基于低共熔溶劑的新型吸附劑合成及其在吸附脫硫中的應用
發(fā)布時間：2018-08-12 08:54
【摘要】：隨著人類對環(huán)境問題的關注,所有的發(fā)達國家與發(fā)展中國家都針對燃油中污染物制定了嚴格的油品質(zhì)量標準。為了與歐V排放標準同步,2013年國務院常務會議明確制定了國V標準,將硫含量降低至10 ppm,并要求于2018年在全國范圍內(nèi)強制實行。在目前眾多的脫硫技術中,吸附脫硫作為一種利用吸附原理的新興的脫硫技術,相比于工業(yè)加氫脫硫與其他脫硫技術有較多的優(yōu)點,故值得被深度發(fā)掘與研究。本工作首次使用理論計算與實驗相結(jié)合的方式來討論實驗結(jié)果與現(xiàn)象,分別對三種非金屬型低共熔溶劑(氯化膽堿/甘油,氯化膽堿/乙酸和氯化膽堿/尿素)的紅外,拉曼,結(jié)構,形成機理等角度來深入討論。結(jié)果表明先前實驗工作的振動模型的歸屬是合理的,并且所有的實驗特征峰都能夠得到歸屬,計算所得的光譜與實驗結(jié)果符合的較好。通過結(jié)構分析,靜電勢分析,約化密度梯度分析證明低共熔溶劑中共存著氫鍵作用與靜電作用,進而從理論角度證明了實驗紅外中的紅移藍移現(xiàn)象。隨后從π絡合作用吸附機理出發(fā),將ZnCl2/urea,SnCl2/urea作為原料,分別將金屬Zn和Sn摻雜到h-BN中。結(jié)果發(fā)現(xiàn)在h-BN的合成過程中,此類金屬型低共熔溶劑會與硼酸結(jié)合,將Zn和Sn以單質(zhì)或化合物形式(Zn(CN2),SnO2)負載到h-BN表面,形成類似于異質(zhì)結(jié)的復合材料。所合成的金屬摻雜h-BN材料在吸附脫硫活性方面優(yōu)于商品級氮化硼,其中SnO2負載BN的吸附容量可達17.93 mg/g�；谝陨鲜聦�,本文從另一吸附機理出發(fā),即軟硬酸堿作用,通過在h-BN骨架中引入碳原子的方式來降低吸附劑的化學硬度,從而增強了吸附劑吸附硫化物的能力。首先通過概念密度泛函分析了不同碳原子摻雜的BN_xC材料模型的前線軌道與化學硬度。計算結(jié)果發(fā)現(xiàn)化學硬度都隨著碳含量的提升而降低,基于這一結(jié)果本文合成了一系列不同碳含量的BCN-x用于吸附脫硫。實驗結(jié)果進一步驗證了猜想:BCN-x吸附劑的吸附容量隨著骨架中碳原子含量的提升而提升,最高可達27.43 mg/g,成功從活性的角度證明了硬度與其吸附性能之間的構效關系。通過吸附能的計算,證實了隨著含碳量的升高,BCN的吸附性能也會相應地提升。
[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.
【學位授予單位】：江蘇大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36;O647.3
本文編號：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.
【學位授予單位】：江蘇大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36;O647.3
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