基于低共熔溶剂的新型吸附剂合成及其在吸附脱硫中的应用
发布时间：2018-08-12 08:54
【摘要】：随着人类对环境问题的关注,所有的发达国家与发展中国家都针对燃油中污染物制定了严格的油品质量标准。为了与欧V排放标准同步,2013年国务院常务会议明确制定了国V标准,将硫含量降低至10 ppm,并要求于2018年在全国范围内强制实行。在目前众多的脱硫技术中,吸附脱硫作为一种利用吸附原理的新兴的脱硫技术,相比于工业加氢脱硫与其他脱硫技术有较多的优点,故值得被深度发掘与研究。本工作首次使用理论计算与实验相结合的方式来讨论实验结果与现象,分别对三种非金属型低共熔溶剂(氯化胆碱/甘油,氯化胆碱/乙酸和氯化胆碱/尿素)的红外,拉曼,结构,形成机理等角度来深入讨论。结果表明先前实验工作的振动模型的归属是合理的,并且所有的实验特征峰都能够得到归属,计算所得的光谱与实验结果符合的较好。通过结构分析,静电势分析,约化密度梯度分析证明低共熔溶剂中共存着氢键作用与静电作用,进而从理论角度证明了实验红外中的红移蓝移现象。随后从π络合作用吸附机理出发,将ZnCl2/urea,SnCl2/urea作为原料,分别将金属Zn和Sn掺杂到h-BN中。结果发现在h-BN的合成过程中,此类金属型低共熔溶剂会与硼酸结合,将Zn和Sn以单质或化合物形式(Zn(CN2),SnO2)负载到h-BN表面,形成类似于异质结的复合材料。所合成的金属掺杂h-BN材料在吸附脱硫活性方面优于商品级氮化硼,其中SnO2负载BN的吸附容量可达17.93 mg/g。基于以上事实,本文从另一吸附机理出发,即软硬酸碱作用,通过在h-BN骨架中引入碳原子的方式来降低吸附剂的化学硬度,从而增强了吸附剂吸附硫化物的能力。首先通过概念密度泛函分析了不同碳原子掺杂的BN_xC材料模型的前线轨道与化学硬度。计算结果发现化学硬度都随着碳含量的提升而降低,基于这一结果本文合成了一系列不同碳含量的BCN-x用于吸附脱硫。实验结果进一步验证了猜想:BCN-x吸附剂的吸附容量随着骨架中碳原子含量的提升而提升,最高可达27.43 mg/g,成功从活性的角度证明了硬度与其吸附性能之间的构效关系。通过吸附能的计算,证实了随着含碳量的升高,BCN的吸附性能也会相应地提升。
[Abstract]:With the attention of human beings to environmental problems, all developed and developing countries have formulated strict oil quality standards for pollutants in fuel oil. In order to keep pace with European V emission standards, the State Council executive meeting in 2013 explicitly set a national V standard, reducing sulphur to 10 ppm and requiring it to be enforced nationwide in 2018. As a new desulfurization technology based on adsorption principle, adsorption desulfurization has more advantages than industrial hydrodesulfurization and other desulphurization technologies, so it is worth to be deeply explored and studied. In this work, the experimental results and phenomena are discussed for the first time by combining theoretical calculations with experiments. The infrared, Raman, and Raman spectra of three non-metallic eutectic solvents (choline chloride / glycerol, choline chloride / acetic acid and choline chloride / urea) are studied respectively. The structure, formation mechanism and so on are discussed in depth. The results show that the ascription of the vibration model is reasonable and all the experimental characteristic peaks can be assigned. The calculated spectra are in good agreement with the experimental results. The structure analysis, electrostatic potential analysis and reduced density gradient analysis show that hydrogen bond and electrostatic interaction coexist in low eutectic solvent. Furthermore, the phenomenon of red shift blue shift in experimental infrared is proved theoretically. Then, based on the adsorption mechanism of 蟺 complexation, ZnCl _ 2 / urea ~ (2 +) SnCl _ 2 / urea was used as raw material to doping Zn and Sn into h-BN, respectively. The results show that in the process of h-BN synthesis, this kind of metal eutectic solvent binds to boric acid and supports Zn and Sn on the surface of h-BN in the form of simple or compound (Zn (CN2) Sno _ 2), forming a composite similar to heterojunction. The adsorbed desulfurization activity of the metal-doped h-BN is superior to that of commercial boron nitride, and the adsorption capacity of SnO2 supported BN can reach 17.93 mg / g. Based on the above facts, another adsorption mechanism, soft and hard acid-base interaction, is used to reduce the chemical hardness of adsorbent by introducing carbon atoms into the h-BN skeleton, thus enhancing the adsorbent's ability to adsorb sulphide. Firstly, the forward orbital and chemical hardness of different carbon atom doped BN_xC material models are analyzed by the concept density functional theory. The results show that the chemical hardness decreases with the increase of carbon content. Based on this result, a series of BCN-x with different carbon content have been synthesized for adsorption desulfurization. The experimental results further verify the conjecture that the adsorption capacity of the BCN-x adsorbent increases with the increase of the carbon atom content in the skeleton, reaching a maximum of 27.43 mg / g. The structure-activity relationship between hardness and its adsorption properties has been proved successfully from the point of view of activity. The calculation of adsorption energy shows that the adsorption performance of BCN will increase with the increase of carbon content.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;O647.3
本文编号：2178563
[Abstract]:With the attention of human beings to environmental problems, all developed and developing countries have formulated strict oil quality standards for pollutants in fuel oil. In order to keep pace with European V emission standards, the State Council executive meeting in 2013 explicitly set a national V standard, reducing sulphur to 10 ppm and requiring it to be enforced nationwide in 2018. As a new desulfurization technology based on adsorption principle, adsorption desulfurization has more advantages than industrial hydrodesulfurization and other desulphurization technologies, so it is worth to be deeply explored and studied. In this work, the experimental results and phenomena are discussed for the first time by combining theoretical calculations with experiments. The infrared, Raman, and Raman spectra of three non-metallic eutectic solvents (choline chloride / glycerol, choline chloride / acetic acid and choline chloride / urea) are studied respectively. The structure, formation mechanism and so on are discussed in depth. The results show that the ascription of the vibration model is reasonable and all the experimental characteristic peaks can be assigned. The calculated spectra are in good agreement with the experimental results. The structure analysis, electrostatic potential analysis and reduced density gradient analysis show that hydrogen bond and electrostatic interaction coexist in low eutectic solvent. Furthermore, the phenomenon of red shift blue shift in experimental infrared is proved theoretically. Then, based on the adsorption mechanism of 蟺 complexation, ZnCl _ 2 / urea ~ (2 +) SnCl _ 2 / urea was used as raw material to doping Zn and Sn into h-BN, respectively. The results show that in the process of h-BN synthesis, this kind of metal eutectic solvent binds to boric acid and supports Zn and Sn on the surface of h-BN in the form of simple or compound (Zn (CN2) Sno _ 2), forming a composite similar to heterojunction. The adsorbed desulfurization activity of the metal-doped h-BN is superior to that of commercial boron nitride, and the adsorption capacity of SnO2 supported BN can reach 17.93 mg / g. Based on the above facts, another adsorption mechanism, soft and hard acid-base interaction, is used to reduce the chemical hardness of adsorbent by introducing carbon atoms into the h-BN skeleton, thus enhancing the adsorbent's ability to adsorb sulphide. Firstly, the forward orbital and chemical hardness of different carbon atom doped BN_xC material models are analyzed by the concept density functional theory. The results show that the chemical hardness decreases with the increase of carbon content. Based on this result, a series of BCN-x with different carbon content have been synthesized for adsorption desulfurization. The experimental results further verify the conjecture that the adsorption capacity of the BCN-x adsorbent increases with the increase of the carbon atom content in the skeleton, reaching a maximum of 27.43 mg / g. The structure-activity relationship between hardness and its adsorption properties has been proved successfully from the point of view of activity. The calculation of adsorption energy shows that the adsorption performance of BCN will increase with the increase of carbon content.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;O647.3
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