微介孔材料的制備、表征及氣體吸附性能研究
發(fā)布時(shí)間：2018-09-11 10:58
【摘要】：近年來隨著工業(yè)生產(chǎn)發(fā)展和人民生活水平提高,石化資源的過度消耗和排放以及人口暴漲等問題造成的能源枯竭和“溫室效應(yīng)”等環(huán)境壓力與日俱增。無論氫氣、甲烷等清潔氣態(tài)能源的開發(fā)利用,還是環(huán)境保護(hù)中二氧化碳等排放氣體的回收治理都迫在眉睫。目前,解決氣態(tài)能源回收和利用過程中存在的關(guān)鍵問題之一在于氣體的吸附存儲。多孔固體材料包含巨大的比表面積和豐富的孔道結(jié)構(gòu),具有吸附性能強(qiáng),熱穩(wěn)定性高,環(huán)境友好,使用成本低等優(yōu)點(diǎn),因而在氣體的吸附、分離和儲存方面有廣泛的應(yīng)用前景。在文中,我們制備了氮化硼、氧化鋁和金屬-有機(jī)框架MIL-53(Al)三種非金屬多孔材料,分別考察了它們對二氧化碳和甲烷氣體的吸附性能。論文研究成果如下:(1)在氨氣氣氛中不同溫度熱處理制備了一系列的氨化氮化硼并進(jìn)行表征,考察了熱處理溫度對氨化氮化硼吸附二氧化碳和甲烷的影響,并與在氮?dú)鈿夥罩袩崽幚砗铣傻牡鸬臍怏w吸附性能進(jìn)行比較。結(jié)果表明:熱處理溫度對氨化氮化硼的結(jié)晶度、微觀形貌、熱穩(wěn)定性、孔結(jié)構(gòu)等性質(zhì)都有影響,其中1400?C熱處理制備的氨化氮化硼比表面積和孔容最大,相對應(yīng)的二氧化碳?xì)怏w和甲烷氣體吸附量也最高,分別為2.14mmol/g和0.07mmol/g;由于表面氨基的影響,氨化氮化硼比在氮?dú)鈿夥罩泻铣傻妮^高比表面積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)采用新工藝制備得到介孔?氧化鋁,結(jié)果顯示該介孔?氧化鋁呈現(xiàn)納米線形貌,比表面積高達(dá)120m2/g,在0?C、常壓條件下的二氧化碳和甲烷的吸附量分別為0.7mmol/g和0.06mmol/g。?氧化鋁對氫氣吸附為多層吸附,在3.0MPa、液氮溫度和25?C氫氣的吸附量分別為5.57wt%和1.51wt%,可以應(yīng)用于氫氣氣體的存儲。同時(shí),根據(jù)表征數(shù)據(jù)對?氧化鋁納米線的形成機(jī)制進(jìn)行了推理。(3)以氯化鋁為鋁源反應(yīng)物,在190°C溫度條件下,合成的金屬-有機(jī)框架材料MIL-53(Al)在常壓下對二氧化碳的吸附量高達(dá)4.49mmol/g,優(yōu)于介孔活性炭最高吸附量2.25mmol/g;反應(yīng)過程中添加鹽酸和醋酸,框架材料的結(jié)晶度增高,產(chǎn)率增加,微觀形貌發(fā)生變化,比表面積增大,具有單一孔徑的微孔結(jié)構(gòu),熱穩(wěn)定性提高;特別是鹽酸輔助合成的MIL-53(Al)HCl材料不僅可以作為低濃度二氧化碳的潛在吸附劑,同時(shí)對甲烷氣體的吸附能力高于醋酸和未加酸合成的樣品。(4)綜合比較上述三種非金屬多孔吸附材料對氣體的吸附能力,研究發(fā)現(xiàn)金屬-有機(jī)框架材料MIL-53(Al)對二氧化碳和甲烷的吸附都高于氮化硼和氧化鋁,而且三種材料對二氧化碳的吸附力都大大高于對甲烷的吸附力,有利于氣體選擇性吸附。
[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 擄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.
【學(xué)位授予單位】：河北工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：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 擄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.
【學(xué)位授予單位】：河北工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TB383.4;O647.3
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