CN114702723A - 一种以芦苇为原料制备纤维素复合气凝胶的方法 - Google Patents
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Abstract
本发明公开了一种以芦苇为原料制备纤维素复合气凝胶的方法,将芦苇秸秆切割粉碎得到芦苇粉末,去离子水水洗、搅拌、过滤后烘干;经过碱洗、酸洗和漂白去除半纤维素和木质素杂质,得到白色纤维素;所得纤维素溶解在预冷的氢氧化钠/尿素/水混合溶液中,搅拌得到淡黄色的纤维素溶液;同样的方式制备得到透明的壳聚糖溶液;两种溶液分别在低温下冷冻;室温解冻后将上述两种溶液混合搅拌,向其中加入环氧氯丙烷交联剂,‑3℃~3℃交联反应0.5~2h;转移至模具中,升温至50~70℃加热1~3h,水洗至中性,冷冻干燥即可得到纤维素/壳聚糖复合气凝胶。
Description
技术领域
本发明属于复合材料技术领域,具体涉及一种纤维素复合气凝胶的制备方法。
背景技术
随着社会的不断发展进步,环境污染问题也日趋严重,各种环境污染问题已经成为制约人类可持续发展的重要因素。其中,与人类生活密切相关的水污染问题成为一个亟需解决的问题。刚果红,作为一种阴离子型偶氮染料,在服装印染、油漆着色等行业广泛应用。然而大量染料废水未经处理肆意排放,对生物、植物乃至人体健康造成了严重危害。由于染料在水中具有潜在致癌性、持久性、高毒性、难降解等特点,已经引起了科学研究者的特别关注,如何高效去除此类污染物是一个研究热点。
目前,已有多种方法用来处理含刚果红的废水,包括高级氧化,光催化降解,膜分离法等。但是这些处理方法成本高,操作繁琐,降解后的副产物有可能对环境造成二次污染危害。其中,吸附法因其具有成本低、操作方便、环境友好等优点,是目前去除刚果红废水的常用方法。常见的吸附剂有活性炭、金属氧化物、有机聚合物、生物质碳材料等。但这些吸附剂由于官能团欠缺、容易堆积团聚、粉体难回收分离等缺点,导致了对刚果红吸附效果不佳,极大地限制了在水处理中的应用。因此,开发一种易回收分离,能实现二次利用的吸附剂是十分必要的。气凝胶,被誉为“21世纪最轻的材料”,具有丰富的三维网络交联结构和孔隙率,在水中可以保持一定的形状,有效地解决粉体吸附剂在水中难回收分离的问题,已经广泛地应用在水处理领域。纤维素气凝胶除具备传统气凝胶固有的质轻、高孔隙率外,还展现出良好的生物相容性、生物可降解性、高强度和延展性等,是一类很有前景的废水净化材料。
单一纤维素气凝胶用作吸附剂时,存在吸附量低、选择性差等缺点,如何利用生物质原料制得一种针对刚果红选择性高,吸附量大的吸附材料成为亟待解决的问题。
发明内容
本发明目的在于提供一种纤维素复合气凝胶的制备方法,所得复合气凝胶呈现出更加丰富的立体交联网络结构,对刚果红的吸附性和选择性大大提升。
为达到上述目的,采用技术方案如下:
一种以芦苇为原料制备纤维素复合气凝胶的方法,包括以下步骤:
(1)将芦苇秸秆切割粉碎得到芦苇粉末,去离子水水洗、搅拌、过滤后烘干;经过碱洗、酸洗和漂白去除半纤维素和木质素杂质,得到白色纤维素;
(2)所得纤维素溶解在预冷的氢氧化钠/尿素/水混合溶液中,搅拌得到淡黄色的纤维素溶液;同样的方式制备得到透明的壳聚糖溶液;两种溶液分别在低温下冷冻;室温解冻后将上述两种溶液混合搅拌,向其中加入环氧氯丙烷交联剂,-3℃~3℃交联反应0.5~2h;转移至模具中,升温至50~70℃加热1~3h,水洗至中性,冷冻干燥即可得到纤维素/壳聚糖复合气凝胶(CE/CSA)。
按上述方案,步骤(1)中芦苇秸秆切割粉碎过100目筛子得到芦苇粉末。
按上述方案,步骤(1)中所述芦苇粉末水洗后搅拌1~3h,过滤后在50~70℃烘干。
按上述方案,步骤(1)中重复进行碱洗、酸洗和漂白完全去除半纤维素和木质素杂质。
按上述方案,步骤(2)中预冷的氢氧化钠/尿素/水混合溶液温度在-12℃~-30℃;1000~1500r/min快速搅拌3~10min,得到淡黄色的纤维素溶液。
按上述方案,步骤(2)中低温冷冻温度为-12℃~-30℃,时间为10~15h。
按上述方案,步骤(2)中纤维素溶液的浓度为5wt%~8wt%,壳聚糖溶液的浓度为5wt%~8wt%;两种溶液混合的质量比为纤维素溶液:壳聚糖溶液1:(1-5)。
目前,纤维素可以从多种物质中被提取,包括秸秆、甘蔗渣、棉花等,但是这些物质本身并不具备水净化的功能。而芦苇作为一种生长在水边的植物,可以吸收水中的无机盐,亦可以抑制蓝藻的生长。同时,它的叶、叶鞘、茎杆、根等部位都具有通气组织,可以在净化污水中起到重要的作用。结合这一点来看,芦苇相比其他的生物质在水处理方面更具有自身优势。从本文的附图1a也可以看出,芦苇内部本身具有层状大孔结构,类似于分子的传输通道,该结构有利于刚果红分子进行内部传输。因此,从芦苇中提取纤维素制备气凝胶对刚果红具有优异的吸附性能。另外,该吸附机理主要为:纤维素链上包含大量羟基官能团,而壳聚糖链上又包含大量羟基和氨基官能团,两者在化学交联剂的作用下形成网络结构丰富的三维立体交联剂,这些三维网状结构有利于大分子刚果红的传输,有助于刚果红的快速吸附;另一方面,刚果红分子中含有氨基和磺酸基等基团,可以和吸附剂上的氨基或羟基形成强有力的氢键作用,这使得对刚果红呈现了优异的吸附性能。在者,静电吸引作用在吸附过程中也发挥了重要作用。
相对于现有技术,本发明有益效果在于:
本发明首次从芦苇中提取得到纤维素,并成功制备纤维素气凝胶用于去除染料废水,实现了“以废制废”,资源化利用的绿色理念;
本发明用廉价绿色的原料所制备的块状纤维素复合气凝胶,具有丰富的孔隙率和低密度,避免了传统粉末状吸附材料难回收的缺点。
本发明所制备的CE/CSA气凝胶有丰富的三维网络交联结构和低的密度(0.062g/cm3);对20mg/L的刚果红染料在200min左右呈现了95%以上的去除率,相比单一的纤维素气凝胶(28.35%)去除效果大大提升;在298K时,对刚果红的最大吸附量为255.10mg/g。
附图说明
图1:实施例1所得芦苇粉末和纤维素扫描电镜图。
图2:实施例所得产品扫描电镜图。
图3:实施例所得产品对刚果红的去除率时间曲线(图3A)以及刚果红吸附前后的光谱扫描图(图3B)。
具体实施方式
以下实施例进一步阐释本发明的技术方案,但不作为对本发明保护范围的限制。
具体实施方式中提供了一种以芦苇为原料制备纤维素复合气凝胶的方法,包括以下步骤:
(1)纤维素的提取
将芦苇秸秆用切割机切成小段,然后粉碎,过100目筛子,得到芦苇粉末。取10~20g芦苇粉末用大量去离子水洗,搅拌1~3h后过滤,在50~70℃烘箱中烘干备用。接着,对芦苇粉末进行碱洗、酸洗和漂白多次操作,以去除芦苇中半纤维素和木质素等杂质。最后,白色的纤维素成功提取。
(2)纤维素/壳聚糖复合气凝胶的制备
称取0.25~1g步骤1中提取的纤维素,溶解在-12℃~-30℃预冷的氢氧化钠/尿素/水的混合溶液中,1000~1500r/min快速搅拌3~10min,得到淡黄色的纤维素溶液。壳聚糖溶液也按上述步骤制备,得到透明的溶液。而后将两种溶液在-12℃~-30℃冰箱中冷冻10~15h。室温解冻后,称取一定质量的纤维素和壳聚糖溶液(质量比为1:1~1:5),充分搅拌后加入1-5mL的环氧氯丙烷交联剂,在-3℃~3℃交联0.5~2h。反应结束后,将混合溶液倒入特定的模具中,在50~70℃的水浴锅中加热1~3h。最后,用大量的水洗涤该复合水凝胶直至中性,用冷冻干燥机冻干12~36h,即可得到CE/CSA。
实施例1
将芦苇秸秆切断,放入粉碎机中进行搅碎处理,过100目筛。取10g芦苇粉末,放入去离子水中,室温下搅拌处理2h后抽滤,在60℃烘箱中烘干备用。将预处理后的芦苇加入适量的氢氧化钠溶液中,70℃处理2h后,抽滤、去离子水洗涤至中性。然后,将碱处理后的产品加入稀盐酸溶液中,70℃处理2h后,抽滤、去离子水洗涤至中性。最后,将酸处理后的产品放入次氯酸钠/乙酸溶液中进行漂白,80℃处理3h,该操作反复多次,直至得到白色的纤维素为止。所用的芦苇原料和纤维素的扫描电镜图(SEM)如图1所示,从图中可以看出芦苇粉末呈现了明显的层状结构,而纤维素则呈现的是棒状结构。
称取一定量纤维素,溶解在预冷的氢氧化钠/尿素/水的混合溶液中,快速搅拌几分钟,制备得到5wt%的纤维素溶液。同样,称取一定量的壳聚糖,溶解在上述体系中,制备得到5wt%的壳聚糖溶液。随后将两种溶液冷冻12h,室温解冻后,将两种溶液以质量比1:1混合,加入适当环氧氯丙烷交联剂,在0℃搅拌1h。反应结束后,将混合溶液倒入模具中,60℃加热2h,即可得到复合水凝胶。用大量去离子水洗涤水凝胶至中性,在冷冻干燥机中冷干24h,得到纤维素/壳聚糖复合气凝胶,简称CE/CSA-1。
该CE/CSA-1凝胶的SEM图见图2c所示,可以看出CE/CSA-1呈现出明显的三维网络结构,有助于吸附发生。经过测量密度在0.062g/cm3。
将CE/CSA-1作为吸附剂对刚果红溶液吸附处理,结果表明,在200min左右对刚果红(20mg/L)的去除率为95%左右,且在298K时,对100mg/L刚果红的最大吸附量为255.10mg/g。
实施例2
称取一定量实施例1中提取的纤维素,溶解在预冷的氢氧化钠/尿素/水的混合溶液中,快速搅拌几分钟,制备得到5wt%的纤维素溶液。同样,称取一定量的壳聚糖,溶解在上述体系中,制备得到5wt%的壳聚糖溶液。随后将两种溶液冷冻12h,室温解冻后,将两种溶液以质量比1:2混合,加入适当环氧氯丙烷交联剂,在0℃搅拌1h。反应结束后,将混合溶液倒入模具中,60℃加热2h,即可得到复合水凝胶。用大量去离子水洗涤水凝胶至中性,在冷冻干燥机中冷干24h,得到纤维素/壳聚糖复合气凝胶,简称CE/CSA-2。
该凝胶的SEM图如图2d所示。
将CE/CSA-2作为吸附剂对刚果红溶液吸附处理,结果表明,在200min左右对刚果红(20mg/L)的去除率为85%左右,且在298K时,对100mg/L刚果红的最大吸附量为226.24mg/g。
对比例1
称取一定量实施例1中提取的纤维素,溶解在预冷的氢氧化钠/尿素/水的混合溶液中,快速搅拌几分钟,制备得到5wt%的纤维素溶液。随后将该溶液冷冻12h,室温解冻后,加入适当环氧氯丙烷交联剂,在0℃搅拌1h。反应结束后,将溶液倒入模具中,60℃加热2h,即可得到纤维素水凝胶。用大量去离子水洗涤水凝胶至中性,在冷冻干燥机中冷干24h,得到纤维素气凝胶,简称CEA。
该凝胶的SEM图见图2a。
将CEA作为吸附剂对刚果红溶液吸附处理,结果表明,在200min左右对刚果红(20mg/L)的去除率为28%左右,且在298K时,对100mg/L刚果红的最大吸附量为105.26mg/g。可以看出,单一CEA的吸附性能远低于CE/CSA-1和CE/CSA-2。
对比例2
称取一定量的壳聚糖,溶解在预冷的氢氧化钠/尿素/水的混合溶液中,快速搅拌几分钟,制备得到5wt%的壳聚糖溶液。随后将该溶液冷冻12h,室温解冻后,加入适当环氧氯丙烷交联剂,在0℃搅拌1h。反应结束后,将溶液倒入模具中,60℃加热2h,即可得到壳聚糖水凝胶。用大量去离子水洗涤水凝胶至中性,在冷冻干燥机中冷干24h,得到壳聚糖气凝胶,简称CSA。
该凝胶的SEM图见图2b。
将CSA作为吸附剂对刚果红溶液吸附处理,结果表明,在200min左右对刚果红(20mg/L)的去除率为80%左右,且在298K时,对100mg/L刚果红的最大吸附量为181.82mg/g。可以看出,单一CSA对刚果红具有较高的去除效果,但比复合气凝胶还略差。正因为如此,在纤维素溶液中加入壳聚糖,可以大大改善单一纤维素的吸附性能。
下表为以上实施例所得产品对刚果红吸附效果参数。
图3为上述实施例所得产品对刚果红的去除率时间曲线(图3A)以及刚果红吸附前后的光谱扫描图(图3B)。从图3A可以看出,随着吸附时间的变化,气凝胶吸附剂对刚果红的去除率在逐渐增加。尤其是在前100min内,刚果红去除率快速增加,在之后吸附速率趋于平缓,最后在200min左右达到吸附平衡。图3B呈现的是四种气凝胶对刚果红吸附前后吸光度变化的图谱,可以看出,初始刚果红溶液在未吸附时(a曲线)呈现了较大的吸光度。b,c,d,e四条曲线分别代表加入CEA,CSA,CE/CSA-1和CE/CSA-2吸附剂吸附后的曲线。可以看出,d曲线呈现了最低的吸光度,证明该吸附剂对刚果红的吸附效果最好,这和图3A的效果是相对应的。
Claims (7)
1.一种以芦苇为原料制备纤维素复合气凝胶的方法,其特征在于包括以下步骤:
(1)将芦苇秸秆切割粉碎得到芦苇粉末,去离子水水洗、搅拌、过滤后烘干;经过碱洗、酸洗和漂白去除半纤维素和木质素杂质,得到白色纤维素;
(2)所得纤维素溶解在预冷的氢氧化钠/尿素/水混合溶液中,搅拌得到淡黄色的纤维素溶液;同样的方式制备得到透明的壳聚糖溶液;两种溶液分别在低温下冷冻;室温解冻后将上述两种溶液混合搅拌,向其中加入环氧氯丙烷交联剂,-3℃~3℃交联反应0.5~2h;转移至模具中,升温至50~70℃加热1~3h,水洗至中性,冷冻干燥即可得到纤维素/壳聚糖复合气凝胶。
2.如权利要求1所述以芦苇为原料制备纤维素复合气凝胶的方法,其特征在于包括以下步骤:步骤(1)中芦苇秸秆切割粉碎过100目筛子得到芦苇粉末。
3.如权利要求1所述以芦苇为原料制备纤维素复合气凝胶的方法,其特征在于步骤(1)中所述芦苇粉末水洗后搅拌1~3h,过滤后在50~70℃烘干。
4.如权利要求1所述以芦苇为原料制备纤维素复合气凝胶的方法,其特征在于步骤(1)中重复进行碱洗、酸洗和漂白完全去除半纤维素和木质素杂质。
5.如权利要求1所述以芦苇为原料制备纤维素复合气凝胶的方法,其特征在于步骤(2)中预冷的氢氧化钠/尿素/水混合溶液温度在-12℃~-30℃;1000~1500r/min快速搅拌3~10min,得到淡黄色的纤维素溶液。
6.如权利要求1所述以芦苇为原料制备纤维素复合气凝胶的方法,其特征在于步骤(2)中低温冷冻温度为-12℃~-30℃,时间为10~15h。
7.如权利要求1所述以芦苇为原料制备纤维素复合气凝胶的方法,其特征在于步骤(2)中纤维素溶液的浓度为5wt%~8wt%,壳聚糖溶液的浓度为5wt%~8wt%;两种溶液混合的质量比为纤维素溶液:壳聚糖溶液1:(1-5)。
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