CN108484861A - 亲水膨胀性聚氨酯网状生物填料及其制备方法 - Google Patents
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Abstract
本发明属于环保技术领域,涉及一种聚氨酯填料制备方法,特别涉及一种亲水膨胀性聚氨酯网状生物填料及其制备方法。一种亲水膨胀性聚氨酯网状生物填料,该生物填料主要是由以下以重量份计的主料、催化剂、发泡剂和稳定剂制成:聚醚多元醇 100份,异氰酸酯 0.8~1.2份,聚合物多元醇 30~50份,三乙醇胺 2~6份,二羟甲基丁酸 1~3份,催化剂 1.5~4.5份,发泡剂3~7份,稳定剂 0.5~4份。本发明所述的亲水膨胀性聚氨酯网状生物填料应用于污水处理中。该生物填料具有储存运输体积小、无需真空抽气压缩包装、亲水膨胀速度快、膨胀倍率达2~3倍、硬度大抗磨性能强和生物挂膜效果好等特点。
Description
技术领域
本发明属于环保技术领域,涉及一种聚氨酯填料制备方法,特别涉及一种亲水膨胀性聚氨酯网状生物填料及其制备方法。
背景技术
近些年来,随着工业化和城镇化的快速发展,产生了诸多环境问题,特别是城市水体的污染问题更为突出,严重影响了城市水体景观,威胁着人们的身体健康。水体污染的治理首先应重视排放污水的处理。当前污水处理技术按照原理可分为物理处理法、化学处理法和生物处理法。其中,生物处理法就是利用微生物来降解代谢有机物,将它们转化为无机物,这个是目前应用最广泛、最有效的方法,包括活性污泥法、生物膜法等好氧处理和微生物厌氧处理法等。特别是,针对活性污泥法和生物膜法研究的比较多,技术比较成熟,但是这些方法也在不断地改革和创新,以处理不断变化的污水水质。
关于提高生物法处理污水效率的研究领域中,重点方向之一就是如何提高生物量。因此,近年来,生物膜法污水处理工艺研究得到了普遍重视,是污水处理中既经济又环保的方法,受到国内外学者的广泛关注,其在实际工程中的应用也十分广泛。生物膜法中一项关键的技术因素就是选择良好的填料,填料作为生物膜附着生长的载体,起到了关键的作用,填料性能很大程度上决定着此项技术的成败。
现有生物填料主要有固定式填料、悬挂式填料、悬浮填料和新型生物填料。这些生物填料主要以聚丙烯、聚乙烯、聚氯乙烯或聚酯等为原料制成,填料开发的侧重点在填料的比表面积、填料结构与布水、布气性能及生物膜更新等方面。CN201510367370公开了“一种改性聚氨酯悬浮填料、制备方法及其应用”,它的目的是提供一种改性聚氨酯悬浮填料的制备方法和采用该填料处理污水的方法。其不足之处是:在实际应用中聚氨酯填料由于孔隙为网状,内部结构多为五边形的十二面体,体积大,密度小。填料即使经抽气压缩处理后,体积减少了但长久储存后仍会漏气膨胀,储存运输过程中需要配备真空抽气处理装置,给储存和运输带来了许多不便。因此,如何制备一种储存运输体积小、无需真空抽气压缩包装、硬度大抗磨性能强、生物挂膜效果优的填料具有实际意义。
发明内容
本发明克服现有生物填料中存在的空间堆积体积大、储存运输不便、密度小亲水性差等不足,提供一种亲水膨胀性聚氨酯网状填料。
本发明还提供一种亲水膨胀性聚氨酯网状填料的制备方法。
本发明解决其技术问题所采用的技术方案是:
一种亲水膨胀性聚氨酯网状生物填料,该生物填料主要是由以下以重量份计的主料、催化剂、发泡剂和稳定剂制成:
本发明所述的亲水膨胀性聚氨酯网状生物填料应用于污水处理中。该生物填料具有储存运输体积小、无需真空抽气压缩包装、亲水膨胀速度快、膨胀倍率达2~3倍、硬度大抗磨性能强和生物挂膜效果好等特点。此外,根据不同重量份配比的原料可制得不同密度聚氨酯软泡。
作为优选,所述聚醚多元醇采用两官能度或三官能度,所述两官能度的聚醚多元醇的分子量是500~20000,含两个活泼氢起始剂的亲水型聚醚多元醇;所述三官能度的聚醚多元醇为分子量为2000~5000的聚氧化丙烯多元醇。
作为优选,所述异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或甲基环已基二异氰酸酯中的任一种。
作为优选,所述催化剂为三乙烯二胺,双(2,2-二甲胺基乙基)醚、辛酸亚锡和二月桂酸二丁基锡中的任两种或三种。
作为优选,所述发泡剂为水或二氯甲烷中的任一种或两种;所述稳定剂为硅油。
作为优选,该生物填料是由以下以重量份计的主料、催化剂、发泡剂和稳定剂制成(制得密度为20.0±1.0kg/m3聚氨酯软泡):
作为优选,该生物填料主要是由以下以重量份计的主料、催化剂、发泡剂和稳定剂制成(制得密度为18.0±1.0kg/m3聚氨酯软泡):
一种所述的亲水膨胀性聚氨酯网状生物填料的制备方法,该方法包括如下步骤:
步骤一:按配方量将所述主料、催化剂、发泡剂和稳定剂在真空度0.10~0.12MPa,温度为25±2℃的条件下进行转速为600~900rpm的分散搅拌2~4h,熟化制得聚氨酯软泡;
步骤二:将所述步骤一制得的聚氨酯软泡置于密封网化装置中在纯度为98.0~99.5%的氮气保护下充入氢气和氧气,氢气和氧气的体积比为(1~2):1,充气压力0.10~0.11MPa,经气相爆轰熔膜网化后制成网状聚氨酯填料;
步骤三:将所述步骤二制得的网状聚氨酯填料在真空度不小于0.08~0.10MPa条件下,脱出水分子成型制得亲水膨胀性聚氨酯填料。
本发明的有益效果是:与现有生物填料相比,本发明所制得的亲水膨胀性聚氨酯生物填料具有以下优点:
(1)立体网状结构,填料孔径范围10~30PPI;
(2)应用于污水生物膜法处理中,填料内外层形成好氧-兼氧-厌氧环境,生物挂膜效果优,生物量可达(25.0~27.0)g/L;
(3)空间堆积体积小,无需真空抽气压缩包装,储存运输方便,不存在漏气膨胀问题;
(4)亲水性填料,亲水膨胀倍数达(2~3)倍,密度选择范围大(17.0~21.0kg/m3),更易处于水中悬浮状态和生物附着生长;
(5)填料硬度大(70±5°),污水处理曝气冲刷中抗磨性能强,减少后期生物填料的补充量。
具体实施方式
下面通过具体实施例,对本发明的技术方案作进一步的具体说明。应当理解,本发明的实施并不局限于下面的实施例,对本发明所做的任何形式上的变通和/或改变都将落入本发明保护范围。
在本发明中,若非特指,所有的份、百分比均为重量单位,所采用的设备和原料等均可从市场购得或是本领域常用的。下述实施例中的方法,如无特别说明,均为本领域的常规方法。
以下实施例用到的原料来源:
聚醚多元醇,TMN3050,天津石化三厂;
甲苯二异氰酸酯,工业品,沧州大化化工;
聚合物多元醇,BH-H30,济南海源化工;
异丙醇,AR,天津富宇化工;
三乙醇胺,TEA,广州银霖化工;
二羟甲基丁酸,012,山东嘉颖化工;
三乙烯二胺,AR,北京化学试剂公司;
辛酸亚锡,AR,国药集团化学试剂公司;
二月桂酸二丁基锡,化学纯,上海表析化工;
二氯甲烷,苏州纳川化工;
有机硅表面活性剂,9905,南京德美世创化工;
硅油,KF-202,东莞科丰化工。
实施例1
一种亲水膨胀性聚氨酯网状生物填料的制备方法,该方法的具体步骤为:
步骤一:聚氨酯软泡的制得。将分子量是5000的两官能度的亲水型聚醚多元醇650g、二苯基甲烷二异氰酸酯7.6g、聚合物多元醇260g、三乙醇胺32.5g、二羟甲基丁酸13g、三乙烯二胺11g、双(2,2-二甲胺基乙基)醚5g、辛酸亚锡4.5g、水45.5g、二氯甲烷19.5g和硅油18.2g加入到反应器中,在真空度为0.10MPa,温度为26℃的条件下进行转速800rpm的分散搅拌3.5h,得到制备亲水膨胀性生物性填料的聚氨酯软泡;
步聚二:网状聚氨酯填料的制得。将所得到的聚氨酯软泡1000g置于密封网化装置中用纯度为99.0%的高纯氮气保护下充入氢气和氧气,氢气和氧气的体积比为1:1,充气压力0.10MPa,经气相爆轰熔膜网化后得到制备亲水膨胀性生物填料的网状聚氨酯填料;
步聚三:亲水膨胀性网状聚氨酯填料的制备。将所得到的网状聚氨酯填料在真空度为0.10MPa条件下,脱出水分子成型制备成亲水膨胀性网状聚氨酯填料。
通过实验测得,该条件下制得的亲水膨胀性网状聚氨酯填料密度为20.5kg/m3,硬度达72°,应用于污水生物处理中膨胀倍数达2.2倍,生物量可达25.2g/L。
实施例2
一种亲水膨胀性聚氨酯网状生物填料的制备方法,该方法的具体步骤为:
步骤一:聚氨酯软泡的制得。将分子量是12000的两官能度的亲水型聚醚多元醇650g、甲苯二异氰酸酯7.4g、聚合物多元醇227.5g、三乙醇胺39g、二羟甲基丁酸19.5g、三乙烯二胺6.5g、辛酸亚锡10.4g、水29.2g、二氯甲烷26g和硅油8.45g加入到反应器中,在真空度为0.12MPa,温度为27℃的条件下进行转速700rpm的分散搅拌3.0h,得到制备亲水膨胀性生物填料的聚氨酯软泡;
步聚二:网状聚氨酯填料的制得。将所得到的聚氨酯软泡1000g置于密封网化装置中用纯度为99.5%的高纯氮气保护下充入氢气和氧气,氢气和氧气的体积比为1.2:1,充气压力0.10MPa,经气相爆轰熔膜网化后得到制备亲水膨胀性生物填料的网状聚氨酯填料;
步聚三:亲水膨胀性网状聚氨酯填料的制备。将所得到的网状聚氨酯填料在真空度为0.08MPa条件下,脱出水分子成型制备成亲水膨胀性网状聚氨酯填料。
通过实验测得,该条件下制得的亲水膨胀性网状聚氨酯填料密度为18.5kg/m3,硬度达68°,应用于污水生物处理中膨胀倍数达2.7倍,生物量可达26.3g/L。
实施例3
一种亲水膨胀性聚氨酯网状生物填料的制备方法,该方法的具体步骤为:
步骤一:聚氨酯软泡的制得。将分子量是3000的三官能度的亲水型聚氧化丙烯多元醇650g、甲基环已基二异氰酸酯6.5g、聚合物多元醇292.5g、异丙醇15g、三乙醇胺32.5g、二羟甲基丁酸16.3g、三乙烯二胺13.0g、辛酸亚锡11.4g、二月桂酸二丁基锡5.4g、有机硅表面活性剂24g、水23.3g、二氯甲烷27.3g和硅油9.43g加入到反应器中,在真空度为0.11MPa,温度为23℃的条件下进行转速750rpm的分散搅拌2.5h,得到制备亲水膨胀性生物填料的聚氨酯软泡;
步聚二:网状聚氨酯填料的制得。将所得到的聚氨酯软泡1000g置于密封网化装置中用纯度为98.0%的高纯氮气保护下充入氢气和氧气,氢气和氧气的体积比为1.6:1,充气压力0.11MPa,经气相爆轰熔膜网化后得到制备亲水膨胀性生物填料的网状聚氨酯填料;
步聚三:亲水膨胀性网状聚氨酯填料的制备。将所得到的网状聚氨酯填料在真空度为0.09MPa条件下,脱出水分子成型制备成亲水膨胀性网状聚氨酯填料。
通过实验测得,该条件下制得的亲水膨胀性网状聚氨酯填料密度为18.9kg/m3,硬度达69°,应用于污水生物处理中膨胀倍数达2.8倍,生物量可达26.5g/L。
最后应说明的是:以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明实施例技术方案的范围。
Claims (8)
1.一种亲水膨胀性聚氨酯网状生物填料,其特征在于该生物填料主要是由以下以重量份计的主料、催化剂、发泡剂和稳定剂制成:
2.根据权利要求1所述的亲水膨胀性聚氨酯网状生物填料,其特征在于:所述聚醚多元醇采用两官能度或三官能度,所述两官能度的聚醚多元醇的分子量是500~20000,含两个活泼氢起始剂的亲水型聚醚多元醇;所述三官能度的聚醚多元醇为分子量为2000~5000的聚氧化丙烯多元醇。
3.根据权利要求1所述的亲水膨胀性聚氨酯网状生物填料,其特征在于:所述异氰酸酯为二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或甲基环已基二异氰酸酯中的任一种。
4.根据权利要求1所述的亲水膨胀性聚氨酯网状生物填料,其特征在于:所述催化剂为三乙烯二胺,双(2,2-二甲胺基乙基)醚、辛酸亚锡和二月桂酸二丁基锡中的任两种或三种。
5.根据权利要求1所述的亲水膨胀性聚氨酯网状生物填料,其特征在于:所述发泡剂为水或二氯甲烷中的任一种或两种;所述稳定剂为硅油。
6.根据权利要求1所述的亲水膨胀性聚氨酯网状生物填料,其特征在于:该生物填料是由以下以重量份计的主料、催化剂、发泡剂和稳定剂制成:
7.根据权利要求1所述的亲水膨胀性聚氨酯网状生物填料,其特征在于:该生物填料主要是由以下以重量份计的主料、催化剂、发泡剂和稳定剂制成:
8.一种权利要求1所述的亲水膨胀性聚氨酯网状生物填料的制备方法,其特征在于该方法包括如下步骤:
步骤一:按配方量将所述主料、催化剂、发泡剂和稳定剂在真空度0.10~0.12MPa,温度为25±2℃的条件下进行转速为600~900rpm的分散搅拌2~4h,熟化制得聚氨酯软泡;
步骤二:将所述步骤一制得的聚氨酯软泡置于密封网化装置中在纯度为98.0~99.5%的氮气保护下充入氢气和氧气,氢气和氧气的体积比为(1~2):1,充气压力0.10~0.11MPa,经气相爆轰熔膜网化后制成网状聚氨酯填料;
步骤三:将所述步骤二制得的网状聚氨酯填料在真空度不小于0.08~0.10MPa条件下,脱出水分子成型制得亲水膨胀性聚氨酯填料。
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