INFLUENCE OF FLUE GAS COMPONENTS ON NO ABSORPTION BY METHYLUREA-BASED DEEP EUTECTIC SOLVENT
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摘要: 低共熔溶剂(deep eutectic solvents, DESs)作为一种新型的“绿色溶剂”,具有无毒无害、不易蒸发、热稳定性良好等特点,被用于吸收烟气中的有毒气体(NO)。采用甲基脲(MTU)和氯化乙酰胆碱(AchCl)制备低共熔溶剂(MTU-AchCl DESs)进行NO吸收性能研究,重点探究了DESs配比、NO浓度、O2、H2O和CO2对其吸收效果的影响。结果表明:MTU-AchCl DESs在摩尔比为2∶1时的脱硝性能最佳。当烟气中存在O2时,MTU-AchCl DESs对NO由最大吸收量为0.223 g/g,O2通过转化NO为NO2促进其吸收。当烟气中通入CO2时,MTU-AchCl DESs对NO的吸收效果有一定促进。当通入H2O时,DESs的吸收量下降,H2O对DESs体系吸收NO有抑制效果。通过FI-IR和Gaussian模拟计算结果发现,MTU-AchCl DESs与NO以氮氧双键(NO)、氮氧单键(N—O)以及氮氮单键(N—N)的形式结合。加入O2、CO2和H2O后,DESs体系的反应焓从-53.334 kJ/mol分别变化到-56.212,-55.423,-50.982 kJ/mol,模拟结果进一步验证了烟气组分对NO的吸收效果有不同影响。Abstract: Deep eutectic solvents (DESs), as a new kind of green solvent, are non-toxic and harmless, hard to evaporate, and have good thermal stability. Using deep eutectic solvents to soak up toxic gases in flue (especially NO) becomes one of the key lookup contents. In this study, methyl urea (MTU) and acetylcholine chloride (AchCl) were used to prepare a deep eutectic solvent (MTU-AchCl DES) to learn about its NO absorption performance, and impact of DESs’ mixing ratio, NO concentration, O2, H2O and carbon dioxide on the absorption performance. The experimental consequences showed that the overall denitrification performance of MTU-AchCl DESs was best when the molar ratio was 1∶2. When there was O2 in the flue gas, the highest absorption capacity of NO by MTU-AchCl DESs was 0.223 g/g. O2 promoted the absorption with the aid of oxidizing NO into NO2. When CO2 was delivered into the flue gas, the absorption of MTU-AchCl DESs on NO had promotion in a certain degree. When H2O was once introduced, the absorption of DESs decreased, and H2O had an inhibitory impact on the absorption of NO in the DESs system. Through FI-IR and Gaussian simulation results, it was discovered that MTU-AchCl DESs and NO were mixed in the structure of nitrogen-oxygen double bond (NO), nitrogen-oxygen single bond (N—O) and nitrogen-nitrogen single bond (N—N). After the addition of O2, CO2 and H2O, the response enthalpy of the DESs machine changed from -53.334 kJ/mol to -56.212 kJ/mol, -55.423 kJ/mol and -50.982 kJ/mol. The simulation result was further verified that the components of flue gas had different effects on the absorption of NO.
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Key words:
- deep eutectic solvent /
- flue gas components /
- denitration /
- methyl urea /
- absorption
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[1] 段晓谞, 窦金孝, 魏傲然, 等. 粉煤灰负载锰基催化剂低温脱硝活性及水硫抗性的实验研究[J]. 中国电机工程学报, 2022, 42(11): 4102-4112. [2] 梁宝瑞, 王斌, 马志亮, 等. 负载Mn型类水滑石结构催化剂同时催化净化NOx和o-DCB研究[J]. 环境工程, 2022, 40(2): 8-13. [3] 滕玉婷, 张亚平, 王玲, 等. 干湿法结合工艺回收废弃SCR脱硝催化剂中的钛、钒和钨[J]. 环境工程, 2020, 38(11): 163-167. [4] 窦金孝, 赵永奇, 段晓谞, 等. 络合亚铁乙二醇-四丁基溴化铵低共熔溶剂协同吸收SO2和NO[J]. 化工进展, 2020,39(2): 453-460. [5] CHEN Y, HAN X X, LIU Z H, et al. Capture of toxic gases by deep eutectic solvents[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(14): 5410-5430. [6] 裴鉴禄, 王坤俊, 陈欣, 等. 氨基离子液体负载活性炭CO2吸附性能的负协同效应[J]. 环境工程, 2022, 40(11): 78-83. [7] CATARINA F, FILIPA L, BERNARDO D R, et al. Deep eutectic solvents: overcoming 21st century challenges[J]. Current Opinion in Green and Sustainable Chemistry, 2019, 18: 31-36. [8] CHEN Y, MU T. Application of deep eutectic solvents in biomass pretreatment and conversion[J]. Green Energy & Environment, 2019, 4: 95-115. [9] CHEN W J, JIANG J Y, LAN X, et al. A strategy for the dissolution and separation of rare earth oxides by novel BrØnsted acidic deep eutectic solvents[J]. Green Chemistry, 2019, 21: 4748-4756. [10] MOU H Y, WANG J F, ZHANG D L, et al. A one-step deep eutectic solvent assisted synthesis of carbon nitride/metal oxide composites for photocatalytic nitrogen fixation[J]. Journal of Materials Chemistry A, 2019, 7(10): 5719-5725. [11] DOU J X, ZHAO Y Q, YIN F K, et al. Mechanistic study of selective absorption of NO in flue gas using EG-TBAB deep eutectic solvents[J]. Environmental Science & Technology, 2019, 53(2): 1031-1038. [12] ZHAO Y Q, DOU J Q, WEI A R, et al. Highly efficient and reversible low-concentration SO2 absorption in flue gas using novel phosphonium-based deep eutectic solvents with different substituents[J]. Journal of Molecular Liquids, 2021, 340: 117228. [13] WAITE S L, LI H, PAGE A J, et al. NO2 solvation structure in choline chloride deep eutectic solvents-the role of the hydrogen bond donor[J]. The Journal of Physical Chemistry B, 2018, 122(15): 4336-4344. [14] HOU Y C, YAO C F, WU W Z. Deep eutectic solvents: green solvents for separation applications[J]. Journal of the Air & Waste Management Association, 2018, 61(12): 873-885. [15] SUN Y L, WEI G S, TANTAI X W, et al. Highly efficient nitric oxide absorption by environmentally friendly deep eutectic solvents based on 1,3-dimethylthiourea[J]. Energy & Fuels, 2017, 31(11): 12439-12445. [16] ZHANG L H, MA H P, WEI G S, et al. Efficient and reversible nitric oxide absorption by low-viscosity, azole-derived deep eutectic solvents[J]. Journal of Chemical & Engineering Data, 2019, 64(7): 3068-3077. [17] YU D K, MOU H Y, ZHAO X H, et al. Eutectic Molecular Liquids Based on Hydrogen Bonding and π-π Interaction for Exfoliating Two-dimensional Materials and Recycling Polymers[J]. Chemistry-An Asian Journal, 2019, 14(19): 3350-3356. [18] CUI G K, LI Y N, LIU J X, et al.Tuning Environmentally Friendly Chelate-Based Ionic Liquids for Highly Efficient and Reversible SO2 Chemisorption[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 15292-15300. [19] 张盈盈, 陆小华, 冯新, 等. 胆碱类低共熔溶剂的物性及应用[J]. 化学进展, 2013, 25(6): 881-892. [20] SUN Y, GAO M J, REN S H, et al. Highly efficient absorption of NO by amine-based functional deep eutectic solvents[J]. Energy & Fuels, 2020, 34(1): 690-697. [21] MERT A, SANTIAGO A. A nanoscopic explanation of nitric oxide solubility in natural deep eutectic solvents[J]. Journal of Molecular Liquids, 2021, 324: 114673. [22] 张吕鸿, 马号朋, 澹台晓伟, 等. 苯甲酸型低共熔溶剂吸收一氧化氮的性能研究[J].化工学报, 2020, 71(8): 3644-3651. [23] CHEN C C, WANG C Y, HUANG Y H. Reversible absorption of nitrogen dioxide by choline chloride-based deep eutectic solvents and their aqueous mixtures[J]. Chemical Engineering Journal, 2021, 405: 126760. [24] ZHOU T T, ZHAO Y Q, XIAO X X, et al. Effective absorption mechanism of SO2 and NO2 in the flue gas by ammonium-bromide-based deep eutectic solvents[J]. ACS Omega, 2022, 7(33): 29171-29180. [25] MOURA L, KOLLAU L, GOMES M C. Solubility of gases in deep eutectic solvents[J]. Environmental Chemistry for a Sustainable World, 2020, 56: 131-155. [26] WAZEER I, HADJ-KALI M K, AL-NASHEF I M. Utilization of deep eutectic solvents to reduce the release of hazardous gases to the atmosphere: a critical review[J]. Molecules, 2021, 26: 75. [27] ZHENG W T, XIA G B, YU G W, et al. Efficient absorption and thermodynamic modeling of nitric oxide by low viscous DBU-based N-heterocyclic deep eutectic solvents[J]. Journal of Molecular Liquids, 2022, 360: 119469. [28] CAO N N, GAN L, XIAO Q X, et al. Highly efficient and reversible nitric oxide capture by functionalized ionic liquids through multiple-site absorption[J]. Journal of Chemical & Engineering Data, 2020, 8: 2990-2995. [29] JIANG B, LIN W R, ZHANG L H, et al. 1, 3-Dimethylurea tetrabutylphosphonium bromide ionic liquids for NO efficient and reversible capture[J]. Energy & Fuels, 2016, 30(1): 735-739. [30] 徐环斐, 彭建军, 宋晓明, 等. 低共熔溶剂的分子模拟研究进展[J].齐鲁工业大学学报, 2019, 33(5): 1-9. [31] ALI M C, YANG Q W, ANDREW A, et al. Efficient removal of both basic and non-basic nitrogen compounds from fuels by deep eutectic solvents[J]. Green Chemistry, 2016, 18(1): 157-164. [32] FILIPA L, MAXIME D, ARMANDO J D, et al. Concurrent desulfurization and denitrogenation of fuels using deep eutectic solvents[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(13): 11341-11349.
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