CN104231213B - 一种低成本高吸油功能材料的制备 - Google Patents
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Abstract
本发明公开了一种吸油材料，该吸油材料以农林作物废弃物、聚醚多元醇、二异氰酸酯、复合催化剂、泡沫稳定剂和发泡剂为原料，通过聚合反应制备得到；该吸油材料的密度为8～20Kg/m3，吸原油倍率为30～50倍。该吸油材料具有可生物降解、无毒、无污染、成本低、可现场发泡等优点。作为生态型吸油材料，可用于水面溢油的吸附，尤其适合江河湖海水面溢油应急处理；另外对于厨房吸油烟机、工厂含油废气回收装置等吸收或回收油类废弃物等场合均适用。
Description
技术领域
本发明属于吸油材料领域，具体涉及一种低成本发明的吸油材料以及这种材料的制备方法。
背景技术
随着世界工业的不断发展，油污排放日益增加，油品泄漏的途径和机会也越来越多，特别是海上航运造成的大规模泄漏油事故。如2010年4月20日，英国石油公司在美国墨西哥湾租用的钻井平台“深去离子水地平线”发生爆炸，导致大量石油泄漏，酿成一场经济和环境惨剧；2010年7月16日，大连石油管线爆炸致1500吨原油泄漏入海。海洋油污染已经严重威胁到近海的生态环境，治理近海水环境的油污染已是刻不容缓。但是海洋油污治理还缺乏行之有效的方法，主要依靠减少污染机会，对污染源的含油废水进行预处理，控制油污排海总量等。吸油材料正是在这种情况下引起广人们的高度重视。如申请号为CN201110415527.7的发明专利公开了一种将经剪裁聚氨酯泡沫加入到溶有引发剂的甲苯溶液中，在氮气保护下搅拌升温，活化，再加入的疏水性丙烯酸酯单体和交联剂，反应结束后产物用乙醇和水洗涤下烘干，得到改性的疏水亲油聚氨酯高吸油功能材料。该方法工艺复杂，成本较高，吸油材料不具有降解性能，后期处理会产生污染。
发明内容
本发明的目的是为了克服现有吸油材料不具有可生物降解性、污染环境、成本高等问题，提供一种具有可生物降解、无毒、无污染、成本低、可现场发泡等优点的吸油材料。
本发明的目的可以通过以下措施达到：
一种吸油材料，该吸油材料为高分子泡沫吸油材料，该吸油材料以农林作物废弃物、聚醚多元醇、二异氰酸酯、复合催化剂、泡沫稳定剂和发泡剂为原料，通过聚合反应制备得到；该吸油材料的密度为8～20Kg/m3，吸原油倍率为30～50倍。
吸油材料各原料的质量份用量为：羟值为30~100mgKOH/g的聚醚多元醇100份，亲油助剂10-50份，二异氰酸酯20～80份，农林作物废弃物20~60份，复合催化剂0.3～2.0份，泡沫稳定剂0.4～2.5份，发泡剂4～12份。。
本发明中的亲油助剂为蓖麻油、大豆油或棕榈油中一种；二异氰酸酯为甲苯二异氰酸酯，其中异氰酸酯的指数为0.65~1.15。
本发明中的农林作物废弃物为木屑、甘蔗渣、玉米秸秆或小麦秸秆中一种。农林作物废弃物经预处理成粉末后再使用，预处理方法包括以下步骤：首先将农林作物废弃物除杂，置于浓度为5%NaOH溶液中，在20-30℃下处理5-6小时，脱液后用自来水洗涤至中性，干燥，粉碎成粒径小于150μm的粉末。
本发明中的复合催化剂为二月桂酸二丁基锡、辛酸亚锡中一种及三乙烯二胺、四乙烯三胺中一种；泡沫稳定剂为有机硅表面活性剂；发泡剂为去离子水。
本发明进一步公开了上述吸油材料的制备方法包括以下步骤：将聚醚多元醇、亲油助剂、农林作物废弃物粉末、复合催化剂、泡沫稳定剂和发泡剂，按照一定比例搅拌均匀，静置5~40分钟；加入多异氰酸酯，在1000r/min转速下高速搅拌，当混合物发白时迅速倒入模具成型，在20℃~30℃下熟化2~8小时脱模得到吸油材料，该吸油材料的密度为8～20Kg/m3，吸原油倍率为30～50倍。
其中吸油倍率测试方法如下：
将无纺空布袋浸入原油中一定时间后，取出滴淌5min后称重m1，再将m0吸油材料装入布袋并浸入待测油品中，当吸油材料达饱和吸油状态取出滴淌后称重m2。
吸油倍率(g油/g吸油材料)=（m2-m1-m0）/m0
式中：m0—吸油前吸油材料质量，g;
m1—吸油后空袋质量，g;
m2—饱和吸油后吸油材料与空袋质量，g。
吸油材料的密度按照GB/T 6343-2009（泡沫塑料及橡胶 表观密度的测定）进行测定。
本发明的有益效果：
1、本发明的吸油材料吸油倍率高，吸原油倍率为30～50倍，远超过国内外市场现有的吸原油倍率低于10倍的吸油材料。
2、本发明的吸油材料采用农林作物废弃物作原料，成本低廉，具有很好的应用价值和推广前景。
3、与现有一般的吸油材料相比，本发明的吸油材料具有良好的可生物降解性和环境友善性。
4、本发明的吸油材料可在溢油现场发泡成型，运输方便，与现有吸油材料相比，可以大大减少存储和运输空间。
5、本发明的吸油材料成型工艺简单，投资少，生产效率高，尤其适合江河湖海水面溢油应急处理；另外对于厨房吸油烟机、工厂含油废气回收装置等吸收或回收油类废弃物等场合均适用。
附图说明
图1是实施例1和对比例1的吸油材料重量损失率图。
具体实施方式
以下结合实施例对本发明做进一步说明，但下述内容并不是对本发明的限制。
实施例
1
首先将木屑除杂，置于浓度为5%NaOH溶液中，在20-30℃下处理5-6小时，脱液后用自来水洗涤至中性，干燥，粉碎成粒径小于150μm的粉末。然后在装有搅拌器的反应器中，加入上述的木粉35g，羟值为50mgKOH/g的聚醚多元醇100g，蓖麻油32g，辛酸亚锡0.28 g，三乙烯二胺0.55 g，有机硅表面活性剂1.6g，去离子水8 g，在室温下搅拌均匀，静置25分钟；迅速加入甲苯二异氰酸酯90g，搅拌8s，立即倒入发泡模具进行发泡；泡沫在室温下熟化2小时脱模，得到吸油材料。其性能如下：密度为13Kg/m3，吸原油倍率为47倍。
实施例
2
首先将甘蔗渣除杂，置于浓度为5%NaOH溶液中，在20-30℃下处理5-6小时，脱液后用自来水洗涤至中性，干燥，粉碎成粒径小于150μm的粉末。然后在装有搅拌器的反应器中，加入上述的甘蔗渣20g，羟值为30mgKOH/g的聚醚多元醇100g，大豆油48g，二月桂酸二丁基锡0.38 g，四乙烯三胺0.53 g，有机硅表面活性剂0.88g，去离子水6 g，在室温下搅拌均匀，静置10分钟；迅速加入甲苯二异氰酸酯78 g，搅拌8s，立即倒入发泡模具进行发泡；泡沫在室温下熟化2小时脱模，得到吸油材料。其性能如下：密度为18Kg/m3，吸原油倍率为36倍。
实施例
3
首先将玉米秸秆除杂，置于浓度为5%NaOH溶液中，在20-30℃下处理5-6小时，脱液后用自来水洗涤至中性，干燥，粉碎成粒径小于150μm的粉末。然后在装有搅拌器的反应器中，加入上述的玉米秸秆粉80g，羟值为100mgKOH/g的聚醚多元醇100g，棕榈油20g，二月桂酸二丁基锡0.38 g，三乙烯二胺0.52 g，有机硅表面活性剂0.56g，去离子水5 g，在室温下搅拌均匀，静置25分钟；迅速加入甲苯二异氰酸酯56 g，搅拌8s，立即倒入发泡模具进行发泡；泡沫在室温下熟化2小时脱模，得到吸油材料。其性能如下：密度为20Kg/m3，吸原油倍率为31倍。
实施例
4
首先将小麦秸秆除杂，置于浓度为5%NaOH溶液中，在20-30℃下处理5-6小时，脱液后用自来水洗涤至中性，干燥，粉碎成粒径小于150μm的粉末。然后在装有搅拌器的反应器中，加入上述的小麦秸秆粉20g，羟值为50mgKOH/g的聚醚多元醇100g，蓖麻油34g，辛酸亚锡0.18 g，三乙烯二胺0.52g，有机硅表面活性剂1.5g，去离子水7 g，在室温下搅拌均匀，静置25分钟；迅速加入甲苯二异氰酸酯81 g，搅拌8s，立即倒入发泡模具进行发泡；泡沫在室温下熟化2小时脱模，得到吸油材料。其性能如下：密度为16Kg/m3，吸原油倍率为39倍。
对比例
1
在装有搅拌器的反应器中，加入羟值为50mgKOH/g的聚醚多元醇100g，辛酸亚锡0.28 g，三乙烯二胺0.55 g，有机硅表面活性剂1.6g，去离子水8 g，在室温下搅拌均匀，静置25分钟；迅速加入甲苯二异氰酸酯90g，搅拌8s，立即倒入发泡模具进行发泡；泡沫在室温下熟化2小时脱模，得到吸油材料。其性能如下：密度为10Kg/m3，吸原油倍率为21倍。
效果例
1
将实施例1、对比例1合成的吸油材料准确称取1g左右的样品，放入50ml含有15mg淀粉酶的缓冲溶液中（缓冲溶液的制备：0.025mole Na2HPO4+0.025mole
kH2PO4以去离子水溶解、稀释至1L，控制PH=7），于27℃的恒温水槽中分别静置18, 36, 72, 120h后取出，以去离子水反复冲洗数次，再将薄膜在真空烘箱中烘干至恒重，计算其重量损失率，重量损失率（%）=（样品原重-分解后样品重）/样品原重×100。结果如图1所示。结果表明，在静置降解120h后，实施例1得到的吸油材料重量损失率高达30.54%以上，而对比例1得到的吸油材料在静置降解120h后，重量损失率仅为4.32%左右。说明本发明淀粉接枝水性生物降解效果明显得到提高。
Claims (6)
1.一种低成本高吸油功能材料，其特征在于：该吸油材料以农林作物废弃物、聚醚多元醇、亲油助剂、二异氰酸酯、复合催化剂、泡沫稳定剂和发泡剂为原料，通过聚合反应制备得到；该吸油材料各原料的质量份用量为：羟值为30~100mgKOH/g的聚醚多元醇100份，亲油助剂10-50份，二异氰酸酯20～80份，农林作物废弃物20~60份，复合催化剂0.3～2.0份，泡沫稳定剂0.4～2.5份，发泡剂4～12份；亲油助剂为蓖麻油、大豆油或棕榈油中一种；该吸油材料的密度为8～20kg/m3，吸原油倍率为30～50倍。
2.根据权利要求1所述的一种低成本高吸油功能材料，其特征在于所述的二异氰酸酯为甲苯二异氰酸酯，其中异氰酸酯的指数为0.65~1.15。
3.根据权利要求1所述的一种低成本高吸油功能材料，其特征在于所述的农林作物废弃物为木屑、甘蔗渣、玉米秸秆或小麦秸秆中一种。
4.根据权利要求1所述的一种低成本高吸油功能材料，其特征在于所述的复合催化剂为二月桂酸二丁基锡、辛酸亚锡中一种及三乙烯二胺、四乙烯三胺中一种；所述的泡沫稳定剂为有机硅表面活性剂；所述的发泡剂为去离子水。
5.根据权利要求3所述的一种低成本高吸油功能材料，其特征在于农林作物废弃物需进行预处理，该预处理方法包括以下步骤：首先将农林作物废弃物除杂，置于浓度为5%NaOH溶液中，在20-30℃下处理5-6小时，脱液后用自来水洗涤至中性，干燥，粉碎成粒径小于150μm的粉末。
6.权利要求1所述的一种低成本高吸油功能材料，其特征在于按以下步骤进行制备：将聚醚多元醇、亲油助剂、农林作物废弃物粉末、复合催化剂、泡沫稳定剂和发泡剂，按照一定比例搅拌均匀，静置10~40分钟；加入多异氰酸酯，在1000r/min转速下高速搅拌，当混合物发白时迅速倒入模具成型，在20℃~30℃下熟化2~8小时脱模得到吸油材料。
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