CN105348448A - 一种具有互穿网络结构的网状聚氨酯微生物载体的制备方法 - Google Patents
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Abstract
本发明属于微生物载体制备方法技术领域,涉及一种具有互穿网络结构的网状聚氨酯微生物载体的制备方法,将乙烯基聚醚多元醇、聚醚多元醇、聚酯多元醇、H2O、硅油、锡类催化剂、胺类催化剂、烯烃单体加入反应釜中,搅拌均匀并保温作为组分1;将异氰酸酯、自由基聚合引发剂,加入反应釜搅拌均匀作为组分2;将组分1和组分2混合搅拌均匀,发泡得到聚氨酯软泡;将聚氨酯软泡通过碱液浸泡或爆炸法进行网化处理,得到具有互穿网络结构的网状聚氨酯微生物载体;通过互穿网络结构在网状聚氨酯载体内部引入烯烃聚合物,增强载体的耐水解和耐生物降解性,提高使用寿命;增强聚氨酯组分和烯烃聚合物组分的相容性,并保留各组分的特性。
Description
技术领域
本发明属于微生物载体制备方法技术领域,具体地说,涉及一种具有互穿网络结构的网状聚氨酯微生物载体的制备方法,用于生物法处理城市生活污水。
背景技术
随着我国工农业的快速发展和城市化进程的不断加快,城市生活污水处理成为实现我国经济社会可持续发展、构建生态和谐家园首要解决的问题。以活性污泥为代表的生物处理污水技术已广泛应用于城市和工业污水的处理中。然而,传统的活性污泥技术在降低污水厂出水总氮能力方面还有待进一步提高,同时产生的大量剩余污泥也成为了二次污染源。移动床生物膜反应器(MBBR)工艺,运用了生物膜法污水处理的基本原理,又充分利用了活性污泥法的优点,在降低污水厂出水总氮和剩余污泥减量方面效果良好。
通过引入微生物载体,可以为污水处理微生物提供大量的附着位点,在载体表面提供好氧环境提高硝化细菌的硝化反应速率,在载体内部提供厌氧环境以提高反硝化细菌的反硝化反应速率,最终提高处理总氮的能力;同时,微生物载体还能够促进剩余污泥的原位分解,实现剩余污泥减量化。
目前,高分子材料是应用最广泛的生物载体填料,主要包括聚烯烃类和聚氨酯类。在实际应用当中,简单的聚合物生物载体填料亲水性和生物附着性较差,导致微生物挂膜速度较慢,降低了污水处理效率,且耐水解和微生物降解性差,使用寿命短,使用成本相对较高。
发明内容
本发明的目的在于克服现有技术存在的缺点,寻求设计一种具有互穿网络结构的网状聚氨酯微生物载体的制备方法,提高载体的耐水解和耐生物降解性,增加聚氨酯生物载体吸附的生物量,提高污水生物处理能力。
为了实现上述目的,本发明采用的技术方案为:一种具有互穿网络结构的网状聚氨酯微生物载体的制备方法,包括以下步骤:
步骤1:将乙烯基聚醚多元醇5~15份、聚醚多元醇50~120份、聚酯多元醇0~30份、H2O5~8份、硅油1~3份、锡类催化剂0.05~0.2份、胺类催化剂0.1~0.8份、烯烃单体5~50份加入反应釜中,搅拌均匀,并保温至35~45℃,作为组分1;上述份数为质量份;
步骤2:将异氰酸酯120~140份、自由基聚合引发剂0.01~0.15份,加入反应釜,搅拌均匀,作为组分2;上述份数为质量份;
优选的是,所述乙烯基聚醚多元醇为乙烯基聚氧化丙烯多元醇或乙烯基聚环氧乙烷多元醇;
优选的是,所述聚醚多元醇为乙二醇聚醚多元醇、乙二醇四氢呋喃聚醚多元醇或氧化丙烯聚醚多元醇;
优选的是,所述聚酯多元醇为己二酸聚酯多元醇或芳香族聚酯多元醇;
优选的是,所述锡类催化剂为辛酸亚锡或二丁基二月桂酸锡,胺类催化剂为三乙烯二胺、三乙醇胺、三乙胺或N-乙基吗啉中的一种,锡类和胺类催化剂用于催化异氰酸酯与聚醚多元醇、聚酯多元醇反应,调节聚氨酯发泡反应活性。
优选的是,所述自由基聚合引发剂为过氧化苯甲酰(BPO)、偶氮二异丁腈、偶氮二异庚腈中的一种,用于引发烯烃单体及乙烯基聚醚多元醇的自由基聚合反应。
优选的是,所述烯烃单体为苯乙烯或二乙烯苯,烯类单体在自由基聚合引发剂作用下自聚并与乙烯基聚醚多元醇反应,在聚氨酯内部生成互穿网络结构。
优选的是,所述异氰酸酯为二苯基甲烷二异氰酸酯MDI。
乙烯基聚醚多元醇含有碳碳双键和羟基两种官能团,可以分别与含双键的烯烃单体及异氰酸酯反应,在聚氨酯体系中引入互穿网络结构。聚醚多元醇提供大量羟基,与异氰酸酯反应生成聚氨酯。
步骤3:将组分1和组分2混合,搅拌均匀后倒入模具中发泡12~24h,室温下进行发泡,得到聚氨酯软泡;
步骤4:将步骤3制备的聚氨酯软泡通过碱液浸泡或爆炸法进行网化处理,切割得到具有互穿网络结构的网状聚氨酯微生物载体。
优选的是,所述碱液浸泡法是将聚氨酯软泡浸没于碱液中,浸泡处理12~24h,碱液组成为:质量分数为40%的NaOH水溶液、异丙醇、丙二醇按体积比4:1~3:1配成混合溶液;然后用蒸馏水洗涤2~3次。
优选的是,所述爆炸法是将制备的聚氨酯软泡放入处理反应器中,先抽真空,后冲入一定压力的爆炸性气体,扩散一段时间后点火引爆,得到网化处理的聚氨酯软泡。
具有互穿网络结构的网状聚氨酯微生物载体用于城市生活污水的生化处理。
本发明的有益效果为:
(1)通过互穿网络结构在网状聚氨酯载体内部引入烯烃聚合物,能够增强载体的耐水解和耐生物降解性,提高使用寿命;能够增强聚氨酯组分和烯烃聚合物组分的相容性,并保留各组分的特性;能够降低载体填料的生产原料成本;载体软硬度可调。
(2)采用MDI作为合成载体填料的异氰酸酯,安全性高,生物亲和性好。
(3)本方法制备的生物载体具有多孔性和亲水性,为污水处理微生物提供大量附着位点和良好的好氧、厌氧生活环境,微生物挂膜速度快,生物量大,在填料表面为硝化细菌提供好氧环境以提高硝化反应速率,在填料内部为反硝化细菌提供厌氧环境以提高反硝化反应速率,能显著提高生物处理效果和稳定性,降低总氮,实现剩余污泥减量化。
具体实施方式
下面通过具体实施例对本发明作进一步描述:
实施例1
本实施例的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,包括以下步骤:
步骤1:将乙烯基聚氧化丙烯多元醇10份、乙二醇聚醚多元醇80份、H2O5份、硅油1份、锡类催化剂辛酸亚锡0.1份、胺类催化剂三乙烯二胺0.3份、烯烃单体苯乙烯20份加入反应釜中,搅拌均匀,并保温至40℃,作为组分1;上述份数为质量份;
步骤2:将二苯基甲烷二异氰酸酯(MDI)125份、自由基聚合引发剂过氧化苯甲酰(BPO)0.08份,加入反应釜,搅拌均匀,作为组分2;上述份数为质量份;
步骤3:将组分1和组分2混合,搅拌均匀后倒入模具中发泡12~24h,室温下进行发泡,得到聚氨酯软泡;
步骤4:将步骤3制备的聚氨酯软泡通过碱液浸泡法进行网化处理,将聚氨酯软泡浸没于碱液中,浸泡处理12h,碱液组成为:质量分数为40%的NaOH水溶液、异丙醇、丙二醇按体积比4:1:1配成混合溶液;然后用蒸馏水洗涤2次;切割得到具有互穿网络结构的网状聚氨酯微生物载体。
实施例2
本实施例的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,包括以下步骤:
步骤1:将乙烯基聚环氧乙烷多元醇15份、乙二醇四氢呋喃聚醚多元醇100份、己二酸聚酯多元醇30份、H2O6份、硅油2份、锡类催化剂辛酸亚锡0.15份、胺类催化剂三乙烯二胺0.5份、烯烃单体苯乙烯15份加入反应釜中,搅拌均匀,并保温至40℃,作为组分1;上述份数为质量份;
步骤2:将二苯基甲烷二异氰酸酯(MDI)130份、自由基聚合引发剂偶氮二异丁腈0.06份,加入反应釜,搅拌均匀,作为组分2;上述份数为质量份;
步骤3:将组分1和组分2混合,搅拌均匀后倒入模具中发泡24h,室温下进行发泡,得到聚氨酯软泡;
步骤4:将步骤3制备的聚氨酯软泡通过爆炸法进行网化处理,将制备的聚氨酯软泡放入处理反应器中,先抽真空,后冲入一定压力的爆炸性气体,扩散一段时间后点火引爆,得到网化处理的聚氨酯软泡;切割得到具有互穿网络结构的网状聚氨酯微生物载体。
实施例3
本实施例的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,包括以下步骤:
步骤1:将乙烯基聚醚多元醇5份、氧化丙烯聚醚多元醇70份、芳香族聚酯多元醇10份、H2O8份、硅油2份、锡类催化剂二丁基二月桂酸锡0.05份、胺类催化剂三乙胺0.8份、烯烃单体二乙烯苯5份加入反应釜中,搅拌均匀,并保温至35℃,作为组分1;上述份数为质量份;
步骤2:将二苯基甲烷二异氰酸酯(MDI)120份、自由基聚合引发剂过氧化苯甲酰(BPO)0.01份,加入反应釜,搅拌均匀,作为组分2;上述份数为质量份;
步骤3:将组分1和组分2混合,搅拌均匀后倒入模具中发泡12~24h,室温下进行发泡,得到聚氨酯软泡;
步骤4:将步骤3制备的聚氨酯软泡通过碱液浸泡法进行网化处理,将聚氨酯软泡浸没于碱液中,浸泡处理18h,碱液组成为:质量分数为40%的NaOH水溶液、异丙醇、丙二醇按体积比4:3:1配成混合溶液;然后用蒸馏水洗涤3次;切割得到具有互穿网络结构的网状聚氨酯微生物载体。
实施例4
本实施例的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,包括以下步骤:
步骤1:将乙烯基聚醚多元醇12份、聚醚多元醇120份、芳香族聚酯多元醇20份、H2O7份、硅油3份、锡类催化剂二丁基二月桂酸锡0.2份、胺类催化剂三乙醇胺0.1份、烯烃单体二乙烯苯50份加入反应釜中,搅拌均匀,并保温至45℃,作为组分1;上述份数为质量份;
步骤2:将二苯基甲烷二异氰酸酯(MDI)140份、自由基聚合引发剂偶氮二异庚腈0.15份,加入反应釜,搅拌均匀,作为组分2;上述份数为质量份;
步骤3:将组分1和组分2混合,搅拌均匀后倒入模具中发泡20h,室温下进行发泡,得到聚氨酯软泡;
步骤4:将步骤3制备的聚氨酯软泡通过爆炸法进行网化处理,将制备的聚氨酯软泡放入处理反应器中,先抽真空,后冲入一定压力的爆炸性气体,扩散一段时间后点火引爆,得到网化处理的聚氨酯软泡;切割得到具有互穿网络结构的网状聚氨酯微生物载体。
Claims (6)
1.一种具有互穿网络结构的网状聚氨酯微生物载体的制备方法,其特征在于,包括以下步骤:
步骤1:将乙烯基聚醚多元醇5~15份、聚醚多元醇50~120份、聚酯多元醇0~30份、H2O5~8份、硅油1~3份、锡类催化剂0.05~0.2份、胺类催化剂0.1~0.8份、烯烃单体5~50份加入反应釜中,搅拌均匀,并保温至35~45℃,作为组分1;上述份数为质量份;
步骤2:将异氰酸酯120~140份、自由基聚合引发剂0.01~0.15份,加入反应釜,搅拌均匀,作为组分2;上述份数为质量份;
步骤3:将组分1和组分2混合,搅拌均匀后倒入模具中发泡12~24h,室温下进行发泡,得到聚氨酯软泡;
步骤4:将步骤3制备的聚氨酯软泡通过碱液浸泡或爆炸法进行网化处理,切割得到具有互穿网络结构的网状聚氨酯微生物载体。
2.根据权利要求1所述的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,其特征在于,所述锡类催化剂为辛酸亚锡或二丁基二月桂酸锡,胺类催化剂为三乙烯二胺、三乙醇胺、三乙胺或N-乙基吗啉中的一种。
3.根据权利要求1所述的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,其特征在于,所述自由基聚合引发剂为过氧化苯甲酰、偶氮二异丁腈、偶氮二异庚腈中的一种。
4.根据权利要求1所述的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,其特征在于,所述烯烃单体为苯乙烯或二乙烯苯,所述异氰酸酯为二苯基甲烷二异氰酸酯。
5.根据权利要求1-4任一项所述的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,其特征在于,所述碱液浸泡法是将聚氨酯软泡浸没于碱液中,浸泡处理12~24h,碱液组成为:质量分数为40%的NaOH水溶液、异丙醇、丙二醇按体积比4:1~3:1配成混合溶液;然后用蒸馏水洗涤2~3次。
6.根据权利要求1-4任一项所述的具有互穿网络结构的网状聚氨酯微生物载体的制备方法,其特征在于,所述爆炸法是将制备的聚氨酯软泡放入处理反应器中,先抽真空,后冲入一定压力的爆炸性气体,扩散一段时间后点火引爆,得到网化处理的聚氨酯软泡。
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