生物活性炭纤维负载CuO降解苯酚的研究
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摘要
生物模板法是近年来发展起来的制备纳米材料的一种新技术。其方法是利用生物天然形成的结构作为模板,通过模板在前驱体溶液浸渍、焙烧两步法形成目标材料。然而利用这种技术制备得到的目标材料为单一氧化物,未能保留生物模板中的炭,而生物活性炭有很好的吸附性能,在许多领域尤其是催化方面有广泛应用。
在以前的相关研究中,生物模板中的炭元素没有得到充分利用。针对这一问题,本论文研究了活性炭纤维负载CuO的复合催化剂。CuO是降解苯酚的良好催化剂,而生物活性炭纤维由于其特殊的孔道结构具有很好的吸附性能,生物活性炭纤维负载CuO催化剂具备二者的复合作用,能有效地催化降解污水中的苯酚等有机物。
作为基础研究,本文选取具有典型结构的天然植物木棉纤维为模板材料,进行炭化、活化处理,制备具有高比表面积的生物活性炭纤维。然后再经金属盐溶液的浸渍、气氛保护烧结,制备出保留有原生物模板形态的复合催化剂。
本论文探索了一种利用生物模板制备生物活性炭负载氧化物的复合催化剂的工艺方法。利用硝酸铜溶液为前驱体溶液,木棉纤维为模板,研究了实验工艺条件对合成的目标材料的影响,确定了制备活性炭纤维的最佳工艺条件。通过对实验工艺的探索,实现了对目标材料形貌的合理控制,成功制备出目标材料并对其催化性能进行了表征。
本论文研究了物理和化学两种活化方法对木棉基活性炭纤维的结构与性能的影响。制备了木棉基活性炭纤维负载的CuO复合催化剂,分析了不同CuO负载量的催化剂在结构、形貌等方面的特征,并测试了所制备的催化剂对苯酚的吸附和降解作用。通过能谱仪(EDS)、扫描电子显微镜(SEM)、拉曼光谱仪、X射线衍射仪(XRD)和红外(FTIR)、氮气吸附脱附等测试方法对材料进行结构分析和表征。利用亚甲基蓝吸附及苯酚降解实验对目标材料的性能进行了表征。
得到如下主要结论:
1.以木棉纤维作为模板,通过模板炭化、活化处理,成功制备出了木棉基生物活性炭纤维(ACFs)。得到制备高比表面积的活性炭纤维的炭化温度为850℃、最佳活化温度为1000℃,活化剂CO_2通气量为20 ml/min,活化时间为2h时制备的活性炭纤维具有最大比表面积(1400 m2/g)。
2.采用不同浓度的KOH、NaOH和ZnCl_2对木棉炭纤维进行活化,制备了活性炭纤维并测试分析了各组样品的结构和形貌特征。结果表明经过10%的KOH和10%与40%的NaOH活化的木棉基炭纤维的比表面积较大。
3.以生物活性炭纤维为模板,通过其在硝酸铜溶液中浸渍、烘干、氮气保护焙烧制得了负载CuO的活性炭纤维复合催化剂。活性炭纤维/CuO复合催化剂的制备工艺为:浸渍时间为24 h,活性炭纤维和CuO质量比为1:1和1:9,氮气保护焙烧温度为350℃。
4.用不同CuO负载量的CuO/生物活性炭纤维复合催化剂催化降解苯酚,催化结果表明:活性炭纤维和CuO质量比为1:1的样品物理吸附速度较快而活性炭纤维和CuO质量比为1:9的样品对苯酚的降解作用较强。这是因为前者活性炭纤维含量较大,在与苯酚的反应过程中活性炭的物理吸附作用占主导地位,后者是因为大量的CuO附着在活性炭上,降低了孔结构的含量,因此物理吸附速度不如前者快但是催化降解作用更强。
Biological template method is a new technology developed in recent years for preparing nano materials. The method is that the nano structures of inartificial biological materials are used as the templates and the target materials can be formed through two steps of impregnation in precursor and air calcination. The target materials prepared by this technology are always single oxides without the remaining of carbon element in the templates. However, the biological activated carbon exhibits excellent properties of physical adsorption, which can be employed widely in many fields especially for the catalytic applications.
In the relative investigations before, the carbon element in the bio-template has not been utilized adequately. Aiming to this problem, the study to obtain the composite materials of CuO/ activated carbon fibers is performed in this thesis. Because CuO is an excellent catalyst for phenol degradation, and biological activated carbon fibers possess superior properties of physical adsorption due to their unique structure with pore channels. Proceed from the composite effect, the biological activated carbon fibers loading with CuO catalyst can effectively catalyze the degradation of phenol and other organic matters in sewage.
As a basic study, natural plant kapok fiber with a typical structure is chosen as the template materialin this thesis. The biological activated carbon fibers with high surface area and good morphology are prepared through the process of carbonization and activation for kapok fiber. And the composite materials retaining the original biological template form are fabricated by impregnating the template in metal salt solution and the process of sintering under atmosphere protection.
A simple process route for preparing composite catalyst of biological activated carbon supported oxide through biological templates is attempted in this thesis. With copper nitrate solution as the precursor solution and kapok as the template, the optimum preparing conditions for activated carbon fibers are determined and the effect of experimental conditions on the synthesized target materials is studied. Through the exploration for experimental process, the reasonable control for the morphology of the target material is achieved. As a result, the target material CuO/ activated carbon fibers are prepared successfully and their catalytic properties are characterized.
In this thesis, the effect of physical and chemical activation methods on the structures and properties of kapok based biological activated carbon fiber (kapok-ACFs) is studied. CuO/ACF composite catalyst is prepared and the characters on structure and mophology as well as the adsorption and degradation to phenol of catalyst with different CuO contents are analyzied. Energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), infrared (FTIR), and nitrogen adsorption-desorption test method are adopted for the analysis and characterization on structure of materials. Methylene blue adsorption and phenol degradation test are utilized to characterize the properties of materials.
The main conclusions are as follows:
1. Using the kapok fiber as a template, kapok-ACFs are successfully prepared through carbonization and activation for template. For fabricating kapok-ACFs with high specific surface, the best carbonization temperature is 850℃, activation temperature is 1000, ventilation of activator CO_2 is 20 ml/min and activation time is 2h. Under this preparing process, the obtained kapok-ACFs show the largest specific surface of 1400 m2/g.
2. Employing different concentrations of KOH, NaOH and ZnCl_2 for the activators, the kapok-ACFs are prepared and their structures and morphologies are analyzed. The results show that the kapok-ACFs activating by KOH of 10% and 40%as well as NaOH of 40% possess larger specific surface.
3. With biological activated carbon fiber (kapok-ACFs) as a template, through immersing of the template in the copper nitrate solution, drying and calcination in nitrogen atmophere, CuO/ACF composite catalyst is obtained. The immersing time of 24 h, activated carbon fibers and CuO mass ratio of 1:1 and 1:9, and calcination temperature of 350℃in nitrogen are adopted as the process parameters for preparing CuO/ACF composite catalyst.
4. The CuO /ACF composite catalyst with different CuO contents are used to the degradation of phenol. The catalytic results show that sample with activated carbon fiber and CuO mass ratio of 1:1 exhibits faster physical adsorption while that with activated carbon fibers and CuO mass ratio of 1:9 shows stronger degradation capability to phenol. This phenomenon is due to the higher content of the activated carbon fiber in the former which result in that the physical adsorption of activated carbon fibers is dominate in the reaction between CuO/ACF and phenol. However, the activated carbon fibers attached by a large number of CuO shows reducing content of the pore, and possess a slower physical adsorption rate while a stronger ability of the catalytic degradation.
在以前的相关研究中,生物模板中的炭元素没有得到充分利用。针对这一问题,本论文研究了活性炭纤维负载CuO的复合催化剂。CuO是降解苯酚的良好催化剂,而生物活性炭纤维由于其特殊的孔道结构具有很好的吸附性能,生物活性炭纤维负载CuO催化剂具备二者的复合作用,能有效地催化降解污水中的苯酚等有机物。
作为基础研究,本文选取具有典型结构的天然植物木棉纤维为模板材料,进行炭化、活化处理,制备具有高比表面积的生物活性炭纤维。然后再经金属盐溶液的浸渍、气氛保护烧结,制备出保留有原生物模板形态的复合催化剂。
本论文探索了一种利用生物模板制备生物活性炭负载氧化物的复合催化剂的工艺方法。利用硝酸铜溶液为前驱体溶液,木棉纤维为模板,研究了实验工艺条件对合成的目标材料的影响,确定了制备活性炭纤维的最佳工艺条件。通过对实验工艺的探索,实现了对目标材料形貌的合理控制,成功制备出目标材料并对其催化性能进行了表征。
本论文研究了物理和化学两种活化方法对木棉基活性炭纤维的结构与性能的影响。制备了木棉基活性炭纤维负载的CuO复合催化剂,分析了不同CuO负载量的催化剂在结构、形貌等方面的特征,并测试了所制备的催化剂对苯酚的吸附和降解作用。通过能谱仪(EDS)、扫描电子显微镜(SEM)、拉曼光谱仪、X射线衍射仪(XRD)和红外(FTIR)、氮气吸附脱附等测试方法对材料进行结构分析和表征。利用亚甲基蓝吸附及苯酚降解实验对目标材料的性能进行了表征。
得到如下主要结论:
1.以木棉纤维作为模板,通过模板炭化、活化处理,成功制备出了木棉基生物活性炭纤维(ACFs)。得到制备高比表面积的活性炭纤维的炭化温度为850℃、最佳活化温度为1000℃,活化剂CO_2通气量为20 ml/min,活化时间为2h时制备的活性炭纤维具有最大比表面积(1400 m2/g)。
2.采用不同浓度的KOH、NaOH和ZnCl_2对木棉炭纤维进行活化,制备了活性炭纤维并测试分析了各组样品的结构和形貌特征。结果表明经过10%的KOH和10%与40%的NaOH活化的木棉基炭纤维的比表面积较大。
3.以生物活性炭纤维为模板,通过其在硝酸铜溶液中浸渍、烘干、氮气保护焙烧制得了负载CuO的活性炭纤维复合催化剂。活性炭纤维/CuO复合催化剂的制备工艺为:浸渍时间为24 h,活性炭纤维和CuO质量比为1:1和1:9,氮气保护焙烧温度为350℃。
4.用不同CuO负载量的CuO/生物活性炭纤维复合催化剂催化降解苯酚,催化结果表明:活性炭纤维和CuO质量比为1:1的样品物理吸附速度较快而活性炭纤维和CuO质量比为1:9的样品对苯酚的降解作用较强。这是因为前者活性炭纤维含量较大,在与苯酚的反应过程中活性炭的物理吸附作用占主导地位,后者是因为大量的CuO附着在活性炭上,降低了孔结构的含量,因此物理吸附速度不如前者快但是催化降解作用更强。
Biological template method is a new technology developed in recent years for preparing nano materials. The method is that the nano structures of inartificial biological materials are used as the templates and the target materials can be formed through two steps of impregnation in precursor and air calcination. The target materials prepared by this technology are always single oxides without the remaining of carbon element in the templates. However, the biological activated carbon exhibits excellent properties of physical adsorption, which can be employed widely in many fields especially for the catalytic applications.
In the relative investigations before, the carbon element in the bio-template has not been utilized adequately. Aiming to this problem, the study to obtain the composite materials of CuO/ activated carbon fibers is performed in this thesis. Because CuO is an excellent catalyst for phenol degradation, and biological activated carbon fibers possess superior properties of physical adsorption due to their unique structure with pore channels. Proceed from the composite effect, the biological activated carbon fibers loading with CuO catalyst can effectively catalyze the degradation of phenol and other organic matters in sewage.
As a basic study, natural plant kapok fiber with a typical structure is chosen as the template materialin this thesis. The biological activated carbon fibers with high surface area and good morphology are prepared through the process of carbonization and activation for kapok fiber. And the composite materials retaining the original biological template form are fabricated by impregnating the template in metal salt solution and the process of sintering under atmosphere protection.
A simple process route for preparing composite catalyst of biological activated carbon supported oxide through biological templates is attempted in this thesis. With copper nitrate solution as the precursor solution and kapok as the template, the optimum preparing conditions for activated carbon fibers are determined and the effect of experimental conditions on the synthesized target materials is studied. Through the exploration for experimental process, the reasonable control for the morphology of the target material is achieved. As a result, the target material CuO/ activated carbon fibers are prepared successfully and their catalytic properties are characterized.
In this thesis, the effect of physical and chemical activation methods on the structures and properties of kapok based biological activated carbon fiber (kapok-ACFs) is studied. CuO/ACF composite catalyst is prepared and the characters on structure and mophology as well as the adsorption and degradation to phenol of catalyst with different CuO contents are analyzied. Energy dispersive spectroscopy (EDS), scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), infrared (FTIR), and nitrogen adsorption-desorption test method are adopted for the analysis and characterization on structure of materials. Methylene blue adsorption and phenol degradation test are utilized to characterize the properties of materials.
The main conclusions are as follows:
1. Using the kapok fiber as a template, kapok-ACFs are successfully prepared through carbonization and activation for template. For fabricating kapok-ACFs with high specific surface, the best carbonization temperature is 850℃, activation temperature is 1000, ventilation of activator CO_2 is 20 ml/min and activation time is 2h. Under this preparing process, the obtained kapok-ACFs show the largest specific surface of 1400 m2/g.
2. Employing different concentrations of KOH, NaOH and ZnCl_2 for the activators, the kapok-ACFs are prepared and their structures and morphologies are analyzed. The results show that the kapok-ACFs activating by KOH of 10% and 40%as well as NaOH of 40% possess larger specific surface.
3. With biological activated carbon fiber (kapok-ACFs) as a template, through immersing of the template in the copper nitrate solution, drying and calcination in nitrogen atmophere, CuO/ACF composite catalyst is obtained. The immersing time of 24 h, activated carbon fibers and CuO mass ratio of 1:1 and 1:9, and calcination temperature of 350℃in nitrogen are adopted as the process parameters for preparing CuO/ACF composite catalyst.
4. The CuO /ACF composite catalyst with different CuO contents are used to the degradation of phenol. The catalytic results show that sample with activated carbon fiber and CuO mass ratio of 1:1 exhibits faster physical adsorption while that with activated carbon fibers and CuO mass ratio of 1:9 shows stronger degradation capability to phenol. This phenomenon is due to the higher content of the activated carbon fiber in the former which result in that the physical adsorption of activated carbon fibers is dominate in the reaction between CuO/ACF and phenol. However, the activated carbon fibers attached by a large number of CuO shows reducing content of the pore, and possess a slower physical adsorption rate while a stronger ability of the catalytic degradation.
引文
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