CN106758520A - 戊二醛交联聚乙烯亚胺纸基薄膜的制备方法 - Google Patents
戊二醛交联聚乙烯亚胺纸基薄膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种戊二醛交联聚乙烯亚胺纸基薄膜的制备方法,该方法文化用纸作为纤维素基质,经裁剪、干燥后进行氢氧化钠和硫酸两段净化,处理后的干燥纸片在聚乙烯亚胺水溶液中浸泡,使其充分润胀,继而滴加入戊二醛/磷酸混合液进行交联反应,制得吸附重金属离子的纸基戊二醛交联聚乙烯亚胺功能薄片;通过该方法制得的吸附纸呈不透明薄膜状,对Cr(VI)、Ni2+、Cd3+和Cu2+等重金属离子具有良好的吸附能力。
Description
技术领域
本发明涉及一种利用生活中极易获取的文化用纸,功能化改性制备高吸附重金属离子的纸基吸附薄膜的工艺技术,属于天然高分子改性材料技术领域。
背景技术
随着工业的大规模化发展,人们使用金属离子的种类与数量与日俱增,因而在废弃物、废水中含有Cd2+、Cr3+、Cu2+、Pb2+等重金属离子。这些重金属离子进入水体或土壤后具有很强的扩散性,不容易代谢、降解,且容易被生物富集。所以含有毒重金属离子的废水一旦进入生态系统之后破坏生态环境,并通过食物链严重影响人类健康。常见处理重金属离子废水的方法有:化学转化技术、介质提取技术、物理化学浓缩技术等。化学转化技术包括化学沉淀法、点解法;介质提取技术包括溶剂萃取法、吸附法、有机絮凝法、离子交换法和生物处理法;物理化学浓缩技术包括渗透析和膜技术。其中,化学沉淀法、电解法是最早处理重金属废水方法,通过改变重金属离子的形态,以不溶物的形式除去,主要应用于处理高浓度重金属离子废水,成本低,易于操作;离子交换法和膜技术等主要是维持重金属离子的原有形态,浓缩废液中的重金属离子,从而达到回收重金属离子,主要应用于低浓度的重金属离子废水的处理,离子交换装置、膜组件均比较昂贵且容易污染,不易再生;吸附法是通过吸附剂的高比表面积及特殊的内部结构对废水重金属离子进行的物理化学吸附,可广泛处理各类水量大低浓度重金属离子废水最经济有效的方法之一。
吸附法是利用固体表面张力把气体、蒸汽、液体或溶质、分散物质或胶体物质等浓缩、捕集在固体表面上的现象。吸附剂包括生物类和非生物类两种类型,其中生物类吸附剂主要包括活性污泥和生物体制剂等;非生物类吸附剂的种类比较广泛,如活性炭、矿物质材料、纤维素等。目前具有一定吸附能力的天然资源或农林废弃物,是吸附法中比较有潜力的一类生物吸附材料。
与循环利用较弱、运行投资费用较高的活性炭或矿物质材料相比较,纤维素类吸附剂吸附去除重金属离子,具有的明显优势:1)以纤维素为基础制备的材料是一种成本低廉、吸附性能强的吸附剂,不仅原料低廉,来源丰富,可以制备多种吸附剂,处理多种重金属离子;2)吸附剂的吸附金属离子容量大、效率高,吸附操作过程简单;3)此类吸附剂可以再生回收。综上所述,纤维素类吸附法作为一种新兴的处理重金属离子的方法,在去除水中重金属离子方面有着广阔的应用前景。迄今为止,纤维素为基质的功能化材料用于水体中重金属离子吸附的研究报道层出不穷。Cai等人报道了静电纺丝法制备纤维素纳米复合物,处理含Cd6+废水,研究结果发现,该吸附剂对铬离子的去除率可达到20mg/g以上。Ozbas等人以纤维素为骨架,接枝共聚N-异丙基丙烯酰胺制备得到温敏性吸附剂,用于处理含铜、铅、镍和铬等离子的废水,结果发现,吸附剂的吸附和脱附可由温度控制,不同离子吸附能力大小也可由废液性质所决定。Bediako等人通过羧甲基化改性废布料制备重金属吸附剂,研究结果表明,该吸附剂具有较快的吸附速率,脱附简单,且对重金属吸附能力较理想。
结合现代工业造成的水体重金属污染问题,本申请详述以文化用纸为原料快速、简便地制备高效吸附重金属离子戊二醛交联聚乙烯亚胺功能纸的工艺流程,为生活用纸的功能化利用提供技术指导,具有较好的应用价值。
发明内容
由于重金属吸附材料主要依赖于合成类或半合成类高分子,以文化用纸为基质的吸附剂的开发还未见报道,且无相关技术支撑,因此兼具环境友好型和良好物理性能的吸附纸暂无开发应用。因此,本发明提供了一种高吸附重金属离子戊二醛交联聚乙烯亚胺纸基薄膜的制备方法,该方法以文化用纸为原料,裁剪后的纸片经过碱、酸及水清洗,放入聚乙烯亚胺水溶液中充分浸泡润胀,在该体系中滴加入酸性戊二醛,交联反应后清洗并干燥,制得戊二醛交联聚乙烯亚胺纸基薄膜,进一步拓展吸附剂的种类,使纸张这种生活中极为易得的可降解材料得到高附加值的利用。
实现本发明目的采取的工艺技术方案如下:
(1)选用A1~A8的文化用纸作为原料,并将纸张裁剪为长方形、正方形或圆形的规则片状,低温短时干燥,备用;
(2)裁剪后的纸片先放入碱溶液中搅拌清洗,继而在去离子水中洗脱碱,放入酸溶液中搅拌清洗,再次用去离子水将纸片中的酸脱除,低温干燥,备用;
(3)净化的纸片放入聚乙烯亚胺水溶液中长时浸泡后,滴加入戊二醛和磷酸的混合溶液,加热、震荡进行交联反应;
(4)交联产物用去离子水进行反复洗涤至换洗水pH值为中性,低温干燥,得到薄片状戊二醛交联聚乙烯亚胺功能纸。
所述碱溶液为氢氧化钠、氢氧化钾或氢氧化钙水溶液。
所述酸溶液为硫酸或盐酸的水溶液。
本发明吸附重金属离子的聚乙烯亚胺功能纸的制备方法,具体操作如下:
①纸张的备料过程:实现本发明吸附剂的原料为定量60 g/m2~80 g/m2的A1~A8文化用纸,将纸裁剪成长度为0.5 cm~5 cm,宽度为0.15 cm~2 cm,或者裁剪为直径为0.1 cm~5 cm的小圆片,并在30℃~50℃温度条件下干燥1 h~6 h,备用;
②纸张净化过程:将裁剪后的纸片放入0.1 mol/L~2.0 mol/L碱溶液中,磁力搅拌5min~20 min,碱净化完成后,用去离子水洗脱纸片中的残余碱液,继而放入0.5%(v/v)~2.0%(v/v)浓度的酸溶液中,磁力搅拌5 min~20 min,酸净化完成后,用去离子水洗脱纸片中的残余酸液,洗净后在30℃~60℃温度条件下干燥,备用;净化剂用量为:碱溶液(酸溶液)用量为100 mL/g纸张质量~500 mL/g纸张质量;
③净化纸张交联改性:先将净化后的干燥纸片放入浓度为0.5%(v/v)~10%(v/v)的聚乙烯亚胺水溶液中,浸泡36 h~60 h,其中,聚乙烯亚胺水溶液与纸张质量之比为80 mL:1 g~800 mL:1 g;继而,在此体系中滴加入戊二醛和磷酸混合液(戊二醛与磷酸体积比为5:1~1:2),戊二醛的用量与纸张质量之比为3:1(mL/g)~10:1(mL/g) 调节温度为30℃~50℃,摇晃速度100 rpm~350 rpm,反应1 h~6 h;
④戊二醛交联聚乙烯亚胺功能纸的后处理过程:交联反应结束后,聚乙烯亚胺功能赋性纸浸泡于过量的去离子水中,每隔6 h~24 h换一次去离子水,直至换洗水pH值为中性,洗净后在30℃~60℃温度条件下干燥,得到薄片状戊二醛交联乙烯亚胺吸附纸。
本发明的有益效果是:以生活中极易得到文化用纸作为纤维素吸附基质的来源,通过碱和酸两段净化去除纸表面涂布层,使纸张中纤维素充分暴露,纤维网络孔隙扩张,利于后续反应进行,净化后的干燥纸片在聚乙烯亚胺水溶液中充分浸泡润胀后,滴加入酸性戊二醛进行交联反应,得到吸附重金属离子的纸基戊二醛交联聚乙烯亚胺功能薄片。天然高分子类吸附薄膜具有合成高分子类吸附材料的共性,可在矿山开采、冶金、机械制造、化工、电子和仪表等多个行业所产生的重金属废液的处理方面能够发挥良好的应用前景。同时,该天然高分子基吸附凝胶膜还具有原料来源广泛、制备简易、良好的吸附性能、环境友好性等优势,是现今主流发展的一类新型、绿色的功能材料,此类吸附薄片的实现为生活用纸的附加值利用提供一条可行性方案。
具体实施方式
下面结合实施例对本发明作进一步详细说明,但本发明保护范围不局限于所述内容。
实施例1:戊二醛交联聚乙烯亚胺功能纸的制备方法,具体操作如下:
(1)纸张的备料过程
选取定量为60 g/m2的A8文化用纸作为基质材料,将此纸裁剪成长度为0.5 cm,宽度为0.15 cm的长方形小纸片,在30℃的温度条件下干燥6 h,备用。
(2)纸张净化过程
将0.3 g裁剪并干燥的纸片放入30 mL 0.1 mol/L的氢氧化钠水溶液中,磁力搅拌5min,碱净化完成后,用去离子水洗脱纸片中的残余碱液,继而放入30 mL 0.5%(v/v)浓度的硫酸水溶液中,磁力搅拌5 min,酸净化完成后,用去离子水洗脱纸片中的残余酸液,并在30℃温度条件下干燥,备用。
(3)净化纸张交联改性
先将0.1 g净化处理后的干燥纸片放入8 mL浓度为0.5%(v/v)的聚乙烯亚胺水溶液中,浸泡36 h后,在该体系中滴加入含有0.3 mL的戊二醛和0.6 mL的磷酸混合液(戊二醛用量与纸片质量为3 mL:1 g,戊二醛与磷酸体积比为1:2),调节温度为30℃,摇晃速度100 rpm,反应1 h。
(4)戊二醛交联聚乙烯亚胺功能纸的后处理
步骤(3)的交联反应结束后,产物浸泡于过量的去离子水中,每隔6 h换一次去离子水,直至换洗水pH值为中性,洗净后在30℃温度条件下干燥,得到薄片状戊二醛交联乙烯亚胺吸附纸。
(5)聚乙烯亚胺赋性纸的性状
金属离子吸附测定方法:取数个2 mg的吸附纸分别浸没于10 mL浓度为100 mg/L的Cr(VI)、Ni2+、Cd3+和Cu2+溶液中,在25℃水温下静置72h,吸附平衡后,取出功能纸,擦拭去纸表层液体,利用元素分析仪检测吸附纸中吸附的重金属含量。
通过上述反应所得吸附纸具有较高金属吸附能力,对Cr(VI)、Ni2+、Cd3+和Cu2+吸附能力分别可达到85 mg/g,101 mg/g,135 mg/g和176 mg/g。
实施例2:戊二醛交联聚乙烯亚胺功能纸的制备方法,具体操作如下:
(1)纸张的备料过程
选取定量为70 g/m2的A4文化用纸作为基质材料,将此纸裁剪成长度为3 cm,宽度为1.5 cm的长方形小纸片,在40℃的温度条件下干燥3 h,备用。
(2)纸张净化过程
将0.3 g裁剪并干燥的纸片放入90 mL 1.0 mol/L的氢氧化钾水溶液中,磁力搅拌15min,碱净化完成后,用去离子水洗脱纸片中的残余碱液,继而放入90 mL 1.0%(v/v)浓度的硫酸水溶液中,磁力搅拌15 min,酸净化完成后,用去离子水洗脱纸片中的残余酸液,并在50℃温度条件下干燥,备用。
(3)净化纸张交联改性
先将0.1 g净化处理后的干燥纸片放入50 mL浓度为2.5%(v/v)的聚乙烯亚胺水溶液中,浸泡48 h后,在该体系中滴加入含有0.7 mL的戊二醛和0.7 mL的磷酸混合液(戊二醛用量与纸片质量为7 mL:1 g,戊二醛与磷酸体积比为1:1),调节温度为40℃,摇晃速度250rpm,反应3 h。
(4)戊二醛交联聚乙烯亚胺功能纸的后处理
步骤(3)的交联反应结束后,产物浸泡于过量的去离子水中,每隔12 h换一次去离子水,直至换洗水pH值为中性,洗净后在50℃温度条件下干燥,得到薄片状戊二醛交联乙烯亚胺吸附纸。
(5)聚乙烯亚胺赋性纸的性状
金属离子吸附测定方法:取数个2 mg的吸附纸分别浸没于10 mL浓度为100 mg/L的Cr(VI)、Ni2+、Cd3+和Cu2+溶液中,在25℃水温下静置72h,吸附平衡后,取出功能纸,擦拭去纸表层液体,利用元素分析仪检测吸附纸中吸附的重金属含量。
通过上述反应所得的吸附纸具有较高金属吸附能力,对Cr(VI)、Ni2+、Cd3+和Cu2+吸附能力分别可达到132 mg/g,257 mg/g,365 mg/g和436 mg/g。
实施例3:戊二醛交联聚乙烯亚胺功能纸的制备方法,具体操作如下:
(1)纸张的备料过程
选取定量为80 g/m2的A1文化用纸作为基质材料,将此纸裁剪成长度为5 cm,宽度为2cm的长方形小纸片,在50℃的温度条件下干燥1 h,备用。
(2)纸张净化过程
将0.3 g裁剪并干燥的纸片放入150 mL 2.0 mol/L的氢氧化钙水溶液中,磁力搅拌20min,碱净化完成后,用去离子水洗脱纸片中的残余碱液,继而放入150 mL 2.0%(v/v)浓度的盐酸水溶液中,磁力搅拌20 min,酸净化完成后,用去离子水洗脱纸片中的残余酸液,并在60℃温度条件下干燥,备用。
(3)净化纸张交联改性
先将0.1 g净化处理后的干燥纸片放入80 mL浓度为10%(v/v)的聚乙烯亚胺水溶液中,浸泡60 h后,在该体系中滴加入含有1.0 mL的戊二醛和0.2 mL的磷酸混合液(戊二醛用量与纸片质量为10 mL:1 g,戊二醛与磷酸体积比为5:1),调节温度为50℃,摇晃速度350rpm,反应6 h。
(4)戊二醛交联聚乙烯亚胺功能纸的后处理
步骤(3)的交联反应结束后,产物浸泡于过量的去离子水中,每隔24 h换一次去离子水,直至换洗水pH值为中性,洗净后在60℃温度条件下干燥,得到薄片状戊二醛交联乙烯亚胺吸附纸。
(5)聚乙烯亚胺赋性纸的性状
金属离子吸附测定方法:取数个2 mg的吸附纸分别浸没于10 mL浓度为100 mg/L的Cr(VI)、Ni2+、Cd3+和Cu2+溶液中,在25℃水温下静置72h,吸附平衡后,取出功能纸,擦拭去纸表层液体,利用元素分析仪检测吸附纸中吸附的重金属含量。
通过上述反应所得的吸附纸具有较高金属吸附能力,对Cr(VI)、Ni2+、Cd3+和Cu2+吸附能力分别可达到116 mg/g,203 mg/g,332 mg/g和420 mg/g。
实施例4:戊二醛交联聚乙烯亚胺功能纸的制备方法,具体操作如下:
(1)纸张的备料过程
选取定量为70 g/m2的A4文化用纸作为基质材料,将此纸裁剪成直径为3 cm圆形小纸片,在35℃的温度条件下干燥4 h,备用。
(2)纸张净化过程
将0.3 g裁剪并干燥的纸片放入80 mL 1.5 mol/L的氢氧化钠水溶液中,磁力搅拌10min,碱净化完成后,用去离子水洗脱纸片中的残余碱液,继而放入80 mL 1.5%(v/v)浓度的盐酸水溶液中,磁力搅拌10 min,酸净化完成后,用去离子水洗脱纸片中的残余酸液,并在45℃温度条件下干燥,备用。
(3)净化纸张交联改性
先将0.1 g净化处理后的干燥纸片放入50 mL浓度为5%(v/v)的聚乙烯亚胺水溶液中,浸泡50 h后,在该体系中滴加入含有0.8 mL的戊二醛和0.8 mL的磷酸混合液(戊二醛用量与纸片质量为8 mL:1 g,戊二醛与磷酸体积比为1:1),调节温度为45℃,摇晃速度300 rpm,反应5 h。
(4)戊二醛交联聚乙烯亚胺功能纸的后处理
步骤(3)的交联反应结束后,产物浸泡于过量的去离子水中,每隔15 h换一次去离子水,直至换洗水pH值为中性,洗净后在40℃温度条件下干燥,得到薄片状戊二醛交联乙烯亚胺吸附纸。
(5)聚乙烯亚胺赋性纸的性状
金属离子吸附测定方法:测定取数个2 mg的吸附纸分别浸没于10 mL浓度为100 mg/L的Cr(VI)、Ni2+、Cd3+和Cu2+溶液中,在25℃水温下静置72h,吸附平衡后,取出功能纸,擦拭去纸表层液体,利用元素分析仪检测吸附纸中吸附的重金属含量。
通过上述反应所得的吸附纸具有较高金属吸附能力,对Cr(VI)、Ni2+、Cd3+和Cu2+吸附能力分别可达到143 mg/g,285 mg/g,377mg/g和460 mg/g。
Claims (4)
1.一种戊二醛交联聚乙烯亚胺纸基薄膜的制备方法,其特征在于按如下步骤进行:
①文化用纸经裁剪、干燥后用碱溶液进行净化处理,处理后的纸片用去离子水洗脱残余碱液,继而用酸溶液进行净化处理,处理后的纸片用去离子水洗脱残余酸液,低温干燥后,得净化纸片,作为反应基质;
②净化纸片放入聚乙烯亚胺水溶液中浸泡后,滴加入戊二醛和磷酸的混合溶液,加热、震荡进行交联反应;
③交联产物用去离子水进行浸泡洗涤,更换洗涤水直至换洗水pH值为中性,低温干燥,制得戊二醛交联聚乙烯亚胺纸基薄膜。
2.根据权利要求1所述的戊二醛交联聚乙烯亚胺纸基薄膜的制备方法,其特征在于:碱溶液为氢氧化钠、氢氧化钾或氢氧化钙水溶液。
3.根据权利要求1所述的戊二醛交联聚乙烯亚胺纸基薄膜的制备方法,其特征在于:酸溶液为硫酸或盐酸的水溶液。
4.根据权利要求1所述的戊二醛交联聚乙烯亚胺纸基薄膜的制备方法,其特征在于具体操作如下:
①以60g/m2~80g/m2的文化用纸作为纤维素反应基质,将纸裁剪后在30℃~50℃温度条件下干燥1h~6 h;
②将裁剪后的纸片放入0.1mol/L~2.0 mol/L碱溶液中,磁力搅拌5 min~20 min,碱净化完成后,用去离子水洗脱纸片中的残余碱液,继而放入体积百分比浓度为0.5%~2.0%的酸溶液中,磁力搅拌5min~20 min,酸净化完成后,用去离子水洗脱纸片中的残余酸液,纸片在30℃~60℃温度条件下干燥;
③将净化后的干燥纸片放入体积百分比浓度为0.5%~10%的聚乙烯亚胺水溶液中,浸泡36 h~60 h,其中,聚乙烯亚胺水溶液与纸张质量之比为80 mL ~800 mL:1 g;继而,在此体系中滴加入戊二醛和磷酸混合液,戊二醛的体积与纸张质量之比mL:g为3:1~10:1,在30℃~50℃、100 rpm~350 rpm下震荡反应1 h~6 h,制得交联产物,其中戊二醛与磷酸的体积比为5:1~1:2;
④交联产物浸泡于去离子水中,每隔6 h~24 h换一次去离子水,直至换洗水pH值为中性,洗净后在30℃~60℃下干燥,得到戊二醛交联聚乙烯亚胺纸基薄膜。
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