CN107952416B - 一种吸附重金属的贝壳粉壳聚糖复合微球及其制备方法 - Google Patents
一种吸附重金属的贝壳粉壳聚糖复合微球及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种吸附重金属的贝壳粉壳聚糖复合微球及其制备方法,复合微球中壳聚糖粉末和贝壳粉的重量比为1:0.3‑0.45。其制备方法为:将贝壳用酸浸泡,洗净,烘干,煅烧,研磨得粗贝壳粉;粉碎得纳米贝壳粉;将壳聚糖粉末和贝壳粉液滴成型,交联改性,清洗干净,烘干得复合微球;将复合微球加入到含硫脲及环氧氯丙烷溶液中,反应得复合微球产品。本发明复合微球综合了贝壳粉和壳聚糖的优势,贝壳粉的加入不仅增加壳聚糖载体的机械稳定性,而且可以提高载体与过渡金属的络合能力,可实现重金属的回收再利用;本发明制备方法制备的微球具有高单分散性,微球粒径大小、形貌、粒径和组分均可控,粒径均匀,机械强度高。
Description
技术领域
本发明涉及环保材料技术领域,尤其是涉及一种吸附重金属的贝壳粉壳聚糖复合微球及其制备方法。
背景技术
随着经济的发展,矿冶、机械制造、化工、电子、仪表等工业生产过程中产生的重金属废水(含有铬、镉、铜、汞、镍、锌等重金属离子)是对水体污染最严重和对人类危害最大的工业废水之一。废水中的重金属是各种常用水处理方法不能分解破坏的,而只能转移它们的存在位置和转变它们的物理化学状态。因此,重金属废水应当在产生地点就地处理,不同其他废水混合。如果用含有重金属离子的污泥和废水作为肥料和灌溉农田,会使土壤受污染,造成农作物中及进入水体后造成水生生物中重金属离子的富集,通过食物链对人体产生严重危害。20世纪60年代震惊世界的日本公害病-水俣病和痛痛病,就是分别由含汞废水和含镉废水污染水体造成的。处理重金属离子废水的技术目前有有化学沉淀法、电化学法、吸附法和膜分离法等;还有一些新的技术如纳米技术、光催化法、新型介孔材料和基因处理技术等。其中利用绿色环保、价格低廉的天然吸附剂治理废水中重金属污染近年来更是受到普遍关注。
随着人们对于贝类软体部分的开发,造成大量的废弃贝壳资源,这些贝壳被大量堆积起来,未能得到有效的利用,贝壳上残余的软体组织发生腐败变质从而产生一系列有毒有害的物质,从而对环境造成不可避免的伤害,将贝壳粉加以利用,有利于治理日益严重的环境污染问题。贝壳粉的主要成分为碳酸钙,含少量氧化钙、氢氧化钙等钙化物,其本身又为多孔纤维状双螺旋体结构,高强度,多孔性,贻贝贝壳微纳米骨架结构具有多孔性,尺寸可控制在100纳米到5微米之间,贝壳粉自身对重金属就具有良好的吸附效果。此外,微纳米尺寸通常显示比正常尺寸相同的材料有更高的反应活性和吸附能力,纳米技术已经逐渐应用于污水处理领域中。但是,对于纳米贝壳粉复合材料在污水处理方面的研究还很少。
壳聚糖是甲壳素部分脱乙酰后的产物,凭借其丰富的官能团组成、生物相容性、生物可降解性和无毒性,壳聚糖对许多物质具有螯合吸附作用,其分子中的氨基和与氨基相临的羟基与许多金属离子(如Hg2+、Ni2+、Cu2+、pb2+、CA2+、Ag+等)能形成稳定的螯合物,用于治理重金属废水、净化自来水及在湿法冶金中分离金属离子等。日本是最早利用壳聚糖治理废水的国家,每年用量达500吨;美国环保局也已批准将壳聚糖用于饮用水的纯化。此外,壳聚糖能通过络合及离子交换的作用,对染料、蛋白质、氨基酸、核酸、酶、卤素等进行吸附,用于染料废水、印染废水、食品工业废水的处理,从而净化环境,保护人类健康。然而,壳聚糖的比重和机械强度较低,并且对酸碱不稳定,这些不足之处限制了其应用的推广。为改善壳聚糖的使用性能,可将其固定在无机物上制备有机无机复合吸附剂。贝壳是一类有机无机复合的生物矿化材料,其组成中碳酸钙约占95%,其余5%是蛋白质和多糖等有机质,这种特殊结构使贝壳粉体天生具有较好的有机亲和性。利用贝壳粉自身在水中的沉水性能,吸附去除重金属的贝壳粉壳聚糖复合微纳米球通过沉淀过滤能够很好的从水中分离,回收。
发明内容
本发明的目的之一在于提供一种吸附重金属的贝壳粉壳聚糖复合微球,该复合微球具有较高的吸附容量和更快的吸附速率,吸附重金属的能力强,具有抗菌性,可重复利用性强,在经历6次吸附-脱附循环后依然表现出较强的吸附能力。
本发明的目的之一在于提供一种贝壳粉壳聚糖复合微球的制备方法,该制备方法结合液滴成型和交联改性,将壳聚糖固定在贝壳粉上,使得制备的微球具有高单分散性,微球粒径大小、形貌、粒径和组分均可控,粒径均匀,机械强度高。
本发明针对上述技术中提到的问题,采取的技术方案为:
一种吸附重金属的贝壳粉壳聚糖复合微球,复合微球中壳聚糖粉末和贝壳粉的重量比为1:0.3-0.45,复合微球的直径在为0.4-0.6mm。上述复合微球具有较高的吸附容量和更快的吸附速率,吸附重金属的能力强,伴随电子转移的化学整合在吸附过程中占据主导地位,用于吸附重金属后能够通过沉淀过滤能够很好的从水中分离、回收,可重复利用性强,在经历6次吸附-脱附循环后依然表现出较强的吸附能力,同时该复合微球具有一定的抗菌性,用于处理重金属废水时,不需要额外添加抗菌剂。
一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,包括粗贝壳粉制备、纳米贝壳粉制备、复合微球制备、复合微球改性,具体包括以下步骤:
粗贝壳粉制备:将贝壳清洗干净,用稀酸溶液浸泡4-5h,再用稀碱液中和洗涤,去除贝壳表面杂质,最后用清水洗净,烘干,再在900-1000℃下煅烧2-3h,冷却至室温,研磨后过150-200目筛,即得粗贝壳粉,该步骤使得贝壳粉体中碳酸钙转化为氧化钙,降低碳酸钙的含量,增加有机物的含量,并大大增加贝壳粉中活性官能团的含量,煅烧可使贝壳粉中的碳酸钙变为多孔纤维状双螺旋体结构,具有出色的吸附性,有利于吸附更多的壳聚糖,使得吸附重金属的效果更好,也具有抑菌,杀菌能力;
纳米贝壳粉制备:向粗贝壳粉中加入粗贝壳粉重量1.7-2.2%的粉碎分散剂,然后使用纳米粉碎机粉碎,即得纳米贝壳粉,粉碎分散剂为重量比为1:1.1-1.3:0.02-0.03的PEG2000、六偏磷酸钠和右旋糖酐的混合物,该粉碎分散剂各成分能够发挥协同作用,使贝壳粉的Zeta电位绝对值增大,颗粒之间不易团聚,很容易扩散到贝壳粉粒子表面上,形成了牢固的包膜层,有效地降低粒子的表面活性,从而使外加的粉碎能量更集中于粒子的粉碎上,达到较为满意的粉碎分散状态,提高物料粉碎效率及其水分散性,纳米贝壳粉的粒径为20-100nm,该细度的纳米贝壳粉在制备复合微球时易于分散,能够增加和壳聚糖的接触面积,使得贝壳粉上能够固定更多的壳聚糖,进而提高复合微球吸附重金属的能力;
复合微球制备:将壳聚糖粉末和贝壳粉混合溶于1.8-2.2wt%乙酸水溶液中,配成含有3-5wt%的壳聚糖粉末和贝壳粉的混合溶液,作为分散相,将1.8-2.2wt%斯潘60加入到96-99wt%正辛烷溶液中,混合搅拌后用作连续相,液滴成型,然后在水浴固化液中进行交联改性,清洗干净,烘干,即得复合微球,贝壳粉的加入不仅增加壳聚糖载体的机械稳定性,而且可以提高载体与过渡金属的络合能力,改变贝壳粉以及交联剂的应用量,可实现对微球载体综合性能的调控;
复合微球改性:将8-10wt%复合微球加入到含1.8-2.2wt%硫脲及0.8-1.2wt%环氧氯丙烷的丙酮溶液中,在50-70℃下搅拌反应4-6h,清洗干净,干燥,即得复合微球产品,该步骤中以环氧氯丙烷为引发剂,取代交联后壳聚糖分子上的氨基的氯原子,形成中间产物,再将硫脲作为引发剂,其氨基的氨原子可取代中间产物上的氯原子,使得改性后的微球的氨基数量可达到未改性复合微球的三倍,使得复合微球具有较高的吸附容量和更快的吸附速率,大大提高复合微球吸附重金属的能力。
优选的,液滴成型为:用单通道注射泵将分散相通入微流控芯片通道内,使用双通道注射泵将连续相通入微流控芯片的连续相入口,使其在微流控芯片的十字通道内对分散相进行剪切,液滴剪切成球后随微流控芯片的出口引入到水浴固化液中。该步骤中分散相受到剪切力的作用及自身存在的表面张力而被剪断为一个个小液滴,所制备的微球具有高单分散性,粒径均匀。
优选的,水浴固化液采用0.4-0.6wt%戊二醛水溶液,1.8-2.2wt%斯潘60及正辛烷溶液混合配制而成。剪切好的小液滴进入水浴固化液后,戊二醛会从水浴固化液中从外而内的扩散到小液滴中,戊二醛作为交联剂,壳聚糖上的氨基会与戊二醛的醛基发生席夫碱反应,将壳聚糖分子的链状结构交联成三维网状结构,交联反应先发生在外表面,继而在内部发生,固化后,通过接收相中的正辛醇对微球进一步缩水,使得颗粒变得更加紧实,稳定,具有弹性。
与现有技术相比,本发明的优点在于:1)本发明复合微球综合了贝壳粉和壳聚糖的优势,贝壳粉的加入不仅增加壳聚糖载体的机械稳定性,而且可以提高载体与过渡金属的络合能力,可实现重金属的回收再利用;2)该复合微球具有较高的吸附容量和更快的吸附速率,吸附重金属的能力强,可重复利用性强,在经历6次吸附-脱附循环后依然表现出较强的吸附能力,同时具有抗菌性;3)本发明制备方法结合液滴成型和交联改性,使得制备的微球具有高单分散性,微球粒径大小、形貌、粒径和组分均可控,粒径均匀,机械强度高;4)该制备方法将壳聚糖固定在贝壳粉上,解决了壳聚糖物理化学性质不稳定、易溶于稀酸、机械强度不高、不易成型等问题,改善壳聚糖的使用性能。
具体实施方式
下面通过实施例对本发明方案作进一步说明:
实施例1:
一种吸附重金属的贝壳粉壳聚糖复合微球,复合微球中壳聚糖粉末和贝壳粉的重量比为1:0.3-0.45,复合微球的直径在为0.4-0.6mm。
一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,包括粗贝壳粉制备、纳米贝壳粉制备、复合微球制备、复合微球改性,具体包括以下步骤:
1)粗贝壳粉制备:将贝壳清洗干净,用稀酸溶液浸泡4-5h,再用稀碱液中和洗涤,去除贝壳表面杂质,最后用清水洗净,烘干,再在900-1000℃下煅烧2-3h,冷却至室温,研磨后过150-200目筛,即得粗贝壳粉;
2)纳米贝壳粉制备:向粗贝壳粉中加入粗贝壳粉重量1.7-2.2%的粉碎分散剂,然后使用纳米粉碎机粉碎,即得粒径为20-100nm的纳米贝壳粉,粉碎分散剂为重量比为1:1.1-1.3:0.02-0.03的PEG2000、六偏磷酸钠和右旋糖酐的混合物;
3)复合微球制备:将壳聚糖粉末和贝壳粉混合溶于1.8-2.2wt%乙酸水溶液中,配成含有3-5wt%的壳聚糖粉末和贝壳粉的混合溶液,作为分散相,将1.8-2.2wt%斯潘60加入到96-99wt%正辛烷溶液中,混合搅拌后用作连续相,液滴成型,然后在水浴固化液中进行交联改性,清洗干净,烘干,即得复合微球;
4)复合微球改性:将8-10wt%复合微球加入到含1.8-2.2wt%硫脲及0.8-1.2wt%环氧氯丙烷的丙酮溶液中,在50-70℃下搅拌反应4-6h,清洗干净,干燥,即得复合微球产品。
上述步骤3中液滴成型为:用单通道注射泵将分散相通入微流控芯片通道内,使用双通道注射泵将连续相通入微流控芯片的连续相入口,使其在微流控芯片的十字通道内对分散相进行剪切,液滴剪切成球后随微流控芯片的出口引入到水浴固化液中。
上述步骤3中水浴固化液采用0.4-0.6wt%戊二醛水溶液,1.8-2.2wt%斯潘60及正辛烷溶液混合配制而成。
实施例2:
一种吸附重金属的贝壳粉壳聚糖复合微球,复合微球中壳聚糖粉末和贝壳粉的重量比为1:0.45,复合微球的直径在为0.4-0.6mm。
一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,具体包括以下步骤:
1)粗贝壳粉制备:将贝壳清洗干净,用稀酸溶液浸泡5h,再用稀碱液中和洗涤,去除贝壳表面杂质,最后用清水洗净,烘干,再在900℃下煅烧3h,冷却至室温,研磨后过150目筛,即得粗贝壳粉;
2)纳米贝壳粉制备:向粗贝壳粉中加入粗贝壳粉重量2.2%的粉碎分散剂,然后使用纳米粉碎机粉碎,即得粒径为20-100nm的纳米贝壳粉,粉碎分散剂为重量比为1:1.3:0.02的PEG2000、六偏磷酸钠和右旋糖酐的混合物;
3)复合微球制备:将壳聚糖粉末和贝壳粉混合溶于2.1wt%乙酸水溶液中,配成含有5wt%的壳聚糖粉末和贝壳粉的混合溶液,作为分散相,将1.8wt%斯潘60加入到96wt%正辛烷溶液中,混合搅拌后用作连续相,液滴成型,然后在水浴固化液中进行交联改性,清洗干净,烘干,即得复合微球;
4)复合微球改性:将10wt%复合微球加入到含1.8wt%硫脲及1.2wt%环氧氯丙烷的丙酮溶液中,在50℃下搅拌反应6h,清洗干净,干燥,即得复合微球产品。
上述步骤3中液滴成型为:用单通道注射泵将分散相通入微流控芯片通道内,使用双通道注射泵将连续相通入微流控芯片的连续相入口,使其在微流控芯片的十字通道内对分散相进行剪切,液滴剪切成球后随微流控芯片的出口引入到水浴固化液中。
上述步骤3中水浴固化液采用0.4wt%戊二醛水溶液,2.2wt%斯潘60及正辛烷溶液混合配制而成。
实施例3:
一种吸附重金属的贝壳粉壳聚糖复合微球,复合微球中壳聚糖粉末和贝壳粉的重量比为1:0.38,复合微球的直径在为0.4-0.6mm。
一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,包括粗贝壳粉制备、纳米贝壳粉制备、复合微球制备、复合微球改性,具体包括以下步骤:
1)粗贝壳粉制备:将贝壳清洗干净,用稀酸溶液浸泡4.5h,再用稀碱液中和洗涤,去除贝壳表面杂质,最后用清水洗净,烘干,再在950℃下煅烧2.5h,冷却至室温,研磨后过180目筛,即得粗贝壳粉;
2)纳米贝壳粉制备:向粗贝壳粉中加入粗贝壳粉重量2.0%的粉碎分散剂,然后使用纳米粉碎机粉碎,即得粒径为20-100nm的纳米贝壳粉,粉碎分散剂为重量比为1:1.2:0.025的PEG2000、六偏磷酸钠和右旋糖酐的混合物;
3)复合微球制备:将壳聚糖粉末和贝壳粉混合溶于2.0wt%乙酸水溶液中,配成含有4wt%的壳聚糖粉末和贝壳粉的混合溶液,作为分散相,将2.0wt%斯潘60加入到98wt%正辛烷溶液中,混合搅拌后用作连续相,液滴成型,然后在水浴固化液中进行交联改性,清洗干净,烘干,即得复合微球;
4)复合微球改性:将9wt%复合微球加入到含2.0wt%硫脲及1.0wt%环氧氯丙烷的丙酮溶液中,在60℃下搅拌反应5h,清洗干净,干燥,即得复合微球产品。
上述步骤3中液滴成型为:用单通道注射泵将分散相通入微流控芯片通道内,使用双通道注射泵将连续相通入微流控芯片的连续相入口,使其在微流控芯片的十字通道内对分散相进行剪切,液滴剪切成球后随微流控芯片的出口引入到水浴固化液中。
上述步骤3中水浴固化液采用0.5wt%戊二醛水溶液,2.0wt%斯潘60及正辛烷溶液混合配制而成。
实施例4:
一种吸附重金属的贝壳粉壳聚糖复合微球,复合微球中壳聚糖粉末和贝壳粉的重量比为1:0.38,复合微球的直径在为0.4-0.6mm。
一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,包括粗贝壳粉制备、纳米贝壳粉制备、复合微球制备、复合微球改性,具体包括以下步骤:
1)粗贝壳粉制备:将贝壳清洗干净,用稀酸溶液浸泡4.5h,再用稀碱液中和洗涤,去除贝壳表面杂质,最后用清水洗净,烘干,再在950℃下煅烧2.5h,冷却至室温,研磨后过180目筛,即得粗贝壳粉;
2)纳米贝壳粉制备:按重量比为100:0.38-0.52向粗贝壳粉中加入酒石酸二乙酯,搅拌1-2h,搅拌3-5h,过滤干燥,然后向干燥粉末中加入粗贝壳粉重量2.0%的粉碎分散剂,然后使用纳米粉碎机粉碎,即得粒径为20-100nm的纳米贝壳粉,粉碎分散剂为重量比为1:1.2:0.025的PEG2000、六偏磷酸钠和右旋糖酐的混合物,上述酒石酸二乙酯中L-酒石酸二乙酯和D-酒石酸二乙酯的重量比为100:1.32-1.36,酒石酸二乙酯的加入可以与粗贝壳粉中的活性基团发生聚合反应,为贝壳粉提供更多的活性基团,同时可得到新的手性物质,大大提高贝壳粉识别真菌等细菌的能力,进而可快速灭杀废水中的细菌,而D-酒石酸二乙酯的加入提高反应的立体选择性,增加手性反应物的得率;
3)复合微球制备:将壳聚糖粉末和贝壳粉混合溶于2.0wt%乙酸水溶液中,配成含有4wt%的壳聚糖粉末和贝壳粉的混合溶液,作为分散相,将2.0wt%斯潘60加入到98wt%正辛烷溶液中,混合搅拌后用作连续相,液滴成型,然后在水浴固化液中进行交联改性,清洗干净,烘干,即得复合微球;
4)复合微球改性:将9wt%复合微球加入到含2.0wt%硫脲及1.0wt%环氧氯丙烷的丙酮溶液中,在60℃下搅拌反应5h,清洗干净,干燥,即得复合微球产品。
上述步骤3中液滴成型为:用单通道注射泵将分散相通入微流控芯片通道内,使用双通道注射泵将连续相通入微流控芯片的连续相入口,使其在微流控芯片的十字通道内对分散相进行剪切,液滴剪切成球后随微流控芯片的出口引入到水浴固化液中。
上述步骤3中水浴固化液采用0.5wt%戊二醛水溶液,2.0wt%斯潘60及正辛烷溶液混合配制而成。
实施例5:
吸附重金属性能测试:
将实施例2、实施例3产品设为试验组,吸附重金属的微球设为对照组。
取三份100ml电镀废水,该电镀废水的pH为3.4,其主要化学组成为:CN-:20mg/L,Cr6+:82mg/L,Cu2+:28mg/L,Zn2+:40mg/L,Ni2+:20mg/L,调节pH至7~7.5后,分别加入实施例2、实施例3产品和吸附重金属的微球,加入量为20g/L,静置吸附24h后过滤作为待测液,待测液用原子吸收分光光度计测定溶液中CN-、Cr6+、Cu2+、Zn2+和Ni2+的浓度,计算对重金属的吸附。得到的吸附率如下:
实施例2:CN-的吸附率=99.89%,Cr6+的吸附率=99.91%,Cu2+的吸附率=98.54%,Zn2+的吸附率=99.94%,Ni2+的吸附率=99.72%。
实施例3:CN-的吸附率=99.92%,Cr6+的吸附率=99.94%,Cu2+的吸附率=99.90%,Zn2+的吸附率=99.97%,Ni2+的吸附率=99.78%。
对照组:CN-的吸附率=92.31%,Cr6+的吸附率=87.52%,Cu2+的吸附率=80.49%,Zn2+的吸附率=93.45%,Ni2+的吸附率=90.68%。
由上述数据可知,通过实施例2和实施例3产品处理的电镀废水中重金属吸附率明显优于对照例,说明实施例2和实施例3产品对重金属离子废水的吸附效果好。
本发明的操作步骤中的常规操作为本领域技术人员所熟知,在此不进行赘述。
以上所述的实施例对本发明的技术方案进行了详细说明,应理解的是以上所述仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种吸附重金属的贝壳粉壳聚糖复合微球,其特征在于:所述复合微球中壳聚糖粉末和贝壳粉的重量比为1:0.3-0.45;
所述复合微球的直径在为0.4-0.6mm;
所述的一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,包括粗贝壳粉制备、纳米贝壳粉制备、复合微球制备、复合微球改性;
所述纳米贝壳粉的制备:向粗贝壳粉中加入粗贝壳粉重量1.7-2.2%的粉碎分散剂,然后使用纳米粉碎机粉碎,即得粒径为20-100nm的纳米贝壳粉,粉碎分散剂为重量比为1:1.1-1.3:0.02-0.03的PEG2000、六偏磷酸钠和右旋糖酐的混合物;
所述粉碎分散剂加入前,按重量比为100:0.38-0.52向粗贝壳粉中加入酒石酸二乙酯,所述酒石酸二乙酯中L-酒石酸二乙酯和D-酒石酸二乙酯的重量比为100:1.32-1.36;
所述复合微球改性步骤为:将8-10wt%复合微球加入到含1.8-2.2wt%硫脲及0.8-1.2wt%环氧氯丙烷的丙酮溶液中,在50-70℃下搅拌反应4-6h,清洗干净,干燥,即得复合微球产品。
2.权利要求1所述的一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,包括粗贝壳粉制备、纳米贝壳粉制备、复合微球制备、复合微球改性,其特征在于:所述纳米贝壳粉制备步骤为:向粗贝壳粉中加入粉碎分散剂,然后使用纳米粉碎机粉碎,即得纳米贝壳粉;
所述纳米贝壳粉制备步骤中粉碎分散剂的添加量为粗贝壳粉重量1.7-2.2%,所述粉碎分散剂为重量比为1:1.1-1.3:0.02-0.03的PEG2000、六偏磷酸钠和右旋糖酐的混合物。
3.根据权利要求2所述的一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,其特征在于:所述纳米贝壳粉的粒径为20-100nm。
4.根据权利要求2所述的一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,其特征在于:所述粗贝壳粉制备步骤为:将贝壳清洗干净,用稀酸溶液浸泡4-5h,洗净,烘干,再在900-1000℃下煅烧2-3h,冷却至室温,研磨后过150-200目筛,即得粗贝壳粉。
5.根据权利要求2所述的一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,其特征在于:所述复合微球制备步骤为:将壳聚糖粉末和贝壳粉混合溶于1.8-2.2wt%乙酸水溶液中,配成含有3-5wt%的壳聚糖粉末和贝壳粉的混合溶液,作为分散相,将1.8-2.2wt%斯潘60加入到96-99wt%正辛烷溶液中,混合搅拌后用作连续相,液滴成型,然后在水浴固化液中进行交联改性,清洗干净,即得复合微球。
6.根据权利要求5所述的一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,其特征在于:所述复合微球制备步骤中液滴成型为:用单通道注射泵将分散相通入微流控芯片通道内,使用双通道注射泵将连续相通入微流控芯片的连续相入口,使其在微流控芯片的十字通道内对分散相进行剪切,液滴剪切成球后随微流控芯片的出口引入到水浴固化液中。
7.根据权利要求5所述的一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,其特征在于:所述复合微球制备步骤中水浴固化液采用0.4-0.6wt%戊二醛水溶液,1.8-2.2wt%斯潘60及正辛烷溶液混合配制而成。
8.根据权利要求2所述的一种吸附重金属的贝壳粉壳聚糖复合微球的制备方法,其特征在于:所述复合微球改性步骤为:将8-10wt%复合微球加入到含1.8-2.2wt%硫脲及0.8-1.2wt%环氧氯丙烷的丙酮溶液中,在50-70℃下搅拌反应4-6h,清洗干净,干燥,即得复合微球产品。
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