CN107999052A - 一种光催化降解复合材料的制备方法 - Google Patents
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Abstract
本发明公开了一种光催化降解复合材料的制备方法,由硅烷偶联剂、酞酸丁酯、无水乙醇、椰壳、苯酚、聚乙烯醇等原料制成,本发明以椰壳制备多孔碳纤维,经多次改性工艺处理,得到高机械强度、高吸附性的多孔碳纤维,能够有效的负载并分散二氧化钛光催化剂,提高接触面积,增加催化效率,且碳结构的稳定性保证了材料的长效使用,由此获得的活性碳纤维具备吸附与降解双重功能,同时制备成本低廉,方法简单,可以进行大量生产,针对各类封闭及半开放环境中的杀菌和环境净化具有显著作用。
Description
技术领域
本发明涉及环境工程技术领域,尤其涉及一种光催化降解复合材料的制备方法。
背景技术
近年来伴随着我国的工业发展,环境污染已经严重影响了人民的生活和身体健康,随着人类对生活环境要求的日益提高,除了对外界周围开放环境的质量要求较高外,还对其所生活和娱乐的封闭或半封闭环境质量也提出了较高的要求,此类封闭环境如酒吧、迪厅、K 歌房、汽车车厢等,由于人流量巨大、装修装饰材料及家具的污染,使得其中的细菌、真菌等含量偏高,对其的处理成为一个亟待解决的问题。
多孔碳纤维是一种新型的多孔纤维状吸附材料,因其独特的孔隙结构和形态而具有较一般多孔炭更大的比表面积、更高的孔容、更快的吸附速率和更强的再生能力。自从上世纪七十年代问世以来,就被广泛应用于空气净化、废气废水处理、军事防护、金属回收、电子器材等方面。目前,市场上的多孔碳纤维主要有聚丙烯腈基多孔碳纤维、沥青基多孔碳纤维、粘胶基多孔碳纤维和酚醛基多孔碳纤维等,不同碳纤维在碳化速度、产碳率、孔隙率以及碳化后的韧性均不一样。因此,需要结合传统碳纤维制备方法,通过优化改进工艺,提供孔径小、孔隙率高、纤维均一性好以及结合力强的多孔碳纤维。
碳纤维尽管具有较大的吸附能力及效果,但其自身不能消纳污染物,容易造成二次污染。光催化处理技术由于可以将有机污染物还原成无机物,且反应速度快,光的利用效率高及无二次污染等特性被广泛关注。其中,如何提高光催化材料对于环境污染的处理能力成为研究的热点。其中一种方法是将碳与光催化剂复合,利用碳的导电性,提高光催化剂的性能。
由于碳纤维的制备工艺包括碳化或石墨化,使得碳纤维表面的碳原子堆叠取向更一致,原子层间距更小,所以纤维表面表现为非极性和化学惰性,另外碳纤维表面有疏水、光滑、吸附性能低等缺点,导致碳纤维与其复合的材料间界面粘结性差。因此,需要对碳纤维表面进行改性,提高其与复合材料的界面粘结强度。
发明内容
本发明目的就是为了弥补已有技术的缺陷,提供一种光催化降解复合材料的制备方法。
本发明是通过以下技术方案实现的:
一种光催化降解复合材料的制备方法,包括以下步骤:
(1)将硅烷偶联剂和80%乙醇溶液按质量比(0.5-1):20混合搅拌均匀,得混合液A备用,将酞酸丁酯和无水乙醇按质量比1:(10-15)混合搅拌均匀,得混合液B备用;
(2)将纺丝液置于静电纺丝仪中,使用铝箔纸包裹接收器,使初纺纤维收集在铝箔纸上,纺丝过程工艺参数为正压15-16kV,负压1.5-2kV,推进速率0.04-0.05mm/min,接收速率30-32r/min,针头与接收器之间距离为15-18cm,环境温度30-40℃,纺丝完成后在室温下静置一天,得到初纺纤维,再将其置于烘箱中,升温至160-170℃固化60-70分钟,取出后再送入管式炉中,在氮气气氛下以5-10℃/min的升温速率从室温升至750-850℃,保温1-2小时,自然冷却后得到碳纤维备用;
(3)以步骤2所得碳纤维作为阳极,石墨为阴极,在质量分数为8-10%的磷酸铵电解质中,控制电流密度为0.3-0.35A/m2,阳极氧化处理1.5-2分钟,收集碳纤维用清水冲洗净,得到改性碳纤维备用;
(4)将步骤3所得改性碳纤维浸入步骤1所得混合液A中,浸润后收集并送入干燥箱中于65-85℃烘干备用;
(5)将步骤4所得产物与步骤1所得混合液B按质量比1:(8-10)混合,再用乙酸溶液调节pH至3.5-4.5,之后置于水热高压反应釜中,在150-160℃下恒温反应20-24小时,反应结束后将反应釜内碳纤维用乙醇和清水反复清洗,并于50-60℃下干燥,即得本发明复合材料。
所述硅烷偶联剂为疏丙基三乙氧基硅烷、氨丙基三乙氧基硅烷、疏丙基三甲氧基硅烷中的任意一种。
所述步骤2中纺丝液的制备方法为将椰壳粉碎过100-120目筛,烘干后与苯酚、浓硫酸按质量比(5-7):(20-25):(0.6-0.9)混合并搅拌均匀,置于140-160℃油浴锅中反应100-120分钟,之后降至室温,加入氢氧化钠中和pH至中性,将产物与80%二恶烷水溶液按体积比1:(9-11)混合搅拌60-80分钟,离心并过滤,除去残渣后将滤液经旋转蒸发仪在60-70℃下浓缩,除去二恶烷,得纯液化物,再与聚乙烯醇按质量比(45-46):(4-5)混合后用氢氧化钠调节pH至10-11,之后加入甲醛溶液,升温至80-85℃,反应2-3小时后冷却至室温,得到纺丝液。
所述步骤4中浸渍过程循环3-6次,每次待改性碳纤维全部浸润后取出并滤干,之后再次浸渍。
所述步骤5中乙酸溶液物质的量浓度为0.5mol/L。
所述的纺丝液的制备方法,加入的甲醛和苯酚物质的量之比为n(甲醛):n(苯酚)=(1.4-1.5):1。
本发明的优点是:
本发明采用苯酚液化的方法,将椰壳液化为多活性小分子,避免传统木质素因结构复杂且含大量杂质,直接用于纺丝效果不理想的缺陷,再以酚醛为单元连接为高聚物,具有更快的碳化速度、更高的产碳率和孔隙率,并且酚醛树脂由于形成交联结构,所以碳化后仍可保持一定韧性,再结合静电纺丝优化的工艺参数处理,较传统的熔融纺丝,使纤维直径更细,达到纳米级,从而具有更大的比表面积,以此得到的巨大吸附性能能够有效的负载并分散二氧化钛光催化剂,提高接触面积,增加催化效率,且碳结构的稳定性保证了材料的长效使用,由此获得的活性碳纤维具备吸附与降解双重功能,同时制备成本低廉,方法简单,可以进行大量生产,针对各类封闭及半开放环境中的杀菌和环境净化具有显著作用。
具体实施方式
一种光催化降解复合材料的制备方法,包括以下步骤:
(1)将氨丙基三乙氧基硅烷和80%乙醇溶液按质量比0.8:20混合搅拌均匀,得混合液A备用,将酞酸丁酯和无水乙醇按质量比1:12混合搅拌均匀,得混合液B备用;
(2)将纺丝液置于静电纺丝仪中,使用铝箔纸包裹接收器,使初纺纤维收集在铝箔纸上,纺丝过程工艺参数为正压15kV,负压1.5kV,推进速率0.04mm/min,接收速率30r/min,针头与接收器之间距离为15cm,环境温度30℃,纺丝完成后在室温下静置一天,得到初纺纤维,再将其置于烘箱中,升温至160℃固化60分钟,取出后再送入管式炉中,在氮气气氛下以5℃/min的升温速率从室温升至750℃,保温1小时,自然冷却后得到碳纤维备用;
(3)以步骤2所得碳纤维作为阳极,石墨为阴极,在质量分数为8%的磷酸铵电解质中,控制电流密度为0.3A/m2,阳极氧化处理1.5分钟,收集碳纤维用清水冲洗净,得到改性碳纤维备用;
(4)将步骤3所得改性碳纤维浸入步骤1所得混合液A中,浸润后收集并送入干燥箱中于65℃烘干备用,浸渍过程循环3次,每次待改性碳纤维全部浸润后取出并滤干,之后再次浸渍;
(5)将步骤4所得产物与步骤1所得混合液B按质量比1:9混合,再用物质的量浓度为0.5mol/L乙酸溶液调节pH至3.5,之后置于水热高压反应釜中,在150℃下恒温反应20小时,反应结束后将反应釜内碳纤维用乙醇和清水反复清洗,并于50℃下干燥,即得本发明复合材料。
所述纺丝液的制备方法为将椰壳粉碎过100目筛,烘干后与苯酚、浓硫酸按质量比6:22:0.8混合并搅拌均匀,置于140℃油浴锅中反应100分钟,之后降至室温,加入氢氧化钠中和pH至中性,将产物与80%二恶烷水溶液按体积比1:10混合搅拌60分钟,离心并过滤,除去残渣后将滤液经旋转蒸发仪在60℃下浓缩,除去二恶烷,得纯液化物,再与聚乙烯醇按质量比45:4混合后用氢氧化钠调节pH至10,之后加入甲醛溶液,加入的甲醛和苯酚物质的量之比为n(甲醛):n(苯酚)=1.5:1,升温至80℃,反应2小时后冷却至室温,得到纺丝液。
Claims (6)
1.一种光催化降解复合材料的制备方法,其特征在于,包括以下步骤:
(1)将硅烷偶联剂和80%乙醇溶液按质量比(0.5-1):20混合搅拌均匀,得混合液A备用,将酞酸丁酯和无水乙醇按质量比1:(10-15)混合搅拌均匀,得混合液B备用;
(2)将纺丝液置于静电纺丝仪中,使用铝箔纸包裹接收器,使初纺纤维收集在铝箔纸上,纺丝过程工艺参数为正压15-16kV,负压1.5-2kV,推进速率0.04-0.05mm/min,接收速率30-32r/min,针头与接收器之间距离为15-18cm,环境温度30-40℃,纺丝完成后在室温下静置一天,得到初纺纤维,再将其置于烘箱中,升温至160-170℃固化60-70分钟,取出后再送入管式炉中,在氮气气氛下以5-10℃/min的升温速率从室温升至750-850℃,保温1-2小时,自然冷却后得到碳纤维备用;
(3)以步骤2所得碳纤维作为阳极,石墨为阴极,在质量分数为8-10%的磷酸铵电解质中,控制电流密度为0.3-0.35A/m2,阳极氧化处理1.5-2分钟,收集碳纤维用清水冲洗净,得到改性碳纤维备用;
(4)将步骤3所得改性碳纤维浸入步骤1所得混合液A中,浸润后收集并送入干燥箱中于65-85℃烘干备用;
(5)将步骤4所得产物与步骤1所得混合液B按质量比1:(8-10)混合,再用乙酸溶液调节pH至3.5-4.5,之后置于水热高压反应釜中,在150-160℃下恒温反应20-24小时,反应结束后将反应釜内碳纤维用乙醇和清水反复清洗,并于50-60℃下干燥,即得本发明复合材料。
2.根据权利要求1所述的光催化降解复合材料的制备方法,其特征在于,所述硅烷偶联剂为疏丙基三乙氧基硅烷、氨丙基三乙氧基硅烷、疏丙基三甲氧基硅烷中的任意一种。
3.根据权利要求1所述的光催化降解复合材料的制备方法,其特征在于,所述步骤2中纺丝液的制备方法为将椰壳粉碎过100-120目筛,烘干后与苯酚、浓硫酸按质量比(5-7):(20-25):(0.6-0.9)混合并搅拌均匀,置于140-160℃油浴锅中反应100-120分钟,之后降至室温,加入氢氧化钠中和pH至中性,将产物与80%二恶烷水溶液按体积比1:(9-11)混合搅拌60-80分钟,离心并过滤,除去残渣后将滤液经旋转蒸发仪在60-70℃下浓缩,除去二恶烷,得纯液化物,再与聚乙烯醇按质量比(45-46):(4-5)混合后用氢氧化钠调节pH至10-11,之后加入甲醛溶液,升温至80-85℃,反应2-3小时后冷却至室温,得到纺丝液。
4.根据权利要求1所述的光催化降解复合材料的制备方法,其特征在于,所述步骤4中浸渍过程循环3-6次,每次待改性碳纤维全部浸润后取出并滤干,之后再次浸渍。
5.根据权利要求1所述的光催化降解复合材料的制备方法,其特征在于,所述步骤5中乙酸溶液物质的量浓度为0.5mol/L。
6.根据权利要求3所述的纺丝液的制备方法,其特征在于,加入的甲醛和苯酚物质的量之比为n(甲醛):n(苯酚)=(1.4-1.5):1。
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