CN106832087B - 中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法和应用 - Google Patents
中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法及其应用,包括聚丙烯酸水凝胶的制备和中性红接枝反应,具体包括以下步骤:A、以丙烯酸为单体、N,N‑亚甲基双丙烯酰胺为交联剂、过硫酸钾为引发剂,在30~80℃条件下反应生成聚丙烯酸水凝胶;B、称取1‑(3‑二甲氨基丙基)‑3‑乙基碳二亚胺盐酸盐、N‑羟基琥珀酰亚胺和中性红配成混合液,将步骤A制备的聚丙烯酸水凝胶置于所述混合液中,于10~50℃反应24h,得中性红改性的聚丙烯酸水凝胶粗品。本发明中聚丙烯酸水凝胶载体材料具有较大的比表面积,有利于提高非醌介体的负载率,从而实现高性能的生物催化效率。
Description
技术领域
本发明属于环境治理用功能材料领域,具体涉及中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法及其应用。
背景技术
随着我国经济的持续快速增长,水资源消耗大幅度增加,使得水环境污染问题日趋严重,而纺织印染行业废水的排放是水污染的主要来源之一,偶氮染料是纺织废水中典型的污染物,它排入河流后,不仅影响河水的色度和浊度,而且造成水环境污染,影响人类的健康。偶氮染料因其难生物降解性和传统生物处理法效果差的特点,致使其有效处理成为目前环境领域研究的难点。现有的微生物处理方法中,厌氧-好氧联合生物处理法是处理这类污染物最常用的方法之一。其中,厌氧段主要完成大分子难降解化合物的还原转化。然而,多数偶氮染料脱色菌在厌氧条件下,代谢速率缓慢、厌氧脱色效率低。因此,厌氧阶段的脱色速率低成为偶氮染料生物降解的限速步骤。
研究发现氧化还原介体可催化强化难降解污染物生物转化的过程,为难降解污染物高效生物降解提供了新的研究思路。醌类氧化还原介体,如蒽醌-2,6-二磺酸钠、蒽醌-2-磺酸钠等对于偶氮染料的厌氧脱色具有催化加速的作用。然而水溶性的氧化还原介体会随出水流失,造成二次污染,且持续投加也会增加运行成本。因此,研究氧化还原介体的固定技术对氧化还原介体的工程应用具有重要的意义。近年来,国内外许多学者研发了多种氧化还原介体固定的载体材料,如聚氨酯泡沫、陶粒、海藻酸钠小球等。但是固定方法以吸附、包埋为主,介体容易解吸,仍存在二次污染等问题。且固定后的介体由于材料性能的局限,亲水性有待改善,不利于水中污染物的扩散,无法实现催化效率的最大化。另外,目前研究主要集中于醌基介体催化的基础和应用研究,限制了此技术的应用范围。基于生物电子传递理论,若能在生物电子传递链不同位点加入不同高效介体,将为介体催化理论和技术的拓展和应用提供重要的理论支撑。因而如何创新性的拓展非醌基介体研究将成为介体催化调控厌氧生物净化技术的重要问题。
水凝胶是聚合物交联的三维网络结构,它可以在水中溶胀但不溶解,水凝胶体系中90%以上的都是水分子,因而具有良好的亲水性和优异的生物相容性。水凝胶贯穿的三维网络结构,有利于物质在水凝胶体系和水环境之间的穿梭和转运,因而其在环境领域具有非常广泛的应用前景。一般来说,构建氧化还原介体修饰的水凝胶有两种策略:第一,介体修饰单体后再进行聚合反应;但是大多数氧化还原介体是自由基聚合的淬灭剂,因此,介体改性水凝胶的构建不宜采用该策略。第二,先构建水凝胶,后修饰介体。然而,水凝胶具有优良的亲水性能,也只有在水体系中,才具有相对较高的反应活性。而大多数的介体水溶性较差,且由于水分子的活性强,水分子参与的副反应占据了主导地位,因此,大多数的合成反应在水体系中的产率极低。因而,关于在水凝胶体系中化学接枝氧化还原介体的研究尚未有报道。
发明内容
本发明要解决的技术问题是提供一种中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法及其应用,其将中性红介体通过化学键合的方法修饰在聚丙烯酸水凝胶上,制备得到具有生物催化作用的功能材料,加速环境污染物的生物转化。
为解决上述技术问题,本发明采用的技术方案是:
一种中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法,包括聚丙烯酸水凝胶的制备和中性红接枝反应,具体包括以下步骤:
A、以丙烯酸为单体、N,N-亚甲基双丙烯酰胺为交联剂、过硫酸盐为引发剂,在30~80℃条件下反应生成聚丙烯酸水凝胶;
B、称取1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(以下简写为EDC·HCl)、N-羟基琥珀酰亚胺(简写NHS)和中性红配成混合液,将步骤A制备的聚丙烯酸水凝胶置于所述混合液中,于10~50℃反应24h,得中性红改性的聚丙烯酸水凝胶粗品。中性红学名为3-氨基-7-二甲基氨基-2-甲基吩嗪盐酸盐。
优选的,还包括步骤C、将所述中性红改性的聚丙烯酸水凝胶粗品用蒸馏水洗脱至无色,得中性红改性的聚丙烯酸水凝胶功能材料(以下简写为NR-PAaH)。
步骤A中所述N,N亚甲基双丙烯酰胺和过硫酸盐与丙烯酸的摩尔比分别为0.5~10:100和0.5~10:100。所述过硫酸盐为过硫酸钾、过硫酸钠或过硫酸氨。
步骤B中1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐与N-羟基琥珀酰亚胺的质量比为0.5~2:1。
采用上述技术方案产生的有益效果在于:(1)本发明中聚丙烯酸水凝胶载体材料具有较大的比表面积,有利于提高中性红介体的负载率,从而实现高性能的生物催化效率;(2)聚丙烯酸水凝胶具有优异的溶胀性能和亲水性能,生物相容性好,聚丙烯酸水凝胶呈现贯穿的三维网络结构,有利于物质的扩散与交换;(3)中性红介体以化学键合的形式固定,具有较高的稳定性,有效的避免了二次污染,又可循环利用,具有优良的环境友好性和经济性。
附图说明
图1是实施例1制备的NR-PAaH功能材料的扫描电镜照片;
图2是实施例1中制备的NR-PAaH功能材料的红外光谱比较图,其中A代表聚丙烯酸水凝胶,B代表NR-PAaH功能材料,C代表中性红;
图3是实施例1制备的NR-PAaH功能材料在偶氮染料脱色中的应用,其中,■、●、▲和▼分别代表编号为a1、b1、c1、d1组中偶氮染料的脱色率。
具体实施方式
实施例1
将1.5g丙烯酸、0.062 g N,N-亚甲基双丙烯酰胺和0.05 g过硫酸钾溶于2 mL乙醇和17 mL蒸馏水的混合液中,水浴加热至60℃,机械搅拌至形成水凝胶。其水凝胶化时间为20 min,水凝胶溶胀率为22.29。
中性红通过EDC缩合反应枝在聚丙烯酸水凝胶上。具体操作步骤如下:将400 mgEDC.HCl、500 mg NHS和500 mg中性红溶于100 mL的蒸馏水中,制成反应溶液,将凝胶切成小立方体的块浸渍置于所述反应溶液中,室温下反应24 h。将反应后的凝胶用蒸馏水洗涤三次,置于蒸馏水中浸泡,并每隔4 h置换蒸馏水,直至蒸馏水为无色透明,继续浸泡24 h,制得NR-PAaH功能材料。中性红在聚丙烯酸水凝胶的接枝量为45.3 mg/g。
扫描电镜分析制备的NR-PAaH功能材料的形貌,参见图1,结果表明:NR-PAaH功能材料表面积较大,呈现贯穿的三维网络结构。
并对NR-PAaH功能材料进行了红外测试,如图2所示。在NR-PAaH功能材料的红外谱图中,在2960 cm-1为苯环中C-H的吸收峰,1198,1327,1627 cm-1处为苯环的骨架振动峰,这些数据表明中性红通过化学键合成功修饰到聚丙烯酸水凝胶功能材料上。
应用实施例1
采用逐步提高染料浓度的驯化方法,从污泥样品中驯化出能够降解偶氮染料活性艳红K-2BP的混合菌群。取10 mL处于对数生长期的菌体接种到200 mL LB降解培养基中,在35℃下,摇床转速为140 r/min的条件下培养12 h,待菌液吸光度值达到0.8(λ=600 nm)左右时,加入活性红染料并使其初始浓度为200 mg/L。
取4个300 mL血清瓶,分别编号为a1、b1、c1、d1。迅速将上述菌液与活性艳红染料的混合液分装到编号为b1、c1、d1血清瓶中,并在编号为c1、d1的血清瓶中分别加入湿重为1.0 g、2.0 g 实施例2制备的NR-PAaH功能材料;编号为a1的血清瓶中加入LB降解培养基(无接种细菌)和1.0 g 的NR-PAaH功能材料以及浓度为200 mg/L活性红染料水溶液作为空白组。所有血清瓶均用橡胶盖和铝塑盖封瓶,保证血清瓶内维持厌氧环境。
每隔2h取样,离心取上清液稀释后于540 nm波长下测定其吸光度,通过标准曲线计算染料的浓度,进而得到染料降解率情况,详细结果如附图3所示。从图3中可以看出2h后,对照组b1的脱色率不达5%时,实验组c1和d1脱色率已达到86%左右。表明由于聚丙烯酸功能材料的加入催化加速了偶氮染料的生物脱色效率。
实施例2
将1.5 g丙烯酸、0.09 g N,N-亚甲基双丙烯酰胺和0.05 g过硫酸钾溶于2 mL乙醇和17 mL蒸馏水的混合液中,水浴加热至50℃,机械搅拌至形成水凝胶。该水凝胶化时间为8min,水凝胶溶胀率为24.18。
中性红通过EDC缩合反应枝在聚丙烯酸水凝胶上。具体操作步骤如下:将400 mgEDC.HCl、500 mg NHS和500 mg中性红溶于100 mL的蒸馏水中,制成反应溶液,将凝胶切成小立方体的块置于所述反应溶液中,室温下反应24 h。将反应后的凝胶用蒸馏水洗涤三次,置于蒸馏水中浸泡,并每隔4 h置换蒸馏水,直至蒸馏水为无色透明,,继续浸泡24 h,制得NR-PAaH功能材料。中性红在聚丙烯酸水凝胶的接枝量采用差量法测得为46.2 mg/g。
应用实施例2
采用逐步提高高氯酸盐浓度的驯化方法,从污泥样品中驯化出能够降解高氯酸盐的混合菌群。取10 mL处于对数生长期的菌体接种到200 mL 高氯酸盐降解培养基中,在35℃下,摇床转速为140 r/min的条件下培养12 h,待菌液吸光度值达到0.3(λ=600 nm)左右时,加入高氯酸钠并使ClO4 -初始浓度为50 mg/L。
取3个300 mL血清瓶,分别编号为a2、b2和c2。将上述菌群与高氯酸盐的混合溶液分装到编号为b2和c2血清瓶中,其中c2瓶加入湿重为1.0 g的实施例2制备的NR-PAaH功能材料。编号为a2血清瓶中加入高氯酸盐降解培养基(无接种细菌)和1.0 g 的NR-PAaH功能材料以及ClO4 -初始浓度为50 mg/L的高氯酸钠溶液作为空白组。所有血清瓶均用橡胶盖和铝塑盖封瓶,保证血清瓶内维持厌氧环境。
每隔一段时间取样一次,采用离子色谱测定 ClO4 -浓度,计算高氯酸盐降解率。通过比较实验组c2组和对照组b2组以及空白组a2,结果表明:空白组a2的高氯酸盐浓度基本没有变化;与对照组b2相比,加入NR-PAaH功能材料的c2组催化加速了ClO4 -的生物还原。
实施例3
将1.5 g丙烯酸、0.062 g N,N-亚甲基双丙烯酰胺和0.05 g过硫酸钠溶于2 mL乙醇和17mL蒸馏水的混合液中,水浴加热至50℃,机械搅拌至形成水凝胶。该水凝胶化时间为20 min,水凝胶溶胀率为22.29。
中性红通过EDC缩合反应枝在聚丙烯酸水凝胶上。具体操作步骤如下:将400 mgEDC.HCl、400 mg NHS和500 mg中性红溶于100 mL的蒸馏水中,制成反应溶液,将凝胶切成小立方体的块置于所述反应溶液中,室温下反应24 h。将反应后的凝胶用蒸馏水洗涤三次,置于蒸馏水中浸泡,并每隔4 h置换蒸馏水,直至蒸馏水为无色透明,使吸附在水凝胶上的中性红洗脱掉,继续浸泡24 h,制得NR-PAaH功能材料。中性红在聚丙烯酸水凝胶的接枝量采用差量法测得为44.8 mg/g。
应用实施例3
采用逐步提高硝酸盐浓度的驯化方法,从污泥样品中驯化出反硝化菌群。取10 mL处于对数生长期的菌体接种到200 mL 硝酸盐降解培养基中,在35℃下,摇床转速为140 r/min的条件下培养12 h,待菌液吸光度值达到0.6(λ=600 nm)左右时,加入硝酸钠并使其初始浓度为200 mg/L。
取3个300 mL血清瓶,分别编号为a3、b3和c3。将上述菌群与高氯酸盐的混合溶液均匀分装到编号为b3和c3血清瓶中,其中编号为c3血清瓶加入湿重为1.0 g实施例2制备的NR-PAaH功能材料。编号为a3的血清瓶中加入硝酸盐降解培养基(无接种细菌)和1.0 g NR-PAaH功能材料以及浓度为200 mg/L硝酸钠溶液作为空白组。所有血清瓶均用橡胶盖和铝塑盖封瓶,保证血清瓶内维持厌氧环境。
每隔一段时间取样,离心取上清液稀释后于220 nm和275 nm波长下测定其吸光度,通过标准曲线计算硝氮的浓度,进而得到硝氮降解率情况,并于540 nm波长下测得亚氮吸光度,计算亚氮积累程度。通过比较实验组c3和对照组b3以及空白组a3,结果表明:空白组a3中硝酸盐的浓度基本不变;与对照组b2相比,加入NR-PAaH功能材料的c3组催化加速了微生物的反硝化过程。
综上所述,本发明制备的聚丙烯酸水凝胶载体材料具有较大的比表面积,有利于提高中性红介体的负载率,从而实现高性能的生物催化效率,如NR-PAaH功能材料催化加速了偶氮染料降解、反硝化反应以及高氯酸盐还原。
Claims (7)
1.一种中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法,包括聚丙烯酸水凝胶的制备和中性红接枝反应,其特征在于具体包括以下步骤:
A、以丙烯酸为单体、N,N-亚甲基双丙烯酰胺为交联剂、过硫酸盐为引发剂,在30~80℃条件下反应生成聚丙烯酸水凝胶;
B、称取1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐、N-羟基琥珀酰亚胺和中性红配成混合液,将步骤A制备的聚丙烯酸水凝胶置于所述混合液中,于10~50℃反应24h,得中性红改性的聚丙烯酸水凝胶粗品。
2.根据权利要求1所述的中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法,其特征在于还包括步骤C、将所述中性红改性的聚丙烯酸水凝胶粗品用蒸馏水洗脱至无色,得中性红改性的聚丙烯酸水凝胶功能材料。
3.根据权利要求1所述的中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法,其特征在于步骤A中所述N,N亚甲基双丙烯酰胺和过硫酸钾与丙烯酸的摩尔比分别为0.5~10:100和0.5~10:100。
4.根据权利要求1或3所述的中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法,其特征在于步骤A中采用的丙烯酸单体的质量浓度为1~15%的溶液,溶剂为水和乙醇的混合液。
5.根据权利要求4所述的中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法,其特征在于水与乙醇的质量比为1~10:1。
6.根据权利要求1所述的中性红改性的聚丙烯酸水凝胶介体功能材料的制备方法,其特征在于步骤B中1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐与N-羟基琥珀酰亚胺的质量比为0.5~2:1。
7.权利要求1所述的制备方法制得的中性红改性的聚丙烯酸水凝胶介体功能材料在催化环境污染物生物降解中的应用。
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