CN110124642B - 一种用于油污处理的吸蓄油颗粒及其制备方法 - Google Patents
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Abstract
本发明涉及一种用于油污处理的吸蓄油颗粒及其制备方法,包括芯材颗粒、包裹于芯材颗粒表面的疏水亲油膜及疏水亲油膜表面的微‑纳二级粗糙结构;疏水亲油膜由疏水型树脂及相应的固化剂在颗粒芯材表面交联固化制得;微‑纳二级粗糙结构是在疏水型树脂未固化前,先后加入微米级憎水材料和纳米级憎水材料制得。与现有技术相比,本发明解决了目前吸油棉等吸油材料吸油率低、机械强度不高、耐久性差等问题,具有超亲油、高蓄油和耐久性好等特性,且其制备工艺简单、应用技术便捷,具有非常广阔的应用前景。
Description
技术领域
本发明涉及环境工程技术领域,尤其是涉及一种用于油污处理的吸蓄油颗粒及其制备方法。
背景技术
作为重要的战略资源,石油对国家的经济发展起着极其重要的作用。然而,在石油的开采及运输过程中,会不可避免地造成石油泄漏,造成水域污染,对人类及海洋生态环境造成极其重大的威胁。因此,如何高效地实现水域油污治理已成为非常重要的时代课题。
目前,水域油污治理的方法主要有分散法、凝固法和吸附法。其中,分散法多采用分散剂,将油污分散,渗入到水中,使油污生物降解。但分散剂化油效率较低,且毒性较大,不适用于清理大面积油污。凝固法通常采用凝固剂,增强油相粘度,使其快速凝结,油污沿垂直方向沉入水底,达到净化水面油污的目的。但其生产成本高、工艺复杂,且会危及海洋生物的生存环境,限制了其在油污治理方面的应用。吸附法即采用吸油材料,将油污吸附于其表面,实现油污清理。吸油棉是应用较广的吸油材料,但其吸油量较低且机械强度不高、在回收过程中很容易破损,造成水域的二次污染。
专利CN107856378A公开了一种防静电吸油棉,该吸油棉主要由芯棉、隔离层和吸附层组成,其中,吸附层是一种纳米级复合材料,其间含有亲水性聚合物链段和亲油性聚合物链段规则排列所组成的纳米级空间,可以将油污包裹于其中。但该吸油棉亲油的同时,也会吸水,使得其油水分离效果变差,油污清理不完全。同时,该吸油棉的吸油率较低,机械强度较差,回收时易碎裂,进而造成二次污染。因此,亟需开发一种新型超亲油、高蓄油的吸蓄油颗粒。
发明内容
本发明的目的就是为了克服上述现有技术中吸油材料吸油效果不佳、机械强度低、长效性差等问题而提供一种具有超亲油、高蓄油和耐久性好等特性,且其制备工艺简单、应用技术便捷,具有非常广阔的应用前景的用于油污处理的吸蓄油颗粒及其制备方法。
本发明的目的可以通过以下技术方案来实现:
一种用于油污处理的吸蓄油颗粒,包括芯材颗粒、包裹于芯材颗粒表面的疏水亲油膜及疏水亲油膜表面的微-纳二级粗糙结构。
优选地,所述的芯材颗粒为大比表面积轻质材料,选自粉煤灰、玻化微珠、尾矿粉中的一种或几种,粒径为70-150um。
优选地,所述的疏水亲油膜由疏水型树脂及相应的固化剂在颗粒芯材表面交联固化制得。
优选地:
所述的疏水型树脂选自甲基硅树脂、环氧改性有机硅树脂、石油树脂、酚醛树脂、氟硅树脂和氟碳树脂中的一种或几种;
所述固化剂选自己二胺、二乙烯三胺、三乙烯四胺、六次甲基四胺和异氰酸酯中的一种或几种。
进一步优选地,所述疏水型树脂采用甲基硅树脂、环氧改性有机硅树脂或石油树脂时,所述固化剂采用己二胺、二乙烯三胺或三乙烯四胺中的一种;
所述疏水型树脂采用酚醛树脂时,所述固化剂采用六次甲基四胺;
所述疏水型树脂采用氟硅树脂或氟碳树脂时,所述固化剂采用异氰酸酯。
优选地,所述的微-纳二级粗糙结构是在疏水型树脂未固化前,先后加入微米级憎水材料和纳米级憎水材料制得。
优选地:
所述的微米级憎水材料选自聚四氟乙烯微粉和硅烷粉末憎水剂中的至少一种,粒径为5-70um;
所述的纳米级憎水材料选自纳米SiO2、ZnO2和TiO2中的一种或几种,粒径为5-80nm。
优选地,该吸蓄油颗粒包括以下重量份含量的组分:颗粒芯材80-82份、疏水型树脂10-12份、固化剂3-4份、微米级憎水材料4-5份和纳米级憎水材料0.5-1份。
本发明还提供一种用于油污处理的吸蓄油颗粒的制备方法,包括以下步骤:
(1)将颗粒芯材加热,烘干其表面水分后,静置、冷却;
(2)待颗粒芯材冷却,加入搅拌锅中,并加入疏水型树脂和固化剂搅拌均匀;
(3)在树脂未固化前,再依次加入微米级憎水材料和纳米级憎水材料,搅拌均匀,即制得所述的用于油污处理的吸蓄油颗粒。
优选地:
步骤(1)中,烘干的温度为150-200℃;
步骤(2)中,将颗粒芯材冷却至50-70℃时,加入搅拌锅中。
本发明所用覆膜材料(疏水型树脂及固化剂)的表面能低于水,但高于一般油类。覆膜材料在颗粒芯材表面包覆,形成疏水亲油膜,同时提高了颗粒芯材的机械强度。
其中,其中,r为表面粗糙度因子,θw为粗糙表面的表观接触角。
增加材料的表观粗糙度,会使原来疏水(油)的表面更加疏水(油);亲水(油)的表面更加亲水(油)。基于此,本发明在疏水亲油膜表面构建微-纳二级粗糙结构,增强吸蓄油颗粒的疏水亲油性,同时,通过树脂的粘结及固化作用,将微米级憎水材料和纳米级憎水材料构建的粗糙结构牢牢黏附在颗粒芯材表面,有效提升该吸蓄油颗粒疏水亲油功能的耐久性。浸水时,超疏水特性吸蓄油颗粒会自发团聚,颗粒间形成间隙空腔。其巨大的比表面积及具有毛细作用的间隙空腔能够吸蓄并存储大量油污,捞除水面吸载油颗粒即可快捷清除油污。回收吸载油污的颗粒经固油分离处理后还可重用。
与现有技术相比,本发明具有以下优点:该吸蓄油颗粒解决了传统吸油棉面临的吸油率低、机械强度差等问题,具有超亲油、高蓄油和耐久性好等特性,且其制备工艺简单、应用技术便捷,具有非常广阔的应用前景。
附图说明
图1为Wenzel模型。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
将80份粉煤灰加热至200℃,烘干其表面水分,静置;待其冷却至70℃时,加入搅拌锅中,并加入12份氟硅树脂和3.5份异氰酸酯固化剂搅拌均匀;然后依次加入4份粒径为10-50um的聚四氟乙烯微粉和0.5份粒径为10-70nm的纳米SiO2,搅拌均匀,制得吸蓄油颗粒。
实施例2
将81份玻化微珠加热至180℃,烘干其表面的水分后,静置;待其冷却至60℃时,将其加入搅拌锅中,并加入11份环氧改性有机硅树脂和3份己二胺搅拌均匀;然后依次加入4.5份粒径为5-70um的聚硅烷粉末憎水剂和0.5份粒径为5-80nm的纳米TiO2,搅拌均匀,制得吸蓄油颗粒。
实施例3
将82份尾矿粉加热至170℃,烘干其表面的水分后,静置;待其冷却至50℃时,将其加入搅拌锅中,并加入10份甲基硅树脂和3份三乙烯四胺搅拌均匀;然后依次加入4.5份粒径为10-50um的聚四氟乙烯微粉和0.5份粒径为10-80nm的纳米ZnO2,搅拌均匀,制得吸蓄油颗粒。
对实施例1、2和3制得的吸蓄油颗粒进行油滴在其表面的接触角测试,并测定其对机油的吸油率,结果见表1。
表1吸蓄油颗粒性能测试
由表1可知,本发明所制备的吸蓄油颗粒超亲油和高蓄油性能优异,吸油率高,蓄油量大。
为检测产品的耐久性,将实施例1、2和3制得的吸蓄油颗粒于自然条件下放置6个月后,测定其对机油的吸油率,结果如表2所示。
表2吸蓄油颗粒耐久性测试(6个月后)
由表2可知,本发明所制备的吸蓄油颗粒6个月后的超亲油和高蓄油性能依然优异,具有良好的耐久性能。
实施例4
本实施例与实施例1基本相同,不同之处在于,本实施例中,疏水型树脂选择酚醛树脂,固化剂选择六次甲基四胺。
实施例5本实施例与实施例1基本相同,不同之处在于,本实施例中,颗粒芯材80份、疏水型树脂10份、固化剂4份、微米级憎水材料5份和纳米级憎水材料1份。
实施例6
本实施例与实施例1基本相同,不同之处在于,本实施例中,颗粒芯材81份、疏水型树脂10.5份、固化剂3.2份、微米级憎水材料4.5份和纳米级憎水材料0.8份。
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (3)
1.一种用于油污处理的吸蓄油颗粒,其特征在于,包括芯材颗粒、包裹于芯材颗粒表面的疏水亲油膜及疏水亲油膜表面的微-纳二级粗糙结构;
所述的疏水亲油膜由疏水型树脂及相应的固化剂在颗粒芯材表面交联固化制得;
所述的微-纳二级粗糙结构是在疏水型树脂未固化前,先后加入微米级憎水材料和纳米级憎水材料制得;
该吸蓄油颗粒包括以下重量份含量的组分:颗粒芯材80-82份、疏水型树脂10-12份、固化剂3-4份、微米级憎水材料4-5份和纳米级憎水材料0.5-1份;
所述的芯材颗粒为大比表面积轻质材料,选自粉煤灰、玻化微珠、尾矿粉中的一种或几种,粒径为70-150um;
所述的疏水型树脂选自甲基硅树脂、环氧改性有机硅树脂、石油树脂、酚醛树脂、氟硅树脂和氟碳树脂中的一种或几种;
所述固化剂选自己二胺、二乙烯三胺、三乙烯四胺、六次甲基四胺和异氰酸酯中的一种或几种;
所述的微米级憎水材料选自聚四氟乙烯微粉和硅烷粉末憎水剂中的至少一种,粒径为5-70um;
所述的纳米级憎水材料选自纳米SiO2和TiO2中的一种或几种,粒径为5-80nm;
所述的吸蓄油颗粒对机油的接触角为0°。
2.如权利要求1所述的用于油污处理的吸蓄油颗粒的制备方法,其特征在于,包括以下步骤:
(1)将颗粒芯材加热,烘干其表面水分后,静置、冷却;
(2)待颗粒芯材冷却,加入搅拌锅中,并加入疏水型树脂和固化剂搅拌均匀;
(3)在树脂未固化前,再依次加入微米级憎水材料和纳米级憎水材料,搅拌均匀,即制得所述的用于油污处理的吸蓄油颗粒。
3.如权利要求2所述的用于油污处理的吸蓄油颗粒的制备方法,其特征在于:
步骤(1)中,烘干的温度为150-200℃;
步骤(2)中,将颗粒芯材冷却至50-70℃时,加入搅拌锅中。
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