多孔聚合物—活性炭纳米复合材料的制备及性能研究
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摘要
活性炭作为一种典型的多孔材料,具有比表面积高、孔结构发达、耐高温、耐腐蚀、导电、传热、抗酸耐碱、化学稳定性好和生物相容性好等一系列优点。活性炭在吸附方面的应用已经成为研究的热点之一,它可用于气相和液相的吸附分离过程,用作防毒面具、分离精制气体、回收有机溶剂、去除重金属离子和净化污水源等。
目前,关于活性炭的吸附研究主要停留在利用活性炭的多孔特性,以物理吸附为主,但活性炭的吸附特性不仅取决于其孔结构,与表面化学性质也有很大关系,因此,研究者对活性炭表面进行化学改性使其吸附性能增强。本文中研究了将具有特殊基团的功能性聚合物引入到活性炭孔内,制备出多孔聚合物-活性炭纳米复合材料,这种材料既可以发挥活性炭的孔结构优势,还能利用聚合物链段的特殊基团对废水中有机污染物进行吸附。
多孔聚合物-无机纳米复合材料不仅能将无机材料的光、电、磁等性能与聚合物的力学性能、功能性相结合,更重要的是纳米孔的存在为材料的实际应用提供了通道,比如质子的传送、溶液的运输、气体的扩散、各种生物反应的快速进行等,使这种材料在电学、光学、生物、医药和环保等领域具有广阔的应用前景。
本文首先采用资源丰富,价格低廉的稻壳作为原料,用NaOH作为活化剂的化学活化法制备活性炭,讨论了浸渍比、活化方式、活化温度和活化时间对活性炭碘吸附值和产率的影响,并对稻壳在450℃氮气保护下炭化4h,浸渍比为3.0,在400℃下预处理30min,再升温到800℃,进行高温活化2h,洗净烘干,制备出的活性炭进行表征,发现其氮气吸附/脱附等温线为Ⅳ型,比表面为1200m~2.g~(-1),平均孔径为3.7nm,孔容积为0.67cm~3.g~(-1)。
其次,探索了将聚合物合成到活性炭孔内的方法,用冷冻充气法成功地将丙烯酸直接原位聚合在活性炭孔内。发现丙烯酸与活性炭的质量比、聚合温度和聚合时间都会对多孔聚丙烯酸-活性炭纳米复合材料的性能产生影响,当聚合反应温度为80℃,聚合反应时间达到22h,聚丙烯酸含量约为20%时,比表面积下降为349m~2.g~(-1),平均孔径下降为2.7nm,孔容积下降为0.34 cm~3.g~(-1),其红外谱图显出具有活性炭C-C键产生的峰和PAA特征键的偏移峰。并用所制备的复合材料对苯胺和硝基苯进行吸附,发现其对苯胺和硝基苯的吸附以化学吸附为主,聚合物含量越高,吸附容量越大;吸附容量随着时间的延长而增加,直至20h后趋于平衡;吸附剂用量越增加,吸附容量越大,而且吸附过程更加适用Langmuir吸附等温方程和准二级动力学方程。
最后,用搅拌法以溶液聚合法将丙烯酰胺聚合在活性炭孔内,当聚合反应的温度为90℃,反应时间达到24h,制备的出多孔聚丙烯酰胺-活性炭纳米复合材料的比表面积为611m~2.g~(-1),平均孔径为2.6nm,孔容积为0.42cm~3.g~(-1)。并用所制备的复合材料对苯酚、4-氯苯酚、五氯苯酚钠进行吸附,发现其对酚类化合物以化学吸附为主,吸附容量随着时间的延长而增加,直至20h后趋于平衡;吸附剂用量越增加,吸附容量越大,而且吸附过程更加适用Langmuir吸附等温方程和准二级动力学方程。
Activated carbon materials is a kind of typic porous nanocomposite materials which have many excellent properties such as high surface area and pore volume,a more uniform distribution of the hole diameter,high temperature and corrosion resistance,high electrical conductivity,good chemical resistant and biocompatibility stability.It has been used in gas and liquid adsorption separation process,which has become one of the research hot spots. Now activated carbon is usually used for gas masks,gas separation refuting,organic recycle, inorganic ions and heavy metals remove,sewage purification and so on.
At present,we research on activated carbon adsorption primarily relying on its porosity which is mainly in physisorption.Activated carbon adsorption characteristic is not only decided by its structure,also has the very big relations with the surface chemistry nature. Therefore,people start to modify its chemic property to improve adsorption selectivity.In this article,we introduced functionality polymer in the activated carbon holes to prepared polymer-activated carbon nanocomposite materials.The material could adsorb organic pollutant in waste water which combines porous activated carbon and polymer with special groups.
The porous polymer-inorganic nanocomposite materials could unite the light,electricity, magnetism properties of inorganic nanometer crystal and the mechanical properties, functional properties of polymer.Nanometer holes existence have provided chunnel for the material practical application such as the proton transmission,the solution transportation,the gas proliferation,biological response carrying on and so on.The kind of materials have broad application prospect in electricity,optics and biology,medicine,environmental protection field.
In this paper first we prepared activated carbon using rice husk which is low in price and fruitful and NaOH as chemistry activation.And we discussed activated carbon iodine adsorption value and the activated carbon production rate influence by soaked proportion,the activation way,the activation temperature and the activation time.We prepared activated carbon as follow:the drying rice husk was carbonized at 450℃in nitrogen for 4h,then,the carbonized product was heated in the presence of sodium hydroxide(NaOH:C=3:1) at 400℃for 30 min to dehydrate the mixture,thereafter the temperature was raised to 800℃and this temperature was held for 2 hours to activate the combination,last the activated product were washed with water and dried.Then we found its nitrogen adsorption/desorption isothermal wasⅣ,The specific surface is 1200m~2.g~(-1),the average hole diameter is 3.7nm,and the holes volume is 0.67cm~3.g~(-1).
Next,we explored the method of synthesizing the polymer in the activated carbon holes, then we successfully made acrylic acid in situ directly polymerizing in activated carbon holes with freezing aeration.We found the properties of polyacrylic acid-activated carbon nanocomposite materials influence by the acrylic acid and the activated carbon mass ratio,the polymerization temperature and the polymerization time.When the polyreaction temperature is 80℃,the reaction time is 22h,and the polypropylene acid content is approximately 20%, the specific surface reduced to 349m~2.g~(-1),the average hole diameter reduced to 2.7nm,the holes volume reduced to 0.34 cm~3.g~(-1).And we found its infrared spectrogram appears the activated carbon C-C peak and displacement peak of PAA characteristic structure.Then we used the compound materials for aniline and nitrobenzene adsorption,and we discovered that it is mainly chemical adsorption;the polymer content is higher,the adsorption effect is better; the adsorption capacity increased with the time prolonging till 20h;the absorbent amount used more,the adsorption effect is better;moreover the adsorption process is more suitable Langmuir equation and the second-level equation dynamic equation.
Finally,we prepared polyacrylamide-activated carbon nanocomposite materials using mixing solution.When the polyreaction temperature is 90℃,the reaction time is 24h,the specific surface reduced to 611m~2.g~(-1),the average hole diameter reduced to 2.6nm,the holes volume reduced to 0.42 cm~3.g~(-1).Then we used the compound materials for phenol compound, and we discovered that it is mainly chemical adsorption;the adsorption capacity increased with the time prolonging till 20h;the absorbent amount used more,the adsorption effect is better;moreover the adsorption process is more suitable Langmuir equation and the second-level equation dynamic equation.
目前,关于活性炭的吸附研究主要停留在利用活性炭的多孔特性,以物理吸附为主,但活性炭的吸附特性不仅取决于其孔结构,与表面化学性质也有很大关系,因此,研究者对活性炭表面进行化学改性使其吸附性能增强。本文中研究了将具有特殊基团的功能性聚合物引入到活性炭孔内,制备出多孔聚合物-活性炭纳米复合材料,这种材料既可以发挥活性炭的孔结构优势,还能利用聚合物链段的特殊基团对废水中有机污染物进行吸附。
多孔聚合物-无机纳米复合材料不仅能将无机材料的光、电、磁等性能与聚合物的力学性能、功能性相结合,更重要的是纳米孔的存在为材料的实际应用提供了通道,比如质子的传送、溶液的运输、气体的扩散、各种生物反应的快速进行等,使这种材料在电学、光学、生物、医药和环保等领域具有广阔的应用前景。
本文首先采用资源丰富,价格低廉的稻壳作为原料,用NaOH作为活化剂的化学活化法制备活性炭,讨论了浸渍比、活化方式、活化温度和活化时间对活性炭碘吸附值和产率的影响,并对稻壳在450℃氮气保护下炭化4h,浸渍比为3.0,在400℃下预处理30min,再升温到800℃,进行高温活化2h,洗净烘干,制备出的活性炭进行表征,发现其氮气吸附/脱附等温线为Ⅳ型,比表面为1200m~2.g~(-1),平均孔径为3.7nm,孔容积为0.67cm~3.g~(-1)。
其次,探索了将聚合物合成到活性炭孔内的方法,用冷冻充气法成功地将丙烯酸直接原位聚合在活性炭孔内。发现丙烯酸与活性炭的质量比、聚合温度和聚合时间都会对多孔聚丙烯酸-活性炭纳米复合材料的性能产生影响,当聚合反应温度为80℃,聚合反应时间达到22h,聚丙烯酸含量约为20%时,比表面积下降为349m~2.g~(-1),平均孔径下降为2.7nm,孔容积下降为0.34 cm~3.g~(-1),其红外谱图显出具有活性炭C-C键产生的峰和PAA特征键的偏移峰。并用所制备的复合材料对苯胺和硝基苯进行吸附,发现其对苯胺和硝基苯的吸附以化学吸附为主,聚合物含量越高,吸附容量越大;吸附容量随着时间的延长而增加,直至20h后趋于平衡;吸附剂用量越增加,吸附容量越大,而且吸附过程更加适用Langmuir吸附等温方程和准二级动力学方程。
最后,用搅拌法以溶液聚合法将丙烯酰胺聚合在活性炭孔内,当聚合反应的温度为90℃,反应时间达到24h,制备的出多孔聚丙烯酰胺-活性炭纳米复合材料的比表面积为611m~2.g~(-1),平均孔径为2.6nm,孔容积为0.42cm~3.g~(-1)。并用所制备的复合材料对苯酚、4-氯苯酚、五氯苯酚钠进行吸附,发现其对酚类化合物以化学吸附为主,吸附容量随着时间的延长而增加,直至20h后趋于平衡;吸附剂用量越增加,吸附容量越大,而且吸附过程更加适用Langmuir吸附等温方程和准二级动力学方程。
Activated carbon materials is a kind of typic porous nanocomposite materials which have many excellent properties such as high surface area and pore volume,a more uniform distribution of the hole diameter,high temperature and corrosion resistance,high electrical conductivity,good chemical resistant and biocompatibility stability.It has been used in gas and liquid adsorption separation process,which has become one of the research hot spots. Now activated carbon is usually used for gas masks,gas separation refuting,organic recycle, inorganic ions and heavy metals remove,sewage purification and so on.
At present,we research on activated carbon adsorption primarily relying on its porosity which is mainly in physisorption.Activated carbon adsorption characteristic is not only decided by its structure,also has the very big relations with the surface chemistry nature. Therefore,people start to modify its chemic property to improve adsorption selectivity.In this article,we introduced functionality polymer in the activated carbon holes to prepared polymer-activated carbon nanocomposite materials.The material could adsorb organic pollutant in waste water which combines porous activated carbon and polymer with special groups.
The porous polymer-inorganic nanocomposite materials could unite the light,electricity, magnetism properties of inorganic nanometer crystal and the mechanical properties, functional properties of polymer.Nanometer holes existence have provided chunnel for the material practical application such as the proton transmission,the solution transportation,the gas proliferation,biological response carrying on and so on.The kind of materials have broad application prospect in electricity,optics and biology,medicine,environmental protection field.
In this paper first we prepared activated carbon using rice husk which is low in price and fruitful and NaOH as chemistry activation.And we discussed activated carbon iodine adsorption value and the activated carbon production rate influence by soaked proportion,the activation way,the activation temperature and the activation time.We prepared activated carbon as follow:the drying rice husk was carbonized at 450℃in nitrogen for 4h,then,the carbonized product was heated in the presence of sodium hydroxide(NaOH:C=3:1) at 400℃for 30 min to dehydrate the mixture,thereafter the temperature was raised to 800℃and this temperature was held for 2 hours to activate the combination,last the activated product were washed with water and dried.Then we found its nitrogen adsorption/desorption isothermal wasⅣ,The specific surface is 1200m~2.g~(-1),the average hole diameter is 3.7nm,and the holes volume is 0.67cm~3.g~(-1).
Next,we explored the method of synthesizing the polymer in the activated carbon holes, then we successfully made acrylic acid in situ directly polymerizing in activated carbon holes with freezing aeration.We found the properties of polyacrylic acid-activated carbon nanocomposite materials influence by the acrylic acid and the activated carbon mass ratio,the polymerization temperature and the polymerization time.When the polyreaction temperature is 80℃,the reaction time is 22h,and the polypropylene acid content is approximately 20%, the specific surface reduced to 349m~2.g~(-1),the average hole diameter reduced to 2.7nm,the holes volume reduced to 0.34 cm~3.g~(-1).And we found its infrared spectrogram appears the activated carbon C-C peak and displacement peak of PAA characteristic structure.Then we used the compound materials for aniline and nitrobenzene adsorption,and we discovered that it is mainly chemical adsorption;the polymer content is higher,the adsorption effect is better; the adsorption capacity increased with the time prolonging till 20h;the absorbent amount used more,the adsorption effect is better;moreover the adsorption process is more suitable Langmuir equation and the second-level equation dynamic equation.
Finally,we prepared polyacrylamide-activated carbon nanocomposite materials using mixing solution.When the polyreaction temperature is 90℃,the reaction time is 24h,the specific surface reduced to 611m~2.g~(-1),the average hole diameter reduced to 2.6nm,the holes volume reduced to 0.42 cm~3.g~(-1).Then we used the compound materials for phenol compound, and we discovered that it is mainly chemical adsorption;the adsorption capacity increased with the time prolonging till 20h;the absorbent amount used more,the adsorption effect is better;moreover the adsorption process is more suitable Langmuir equation and the second-level equation dynamic equation.
引文
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