CN113600150B - 一种以减压渣油制备磁性超交联聚合物的方法 - Google Patents
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Abstract
本发明公开了一种以减压渣油制备磁性HCPs的方法,首先,以共沉淀法制备磁性纳米颗粒,并以4‑苯基丁酸或5‑苯基戊酸为纳米颗粒的表面稳定剂,其中的羧基与Fe3O4表面形成络合,苯环则可参与后续的傅克反应,使聚合物与纳米颗粒之间形成化学键合,提高磁性HCPs的稳定性。然后,将减压渣油、磁性纳米颗粒、无水FeCl3、硝基甲烷、交联剂,升温到80oC反应6h,以甲醇和二氯甲烷抽提产物后,即可获得磁性HCPs。产物可应用于含苯酚废水处理,且具有良好的重复使用效率。
Description
技术领域
本发明属于高分子化学领域,具体涉及一种以减压渣油制备磁性HCPs的方法。
背景技术
超交联聚合物(Hypercrosslinked Polymers,HCPs)是指通过分子间内的交联反应制备具有永久微孔性的网络聚合物。HCPs材料具有高比表面积、微孔结构、低的骨架密度、大的孔体积、高的化学稳定性和热稳定性以及易于功能化等特点,在废水处理中具有广阔的应用前景。然而,从废水中回收HCPs是其应用的一个难题,而赋予HCPs磁性则可将其从废水中快速回收,简化处理工艺和效率,因此,多年来,磁性HCPs的制备与应用是废水处理领域的研究热点。
中国专利2007100552045公开了一种磁性粒子/聚合物/二氧化硅结构磁性微球的制备方法,作者通过三步法获得磁性复合微球,产物具有良好的生物相容性与化学稳定性,并且易于进一步的功能化。
中国专利202011351324.1公开了一种吸附阳离子染料的松香基磁性多孔微球的制备方法及应用,作者通过悬浮聚合法得到多孔的松香基磁性微球,所得微球可用于吸附水溶液中的阳离子染料,具有良好的吸附效果。
中国专利202010999863.X公开了一种用于废水净化的磁性多孔聚氨酯泡沫材料及制备方法,该材料具有均匀的孔隙结构,对水中污染物吸附性良好且吸附量大,并且由于含有磁性粒子,使其可以很好的回收再利用,可广泛用于污水处理等领域中。
中国专利201811378475.9公开了一种壳聚糖改性密胺树脂磁性多孔吸附剂及其制备方法,该吸附剂具有良好吸附效果,对废水中新胭脂红染料的去除率可达到99%,在污水处理领域具有良好的应用前景。
减压渣油廉价且来源丰富,是石油化工冶炼厂难以处理的固废,其主要成分为酚类、多环芳烃、杂环化合物,含有致癌性的物质,会对大气和水体造成污染。因此,寻找和开发减压渣油的高值转化具有重要的意义。
发明内容
本发明的目的是针对磁性超交联聚合物(HCPs)原料成本较高、制备步骤较多等问题,提供一种以减压渣油为主要原料,通过傅克反应,制备低成本的磁性HCPs的方法,制备的磁性HCPs可应用于治理难度大、危害大的苯酚废水处理,磁性HCPs具有吸附量大、回收快、循环利用率高的特点。
本发明采用的技术方案:一种以减压渣油制备磁性HCPs的方法,包括以下步骤:
(1) 磁性纳米颗粒的制备:在容器中分别加入FeCl3、FeCl2、去离子水,在氮气气氛下,搅拌并逐渐升温至80℃后,将氨水和表面修饰剂注射到溶液中,持续充分搅拌后,降温、用稀盐酸中和、磁分离、洗涤、干燥,即获得表面修饰的磁性纳米颗粒;
(2) 磁性HCPs的制备:将减压渣油和磁性纳米颗粒加入二氯乙烷,超声分散,加入无水FeCl3、硝基甲烷溶液和交联剂,除氧后升温至80℃,回流,抽滤、洗涤,以甲醇和二氯甲烷为溶剂,分别抽提产物,真空干燥,获得磁性HCPs。硝基甲烷的作用在于提高FeCl3在反应介质中的溶解能力,从而提高其催化效率、提高交联度、缩短反应时间。
作为优选,所述的磁性纳米颗粒的表面修饰剂为4-苯基丁酸或5-苯基戊酸,其中的苯环参与后续的傅克反应,使聚合物与磁性纳米颗粒之间形成化学键合,提高HCPs在应用过程中的磁响应稳定性。
作为优选,所述的减压渣油为黑色粘稠状物质,密度约1.02g/cm3,平均分子量约1220。
作为优选,反应介质为二氯乙烷,其用量是所有反应物重量的2-3倍。
作为优选,所述的减压渣油、磁性纳米颗粒、无水FeCl3、硝基甲烷、交联剂的质量百分含量分别为40-60 wt%、7-9 wt%、15-25 wt%、5-8 wt%、10-15wt%。
作为优选,所述的交联剂为对二甲氧基苯、二甲醇缩甲醛或原甲酸三甲酯。
本发明提出的一种以减压渣油制备磁性HCPs的方法,以4-苯基丁酸或5-苯基戊酸为磁性纳米颗粒的表面稳定剂,目的是利用磁性纳米颗粒表面的苯环,参与傅克反应,使磁性纳米颗粒与聚合物之间形成化学键合,一方面提高磁性HCPs化学稳定性,可以强酸或强碱溶液等苛刻环境中使用;另一方面在机械搅拌或超声分散等吸附实验中,避免磁性纳米颗粒脱落,从而提高磁性HCPs的磁响应稳定性。
本发明提出的一种以减压渣油制备磁性HCPs的方法,以减压渣油为制备HCPs的主要原料,减压渣油来自长岭石化,为黑色粘稠状物质,密度约1.02g/cm3,平均分子量1220。减压渣油是炼油厂减压塔底抽出的残渣油,产量大,处理难度大,如何充分利用和合理加工是目前石油行业的重要课题之一。本发明创造性提出以减压渣油为主要原料,制备低成本磁性HCPs,应用于含酚废水处理,提供了一条减压渣油高值转化的有效途径。
本发明首次以减压渣油为主要原料,通过傅克反应制备了低成本磁性HCPs。在傅克反应中,因FeCl3催化剂在二氯乙烷中的溶解度小,加入CH3NO3作为FeCl3的助溶剂,从而提高FeCl3的催化效率,提高交联度,缩短傅克反应时间。不仅为减压渣油的处理提供了一条有效途径,而且将其高值转化成可用于废水处理的多孔聚合物。产物的性能与特征在于:
(1)在外加磁场的作用下,HCPs具有显著的磁响应性;
(2)产物具有优秀的化学稳定性,在强酸强碱介质浸泡24h后,磁性HCPs无失重;
(3)磁性HCPs具有良好的热稳定性,在惰性气氛下,加热至220oC时,产物开始显著分解失重;
(4)磁性HCPs比表面积在90~160 m2/g可调,孔径分布以微孔和介孔为主;
(5)磁性HCPs可用于含酚废水处理,且具有良好的循环使用率,并有望推广至含重金属离子、其它有机污染物的废水处理。
具体实施方式
为使本领域技术人员更好理解本发明的技术方案和路线,下面结合实例对本发明作详细的描述,来说明本发明方法的作用和效果,但并不局限于以下实施例。
本发明提出以减压渣油为主要原料,通过傅克反应,制备低成本的磁性HCPs,并将其应用于苯酚废水处理。磁性HCPs的制备与应用包括以下步骤:
(1) 磁性纳米颗粒的制备:将FeCl3和FeCl2加入去离子水中,搅拌溶解,脱氧处理后升温至80℃;然后加入氢氧化铵(NH4OH,28%)和表面修饰剂,继续搅拌3.0 h。反应结束后降温,用盐酸中和溶液后,磁分离,用H2O洗涤3次,真空干燥,即可获得磁性纳米颗粒。
(2)磁性HCPs的制备:在带有机械搅拌装置的三颈烧瓶中,加入减压渣油、磁性纳米颗粒和1,2-二氯乙烷(DCE)中,超声分散形成均匀的悬浮液;然后,加入无水FeCl3、硝基甲烷和交联剂,脱氧处理后,升温至80℃回流6 h。反应结束后降温,磁分离,以去离子水洗涤3次,再以甲醇和二氯甲烷分别抽提产物12 h,真空干燥,即可获得低成本磁性HCPs。
(4) 磁性HCPs再生与循环实验:在吸附了苯酚的磁性HCPs中加入甲醇,磁力搅拌3h后,磁分离并重复上述实验1次,经去离子水冲洗后,真空干燥,即获得再生的磁性HCPs。循环实验与步聚(3)一样,固定磁性HCPs的用量和含苯酚废水的浓度与体积,考察循环实验中磁性HCPs对苯酚的去除率,去除率由下式计算得到:
实施例中所用的原料和设备如下:
减压渣油:工业级,湖南长岭石化科技开发有限公司;
1,2-二氯乙烷(DCE):分析纯,国药集团化学试剂有限公司;
二甲氧基苯:分析纯,国药集团化学试剂有限公司;
二甲醇缩甲醛:分析纯,国药集团化学试剂有限公司;
原甲酸三甲酯:分析纯,国药集团化学试剂有限公司;
无水氯化铁:分析纯,萨恩化学技术(上海)有限公司;
无水氯化亚铁:分析纯,萨恩化学技术(上海)有限公司;
氢氧化铵(NH4OH):分析纯,萨恩化学技术(上海)有限公司;
4-苯基丁酸:分析纯,萨恩化学技术(上海)有限公司;
5-苯基戊酸:分析纯,萨恩化学技术(上海)有限公司;
甲醇:分析纯,广州市金华大化学试剂有限公司;
二氯甲烷:分析纯,广东光华科技股份有限公司;
硝基甲烷:分析纯,萨恩化学技术(上海)有限公司;
苯酚:分析纯,广东光华科技股份有限公司;
比表面仪: ASAP2020,美国麦克仪器;
紫外分光光度计: Lambda-35,美国PE公司
真空干燥箱:上海一恒科学仪器有限公司。
磁性纳米颗粒合成示例1
将1.1 g FeCl3和0.4 g FeCl2加入20 mL去离子水中,搅拌溶解,脱氧处理后升温至80℃;然后加入5.0 mL氢氧化铵(NH4OH,28%)和0.5g 4-苯基丁酸,继续搅拌3.0 h。反应结束后降温,用盐酸中和溶液后,磁分离,用H2O洗涤3次,真空干燥,即可获得磁性纳米颗粒(MNPs-1)。
磁性纳米颗粒合成示例2
将3.0 g FeCl3和1.1 g FeCl2加入50 mL去离子水中,搅拌溶解,脱氧处理后升温至80℃;然后加入15.0 mL氢氧化铵(NH4OH,28%)和1.5 g 5-苯基戊酸,继续搅拌3.0 h。反应结束后降温,用盐酸中和溶液后,磁分离,用H2O洗涤3次,真空干燥,即可获得磁性纳米颗粒(MNPs-2)。
磁性HCPs制备实施例1
在带有机械搅拌装置的三颈烧瓶中,加入0.30 g减压渣油、0.05g MNPs-1和10.0mL 1,2-二氯乙烷(DCE)中,超声分散15min形成均匀的悬浮液;然后,加入0.12 g 无水FeCl3、0.05 g硝基甲烷和0.08 g二甲氧基苯,脱氧处理后,升温至80℃回流6 h。反应结束后降温,磁分离,以去离子水洗涤3次,再以甲醇和二氯甲烷分别抽提产物12 h,真空干燥,即可获得磁性HCPs-1。
磁性HCPs制备实施例2
在带有机械搅拌装置的三颈烧瓶中,加入0.90 g减压渣油、0.15 g MNPs-2和30.0mL 1,2-二氯乙烷(DCE)中,超声分散15min形成均匀的悬浮液;然后,加入0.4 g 无水FeCl3、0.12 g硝基甲烷和0.2 g二甲醇缩甲醛,脱氧处理后,升温至80℃回流6 h。反应结束后降温,磁分离,以去离子水洗涤3次,再以甲醇和二氯甲烷分别抽提产物12 h,真空干燥,即可获得磁性HCPs-2。
磁性HCPs制备实施例3
在带有机械搅拌装置的三颈烧瓶中,加入1.5 g减压渣油、5 g MNPs-2和250.0 mL1,2-二氯乙烷(DCE)中,超声分散15min形成均匀的悬浮液;然后,加入0.6 g 无水FeCl3、0.25 g硝基甲烷和0.6 g原甲酸三甲酯,脱氧处理后,升温至80℃回流6 h。反应结束后降温,磁分离,以去离子水洗涤3次,再以甲醇和二氯甲烷分别抽提产物12 h,真空干燥,即可获得磁性HCPs-3。
磁性HCPs制备实施例4
在带有机械搅拌装置的三颈烧瓶中,加入30 g减压渣油、5.0 g MNPs-1和30.0 mL1,2-二氯乙烷(DCE)中,超声分散15min形成均匀的悬浮液;然后,加入12 g 无水FeCl3、5.0g硝基甲烷和7.5 g二甲醇缩甲醛,脱氧处理后,升温至80℃回流6 h。反应结束后降温,磁分离,以去离子水洗涤3次,再以甲醇和二氯甲烷分别抽提产物12 h,真空干燥,即可获得磁性HCPs-4。
上述4个实施例制备磁性HCPs均以氮气吸脱附测试其孔结构,孔结构参数如表1所示。
表1 磁性HCPs的孔结构数据
将上述磁性HCPs应用于含苯酚废水处理,其饱和吸附量如表2所示,饱和吸附量与磁性HCPs的比表面积相关。
表2 磁性HCPs对苯酚的饱和吸附量
样品名称 | 磁性HCPs-1 | 磁性HCPs-2 | 磁性HCPs-3 | 磁性HCPs-4 |
<i>Q</i><sub><i>e</i></sub>(mg/g) | 22.5 | 31.2 | 24.9 | 32.3 |
以甲醇为洗脱液,再生磁性HCPs-4,干燥后再次将其应用于同体积同浓度的苯酚废水处理,上述过程重复4次,循环实验中磁性HCPs-4对苯酚的去除效率如表3所示。
表3 磁性HCPs-4在循环实验中对苯酚的去除效率
本发明的实验结果表明,以石油工业中处理难度大的减压渣油为原料,可制备低成本磁性HCPs-4,产物具有中等孔隙率。磁性HCPs可应用于含苯酚废水处理,并具有良好的重复应用效率。总之,本发明为大规模高值转化减压渣油提供了一条有效途径。
上述实例仅是本发明的较佳实施例子,而并非用以限定本发明,任何熟悉本专业的技术人员在不脱离本发明的技术方案范围内,可利用上述揭示的技术内容做出些许更改或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所做的任何简单修改,仍属于本发明技术方案的范围。
Claims (5)
1.一种以减压渣油制备磁性HCPs的方法,其特征在于包括以下步骤:
(1) 磁性纳米颗粒的制备:在容器中分别加入FeCl3、FeCl2、去离子水,在氮气气氛下,搅拌并逐渐升温至80℃后,将氨水和表面修饰剂注射到溶液中,持续充分搅拌后,降温、用稀盐酸中和、磁分离、洗涤、干燥,即获得表面修饰的磁性纳米颗粒;
(2) 磁性HCPs的制备:将减压渣油和磁性纳米颗粒加入二氯乙烷,超声分散,加入无水FeCl3、硝基甲烷溶液和交联剂,除氧后升温至80℃,回流,抽滤、洗涤,以甲醇和二氯甲烷为溶剂,分别抽提产物,真空干燥,获得磁性HCPs, HCPs为磁性超交联聚合物;
所述的磁性纳米颗粒的表面修饰剂为4-苯基丁酸或5-苯基戊酸,其中的苯环参与后续的傅克反应,使聚合物与磁性纳米颗粒之间形成化学键合,提高HCPs在应用过程中的磁响应稳定性。
2.根据权利要求1中所述的一种以减压渣油制备磁性HCPs的方法,其特征在于,所述的减压渣油为黑色粘稠状物质,密度约1.02g/cm3,平均分子量约1220。
3.根据权利要求1中所述的一种以减压渣油制备磁性HCPs的方法,其特征在于,步骤(2)中的反应介质为二氯乙烷,其用量是所有反应物重量的2-3倍。
4. 根据权利要求1中所述的一种以减压渣油制备磁性HCPs的方法,其特征在于,所述的减压渣油、磁性纳米颗粒、无水FeCl3、硝基甲烷、交联剂的质量百分含量分别为40-60wt%、7-9 wt%、15-25 wt%、5-8 wt%、10-15wt%。
5.根据权利要求1中所述的一种以减压渣油制备磁性HCPs的方法,其特征在于,所述的交联剂为对二甲氧基苯、二甲醇缩甲醛或原甲酸三甲酯。
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