纳米管,然后以淀粉为模板使磁性纳米颗粒在淀粉接枝碳纳米管表面生长,得到磁性淀粉/碳纳米管吸附材料,甲基橙和亚甲基蓝吸附容量分别达135.8mg/g和94.1mg/g。Pourjavadi等首先合成磁性Fe3O4@SiO2纳米粒子,然后加入淀粉和丙烯酸单体进行接枝共聚制备磁性淀粉接枝聚丙烯酸水凝胶,结晶紫染料去除率接近90%。Baldikova等采用柠檬酸钠-氢氧化钠改性小麦秸秆,然后采用微波合成法制备磁性小麦秸秆吸附剂,吖啶橙和甲基绿吸附容量分别为208.3mg/g和384.6mg/g。
虽然磁性聚合物染料吸附剂越来越受到人们的广泛关注并逐渐成为国内外的研究热点,但如何有效改善磁性纳米粒子和聚合物基体的相容性,避免磁性纳米粒子的团聚以及抑制磁性纳米粒子和聚合物基体的宏观相分离,仍然是影响磁性聚合物染料吸附剂磁性能和染料吸附性能的关键科学和瓶颈技术问题。
三、发明内容
有鉴于此,本发明的目的就是在提供一种磁性聚合物染料吸附剂的制备方法。首先采用改良化学共沉淀法制备磁性纳米粒子,然后分别用γ-氯丙基三甲氧基硅烷和聚乙烯亚胺对其进行表面改性,得到聚乙烯亚胺改性磁性纳米粒子,最后将聚乙烯亚胺改性磁性纳米粒子和功能性单体进行共聚,制备具有多层级交联结构和多种染料吸附基团的磁性聚合物染料吸附剂,通过聚乙烯亚胺改性磁性纳米粒子,改善磁性纳米粒子和聚合物基体的相容性,通过磁性纳米粒子表面接枝的聚乙烯亚胺大分子链与聚合物基体的物理缠结和氢键作用,避免磁性纳米粒子的团聚,抑制磁性纳米粒子和聚合物基体的宏观相分离,实现磁性聚合物染料吸附的磁性智能分离,较好解决普通染料吸附剂固液分离难、易产生二次污染的缺点。
根据本发明的目的,提出了一种磁性聚合物染料吸附剂的制备方法,其特征有如下工艺步骤:
a)将FeCl3·6H2O、FeCl2·4H2O和去离子水加入到三口烧瓶中,搅拌均匀,氮气保护30min后升温到50~80℃,然后滴加质量浓度为25~30%的氨水溶液,氨水溶液滴加完毕后氮气保护恒温反应3~6h,降温至室温,去离子水洗涤3~5次,磁铁分离,得到磁性纳米粒子;FeCl3·6H2O、FeCl2·4H2O、质量浓度为25~30%的氨水溶液和去离子水的质量比为10~30:5~10:25~60:100~200;
b)将磁性纳米粒子、γ-氯丙基三甲氧基硅烷和去离子水加入到三口烧瓶中搅拌均匀,氮气保护30min后升温到50~80℃,然后滴加质量浓度为25~30%的氨水溶液,氮气保护恒温反应3~6h后降温至室温,去离子水洗涤3~5次,磁铁分离,得到氯丙基改性纳米磁性粒子;磁性纳米粒子、γ-氯丙基三甲氧基硅烷、质量浓度为25~30%的氨水溶液和去离子水的质量比为1~5:2~15:2~15:100~200;
c)将氯丙基改性纳米磁性粒子、聚乙烯亚胺和去离子水加入到三口烧瓶中搅拌均匀,升温到40~70℃,氮气保护恒温反应2~5h后降温至室温,去离子水洗涤3~5次,磁铁分离,得到聚乙烯亚胺改性纳米磁性粒子;氯丙基改性纳米磁性粒子、聚乙烯亚胺和去离子水的质量比为1~5:1~5:100~200;
d)将NaOH溶解于200mL去离子水,冰浴中将丙烯酸缓慢滴加到NaOH水溶液,搅拌反应0.5~2h,得到部分中和丙烯酸水溶液;将聚乙烯亚胺改性磁性纳米粒子、丙烯酰胺和交联剂加入到部分中和丙烯酸水溶液,搅拌均匀,升温至50~60℃,加入氧化还原引发剂,引发聚合反应3~5小时,最后将产物用无水乙醇洗涤3~5次,磁性分离,80℃烘干,粉碎,得到磁性聚合物染料吸附剂;丙烯酸和NaOH的摩尔比为1:0.5~0.8;丙烯酸与丙烯酰胺的质量比为1~5:1~5;交联剂占丙烯酸和丙烯酰胺单体质量总量的0.1~0.8%;氧化还原引发剂占丙烯酸和丙烯酰胺单体质量总量的0.1%~2.0%,氧化还原引发剂包括氧化剂和还原剂,氧化剂选自过硫酸铵、过硫酸钾和过硫酸钠,还原剂选自亚硫酸氢钠、亚硫酸钠、硫代硫酸钠和硫酸亚铁,氧化剂和还原剂的摩尔比为1~2:1;聚乙烯亚胺改性磁性纳米粒子占丙烯酸和丙烯酰胺单体质量总量的5~30%;
e)磁性聚合物染料吸附剂饱和磁化强度为3.5~15.5emu/g,剩磁和矫顽力均趋于零,具有顺磁性和磁响应性,对于初始浓度为100~1000mg/L染料水溶液,染料吸附容量达到50~600mg/g,60~150min达到吸附平衡,再生循环利用5次后的染料吸附容量超过第一次吸附容量的90%。
本发明所使用的交联剂选自N,N’-亚甲基双丙烯酰胺、乙二醇双丙烯酸酯、一缩乙二醇双丙烯酸酯、二缩乙二醇双丙烯酸酯、1,3-丙二醇双丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、甲基丙烯酸缩水甘油酯和聚乙二醇双丙烯酸酯。
本发明所使用的亚甲基蓝、阳离子蓝FGL、阳离子橙R、阳离子嫩黄7GL、阳离子桃红FG、甲基绿、结晶紫、甲基橙、活性黑RB5、刚果红、茜素红、日落黄、茜素绿、酸性铬蓝K和曙红Y。
本发明的优点和效果是:
1)聚合反应直接在水溶液中进行,无环境污染,方法简便易行,无需氮气保护,因此省去了氮气装置,降低了设备的投入费用。
2)通过聚乙烯亚胺改性磁性纳米粒子,改善磁性纳米粒子和聚合物基体的相容性,通过磁性纳米粒子表面接枝的聚乙烯亚胺大分子链与聚合物基体的物理缠结和氢键作用,避免磁性纳米粒子的团聚,抑制磁性纳米粒子和聚合物基体的宏观相分离,实现磁性聚合物染料吸附剂染料吸附的磁性智能分离,较好解决普通染料吸附剂固液分离难、易产生二次污染的缺点。
3)将聚乙烯亚胺改性磁性纳米粒子和功能性单体进行共聚,制备具有多层级交联结构和多种染料吸附基团的磁性聚合物染料吸附剂,通过多种吸附基团的协同效应,进一步提高磁性聚合物吸附剂染料的吸附性能;
本发明所述的磁性聚合物染料吸附剂的磁滞性能、染料吸附速率、吸附容量、再生循环利用性能测定方法如下。
采用LDJ-9600型振动磁强计(VSM)测定磁性聚合物染料吸附剂的磁滞性能。
将浓度为100-1000mg/L的染料溶液和0.2g干燥、研细的磁性聚合物染料吸附剂放入250mL锥形瓶中,然后置于振荡器中振荡吸附,振荡一定时间后取样,采用紫外/可见分光光度计在染料最大吸收波长处测定样品的吸光度,每个样品测量3次取平均值,染料吸附量qt、吸附容量qe分别按下式计算:
qt(mg/g)={(C0-Ct)V}/m (1)
qe(mg/g)={(C0-Ce)V}/m (2)
其中C0、Ct、和Ce分别为染料初始浓度、振荡吸附一定时间染料浓度、染料吸附平衡浓度(mg.L-1),V为溶液体积(L),m为磁性聚合物染料吸附剂的质量(g)。
将饱和吸附染料的磁性聚合物染料吸附剂用50mL 0.5mol/L的盐酸溶液震荡解吸,解吸一定时间后采用紫外/可见分光光度计测定溶液中染料浓度,直到达到解吸附平衡。将解吸后的磁性聚合物染料吸附剂烘干并粉碎,再在相同条件下再次对染料进行吸附,采用紫外/可见分光光度计测定磁性聚合物染料吸附剂的染料吸附容量,并与第一次染料的吸附容量作对比,表征磁性聚合物染料吸附剂的再生循环利用性能,反复再生循环吸附5次以评估磁性聚合物染料吸附剂的再生循环利用性能。
四、具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐述本发明的内容,但是本发明的内容不仅仅局限于下面的实施例。
实施例1:
将19.6g FeCl3·6H2O和7.2g FeCl2·4H2O和150mL去离子水加入到三口烧瓶中,搅拌均匀,氮气保护30min后升温到60℃,然后滴加50g质量浓度为25~30%的氨水溶液,氨水溶液滴加完毕后氮气保护恒温反应5h,降温至室温,去离子水洗涤3次,磁铁分离,得到磁性纳米粒子;将1g磁性纳米粒子、2gγ-氯丙基三甲氧基硅烷和100mL去离子水加入到三口烧瓶中搅拌均匀,氮气保护30min后升温到60℃,然后滴加2g质量浓度为25~30%的氨水溶液,氮气保护恒温反应5h后降温至室温,去离子水洗涤5次,磁铁分离,得到氯丙基改性纳米磁性粒子。将1g氯丙基改性纳米磁性粒子、1g聚乙烯亚胺和100mL去离子水加入到三口烧瓶中搅拌均匀,升温到40℃,氮气保护恒温反应5h后降温至室温,去离子水洗涤3次,磁铁分离,得到聚乙烯亚胺改性纳米磁性粒子。
将9g NaOH溶解于200mL去离子水中,冰浴中将24g丙烯酸缓慢滴加到NaOH水溶液,搅拌反应2h,得到部分中和丙烯酸水溶液;将12g聚乙烯亚胺改性纳米磁性粒子、16g丙烯酰胺和0.12g乙二醇双丙烯酸酯加入到部分中和丙烯酸水溶液,搅拌均匀,升温至60℃,加入0.48g过硫酸铵和0.16g亚硫酸氢钠,引发聚合反应3小时,最后将产物用无水乙醇洗涤3次,磁性分离,80℃烘干,粉碎,得到磁性聚合物染料吸附剂,饱和磁化强度为15.5emu/g,剩磁和矫顽力均趋于零,具有顺磁性和磁响应性;对于初始浓度为100mg/L的结晶紫、阳离子嫩黄7GL、日落黄和茜素绿水溶液,磁性聚合物染料吸附剂结晶紫、阳离子嫩黄7GL、甲基橙和茜素绿吸附容量分别达到95mg/g、86mg/g、74mg/g和50mg/g,150min达到吸附平衡,再生循环利用5次后的结晶紫、阳离子嫩黄7GL、甲基橙和刚果红吸附容量均超过第一次吸附容量的90%。
实施例2:
将30gFeCl3·6H2O和10gFeCl2·4H2O和200mL去离子水加入到三口烧瓶中,搅拌均匀,氮气保护30min后升温到70℃,然后滴加60g质量浓度为25~30%的氨水溶液,氨水溶液滴加完毕后氮气保护恒温反应4h,降温至室温,去离子水洗涤5次,磁铁分离,得到磁性纳米粒子;将5g磁性纳米粒子、15gγ-氯丙基三甲氧基硅烷和200mL去离子水加入到三口烧瓶中搅拌均匀,氮气保护30min后升温到70℃,然后滴加15g质量浓度为25~30%的氨水溶液,氮气保护恒温反应4h后降温至室温,去离子水洗5次左右,磁铁分离,得到氯丙基改性纳米磁性粒子。将2.5g氯丙基改性纳米磁性粒子、3g聚乙烯亚胺和150mL去离子水加入到三口烧瓶中搅拌均匀,升温到70℃,氮气保护恒温反应2h后降温至室温,去离子水洗涤5次,磁铁分离,得到聚乙烯亚胺改性纳米磁性粒子。
将7.2g NaOH溶解于200mL去离子水中,冰浴中将20g丙烯酸缓慢滴加到NaOH水溶液,搅拌反应2h,得到部分中和丙烯酸水溶液;将6g聚乙烯亚胺改性纳米磁性粒子、20g丙烯酰胺和0.08g一缩乙二醇双丙烯酸酯加入到部分中和丙烯酸水溶液,搅拌均匀,升温至60℃,加入0.36g过硫酸钠和0.12g亚硫酸氢钠,引发聚合反应3小时,最后将产物用无水乙醇洗涤5次,磁性分离,80℃烘干,粉碎,得到磁性聚合物染料吸附剂,饱和磁化强度为8.6emu/g,剩磁和矫顽力均趋于零,具有顺磁性和磁响应性;对于初始浓度为300mg/L的亚甲基蓝、甲基绿、活性黑RB5和茜素红水溶液,磁性聚合物染料吸附剂亚甲基蓝、甲基绿、活性黑RB5和茜素红吸附容量分别达到175mg/g、154mg/g、141mg/g和126mg/g,120min达到吸附平衡,再生循环利用5次后的亚甲基蓝、甲基绿、活性黑RB5和茜素红吸附容量均超过第一次吸附容量的90%。
实施例3:
将10gFeCl3·6H2O和5gFeCl2·4H2O和100mL去离子水加入到三口烧瓶中,搅拌均匀,氮气保护30min后升温到80℃,然后滴加25g质量浓度为25~30%的氨水溶液,氨水溶液滴加完毕后氮气保护恒温反应3h,降温至室温,去离子水洗涤4次,磁铁分离,得到磁性纳米粒子;将3g磁性纳米粒子、8gγ-氯丙基三甲氧基硅烷和150mL去离子水加入到三口烧瓶中搅拌均匀,氮气保护30min后升温到80℃,然后滴加10g质量浓度为25~30%的氨水溶液,氮气保护恒温反应3h后降温至室温,去离子水洗涤3次,磁铁分离,得到氯丙基改性纳米磁性粒子。将5g氯丙基改性纳米磁性粒子、5g聚乙烯亚胺和200mL去离子水加入到三口烧瓶中搅拌均匀,升温到60℃,氮气保护恒温反应3h后降温至室温,去离子水洗涤5次,磁铁分离,得到聚乙烯亚胺改性纳米磁性粒子。
将5.4g NaOH溶解于200mL去离子水中,冰浴中将16g丙烯酸缓慢滴加到NaOH水溶液,搅拌反应2h,得到部分中和丙烯酸水溶液;将8g聚乙烯亚胺改性纳米磁性粒子、24g丙烯酰胺和0.10g二缩乙二醇双丙烯酸酯加入到部分中和丙烯酸水溶液,搅拌均匀,升温至50℃,加入0.54g过硫酸钾和0.18g硫代硫酸钠,引发聚合反应5小时,最后将产物用无水乙醇洗涤3次,磁性分离,80℃烘干,粉碎,得到磁性聚合物染料吸附剂,饱和磁化强度为11.2emu/g,剩磁和矫顽力均趋于零,具有顺磁性和磁响应性;对于初始浓度为600mg/L的结晶紫、亚甲基蓝、日落黄和茜素绿水溶液,磁性聚合物染料吸附剂结晶紫、亚甲基蓝、日落黄和茜素绿吸附容量分别达到334mg/g、278mg/g、185mg/g和142mg/g,100min达到吸附平衡,再生循环利用5次后的结晶紫、亚甲基蓝、日落黄和茜素绿吸附容量均超过第一次吸附容量的90%。
实施例4:
将15gFeCl3·6H2O和6gFeCl2·4H2O和150mL去离子水加入到三口烧瓶中,搅拌均匀,氮气保护30min后升温到50℃,然后滴加35g质量浓度为25~30%的氨水溶液,氨水溶液滴加完毕后氮气保护恒温反应6h,降温至室温,去离子水洗涤5次,磁铁分离,得到磁性纳米粒子;将2.5g磁性纳米粒子、5gγ-氯丙基三甲氧基硅烷和100mL去离子水加入到三口烧瓶中搅拌均匀,氮气保护30min后升温到50℃,然后滴加6g质量浓度为25~30%的氨水溶液,氮气保护恒温反应6h后降温至室温,去离子水洗涤5次,磁铁分离,得到氯丙基改性纳米磁性粒子。将氯丙基改性纳米磁性粒子、聚乙烯亚胺和去离子水加入到三口烧瓶中搅拌均匀,升温到50℃,氮气保护恒温反应4h后降温至室温,去离子水洗涤3次,磁铁分离,得到聚乙烯亚胺改性纳米磁性粒子。
将9g NaOH溶解于200mL去离子水中,冰浴中将24g丙烯酸缓慢滴加到NaOH水溶液,搅拌反应2h,得到部分中和丙烯酸水溶液;将2g聚乙烯亚胺改性纳米磁性粒子、16g丙烯酰胺和0.16g 1,3-丙二醇双丙烯酸酯加入到部分中和丙烯酸水溶液,搅拌均匀,升温至50℃,加入0.60g过硫酸钾和0.20g亚硫酸钠,引发聚合反应5小时,最后将产物用无水乙醇洗涤5次,磁性分离,80℃烘干,粉碎,得到磁性聚合物染料吸附剂,饱和磁化强度为3.5emu/g,剩磁和矫顽力均趋于零,具有顺磁性和磁响应性;对于初始浓度为800mg/L的阳离子嫩黄7GL、活性黑RB5、茜素红和日落黄水溶液,磁性聚合物染料吸附剂阳离子嫩黄7GL、活性黑RB5、茜素红和日落黄吸附容量分别达到457mg/g、320mg/g、277mg/g和216mg/g,80min达到吸附平衡,再生循环利用5次后的阳离子嫩黄7GL、活性黑RB5、茜素红和日落黄吸附容量均超过第一次吸附容量的90%。
实施例5:
将20gFeCl3·6H2O和8gFeCl2·4H2O和200mL去离子水加入到三口烧瓶中,搅拌均匀,氮气保护30min后升温到70℃,然后滴加50g质量浓度为25~30%的氨水溶液,氨水溶液滴加完毕后氮气保护恒温反应4h,降温至室温,去离子水洗涤4次,磁铁分离,得到磁性纳米粒子;将4g磁性纳米粒子、12gγ-氯丙基三甲氧基硅烷和200mL去离子水加入到三口烧瓶中搅拌均匀,氮气保护30min后升温到80℃,然后滴加12g质量浓度为25~30%的氨水溶液,氮气保护恒温反应3h后降温至室温,去离子水洗涤3次,磁铁分离,得到氯丙基改性纳米磁性粒子。将3g氯丙基改性纳米磁性粒子、2g聚乙烯亚胺和150mL去离子水加入到三口烧瓶中搅拌均匀,升温到40℃,氮气保护恒温反应5h后降温至室温,去离子水洗涤5次,磁铁分离,得到聚乙烯亚胺改性纳米磁性粒子。
将8g NaOH溶解于200mL去离子水中,冰浴中将24g丙烯酸缓慢滴加到NaOH水溶液,搅拌反应2h,得到部分中和丙烯酸水溶液;将4g聚乙烯亚胺改性纳米磁性粒子、18g丙烯酰胺和0.10g N,N’-亚甲基双丙烯酰胺加入到部分中和丙烯酸水溶液,搅拌均匀,升温至50℃,加入0.62g过硫酸铵和0.21g亚硫酸氢钠,引发聚合反应5小时,最后将产物用无水乙醇洗涤3次,磁性分离,80℃烘干,粉碎,得到磁性聚合物染料吸附剂,饱和磁化强度为5.9emu/g,剩磁和矫顽力均趋于零,具有顺磁性和磁响应性;对于初始浓度为1000mg/L的结晶紫、阳离子嫩黄7GL、活性黑RB5和甲基橙水溶液,磁性聚合物染料吸附剂结晶紫、阳离子嫩黄7GL、活性黑RB5和甲基橙吸附容量分别达到600mg/g、517mg/g、476mg/g和414mg/g,60min达到吸附平衡,再生循环利用5次后的结晶紫、阳离子嫩黄7GL、活性黑RB5和甲基橙吸附容量均超过第一次吸附容量的90%。
Claims (3)
1.一种磁性聚合物染料吸附剂在染料吸附方面的应用,其特征在于有如下工艺步骤:
将FeCl3·6H2O、FeCl2·4H2O和去离子水加入到三口烧瓶中,搅拌均匀,氮气保护30min后升温到50~80°C,然后滴加质量浓度为25~30%的氨水溶液,氨水溶液滴加完毕后氮气保护恒温反应3~6h,降温至室温,去离子水洗涤3~5次,磁铁分离,得到磁性纳米粒子;FeCl3·6H2O、FeCl2·4H2O、质量浓度为25~30%的氨水溶液和去离子水的质量比为10~30:5~10:25~60:100~200;
将磁性纳米粒子、γ-氯丙基三甲氧基硅烷和去离子水加入到三口烧瓶中搅拌均匀,氮气保护30min后升温到50~80°C,然后滴加质量浓度为25~30%的氨水溶液,氮气保护恒温反应3~6h后降温至室温,去离子水洗涤3~5次,磁铁分离,得到氯丙基改性纳米磁性粒子;磁性纳米粒子、γ-氯丙基三甲氧基硅烷、质量浓度为25~30%的氨水溶液和去离子水的质量比为1~5: 2~15:2~15:100~200;
将氯丙基改性纳米磁性粒子、聚乙烯亚胺和去离子水加入到三口烧瓶中搅拌均匀,升温到40~70°C,氮气保护恒温反应2~5h后降温至室温,去离子水洗涤3~5次,磁铁分离,得到聚乙烯亚胺改性纳米磁性粒子;氯丙基改性纳米磁性粒子、聚乙烯亚胺和去离子水的质量比为1~5: 1~5:100~200;
将NaOH溶解于200mL去离子水,冰浴中将丙烯酸缓慢滴加到NaOH水溶液,搅拌反应0.5~2h,得到部分中和丙烯酸水溶液;将聚乙烯亚胺改性磁性纳米粒子、丙烯酰胺和交联剂加入到部分中和丙烯酸水溶液,搅拌均匀,升温至50~60℃,加入氧化还原引发剂,引发聚合反应3~5小时,最后将产物用无水乙醇洗涤3~5次,磁性分离,80℃烘干,粉碎,得到磁性聚合物染料吸附剂;丙烯酸和NaOH的摩尔比为1:0.5~0.8;丙烯酸与丙烯酰胺的质量比为1~5:1~5;交联剂占丙烯酸和丙烯酰胺单体质量总量的0.1~0.8%;氧化还原引发剂占丙烯酸和丙烯酰胺单体质量总量的0.1%~2.0%,所述的氧化还原引发剂包括氧化剂和还原剂,氧化剂选自过硫酸铵、过硫酸钾和过硫酸钠,还原剂选自亚硫酸氢钠、亚硫酸钠、硫代硫酸钠和硫酸亚铁,氧化剂和还原剂的摩尔比为1~2:1;聚乙烯亚胺改性磁性纳米粒子占丙烯酸和丙烯酰胺单体质量总量的5~30%;
磁性聚合物染料吸附剂饱和磁化强度为3.5~15.5 emu/g,剩磁和矫顽力均趋于零,具有顺磁性和磁响应性,对于初始浓度为100~1000mg/L染料水溶液,染料吸附容量达到50~600mg/g,60~150min达到吸附平衡,再生循环利用5次后的染料吸附容量超过第一次吸附容量的90%。
2.根据权利要求1所述的一种磁性聚合物染料吸附剂在染料吸附方面的应用,其特征在于:所述的交联剂选自N,N’-亚甲基双丙烯酰胺、乙二醇双丙烯酸酯、一缩乙二醇双丙烯酸酯、二缩乙二醇双丙烯酸酯、1,3-丙二醇双丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、甲基丙烯酸缩水甘油酯和聚乙二醇双丙烯酸酯。
3.根据权利要求1所述的一种磁性聚合物染料吸附剂在染料吸附方面的应用,其特征在于:所述的染料选自亚甲基蓝、阳离子蓝FGL、阳离子橙R、阳离子嫩黄7GL、阳离子桃红FG、甲基绿、结晶紫、甲基橙、活性黑RB5、刚果红、茜素红、日落黄、茜素绿、酸性铬蓝 K和曙红Y。
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