CN107501443B - 一种磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂的制备方法 - Google Patents
一种磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂的制备方法 Download PDFInfo
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Abstract
本发明提供了一种磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂的制备方法,属于环保水处理技术领域。该方法将十二烷基葡萄苷(或椰子油脂肪酸二乙醇酰胺)、二甲基二烯丙基氯化铵、丙烯酰胺、光引发剂溶解于水中,调整pH值,通入氮气并密封反应瓶,再置于低压紫外灯下光照聚合生成乳色胶体,再溶解在超纯水中,添加磁性纳米四氧化三铁颗粒和过硫酸铵搅拌,水洗、干燥、研磨最终得到黑色粉末状除油絮凝剂。本发明的聚合时间短、反应温度低、不需冷凝降温,节能降耗;疏水单体的引入,降低了絮凝剂的亲水性,增强了对油类物质的吸附性能,强化了絮凝剂破乳能力;引入的磁性纳米四氧化三铁微粒在附加磁场作用下,沉淀速度快、易分离。
Description
技术领域
本发明属于环保水处理技术领域,具体涉及一种水溶性磁性有机高分子水处理除油絮凝剂的制备方法,特别涉及一种磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂的制备方法。
背景技术
随着工业的发展,油品的使用量越来越大,在石油工业的采油、炼油、贮油、运输过程及石油化学工业的生产过程中都会产生大量含油废水,由于各种技术的发展滞后和管理不尽完善等原因使得大量油品进入水体,形成污染,影响饮用水资源和地下水资源,危害水产资源;人体健康;污染大气;影响农作物生产;破坏自然景观,甚至还有可能因为聚结的油品燃烧而产生安全问题。因此含油废水治理是当今环保领域急需解决的问题。其中乳化油的去除是含油废水治理的重点和难点,乳化油是粒度为0.1~3μm的极细油滴,由于油水界面有表面活性剂的存在,通常以水包油的形式稳定地分散在水中,很难被去除。
目前,含油废水的处理方法主要包括:浮选法、絮凝法、电磁法、膜分离法、生物法等。其中,絮凝法由于其适应性强、可去除乳化油和溶解油以及部分难以生化降解的复杂高分子有机物的特点而被广泛应用于含油废水的处理,并呈现良好的发展势头。随着该法在除油工艺中的应用,新型除油絮凝剂的研究日渐增多,在絮凝剂中引入疏水单体的方法逐步发展,如专利公开号为CN103319652A“一种疏水改性阳离子聚丙烯酰胺絮凝剂的制备方法”以丙烯酰胺、丙烯酰氧乙基三甲基氯化铵、丙烯酸丁酯、全氟辛基乙基丙烯酸酯以及表面活性剂合成疏水改性聚丙烯酰胺絮凝剂;又如专利公开号为CN103319653A“一种疏水改性阳离子聚丙烯酰胺絮凝剂的制备方法”则使用丙烯酰胺、二甲基二烯丙基氯化铵、丙烯酸丁酯与表面活性剂等合成疏水改性聚丙烯酰胺;又如专利公开号为CN106497599A“表面电荷与亲疏水性可控的pH敏感型磁性破乳剂的制备方法及应用”将二氧化硅负载到四氧化三铁纳米粒子上,并通过接枝共聚反应引入表面活性单体与pH敏感型单体获得破乳剂。上述方法取得了一定的效果,但仍有需要进一步的改进和发展:1)丙烯酸丁酯作为合成材料不宜大量存储,容易产生二次污染,且在温度升高时容易发生自聚;2)表面活性剂的使用提高了制备的成本;3)传统的聚丙烯酰胺絮凝剂的聚合制备反应温度会升高,聚合产生交联反应,导致产物溶解性能差;4)二氧化硅负载和接枝反应,因成分复杂,反应难以控制,且温度需调整至20~80℃,能耗高;5)有机高分子絮凝剂在混凝除油时沉淀效果不好,不容易分离,且选择性除油能力较差。
发明内容
针对现有技术存在的上述不足,本发明解决疏水单体易自聚、传统聚合方法放热大、温度高、难沉降的问题,以及改进传统聚丙烯酰胺吸附性不足、溶解时间长,无法回收利用等问题,提供一种制备工艺简单、反应条件温和、节能环保、易于产业化的高吸附性、快速沉淀性磁性疏水亲油改性阳离子聚丙烯酰胺絮凝剂的合成方法。
本发明采用如下技术方案来实现:一种磁性疏水亲油改性阳离子聚丙烯酰胺絮凝剂的合成方法,包括以下步骤:
(1)称取质量分数(占单体总质量的比例)为20%~30%的疏水亲油单体十二烷基葡萄苷(或椰子油脂肪酸二乙醇酰胺)、20%~40%的阳离子单体二甲基二烯丙基氯化铵和40%~60%的丙烯酰胺加入广口瓶中,加一定量的去离子水后搅拌至完全溶解,再加入光引发剂至完全溶解得到混合液,并调节pH至5~9。
(2)向上述混合液通氮一定时间至广口瓶内氧气完全排空,在室温下将瓶口密封置于低压紫外光灯管下光照1h通过聚合反应得到乳白色胶体,将胶状物在索式提取器中用丙酮提纯48h,得到白色固体样品,即为疏水改性阳离子聚丙烯酰胺。
(3)将提纯过后的白色样品溶解在超纯水中,在恒温水浴锅中30℃~40℃下加入与疏水改性阳离子聚丙烯酰胺质量比为1:(1~3)的纳米四氧化三铁颗粒,以及适量的引发剂过硫酸铵,高速搅拌12h,得到黑色溶液,在磁铁吸附下用超纯水洗涤3~5次后烘干研磨成粉得到黑色粉末,即为磁性疏水改性阳离子聚丙烯酰胺絮凝剂。
所述第二步和第二步中,聚合反应采用的紫外光由功率为10W-100W的低压汞灯产生,且产生的紫外光主波长为253.7nm或185nm。该波长的紫外光具有足够的穿透力,释放的能量能够加快单体中化学键的断裂,缩短引发时间,且发热量小,反应体系温度增加不明显,且节能环保,实用安全。所述第二步中,聚合反应所使用的光引发剂为2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮,上述引发剂用量低、引发效率高,无毒无害。所述第二步中,聚合反应在2~20℃的室温下通过紫外光引发。所述第三步中,使用过硫酸铵作为引发剂,将磁性纳米颗粒复合至高分子有机物上,其过程简单,操作简便,易分离。
上述得到的磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂可以在含油废水絮凝处理中加以应用。尤其在含油废水浓度为100~300mg/L、油粒尺寸为0.5~3μm时,除油效果更为显著。
相比现有技术,本发明具有如下有益的效果:
1、十二烷基葡萄苷已经被广泛应用于化妆品行业,价格廉价,易获得,其分子链上含有的长链烷基结构对油类物质有很好的吸附性,在水溶液中它同样有着很好的缔合性能,且其分子上的C-O-C结构能够有效地破坏油水界面的乳化膜,释放乳化油滴中的油类物质;椰子油脂肪酸二乙醇酰胺也属于长链烷基结构,亲油性能良好。因此,在阳离子聚丙烯酰胺长链上引入十二烷基葡萄苷(或椰子油脂肪酸二乙醇酰胺)改善了聚丙烯酰胺絮凝剂的吸附乳化油性能,使得改性后的絮凝剂兼具破乳除油的能力和缔合聚集能力;且共聚阳离子单体二甲基二烯丙基氯化铵正电荷密度大,具有强烈的电中和吸附性能。
2、将磁性纳米四氧化三铁粒子复合到有机高分子絮凝剂中,能够在外加磁场的条件下,提高絮凝处理时固液分离性能,可以有选择的聚集絮体,从而减小水力停留时间。且纳米级的颗粒具有量子尺寸效应、表面效应和宏观量子隧道效应,使用其对阳离子聚丙烯酰胺表面进行修饰,可以有效提高絮凝剂絮凝效率;在絮凝过程中水力搅拌状态下,纳米四氧化三铁与乳化油切向转速不同,导致物理剪切起到破乳作用,进一步提高除油效率。使用磁性疏水改性阳离子聚丙烯酰胺絮凝剂,经过实验测得沉降分离时间3~5min,而使用不含磁性的疏水改性阳离子聚丙烯酰胺絮凝剂,沉降分离时间则需要20~30min。
3、对油类物质有着很好的去除效果。十二烷基葡萄苷(或椰子油脂肪酸二乙醇酰胺)分子中的醚键或酰胺键能够破除乳化油的油水界面,而且其本身可以置换出油水界面的天然表面活性剂,释放被乳化膜包裹的油类,另外阳离子单体的季胺基团所带的正电荷可以破坏乳化油外层包裹的负电子层,从而达到破乳效果;疏水长链烷基可以有效的亲附被释放出来的油类物质,将其应用于含油废水中,具有很好的选择性和特异性。经过实验对比,使用磁性疏水改性阳离子聚丙烯酰胺絮凝剂,测得含油废水的浊度去除率达到93.85%~98.08%,乳化油含量去除率达到78.83%~85.22%;而使用相同单体的阳离子聚丙烯酰胺絮凝剂(未疏水改性、不含磁性),测得含油废水的浊度去除率达到81.37%~87.42%,乳化油含量去除率达到56.47%~69.24%。
4、低压紫外光引发聚合能在室温下引发,反应过程中温度也不会明显升高。例如在室温20℃情况下,经检测反应过程中温度增加缓慢,最大达到30℃~36℃,远低于传统热引发、或高压紫外光引发的50℃~80℃;如果室温更低,反应过程中温度达到的最高温度也会降低。因此不需要对温度进行冷凝控制,简化了操作步骤,且条件温和、易于控制,节能环保,更适用于工业化生产。
5、本发明所提供合成方法所选用的丙烯酰胺、十二烷基葡萄苷(或椰子油脂肪酸二乙醇酰胺)、二甲基二烯丙基氯化铵、纳米四氧化三铁、过硫酸铵均为易于获得的市售材料,价格低廉,且小功率低压紫外灯节省能耗,整体生产成本低;产品环保无害,可回收,不会产生二次污染。
具体实施方式
下面通过具体实施例对本发明作详细说明,但本发明不局限于下述实施例。
实施例1
(1)取质量分数(占单体总质量的比例)为20%的十二烷基葡萄苷、20%的二甲基二烯丙基氯化铵和60%丙烯酰胺,磁力搅拌下溶解在超纯水中,达到完全溶解的状态后向溶液中加入质量分数为1‰的光引发剂2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮,搅拌使其完全溶解,调整pH为9,后通入纯度为99.999%的氮气15分钟驱除氧气,在15℃的室温条件下将瓶口密封置于功率为20W、波长为253.7nm的低压紫外灯下光照1h后得到乳白色胶状物。
(2)将胶状物用滤纸包裹于丙酮溶液在索式提取器中提纯24h后,用蒸馏水冲洗,于105℃下干燥24h,研磨、过筛得到白色粉末状样品。经过分析与检测,测得最终得到的疏水改性阳离子聚丙烯酰胺的特性粘度为747mL·g-1,正电荷密度为20.1mmol·g-1,溶解时间为60min。
(3)将上述粉末取适量溶解在超纯水中,加入与疏水改性阳离子聚丙烯酰胺质量比为1:1的纳米四氧化三铁颗粒和质量分数(占单体总质量的比例)为0.1%的过硫酸铵,高速搅拌12h后得到黑色溶液,在附加磁场情况下用超纯水洗涤3遍,烘干得到黑色磁性疏水改性阳离子聚丙烯酰胺粉末。
(4)取1L浓度为100mg/L的乳化油溶液置于混凝搅拌机上,加入上述黑色粉末0.12g,混凝搅拌过后即可去除水中的油类物质。经过分析与检测,磁絮凝沉降时间3min,处理后的上清液浊度降低了93.85%,含油量降低了88.22%。
实施例2
(1)取质量分数(占单体总质量的比例)为20%的十二烷基葡萄苷、40%的二甲基二烯丙基氯化铵和40%丙烯酰胺,磁力搅拌下溶解在超纯水中,达到完全溶解的状态后向溶液中加入质量分数为1‰的光引发剂2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮,搅拌使其完全溶解,调整pH为7,后通入纯度为99.999%的氮气15分钟驱除氧气,在20℃的室温条件下将瓶口密封置于功率为40W、波长为253.7nm的低压紫外灯下光照2h后得到乳白色胶状物。
(2)将胶状物用滤纸包裹于丙酮溶液在索式提取器中提纯24h后,用蒸馏水冲洗,于105℃下干燥24h,研磨、过筛得到白色粉末状样品。经过分析与检测,测得最终得到的疏水改性阳离子聚丙烯酰胺的特性粘度为572mL·g-1,正电荷密度为42.6mmol·g-1,溶解时间为55min。
(3)将上述粉末取适量溶解在超纯水中,加入与疏水改性阳离子聚丙烯酰胺质量比为1:1.5的纳米四氧化三铁颗粒和质量分数(占单体总质量的比例)为0.3%的过硫酸铵,高速搅拌12h后得到黑色溶液,在附加磁场情况下用超纯水洗涤4遍,烘干得到黑色磁性疏水改性阳离子聚丙烯酰胺粉末。
(4)取1L浓度为200mg/L的乳化油废水置于混凝搅拌机上,加入上述黑色粉末0.15g,混凝搅拌过后即可去除水中的油类物质。经过分析与检测,磁絮凝沉降时间4min,处理后的液体浊度降低了98.08%,含油量降低了86.52%,。
实施例3
(1)取质量分数(占单体总质量的比例)为30%的椰子油脂肪酸二乙醇酰胺、20%的二甲基二烯丙基氯化铵和50%丙烯酰胺,磁力搅拌下溶解在超纯水中,达到完全溶解的状态后向溶液中加入质量分数为1‰的光引发剂2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮,搅拌使其完全溶解,调整pH为5,后通入纯度为99.999%的氮气15分钟驱除氧气,在2℃的室温条件下将瓶口密封置于功率为80W、波长为185nm的低压紫外灯下光照3h后得到乳白色胶状物。
(2)将胶状物用滤纸包裹于丙酮溶液在索式提取器中提纯24h后,用蒸馏水冲洗,于105℃下干燥24h,研磨、过筛得到白色粉末状样品。经过分析与检测,测得最终得到的疏水改性阳离子聚丙烯酰胺的特性粘度为600mL·g-1,正电荷密度为21.2mmol·g-1,溶解时间为65min。
(3)将上述粉末取适量溶解在超纯水中,加入与疏水改性阳离子聚丙烯酰胺质量比为1:3的纳米四氧化三铁颗粒和质量分数(占单体总质量的比例)为0.5%的过硫酸铵,高速搅拌12h后得到黑色溶液,在附加磁场情况下用超纯水洗涤3遍,烘干得到黑色磁性疏水改性阳离子聚丙烯酰胺粉末。
(4)取1L浓度为200mg/L的乳化油废水置于混凝搅拌机上,加入上述黑色粉末0.13g,混凝搅拌过后即可去除水中的油类物质。经过分析与检测,磁絮凝沉降时间5min,处理后的液体浊度降低了95.79%,含油量降低了78.03%。
Claims (4)
1.一种磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂的制备方法,其特征在于,所述方法包括以下步骤:
(1)称取占单体总质量比例为20%~30%的疏水亲油单体、20%~40%的阳离子单体二甲基二烯丙基氯化铵和40%~60%的丙烯酰胺加入广口瓶中,加入去离子水后搅拌至完全溶解,再加入光引发剂至完全溶解得到混合液,并调节pH至5~9;
(2)向上述混合液通氮至广口瓶内氧气完全排空,在室温下将瓶口密封置于低压紫外光灯管下光照1~3h通过聚合反应得到乳白色胶体,将乳白色胶体在索式提取器中用丙酮提纯24~48h,得到白色固体,即疏水改性阳离子聚丙烯酰胺;
(3)将步骤(2)提纯过后的疏水改性阳离子聚丙烯酰胺溶解在超纯水中,在恒温水浴锅中30℃~40℃下加入纳米四氧化三铁颗粒和引发剂过硫酸铵,高速搅拌时间12~24h,得到黑色溶液,在磁铁吸附下用超纯水洗涤3~5次后烘干研磨成粉得到黑色粉末,即为磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂;所述纳米四氧化三铁颗粒与疏水改性阳离子聚丙烯酰胺质量比为1:1~3;
所述步骤(1)中的疏水亲油单体为十二烷基葡萄糖苷或椰子油脂肪酸二乙醇酰胺;所述步骤(2)中的低压紫外光灯功率为10~100W、波长为253.7nm或185nm;所述步骤(2)中的室温是2~20℃。
2.如权利要求1所述磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂的制备方法,其特征在于,所述步骤(1)中的光引发剂为2-羟基-4'-(2-羟乙氧基)-2-甲基苯丙酮。
3.如权利要求1所述制备方法得到的磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂在含油废水絮凝处理中的应用。
4.如权利要求3所述磁性疏水改性阳离子聚丙烯酰胺除油絮凝剂在含油废水絮凝处理中的应用,其特征在于,所述含油废水浓度为100~300mg/L、油粒尺寸为0.5~3μm。
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