微介孔材料的制备、表征及气体吸附性能研究
发布时间：2018-09-11 10:58
【摘要】：近年来随着工业生产发展和人民生活水平提高,石化资源的过度消耗和排放以及人口暴涨等问题造成的能源枯竭和“温室效应”等环境压力与日俱增。无论氢气、甲烷等清洁气态能源的开发利用,还是环境保护中二氧化碳等排放气体的回收治理都迫在眉睫。目前,解决气态能源回收和利用过程中存在的关键问题之一在于气体的吸附存储。多孔固体材料包含巨大的比表面积和丰富的孔道结构,具有吸附性能强,热稳定性高,环境友好,使用成本低等优点,因而在气体的吸附、分离和储存方面有广泛的应用前景。在文中,我们制备了氮化硼、氧化铝和金属-有机框架MIL-53(Al)三种非金属多孔材料,分别考察了它们对二氧化碳和甲烷气体的吸附性能。论文研究成果如下:(1)在氨气气氛中不同温度热处理制备了一系列的氨化氮化硼并进行表征,考察了热处理温度对氨化氮化硼吸附二氧化碳和甲烷的影响,并与在氮气气氛中热处理合成的氮化硼的气体吸附性能进行比较。结果表明:热处理温度对氨化氮化硼的结晶度、微观形貌、热稳定性、孔结构等性质都有影响,其中1400?C热处理制备的氨化氮化硼比表面积和孔容最大,相对应的二氧化碳气体和甲烷气体吸附量也最高,分别为2.14mmol/g和0.07mmol/g;由于表面氨基的影响,氨化氮化硼比在氮气气氛中合成的较高比表面积的多孔氮化硼和活性氮化硼具有更高的二氧化碳和甲烷的吸附能力。(2)采用新工艺制备得到介孔?氧化铝,结果显示该介孔?氧化铝呈现纳米线形貌,比表面积高达120m2/g,在0?C、常压条件下的二氧化碳和甲烷的吸附量分别为0.7mmol/g和0.06mmol/g。?氧化铝对氢气吸附为多层吸附,在3.0MPa、液氮温度和25?C氢气的吸附量分别为5.57wt%和1.51wt%,可以应用于氢气气体的存储。同时,根据表征数据对?氧化铝纳米线的形成机制进行了推理。(3)以氯化铝为铝源反应物,在190°C温度条件下,合成的金属-有机框架材料MIL-53(Al)在常压下对二氧化碳的吸附量高达4.49mmol/g,优于介孔活性炭最高吸附量2.25mmol/g;反应过程中添加盐酸和醋酸,框架材料的结晶度增高,产率增加,微观形貌发生变化,比表面积增大,具有单一孔径的微孔结构,热稳定性提高;特别是盐酸辅助合成的MIL-53(Al)HCl材料不仅可以作为低浓度二氧化碳的潜在吸附剂,同时对甲烷气体的吸附能力高于醋酸和未加酸合成的样品。(4)综合比较上述三种非金属多孔吸附材料对气体的吸附能力,研究发现金属-有机框架材料MIL-53(Al)对二氧化碳和甲烷的吸附都高于氮化硼和氧化铝,而且三种材料对二氧化碳的吸附力都大大高于对甲烷的吸附力,有利于气体选择性吸附。
[Abstract]:In recent years, with the development of industrial production and the improvement of people's living standard, the energy depletion caused by excessive consumption and emission of petrochemical resources and population explosion, and environmental pressures such as "Greenhouse Effect" are increasing day by day. No matter hydrogen, methane and other clean gas energy development and utilization, or environmental protection of carbon dioxide emissions recovery treatment are urgent. At present, one of the key problems in the recovery and utilization of gaseous energy is the adsorption and storage of gas. Porous solid materials have many advantages, such as large specific surface area and abundant pore structure, such as high adsorption performance, high thermal stability, environmental friendliness, low cost and so on. Therefore, porous solid materials have a wide application prospect in gas adsorption, separation and storage. In this paper, three kinds of nonmetallic porous materials, boron nitride, alumina and metal-organic frame MIL-53 (Al), were prepared and their adsorption properties for carbon dioxide and methane were investigated. The results are as follows: (1) A series of boron nitride were prepared and characterized by heat treatment at different temperatures in ammonia atmosphere. The effects of heat treatment temperature on adsorption of carbon dioxide and methane by boron nitride were investigated. The adsorption properties of boron nitride prepared by heat treatment in nitrogen atmosphere were compared. The results show that the heat treatment temperature has an effect on the crystallinity, micromorphology, thermal stability and pore structure of boron nitride, among which the specific surface area and pore volume of boron nitride prepared by 1400C heat treatment are the largest. The corresponding carbon dioxide gas and methane gas have the highest adsorption capacity, which are 2.14mmol/g and 0.07 mmol / g, respectively; due to the influence of surface amino groups, The porous boron nitride and active boron nitride synthesized in nitrogen atmosphere have higher adsorption capacity of carbon dioxide and methane. (2) mesoporous? Alumina, the results show that the mesoporous? Alumina exhibits nanowire morphology with a specific surface area of 120 m2 / g. The adsorption amounts of carbon dioxide and methane at normal pressure are 0.7mmol/g and 0.06 mmol / g 路? The adsorption of aluminum oxide to hydrogen is multilayer adsorption. At 3.0 MPA, the adsorption capacity of liquid nitrogen temperature and 25 C hydrogen are 5.57 wt% and 1.51wt, respectively, which can be applied to the storage of hydrogen gas. At the same time, according to the representation data? The formation mechanism of alumina nanowires was inferred. (3) using aluminum chloride as aluminum source reactant, at 190 掳C temperature, The adsorbed amount of carbon dioxide by MIL-53 (Al) at atmospheric pressure is up to 4.49 mmol / g, which is better than the maximum adsorption capacity of mesoporous activated carbon at 2.25 mmol / g. The crystallinity and yield of the frame material increase with the addition of hydrochloric acid and acetic acid in the reaction process. The microcosmic morphology changed, the specific surface area increased, the micropore structure with a single pore size and the thermal stability were improved. Especially, the MIL-53 (Al) HCl material assisted by hydrochloric acid could not only be used as a potential adsorbent for low concentration carbon dioxide. At the same time, the adsorption capacity of methane gas was higher than that of acetic acid and non-acid-added samples. (4) the adsorption capacity of the above three non-metallic porous adsorption materials was compared. It is found that the adsorption of carbon dioxide and methane by metal-organic framework material MIL-53 (Al) is higher than that of boron nitride and alumina, and the adsorption power of the three materials to carbon dioxide is much higher than that of methane, which is favorable for gas selective adsorption.
【学位授予单位】：河北工业大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB383.4;O647.3
[Abstract]:In recent years, with the development of industrial production and the improvement of people's living standard, the energy depletion caused by excessive consumption and emission of petrochemical resources and population explosion, and environmental pressures such as "Greenhouse Effect" are increasing day by day. No matter hydrogen, methane and other clean gas energy development and utilization, or environmental protection of carbon dioxide emissions recovery treatment are urgent. At present, one of the key problems in the recovery and utilization of gaseous energy is the adsorption and storage of gas. Porous solid materials have many advantages, such as large specific surface area and abundant pore structure, such as high adsorption performance, high thermal stability, environmental friendliness, low cost and so on. Therefore, porous solid materials have a wide application prospect in gas adsorption, separation and storage. In this paper, three kinds of nonmetallic porous materials, boron nitride, alumina and metal-organic frame MIL-53 (Al), were prepared and their adsorption properties for carbon dioxide and methane were investigated. The results are as follows: (1) A series of boron nitride were prepared and characterized by heat treatment at different temperatures in ammonia atmosphere. The effects of heat treatment temperature on adsorption of carbon dioxide and methane by boron nitride were investigated. The adsorption properties of boron nitride prepared by heat treatment in nitrogen atmosphere were compared. The results show that the heat treatment temperature has an effect on the crystallinity, micromorphology, thermal stability and pore structure of boron nitride, among which the specific surface area and pore volume of boron nitride prepared by 1400C heat treatment are the largest. The corresponding carbon dioxide gas and methane gas have the highest adsorption capacity, which are 2.14mmol/g and 0.07 mmol / g, respectively; due to the influence of surface amino groups, The porous boron nitride and active boron nitride synthesized in nitrogen atmosphere have higher adsorption capacity of carbon dioxide and methane. (2) mesoporous? Alumina, the results show that the mesoporous? Alumina exhibits nanowire morphology with a specific surface area of 120 m2 / g. The adsorption amounts of carbon dioxide and methane at normal pressure are 0.7mmol/g and 0.06 mmol / g 路? The adsorption of aluminum oxide to hydrogen is multilayer adsorption. At 3.0 MPA, the adsorption capacity of liquid nitrogen temperature and 25 C hydrogen are 5.57 wt% and 1.51wt, respectively, which can be applied to the storage of hydrogen gas. At the same time, according to the representation data? The formation mechanism of alumina nanowires was inferred. (3) using aluminum chloride as aluminum source reactant, at 190 掳C temperature, The adsorbed amount of carbon dioxide by MIL-53 (Al) at atmospheric pressure is up to 4.49 mmol / g, which is better than the maximum adsorption capacity of mesoporous activated carbon at 2.25 mmol / g. The crystallinity and yield of the frame material increase with the addition of hydrochloric acid and acetic acid in the reaction process. The microcosmic morphology changed, the specific surface area increased, the micropore structure with a single pore size and the thermal stability were improved. Especially, the MIL-53 (Al) HCl material assisted by hydrochloric acid could not only be used as a potential adsorbent for low concentration carbon dioxide. At the same time, the adsorption capacity of methane gas was higher than that of acetic acid and non-acid-added samples. (4) the adsorption capacity of the above three non-metallic porous adsorption materials was compared. It is found that the adsorption of carbon dioxide and methane by metal-organic framework material MIL-53 (Al) is higher than that of boron nitride and alumina, and the adsorption power of the three materials to carbon dioxide is much higher than that of methane, which is favorable for gas selective adsorption.
【学位授予单位】：河北工业大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TB383.4;O647.3
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