本文關(guān)鍵詞： 金屬-有機(jī)骨架材料 硫化物 吸附/分離 分子模擬　出處：《浙江理工大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：隨著煤、石油、天然氣等能源的大量消耗,空氣中SO_2、H_2S等硫化物日益增加,硫化物的存在不僅污染環(huán)境,同時(shí)也將危害人類健康及腐蝕天然氣輸運(yùn)管道設(shè)備等。因此,篩選高效捕獲及分離硫化物的微孔材料有重要的意義。金屬-有機(jī)骨架材料(Metal-organic frameworks,MOFs)因具有較高的比表面積和孔隙率、孔徑可調(diào)性以及高的熱穩(wěn)定性和化學(xué)穩(wěn)定性等獨(dú)特優(yōu)勢(shì),被認(rèn)為是用于硫化物吸附與分離最有前途的新型多孔材料。雖然研究者可通過突破實(shí)驗(yàn)、吸附實(shí)驗(yàn)等方式研究硫化物在不同MOFs材料中的吸附與分離行為,但是目前已經(jīng)報(bào)道和合成的MOFs材料高達(dá)數(shù)萬種,若利用上述方法測(cè)定硫化物在其中的吸附等溫線,成本高、效率低。近年來發(fā)展起來的分子模擬方法能夠快速對(duì)大量MOFs材料進(jìn)行研究,獲得有效的構(gòu)-效關(guān)系,同時(shí)能夠?qū)鹘y(tǒng)實(shí)驗(yàn)手段做出補(bǔ)充,從分子層面揭示吸附機(jī)制。本論文針對(duì)硫化物在不同MOFs材料中的吸附與分離行為與其結(jié)構(gòu)性質(zhì)之間的構(gòu)-效關(guān)系不清楚這一問題,擬采用巨正則系統(tǒng)蒙特卡羅模擬方法探討煙道氣中SO_2及天然氣中H_2S在不同MOFs材料中的吸附與分離行為,揭示MOFs材料與硫化物(SO_2、H_2S)之間的相互作用機(jī)制,闡述MOFs材料的拓?fù)浣Y(jié)構(gòu)、金屬離子以及有機(jī)配體等因素對(duì)硫化物吸附分離性能的影響,為設(shè)計(jì)對(duì)硫化物具有良好吸附與分離性能的MOFs材料提供理論指導(dǎo)和依據(jù)。論文的主要研究結(jié)果如下:(1)拓?fù)浣Y(jié)構(gòu)不同,孔徑不同,低壓下孔徑越小,硫化物與ZIFs材料之間的相互作用越強(qiáng),吸附性能越好。低壓時(shí)硫化物在孔徑較小的ZIF-2中的吸附量最大。高壓時(shí)硫化物在ZIFs材料中的吸附量隨著孔徑或比表面積增大而增加。ZIF-3對(duì)煙道氣中SO_2及天然氣中H_2S具有較優(yōu)的捕獲和選擇性。(2)對(duì)于M-DOBDCs系列材料,不飽和金屬位點(diǎn)和有機(jī)配體配位時(shí)所構(gòu)成角度越大,煙道氣中SO_2與不飽和金屬位點(diǎn)接觸概率越大,其與M-DOBDCs之間相互作用越強(qiáng),而CO2與該M-DOBDCs之間相互作用則越弱,角度最大的Zn-DOBDC材料對(duì)煙道氣中SO_2捕獲與分離性能最優(yōu)。M-DOBDCs系列材料對(duì)天然氣中H_2S的捕獲與分離性能則與不飽和金屬位點(diǎn)和有機(jī)配體配位時(shí)所構(gòu)成角度成反比,角度最小的Mg-DOBDC材料對(duì)H_2S的捕獲與分離性能最佳。(3)對(duì)于有機(jī)配體不同的UMCMs系列材料,N原子的位置不同導(dǎo)致孔道電荷密度分布不同。硫化物傾向于吸附在N原子朝向主孔道的UMCM-150(N)1材料中,該材料對(duì)煙道氣中SO_2及天然氣中H_2S具有較優(yōu)的捕獲和分離性能,向UMCM-150(N)1中引入極性功能化基團(tuán)可以改善其對(duì)硫化物的分離性能,其中極性較大基團(tuán)(硝基和羧基)改性的UMCM-150(N)1材料對(duì)煙道氣中SO_2捕獲和分離性能較佳,經(jīng)過(氨基和羧基)改性的UMCM-150(N)1材料對(duì)天然氣中H_2S具有較優(yōu)的捕獲和分離性能。
[Abstract]:With the massive consumption of coal, oil, natural gas and other energy sources, the number of sulfides such as SO2H2S in the air is increasing day by day. The presence of sulfides will not only pollute the environment, but also endanger human health and corrode natural gas transportation pipeline equipment and so on. It is of great significance to screen microporous materials for high efficiency capture and separation of sulfides. Metal-organic frameworks / MOFss have unique advantages such as high specific surface area and porosity, adjustable pore size, high thermal and chemical stability, etc. It is considered to be the most promising new porous material for the adsorption and separation of sulfides, although researchers can study the adsorption and separation behavior of sulfides in different MOFs materials by breakthrough experiments, adsorption experiments, etc. However, tens of thousands of MOFs materials have been reported and synthesized at present. If the adsorption isotherms of sulfides in them are determined by the above methods, the cost will be high. Low efficiency. Molecular simulation methods developed in recent years can rapidly study a large number of MOFs materials, obtain effective structure-activity relationships, and complement traditional experimental methods. The adsorption mechanism is revealed at the molecular level. In this paper, the structure-activity relationship between the adsorption and separation behavior of sulfides in different MOFs materials and their structural properties is not clear. The adsorption and separation behavior of SO_2 in flue gas and H2S in natural gas in different MOFs materials is studied by means of Monte Carlo simulation of grand canonical system. The mechanism of interaction between MOFs material and so _ 2 / S _ 2 / S _ 2S _ S is revealed, and the topological structure of MOFs material is expounded. Effects of metal ions and organic ligands on the adsorption and separation of sulphide, It provides theoretical guidance and basis for the design of MOFs materials with good adsorption and separation properties for sulfides. The main results of this paper are as follows: the topological structure is different, the pore size is different, and the pore size is smaller at low pressure. The stronger the interaction between sulfides and ZIFs materials, The adsorption capacity of sulfides in ZIF-2 with small pore size is the highest at low pressure. The adsorption capacity of sulfide in ZIFs materials increases with the increase of pore size or specific surface area. ZIF-3 increases the adsorption of SO_2 in flue gas and H2S in natural gas at high pressure. Have better capture and selectivity. 2) for M-DOBDCs, The greater the angle of coordination between unsaturated metal sites and organic ligands, the greater the contact probability between SO_2 and unsaturated metal sites in flue gas, the stronger the interaction between CO2 and M-DOBDCs, but the weaker the interaction between CO2 and M-DOBDCs. The best capture and separation performance of SO_2 in flue gas by the most angled Zn-DOBDC materials. M-DOBDCs series of materials for the capture and separation of H 2S in natural gas are inversely proportional to the angle formed by the coordination of unsaturated metal sites and organic ligands. For organic ligands with different UMCMs series, different positions of N atoms lead to different distribution of pore charge density. Sulfides tend to adsorb toward N atoms. In the UMCM-150(N)1 material of the main pore, The material has better capture and separation performance for SO_2 in flue gas and H2S in natural gas. The introduction of polar functional groups into UMCM-150(N)1 can improve the separation performance of sulfides. The modified UMCM-150(N)1 materials with larger polar groups (nitro and carboxyl groups) have better capture and separation performance for SO_2 in flue gas, and the modified UMCM-150(N)1 materials (amino and carboxylic groups) have better capture and separation performance for H2S in natural gas.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O647.3;X701

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